EP1874982A1 - Methode d'electrodeposition de bronzes - Google Patents

Methode d'electrodeposition de bronzes

Info

Publication number
EP1874982A1
EP1874982A1 EP06750231A EP06750231A EP1874982A1 EP 1874982 A1 EP1874982 A1 EP 1874982A1 EP 06750231 A EP06750231 A EP 06750231A EP 06750231 A EP06750231 A EP 06750231A EP 1874982 A1 EP1874982 A1 EP 1874982A1
Authority
EP
European Patent Office
Prior art keywords
thioether
concentration
electrolytic composition
thiobis
substituted
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
Application number
EP06750231A
Other languages
German (de)
English (en)
Other versions
EP1874982B1 (fr
EP1874982A4 (fr
Inventor
Katrin Zschintzsch
Joachim Heyer
Marlies Kleinfeld
Stefan Schafer
Ortrud Steinius
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.)
MacDermid Enthone Inc
Original Assignee
Enthone Inc
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 Enthone Inc filed Critical Enthone Inc
Publication of EP1874982A1 publication Critical patent/EP1874982A1/fr
Publication of EP1874982A4 publication Critical patent/EP1874982A4/fr
Application granted granted Critical
Publication of EP1874982B1 publication Critical patent/EP1874982B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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

  • This invention concerns a method for electrodeposition of bronzes, with which the substrate to be coated is plated in an acid electrolyte that contains at least tin and copper ions, an alkylsulfonic acid and a wetting agent, and the preparation of such an electrolyte.
  • acid electrolytes and methods for deposition of qualitatively high grade tin or tin alloys with a higher deposition rate are known from EP 1 111 097 A2 and US 6,176,996 Bl. These are electrolytes that contain at least two divalent metal salts of an organic sulfonic acid and from which are deposited solderable and corrosion resistant coatings that can be used, for example, as substitutes for lead-containing solderable coatings in electronics for manufacture of circuit boards, etc.
  • bronze coatings are used in the jewelry industry as a substitute for expensive silver or allergy-triggering nickel.
  • methods for electrodeposition of bronzes are also gaining importance in some technical fields, for example in electronics for coating electronic components or in mechanical engineering and/or in process technology for coating bearing overlays and friction layers.
  • chiefly white bronzes or the so-called "false bronzes,” whose copper content can be kept quite low due to process conditions, are deposited as nickel substitutes.
  • the invention is based on the task of providing a method for deposition of bronzes that, in contrast to the methods known from the prior art, enables uniform deposition of at least tin and copper side by side from an acid electrolyte at considerably higher deposition rates. Moreover, with this method firmly bonding and pore- free bronze coatings with high copper contents as well as various decorative and mechanical properties are said to be deposited.
  • an acid electrolyte that can have a high content of divalent copper ions, is stable with respect to oxidation-caused sludge formation, and is both economical and environmentally friendly when used over a long period of time, is to be made available.
  • the task is solved in accordance with the invention by a method of the kind mentioned at the start, which is characterized by the fact that an aromatic, nonionic wetting agent is added to the electrolyte.
  • a method for electrodeposition of bronzes is made available, where an anode of a copper-tin alloy and a cathode are connected to the substrate that is to be coated by means of an electrolyte, and coating takes place by passing a direct current through them.
  • an electrolyte that is usable in particular for this method and the coatings that are obtainable by this method are made available .
  • the disadvantages known in the prior art are remedied with the offering of a new electrolyte composition and in this way considerably better deposition results are achieved.
  • the conduct of the method is made to be simpler and more economical. This, too, is chiefly based on the advantageous composition of the electrolyte.
  • the method is carried out at room temperature, or between 17 and 25°C, and the substrate to be coated is plated in a highly acid environment at a pH ⁇ 1.
  • the electrolyte is particularly stable in this temperature range.
  • there are no longer any costs for heating the electrolyte and the plated substrates also do not have to be cooled very much, with large expenditures of time and money.
  • deposition rates of 0.25 microns/min at a current density of 1 A/dm 2 are achieved due to, among other things, the pH value and the advantageous addition of at least one aromatic non-ionic wetting agent. By increasing the metal content this rate can be raised up to 7 A/dm 2 in rack operation and even up to 120 A/dm 2 for continuous plants.
  • usable current densities in a range from 0.1-120 A/dm 2 are reached in each case according to plant type .
  • the wetting of the surfaces to be plated is considerably improved in particular through the addition of at least one nonionic wetting agent to the electrolyte.
  • nonionic wetting agent that is used is that because of the advantageous wetting properties the electrolyte and/or the substrate in the electrolyte need to be agitated only a little or even not at all, in order to achieve the desired deposition results, so that additional devices for agitation of the electrolyte can be omitted.
  • aromatic nonionic wetting agent because of the advantageous use of the aromatic nonionic wetting agent, electrolyte residues drain from the plated substrate better when it is removed from the electrolyte, which leads to reduced entrainment losses and thus to lower process costs .
  • the proposed method is therefore advantageously economical and environmentally friendly compared to the cyanide processes .
  • anionic and/or aliphatic nonionic wetting agent that is known from the prior art is also optionally possible, provided these wetting agents support or even enhance the advantageous effects of the aromatic nonionic wetting agent.
  • polyethylene glycols and/or anionic surfactants are preferably added to the electrolyte as anionic and/or aliphatic nonionic wetting agents .
  • Additional exemplary aliphatic nonionic wetting agents include aliphatic fatty alcohol ethoxylates, with compounds having from 13 to 15 carbon atoms (C-13 to C-15) being especially preferred.
  • the fatty alcohol ethoxylate is incorporated in a concentration of, for example, about 0.1 to 10 g/L; preferably about 0.5 to about 5 g/L.
  • concentration of, for example, about 0.1 to 10 g/L; preferably about 0.5 to about 5 g/L.
  • substituted dithioglycols act advantageously as wetting agents and brighteners . These compounds provide a source of sulphur which has a positive effect on copper plating. Therefore, certain embodiments of the invention include substituted dithioglycols, such as, for example, those selected from the group consisting of:
  • Dithiobis (hentetracontaethyleneglycol) represented by H- (OCH 2 CH 2 ) 4 1 -S-S- (CH 2 CH 2 O) 4X -H,
  • Dithiobis (icosaethyleneglycolpentapropyleneglycol) represented by H- (OC 3 H 6 ) 5 - r (OC 2 H 4 ) 20 -S-S- (OC 2 H 4 ) 20 - (OC 3 H 6 ) 5 -H,
  • (22) 1, 4-Buthanedithiolbis (pentadecaglycerol) thioether represented by H- (OCH 2 CH (OH) CH 2 ) I5 -S-C 4 H 8 -S- (CH 2 CH (OH) CH 2 O) 15 -H,
  • Triacontaethyleneglycolmono (4 -cyanobenzyl) thioether represented by NC-Ph-CH 2 -S-(CH 2 CH 2 O) 30 -H,
  • Tricosaethyleneglycolmono (4 -formylphenetyl) thioether represented by OHC-Ph-CH 2 CH 2 -S-(CH 2 CH 2 O) 2S -H,
  • Pentadecaethyleneglycolmono ⁇ (acetylmethyl) thioethyl ⁇ thioether represented by CH 3 COCH 2 -S-CH 2 CH 2 -S-(CH 2 CH 2 O) 15 -H,
  • Pentatriacontaethyleneglycolmono (2-n- butyldithioethyl) dithioether represented by C 4 H 9 -S-S-CH 2 CH 2 -S-S- (CH 2 CH 2 O) 35 -H,
  • Tridecaethyleneglycolmonomethylthioether represented by CH 3 -S- (CH 2 CH 2 O) I0 -H,
  • Ph represents a phenyl group.
  • the substituted dithioglycol in incorporated in a concentration of about 5 to about 100 mg/L; preferably about 10 to about 50 mg/L.
  • the method in accordance with the invention is characterized in particular by the special composition of the electrolyte. It contains essentially tin and copper ions, an alkylsulfonic acid and an aromatic nonionic wetting agent.
  • stabilizers and/or complexing agents, anionic and/or nonionic, aliphatic and/or substituted dithioglycol wetting agents, oxidation inhibitors, brighteners, and other metal salts can optionally be contained in the electrolyte.
  • the metals that are primarily added to the electrolyte for deposition of bronzes in accordance with the invention - tin and copper - can first and foremost be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates, or as salts of mineral acids, preferably as sulfates.
  • Tin methanesulfonate is especially preferably used as tin salt in the electrolyte preferably in an amount of 5-195 g/L of electrolyte, preferably 11-175 g/L of electrolyte. This corresponds to a use of 2-75 g/L, preferably 4-57 g/L divalent tin ions.
  • Copper methanesulfonate is especially preferably used in the electrolyte as the copper salt, which is advantageously added to the electrolyte in an amount of 8-280 g/L of electrolyte, preferably 16-260 g/L of electrolyte. This corresponds to the use of 2-70 g/L, preferably 4-65 g/L divalent copper ions.
  • an acid preferably a mineral and/or an alkylsulfonic acid
  • an acid is added to the electrolyte in amounts of 140-382 g/L of electrolyte, preferably 175-245 g/L of electrolyte.
  • methanesulfonic acid turned out to be especially advantageous, since for one thing this produces advantageous solubility of metal salts and for another, because of its acid strength, it produces or facilitates the adjustment of the pH needed for the process.
  • methanesulfonic acid has the advantageous property of contributing considerably 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 has a considerable effect on the properties of the deposited coatings.
  • the metals zinc and/or bismuth added to the electrolyte can namely be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates or as salts of mineral acids, preferably as sulfates.
  • Zinc sulfate is especially preferably uses in the electrolytes as zinc salt, and is advantageously added in an amount of 0-25 g/L of electrolyte, preferably 15-20 g/L of electrolyte.
  • Bismuth methane sulfate is especially preferably used in the electrolyte as bismuth salt and is advantageously added to the electrolyte in an amount of 0-5 g/L of electrolyte, preferably 0.05-0.2 g/L of electrolyte.
  • additives for example stabilizers and/or complexing agents, oxidation inhibitors and brighteners, that are usually used in acid electrolytes for deposition of tin alloys can be added to the electrolyte.
  • Gluconates are advantageously added to the electrolyte and stabilizers and/or complexing agents.
  • the concentration of the stabilizers and/or complexing agents is 0-50 g/L of electrolyte, preferably 20-30 g/L of electrolyte.
  • Compounds from the class of the dihydroxybenzenes, for example mono- or polyhydroxyphenyl compounds like pyrocatechol or phenolsulfonic acid are preferably used as oxidation inhibitors.
  • the concentration of oxidation inhibitors is 0-5 g/L of electrolyte.
  • Sodium hypophosphite is optionally used as an additional oxidation inhibitor.
  • the electrolyte contains hydroquinone as oxidation inhibitor.
  • the conduct of the method in accordance with the invention enables the deposition of bronzes onto various substrates.
  • all of the usual methods for making electronic components can be used.
  • especially hard and wear-resistant bronze coatings can be deposited on materials like bearings, etc., to the method in accordance with the invention.
  • the method in accordance with the invention is advantageously also used in the fields of decorative coating of, for example, fixtures and jewelry, etc., where the deposition of multi-component alloys that contain tin, copper, zinc and bismuth is particularly advantageous in these areas .
  • a really special advantage is that the so-called "true" bronzes that have a copper content >60% can be deposited with the method in accordance with the invention, where the copper content can be up to 95 wt% in each according to the desired properties.
  • the ratio of the amount of copper to the amount of tin in the electrolyte has a considerable effect of properties like hardness and color of the bronze coatings. For instance, at a tin/copper ratio of 40/60 silver-colored coatings, the so-called white bronzes, which are relatively soft, are deposited.
  • the invention is effective for forming white bronze deposits having a tin/copper weight ratio of about 40/60 or less, yellow bronze deposits having a tin/copper weight ratio of about 20/80 or less, and even red bronze deposits having a tin/copper weight ratio of about 10/90 or less.
  • the electrolyte contains brighteners from the class of the aromatic carbonyl compounds and/or a,a- unsaturated carbonyl compounds .
  • the concentration of brighteners is 0-5 g/L of electrolyte.
  • Electrolyte composition :
  • the base electrolyte of the highly acid electrolyte in accordance with the invention contains essentially (per liter of electrolyte)
  • electrolyte per liter of electrolyte: 0-10 g of an anionic and/or aliphatic nonionic wetting agent,
  • the electrolyte is prepared by varying the individual components, as given below as a matter of example Additional information about the corresponding process conditions as well as other properties of the individual coatings can be seen in Table 1.
  • Example 1 (red bronze) 4 g/L Sn 2+ 18 g/L Cu 2+ 286 g/L methanesulfonic acid
  • Example 2b (yellow bronze) 4 g/L Sn 2+ 18 g/L Cu 2+
  • Example 4_ (matte white bronze) 18 g/L Sn 2+
  • Example j5 (high ductility) 4 g/L Sn 2+ 18 g/L Cu 2+
  • Example 1_ (yellow bronze) 14.5 g/L Sn 2+ 65.5 g/L Cu 2+
  • Example B_ (yellow bronze) 2 g/L Sn 2+ 8 g/L Cu 2+
  • Example 9_ (white bronze) 4 g/L Sn 2+ 8 g/L Cu 2+
  • Electrolytic coating was performed on a copper plated brass substrate at 25 C and a current density of 1.2 A/dm 2 with soluble bronze (60Cu/40Sn) anodes for 8 minutes to a thickness of 3 microns. Ductility was acceptable; uniformity was good; hardness was 350 HV25; gloss was very good. The specimens passed a thio acetimide tarnish resistance test (storage 4 hours at 180 C) .

Landscapes

  • 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)

Abstract

Méthode d'électrodéposition de bronzes, selon laquelle le substrat à enduire est galvanisé dans un électrolyte acide contenant au moins des ions étain et cuivre, un acide alkylsulfonique, et un agent de mouillage, et préparation d'un tel électrolyte.
EP06750231.0A 2005-04-14 2006-04-14 Methode d'electrodeposition de bronzes Expired - Lifetime EP1874982B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/105,947 US20060260948A2 (en) 2005-04-14 2005-04-14 Method for electrodeposition of bronzes
PCT/US2006/014141 WO2006113473A1 (fr) 2005-04-14 2006-04-14 Methode d'electrodeposition de bronzes

Publications (3)

Publication Number Publication Date
EP1874982A1 true EP1874982A1 (fr) 2008-01-09
EP1874982A4 EP1874982A4 (fr) 2011-07-27
EP1874982B1 EP1874982B1 (fr) 2014-05-07

Family

ID=37115474

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06750231.0A Expired - Lifetime EP1874982B1 (fr) 2005-04-14 2006-04-14 Methode d'electrodeposition de bronzes

Country Status (7)

Country Link
US (1) US20060260948A2 (fr)
EP (1) EP1874982B1 (fr)
JP (1) JP2008537017A (fr)
KR (1) KR101361431B1 (fr)
CN (1) CN101194049B (fr)
TW (1) TWI391534B (fr)
WO (1) WO2006113473A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011008836A1 (de) 2010-08-17 2012-02-23 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur Abscheidung von Kupfer-Zinn-Legierungsschichten

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2531163T3 (es) * 2002-10-11 2015-03-11 Enthone Procedimiento y electrolito para la deposición galvánica de bronces
DE102004041701A1 (de) * 2004-08-28 2006-03-02 Enthone Inc., West Haven Verfahren zur elektrolytischen Abscheidung von Metallen
US7296370B2 (en) * 2004-09-24 2007-11-20 Jarden Zinc Products, Inc. Electroplated metals with silvery-white appearance and method of making
US9263609B2 (en) * 2006-05-24 2016-02-16 Atotech Deutschland Gmbh Metal plating composition and method for the deposition of copper—zinc—tin suitable for manufacturing thin film solar cell
US8426241B2 (en) 2010-09-09 2013-04-23 International Business Machines Corporation Structure and method of fabricating a CZTS photovoltaic device by electrodeposition
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
JP6101510B2 (ja) * 2013-02-18 2017-03-22 株式会社シミズ 非シアン銅−錫合金めっき浴
US8945978B2 (en) * 2013-06-28 2015-02-03 Sunpower Corporation Formation of metal structures in solar cells
KR20160094385A (ko) 2013-12-05 2016-08-09 허니웰 인터내셔날 인코포레이티드 조절된 pH를 갖는 주석(II) 메탄술포네이트 용액
US10155894B2 (en) 2014-07-07 2018-12-18 Honeywell International Inc. Thermal interface material with ion scavenger
CA2957587C (fr) * 2014-08-08 2019-03-05 Okuno Chemical Industries Co., Ltd. Bain de placage d'alliage de cuivre-etain
US20160298249A1 (en) * 2014-09-30 2016-10-13 Rohm And Haas Electronic Materials Llc Cyanide-free electroplating baths for white bronze based on copper (i) ions
CN107250317A (zh) 2014-12-05 2017-10-13 霍尼韦尔国际公司 具有低热阻的高性能热界面材料
CN107771227B (zh) * 2015-04-20 2019-04-02 埃托特克德国有限公司 电解铜镀液组合物及其用法
CA2989621A1 (fr) * 2015-06-16 2016-12-22 3M Innovative Properties Company Bronze de placage sur feuilles de polymere
US10312177B2 (en) 2015-11-17 2019-06-04 Honeywell International Inc. Thermal interface materials including a coloring agent
MX393621B (es) 2016-03-08 2025-03-24 Honeywell Int Inc Material de camibo de fase.
US10501671B2 (en) 2016-07-26 2019-12-10 Honeywell International Inc. Gel-type thermal interface material
US11041103B2 (en) 2017-09-08 2021-06-22 Honeywell International Inc. Silicone-free thermal gel
US10428256B2 (en) 2017-10-23 2019-10-01 Honeywell International Inc. Releasable thermal gel
CN108103540B (zh) * 2018-01-24 2020-01-07 永星化工(上海)有限公司 锡合金电镀液
US11072706B2 (en) 2018-02-15 2021-07-27 Honeywell International Inc. Gel-type thermal interface material
CN112236548B (zh) * 2018-07-27 2022-03-04 三菱综合材料株式会社 锡合金镀液
JP6645609B2 (ja) 2018-07-27 2020-02-14 三菱マテリアル株式会社 錫合金めっき液
US11373921B2 (en) 2019-04-23 2022-06-28 Honeywell International Inc. Gel-type thermal interface material with low pre-curing viscosity and elastic properties post-curing

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2854388A (en) * 1955-03-14 1958-09-30 City Auto Stamping Co Electrodeposition of copper-tin alloys
US2916423A (en) * 1957-06-19 1959-12-08 Metal & Thermit Corp Electrodeposition of copper and copper alloys
DE3339541C2 (de) * 1983-11-02 1986-08-07 Degussa Ag, 6000 Frankfurt Alkalisch-cyanidisches Bad zur galvanischen Abscheidung von Kupfer-Zinn-Legierungsüberzügen
DE3934866A1 (de) * 1989-10-19 1991-04-25 Blasberg Oberflaechentech Verfahren zur abscheidung von blei- und bleihaltigen schichten, elektrolyte zur durchfuehrung des verfahrens sowie verwendung von tensiden in sauren blei-elektrolyten
JP2901292B2 (ja) * 1989-12-05 1999-06-07 住友ゴム工業 株式会社 ゴムコーティングタイヤ用ビードワイヤおよびそれを用いたタイヤ
DE4336664A1 (de) * 1993-10-27 1995-05-04 Demetron Gmbh Werkstücke aus nichtkorrosionsbeständigen Metallen mit nach dem PVD-Verfahren aufgebrachten Überzügen
US5385661A (en) * 1993-09-17 1995-01-31 International Business Machines Corporation Acid electrolyte solution and process for the electrodeposition of copper-rich alloys exploiting the phenomenon of underpotential deposition
US6176996B1 (en) * 1997-10-30 2001-01-23 Sungsoo Moon Tin alloy plating compositions
TW577938B (en) * 1998-11-05 2004-03-01 Uyemura C & Co Ltd Tin-copper alloy electroplating bath and plating process therewith
JP4359907B2 (ja) * 1999-08-11 2009-11-11 石原薬品株式会社 スズ−銅合金メッキ浴
JP3433291B2 (ja) * 1999-09-27 2003-08-04 石原薬品株式会社 スズ−銅含有合金メッキ浴、スズ−銅含有合金メッキ方法及びスズ−銅含有合金メッキ皮膜が形成された物品
JP2001107287A (ja) * 1999-10-07 2001-04-17 Ebara Udylite Kk Ｓｎ−Ｃｕ合金めっき浴
JP2001181889A (ja) * 1999-12-22 2001-07-03 Nippon Macdermid Kk 光沢錫−銅合金電気めっき浴
JP2001234387A (ja) * 2000-02-17 2001-08-31 Yuken Industry Co Ltd 錫系電気めっきのウィスカー発生防止剤および防止方法
EP1325175B1 (fr) * 2000-09-20 2005-05-04 Dr.Ing. Max Schlötter GmbH & Co. KG Electrolyte et procede pour deposer des couches d'alliages etain-cuivre
KR20020073434A (ko) * 2001-03-16 2002-09-26 쉬플리 캄파니, 엘.엘.씨. 주석 도금
JP3876383B2 (ja) * 2002-06-03 2007-01-31 京都市 銅−錫合金めっき浴及び該めっき浴を用いた銅−錫合金めっき方法
ES2531163T3 (es) * 2002-10-11 2015-03-11 Enthone Procedimiento y electrolito para la deposición galvánica de bronces
KR20040073974A (ko) * 2003-02-14 2004-08-21 롬 앤드 하스 일렉트로닉 머트어리얼즈, 엘.엘.씨. 전기도금 조성물

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011008836A1 (de) 2010-08-17 2012-02-23 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur Abscheidung von Kupfer-Zinn-Legierungsschichten
WO2012022689A1 (fr) 2010-08-17 2012-02-23 Umicore Galvanotechnik Gmbh Electrolyte et procédé de dépôt de couches en alliage de cuivre-étain
DE102011008836B4 (de) * 2010-08-17 2013-01-10 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur Abscheidung von Kupfer-Zinn-Legierungsschichten

Also Published As

Publication number Publication date
TWI391534B (zh) 2013-04-01
KR20070120600A (ko) 2007-12-24
CN101194049A (zh) 2008-06-04
CN101194049B (zh) 2011-12-07
KR101361431B1 (ko) 2014-02-10
US20060260948A2 (en) 2006-11-23
JP2008537017A (ja) 2008-09-11
EP1874982B1 (fr) 2014-05-07
EP1874982A4 (fr) 2011-07-27
WO2006113473A1 (fr) 2006-10-26
TW200702498A (en) 2007-01-16
US20050263403A1 (en) 2005-12-01

Similar Documents

Publication Publication Date Title
EP1874982B1 (fr) Methode d'electrodeposition de bronzes
US20060137991A1 (en) Method for bronze galvanic coating
USRE35513E (en) Cyanide-free plating solutions for monovalent metals
CN102016130B (zh) 改性铜-锡电解液和沉积青铜层的方法
US6165342A (en) Cyanide-free electroplating bath for the deposition of gold and gold alloys
JPS6362595B2 (fr)
CN102089466B (zh) 改良的铜-锡电解液和沉积青铜层的方法
US9145617B2 (en) Adhesion promotion of cyanide-free white bronze
JP4446040B2 (ja) 錫−銀合金層を電着させるための電解液および方法
US4515663A (en) Acid zinc and zinc alloy electroplating solution and process
CN103069054B (zh) 用于沉积铜-锡合金层的电解质和方法
US20040195107A1 (en) Electrolytic solution for electrochemical deposition gold and its alloys
JP2013534276A5 (fr)
US11643742B2 (en) Silver/tin electroplating bath and method of using the same
US3440151A (en) Electrodeposition of copper-tin alloys
JPS6141999B2 (fr)
US4615774A (en) Gold alloy plating bath and process
GB2167447A (en) Cyanide free copper plating process
US4565611A (en) Aqueous electrolytes and method for electrodepositing nickel-cobalt alloys
JPH09296274A (ja) 金属錯体形成用水溶液、錫−銀合金めっき浴およびこのめっき浴を用いためっき物の製造方法
HK1152352B (en) Modified copper-tin electrolyte and process for the deposition of bronze layers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071025

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20110624

17Q First examination report despatched

Effective date: 20120224

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140107

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 666787

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140515

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006041478

Country of ref document: DE

Effective date: 20140626

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 666787

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140507

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140507

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140907

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140808

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006041478

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150210

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006041478

Country of ref document: DE

Effective date: 20150210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150414

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20150414

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150414

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150414

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20060414

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140507

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: UPC_APP_327740/2023

Effective date: 20230524

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250319

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20250319

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250319

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 602006041478

Country of ref document: DE