EP2205778B1 - Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids - Google Patents

Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids Download PDF

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Publication number
EP2205778B1
EP2205778B1 EP08804009A EP08804009A EP2205778B1 EP 2205778 B1 EP2205778 B1 EP 2205778B1 EP 08804009 A EP08804009 A EP 08804009A EP 08804009 A EP08804009 A EP 08804009A EP 2205778 B1 EP2205778 B1 EP 2205778B1
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Prior art keywords
bath
copper
gold
gold alloy
cyanide
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German (de)
French (fr)
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EP2205778A1 (en
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Giuseppe Aliprandini
Michel Caillaud
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Swatch Group Research and Development SA
G Aliprandini
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Swatch Group Research and Development SA
G Aliprandini
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    • 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 an electrolytic deposit in the form of a gold alloy in a thick layer and its production process.
  • the object of the present invention is to overcome all or part of the disadvantages mentioned above by proposing a method for the deposition in thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.
  • the invention relates to an electrolytic deposit in the form of a gold alloy whose thickness is between 1 and 800 microns and comprises copper characterized in that it comprises indium as third main compound.
  • the invention also relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, a free cyanide characterized in that the alloying metals are copper in the form of copper and potassium double cyanide, and indium in aminocarboxylic or aminophosphonic complexed form for depositing on the electrode a yellow gold alloy brilliant mirror.
  • the electrolysis is preferably followed by a heat treatment at least 450 degrees Celsius for at least 30 minutes to obtain an optimal quality deposit.
  • the bath may further contain a brightener.
  • a brightener This is preferably a butynediol derivative, a pyridinio-propanesulfonate or a mixture of both, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.
  • a gold alloy free of toxic metals or metalloids, in particular free of cadmium, of 2N color. yellow, with a thickness of 200 microns, excellent gloss and having a very high resistance to wear and tarnishing.
  • the electrolytic bath is contained in a polypropylene or PVC tank with heat-insulating coating. Bath heating is achieved by thermo-plungers in quartz, PTFE, porcelain or stabilized stainless steel. Good cathodic stirring as well as a flow of the electrolyte must be maintained.
  • the anodes are platinum titanium, stainless steel, ruthenium, iridium or alloys of the latter two.
  • the bath may contain the following metals Ag, Cd, Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantity.
  • the wetting agent may be of any type capable of wetting in alkaline cyanide medium.

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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)
  • Physical Vapour Deposition (AREA)

Abstract

A galvanic bath, containing: gold metal in the form of alkaline aurocyanide; organometallic components; a wetting agent; a complexing agent; free cyanide; copper metal in the form of copper II cyanide and potassium; and indium metal in the form of a complex indium metal, where the galvanic bath does not contain cadmium and zinc, and where the galvanic bath deposits a yellow gold alloy comprising gold, copper, and indium as main components.

Description

L'invention se rapporte à un dépôt électrolytique sous forme d'un alliage d'or en couche épaisse ainsi que son procédé de production.The invention relates to an electrolytic deposit in the form of a gold alloy in a thick layer and its production process.

Dans le domaine décoratif du placage, on connaît des procédés pour la production de dépôts électrolytiques d'or, de couleur jaune, dont le titre est supérieur ou égal à 9 carats, ductile à une épaisseur de 10 microns, et de grande résistance au ternissement. Ces dépôts sont obtenus par une électrolyse dans un bain galvanique alcalin contenant, en plus de l'or et du cuivre, du cadmium à raison de 0,1 à 3 g/l. Les dépôts obtenus par ces procédés connus présentent cependant des teneurs en cadmium comprises entre 1 et 10 %. Le cadmium facilite le dépôt de couches épaisses, c'est-à-dire entre 1 et 800 microns et permet d'obtenir un alliage de couleur jaune en diminuant la quantité de cuivre contenue dans l'alliage; toutefois le cadmium est extrêmement toxique et interdit dans certains pays.In the decorative field of plating processes are known for the production of electrolytic deposits of gold, yellow color, whose title is greater than or equal to 9 carats, ductile to a thickness of 10 microns, and high resistance to tarnishing . These deposits are obtained by electrolysis in an alkaline galvanic bath containing, in addition to gold and copper, cadmium at a rate of 0.1 to 3 g / l. The deposits obtained by these known methods, however, have cadmium contents of between 1 and 10%. Cadmium facilitates the deposition of thick layers, that is to say between 1 and 800 microns and makes it possible to obtain a yellow-colored alloy by decreasing the quantity of copper contained in the alloy; however, cadmium is extremely toxic and banned in some countries.

D'autres dépôts jaunes connus sont des alliages comportant de l'or et de l'argent.Other known yellow deposits are alloys containing gold and silver.

On connaît aussi des alliages d'or de 18 carats sans cadmium, contenant du cuivre et du zinc. Cependant, ces dépôts sont de teinte trop rose (titre trop riche en cuivre). Enfin, ces dépôts ont une mauvaise résistance à la corrosion ce qui implique un ternissement rapide.Also known are cadmium-free 18-carat gold alloys containing copper and zinc. However, these deposits are too pink (title too rich in copper). Finally, these deposits have a poor resistance to corrosion which implies a rapid tarnishing.

On peut enfin citer les exemples des documents GB 1 156 186 , EP 0 384 679 , DE 1 696 087 , CH 455 434 , FR 2 405 312 , GB 1 134 615 , GB 1 294 601 et US 4,168,214 qui portent sur divers types de bains permettant d'obtenir un alliage d'or.We can finally cite the examples of the documents GB 1 156 186 , EP 0 384 679 , DE 1,696,087 , CH 455 434 , FR 2 405 312 , GB 1,134,615 , GB 1,294,601 and US 4,168,214 which relate to various types of baths making it possible to obtain a gold alloy.

Le but de la présente invention est de pallier tout ou partie les inconvénients cités précédemment en proposant un procédé permettant le dépôt en couche épaisse d'un alliage d'or de couleur jaune n'ayant ni de zinc ni de cadmium comme constituants principaux.The object of the present invention is to overcome all or part of the disadvantages mentioned above by proposing a method for the deposition in thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.

A cet effet, l'invention se rapporte à un dépôt électrolytique sous forme d'un alliage d'or dont l'épaisseur est comprise entre 1 et 800 microns et comporte du cuivre caractérisé en ce qu'il comprend de l'indium comme troisième composé principal.For this purpose, the invention relates to an electrolytic deposit in the form of a gold alloy whose thickness is between 1 and 800 microns and comprises copper characterized in that it comprises indium as third main compound.

Conformément à d'autres caractéristiques avantageuses de l'invention :

  • le dépôt est sensiblement exempt de métaux ou métalloïdes toxiques ;
  • le dépôt comporte une teinte comprise entre les domaines 1 N et 3N (selon norme ISO 8654) ;
  • le dépôt est brillant et possède une très grande résistance à la corrosion.
According to other advantageous features of the invention:
  • the deposit is substantially free of toxic metals or metalloids;
  • the deposit has a hue between the domains 1 N and 3N (according to ISO 8654);
  • the deposit is bright and has a very high resistance to corrosion.

L'invention se rapport également à un procédé de dépôt galvanoplastique d'un alliage d'or sur une électrode plongée dans un bain comportant de l'or métal sous forme d'aurocyanure alcalin, des composés organométalliques, un mouillant, un complexant, du cyanure libre caractérisé en ce que les métaux d'alliage sont du cuivre sous forme de cyanure double de cuivre et potassium, et de l'indium sous forme complexé aminocarboxylique ou aminophosphonique permettant de déposer sur l'électrode un alliage d'or du type jaune miroir brillant.The invention also relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, a free cyanide characterized in that the alloying metals are copper in the form of copper and potassium double cyanide, and indium in aminocarboxylic or aminophosphonic complexed form for depositing on the electrode a yellow gold alloy brilliant mirror.

Conformément à d'autres caractéristiques avantageuses de l'invention :

  • le bain comporte de 1 à 10 g.l-1 d'or métal sous forme d'aurocyanure alcalin et préférentiellement 5 g.l-1 ;
  • le bain comporte de 30 à 80 g.l-1 de cuivre métal sous forme de cyanure double alcalin et préférentiellement 50 g.l-1 ;
  • le bain comporte de 10 mg.l-1 à 5 g.l-1 d'indium métal sous forme complexé et préférentiellement comporte 1 g.l-1 ;
  • le bain comporte de 15 à 35 g.l-1 de cyanure libre
  • le mouillant comporte une concentration comprise entre 0,05 et 10 ml.l-1 et préférentiellement de 3 ml.l-1 ;
  • le mouillant est choisi parmi les types polyoxyalcoylenique, éther phosphate, lauryl sulfate, diméthyldodecylamine-N-oxide, diméthyldodecyl ammonium propane sulfonate ou tout autre type susceptible de mouiller en milieu cyanure alcalin ;
  • le complexant aminocarboxylique comporte une concentration comprise entre 0,1 à 20 g.l-1 ;
  • le bain comporte une amine de concentration comprise entre 0,01 et 5 ml.l-1 ;
  • le bain comporte un dépolarisant de concentration comprise entre 0,1 mg.l-1 à 20 mg.l-1 ;
  • le bain comporte des sels conducteurs du type phosphates, carbonates, citrates, sulfates, tartrates, gluconates et/ou phosphonates ;
  • la température du bain est maintenue entre 50 et 80° C ;
  • le pH du bain est maintenu entre 8 et 12 ;
  • le procédé est réalisé à des densités de courant comprise entre 0,2 et 1,5 A.dm-2.
According to other advantageous features of the invention:
  • the bath comprises from 1 to 10 gl -1 of gold metal in the form of alkaline aurocyanide and preferentially 5 gl -1;
  • the bath comprises from 30 to 80 g / l of copper metal in the form of double alkaline cyanide and preferably 50 g / l;
  • the bath comprises from 10 mg.l-1 to 5 gl-1 of indium metal in complexed form and preferably comprises 1 gl-1;
  • the bath contains from 15 to 35 gl -1 of free cyanide
  • the wetting agent has a concentration of between 0.05 and 10 ml.l -1 and preferably 3 ml.l -1;
  • the wetting agent is chosen from polyoxyalkylene, phosphate ether, lauryl sulfate, dimethyldodecylamine-N-oxide, dimethyldodecyl ammonium propane sulphonate or any other type capable of wetting in an alkaline cyanide medium;
  • the aminocarboxylic complexing agent has a concentration of between 0.1 and 20 gl -1;
  • the bath comprises an amine concentration of between 0.01 and 5 ml.l -1;
  • the bath comprises a depolarizer with a concentration of between 0.1 mg.l-1 and 20 mg.l-1;
  • the bath comprises conducting salts of phosphates, carbonates, citrates, sulphates, tartrates, gluconates and / or phosphonates;
  • the temperature of the bath is maintained between 50 and 80 ° C;
  • the pH of the bath is maintained between 8 and 12;
  • the process is carried out at current densities of between 0.2 and 1.5 A.dm -2.

L'électrolyse est de préférence suivie d'un traitement thermique à au moins 450 degrés Celsius pendant au moins 30 minutes afin d'obtenir un dépôt de qualité optimale.The electrolysis is preferably followed by a heat treatment at least 450 degrees Celsius for at least 30 minutes to obtain an optimal quality deposit.

Le bain peut contenir en outre un brillanteur. Celui-ci est, de préférence, un dérivé du butynediol, un pyridinio-propanesulfonate ou un mélange des deux, un sel d'étain, de l'huile de castor sulfonées, du methylimidozole, de l'acide dithiocarboxylique tels que du thiourée, de l'acide thiobarbiturique, de l'imidazolidinthione ou de l'acide thiomalique.The bath may further contain a brightener. This is preferably a butynediol derivative, a pyridinio-propanesulfonate or a mixture of both, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.

Dans un exemple de dépôt, on a un alliage d'or, exempt de métaux ou métalloïdes toxiques, en particulier exempt de cadmium, de teinte 2N jaune, d'une épaisseur de 200 microns, de brillance excellente et ayant une très grande résistance à l'usure et au ternissement.In an example of a deposit, there is a gold alloy, free of toxic metals or metalloids, in particular free of cadmium, of 2N color. yellow, with a thickness of 200 microns, excellent gloss and having a very high resistance to wear and tarnishing.

Ce dépôt est obtenu par une électrolyse dans un bain électrolytique du type :

  • Exemple 1:
    • Au : 3 g.l-1
    • Cu : 45 g.l-1
    • In : 0,1 g.l-1
    • KCN : 22 g.l-1
    • pH : 10,5
    • Température : 65°C
    • Densité de Courant : 0,5 A.dm-2
    • Mouillant : 0,05 ml.l-1 NN-Diméthyldodecyl N-Oxide
    • Iminodiacetique : 20 g.l-1
    • Ethylènediamine : 0.5 ml l
    • Selenocyalate de potassium : 1 mg.l-1
  • Exemple 2 :
    • Au : 6 g.l-1
    • Cu : 60 g.l-1
    • In : 2 g.l-1
    • KCN : 30 g.l-1
    • NTA : 4 g.l-1
    • Ag : 10 mg.l-1
    • Diethylentriamine : 0,2 ml.l-1
    • Gallium, selenium ou tellure : 5 mg.1-1
    • Hypophosphite de sodium : 0,1 g.l-1
    • Acide thiomalique : 50 mg.l-1
    • Densité de Courant : 0,5 A.dm-2
    • Température : 70°C
    • pH:10,5
    • Mouillant : 2 ml.1-1 étherphosphate
This deposit is obtained by electrolysis in an electrolytic bath of the type:
  • Example 1
    • Au: 3 gl -1
    • Cu: 45 gl -1
    • In: 0.1 gl -1
    • KCN: 22 gl -1
    • pH: 10.5
    • Temperature: 65 ° C
    • Current Density: 0.5 A.dm -2
    • Wetting: 0.05 ml.l -1 NN-Dimethyldodecyl N-Oxide
    • Iminodiacetic: 20 gl -1
    • Ethylenediamine: 0.5 ml
    • Potassium selenocyalate: 1 mg.l -1
  • Example 2
    • Au: 6 gl -1
    • Cu: 60 gl -1
    • In: 2 gl -1
    • KCN: 30 gl -1
    • NTA: 4 gl -1
    • Ag: 10 mg.l -1
    • Diethylentriamine: 0.2 ml.l -1
    • Gallium, selenium or tellurium: 5 mg.1 -1
    • Sodium hypophosphite: 0.1 gl -1
    • Thiomalic acid: 50 mg.l -1
    • Current Density: 0.5 A.dm -2
    • Temperature: 70 ° C
    • pH 10.5
    • Wetting: 2 ml.1 -1 etherphosphate

Dans ces exemples, le bain électrolytique, est contenu dans une cuve en polypropylène ou en PVC avec revêtement calorifuge. Le chauffage du bain est réalisé grâce à des thermo-plongeurs en quartz, en PTFE, en porcelaine ou en acier inoxydable stabilisé. Une bonne agitation cathodique ainsi qu'une circulation de l'électrolyte doit être maintenue. Les anodes sont en titane platiné, en acier inoxydable, en ruthenium, en iridium ou alliages de ces deux derniers.In these examples, the electrolytic bath is contained in a polypropylene or PVC tank with heat-insulating coating. Bath heating is achieved by thermo-plungers in quartz, PTFE, porcelain or stabilized stainless steel. Good cathodic stirring as well as a flow of the electrolyte must be maintained. The anodes are platinum titanium, stainless steel, ruthenium, iridium or alloys of the latter two.

Ces conditions permettent d'obtenir un rendement cathodique de 62 mg.A.min-1 avec une vitesse de déposition de 1 µm en 3 minutes dans l'exemple 1 et, dans l'exemple 2, un dépôt brillant de 10 µm en 30 minutes.These conditions make it possible to obtain a cathodic efficiency of 62 mg.A.min -1 with a deposition rate of 1 μm in 3 minutes in Example 1 and, in Example 2, a glossy deposition of 10 μm in 30 minutes. minutes.

Bien entendu, la présente invention ne se limite pas à l'exemple illustré mais est susceptible de diverses variantes et modifications qui apparaîtront à l'homme de l'art. En particulier, le bain peut contenir les métaux suivants Ag, Cd, Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi en quantité négligeable.Of course, the present invention is not limited to the illustrated example but is susceptible of various variations and modifications that will occur to those skilled in the art. In particular, the bath may contain the following metals Ag, Cd, Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantity.

De plus, le mouillant peut être de tout type susceptible de mouiller en milieu cyanure alcalin.In addition, the wetting agent may be of any type capable of wetting in alkaline cyanide medium.

Claims (16)

  1. Method for the galvanoplasty deposition of a gold alloy on an electrode dipped in a bath including gold metal in the form of alkaline aurocyanide, organometallic components, a wetting agent, a complexing agent and free cyanide, characterized in that the alloy metals are copper in the form of copper II cyanide and potassium, and complex indium for depositing a shiny reflective yellow type gold alloy on the electrode.
  2. Method according to claim 1, characterized in that the complex indium is of the aminocarboxylic or aminophosphonic type.
  3. Method according to claim 1 or 2, characterized in that the bath includes from 1 to 10 g.l-1 of gold mental in the form of alkaline aurocyanide.
  4. Method according to any of the preceding claims, characterized in that the bath includes from 30 to 80 g.l-1 of copper II metal in the form of alkaline cyanide.
  5. Method according to any of the preceding claims, characterized in that the bath includes from 10 m g.l-1 to g.l-1 of complex indium metal.
  6. Method according to any of the preceding claims, characterized in that the bath includes from 15 to 35 g.l-1 of free cyanide.
  7. Method according to any of the preceding claims, characterized in that the wetting agent includes a concentration of between 0.05 and 10 ml.l-1.
  8. Method according to claim 1 or 7, characterized in that the wetting agent is chosen from among the following types: polyoxyalcoylenic, ether phosphate, laurel sulphate, dimethyldodecylamine N oxide, dimethyldodecyl ammonium propane sulfonate.
  9. Method according to any of the preceding claims, characterized in that the bath includes an amius carboxylic complexing concentration of between 0.1 and 20 g. l-1.
  10. Method according to any of the preceding claims, characterized in that the bath includes an amine concentration of between 0.01 to 5 mg.l-1.
  11. Method according to any of the preceding claims, characterized in that the bath includes a depolarising concentration of between 0.1 mg.l-1 to 20 mg.l-1.
  12. Method according to any of the preceding claims, characterized in that the bath includes conductive salts of the following types: phosphates, carbonates, citrates, sulphates, tartrates, gluconates and/or phosphonates.
  13. Method according to any of the preceding claims, characterized in that the temperature of the bath is maintained between 50 and 80°C.
  14. Method according to any of the preceding claims, characterized in that the pH of the bath is maintained between 8 and 12.
  15. Method according to any of the preceding claims, characterized in that the method is performed with current density of between 0.2 and 1.5 A.dm-2.
  16. Electrolytic deposition in the form of gold alloy from a method according to any of the preceding claims, the thickness of which is comprised between 1 and 800 microns and which includes copper, characterized in that it includes indium as the third main compound for obtaining a shiny colour comprised between the fields 1N and 3N.
EP08804009A 2007-09-21 2008-09-11 Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids Active EP2205778B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH01494/07A CH710184B1 (en) 2007-09-21 2007-09-21 Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids.
PCT/EP2008/062042 WO2009037180A1 (en) 2007-09-21 2008-09-11 Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids

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EP2205778A1 EP2205778A1 (en) 2010-07-14
EP2205778B1 true EP2205778B1 (en) 2011-02-23

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EP (1) EP2205778B1 (en)
JP (2) JP5563462B2 (en)
KR (1) KR101280675B1 (en)
CN (1) CN101815814B (en)
AT (1) ATE499461T1 (en)
CH (1) CH710184B1 (en)
DE (1) DE602008005184D1 (en)
HK (1) HK1147782A1 (en)
IN (1) IN2014CN02464A (en)
TW (2) TWI441959B (en)
WO (1) WO2009037180A1 (en)

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CH710184B1 (en) 2007-09-21 2016-03-31 Aliprandini Laboratoires G Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids.
EP2312021B1 (en) 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
EP2505691B1 (en) * 2011-03-31 2014-03-12 The Swatch Group Research and Development Ltd. Process for obtaining a gold alloy deposit of 18 carat 3N
ITFI20120103A1 (en) * 2012-06-01 2013-12-02 Bluclad Srl GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS.
WO2016020812A1 (en) * 2014-08-04 2016-02-11 Nutec International Srl Electrolytic bath, electrolytic deposition method and item obtained with said method
CN109504991B (en) * 2019-01-21 2020-08-07 南京市产品质量监督检验院 Cyanide-free 18k gold electroforming solution, and preparation method and application thereof

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US20140299481A1 (en) 2014-10-09
CN101815814A (en) 2010-08-25
ATE499461T1 (en) 2011-03-15
JP5563462B2 (en) 2014-07-30
HK1147782A1 (en) 2011-08-19
CN101815814B (en) 2012-05-16
TW200930844A (en) 2009-07-16
KR101280675B1 (en) 2013-07-01
TWI507571B (en) 2015-11-11
TW201428143A (en) 2014-07-16
US20100206739A1 (en) 2010-08-19
CH710184B1 (en) 2016-03-31
WO2009037180A1 (en) 2009-03-26
US20190153608A1 (en) 2019-05-23
US10233555B2 (en) 2019-03-19
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US10619260B2 (en) 2020-04-14
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US9683303B2 (en) 2017-06-20
EP2205778A1 (en) 2010-07-14
JP2010539335A (en) 2010-12-16

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