EP2310558B1 - Improved copper-tin electrolyte and process for the deposition of tin-bronze layers - Google Patents

Improved copper-tin electrolyte and process for the deposition of tin-bronze layers Download PDF

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Publication number
EP2310558B1
EP2310558B1 EP09776985A EP09776985A EP2310558B1 EP 2310558 B1 EP2310558 B1 EP 2310558B1 EP 09776985 A EP09776985 A EP 09776985A EP 09776985 A EP09776985 A EP 09776985A EP 2310558 B1 EP2310558 B1 EP 2310558B1
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EP
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Prior art keywords
electrolyte
acid
tin
range
copper
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EP09776985A
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German (de)
English (en)
French (fr)
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EP2310558A1 (en
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Klaus Bronder
Bernd Weyhmueller
Frank Oberst
Sascha Berger
Uwe Manz
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Umicore Galvanotechnik GmbH
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Umicore Galvanotechnik GmbH
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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
    • C25D3/58—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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the invention relates to a copper-tin electrolyte which is free of toxic constituents such as cyanides.
  • the invention relates to a corresponding electrolyte having a novel brightener system. It likewise encompasses a process for the deposition of decorative, white and yellow bronze layers on consumer goods and industrial articles using the electrolyte of the invention.
  • Consumer goods or consumer articles as defined in the consumer articles regulations are finished with thin, oxidation-stable metal layers for decorative reasons and in order to prevent corrosion. These layers have to be mechanically stable and should not display any tarnishing or signs of wear even after prolonged use. Since 2001, the sale of consumer goods coated with nickel-containing finishing alloys has no longer been permitted, or is possible only with observance of strict conditions, in Europe pursuant to EU directive 94/27/EC since nickel and nickel-containing metal layers are contact allergens. Bronze alloys in particular have become established as a replacement for nickel-containing finishing layers and these enable such mass-produced consumer goods to be finished inexpensively in barrel or rack electroplating processes to give allergen-free, attractive products.
  • the solderability of the resulting layer and, if appropriate, its mechanical adhesive strength are the critical properties of the layer to be produced.
  • the appearance of the layers is generally less important than their functionality.
  • the decorative effect (shine and brightness) and also a long service life of the resulting layer with an essentially unchanged appearance are the important target parameters.
  • EP 1 111 097 A2 describes an electrolyte comprising an organosulfonic acid and ions of tin and copper together with dispersants and brightening additives and also, if appropriate, antioxidants.
  • EP 1 408 141 A1 describes a process for the electrochemical deposition of bronzes, in which an acidic electrolyte comprising tin and copper ions together with an alkylsulfonic acid and an aromatic, nonionic wetting agent.
  • DE 100 46 600 A1 describes an alkylsulfonic or alkanolsulfonic acid-containing bath which comprises soluble tin and copper salts together with organic sulfur compounds, and a process using this bath.
  • a significant disadvantage of such electrolytes produced on the basis of organosulfonic acids is their high corrosivity.
  • baths based on methanesulfonic acids frequently have pH values below one.
  • the high corrosivity of these baths limits their use range in respect of the substrate materials to be finished and requires the use of particularly corrosion-resistant working materials for carrying out the process.
  • EP 1 146 148 A2 describes a cyanide-free copper-tin electrolyte based on diphosphoric acid, which in addition to the reaction product of an amine and an epihalohydrin in a molar ratio of 1:1 contains a cationic surfactant.
  • WO 2004/005528 describes a cyanide-free diphosphoric acid-copper-tin electrolyte which contains an additive composed of amine derivative, an epihalohydrin and a glicidyl ether compound. Electrolytes based on diphosphoric acid generally have very limited long-term stabilities and have to be renewed frequently.
  • EP 1 001 054 A2 describes a tin-copper electrolyte which comprises a water-soluble tin salt, a water-soluble copper salt, an inorganic or organic acid or a water-soluble salt thereof and also one or more compounds from the group consisting of generally toxic thiourea or thiol derivatives.
  • the inventive bath described there can additionally contain one or more compounds selected from the group consisting of carboxylic acids, lactones, phosphoric acid condensates, phosphonic acid derivatives or water-soluble salts of these or combinations thereof.
  • WO2004/005528 describes a cyanide-free diphosphoric acid-copper-tin electrolyte which contains an additive composed of an amine derivative, an epichlorohydrin and a glycidyl ether compound in a molar ratio of 1:0.5 - 2:0.1 - 5. It was an object of this document to further widen the current density range in which uniform deposition of the metals in a shiny layer can be achieved. It is explicitly mentioned that such deposition can only be attained when the additive added is made up of all three of the abovementioned components.
  • a nontoxic electrolyte for the deposition of decorative bronze alloy layers on consumer goods and industrial articles which electrolyte contains the metals to be deposited in the form of water-soluble salts and further comprises one or more phosphonic acid derivatives as complexing agents and also a brighter system composed of a disulfide compound and a carbonate or hydrogencarbonate salt, completely surprisingly but nonetheless advantageously achieves the stated objects.
  • the inventive electrolyte having a different composition than in the prior art makes it possible to obtain excellent electrolytic deposits of bronze layers. In particular, the good brightness and shine of the bronze layers can be obtained independently of their thickness.
  • the alloy composition remains approximately constant over a wide current density range, which is in no way suggested by the prior art.
  • the metals copper and tin or copper, tin and zinc to be deposited are present in dissolved form as their ions. They are preferably introduced in the form of water-soluble salts which are preferably selected from the group consisting of pyrophosphates, carbonates, hydroxide-carbonates, hydrogencarbonates, sulfites, sulfates, phosphates, nitrites, nitrates, halides, hydroxides, oxide-hydroxides, oxides or combinations thereof.
  • the metals are used in the form of salts with ions selected from the group consisting of pyrophosphate, carbonate, hydroxide-carbonate, oxide-hydroxide, hydroxide and hydrogencarbonate.
  • ions selected from the group consisting of pyrophosphate, carbonate, hydroxide-carbonate, oxide-hydroxide, hydroxide and hydrogencarbonate.
  • Which salts are introduced in which amount into the electrolyte can determine the color of the resulting decorative bronze layers and can be adjusted according to customer requirements.
  • the metals to be deposited are, as indicated, present in ionically dissolved form in the electrolyte for application of decorative bronze layers to consumer goods and industrial articles.
  • the ion concentration of copper can be set in the range from 0.2 to 10 g/l, preferably from 0.3 to 4 g/l, of electrolyte
  • the ion concentration of tin can be set in the range from 1.0 to 30 g/l, preferably 2 - 20 g/l, of electrolyte
  • the ion concentration of zinc can be set in the range from 1.0 to 20 g/l, preferably 0 - 3 g/l, of electrolyte.
  • the metals to be deposited are particularly preferably introduced as salt of a pyrophosphate, carbonate, hydrogencarbonate or hydroxide-carbonate in such a way that the resulting ion concentration is in the range from 0.3 to 4 gram of copper, from 2 to 20 gram of tin and from 0 to 3 gram of zinc, in case per liter of electrolyte.
  • the electrolyte of the invention has some concentration of carbonate or hydrogencarbonate ions. These can be present in the electrolyte in the form of preferably soluble salts selected from the group consisting of alkali metal and alkaline earth metal salts, in particular sodium or potassium carbonate or sodium or potassium hydrogencarbonate.
  • alkali metal and alkaline earth metal salts in particular sodium or potassium carbonate or sodium or potassium hydrogencarbonate.
  • the embodiment in which the metals which are used and are to be deposited are also added either completely or partly in the form of carbonates or hydrogencarbonates to the electrolyte is preferred.
  • the embodiment in which only copper is present as carbonate in the bath formulation is advantageous. Tin and zinc and also, during operation of the bath, copper are then advantageously added as pyrophosphate.
  • Addition of the abovementioned salts enables a concentration of carbonate or hydrogencarbonate ions in the electrolyte of from 0.5 to 100 g/l of electrolyte to be set.
  • the concentration is particularly preferably in the range from 5 to 40 g/l and very particularly preferably from 15 to 30 g/l.
  • disulfide compounds can advantageously be selected from the group consisting of substituted and unsubstituted bisalkyl or bis(hetero)aryl or alkyl (hetero)aryl disulfides, in particular those of the general formula (I), R-S-S-R' (I) wherein R and R' can each be, independently of one another, substituted or unsubstituted (C 1 -C 8 )-alkyl, (C 3 -C 6 )-cycloalkyl, (C 7 -C 19 )-alkylaryl, (C 6 -C 18 )-aryl, (C 7 -C 19 )-aralkyl, (C 3 -C 18 )-heteroaryl, (C 4 -C 19 )-alkylheteroaryl, (C 4 -C 19 )-heteroaralkyl.
  • R and R' can each be, independently of one another, substituted or unsubstituted (C 1 -C
  • R and R' can also be joined to form a ring.
  • Possible substitutents for R and R' are in principle all groups of substituents which a person skilled in the art would consider for this purpose. These are, in particular, substituents selected from the group consisting of amine radicals, nitro groups, hydroxyl radicals, halide radicals, acid radicals such as carboxylic acids, sulfonic acids and phosphonic acids.
  • Particularly advantageous disulfide compounds are compounds selected from the group consisting of 2,2'-dithiodipyridine, 4,4'-dithiodipyridine, 6,6'-dithiodinicotinic acid, bis(4-aminophenyl) disulfide, 2,2'-dithiosalicylic acid, D-cystine, L-cystine, DL-cystine, 2,2'-dithio(bis)benzothiazole, 2,2'-dithiobis(5-nitropyridine).
  • SPS bis-(3-sodium sulfopropyl) disulfide
  • the disulfide compounds are preferably used in an amount of from 0.01 mg per liter to 10.0 g per liter of electrolyte. Particular preference is given to use in a concentration range from 0.5 mg per liter to 7.5 g per liter of electrolyte.
  • the disulfide compound, in particular the abovementioned SPS, is very particularly preferably used in a concentration range from 0.1 mg per liter to 5 g per liter in the electrolyte.
  • the application of the decorative bronze layers to consumer goods and industrial articles using the electrolyte of the invention is effected, as indicated, in an electroplating process. It is important here that the metals to be deposited are kept permanently in solution during the process, regardless of whether electroplating is carried out in a continuous process or in a batch process.
  • the electrolyte of the invention contains phosphonic acids as complexing agents. Preference is given to using compounds selected from the group consisting of hydroxyphosphonic, nitrilophosphonic or aminophosphonic acid, e.g.
  • 1-aminomethylphosphonic acid AMP aminotris(methylenephosphonic acid) ATMP, 1-aminoethylphosphonic acid AEP, 1-aminopropylphosphonic acid APP, (1-acetylamino-2,2,2-trichloroethyl)phosphonic acid, (1-amino-1-phosphonooctyl) phosphonic acid, (1-benzoylamino-2,2,2-trichloroethyl)phosphonic acid, (1-benzoylamino-2,2-dichlorovinyl)phosphonic acid, (4-chlorophenylhydroxymethyl)phosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) DTPMP, ethylenediaminetetra(methylenephosphonic acid) EDTMP, 1-hydroxyethane(1,1-diphosphonic acid) HEDP, hydroxyethylamino-di(methylenephosphonic acid) HEMPA, hexamethylenediaminetetra(methylphosphonic acid
  • Particular preference is given to using one or more compounds selected from the group consisting of aminotris(methylenephosphonic acid) ATMP, diethylenetriamine-penta(methylenphosphonic acid) DTPMP, ethylenediaminetetra(methylenephosphonic acid) EDTMP, 1-hydroxyethane(1,1-diphosphonic acid) HEDP, hydroxyethylamino-di(methylenephosphonic acid) HEMPA, hexamethylenediaminetetra(methylphosphonic acid) HDTMP, salts derived therefrom and condensates derived therefrom, or combinations thereof.
  • aminotris(methylenephosphonic acid) ATMP diethylenetriamine-penta(methylenphosphonic acid) DTPMP
  • EDTMP ethylenediaminetetra(methylenephosphonic acid)
  • 1-hydroxyethane(1,1-diphosphonic acid) HEDP hydroxyethylamino-di(methylenephosphonic acid) HEMPA
  • HEMPA hydroxyeth
  • the pH of the electrolyte is in the range from 6 to 14 required for the electroplating application. Preference is given to a range of 8 - 12 and very particular preference to about 10.
  • the electrolyte can contain further organic additives which assume functions as complexing ligands, brighteners, wetting agents or stabilizers.
  • the electrolyte of the invention can also dispense with the use of cationic surfactants.
  • the addition of further brighteners and wetting agents is only preferred in the case of the appearance of the decorative bronze layers to be deposited having to meet special requirements. They make it possible to adjust not only the color of the bronze layers, which depends critically on the ratio of the metals to be deposited, but also the shine of the layers in all gradations from matt silk to high gloss.
  • R is substituted or unsubstituted (C 1 -C 8 )-alkyl, (C 3 -C 6 )-cycloalkyl, (C 7 -C 19 )-alkylaryl, (C 6 -C 18 )-aryl, (C 7 -C 19 )-aralkyl, (C 3 -C 18 )-heteroaryl, (C 4 -C 19 )-alkylheteroaryl, (C 4 -C 19 )-heteroaralkyl.
  • R and R' are in principle all groups of substituents which a person skilled in the art would consider for this purpose. These are, in particular, substituents selected from the group consisting of amine radicals, nitro groups, hydroxyl radicals, halide radicals, acid radicals such as carboxylic acids, sulfonic acids and phosphonic acids. This applies analogously to the corresponding salts, in particular salts with cations of the alkali metals or alkaline earth metals.
  • Preferred compounds are those selected from the group consisting of 3-mercapto-1-propanesulfonic acid Na salt, 3-(2-benzothiazolyl-2-mercapto)propanesulfonic acid Na salt, saccharin-N-propylsulfonate Na salt, 3-sulfopropyl N,N-dimethyl dithiocarbamate Na salt, 1-propanesulfonic acid and 3[(ethoxythioxomethyl)thio] K salt.
  • disulfide required for the brightener system and the sulfonic acid being present in one compound as is the case, for example, for bis-(3-sodium sulfopropyl) disulfide.
  • citric acid as carboxylic acid
  • citric acid Die galvanische Abscheidung von Zinn und Zinnlegleiteren, Saulgau 1993, page 156
  • Betaines to be used can preferably be found in WO2004/005528 or in Jordan, Manfred (Die galvanische Abscheidung von Zinn und Zinnlegleiteren, Saulgau 1993, page 156 ). Particular preference is given to those presented in EP636713 . Further additives may be found in the literature ( Jordan, Manfred, Die galvanische Abscheidung von Zinn und Zinnlegleiteren, Saulgau 1993 ).
  • pyrophosphate ions which can be present in the electrolyte and can advantageously be introduced into the electrolyte as anions of the metal salts to be deposited.
  • the embodiment in which the pyrophosphate ions are added in the form of salts of other metals, in particular of alkali and alkaline earth metals in the electrolyte is likewise possible.
  • the amount of pyrophosphate ions can be set in a precise manner by a person skilled in the art. It is limited by the fact that the concentration in the electrolyte should be above a minimum amount in order to be able still to bring about the effect discussed to a sufficient extent.
  • the amount of pyrophosphate to be used is guided by economic aspects. In this context, reference may be made to EP1146148 and the relevant information presented there.
  • the amount of pyrophosphate to be used in the electrolyte is preferably 1 - 400 g/l. Particular preference is given to using an amount of 2 - 200 g/l of electrolyte.
  • the pyrophosphate can, if it is, as indicated, not introduced as salt constituent of the metals to be deposited, be used as sodium or potassium diphosphate or as H 2 P 2 O 7 in combination with a base of the alkali or alkaline earth metals. Preference is given to using K 2 P 2 O 7 for this purpose.
  • the electrolyte of the invention is free of hazardous materials classified as toxic (T) or very toxic (T + ). No cyanides, no thiourea derivatives or similarly toxic materials are present.
  • the nontoxic electrolyte of the invention is particularly suitable for the electrochemical application of decorative bronze layers to consumer goods and industrial articles. It can be used in barrel, rack, belt or reel to reel electroplating plants.
  • the consumer goods and industrial articles to be coated dip into the nontoxic electrolyte of the invention and form the cathode.
  • the electrolyte is preferably maintained in the range from 20 to 70°C. It is possible to set a current density which is in the range from 0.01 to 100 ampere per square decimeter [A/dm 2 ] and depends on the type of plating plant. In barrel plating plants, current densities in the range from 0.05 to 0.75 A/dm 2 are preferred, more preferably from 0.1 to 0.5 A/dm 2 and very particularly preferably about 0.3 A/dm 2 . In rack plating processes, current densities in the range from 0.2 to 10.0 A/dm 2 are preferably chosen, particularly preferably from 0.2 to 5.0 A/dm 2 and very particularly preferably from 0.25 to 1.0 A/dm 2 .
  • anodes can be employed when using the nontoxic electrolyte of the invention.
  • Soluble or insoluble anodes are suitable, as is the combination of soluble and insoluble anodes.
  • soluble anodes preference is given to using anodes made of a material selected from the group consisting of electrolytic copper, phosphorus-containing copper, tin, tin-copper alloy, zinc-copper alloy and zinc-tin-copper alloy. Particular preference is given to combinations of different soluble anodes made of these materials, and also combinations of soluble tin anodes with insoluble anodes.
  • insoluble anodes preference is given to using anodes made of a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon", DLC) or combinations of these anodes.
  • DLC Diamond Like Carbon
  • mixed oxide anodes composed of iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridum-tantalum mixed oxide.
  • insoluble anodes are used, this is a particularly preferred embodiment of the process when the substrates to be provided with decorative bronze layers, which represent the cathode, are separated from the insoluble anode by an ion-exchange membrane so as to form a cathode space and an anode space.
  • an ion-exchange membrane so as to form a cathode space and an anode space.
  • An aqueous solution containing only a conductive salt is preferably present in the anode space.
  • Such an arrangement prevents the anodic oxidation of tin(II) ions Sn 2+ to tin(IV) ions Sn 4+ , which would have an adverse effect on the plating process.
  • the disadvantage of additive-free phosphonate-based copper-tin electrolytes is the restriction to a narrow current density range and the lack of shine and the lower brightness of the layers deposited.
  • the novel brightener system avoids these disadvantages in the phosphonate-based electrolyte system. Only when the electrolyte of the invention is used is the deposition of bright and shiny layers made possible over a wide current density range. None of the known cyanide-free substitute processes (pyrophosphate, phosphonate, alkylsulfonate) achieves the properties of cyanide-containing baths (particularly in the case of shine and brightness, also only to an extent).
  • the use of the brightener combination according to the invention for the first time makes it possible to achieve the shine and brightness which is comparable to the cyanide-containing electrolytes of the prior art and is thus significantly better than in all known cyanide-free substitute processes.
  • the novel brightener system enables the electrolyte to be operated at higher copper contents.
  • the combination of the compounds used, in particular those of the brightener system comprising carbonate ions and disulfide compounds, is critical here. In the presence of carbonate ions, even very small amounts of organic disulfidates influence copper-tin alloy formation. In contrast to additive-free baths, a largely constant alloy composition is obtained over a wider current density range as a result of the addition of the brightener system ( fig. 1 - comparison of copper-tin electrolyte based on phosphonic acid with and without brightener system). In the case of additive-free baths, tin is deposited preferentially at higher current densities, which leads to a loss of shine of the layers.
  • (C 1 -C 8 )-alkyl is an alkyl radical having from 1 to 8 carbon atoms. This can be branched as desired or in the case of (C 3 -C 6 )-cycloalkyl be cyclic. This is, in particular, radicals such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl etc.
  • (C 6 -C 18 )-Arryl is an aromatic system which is made up entirely of from 6 to 18 carbon atoms. This is, in particular, selected from the group consisting of phenyl, naphthyl, anthracenyl etc.
  • (C 7 -C 19 )-Alkylaryl radicals are radicals which have a (C 1 -C 8 )-alkyl radical on the (C 6 -C 18 )-aryl radical.
  • (C 7 -C 19 )-Aralkyl radicals are radicals which have a (C 6 -C 18 )-aryl radical on a (C 1 -C 8 )-alkyl radical, via which the radical is bound to the molecule concerned.
  • a (C 3 -C 18 )-heteroaryl radical is an aromatic system which has at least three carbon atoms.
  • further heteroatoms are present in the aromatic system. These are preferably nitrogen and/or sulfur.
  • Such heteroaromatics are described, for example, in the book Bayer-Walter, Lehrbuch der Organischen Chemie, S. Hirzel Verlag, 22nd edition, p. 703 ff .
  • (C 4 -C 19 )-alkylheteroaryl is a (C 3 -C 18 )-heteroaryl radical which is supplemented by a (C 1 -C 8 )-alkyl substituent.
  • the bonding to the molecule under consideration is via the heteroaromatic here.
  • (C 4 -C 19 )-heteroaralkyl is a (C 3 -C 18 )-heteroaryl which is bound to the molecule concerned via a (C 1 -C 8 )-alkyl substituent.
  • halide encompasses chloride, bromide and fluoride.
  • Alkyl(hetero)aryl is alkylaryl and alkylheteroaryl.
  • Barrel deposition of white bronze layers was carried out using a nontoxic electrolyte according to the invention containing 100 g/l of ethylenediaminetetra(methylenephosphonic acid) EDTMP, 1.5 g/l of copper as copper hydroxide carbonate, 5 g/l of tin as tin pyrophosphate, 2 g/l of zinc as zinc pyrophosphate, 10 m/l of methanesulfonic acid (70%), 20 g/l of potassium hydrogencarbonate and 10 mg/l of bis(3-sodium sulfopropyl) disulfide.
  • the electrolyte was maintained at 50°C.
  • a set current density of from 0.05 to 0.5 A/dm 2 optically uniform, high-shine bronze layers having the color typical of white bronze were obtained in a drum plating apparatus.
  • ATMP 100 g/l of potassium pyrophosphate 20 g/l of citric acid 4.2 g/l of copper hydroxide carbonate 8.66 g/l of tin pyrophosphate 4.5 g/l of zinc pyrophosphate 10 g/l of potassium hydrogencarbonate 0.5 g/l of 6,6'-dithiodinicotinic acid Parameters: pH 9.0 / 60°C / current densities: 0.05 - 0.5 A/dm 2

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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EP09776985A 2008-07-10 2009-07-06 Improved copper-tin electrolyte and process for the deposition of tin-bronze layers Not-in-force EP2310558B1 (en)

Priority Applications (1)

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PL09776985T PL2310558T3 (pl) 2008-07-10 2009-07-06 Ulepszony elektrolit miedziowo-cynowy i sposób osadzania warstw cyny i brązu

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DE102008032398A DE102008032398A1 (de) 2008-07-10 2008-07-10 Verbesserter Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
PCT/EP2009/004879 WO2010003621A1 (en) 2008-07-10 2009-07-06 Improved copper-tin electrolyte and process for the deposition of bronze layers

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EP2310558A1 EP2310558A1 (en) 2011-04-20
EP2310558B1 true EP2310558B1 (en) 2012-03-14

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US (1) US20110174631A1 (enExample)
EP (1) EP2310558B1 (enExample)
JP (1) JP2011527381A (enExample)
KR (1) KR20110031183A (enExample)
CN (1) CN102089466B (enExample)
AT (1) ATE549434T1 (enExample)
DE (1) DE102008032398A1 (enExample)
PL (1) PL2310558T3 (enExample)
TW (1) TW201014935A (enExample)
WO (1) WO2010003621A1 (enExample)

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TW201014935A (en) 2010-04-16
EP2310558A1 (en) 2011-04-20
PL2310558T3 (pl) 2012-09-28
CN102089466A (zh) 2011-06-08
ATE549434T1 (de) 2012-03-15
DE102008032398A1 (de) 2010-01-14
JP2011527381A (ja) 2011-10-27
CN102089466B (zh) 2012-11-07
WO2010003621A1 (en) 2010-01-14
US20110174631A1 (en) 2011-07-21

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