EP1587967A1 - Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung - Google Patents

Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung

Info

Publication number
EP1587967A1
EP1587967A1 EP03782026A EP03782026A EP1587967A1 EP 1587967 A1 EP1587967 A1 EP 1587967A1 EP 03782026 A EP03782026 A EP 03782026A EP 03782026 A EP03782026 A EP 03782026A EP 1587967 A1 EP1587967 A1 EP 1587967A1
Authority
EP
European Patent Office
Prior art keywords
dispersion according
dispersion
percentage
metal salt
concentration
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
EP03782026A
Other languages
English (en)
French (fr)
Other versions
EP1587967B1 (de
Inventor
Olivier Dupuis
Mary-Helene Delvaux
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.)
Semika SA
Original Assignee
Semika SA
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 Semika SA filed Critical Semika SA
Priority to SI200330267T priority Critical patent/SI1587967T1/sl
Publication of EP1587967A1 publication Critical patent/EP1587967A1/de
Application granted granted Critical
Publication of EP1587967B1 publication Critical patent/EP1587967B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the present invention relates to a photosensitive dispersion with adjustable viscosity for depositing metal on an insulating substrate and to its use.
  • Applicant's patent EP 0 687 311 relates to a polymeric resin with adjustable viscosity and pH for the deposition of catalytic palladium on a substrate, comprising, in combination, a palladium salt, a complexing agent of the carboxylic acid or chloride type, a polymer containing water-soluble hydroxyl and / or carboxyl groups, a basic compound and a solvent chosen from water, methanol and ethanol, the pH value being between 1 and 10, as well as in its applications for the deposition of catalytic palladium on the substrate surface and for the metallization of these surfaces.
  • One of the essential aims of the present invention therefore consists in remedying the aforementioned drawbacks and in presenting a photosensitive dispersion with adjustable viscosity which no longer necessarily requires the use of a noble metal such as palladium and which also calls for other more common and less expensive metals whose photosensitivity is extended to a range of wavelengths between 190 and 450 nm and requiring a much lower irradiation energy than the polymeric resins known up to now, less than 100 mJ / cm 2 and not requiring the obligatory passage by an autocatalytic bath for the metallization of the substrate, allowing therefore a direct electrolytic metallization.
  • a noble metal such as palladium
  • other more common and less expensive metals whose photosensitivity is extended to a range of wavelengths between 190 and 450 nm and requiring a much lower irradiation energy than the polymeric resins known up to now, less than 100 mJ / cm 2 and not requiring the obligatory passage by an autocata
  • the photosensitive dispersion comprises, in combination, a pigment conferring redox properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymer formulation, a basic compound, an organic solvent and water.
  • the pigment is titanium dioxide and is in the form of a fine powder.
  • the metal salt is a transition metal salt and in particular chosen from the group comprising copper, gold, platinum, palladium, nickel, cobalt, silver, iron , zinc, cadmium, ruthenium and rhodium, and is preferably copper (II) chloride, copper (II) sulfate, palladium (II) chloride, nickel (II) chloride or a mixture at least two of these salts.
  • the liquid film-forming polymer formulation is in the form of a solution or emulsion, and in particular of a solution of the alkyl, acrylic, polyester or epoxy type, of an acrylic emulsion or a mixture of these.
  • the present invention also relates to a method of depositing metal on the surface of an insulating substrate, using the photosensitive dispersion, which consists in applying said dispersion in the form of a film to the substrate in a selective manner or not, to dry the film applied to said substrate and to irradiate using ultraviolet and / or laser radiation with a range of wavelengths between 190 and 450 nm and an energy between 25 mJ / cm 2 and 100 mj7cm 2 until a selective or non-selective metal layer is obtained on the substrate.
  • the purpose of the photosensitive dispersions with variable viscosity of the invention is to replace the palladium polymer solutions and resins known up to now, the main drawbacks of which have been specified, and to develop dispersions photosensitive with adjustable viscosity and of much wider applicability than known resins, comprising, in combination, a pigment conferring redox properties under light irradiation, a metal salt, a complexing agent for the metal salt, a liquid film-forming polymer formulation , a basic compound, an organic solvent and water.
  • pigment conferring redox properties under light irradiation is understood to mean any pigment capable of forming on the surface a redox system under light irradiation.
  • a pigment particle is a semiconductor and when this is subjected to a selected radiation, the energy of these radiations will allow the formation of an oxidoreductive pigment particle. This is how the particle formed from the so will be able to simultaneously carry out the following two reactions, namely the reduction of a cationic species adsorbed on the surface and the oxidation of an ionic species adsorbed on the surface.
  • These pigments are used in the form of finely divided powders, generally with a particle size ranging from 10 nanometers to 10 micrometers, advantageously with a particle size of 15 nanometers to 1 micrometer. Titanium dioxide is the most suitable pigment for this purpose.
  • the metal of the metal salt is advantageously a transition metal, and is more particularly, copper, gold, platinum, palladium, nickel, cobalt, silver, iron, zinc, cadmium, ruthenium or rhodium or a mixture of at least two of these.
  • Particularly advantageous metal salts are copper (II) chloride, copper (II) sulphate, palladium (II) chloride, nickel (II) chloride and mixtures of at least two of these salts.
  • liquid film-forming polymer formulation means that the polymer is in the form of a solution or emulsion or of any similar composition and in fact serves as an agent for adjusting the viscosity of the dispersion. photosensitive so as to thus obtain a continuous and homogeneous film on the surface of the substrate using various coating means such as spraying, soaking, application with a roller, screen printing, tempography or the like.
  • this polymer also participates in the redox reaction.
  • the pigment made semiconductor under light irradiation reduces the metal cations of the metal salt but, for this reaction to be effective, the pigment must also oxidize another compound, a role which is played in the present case by a film.
  • the pigment on the one hand reduces the metal cations but on the other hand oxidizes the substrate, for the pigment particles which are in contact with it, thus ensuring good adhesion, as well as the film-forming polymer matrix for the particles which are not in contact with the substrate, thus ensuring a good efficiency of the reaction in “solid” film.
  • formulations are film-forming polymer solutions of the alkyl, acrylic, polyester and epoxy type, and acrylic emulsions such as those usually used in the preparation of alkalis, detergents, paints and inks, and mixtures of these. solutions and / or emulsions.
  • the complexing agent for metal salt is advantageously of the carboxylic acid, chloride or sulfate type.
  • the purpose of this complexing agent, by coordinating with the metal salt, is to dissolve the latter.
  • complexing agents of the carboxylic acid type are tartaric acid, citric acid, their derivatives and mixtures of at least two of these compounds.
  • the basic compound used in the context of the photosensitive dispersion serves to neutralize all the acids present in the latter and to adjust the pH above 7. Potassium hydroxide, sodium hydroxide, ammonia and their mixtures are examples of usable bases.
  • a basic salt such as sodium carbonate, potassium carbonate, calcium carbonate and mixtures thereof. Mixtures of a base and a basic salt are also possible.
  • the organic solvent and water have an important role to play in the context of the photosensitive dispersion of the invention.
  • the organic solvent will be chosen from ethers, esters, ketones, alcohols, alone or as a mixture.
  • the role of organic solvents is manifold. They in particular ensure good adhesion of the film to the insulating substrate and thus good adhesion of the pigment to the substrate, good film formation, rapid drying or even good dispersion of the various components in the catalytic paint.
  • the solvents are advantageously used in a mixture so as to measure the property relating to each with respect to their respective role in the product, for the formation of the film or on the substrate.
  • solvents used alone or as a mixture are dioxane, cyclohexanone, 2-methoxy-1-methylethyl acetate, mixtures of methyl ether isomers of dipropylene glycol, mixtures of methyl ether isomers dipropylene glycol, and mixtures of at least two of these.
  • the water is advantageously deionized water.
  • the presence of water in rather small quantities is also important. Indeed, it makes the photosensitive dispersion less corrosive than most formulations of the prior art and allows ease of application in all circumstances by its formulation close to a paint.
  • the presence of organic solvent (s) also makes it possible to avoid chemical and / or mechanical pretreatments of the surface of the substrate and better control over the evaporation temperature than in the case of aqueous solutions containing a much higher proportion. significant amount of water.
  • wetting agent is a modifying agent of the surface tension and has the aim of reducing the latter by forming an adsorbed layer having a surface tension intermediate between the liquid / liquid or liquid / solid phases.
  • interesting wetting agents are silanes, esters of fluoroaliphatic polymers or also products with a high percentage of 2-butoxyethanol. Typical commercial products are Dapro U99 produced by Daniel Product and Schwego-wett (registered trademarks).
  • the dispersing agent is advantageously a pigment dispersing agent compatible with acrylic polymers, polyesters and epoxides.
  • dispersants are Disperse-AYD W-33 (mixture of nonionic and anionic surfactants in solution in water) and Deuteron ND 953 (aqueous solution of sodium polyaldehyde carbonate) (registered trademarks), respectively produced by the companies Elementis and Deuteron .
  • concentrations of the various components of the photosensitive dispersion or catalytic paint of the invention these will of course depend on the nature of these components and on the solvent used.
  • the pigment and more particularly titanium dioxide will be used in a concentration, in percentage by weight, of 1 to 50% and preferably of 5 to 25%, the metal salt in a concentration, in percentage by weight, of 0.01 to 5% and preferably of 0.05 to 1%, the complexing agent in a concentration, in percentage by weight, of 0.01 to 10% and preferably of 0 , 1 to 1%, the film-forming polymeric solution and or emulsion in a concentration, in percentage by weight, of 1 to 50% and preferably of 5 to 25%, the base in a concentration, in percentage by weight, of 0, 01 to 5% and preferably 0.1 to 1%, the organic solvent in a concentration, in percentage by weight, from 0.1 to 55% and preferably from 1 to 40% and water in a concentration, in weight percent, from 1 to 15%.
  • the concentration of wetting agent, in percentage by weight is from 0.1 to 5% and preferably from 0.25 to 1.0%, and the concentration of dispersing agent, in percentage by weight, is from 0.1 to
  • the photosensitive dispersions of the invention are prepared by a simple process of mixing all of the various constituents which it contains.
  • the order of addition of each of these constituents is immaterial and has no consequence on the intrinsic properties of the dispersion.
  • all the components constituting the photosensitive dispersion are mixed, namely the pigment, the metal salt, the complexing agent, the liquid film-forming polymer formulation, the basic compound, the organic solvent and the water as well as the possible additions and said dispersion is applied in the form of a film to the substrate in a selective manner or not depending on the intended application.
  • the film applied to the substrate is dried and irradiated using ultraviolet and / or laser radiation with a range of wavelengths between 190 and 450 nm and an energy between 25 mJ / cm 2 and 100 mJ / cm 2 until a selective or non-selective metal layer is obtained on the substrate.
  • Palladium catalytic paint for the selective metallization or not of a polymeric substrate Palladium catalytic paint for the selective metallization or not of a polymeric substrate.
  • Dispersing agent manufactured by Elementis mixture of nonionic and anionic surfactants in water.
  • the paint or catalytic dispersion is applied to a polymeric substrate, without any pretreatment of the latter, by soaking, spraying, application with a roller or pad printing and is then air dried for a few seconds.
  • the film thus obtained is irradiated using commonly used UV lamps and / or laser and having a spectrum between 250 and 450 nm, the time necessary for the film to receive a minimum energy of 25 mJ / cm 2 . If selective metallization is desired, this irradiation will be done through a mask. This results in the deposition of a layer of selective or non-selective catalytic palladium. In the case of selective metallization, the non-irradiated parts are dissolved in water. A metal overload by electroplating is then made possible, the substrate being made conductive.
  • Example 2 Copper catalytic paint for the selective metallization or not of a polymeric substrate.
  • Dispersing agent manufactured by Elementis mixture of nonionic and anionic surfactants in water.
  • Film-forming acrylic polymer emulsion manufactured by the company Johnson Polymer, registered trademark.
  • Wetting agent manufactured by the Daniel Product company silicone-free interfacial tension modifier.
  • Example 1 The procedure is as in Example 1. This results in the deposition of a layer of selective or non-selective catalytic palladium. In the case of selective metallization, the non-irradiated parts are dissolved in water. A metal overload by electroplating is then made possible.
  • the metal salt could be replaced in the concentrations indicated by all the salts specifically mentioned, namely copper (II) sulphate and palladium and nickel (II) chlorides.
  • the substrates tested in the context of the above examples are common plastics such as ABS, ABS-PC (polycarbonate), certain polyamides, epoxy materials, polycarbonates and the like.
  • the dispersion of the invention is a formulation extremely close to a paint making it easily applicable in all circumstances.
  • the photosensitive catalytic dispersion or paint of the invention does not exhibit any corrosivity unlike the formulations of the prior art which are all very corrosive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)
  • Chemically Coating (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Colloid Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)
  • Catalysts (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Formation Of Insulating Films (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Conductive Materials (AREA)
  • Silicon Compounds (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
EP03782026A 2003-01-03 2003-12-24 Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung Expired - Lifetime EP1587967B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200330267T SI1587967T1 (sl) 2003-01-03 2003-12-24 Fotosenzibilna disperzija z nastavljivo viskoznostjo za nanasanje kovine na izolirno podlago in njena uporaba

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BE2003/0007A BE1015271A3 (fr) 2003-01-03 2003-01-03 Dispersion photosensible a viscosite ajustable pour le depot de metal sur un substrat isolant et son utilisation.
BE200300007 2003-01-03
PCT/BE2003/000229 WO2004061157A1 (fr) 2003-01-03 2003-12-24 Dispersion photosensible a viscosite ajustable pour le depot de metal sur un substrat isolant et son utilisation

Publications (2)

Publication Number Publication Date
EP1587967A1 true EP1587967A1 (de) 2005-10-26
EP1587967B1 EP1587967B1 (de) 2006-05-10

Family

ID=32686676

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03782026A Expired - Lifetime EP1587967B1 (de) 2003-01-03 2003-12-24 Photosensitive dispersion mit einstellbarer viskosität für die abscheidung vom metall auf einem nichtleitenden substrat und ihre verwendung

Country Status (19)

Country Link
US (2) US20060122297A1 (de)
EP (1) EP1587967B1 (de)
JP (1) JP4621505B2 (de)
KR (1) KR100777033B1 (de)
CN (1) CN100587110C (de)
AT (1) ATE325907T1 (de)
AU (1) AU2003289778B2 (de)
BE (1) BE1015271A3 (de)
BR (1) BR0317897B1 (de)
CA (1) CA2512202C (de)
DE (1) DE60305213T2 (de)
DK (1) DK1587967T3 (de)
ES (1) ES2261991T3 (de)
IL (1) IL169463A (de)
MX (1) MXPA05007256A (de)
PT (1) PT1587967E (de)
RU (1) RU2301846C2 (de)
WO (1) WO2004061157A1 (de)
ZA (1) ZA200505512B (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009056348A (ja) * 2007-08-30 2009-03-19 Sumitomo Chemical Co Ltd 光触媒分散液
RU2462537C2 (ru) * 2010-11-11 2012-09-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Санкт-Петербургский государственный университет Раствор для лазерно-индуцированной металлизации диэлектриков и способ лазерно-индуцированной металлизации диэлектриков с его использованием
JP2013000673A (ja) * 2011-06-17 2013-01-07 National Institute Of Advanced Industrial Science & Technology 光触媒高機能化技術
RU2491306C2 (ru) * 2011-07-20 2013-08-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ им. М.В.Ломоносова) Резиновые смеси на основе диеновых и этиленпропиленовых каучуков, наполненные белой сажей
US10049881B2 (en) * 2011-08-10 2018-08-14 Applied Materials, Inc. Method and apparatus for selective nitridation process
WO2014017575A1 (ja) * 2012-07-26 2014-01-30 株式会社サクラクレパス 光触媒塗布液およびその製造方法並びに光触媒体
DE102013114572A1 (de) * 2013-12-19 2015-06-25 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Verfahren zur Herstellung strukturierter metallischer Beschichtungen
CN104329597B (zh) * 2014-09-10 2016-11-23 广东中塑新材料有限公司 一种无基板led灯及其制备方法
CN111575097B (zh) * 2020-06-15 2021-04-16 清华大学 具有光致变粘度的溶液及调控流体粘度的方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719490A (en) * 1967-07-13 1973-03-06 Eastman Kodak Co Photosensitive element containing a photoreducible palladium compound and the use thereof in physical development
US3950290A (en) * 1973-05-01 1976-04-13 A. E. Staley Manufacturing Company Aqueous coating and printing compositions
JPS60155678A (ja) * 1984-01-24 1985-08-15 Toshiba Corp 金属イオンの還元方法
JPS60195077A (ja) * 1984-03-16 1985-10-03 奥野製薬工業株式会社 セラミツクスの無電解めつき用触媒組成物
JPS62109393A (ja) * 1985-11-07 1987-05-20 カルソニックカンセイ株式会社 電気回路基板製造方法
JPH02205388A (ja) * 1989-02-03 1990-08-15 Hitachi Chem Co Ltd 半導体光触媒を用いた無電解めっきによるプリント回路の製造法
US5075039A (en) * 1990-05-31 1991-12-24 Shipley Company Inc. Platable liquid film forming coating composition containing conductive metal sulfide coated inert inorganic particles
CA2065100A1 (en) * 1991-04-05 1992-10-06 Masami Uemae Aqueous dispersion of acrylic polymer
WO1993012267A1 (fr) * 1991-12-11 1993-06-24 Sensors And Synergy S.A. Resine polymerique, en particulier pour le depot de metal sur un substrat et son utilisation
US5264466A (en) * 1992-05-28 1993-11-23 Showa Highpolymer Co., Ltd. Stainproofing paint composition and method for producing same
BE1007879A3 (fr) * 1994-01-05 1995-11-07 Blue Chips Holding Resine polymerique a viscosite ajustable pour le depot de palladium catalytique sur un substrat, son procede de preparation et son utilisation.
CA2188148A1 (en) * 1994-04-19 1995-10-26 Lehigh University Printing ink compositions, methods for making same and uses thereof
US6183944B1 (en) * 1995-11-30 2001-02-06 Eastman Kodak Company Aggregated dyes for radiation-sensitive elements
JP3384544B2 (ja) * 1997-08-08 2003-03-10 大日本印刷株式会社 パターン形成体およびパターン形成方法
US6291025B1 (en) * 1999-06-04 2001-09-18 Argonide Corporation Electroless coatings formed from organic liquids
DE19957130A1 (de) * 1999-11-26 2001-05-31 Infineon Technologies Ag Metallisierungsverfahren für Dielektrika
JP2001152362A (ja) * 1999-11-30 2001-06-05 Nisshin Steel Co Ltd 光触媒被覆金属板
JP3449617B2 (ja) * 2000-09-26 2003-09-22 日本カーリット株式会社 金属酸化物薄膜及びその形成方法
GB0025989D0 (en) * 2000-10-24 2000-12-13 Shipley Co Llc Plating catalysts
FR2824846B1 (fr) * 2001-05-16 2004-04-02 Saint Gobain Substrat a revetement photocatalytique
JP2004136644A (ja) * 2002-08-20 2004-05-13 Konica Minolta Holdings Inc インクジェット記録用紙

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004061157A1 *

Also Published As

Publication number Publication date
ZA200505512B (en) 2007-02-28
ATE325907T1 (de) 2006-06-15
MXPA05007256A (es) 2005-09-08
US20060122297A1 (en) 2006-06-08
CN100587110C (zh) 2010-02-03
BE1015271A3 (fr) 2004-12-07
AU2003289778B2 (en) 2009-06-04
KR20050089087A (ko) 2005-09-07
BR0317897A (pt) 2005-12-06
US20090017221A1 (en) 2009-01-15
JP2006515388A (ja) 2006-05-25
BR0317897B1 (pt) 2012-07-10
RU2301846C2 (ru) 2007-06-27
DK1587967T3 (da) 2006-08-28
CN1735712A (zh) 2006-02-15
EP1587967B1 (de) 2006-05-10
JP4621505B2 (ja) 2011-01-26
RU2005124683A (ru) 2006-02-10
CA2512202C (fr) 2010-11-09
IL169463A (en) 2009-12-24
WO2004061157A1 (fr) 2004-07-22
ES2261991T3 (es) 2006-11-16
AU2003289778A1 (en) 2004-07-29
PT1587967E (pt) 2006-08-31
US7731786B2 (en) 2010-06-08
DE60305213D1 (de) 2006-06-14
KR100777033B1 (ko) 2007-11-16
CA2512202A1 (fr) 2004-07-22
DE60305213T2 (de) 2007-03-01

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