EP1769040A1 - Agent de revetement anticorrosion pour pieces en metal, et procede pour le produire - Google Patents

Agent de revetement anticorrosion pour pieces en metal, et procede pour le produire

Info

Publication number
EP1769040A1
EP1769040A1 EP05759375A EP05759375A EP1769040A1 EP 1769040 A1 EP1769040 A1 EP 1769040A1 EP 05759375 A EP05759375 A EP 05759375A EP 05759375 A EP05759375 A EP 05759375A EP 1769040 A1 EP1769040 A1 EP 1769040A1
Authority
EP
European Patent Office
Prior art keywords
coating
workpiece
corrosion
corrosion protection
metal
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.)
Withdrawn
Application number
EP05759375A
Other languages
German (de)
English (en)
Inventor
Heike Mertens
Gerhard Reusmann
Thomas Kruse
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.)
Ewald Doerken AG
Original Assignee
Ewald Doerken AG
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 Ewald Doerken AG filed Critical Ewald Doerken AG
Publication of EP1769040A1 publication Critical patent/EP1769040A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • the invention relates to a corrosion protection coating composition for workpieces made of metal and metallic materials, a workpiece with corrosion protection.
  • Coating and a method for producing a corrosion protection coating on a workpiece Coating and a method for producing a corrosion protection coating on a workpiece.
  • Anti-corrosive coatings and coating agents are generally known in the art.
  • US 5,334,631 describes an anticorrosive powder consisting of a resin, a curing agent and zinc in particulate form.
  • the workpiece is first heated to 240 0 C.
  • the coating is applied in an electrostatic process in a thickness of 50 ⁇ m.
  • another covering layer consisting of a polyester resin is applied.
  • the entstan ⁇ which layers are then cured at 180 0 C.
  • a disadvantage of this method is that the conductivity and thus the effectiveness of the corrosion protection are not optimally implemented.
  • EP 0 939 111 describes a coating for metallic materials, which in particular counteracts a hydrogen embrittlement of the workpiece.
  • the coating consists of an epoxy resin, zinc dust and an expan ⁇ under temperature-inducing powder.
  • a primer of a silane type epoxy can be beige ⁇ mixed.
  • the expanding powder serves to increase the effective area of the zinc dust.
  • the coating applied to the workpiece is then provided with a topcoat.
  • a disadvantage of this coating is that sufficient mechanical flexibility is not ensured after application.
  • a workpiece with a corrosion protection coating has at least one organic binder with an organosilicon compound and a particulate metal.
  • a workpiece according to the invention - a first coating comprising an organic binder with a silizi ⁇ organic compound and a particulate metal applied as anti-corrosion coating liquid and then applied a second coating whose composition is preferably different from the anti-corrosion coating.
  • Suitable organic binders are, in particular, those materials which crosslink even at the lowest possible temperatures and then form a corresponding mechanically and chemically loadable coating.
  • epoxy compounds as binders, but also polyesters and acrylates.
  • Organosilicon compounds are understood to mean those compounds which have Si-R bonds, where R is an organo group.
  • the silicon-organic compound of the Si-O-Si (siloxane) type is preferred.
  • Such organosilicon compounds form copolymers with customary organic binders which form well-adhering and elastic coatings on metallic surfaces.
  • the particulate metal used should preferably be able to mix well with the binder, have a conductivity which is suitable for establishing the highest possible cathodic corrosion protection, and the particulate metal should be suitable for the formation of a uniform coating.
  • a conductivity which is suitable for establishing the highest possible cathodic corrosion protection
  • the particulate metal should be suitable for the formation of a uniform coating.
  • zinc, aluminum, tin, manganese or alloys of the metals mentioned come into consideration. Additions of conductive fillers are also possible.
  • the coating agent is liquid during application. This is the Applying a uniform layer in a simple manner possible with known Ap rates ⁇ .
  • the anticorrosive coating agent may well be present in a concentrated, pasty or solid form, not least in order to minimize transportation and storage costs.
  • the binder is an acrylate, a polyester or a resin, in particular an epoxy resin, or a combination of these, with an organosilicon compound.
  • an acrylate a polyester or a resin
  • an epoxy resin or a combination of these
  • an organosilicon compound a compound that is used in the art.
  • epoxy resins have very good mechanical and chemical resistance properties, which are required for anticorrosive coatings.
  • the organosilicon compound comprises a polyorganosiloxane.
  • a polyorganosiloxane is particularly advantageous in conjunction with epoxy resins for forming a well-adhering and corrosion-resistant coating.
  • these inorganic / organic binders bind metal particles well.
  • the binder is a polyorganosiloxane resin, in particular a silicone-modified epoxy resin.
  • a polyorganosiloxane resin in particular a silicone-modified epoxy resin.
  • Such resins are industrially available, for example in SILRES EP® from Wacker Chemie or in SILIKOFTAL EW® from Degussa. Preference is furthermore given to methylphenyl, phenyl and methylsilicone resins.
  • Resins with vinyl or allyl groups, acrylic esters, ⁇ thylenimino phenomenon, halogenated phenyl radicals, fluoro derivatives, hydroxyorgano groups, Carboxyorgano- groups, aminoalkyl groups, siloxane-silazane copolymers, phenylene groups or with cocondensation products with organic resins are also suitable.
  • An advantage of silicone-modified epoxy resins is that such resins bind a high proportion of particulate metal while at the same time providing high flexibility of a coating produced with this coating composition. The flexibility of the coating is sufficient, so that coating of spring steel workpieces, such as suspension springs, the coating, even at high mechanical Bela ⁇ stonne, not flaking off. •
  • the particulate metal is zinc.
  • Aluminum, tin, manganese and alloy ments from these are suitable.
  • particulate metal is understood as meaning metal which is used in small parts, preferably in the form of spherical particles, in particular dust, and / or lamellar particles, in particular flakes.
  • Zinc and the other metals mentioned above have good conductivity and good cathodic corrosion protection. It goes without saying that the use of other metals is also conceivable.
  • Corresponding coatings based on zinc and / or the other metals mentioned protect the metal substrate from corrosion by anodically dissolving these materials while the metallic substrate becomes the cathode. This mechanism protects the substrate against decomposition phenomena.
  • flakes offer the advantage of being able to form thin layers in which the contact between the particles required for effective corrosion protection forms safely. However, it must be ensured that the flakes or the dust are sufficiently fine that a sufficiently smooth and thin coating of 1 ⁇ m, 5 ⁇ m, 10 ⁇ m or more can be produced.
  • the binder in the form of a carrier it is preferred for the binder in the form of a carrier to form a proportion of 10 to 35 percent by weight of the coating composition, in particular preferably 14 to 24 percent by weight. It is thus possible to build up an effective cathodic corrosion protection coating with relatively small amounts of binder.
  • the binder in its delivery form preferably has a solids content of 49% to 55%. Depending on the requirements of the application, however, this can be varied within a wide range. It is also possible to use cobinders, in particular organic co-binders, such as acrylate binders, polyvinylidene fluoride or other fluorinated polymers, be it to specifically adjust the properties of the coating composition, be it for reasons of cost.
  • a further advantage is that the metal forms a proportion of 10 to 90 percent by weight of the coating agent in the form of a supply, preferably 35 to 85 percent by weight, more preferably 45 to 70 percent by weight. Tests have shown that such a coating agent offers a particularly high degree of cathodic corrosion protection. Overall, it can be regarded as advantageous that the binder and the particulate metal vary according to the Requirements of the application can be varied in a wide range. In principle, however, it is preferred if the highest possible proportion of metallic particles is incorporated in the coating agent.
  • the coating composition expediently comprises one or more of the following components: crosslinking agents, adhesion promoters, additives, thickeners, catalysts, fillers, corrosion inhibitors, anticorrosive pigments, color pigments and solvents, in particular organic solvents.
  • crosslinking agents By adding crosslinking agents, a completely cured coating can be provided if desired or required.
  • Adhesion promoters can be used if a difficult to coat substrate is specified. In principle, however, it should be noted that even the corrosion protection coating composition according to claim i has excellent adhesion to metallic substrates.
  • Additives and thickeners can be added if the viscosity or rheology of the coating agent is to be adjusted or if the application properties of the product are to be adjusted.
  • Catalysts serve to control the reaction behavior; in particular the reaction rates.
  • Active and passive fillers are added to improve the mechanical and thermal properties of the coating, for example, aluminum silicates, magnesium silicates, mica pigments, graphite and molybdenum sulfide can be used. For particularly corrosive
  • Said anticorrosive coating composition is characterized by a vorteil ⁇ embodiment is characterized in that it in a wide temperature range, preferred wise at temperatures from 50 ° C to 300 ° C, more preferably at low temperatures of 80 0 C to 150 0 C pre-crosslinked. It is therefore particularly applicable to such metallic workpieces that can not be exposed to high heat due to their material properties.
  • a typical example here is the coating of spring steels, which after forming an undesirable structural change when heated above 160 ° C for a long time.
  • the invention is also equally applicable to all other metallic materials.
  • the pre-crosslinking at low temperatures has an advantageous effect there, because less energy than usual must be used to fix the coating. It also results in a good compromise between the temperature and the time required for fixing.
  • a workpiece with anticorrosive coating mindest ⁇ least an organic binder with an organosilicon compound and a particulate metal.
  • the coated workpiece can already be used with this coating.
  • it is also suitable, if appropriate after application of an adhesion promoter, to be provided with further coatings, for example color finishes or finishes, which offer a further improved chemical and / or mechanical protection or improved weather resistance.
  • the applied coating preferably has a dry film thickness of 1-50 ⁇ m, preferably 15-30 ⁇ m. Such a small layer thickness results in improved flexibility of the coating. In the case of a coating of, for example, spring materials, such a flaking off of the coating can be prevented.
  • the workpiece is pretreated prior to coating.
  • the pretreatment should be adapted to the material.
  • Vor harmonysverfah ⁇ ren are known in the art.
  • the pretreatment is preferably carried out by means of cleaning jets. These processes remove contaminants as well as any surface rust from the workpiece. In particular, scale on the surface of the material is also disadvantageous for corrosion protection and is usually removed by cleaning jets.
  • the pretreatment should be carried out in such a way that no material damage occurs after the pretreatment and no residues of a possibly used cleaning agent are present on the surface of the workpiece.
  • the workpiece has at least one further A coating applied to an anticorrosion coating comprising one or more of the following components: thermoplastic polycondensates, in particular polysulfone (PSU), polyphenylene sulfide (PPS), polyphenyl ether sulfone (PPSU), polyether sulfone (PES), polyaryl ether ketone (PAEK), polyether ketone (PEK), polyamide (PA), poly (amide-imide) (PAI), poly (ether-imide) (PEI), poly (imide-sulfone) (PISO) and polyetheretherketone (PEEK) as well as fluorinated polymers, in particular Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), perfluoroalkoxy copolymer (PFA), copolymer of t
  • PVDF polyviny
  • Such further coatings advantageously serve as cover layers for protecting the corrosion protection coating against chemical and mechanical damage as well as against weather influences. Possibly. These can also serve for coloring. So these further coatings should be designed, for example in the automotive sector such that it protects, for example, approximately influences from falling rocks and weathering "the anti-corrosion coating.
  • At least one further coating in particular a topcoat, preferably a powder coating, is applied to the fixed, in particular precrosslinked corrosion protection coating.
  • a topcoat preferably a powder coating
  • Such paints are advantageously available industrially, and protect the anti-corrosion coating from mechanical, chemical and weathering.
  • all commercially available powder coatings for example epoxy, polyester, polyamide, polyurethane and acrylate powder coatings, but also mixed powder coatings come into consideration.
  • a first coating comprising an organic binder with an organosilicon compound and a particulate metal as anticorrosion coating
  • a second coating is applied, the composition of which preferably differs from that of the corrosion protection coating. Since the second layer is no longer serves thodischen corrosion protection, this layer can be advantageous for strengthening the workpiece against further stresses (chemical, mechanical stress, weather) designed and / or decorative purposes serve.
  • the second coating is applied as a powder coating.
  • powder coatings are advantageously industrially available. It comes here all commercially available powder coatings, such as epoxy, polyester, polyamide, polyurethane and acrylate powder coatings, but also mixed powder coatings into consideration. They provide the lower layer with sufficient protection against damage and external influences. Also suitable are the abovementioned thermoplastic polycondensates, fluorinated polymers or thermosets based on phenolic resin.
  • the first coating is fixed after application, but not fully cured.
  • the term "fixed” refers to all those states which make it possible to apply the following layers.
  • the Fixie ⁇ ren of the first coating should have the consequence that on the one hand sufficient adhesion with the substrate is ensured and on the other hand, the application of a further coating is possible. In particular, it should not be possible to re-dissolve the first layer when applying further layers.
  • the at least two-layer coating of the workpiece is expediently completely cured only after the application of the second layer, preferably after the application of the last layer.
  • the term "complete” encompasses all states in which the layers are stable or essentially completely cross-linked with respect to the respective use of the workpiece, thereby reducing the thermal stress on the workpiece, which is advantageous in particular with spring steel materials or similar materials
  • the curing should be done at as low a temperature as possible and in as short a time as possible.
  • the first coating is applied with a dry film thickness of 1-50 ⁇ m, preferably 15-30 ⁇ m.
  • the flexibility of the coating is further improved.
  • the workpiece is pretreated prior to treatment.
  • the pretreatment is a cleaning jet.
  • a correspondingly clean surface is advantageous for improved cathodic corrosion protection.
  • the coated layers Tem ⁇ a temperature of up exposed to 400 0 C, preferably from 13O ° C-24O ° C, particularly preferably from 130 0 C-IOo 0 C.
  • Such treatment of the first layer provides for thermal fixation of the coating.
  • the coating is not completely crosslinked in this case, but is suitable to apply a further coating.
  • the elevated temperature of up to 400 0 C preferably from 13O ° C-24O ° C, more preferably of 130 0 C-10o 0 C cures the coatings.
  • a temperature of up to 400 ° C. is only used for special coatings and drying processes.
  • significantly lower temperatures generally must be used.
  • the method is advantageously applicable in conjunction with suitable binders even at low temperatures, whereby the material properties of heat-sensitive materials, such as spring materials are not changed.
  • the workpiece is heated to the aforementioned temperatures (object temperature). In principle, however, it is sufficient, for example in the case of inductive heating, for the coating or directly the surface to be coated, not the entire workpiece, to be heated to this temperature.
  • the first coating is fixed within a period of at least 5 seconds, preferably within 15-90 minutes. Short periods of time are used, in particular, in inductive warm-up processes; in conventional warm-up processes, the fixation can take a few hours.
  • the layers are advantageously cured for at least 10 seconds, preferably for 15-90 minutes.
  • the raw materials mentioned are temperature dispersed in a dissolver for 15-25 min at maximum Tempe ⁇ of 40 0 C.
  • the application of the coating agent to a workpiece can be carried out by application methods known in the art, for example, a layer can be applied in an HVLP injection method (high volume low pressure).
  • the liquid applied to the workpiece coating agent is then crosslinked vor ⁇ at an object temperature of 130 0 C over a period of 30 minutes.
  • a commercially available black epoxy powder coating is applied to the fixed coating.
  • the dry film thickness of this powder coating is 60-100 microns.
  • the coated workpiece is then brought to an object temperature of 150 ° C.-2 ° C., whereby the two applied layers are cured together. This object temperature is held for 15-25 minutes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

La présente invention concerne un agent de revêtement anticorrosion pour métaux ainsi qu'une pièce dotée d'un revêtement anticorrosion. Selon l'invention, pour permettre une bonne protection contre la corrosion cathodique, l'agent de revêtement anticorrosion comprend un liant organique comprenant un composé de silicium organique et un métal particulaire. L'invention a également pour objet un procédé pour produire une revêtement anticorrosion sur une pièce, le procédé comprenant les étapes suivantes : application sous forme liquide, en tant que revêtement anticorrosion, d'un revêtement primaire comprenant un liant organique qui comprend un composé de silicium organique et un métal particulaire ; puis application d'un second revêtement dont la composition se différencie de préférence de celle du revêtement anticorrosion.
EP05759375A 2004-07-16 2005-07-07 Agent de revetement anticorrosion pour pieces en metal, et procede pour le produire Withdrawn EP1769040A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004034645A DE102004034645A1 (de) 2004-07-16 2004-07-16 Korrosionsschutz-Beschichtungsmittel für Metall und Verfahren zur Herstellung hierfür
PCT/EP2005/007360 WO2006007985A1 (fr) 2004-07-16 2005-07-07 Agent de revetement anticorrosion pour pieces en metal, et procede pour le produire

Publications (1)

Publication Number Publication Date
EP1769040A1 true EP1769040A1 (fr) 2007-04-04

Family

ID=35478469

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05759375A Withdrawn EP1769040A1 (fr) 2004-07-16 2005-07-07 Agent de revetement anticorrosion pour pieces en metal, et procede pour le produire

Country Status (14)

Country Link
US (1) US20080193743A1 (fr)
EP (1) EP1769040A1 (fr)
JP (1) JP2008506835A (fr)
KR (1) KR20070035061A (fr)
CN (1) CN1997717A (fr)
AU (1) AU2005263444B2 (fr)
BR (1) BRPI0513252A (fr)
CA (1) CA2574171A1 (fr)
DE (1) DE102004034645A1 (fr)
EA (1) EA012102B1 (fr)
IL (1) IL180399A0 (fr)
MX (1) MX2007000531A (fr)
WO (1) WO2006007985A1 (fr)
ZA (1) ZA200700418B (fr)

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EA200700163A1 (ru) 2007-06-29
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IL180399A0 (en) 2007-06-03
AU2005263444B2 (en) 2011-03-24
ZA200700418B (en) 2009-09-30
AU2005263444A1 (en) 2006-01-26
MX2007000531A (es) 2007-03-30
CN1997717A (zh) 2007-07-11
DE102004034645A1 (de) 2006-02-09
US20080193743A1 (en) 2008-08-14
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WO2006007985A1 (fr) 2006-01-26
BRPI0513252A (pt) 2008-04-29

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