EP1737919A1 - Systeme multicomposant contenant au moins trois composants, et procede de fabrication et d'utilisation - Google Patents

Systeme multicomposant contenant au moins trois composants, et procede de fabrication et d'utilisation

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Publication number
EP1737919A1
EP1737919A1 EP05731940A EP05731940A EP1737919A1 EP 1737919 A1 EP1737919 A1 EP 1737919A1 EP 05731940 A EP05731940 A EP 05731940A EP 05731940 A EP05731940 A EP 05731940A EP 1737919 A1 EP1737919 A1 EP 1737919A1
Authority
EP
European Patent Office
Prior art keywords
component
iii
components
weight
component system
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Withdrawn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
EP05731940A
Other languages
German (de)
English (en)
Inventor
Christoph Schmidt
Andreas Vogt
Nicole Eggers
Gisela Laumann
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.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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 BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1737919A1 publication Critical patent/EP1737919A1/fr
Withdrawn legal-status Critical Current

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms

Definitions

  • Multicomponent system containing at least three components, process for its production and its use
  • the present invention relates to a new, multi-component system containing at least three components.
  • the present invention also relates to a method for producing a new multicomponent system containing at least three components.
  • the present invention relates to the use of the new multi-component system containing at least three components for the production of adhesion-promoting and energy-absorbing coatings.
  • Multicomponent systems comprising a component curable with polyisocyanates, containing at least one binder with isocyanate-reactive functional groups, at least one chlorinated polyolefin and at least one organic solvent, a component containing at least one polyisocyanate and
  • the known multicomponent systems have the disadvantage that they can mainly be used only as an adhesion promoter or primer on plastic parts which consist of TPO, ie, a blend of maleated polypropylene, an elastomer and an amine-terminated polyether.
  • the storage stability of the component curable with polyisocyanates leaves something to be desired. After storage for two to three months, it tends to separate strongly and to separate the chlorinated polyolefin with the existing additives such as additives, pigments and fillers.
  • the component curable with polyisocyanates has to be homogenized again by intensive stirring, which causes additional costs in the painting operation.
  • the present invention was therefore based on the object of providing a new multicomponent system containing at least three components, which no longer has the disadvantages of the prior art, but whose component curable with polyisocyanates is stable in storage and no phase separation after storage for more than three months and shows no deposition of its components and no irreversible formation of specks even after storage for more than eight months.
  • the new multicomponent system containing at least three components should be simple to manufacture and processable into coating materials.
  • the coating materials in question are said to be very suitable for the production of adhesion-promoting and / or energy-absorbing primer and / or filler coatings on a wide variety of plastic and paint surfaces, so that they can be used with advantage in automotive OEM painting and automotive refinishing.
  • the coatings in question should have a particularly high adhesion to the substrates and to the overcoated layers even after exposure to moisture.
  • a component containing or consisting of at least one polyisocyanate (111.1) contains and which is referred to below as "multi-component system according to the invention".
  • the multi-component system according to the invention could be produced in a particularly simple and reproducible manner using the method according to the invention.
  • multi-component system according to the invention could be processed very well into coating materials within the scope of the use according to the invention.
  • the coating materials in question were very well suited for the production of adhesion-promoting and / or energy-absorbing primer and / or filler coatings on a wide variety of plastic and paint surfaces, so that they could be used to advantage in automotive OEM painting and automotive refinishing.
  • the relevant primer and filler coatings showed a particularly high adhesion to the substrates and to the overcoated layers even after exposure to moisture.
  • the filler coatings also offered excellent protection against damage caused by mechanical influences, such as stone chips.
  • the multicomponent system according to the invention comprises at least three, in particular three, components (I), (II) and (III).
  • Component (I) is free from chlorinated polyolefins and is curable with polyisocyanates.
  • It contains at least one oligomeric or polymeric binder (1.1) with at least two, preferably at least three and in particular at least four isocyanate-reactive functional groups dissolved and / or dispersed in at least one organic solvent (I.2).
  • Suitable binders (I. 1) for use in component (I) can be found in the German patent applications «
  • Component (I) preferably contains the binder (1.1) in an amount of 5 to 50, preferably 10 to 40 and in particular 15 to 30% by weight, based in each case on the solids of component (I).
  • organic solvents (I.2) which do not react with the binders (1.1) under the conditions of production, storage and further processing of component (I) are suitable.
  • the organic solvents may be inert or reactive, i.e. i.e., contain isocyanate-reactive functional groups. They can also reactively i. S. Participation in curing with actinic radiation. If they are reactive, they are so-called reactive thinners.
  • the organic solvents (1.2) are preferably inert.
  • Actinic radiation includes electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, in particular UV radiation, and corpuscular radiation, such as electron radiation, beta radiation, neutron radiation, proton radiation, in particular
  • suitable organic solvents are from the book “Paints Coatings and Solvents”, Dieter Stoye and Werner Freitag (editor), Wiley-VCH, Weinheim,
  • Suitable isocyanate-reactive functional groups are hydroxyl groups, thiol groups and primary and secondary amino groups, especially hydroxyl groups.
  • component (I) can contain customary and known additives (I.3), such as physically curable binders, from the binders described above
  • Light stabilizers such as UV absorbers and reversible radical scavengers (HALS);
  • antioxidants wetting agents; emulsifiers; slip additives; polymerization inhibitors;
  • thermolabile radical initiators thermolabile radical initiators
  • Photoinitiators and coinitiators Adhesion promoters; Veriaufsch; film-forming aids;
  • Rheology aids or rheology control additives thickeners and pseudoplastic
  • Sag control agents SCA
  • Flame retardants Corrosion inhibitors
  • waxes waxes
  • Component (II) is free from binders (1.1). It is preferably also free of additives (I.3). It contains at least one chlorinated polyolefin (11.1) and at least one organic solvent (II.2), preferably at least two and especially two organic solvents (11.2). It preferably consists of these components.
  • the chlorinated polyolefin (11.1) preferably contains, based on its total amount, 10 to 45% by weight, preferably 10 to 25% by weight and in particular 15 to 20% by weight of chlorine and has a number average molecular weight of 7,000 to 200,000 and preferably from 8,000 to 50,000 daltons. Examples of suitable chlorinated polyolefins are described, for example, in German Patent DE 196 46 610 C1, column 3, lines 2 to 34.
  • Component (II) preferably contains, based in each case on its total amount, 5 to 40% by weight and preferably 10 to 35% by weight of the chlorinated polyolefin (11.1).
  • Examples of suitable organic solvents (II.2) are the organic solvents (I.2) described above.
  • component (II) is extremely stable in storage and, as such, can be used directly on plastics for the production of adhesion-promoting primer coatings with a layer thickness of up to 15 ⁇ m, in particular 10 ⁇ m, which is an additional significant advantage.
  • the multicomponent system according to the invention further contains a component (III) containing at least one polyisocyanate (111.1).
  • Component (III) is preferably liquid.
  • Component (III) therefore preferably contains at least one inert organic solvent (III.2).
  • the inert organic solvents (I.2) described above are particularly preferably used for this purpose.
  • the polyisocyanates (III.1) can also contain reactive functional groups which can be activated with actinic radiation and can thus participate in curing with actinic radiation.
  • Such polyisocyanates (111.1) are referred to below as “dual-cure polyisocyanates (111.1)”.
  • Suitable dual-cure polyisocyanates (111.1) for use in component (III) can be found in German patent application DE 101 29 970 A1, page 2, paragraph [0008] with reference to European patent application EP 0 928 800, and Page 6, paragraph [0042], to page 11, paragraph [0099].
  • component (III) may also contain at least one additive (I.3) which is inert to isocyanates under production and processing conditions but is catalytically active with regard to crosslinking or curing, such as dibutyltin dilaurate.
  • additive (I.3) which is inert to isocyanates under production and processing conditions but is catalytically active with regard to crosslinking or curing, such as dibutyltin dilaurate.
  • the multicomponent system according to the invention can also contain at least one component (IV) which preferably contains or can consist of the organic solvents (I.2) described above and / or the additives (I.3) described above.
  • component (IV) which preferably contains or can consist of the organic solvents (I.2) described above and / or the additives (I.3) described above.
  • Components (I), (II) and (III) and optionally (IV) are anhydrous. That is, they contain no water or only traces of water that are inadvertently brought in during the manufacture and / or handling of the components.
  • the preparation of the invention is preferably carried out
  • components (I), (II) and (III) and optionally (IV) are prepared separately from one another by mixing their respective constituents in the desired amounts and homogenizing the resulting mixtures.
  • Common and known mixing methods and devices such as stirred tanks, stirred mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, gear rim dispersers, pressure relief nozzles and / or microfluidizers can be used for this purpose.
  • the preparation is carried out with the exclusion of actinic radiation, provided that the resulting components (I) to (III) and optionally (IV) contain constituents which can be activated by actinic radiation:
  • components (I), (II) and (III) and, if appropriate, (IV) of the multicomponent system according to the invention are stored separately from one another.
  • the components, in particular components (I) and (II) have proven to be extremely stable in storage, so that even after storage for more than nine months there is no longer any phase separation and no irreversible formation of specks.
  • the multicomponent system according to the invention can be used in a variety of ways, for example for the production of adhesives and sealants which are used for the production of adhesive layers and seals. In particular, it is used according to the invention for the production of coating materials.
  • components (I), (II) and (III) and optionally (IV) are mixed together in the desired amounts, after which the resulting mixtures are homogenized.
  • the devices and methods described above can be used for this purpose.
  • the components (I), (II) and (III) and, if appropriate, (IV) are preferably mixed with one another in a ratio such that the equivalent ratio of isocyanate-reactive functional groups to isocyanate groups in the resulting coating materials is 1: 2 to 2: 1, preferably 1 : 1.5 to 1.5: 1 and in particular 1: 1.2 to 1.2: 1.
  • Components (I), (II) and (III) and, if appropriate, (IV) are preferably mixed with one another in a ratio such that the resulting coating materials, based in each case on their solids, are 0.5 to 15% by weight, particularly preferably 1 Contain up to 12 wt .-% and in particular 1.5 to 10 wt .-% of at least one chlorinated polyolefin (11.1).
  • the resulting coating materials are thermally curable. This means that they can be cured at room temperature or at higher temperatures.
  • the usual and known devices such as forced air ovens, hot air blowers or radiant heaters, in particular NIR or IR rays or microwave radiators, can be used.
  • the resulting coating materials can also be curable thermally and with actinic radiation, which experts also refer to as dual-cure.
  • For curing can be carried out using the customary and known devices, such as UV lamps or electron beam sources (cf. also German patent application DE 101 29 970 A1, page 13, paragraph [0132]).
  • the coating materials are preferably thermally curable.
  • the coating materials can be easily and reproducibly produced. They have a processing time or pot life that is more than sufficient for their safe and convenient further processing in the paint shop.
  • the coating materials are preferred for the production of adhesion-promoting and / or energy-absorbing coatings, in particular primer coatings, preferably a layer thickness of 10 to 25 ⁇ m, preferably 15 to 20 ⁇ m, and / or filler coatings, preferably a layer thickness of 25 to
  • the substrates can be planar or three-dimensional. They can consist of metals. In addition, they can be surface coatings made of thermoplastic materials or thermosetting materials such as paints,
  • thermoplastic materials or thermosetting materials have 20 or consist of such thermoplastic materials or thermosetting materials.
  • plastics are ABS, AMMA, ASA, CA, ⁇ GAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA , PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) in 5.
  • the plastics do not have to be roughened by flaming or corona or plasma pretreatment, but it is sufficient that the plastics are pre-cleaned with a suitable solvent, sanded with fine sandpaper or with a sanding pad and then cleaned with the solvent.
  • the coating materials, adhesives and sealing compounds can therefore in particular be used for coating, gluing and sealing bodies of 5 means of transportation, including means of transportation operated with motor power and / or muscle power, such as passenger cars, commercial vehicles, buses, bicycles, rail vehicles, watercraft and aircraft, and parts thereof, Buildings and parts thereof, doors, windows, furniture, small industrial parts, mechanical, optical and electronic components, coils, containers, packaging, hollow glass bodies and everyday objects.
  • the application of the coating materials, adhesives and sealants, in particular the coating materials, to the substrates mentioned can be carried out by all customary application methods, such as e.g. Spraying, knife coating, brushing, pouring, dipping, watering, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated, in particular a coil can also be moved, the application system being at rest relative to the substrate or being moved in a suitable manner.
  • the coating materials prove to be particularly easy and safe to apply.
  • the resulting wet coats can be overcoated wet-on-wet before curing and then cured together with the overcoated coats (wet-on-wet process).
  • the coating materials, adhesives and sealing compounds, in particular the coating materials can also be cured immediately after their application using the devices and methods described above.
  • the resulting adhesive layers create a permanent, adhesive connection between the substrates to be bonded, which is also not released by exposure to moisture, light and / or rapidly changing temperatures.
  • the resulting coatings can also be overcoated very well.
  • the coatings Even after exposure to moisture, the coatings have particularly high adhesion to the substrates and to the overcoated layers.
  • the filler coatings offer excellent protection from the substrates and to the overcoated layers.
  • the quality of the coatings is so excellent that they can be used for automotive serial painting and car repair painting.
  • the Production of Multicomponent Systems 1 and 2 The Production of Components (I): 1.1 The Production of Component (la): For the production of component (la), 25.9 parts by weight (calculated as a solid) of a hydroxyl-containing methacrylate copolymer (Macrynal ® SM 515 from Hoechst) and 0.46 part by weight of Disperbyk ⁇ 110 (dispersing aid from Byk Chemie) and 0.28 part by weight of Byk ® P104S (surface-active additive from Byk Chemie), after which the resulting mixture was homogenized.
  • a hydroxyl-containing methacrylate copolymer Macrynal ® SM 515 from Hoechst
  • Disperbyk ⁇ 110 disperbyk ⁇ 110
  • Byk ® P104S surface-active additive from Byk Chemie
  • Bentone ® 34 from Rheox organically modified smectites and bentonites
  • Aerosil ® R972 from Degussa (pyrogenic silica)
  • Nero Flammruss 101 from Degussa 13 parts by weight of titanium dioxide Tiona® RCL-472 from Millennium, 6.5 parts by weight of aluminum silicate ASP 600 from Langer, 7.4 parts by weight of zinc phosphate ZP-BS-M from Waardals and 13% by weight of Halox® SZP-391 from Heubach (calcium-strontium-zinc-phosphorus-silicates) were stirred in, after which the resulting mixture was ground on a stirrer mill (ZWM from Naintzsch) to a fineness of 15 to 18 ⁇ m.
  • ZWM stirrer mill
  • component (Ia) was added by adding 1.9 parts by weight of Baysilon® OL 44 (leveling agent from Borchers), 0.5 part by weight (calculated as solid resin) of an organic solution Nitrocellulose Chips E 510 from Woiff Walsrode and 0.1 part by weight of a 10 percent organic solution of dibutyltin dilaurate was completed.
  • the resulting component (Ia) was extremely stable in storage and showed no phase separation and no formation of specks even after nine months of storage.
  • component (Ib) For the preparation of component (Ib), 25.41 parts by weight (calculated as a solid) of a methacrylate copolymer containing hydroxyl groups (Macrynal® SM 515 from Hoechst) and 0.28 parts by weight of Disperbyk ⁇ 111 (dispersing aid from Byk Chemie) and 0.23 Parts by weight of Byk ⁇ P104S (surface-active additive from Byk Chemie) were mixed together, after which the resulting mixture was homogenized.
  • a methacrylate copolymer containing hydroxyl groups Macrynal® SM 515 from Hoechst
  • Disperbyk ⁇ 111 dispersing aid from Byk Chemie
  • Byk ⁇ P104S surface-active additive from Byk Chemie
  • Bentone ® 34 from Rheox organically modified smectites and bentonites
  • Aerosil ® R972 from Degussa (pyrogenic silica)
  • component (Ib) 25 parts by weight of ester and 2 parts by weight of aromatics were then added, after which component (Ib) was added by adding 1.9 parts by weight of Baysilon® OL 44 (leveling agent from Borchers), 0.53 parts by weight (calculated as solid resin) of an organic solution of nitrocellulose chips E 510 from Woiff Walsrode and 0.1 part by weight of a 10 percent organic solution of dibutyltin dilaurate was completed.
  • Baysilon® OL 44 leveling agent from Borchers
  • 0.53 parts by weight (calculated as solid resin) of an organic solution of nitrocellulose chips E 510 from Woiff Walsrode and 0.1 part by weight of a 10 percent organic solution of dibutyltin dilaurate was completed.
  • the resulting component (Ib) was extremely stable in storage and showed no phase separation and no formation of specks even after nine months of storage.
  • component (II) 2.1
  • component (Ila) was prepared by mixing 62 parts by weight of ester, 18 parts by weight of aromatics and 20 parts by weight of chlorinated polyolefin CP 343.3 from Eastman and homogenizing the resulting mixture.
  • component (IIb) was prepared by mixing 54.5 parts by weight of ester, 10.5 parts by weight of aromatics and 35 parts by weight of chlorinated polyolefin CP 343.3 from Eastman and homogenizing the resulting mixture. 10 Components (lla) and (llb) were stable in storage and showed no phase separation and no formation of specks even after storage for more than eight months. Surprisingly, they could also be used directly for the production of adhesion-promoting primer coatings with a layer thickness of up to 15 ⁇ m on 15 plastics.
  • component (III) was made from 30 parts by weight of Basonat ® Hl 190 / B / S from BASF Aktiengesellschaft (isocyanurate based on hexamethylene diisocyanate), 20 8.4 parts by weight of an isocyanurate based on Isophorone diisocyanate, 61.2 parts by weight of organic solvents (mixture of esters and aromatics) and 0.4 t parts by weight of a 10 percent solution of dibutyltin dilaurate in an organic solvent.
  • the multicomponent system 1 The multicomponent system 1 of example 1 consisted of the components (la), (lla) and (III).
  • the multicomponent system 2:30 The multicomponent system 2 of example 2 consisted of components (Ib), (IIb) and (III).
  • the multi-component systems 1 and 2 were ideally suited for the production of coating materials.
  • the multi-component system 1 from example 1 was used for example 3.
  • the coating material 1 of Example 3 was produced with the aid of the multicomponent system 1 by mixing components (Ia), (Ila) and (III) together in a weight ratio of 2: 1: 1 and homogenizing the resulting mixture.
  • the coating material 2 of Example 4 was produced with the aid of the multi-component system 2 by mixing components (Ib), (IIb) and (III) together in a weight ratio of 2: 1: 1 and homogenizing the resulting mixture.
  • the components of the multi-component systems 1 and 2 could be mixed with one another in a short time without any problems.
  • the resulting coating materials 1 and 2 had a content of volatile organic compounds (VOC) which met the practical requirements of VOC ⁇ 540 g / l or 4.5 lab / gal.
  • the coating materials 1 and 2 had a processing time or pot life of several hours and could therefore be processed easily. In particular, they could be applied very easily using the customary and known spray application methods.
  • the coating materials 1 and 2 were applied with spray guns SATA ® No. 2000-1.3 mm at a spray pressure of 2 bar in a wet layer thickness to plastic substrates that after drying and curing the wet layers 1 and 2 filler coatings 1 and 2 with Dry layer thicknesses of 30 ⁇ m resulted.
  • the plastic substrates consist of impact-modified polypropylene, polycarbonate and white and black colored TPO (blend of maleated polypropylene, an elastomer and an amine-terminated polyether), the surface of which has been pre-cleaned with a suitable solvent, sanded with fine sandpaper and then cleaned with the solvent had been.
  • the plastic substrates coated with wet layers 1 and 2 were overcoated in a first series wet-on-wet with a customary and known two-component solid-color topcoat from BASF Coatings AG. In a second series, they were coated wet-on-wet with a customary and known metallic basecoat and a customary and known two-component clearcoat (both from BASF Coatings AG). The wet layers were then hardened together (wet-on-wet method). All resulting paintwork was free from surface defects such as specks.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un système multicomposant contenant au moins trois composants, contenant (I) un composant exempt de polyoléfines chlorées, pouvant être durci au moyen de polyisocyanates, contenant (I.1) au moins un liant portant des groupes fonctionnels réagissant avec isocyanate, et (I.2) au moins un solvant organique; (II) un composant exempt de liants (I.1), contenant (II.1) au moins une polyoléfine chlorée et (II.2) au moins un solvant organique; et (III) au moins un composant contenant du polyisocyanate (III.3) ou composé de ce dernier. L'invention concerne également un procédé de fabrication et d'utilisation dudit système multicomposant.
EP05731940A 2004-04-14 2005-03-31 Systeme multicomposant contenant au moins trois composants, et procede de fabrication et d'utilisation Withdrawn EP1737919A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004018014A DE102004018014A1 (de) 2004-04-14 2004-04-14 Mindestens drei Komponenten enthaltendes Mehrkomponentensystem, Verfahren zu seiner Herstellung und seine Verwendung
PCT/EP2005/051530 WO2005100494A1 (fr) 2004-04-14 2005-03-31 Systeme multicomposant contenant au moins trois composants, et procede de fabrication et d'utilisation

Publications (1)

Publication Number Publication Date
EP1737919A1 true EP1737919A1 (fr) 2007-01-03

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EP05731940A Withdrawn EP1737919A1 (fr) 2004-04-14 2005-03-31 Systeme multicomposant contenant au moins trois composants, et procede de fabrication et d'utilisation

Country Status (7)

Country Link
US (1) US20070173600A1 (fr)
EP (1) EP1737919A1 (fr)
JP (1) JP2007532740A (fr)
AU (1) AU2005233315A1 (fr)
BR (1) BRPI0509934A (fr)
DE (1) DE102004018014A1 (fr)
WO (1) WO2005100494A1 (fr)

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Title
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US20070173600A1 (en) 2007-07-26
BRPI0509934A (pt) 2007-09-25
DE102004018014A1 (de) 2005-11-10
JP2007532740A (ja) 2007-11-15
AU2005233315A1 (en) 2005-10-27
WO2005100494A1 (fr) 2005-10-27

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