Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
  • B05D7/57—Three layers or more the last layer being a clear coat
  • B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0209—Multistage baking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
  • B05D7/57—Three layers or more the last layer being a clear coat
  • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
  • B05D3/0263—After-treatment with IR heaters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
  • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
  • B05D3/065—After-treatment
  • B05D3/067—Curing or cross-linking the coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/54—No clear coat specified
  • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer

Definitions

• the invention relates to a method for multi-layer coating of substrates using radiation-curable coating agents.
• the method can advantageously be used in vehicle and industrial painting, preferably in vehicle refinishing.
• UV technology for coating and hardening has long been state of the art, particularly in the wood coating industry. However, it has also become known in other fields of application, such as in vehicle painting, to use coating compositions curable by means of high-energy radiation.
• the advantages of radiation-curable coating agents are also used here, e.g. the very short curing times, the low solvent emissions of the coating agents and the very good hardness of the coatings obtained from them.
• DE-A-196 35 447 describes a process for the production of a multi-layer refinish, a coating agent being applied as a clear coat or pigmented top coat which contains binders which can only be polymerized by UV radiation.
• the applied coating agent is UV-irradiated with UV flash lamps.
• EP-A-0 540 884 describes a process for the production of a multi-layer finish for automotive serial painting by applying a clear coat to a dried or hardened basecoat, the clearcoat containing free-radical curing curable binders and the clearcoat being cured by means of UV radiation .
• the Klariack is applied when illuminated with light with a wavelength of over 550 "nm or in the absence of light.
• Coating agents which can be cured by means of high-energy radiation and which contain binders which can cure by means of high-energy radiation and additionally via a further crosslinking mechanism have also been described.
• DE-A-28 09 715 specifies binders curable by means of high-energy radiation which are based on an NCO- and acryloyl-functional urethane compound, prepared from a hydroxyalkyl ester of (meth) acrylic acid and a polyisocyanate, and on a polyfunctional hydroxyl compound.
• EP-A-0 000 407 describes coating compositions curable by means of high-energy radiation based on an OH-functional polyester resin esterified with acrylic acid, a vinyl compound and a polyisocyanate.
• a first curing step the irradiation with UV light takes place and in a second curing step, the final curing takes place at temperatures of 130 to 200 ° C.
• German patent application P 198 18 735 proposes coating compositions which are curable by means of high-energy radiation and which contain, as binders, compounds A) with free-radically polymerizable double bonds and other functional groups which are reactive in the sense of an addition and / or condensation reaction, and compounds B) with radicals polymerizable double bonds and other functional groups reactive in the sense of an addition and / or condensation reaction, the latter being said to be reactive towards the additional reactive groups of the compounds A).
• the coatings obtained can be heated to higher temperatures, e.g. Exposed to 30 to 120 ° C.
• the object of the invention was therefore to provide a process for multi-layer vehicle painting, in particular for multi-layer vehicle refinishing, using at least partially radiation-curable coating agents, with which coatings are obtained which are free from cracks and have good adhesion to the substrate.
• the coatings obtained are said to have very good chemical and weather resistance and good sandability. They should also show sufficient flexibility even with a high degree of networking.
• the coatings should also show a perfect optical appearance.
• the object is achieved by the process for multi-layer painting, which forms an object of the invention, by applying one or more filler layers and / or further layers, which can be conventional intermediate layers, for example, to a possibly precoated substrate, and then applying a top coat layer from one Basecoat / clearcoat structure or from a pigmented single-layer topcoat, at least one of the layers of the multi-layer structure being produced from a coating agent which is at least partially curable by means of high-energy radiation, which is characterized in that after application of the coating agent or agents which are at least partially curable by means of high-energy radiation (see ) first exposure to infrared radiation (TR radiation) and then exposure to high-energy radiation, preferably ultraviolet radiation (UN radiation), the exposure to IR radiation Radiation can at least partially overlap the subsequent irradiation with high-energy radiation.
• "UV radiation in particular, but also, for example, electron radiation can be used as high-energy radiation.
• a flash-off phase is preferably granted.
• it can be a venting of 5 to 15 minutes, preferably 5 to 10 minutes at room temperature. Irradiation is then carried out.
• the coating compositions which are at least partially curable by means of high-energy radiation in the process according to the invention can be aqueous, diluted with solvents or free from solvents and water.
• the coating compositions can be completely or only partially curable by means of high-energy radiation, preferably by means of UV radiation.
• Coating agents curable by means of high-energy radiation are, in particular, cationically and / or radically curing coating agents known to the person skilled in the art. Radically curing coating compositions are preferred. When high-energy radiation acts on these coating compositions, radicals are generated in the coating composition, which trigger crosslinking by radical polymerization of olefinic double bonds.
• the free-radically curing coating compositions which can be used preferably contain customary prepolymers, such as poly- or oligomers, which have free-radically polymerizable olefinic double bonds, in particular in the form of (meth) acryloyl groups in the molecule.
• the prepolymers can be used in combination with conventional reactive diluents, i.e. reactive liquid monomers.
• prepolymers or oligomers are (meth) acrylic-functional (meth) acrylic copolymers, epoxy resin (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, polyurethane (meth) acrylates, unsaturated polyesters, unsaturated polyurethanes or silicone (meth) acrylates with number average molecular masses (Mn) preferably in the range from 200 to 10,000, particularly preferably from 500 to 3000 and with an average of 2 to 20, preferably 3 to 10, radically polymerizable, olefinic double bonds per molecule.
• Mn number average molecular masses
• (Meth) acrylic here means acrylic and / or methacrylic.
• reactive diluents are used, for example, in amounts of 1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of prepolymers and reactive diluents. These are defined low-molecular compounds that can be mono-, di- or polyunsaturated.
• reactive diluents are: (meth) acrylic acid and its esters, maleic acid and its half esters, vinyl acetate, vinyl ether, substituted vinyl ureas, ethylene and propylene glycol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, Vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri, di and mono (meth) acrylate, trimethylolpropane tri, di and mono (meth) acrylate, styrene, vinyl toluene, divinyl benzene, pentaerythritol tri and - tetra (meth) acrylate, di- and tripropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate.
• the reactive diluents can be used individually or in a mixture.
• Diacrylates such as dipropylene glycol diacrylate, tripropylene glycol diacrylate and / or hexanediol diacrylate are preferably used as reactive thinners.
• the free radical curing coating compositions contain photoinitiators, e.g. in amounts of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the sum of free-radically polymerizable prepolymers, reactive diluents and photoinitiators.
• photoinitiators such as benzoin and derivatives, acetophenone and derivatives, e.g. 2,2-diacetoxyacetophenone, benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds, e.g. Acylphosphine oxides.
• the photoinitiators can be used alone or in combination.
• other synergistic components e.g. tertiary amines can be used.
• the coating compositions which can be at least partially hardened by means of high-energy radiation in the process according to the invention preferably contain one or more further binders in addition to the binder system which is curable by means of high-energy radiation.
• the other binders which may additionally be present, are preferably conventional binder systems which can be hardened by means of addition and / or condensation reactions. However, they can also be conventional physically drying binder systems or combinations of the two binder systems mentioned. It is also possible that this is by means of high energy Radiation-curable binder system in addition to the radically polymerizable double bonds for crosslinking by addition and / or condensation reactions has groups.
• lacquer chemical crosslinking reactions known to the person skilled in the art, such as, for example, the ring-opening addition of an epoxy group to a carboxyl group to form an ester and a hydroxyl group, the addition of a hydroxyl group to an isocyanate group to form a Urethane group, the reaction of a hydroxyl group with a blocked isocyanate group to form a urethane group and elimination of the blocking agent, the reaction of a hydroxyl group with an N-methylol group with elimination of water, the reaction of a hydroxyl group with an N-methylol ether group with elimination of the etherification alcohol, the transesterification reaction of a hydroxyl group with an ester group with elimination of the esterification alcohol, the re-uramation reaction of a hydroxyl group with a carbamate group with alcohol elimination, the reaction of a carbamate group with an N-methylo lether group with elimination of
• Functional groups are preferably contained in the binder system, which enable crosslinking at low temperatures, for example at 20 to 80 ° C. It can particularly preferably be hydroxyl and isocyanate groups.
• the functional groups, in particular the hydroxyl groups and isocyanate groups, can each be present in the binder curable by means of high-energy radiation and / or in a separate binder.
• polyurethane (meth) acrylates, polyester (meth) acrylates and / or (meth) acryloyl-functional poly (meth) acrylates can be used in the clear coat, basecoat or single-layer topcoat and in the filler or other layers, such as intermediate layers, preferably epoxy (meth) acrylates.
• Particularly good results are obtained if the (meth) acryloyl-functional binders mentioned above are combined with binders which are based on a crosslinking mechanism between hydroxyl and isocyanate groups.
• the hydroxyl and / or isocyanate groups can also be present in the (meth) acryloyl-functional binder (s).
• Binder systems which contain (meth) acryloyl and OH-functional components and polyisocyanates are particularly preferred and advantageously to be used, it being possible for the (metfriacryloyl and OH groups to be present in one and / or different binder components, and also binder systems comprising A ) one or more compounds which have free-radically polymerizable double bonds and which additionally contain at least one further functional group which is reactive in the sense of an addition and / or condensation reaction, and B) one or more compounds which have free-radical polymerizable double bonds which additionally contain at least one further in the sense of an addition and / or contain a condensation reaction reactive functional group, the additional reactive functional group being complementary or reactive towards the additional reactive functional groups of component A).
• one or more monomeric, oligomeric and / or polymeric compounds with at least one functional group from component A) or component B) which is present in addition to the radical-polymerizable double bonds can optionally also be reactive in the sense of an addition and / or condensation reaction Group.
• the at least partially curable coating compositions which can be used in the process according to the invention can contain additional components which are customary for the coating formulation.
• the additives are the usual additives that can be used in the paint sector. Examples of such additives are leveling agents, anti-cratering agents, anti-foaming agents, catalysts, adhesion promoters, rheology-influencing additives, thickeners, light stabilizers and emulsifiers.
• the additives are used in customary amounts known to the person skilled in the art.
• the coating compositions which can be used in the process according to the invention can contain proportions of organic solvents and / or water.
• the solvents are common paint solvents. These can come from the manufacture of the binders ' originate or are added separately. Examples of such solvents are monohydric or polyhydric alcohols, for example propanol, butanol, hexanol; Glycol ethers or esters, for example diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, in each case with C1 to C6 alkyl, ethoxypropanol, butyl glycol; Glycols, for example ethylene glycol, propylene glycol and their oligomers, esters, for example butyl acetate and amyl acetate, N-methylpyrrolidone and ketones, for example methyl ethyl ketone, acetone, cyclohexanone; aromatic or aliphatic hydrocarbons, for example toluene,
• the coating compositions which can be used in the process according to the invention can contain pigments and / or fillers. These are the usual fillers and organic or inorganic color and / or effect pigments and corrosion protection pigments that can be used in the paint industry.
• inorganic or organic color pigments are titanium dioxide, micronized titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone and pyrrolopyrrole pigments.
• effect pigments are: metal pigments, for example made of aluminum, copper or other metals; Interference pigments, such as metal oxide-coated metal pigments, for example titanium dioxide-coated or ischoxide-coated aluminum, coated mica, such as titanium dioxide-coated mica and graphite effect pigments.
• fillers are silicon dioxide, aluminum silicate, barium sulfate and talc.
• the coating compositions can advantageously contain special coated fillers to increase the scratch resistance.
• Fillers that can be used here are, for example, micronized aluminum oxide or micronized silicon oxides. These fillers are coated with compounds which contain UV-curable groups, for example with acrylic-functional silanes, and are therefore included in the radiation curing of the coating composition.
• UV-curable groups for example with acrylic-functional silanes
• Such suitable particularly for clearcoats transparent fillers are available as commercial products, for example under the name AKTISIL ® available.
• the general composition of the coating agents that can be used depends on which layer of the multilayer structure is to be created with the respective coating agent, ie whether it is, for example a clear coat, a basecoat or a filler or another common intermediate layer.
• the coating compositions can be applied to various substrates in the process according to the invention.
• Preferred substrates are metal or
• Plastic substrates The application in the multilayer structure is carried out by customary methods, preferably by spray application.
• the substrates can be precoated, for example provided with a customary primer layer.
• TR radiators which are known to the person skilled in the art and are customary for drying the paint can be used.
• the IR radiator is positioned in front of the substrate surface to be irradiated, for example at a distance of 20 to 70 cm.
• the radiation duration with TR radiation can be, for example, 1 to 20 minutes. Depending on the radiation duration and
• temperatures of, for example, 40 to 200 ° C. can be achieved on the substrate surface.
• the settings should be made so that temperatures of, for example, 40 to 100 ° C are reached on the substrate surface.
• Particularly good results are achieved if, after application, the radiation is not irradiated directly with TR radiation, but rather one
• Flash-off phase follows. For example, it can be a venting of 5 to 15 minutes, preferably 5 to 10 minutes at room temperature.
• the irradiation can be carried out with high-energy radiation, preferably with UV radiation.
• the curing of the coating which is curable at least partially by means of high-energy radiation, preferably UV radiation, can preferably be carried out with UV radiation sources with emissions in the wavelength range from 180 to 420 nm, in particular from 200 to 400 nm.
• UV radiation sources that can be used include high-pressure, medium-pressure and low-pressure mercury lamps.
• the lamp length can vary. For example, lamps between 5 and 200 cm in length are common. Depending on the specific application and the radiation energy required, the lamp and reflector geometry can be coordinated with one another in the usual way.
• the respective lamp power can vary, for example, between 20 and 250 W / cm (watts per cm lamp length). Lamps with powers between 80 and 120 W / cm are preferably used.
• the mercury lamps can also be doped by introducing metal halides. Examples of doped emitters are iron or gallium mercury lamps.
• UV radiation sources are gas discharge tubes, e.g. Xenon low pressure lamps, UV lasers, UV spot lamps, e.g. UV emitting diodes and black light tubes.
• discontinuous UV radiation sources can also be used. These are preferably so-called high-energy flash devices (in short: UV flash lamps).
• the UV flash lamps can contain a plurality of flash tubes, for example quartz tubes filled with inert gas such as xenon.
• the UV flash lamps have, for example, an illuminance of at least 10 megalux, preferably from 10 to 80 megalux per flash discharge.
• the energy per flash discharge can be, for example, 1 to 10 kJoules.
• the UV radiation sources are generally integrated in a UV system, which normally consists of the UV radiation sources, the reflector system, the power supply, electrical controls, the shielding, the cooling system and the ozone extraction.
• a UV system normally consists of the UV radiation sources, the reflector system, the power supply, electrical controls, the shielding, the cooling system and the ozone extraction.
• Other arrangements are of course also possible, and individual components can also be omitted.
• the exposure time to UV radiation can be, for example, in the range from 1 millisecond to 400 seconds, preferably from 4 to 160 seconds, depending on the number of flash discharges selected.
• the flashes can be triggered, for example, every 4 seconds.
• the Hardening can, for example, by. 1 to 40 successive lightning discharges.
• the irradiation time can range, for example, from a few seconds to about 5 minutes, preferably less than 5 minutes.
• the distance between the UV radiation sources and the substrate surface to be irradiated can be, for example, 5 to 60 cm.
• the shielding of the UV radiation sources to avoid radiation leakage can e.g. by using an appropriately lined protective housing around a transportable lamp unit or with the help of other safety measures known to the person skilled in the art.
• the process according to the invention for multi-layer painting which is characterized in that after application of the coating agent (s) at least partially curable by means of high-energy radiation, radiation with IR radiation and then radiation with high-energy radiation is carried out in various embodiments.
• the UV radiation phase it is possible to connect the UV radiation phase to the completed IR radiation phase or to start the UV radiation with continuous IR radiation.
• the IR and UV radiation phases can partially or completely overlap, i.e. the IR irradiation phase can be completed before or simultaneously with the termination of the UV irradiation phase.
• IR radiation phase can be, for example, 0.5 to 30 minutes. Otherwise, the statements made above regarding IR radiation apply.
• IR, UV and IR irradiation can be carried out in sequence, or the IR irradiation phase extends over the entire irradiation time, ie the IR irradiation is carried out before, during and also carried out after the UV irradiation phase.
• the irradiation phases IR radiation and subsequent UV radiation can also be repeated several times as required.
• the radiation duration per radiation interval and the total radiation duration can be varied.
• Coupled radiation intervals IR and UV radiation in connection with the implementation of several spray coats, several work steps or in connection with the radiation curing of several successive layers of the multi-layer structure.
• intermediate curing with IR irradiation and subsequent UV irradiation can take place in one spray pass, subsequently the coating agent is applied in one or more further spray passes and again IR and then UV Radiation.
• This method of operation is, for example, when applying thicker layers, e.g. up to 400 ⁇ m, desired filler layers are particularly advantageous.
• an at least partially radiation-curable basecoat in the multi-layer structure It is also possible to first apply an at least partially radiation-curable basecoat in the multi-layer structure and first to subject it to IR and then UV radiation. An at least partially radiation-curable clear lacquer can then be applied and again subjected to IR and then UV radiation. If necessary, a further TR irradiation can follow the UV irradiation in both cases.
• the radiation curing of the individual layers of the multilayer structure and of the layers applied by means of a plurality of spray coats can each be carried out individually with different radiation intensities and with different irradiation times for each layer or together for two or more layers.
• IR and UV lamps can be arranged alternately side by side in the device.
• one or more layers of a customary multi-layer structure which can be at least partially hardened by means of high-energy radiation, can be hardened in the vehicle painting.
• This can be, for example, a multilayer structure consisting of primer, filler, basecoat and clearcoat
• One or more layers of the multilayer structure can be created from at least partially radiation-curable coating agents.
• a filler layer (binder-based: 2-component polyurethane, solvent-based) was applied to a sheet coated by cathodic electrocoating (KTL) in a resulting dry film thickness of approx. 80 ⁇ m and cured at 60 ° C for 30 minutes after a short flash-off time at room temperature.
• KTL cathodic electrocoating
• a water-based lacquer (produced in accordance with DE-A-196 43 802, production example 4) was applied to the filler layer in a resulting dry film layer thickness of 13 to 15 ⁇ m. After a flash-off phase of 20 minutes at room temperature, the UV-curable clearcoat produced as described above was applied in a resulting dry film layer thickness of 40-50 ⁇ m.
• the applied clear lacquer was subjected to IR radiation.
• the irradiation time was 5 minutes.
• the UV radiation was then carried out using a UV flash lamp (power 3500 Ws).
• the irradiation was carried out with 30 flashes, which were triggered at intervals of approximately 4 s, at an object distance of approximately 20 cm.
• Example 2 The procedure was analogous to Example 1, with the difference that after application of the clear lacquer, after a flash-off phase of 30 minutes at room temperature, the UV radiation was carried out directly with a UV flash lamp (power 3500 Ws). The UV radiation was carried out with 30 flashes, which were triggered at intervals of approx. 4 s, at an object distance of approx. 20 cm. Comparison of the paint results

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)
• Medicinal Preparation (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

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• 1998
  • 1998-12-16 DE DE19857941A patent/DE19857941C2/de not_active Expired - Lifetime
• 1999
  • 1999-11-24 JP JP2000587898A patent/JP2002532234A/ja active Pending
  • 1999-11-24 EP EP99962155A patent/EP1152841B2/fr not_active Expired - Lifetime
  • 1999-11-24 ES ES99962155T patent/ES2176040T5/es not_active Expired - Lifetime
  • 1999-11-24 WO PCT/EP1999/009064 patent/WO2000035598A1/fr active IP Right Grant
  • 1999-11-24 DK DK99962155T patent/DK1152841T3/da active
  • 1999-11-24 AT AT99962155T patent/ATE219392T1/de active
  • 1999-11-24 DE DE59901829T patent/DE59901829D1/de not_active Expired - Lifetime
  • 1999-11-24 CA CA002347868A patent/CA2347868C/fr not_active Expired - Fee Related
  • 1999-11-24 PT PT99962155T patent/PT1152841E/pt unknown

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