EP1633496B1 - Örtliche reparatur von beschichteten substraten - Google Patents

Örtliche reparatur von beschichteten substraten Download PDF

Info

Publication number
EP1633496B1
EP1633496B1 EP04739890A EP04739890A EP1633496B1 EP 1633496 B1 EP1633496 B1 EP 1633496B1 EP 04739890 A EP04739890 A EP 04739890A EP 04739890 A EP04739890 A EP 04739890A EP 1633496 B1 EP1633496 B1 EP 1633496B1
Authority
EP
European Patent Office
Prior art keywords
coating
film
coating composition
process according
coated
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.)
Active
Application number
EP04739890A
Other languages
English (en)
French (fr)
Other versions
EP1633496A1 (de
Inventor
Claes Magnus Dellrup
Ann Kerstin Birgitta Kjellqvist-Lindell
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.)
Akzo Nobel Coatings International BV
Original Assignee
Akzo Nobel Coatings International BV
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 Akzo Nobel Coatings International BV filed Critical Akzo Nobel Coatings International BV
Priority to PL04739890T priority Critical patent/PL1633496T3/pl
Priority to EP04739890A priority patent/EP1633496B1/de
Publication of EP1633496A1 publication Critical patent/EP1633496A1/de
Application granted granted Critical
Publication of EP1633496B1 publication Critical patent/EP1633496B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
    • B05D1/42—Distributing applied liquids or other fluent materials by members moving relatively to surface by non-rotary members
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/005—Repairing damaged coatings
    • 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
    • B05D7/06—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 to wood

Definitions

  • the present invention relates to a process for repairing coated substrates. Specifically, it relates to the repair of coated substrates that show minor damage in one or more places. For example, there may be a spot, or a small dent, or a scratch in the coated surface, or locally the substrate may be bare instead of coated.
  • coated substrate represents a substrate that is obtainable by applying a layer of a curable coating composition comprising an organic or primarily organic binder material, for instance a lacquer or a paint, on a substrate, followed by curing of that layer.
  • Non-coated substrates are repaired in a different way from non-coated substrates.
  • Non-coated substrates can, for instance, be repaired as described in JP 09 136359 .
  • This document describes a complex method for repairing a hole in a non-coated bathtub consisting of resin mould goods, such as fibre-reinforced plastic and artificial marble.
  • the hole is filled with a coloured UV curable resin, followed by the application of a transparent UV curable resin on the filled hole and on the surface of the substrate around the hole.
  • a transparent film is placed on the surface.
  • a masking material having a cut open portion is laminated.
  • both UV curable resins are irradiated through the film with UV radiation.
  • the mask and the transparent film are released.
  • the part of the transparent UV curable resin that was covered by the mask, and thus remains uncured, is removed.
  • non-coated substrates as described in DE 42 22 306 .
  • This document relates to the repair of non-coated plastic substrates, for instance, dashboards in cars or the plastic protection layer on the inside of a car door.
  • the document discloses that a notch in such a substrate can be repaired by filling it with a filler material, followed by application of a transparent film. Next, the filler material is cured by irradiation through the film using a light source that preferably emits radiation having a wavelength between 400 and 500 nm.
  • JP 77 025851 Another method to repair non-coated substrates is described in JP 77 025851 .
  • This document relates to a repair process of non-coated substrates in which minor damage is covered with a plastic or metal film that is larger than the damaged area, using an adhesive agent.
  • a curable liquid or paste is injected through the film into the damaged area using a syringe.
  • the curable substance is cured; the document does not specify by what means the curing takes place.
  • the plastic or metal film is peeled off.
  • the repair of coated substrates generally is a cumbersome process.
  • a method is described to repair a defect in a powder-type paint coat on a metal or plastic substrate.
  • the paint defect is hollowed out to form a recess with precisely defined dimensions and defined edge contour.
  • a partially cross-linked filler body is made with dimensions that, after full cure, correspond approximately to the dimensions of the recess.
  • the filler body is connected to the paint outside the recess, preferably by using an adhesive layer and optionally using pressure. Then the filler body is hardened while preferably pressure is applied to the filler body.
  • US 2001/00512030 discloses methods for repairing coated glass surfaces.
  • One option that is described concerns re-coating the whole coated surface with the same coating composition, apply a film, and cure the extra coating layer with UV radiation through the film.
  • Another option is to wipe or roll a very thin layer of the same coating material as present on the surface onto a coated glass surface having scratches, apply a film, and cure the thin coating layer with UV radiation through the film.
  • a disadvantage of these two options is that the whole surface needs to be covered with a new coating layer.
  • Still another option disclosed in this US document is to fill a scratch with the same coating material as present on the surface, and subsequently cure the coating material.
  • the coating composition used comprises a relatively high amount of monomers (up to 40-75 wt%), which gives rise to health and safety concerns.
  • the repair of coated substrates generally is a cumbersome process. This is especially the case when it concerns the repair of coated wooden substrates. For instance, when a plank in a parquet floor has a dent or a scratch, one usually either replaces this plank with another plank or sands and re-coats the whole plank or even the entire floor. However, replacing one plank of a floor may cause damage to the surrounding planks. Further, the new plank may show a colour difference with the rest of the floor.
  • a disadvantage of the above-mentioned alternative is that sanding and re-coating is time consuming and requires, proportionally, an enormous amount of lacquer to repair the minor damage to the coating.
  • planks showing damage in one or more areas are rejected because of their inferior quality.
  • the damaged areas are filled, after which the planks are sanded over their entire surface and returned for a complete re-coating. This process results in pollution and a waste of coating material, and it is time consuming.
  • Substrates that are covered with a layer having a wood-like appearance and, on top of that, a transparent coating, such as furniture and kitchen cabinets, can be repaired as described in US 5,399,373 .
  • This US document describes, among other things, a process for repairing a substrate of which only the protective top layer is damaged. In this process the damaged area is removed, for example by sanding, such that a smooth transition is obtained between the damaged and the non-damaged regions. Next, a transparent material is applied, for example by spraying, and the material is dried or cured.
  • a disadvantage of this method is that removal of the damaged area is necessary. This is time consuming, and during the removal of the damaged area the layer(s) underneath the top layer may be damaged. Further, using this method it is hard to control the gloss of the repair coat.
  • the present invention relates to a process for repair of a damaged coated substrate wherein first a small excess of a radiation curable coating composition is applied on a damaged area, next a radiation permeable film is placed over the uncured coating composition, and by means of pressure on the film, this surplus of coating material on the damaged area is spread out over a small area around the damaged area. Thereafter the coating is cured by irradiation through the film, and in a subsequent step the radiation permeable film is removed from the coated substrate. During this process, the surface configuration on the side of the film facing the coating layer is imparted to the repair coating.
  • This process has various advantages. It requires less coating material and results in less pollution than the processes normally applied to repair coated substrates. Further, minor damage to the coating layer, such as a dent, a scratch, or a bare area, can be repaired in less processing time, with lower energy costs, and without damaging the area around the damaged area. Additionally, this process is very suitable for application both on an industrial scale and in a "do it yourself" environment.
  • the surface configuration on the side of the film facing the coating layer is imparted to the repair coating, an almost invisible repair of coated substrates can be obtained with, in principle, any decorative effect.
  • the surface configuration on the side of the film facing the coating layer that is imparted to the repair coating preferably matches with the gloss and/or the surface texture of the original coating.
  • Low gloss substrates can be repaired using low gloss films, which has the advantage that it is not necessary to add a matting agent to the coating composition.
  • the imparting of the surface configuration is ensured by applying some pressure on the film before and/or during the curing of the coating composition. Such pressure may be applied using for example a pallet knife or a (small) roller.
  • one type of repair coating can thus be used to obtain any desired gloss level.
  • the gloss level is easier to match with the current process than when the gloss is regulated mainly or solely by using matting agents or gloss agents. This is because, when using the current process, the gloss level is not dependent on the coating layer thickness.
  • the gloss does depend on the coating thickness and may thus be different in the centre of a damaged area compared to the edge of the damaged area and/or compared to the area around the damaged area that may be covered with a thin layer of the repair coating composition.
  • the radiation curable coating composition is covered with a film during curing, curing takes place under a reduced amount of oxygen. This results in a more durable cured coating with improved (mechanical) properties.
  • the process according to the present invention can be used not only to perform an esthetical repair, but also to really restore, or renovate, the coating layer. It is possible to obtain a repaired area which has the same good coating properties as the original coating layer in the surrounding areas. For instance, the substrate can be protected in practically the same way, and a similar chemical resistance and abrasion resistance can be obtained as compared to the original, probably industrially applied, coating layer.
  • a very small excess of coating composition is applied on the damaged area that needs to be repaired.
  • this surplus of coating material on the damaged area is spread out over a small area around the damaged area. This results in a smooth transition between the original surface of the (top) coat and the repaired area.
  • One advantage of this is that it is not necessary to abrade the repair until it conforms to the existing surface. This is especially favourable as the surface configuration imparted to the repair coating would be damaged or even lost by such abrading.
  • the type of substrate is not critical when the process of the current invention is used to repair coated substrates. It may be impenetrable or porous, and of any kind of material, for example metal, plastic, or ceramic.
  • the process is especially suitable to repair coated wooden and/or cellulose-containing substrates, regardless whether it for indoor use or outdoor use.
  • coated wooden substrates are coated solid wood, coated wooden planks, coated wooden flooring, coated parquet planks, coated solid wooden flooring, coated wooden furniture or coated wooden parts of furniture, coated wooden window frames, and coated wooden doors.
  • coated cellulose-containing substrates are coated veneer of wood and articles comprising a layer of coated veneer of wood, for example parquet flooring, furniture, office furniture, kitchen tables and kitchen cabinets.
  • coated cellulose-containing substrates are coated reconstituted wood substrates.
  • Reconstituted wood substrates are substrates produced from wood particles, fibres, flakes or chips, such as hardboard, medium density fibre board, an oriented strand board also known as a wafer board, flake board, chip board, and particle board.
  • Typical examples of reconstituted wood substrates are hardboard, Medium Density Fibreboard (MDF), High Density Fibreboard (HDF), and chip board.
  • the process is also very useful to repair substrates that are covered with a print, for instance a wood grain pattern or a piece of paper with a printed image, and (on top of the print) a transparent coating.
  • a print for instance a wood grain pattern or a piece of paper with a printed image, and (on top of the print) a transparent coating.
  • Such printed substrates are, for instance, used in furniture, in kitchen cabinets, and in flooring.
  • the printed substrate may itself be of any material. It may, for example, be plastic, e.g. PVC, or a cellulose-containing substrate such as a reconstituted wood substrate.
  • adhesion primer may be of any conventional type. It may be air drying, for example an acrylic comprising air drying primer, or UV curable.
  • the coating composition applied to the damaged area can be a conventional UV curable coating composition, for instance a UV curable coating composition having a low volatile organic content, i.e. less than 450 grams per litre, or preferably less than 420 grams per litre.
  • the coating composition comprises less than 40 wt.% volatile organic compounds, more preferably less than 30 wt.%. Most preferred are coating compositions comprising less than 5 wt.% of volatile organic compounds.
  • the composition can also contain up to 40 wt.% water, calculated on the total weight of the coating composition. Most preferred are compositions comprising less than 5 wt.% water.
  • the coating composition comprises a volatile organic compound and/or water
  • the surface of the uncured composition will sink slightly.
  • the human eye may see such a sunken surface as a surface having a different gloss from the area around it. Consequently, in the process according to the present invention, the coating composition applied most preferably is a so-called 100% solids UV curable coating composition, i.e. a composition comprising less than 3 wt.% volatile organic compounds and less than 2 wt.% water.
  • a 100% solids system hardly shows sinking problems.
  • High solids systems and so-called 100% solid systems usually comprise a reactive diluent. Such a diluent reacts during curing and hardly evaporates.
  • the coating composition comprises less than 20 wt%, more preferably less than 15 wt% reactive diluent. Highly preferred are compositions that comprise less than 10 wt% or even less than 5 wt% of monomers.
  • a hot melt coating composition can be used.
  • One advantage of a low amount of reactive diluent or no reactive diluent is that the health and safety issues associated with such monomers are reduced or avoided. This is advantageous during handling the uncured material. And, especially when repairing a wooden and/or cellulose-containing substrate with a bare part, penetration of monomers into the substrate is reduced or even avoided.
  • a two-component coating system can be used.
  • This may be a dual cure system in which a slower secondary curing mechanism takes place that makes it possible to obtain a good through-cure.
  • a highly viscous isocyanate composition can be added to a UV curable composition.
  • a post cure of the isocyanate groups can take place.
  • a secondary amine can be added to a UV curable composition. After irradiation, the amines can react with the possibly present uncured double bonds.
  • peroxy systems can be added to a UV curable composition.
  • the UV curing of acrylates can be the second curing mechanism.
  • a system that hardens through both UV curing and oxidative drying e.g. a system comprising an UV-oil, can be used.
  • the coating composition may comprise oligomers or resins with a medium or relatively high molecular weight, for instance radiation curable oligomers or resins having a viscosity in the range of from 15 to 10,000 mPa.s at ambient temperature, i.e. between 5 to 40°C.
  • the coating composition comprises about 50 up to 100 wt%, more preferably 85 to 100 wt%, even more preferably 90 to 100 wt% of oligomers or resins having a viscosity in the range of from 15 to 10,000 mPa.s at ambient temperature.
  • Clear coating compositions preferably comprise between 75 and 90, more preferably between 75 and 85 wt% of oligomers or resins.
  • Pigmented coating compositions preferably comprise above 50 wt%, more preferably above 75 wt% of oligomers or resins.
  • the viscosity at application of the coating composition preferably is 500-20,000 mPa.s, more preferably 2,000 to 20,000 mPa.s, even more preferably 3,000 to 8,000 mPa.s.
  • coating compositions may be used having a viscosity within these ranges at room temperature.
  • a coating composition with a higher viscosity is used which is then pre-heated before application until it has a viscosity within these ranges.
  • the coating composition used preferably has a viscosity at room temperature of 500 to 1,000,000 mPa.s, more preferably of 500 to 50,000 mPa.s. All viscosities referred to are Brookfield viscosities, which can be determined according to the standard measurement method ISO 2884.
  • An advantage of the present invention is that a coated substrate can be repaired with a UV curable coating composition that, after curing, shows less or hardly any yellowing compared to regular UV curable coating compositions.
  • the yellowing of frequently used regular UV curable coating compositions is often caused by the presence of amines.
  • amines such as triethanolamine or acrylated amines are added to UV curable coating compositions because they can act as a synergist for the curing reaction.
  • Sometimes amines are added to increase the surface curing.
  • a high gloss coating can be prepared using less or even no amines. When the current process is used, the coatings on the repaired area, whether low or high gloss or having another surface texture, show almost no yellowing.
  • the coating composition comprises less than 3 wt.%, more preferably less than 2 wt.%, even more preferably less than 1 wt.% of such amines, based on the total weight of the uncured coating composition.
  • Another advantage of a process according to the present invention is that it is possible to apply a low gloss coating to the area that needs to be repaired which shows a better abrasion resistance than regular low gloss coatings.
  • one or more matting agents are added to a coating composition when a low gloss coating needs to be obtained.
  • matting agents especially in high amounts, may have a detrimental effect on the coating performance, such as its abrasion resistance.
  • a damaged area can be repaired with a coating composition that comprises no or only a small amount of matting agent, as the gloss can be controlled by the surface texture of the film used during the repair process.
  • a damaged area can be repaired with a coating that has a low gloss and shows a good abrasion resistance at the same time. This way it can be ensured that the repaired area has a coating quality equal or similar to that of the original coating of the surrounding area.
  • Another advantage of the current process is that a very accurate gloss control can be obtained.
  • the gloss can be adjusted more accurately when the process according to the present invention is used than when a process is used in which the gloss is adjusted by amending the amount of matting agent and/or the processing temperature.
  • Other advantages of the present invention which will be elaborated on below, are that the process requires a relatively small amount of photoinitiators and a relatively high amount of pigments can be present in the coating composition.
  • a radiation curable coating composition is a coating composition which is cured using electromagnetic radiation having a wavelength ⁇ ⁇ 500 nm or electron beam radiation.
  • electromagnetic radiation having a wavelength ⁇ ⁇ 500 nm is UV radiation.
  • Radiation sources which may be used are those customary for electron beam and UV.
  • UV sources such as high-, medium-, and low-pressure mercury lamps can be used.
  • gallium and other doped lamps can be used, especially for pigmented coatings. It is also possible to cure the coating composition by means of short light pulses.
  • the coating composition is cured using low-energy UV sources, i.e. by so-called daylight cure.
  • the intensity of these lamps is lower than that of the aforementioned UV sources.
  • Low-energy UV sources emit hardly any UV C; they predominantly emit UV A, and radiation with a wavelength at the border of UV B and UV A.
  • the coating composition is cured by radiation having a wavelength of 200 nm ⁇ ⁇ ⁇ 500 nm, more preferably 200 nm ⁇ ⁇ ⁇ 450 nm.
  • low-energy UV sources emitting radiation having a wavelength of 370 nm ⁇ ⁇ ⁇ 450 nm may be preferred.
  • One advantage of using a radiation source emitting radiation having a wavelength of 200 nm ⁇ ⁇ ⁇ 500 nm is that it is safer to use than conventional UV sources, which emit a relatively high amount of UV C and/or UV B. This is especially of importance in a "do it yourself' environment.
  • Another advantage is that daylight cure lamps are cheaper than conventional UV lamps.
  • daylight cure lamps are, for instance, solarium-type lamps and specific fluorescent lamps such as TL03, TL05 or TL09 lamps (ex Philips) and BLB UV lamps (ex CLE Design).
  • TL03, TL05 or TL09 lamps ex Philips
  • BLB UV lamps ex CLE Design
  • mercury-free UVNIS flash lamps of Xenon the mercury-free UVNIS flash lamps of Xenon.
  • Most conventional lamps have an output of between 80 and 120, or up to 240 W/cm.
  • Another type of lamp that is very suitable in a process according to the current invention is a lamp with an output in the range of 20 to 240 W/cm.
  • the output and thus the amount of energy used, can be adjusted with the production speed.
  • Preferred is a lamp with an output in the range of 20-80 W/cm.
  • the cure can be performed using both a mercury lamp and a gallium lamp. The use of radiation from a gallium lamp has been found to result in a deep cure/good through-cure of systems.
  • the coating sandwiched between the substrate and the radiation permeable film is cured by irradiation through the film.
  • the film material is not critical, since penetration by the electrons can be ensured by selecting a sufficiently high voltage. Consequently, in the case of cure by electron beam, the film can comprise, e.g., aluminium foil or an aluminised layer, for instance an aluminised polyester film, plastic or paper. Curing by electron beam radiation is useful in industry, but not very practical in a "do it yourself" environment.
  • the film has to be sufficiently transparent to the UV radiation. Curing by regular UV radiation is useful in industry, but not very practical in a "do it yourself" environment. In a "do it yourself” environment preferably low-energy UV radiation is used. In that case, the film has to be transparent to low-energy UV radiation. Consequently, in the case of cure by (low) UV radiation, the film can comprise quartz glass or glass plate or a polymeric material, for example polycarbonate, modified polycarbonate (e.g. plexiglass), polyvinyl chloride, acetate, polyethylene, polyester, an acrylic polymer, polyethylene naphthalate, polyethylene terephthalate or polycarbonate, and co-polymers thereof.
  • the film can be rigid or flexible, and may be of any desired thickness, as long as it permits sufficient transmission of the radiation used to result in a sufficient cure of the coating composition.
  • a coating is chosen that shows good release properties from the film.
  • the film can be removed from the coated substrate with the repair coating remaining virtually undamaged.
  • the coating compositions used in a process according to the present invention are suitable to be combined with a wide range of film types, including untreated films. In order to ensure good release properties from the film, the film may be treated.
  • the type of film treatment used should be adjusted to the type of film and the type of coating used in the repair process according to the present invention.
  • the film can for instance be coated with a release coating.
  • a release coating may contain silicone or a fluoropolymer such as polytetrafluoroethylene as release agent.
  • US 5,037,668 for instance, describes a silicone-free fluoropolymer comprising an acrylate-type release coating.
  • Polyester acrylate oligomers and resins were found to be very suitable for use in the coating composition in the process according to the present invention.
  • suitable commercially available polyester acrylate resins are: Craynor ® UVP-215, Craynor ® UVP-220 (both ex Cray Valley), Genomer ® 3302, Genomer ® 3316 (both ex Rahn), Laromer ® PE 44F (ex BASF), Ebecryl ® 800, Ebecryl ® 810 (both ex UCB), Viaktin ® 5979, Viaktin ® VTE 5969, and Viaktin ® 6164 (100%) (all ex Vianova).
  • Epoxy acrylate oligomers and resins were also found to be very useful in the coating composition in the process according to the present invention.
  • Examples of commercially available epoxy acrylate resins are: Craynor® UVE-107 (100%), Craynor ® UVE-130, Craynor ® UVE-151, CN ® 104 (all ex Cray Valley), Photocryl ® 201 (ex PC resins), Genomer ® 2254, Genomer ® 2258, Genomer ® 2260, Genomer ® 2263 (all ex Rahn), UVP ® 6000 (ex Polymer technologies), and Ebecryl ® 3500 (ex UCB).
  • Polyether acrylate resins can also be used in the coating composition in the process according to the present invention.
  • Examples of commercially available polyether acrylate resins are: Genomer ® 3456 (ex Rahn), Laromer ® PO33F (ex BASF), Viaktin ® 5968, Viaktin ® 5978, and Viaktin ® VTE 6154 (all ex Vianova).
  • Urethane acrylate oligomers and resins can also be used in the coating composition in the process according to the present invention.
  • Examples of commercially available urethane acrylate resins are: CN ® 934, CN ® 976, CN ® 981 (all ex Cray Valley), Ebecryl ® 210, Ebecryl ® 2000, Ebecryl ® 8800 (all ex UCB), Genomer ® 4258, Genomer ® 4652, and Genomer ® 4675 (all ex Rahn).
  • the radiation curable coating composition also use may be made of a radiation curable mixture of (a) photo-induced radical curing resin(s) and (b) photo-induced cationic curing resin(s).
  • a radiation curable mixture of (a) photo-induced radical curing resin(s) and (b) photo-induced cationic curing resin(s).
  • Such systems are sometimes called hybrid systems and may comprise, for example, acrylic oligomers as photo-induced radical curing resins, vinyl ethers as photo-induced cationic curing resins, and radical and cationic photoinitiators.
  • photo-induced radical curing resins and photo-induced cationic curing resins can be used in such hybrid systems.
  • non-radiation curable polymers can be incorporated into the coating composition. These polymers may be used to modify the viscosity, tack, adhesion, or film forming properties of the coating formulation and/or to modify the general film properties of the cured coating, such as stain resistance, flexibility or adhesion. Examples are Cellulose Acetate Butyrate (various grades, ex Eastman), Laropal materials, (ex BASF), Paraloid materials, (ex Rohm and Haas), and Ucar materials (ex Union Carbide).
  • the coating composition used in the process according to the present invention comprises 0 to 20 wt.% non-radiation curable polymers.
  • the composition can comprise a photoinitiator or a mixture of photoinitiators.
  • suitable photoinitiators that can be used in the radiation curable composition according to the present invention are benzoin, benzoin ethers, benzylketals, ⁇ , ⁇ -dialkoxyacetophenones, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, benzophenone, thioxanthones, 1,2-diketones, and mixtures thereof. It is also possible to use copolymerisable bimolecular photoinitiators or maleimide-functional compounds.
  • Co-initiators such as amine based co-initiators can also be present in the radiation curable coating composition.
  • suitable commercially available photoinitiators are: Esacure ® KIP 100F and Esacure ® KIP 150 (both ex Lamberti), Genocure ® BDK, Genocure ® CQ, Genocure ® CQ SE, Genocure ® EHA, Velsicure ® BTF, Quantacure ® BMS, Quantacure ® EPD (all ex Rahn), Speedcure ® EDB, Speedcure ® ITX, Speedcure ® BKL, Speedcure ® BMDS, Speedcure ® PBZ, Speedcure ® BEDB, Speedcure ® DETX (all ex Lambson), Cyracure ® UVI-6990, Cyracure ® UVI-6974, Cyracure ® UVI-6976, Cyracure ® UVI-6992 (all ex Union Carbide), CGI-901
  • the presence of a photoinitiator is not necessary.
  • electron beam radiation is used to cure the composition, it is not necessary to add a photoinitiator.
  • UV radiation in general a photoinitiator is added, but UV curing can also be performed without a photoinitiator.
  • the total amount of photoinitiator in the composition is not critical; it should be sufficient to achieve acceptable curing of the coating when it is irradiated. However, the amount should not be so large that it affects the properties of the cured composition in a negative way.
  • the composition should comprise between 0 and 10 wt.% of photoinitiator, calculated on the total weight of the composition.
  • a smaller amount of photoinitiator can be used to achieve acceptable curing. This effect might be due to the film on top of the coating, as the film may reduce the amount of initiated radicals caught by oxygen in the air. Most photoinitiators have an unpleasant or strong odour. Therefore, one advantage of using only a small amount of photoinitiator, or no photoinitiator at all, is that the coating composition has a better smell.
  • the composition can also contain one or more fillers or additives.
  • the fillers can be any fillers known to those skilled in the art, e.g., barium sulphate, calcium sulphate, calcium carbonate, silicas or silicates (such as talc, feldspar, and china clay).
  • Additives such as aluminium oxide, fumed silica, silicon carbide, for instance carborundum, ceramic particles, glass particles, stabilisers, antioxidants, levelling agents, anti-settling agents, anti-static agents, matting agents, rheology modifiers, surface-active agents, amine synergists, waxes, or adhesion promoters can also be added.
  • the coating composition used in the process according to the present invention comprises 0 to 50 wt.% of fillers and/or additives, calculated on the total weight of the coating composition.
  • the radiation curable coating composition used in the process according to the present invention can also contain one or more pigments.
  • all pigments known to those skilled in the art can be used. However, care should be taken that the pigment does not show a too high absorption of the radiation used to cure the composition.
  • the coating composition comprises 0 to 50 wt.% of pigment, preferably 10-30 wt.% of pigment, calculated on the total weight of the coating composition.
  • Equipment known to those skilled in the art can be used to apply the coating composition to the damaged area, e.g., a syringe, a rod, or, especially on an industrial scale, a spout.
  • the determination of the gloss of the coating surrounding the damaged area in order to be able to choose a film with the correct surface texture, can for example be performed with a commercially available portable gloss meter.
  • Equipment known to those skilled in the art can be used to smoothen the coating underneath the film, e.g., a knife, a rod, or, especially on an industrial scale, a roller coater.
  • the film used in the process is flexible.
  • repairing relatively large substrates, such as planks for parquet flooring, in which several damaged areas are present it is possible to use one or more small pieces of film that each cover one or a few damaged areas.
  • An example of such a piece of film on a damaged area is presented in Figure 1.
  • Figure 1 illustrates a cross section of a substrate (1) that is covered with a coating (2).
  • the coating layer has a damaged area (3) that is filled with an uncured coating composition.
  • On top of the damaged area is a film (4).
  • the repair coating composition can be cured by means of UV unit (5).
  • the flexible film may be a reel of film that can be reused.
  • a reel of film can be useful in a continuous process.
  • the substrates After applying the coating composition to the damaged area(s) on several substrates, the substrates can be put into a continuous process in which the film is delivered from a reel to the substrate, and next the coating composition is cured through the film.
  • Such a reel of film may comprise one or more loops. Examples of such reels are presented in Figures 2 and 3.
  • Figure 2 illustrates a cross section of a substrate that is place on a conveyer belt. The film is delivered from a reel and rewound on another reel.
  • Figure 3 illustrates a cross section of a substrate placed on a conveyer belt, a continuous reel of film, and a UV lamp.
  • planks having one or more damaged areas can for instance be repaired as follows.
  • a coating composition is applied to one or more of these damaged areas.
  • the film can be reeled off a roll onto the substrate, for instance onto part of the substrate.
  • the film is removed from (part of) the substrate and can subsequently be rewound onto a roll.
  • the process can be repeated using the re-reeled film.
  • compositions proved to be suitable to repair coated substrates in a process according to the present invention.
  • the compositions are especially suitable to repair coated wooden and/or cellulose-containing substrates and printed substrates that are covered with a transparent coating.
  • the viscosity of Composition 1 measured at room temperature is 1,000,000 mPa.s.
  • the viscosity of Composition 2 measured at room temperature is 45,000 mPa.s.
  • the viscosity of Composition 3 measured at room temperature is 35,000 mPa.s.
  • the viscosity of Composition 4 measured at room temperature is 45,000 mPa.s.
  • the viscosity of Composition 5 measured at room temperature is 3,000 mPa.s.
  • the viscosity of Composition 6 measured at room temperature is 60,000 mPa.s.
  • the viscosity of Composition 8 measured at room temperature is 50,000 mPa.s.
  • the viscosity of Composition 9 measured at room temperature is 1,500 mPa.s.
  • the viscosity of Composition 10 measured at room temperature is 2,500 mPa.s.
  • the gloss level of the repair coat was obtained by using a film with an appropriate surface configuration.
  • the gloss levels mentioned in the current examples were determined by measuring the percentage of light that was reflected from the surface at a 60 degrees angle.
  • Coated parquet planks with an original coating having a gloss of about 20 to 30 were repaired according to the present invention.
  • compositions 1 to 4 and 6 to 8 were pre-heated from to a temperature between 30 and 60 °C to achieve a suitable application viscosity before application.
  • Composition 5 was applied at room temperature.
  • Each composition was applied to one or more damaged areas on a coated parquet plank.
  • a polyester film was put over the filled damaged area(s) and some pressure was applied to the film.
  • the uncured coating composition in and slightly around the damaged area(s) was cured using a UVNIS flash lamp.
  • the original topcoat was prepared by applying and curing a commercially available UV coating composition for parquet flooring comprising a urethane/polyester acrylate.
  • the abrasion resistance has been measured according to the abrasion resistance test method SIS 923509, a test with classes 1 to 8, in which 8 is the highest value.
  • the chemical resistance has been measured according to EN 12720, using water and coffee. Values 1 to 5 can be assigned; 5 is the highest score. Value 5 indicates that no effect has been determined.
  • Coated MDF boards with an original coating having a white colour and a gloss of more than 80 were repaired according to the present invention.
  • compositions 9 and 10 comprising a white pigment, were applied at room temperature.
  • the compositions were applied to one or more damaged areas on a coated MDF board.
  • a polyester film with a high gloss surface configuration was put in place and the coating was cured using a UVNIS flash lamp.
  • Composition 2 was used to repair a small damage on coated parquet flooring.
  • composition 2 was applied using the same procedure as described for Examples 1.
  • the repair process in which the adhesion primer was used resulted in a repair coat with an improved adhesion compared to a repair process in which such adhesion primer was not used. This was determined using a coin.
  • Composition 1 was used to repair a small damage on a piece of printed furniture board having a topcoat with a gloss level of about 20.
  • Composition 1 was applied to a damaged area in the topcoat on the printed board. Then a polyester film was put over the filled damaged area and some pressure was applied to the film. Subsequently, the uncured coating composition in and slightly around the damaged area was cured using a UV/VIS flash lamp.

Claims (10)

  1. Verfahren zur Reparatur eines beschädigten beschichteten Substrats, das mit einer härtbaren Beschichtungszusammensetzung beschichtet ist, die ein organisches Bindemittel umfasst, wobei zuerst ein kleiner Überschuss einer strahlungshärtbaren flüssigen Beschichtungszusammensetzung auf eine beschädigte Fläche aufgetragen wird, dann eine strahlungsdurchlässige Folie auf der ungehärteten Beschichtungszusammensetzung positioniert wird, wobei ein Überschuss an Beschichtungsmaterial auf dem beschädigten Bereich mittels eines auf die Folie ausgeübten Drucks über einen kleinen Bereich um den beschädigten Bereich herum verteilt wird und die Beschichtung durch ein Bestrahlen durch die Folie gehärtet wird und in einem anschließenden Schritt die strahlungshärtbare Folie vom beschichteten Substrat entfernt wird, wobei beim Verfahren die Oberflächenkonfiguration auf derjenigen Seite der Folie, die der Beschichtungsschicht gegenüberliegt, der Reparaturbeschichtung verliehen wird und mit dem Glanz und/oder der Oberflächentextur der ursprünglichen Beschichtung übereinstimmt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Substrat ein beschichtetes holz- und/oder cellulosehaltiges Substrat ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Substrat mit einem Aufdruck und auf dem Aufdruck mit einer transparenten Beschichtung bedeckt ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das beschichtete Substrat ein Fußboden oder ein Möbelstück ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei die Viskosität der Beschichtungszusammensetzung bei der Auftragstemperatur 500 - 20 000 mPa·s beträgt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Beschichtungszusammensetzung eine Beschichtungszusammensetzung ist, die weniger als 40 Gew.-% flüchtige organische Verbindungen umfasst.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Beschichtungszusammensetzung eine Beschichtungszusammensetzung ist, die weniger als 20 Gew.-% eines reaktiven Verdünnungsmittels umfasst.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass eine Folienrolle verwendet wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Härten durch Bestrahlen unter Verwendung einer Niedrigenergie-UV-Quelle oder einer Mitteldruck-Quecksilberlampe erfolgt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das Bestrahlen mittels kurzer Lichtimpulse erfolgt.
EP04739890A 2003-06-18 2004-06-14 Örtliche reparatur von beschichteten substraten Active EP1633496B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL04739890T PL1633496T3 (pl) 2003-06-18 2004-06-14 Sposób miejscowej naprawy podłóż powlekanych
EP04739890A EP1633496B1 (de) 2003-06-18 2004-06-14 Örtliche reparatur von beschichteten substraten

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP03076904 2003-06-18
US51986003P 2003-11-14 2003-11-14
PCT/EP2004/006418 WO2005000484A1 (en) 2003-06-18 2004-06-14 Local repair of coated substrates
EP04739890A EP1633496B1 (de) 2003-06-18 2004-06-14 Örtliche reparatur von beschichteten substraten

Publications (2)

Publication Number Publication Date
EP1633496A1 EP1633496A1 (de) 2006-03-15
EP1633496B1 true EP1633496B1 (de) 2007-11-07

Family

ID=34923953

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04739890A Active EP1633496B1 (de) 2003-06-18 2004-06-14 Örtliche reparatur von beschichteten substraten

Country Status (5)

Country Link
EP (1) EP1633496B1 (de)
AT (1) ATE377456T1 (de)
DE (1) DE602004009925T2 (de)
PL (1) PL1633496T3 (de)
WO (1) WO2005000484A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070086249A (ko) * 2004-12-15 2007-08-27 아크조노벨코팅스인터내셔널비.브이. 코팅 기재의 보수 방법
DE102005006084B4 (de) * 2005-02-09 2009-12-10 Fritz Egger Gmbh & Co. Verfahren und Vorrichtung zum Erzeugen einer strukturierten Lackoberfläche sowie Paneel mit einer strukturierten Lackoberfläche
WO2023248063A1 (en) * 2022-06-21 2023-12-28 Breton S.P.A. Method and plant for resining and restoring and/or reinforcing articles made of natural or artificial stone or ceramic material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH627132A5 (de) * 1979-01-23 1981-12-31 Sicpa Holding Sa
DE4222306C2 (de) * 1992-07-08 1996-12-19 Daimler Benz Ag Verfahren zum Reparieren kunststoffbeschichteter Oberflächen von Fahrzeugteilen
US5399373A (en) * 1993-09-02 1995-03-21 Mrozinski; John B. Processes for repairing articles having wood appearance formed from synthetic resins
DE19727324C1 (de) * 1997-06-27 1999-04-01 Daimler Benz Ag Verfahren und Vorrichtung zur Reparatur kleiner Lackfehler in Lackschichten
US6743466B2 (en) * 2001-08-03 2004-06-01 E. I. Du Pont De Nemours And Company Process for repairing coated substrate surfaces

Also Published As

Publication number Publication date
DE602004009925D1 (de) 2007-12-20
ATE377456T1 (de) 2007-11-15
DE602004009925T2 (de) 2008-08-28
WO2005000484A1 (en) 2005-01-06
PL1633496T3 (pl) 2008-03-31
EP1633496A1 (de) 2006-03-15

Similar Documents

Publication Publication Date Title
JP3282881B2 (ja) 重ね塗りラッカーコーティングの製造方法
EP1485211B1 (de) Heissschmelzbeschichtungszusammensetzung für folienübertragung und giessprozess
US20040110020A1 (en) Process for coating a substrate
EP1480761A2 (de) Wässrige beschichtungszusammensetzungen für folienübertragung und giessprozess
KR101426834B1 (ko) 판재에의 친환경적 uv 도료 도장 방법
EP1722947B1 (de) Reparatur von natürlicher beschädigung bei der herstellung von holz umfassenden artikeln
EP1343939B1 (de) Verfahren zum beschichten eines substrates
EP1633496B1 (de) Örtliche reparatur von beschichteten substraten
AU779531B2 (en) Radiation curable hot melt composition and a process for the application thereof
KR100929278B1 (ko) 조사 경화성 퍼티 조성물 및 상기 조성물을 사용하는기재의 리피니싱 방법
KR101446598B1 (ko) 판재에의 다양한 패턴 형성이 가능한 uv 도료 도장 방법
JP2019069582A (ja) 積層体、及び積層体の製造方法
JP4601977B2 (ja) 光硬化性塗料組成物からなる塗膜の硬化方法、その方法で形成された塗膜およびその塗膜で被覆された基材
JP2002069332A (ja) 活性エネルギー線硬化型塗料組成物及び塗膜形成方法
JP3892933B2 (ja) 活性エネルギー線硬化型樹脂組成物及びそれを使用した被膜形成方法
WO2023075619A1 (en) A multilayer varnished surface, a method of producing a multilayer varnished surface and a furniture product containing such a surface
JP2006088045A (ja) 硬化塗膜形成方法
JPS62132568A (ja) 塗膜保護層の形成方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20051201

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 602004009925

Country of ref document: DE

Date of ref document: 20071220

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080218

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080207

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

EN Fr: translation not filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080407

26N No opposition filed

Effective date: 20080808

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080208

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080616

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080614

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071107

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230607

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230523

Year of fee payment: 20

Ref country code: DE

Payment date: 20230523

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20230523

Year of fee payment: 20

Ref country code: PL

Payment date: 20230524

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230523

Year of fee payment: 20