EP2983923A1 - Verfahren zur herstellung von paneelen - Google Patents

Verfahren zur herstellung von paneelen

Info

Publication number
EP2983923A1
EP2983923A1 EP14726412.1A EP14726412A EP2983923A1 EP 2983923 A1 EP2983923 A1 EP 2983923A1 EP 14726412 A EP14726412 A EP 14726412A EP 2983923 A1 EP2983923 A1 EP 2983923A1
Authority
EP
European Patent Office
Prior art keywords
layer
print
transparent
substrate
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14726412.1A
Other languages
English (en)
French (fr)
Other versions
EP2983923B1 (de
Inventor
Benjamin Clement
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.)
Unilin BV
Original Assignee
Unilin 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 Unilin BV filed Critical Unilin BV
Priority to PL14726412T priority Critical patent/PL2983923T3/pl
Publication of EP2983923A1 publication Critical patent/EP2983923A1/de
Application granted granted Critical
Publication of EP2983923B1 publication Critical patent/EP2983923B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00Processes for producing special ornamental bodies
    • B44C5/04Ornamental plaques, e.g. decorative panels, decorative veneers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B44DECORATIVE ARTS
    • B44CPRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00Processes for producing special ornamental bodies
    • B44C5/04Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0469Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
    • B44C5/0476Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper with abrasion resistant properties

Definitions

  • This invention relates to a method for manufacturing panels, as well as to panels which can be obtained by such method.
  • the method relates to methods for manufacturing panels of the type which is at least composed of a substrate and, provided on said substrate, a top layer with a printed decor.
  • this may relate, for example, to furniture panels, ceiling panels, floor panels or the like, which substantially consist of an MDF or HDF (Medium or High Density Fiberboard) basic panel or substrate and a top layer provided hereon.
  • it relates to a method wherein one or more material layers are provided on the substrate, wherein at least one of these material layers is provided by means of a print which is performed directly on the substrate, wherein this print then forms at least a portion of said printed decor.
  • Such panels are known as such, for example, from document US 1 ,971 ,067 or document DE 195 32 819 A1.
  • said material layers can comprise one or more basic layers, wherein these basic layers substantially extend underneath said print, and/or can comprise one or more finishing layers, which substantially extend above said print.
  • finishing layers may comprise, for example, transparent or translucent synthetic material layers which form a protective layer above the printed decor and, for example, can comprise wear-resistant particles, such as aluminum oxide. It is not excluded that this protective layer comprises a material sheet, such as a paper sheet.
  • lacquers or synthetic resins can be applied for realizing said material layers.
  • synthetic resins these are applied via a carrier sheet which in advance has been provided with such synthetic resin and is provided on the substrate by means of a heated press.
  • lacquers for example, UV-hardening lacquers can be applied.
  • Floor panels which are realized according to methods of the state of the art may show the disadvantage that the surface is insufficiently waterproof. In particular, such panels are subjected to degradation by exposure to steam of boiling water.
  • the present invention primarily aims at offering an alternative method of the above-mentioned type, which, according to various preferred embodiments thereof, can offer a solution for one or more of the problems with the panels obtained by the methods of the prior art.
  • the invention relates to a method for manufacturing panels of the type which is at least composed of a substrate and, provided on said substrate, a top layer with a printed decor, wherein the top layer comprises at least two material layers, namely at least a first material layer forming a basic layer for a second material layer provided thereon in the form of a print, wherein the method consists at least of applying said two material layers, wherein said print or second material layer is performed directly on the substrate material and this print forms at least a portion of. said printed decor, with the characteristic that, for applying said first material layer or basic layer, it is started from a water-based two-component lacquer, hereinafter also 2K lacquer or 2K primer or 2K basic layer.
  • a water-based two-component lacquer hereinafter also 2K lacquer or 2K primer or 2K basic layer.
  • a water-based two-component lacquer enhances the adherence between substrate and print.
  • said water-based two-component lacquer comprises a dispersion of amine-, hydroxy- or carboxy- functional acrylate copolymer or a polyester polyol or a vinyl polymer.
  • said water-based two-component lacquer preferably comprises a hardening agent, such as an isocyanate and/or an aziridine component which is added to the lacquer, preferably in a concentration of 2 to 15%, or still better between 4 and 9%, wherein 6% is a good value.
  • the second component is an isocyanate
  • an aliphatic isocyanate is used, for example, HDI (Hexamethylene Di-lsocyanate).
  • the isocyanate or aziridine component will react with polyol or hydroxy, carboxy or amine functionalities which are present in the lacquer itself, namely in said first component and/or in the thermo-hardening resin, preferably in the melamine formaldehyde resin of a possible transparent or translucent synthetic material layer, by which urethane compounds are formed.
  • the urethane compounds provide for an increased waterproofness and a good adherence between the substrate and the print and with the thermo-hardening resin or the possible transparent or translucent layer.
  • Isocyanate and aziridine show the feature that they react with water. This feature is particularly useful when such basic layer is combined with further water-containing material layers, such as with a print by means of water-based inks, or with a transparent or translucent synthetic material layer on the basis of a thermo- hardening resin.
  • Thermo-hardening resins such as melamine formaldehyde resin, mostly are water-based and also chemically produce water when polycondensating or hardening. An excess of water in the top layer to be hardened may lead to undesired effects, such as a deficient adherence among the layers of the top layer and/or the substrate, either locally in the form of porous spots, or rather global in the form of blisters.
  • the presence of the isocyanate and/or aziridine can offer a certain remedy for such undesired effects.
  • melamine formaldehyde resin or another thermo-hardening resin comprising hydroxy and/or amine functional groups is used, the risk of the occurrence of such defects is reduced to a major extent.
  • said water-based two-component lacquer comprises at least 2 and preferably at least 5 percent by weight of the component on the basis of isocyanate and/or aziridine.
  • isocyanate preferably aliphatic isocyanate is concerned, for example, HDI. Said percentages are calculated on the total system of water and the aforementioned two components.
  • said water-based two-component lacquer is composed as follows:
  • a water-based lacquer consisting of a dispersion with 40 to 80 percent by weight of dry matter and still better 50 to 75 percent by weight of dry matter, wherein this dry matter preferably is of an amine, hydroxy or carboxy functional copolymer or of a polyester polyol;
  • the method preferably is applied when water-based pigmented inks are employed as a starting point for said print.
  • the invention is also useful when other pigmented inks are applied, such as UV inks.
  • the applied quantity of ink is limited to less than 15 grams per square meter, dry weight. Limiting the quantity of applied ink also means limiting the moisture present in the top layer, which moisture finally will have to be removed.
  • Said two-component lacquer can be made pigmented.
  • a white lacquer can be applied, or a yellow or beige lacquer.
  • the use of a basic color can induce a limiting of the total quantity of ink to be applied for preparing a well- defined printed decor.
  • the method also comprises at least the step of providing a transparent or translucent synthetic material layer above said print.
  • a transparent or translucent synthetic material layer Preferably, for providing said transparent or translucent layer, one starts from a thermo-hardening resin, such as melamine.
  • the 2K basic layer of the invention in particular offers a solution for problems occurring with the finishing with such melamine or melamine formaldehyde resins. These resins are water- based and also chemically produce water as a byproduct of their polycondensation.
  • said transparent or translucent layer comprises hard particles, preferably between 10 and 40 grams per square meter.
  • this preferably relates to aluminum oxide particles.
  • the inventor has found that, by means of the 2K primer and such amount of hard particles in the thermo-hardening resin of the transparent or translucent layer, it is possible to achieve a quantity AC4 according to EN13329-Annex E.
  • said transparent or translucent layer it is started from a paper sheet provided with thermo-hardening resin, or a so-called overlay.
  • a paper sheet provided with thermo-hardening resin, or a so-called overlay.
  • Such paper sheet, without resin preferably has a dry weight situated between 10 and 30 grams per square meter.
  • a quantity of resin is applied which corresponds to one and a half to five times this dry paper weight, wherein this quantity of resin is measured in a condition in which the resin has a residual moisture content of 7% or less.
  • the substrate, the first and the second material layer and said transparent or translucent layer are pressed together in a press device, wherein the thermo-hardening resin of said transparent or translucent layer is hardened.
  • the temperature applied in the press is higher than 100°C, for example, between 150°C and 250°C, and inherently leads to boiling of the water which is present. This moisture or this vapor must be able to disappear approximately completely from the composition.
  • the 2K primer contributes to that.
  • a press device is applied of the short-cycle press (In German: Kurztaktpresse) type.
  • the applied pressures may vary from 3 to 60 kg/cm 2 .
  • a pressure situated between 25 and 50 kg/cm 2 will be applied.
  • a relief is realized, the recesses and/or protrusions of which extend at least in the transparent or translucent layer.
  • the residual moisture content of said water-based two-component lacquer and/or the print and/or the remaining layers of the top layer is less than 11% and still better less than 9% when the pressing is started, in other words, at the moment when the stack of at least the substrate, the first and second material layers and said transparent or translucent layer enter the press device.
  • said stack prior to the press treatment said stack can be dried by hot air and/or by means of infrared heating elements.
  • a print layer on the basis of pigmented inks and a melamine- based finishing layer is of particular interest, as in this manner a stable print, in particular under the influence of sunlight, can be achieved in combination with a hard surface layer.
  • a press treatment such as with heated molds or pressing plates.
  • a discontinuous press device such as a so-called short-cycle press, is applied.
  • the inventors have found that applying pressures situated between 30 and 60 bar and temperatures between 120 and 230°C does not lead to problems for a print on the basis of water-based pigmented inks and may imply a good hardening of the top layer.
  • catalysts or hardening agents can be used for restricting the temperature for hardening the thermally hardening finishing layer.
  • the thermally hardening material of the finishing layer has already been subjected to a partial drying treatment before the press treatment is performed, wherein the final hardening then largely or entirely is obtained in the press device. It is clear that according to this practical example also another polycondensation resin can be applied than the melamine resin mentioned herein.
  • finishing layer which comprises a carrier sheet, such as a paper sheet
  • a finishing layer which is applied in liquid form, which finishing layer, for example, is partially hardened by means of a drying oven before the final hardening largely or entirely is achieved in the press device.
  • the finishing layer of this second practical example is provided with hard particles, such as aluminum oxide, preferably having an average grain size situated between 30 and 100 micrometers. The amount of aluminum oxide particles preferably is between 20 and 35 grams per square meter.
  • thermo-hardening resins are urea formaldehyde, melamine, melamine formaldehyde, methane diphenyl diisocyanate, phenol formaldehyde, resorcinol formaldehyde and resorcin phenol formaldehyde.
  • the print is performed by means of a digital printing technique, such as by means of one or more inkjet print heads.
  • a so-called single-pass printing device as well as a so-called multi-pass printing device can be chosen.
  • said basic layer is free from carrier sheets, such as free from paper sheets.
  • the entire obtained top layer of the panels is free from such carrier sheets or paper sheets.
  • the 2K primer of the invention would be applied on a paper sheet already present on the substrate.
  • this preferably relates to a colorless water-based lacquer, thus, without a pigment.
  • the water-based lacquer of the invention can be provided on a paper sheet which beforehand has been glued to the substrate by means of a thermo-hardening glue, such as urea formaldehyde or phenol formaldehyde glue.
  • the method of the invention provides for one or more basic layers, which are situated underneath the print, and for one or more transparent or translucent finishing layers, which are situated above the print.
  • the basic layer of the invention which comprises the water-based 2K lacquer, can consist of a plurality of material layers, wherein then at least one thereof comprises said water-based 2K lacquer.
  • Providing a plurality of said basic layers, print and/or finishing layers can be performed with one or more intermediate drying treatments, grinding treatments or brushing treatments.
  • said transparent or translucent synthetic material layer as such can be composed of a plurality of finishing layers.
  • embedding hard particles in the finishing layers, namely in the transparent or translucent synthetic material layer can be performed in various manners. So, for example, they can be blended into the material of the respective finishing layer before the latter is provided on the substrate. According to another example, they are provided, by means of, for example, a strewing device, on and/or in the finishing layer concerned, which has already been provided on the panel and which preferably still is moist.
  • other components too, can be embedded into the basic layers and/or finishing layers, such as, for example, cellulose fibers or pigments of any type.
  • the print relates to a print provided by means of a digital printing device, such as an inkjet printer. Due to the fact that the print is digital and is performed directly on the substrate, the motif is controllable and is not or practically not subjected to extension or shrinkage after being provided.
  • water-based pigmented inks are applied for performing the print.
  • the drying of the inks preferably is performed by means of infrared radiation.
  • inks of at least four different colors are used, such as the basic colors cyan, magenta, yellow and black.
  • the applied printing device comprises at least one inkjet print head per color. Possibly, the number of colors can be extended to more than four. Preferably, a maximum limit of ten different colors is applied. Ideally, 6 or 8 different colors are applied.
  • the inkjet print heads concerned can be of the single-pass type or of the multiple-pass type. Further, it is clear that it is not excluded that the applied inks may be UV inks.
  • thermo-hardening resin such as on the basis of melamine or melamine formaldehyde resin.
  • Figure 1 schematically represents some steps of a method with the characteristics of, amongst others, the first aspect of the invention
  • Figure 2 in cross-section and at a larger scale, represents a view according to the line ll-ll represented in figure 1 ;
  • Figure 3 represents a panel, more particularly a floor panel, having the characteristics of the invention.
  • Figure 4 in cross-section and at a larger scale, represents a view according to the line IV-IV represented in figure 3.
  • Figure 1 represents some steps S1-S7 of a method for manufacturing panels or boards 1 with the characteristics of the present invention.
  • this relates to a method for manufacturing panels or boards 1 of the type which is at least composed of a substrate 2 and, provided on said substrate 2, a top layer 3 with a printed decor 4.
  • a method for manufacturing floor panels 5 with a wood-based substrate 2, such as with a substrate 2 on the basis of MDF or HDF is illustrated.
  • the larger board 1 consists of MDF or HDF with a ground surface.
  • the larger board preferably has been ground at least with a grain P180.
  • the larger board is successively ground with grain P150, P180 and P220.
  • the grinding operation is applied for adjusting the thickness of the board and for obtaining a smooth surface.
  • a material layer 6 with a water-based primer 7 is provided on the surface of the larger board 1 in a first step S1 . This step is optional.
  • the amount of applied primer 7 may vary between 5 and 20 grams per square meter, wherein 10 grams per square meter is an appropriate value.
  • the primer is provided over the entire surface to be printed of the board 1 by means of a roller 8.
  • a second material layer 9 is provided on the surface of the larger board 1.
  • this layer which according to the invention comprises a water-based two- component lacquer.
  • this relates to a water-based two-component lacquer which comprises an amine-, hydroxy- or carboxy-functional acrylate copolymer as the first component and comprises an aliphatic isocyanate, namely HDI, as the second component.
  • first material layer 6 as well as the aforementioned second material layer 9 are applied in liquid form. They can also be applied in a plurality of partial layers, the latter either being dried and/or ground in between or not.
  • the material layers 6-9 of the first step S1 and the second step S2 can be applied in any manner. Preferably, they are applied by means of one or more rollers.
  • the water-based two-component lacquer of the invention can be applied, for example, by means of a roller device with a single roller, wherein this roller preferably rotates concurrently with the substrate, or by means of a roller device with two rollers with mutually opposed sense of rotation, wherein the second roller in feeding direction then preferably will rotate in opposite sense to the moving direction of the substrate.
  • a roller device also known as a spreader device, particularly smooth surfaces and finally a better printing quality can be obtained.
  • the applied second material layer 9 is dried, preferably with hot air having a temperature of 40° to 90°, preferably during 15 to 120 seconds.
  • said second material layer 9 is applied in successive partial layers, wherein the following scheme may serve as an example:
  • a material layer 1 is applied in form of a print 12 which is performed directly on the substrate material 2.
  • This print 12 forms at least a portion of the printed decor 4 of the final panels 5.
  • a heating of the lacquered larger board 1 can be performed, preferably by means of one or more infrared heating elements.
  • the represented print 12 relates to a print with a wood pattern. As represented, it is possible that said basic layer 9 contributes to the appearance of the panel 5 or the board 1.
  • the print 12 is performed by means of a digital printing device 13, such as by means of an inkjet printing device.
  • the printing device 13 comprises at least four inkjet print heads.
  • each of the four represented inkjet print heads 14 is responsible for applying ink of a specific color, whereby a multi-color print can be achieved.
  • the inkjet printing device 13 is of the so-called multi-pass principle, wherein a certain print head 14 moves a plurality of times over the surface to be printed of the board 1. During such pass, the respective substrate 2 or the respective board 1 preferably is held still. In between two passes, the print heads 14 and/or the substrate 2 or the board 1 can be moved with the aim of printing another portion of the surface of the board 1 in a subsequent pass. This movement can be similar to, equal to or smaller than the distance between two points of the printing portion provided in a previous pass.
  • the board may lie still, for example, on a vacuum table, whereas a shuttle with print heads moves over the board and prints it in a single movement, or reverse, namely that the print heads stand still and that the board moves in a single movement below the print heads and is printed.
  • the print 12 is performed by means of water-based pigmented inks, which in this case, in a separate step S4, are at least partially dried and/or hardened by means of one or more infrared heating elements 15. Possibly, such light source can be integrated in the printing device 13 or on one or more of the print heads 14.
  • the step S4 can be performed approximately simultaneously with the step S3.
  • UV inks are used, wherein any drying treatment then preferably is performed by means of a UV radiation source.
  • a translucent or transparent synthetic material layer 16 is applied, which, in the final floor panel 5, shall be situated above the material layer 11 which is provided by means of a print 12.
  • the respective synthetic material layer 16 consists of two separately deposited material layers 16A-16B, both substantially consisting of melamine-based thermo-hardening resin.
  • the application itself is performed by means of rollers 10. Of course, other application techniques are not excluded.
  • dashed line 17 possibly a drying operation or a hardening operation can be applied to this first material layer 16A.
  • a hardening of melamine can be performed, for instance, by blending in or applying an appropriate hardening agent.
  • the translucent or transparent synthetic material layer 16 may substantially consist of a carrier sheet provided with a thermo-hardening resin, preferably a paper sheet impregnated with this resin, which sheet is provided on the printed substrate 2.
  • a carrier sheet provided with a thermo-hardening resin, preferably a paper sheet impregnated with this resin, which sheet is provided on the printed substrate 2.
  • Other techniques for depositing the material layers 6-9-16 of the first, second and/or fifth step are, for example, techniques making use of sprinkling or spraying devices, or application techniques making use of negative pressure.
  • a sixth treatment step S6 in the example hard particles 18 are provided on the still moist or wet synthetic material layer 16, in this case by means of a strewing device 19.
  • strewing devices 19 are known as such, for example, from document GB 1 ,003,597 or GB 1 ,035,256.
  • the hard particles 19 are put from a recipient 20 onto a roller 10, such as an anilox roller, from where they then are removed again by means of a brush 21.
  • a rotating brush is represented; however, use can also be made of a to- and fro-moving brush.
  • use can be made of aluminum oxide particles having an average particle size of less than 200 ⁇ .
  • step S6 is optional. Namely, the hard particles 18 may be omitted, or techniques may be used wherein the hard particles 18 are blended into the material which is applied in the partial steps S5A and/or S5B. In the case that in step S5 use is made of a carrier sheet, the hard particles 18 can also be provided on or in this carrier sheet prior to depositing the latter on the substrate.
  • one or more of the above-mentioned layers and/or other layers are provided on the bottom side 22 of the substrate 2 or the board 1.
  • at least one material layer 23 is provided, which realizes a water- and/or vapor- sealing effect on the underside 22 of the board 1 or the panels 5 obtained therefrom.
  • a seventh treatment step S7 the substrate 2 provided with the material layers 6- 9-11-16-23 is brought into a heated press device 24, where it is pressed between press elements 26.
  • a heated press device 24 In this case, schematically a short-cycle press is represented. However, use can also be made of a continuous press device, wherein belt- shaped press elements are applied instead of plate-shaped press elements 25, as represented here.
  • the hardening of the thermally hardening resin is performed at least partially. In the polycondensation of such resin, water is produced as a byproduct.
  • a pressing temperature of 160 to 220°C is applied during 15 to 45 seconds, and a pressure of 25 to 50 kg per square centimeter (25 to 50 bar).
  • a good value determined by the inventor is a temperature of 180°C-195°C during 30 to 45 seconds at a pressure of 40 bar.
  • the residual moisture content of said water-based two-component lacquer 9 and/or the print 12 and/or the remaining layers 16-23 of the top layer 3 is less than 11 % and still better less than 9% at the start of the treatment step S7, in other words, at that moment when the stack of at least the substrate 2, the first and second material layers 9-11 and said transparent or translucent layer 16 enter the press device 24.
  • said stack can be dried prior to the press treatment by means of hot air and/or by means of infrared heating elements, however, this is not represented here.
  • Figure 2 represents the result of such press treatment S6. It is shown clearly that in the surface of the board 1 , more particularly in the material layers 6-9-11-16 provided thereon, a relief 26 can be realized.
  • the press elements 25 from figure 1 are provided with a structure and will press this structure during the press treatment S6 into the surface of the board 1 or the material layers 6-9-11-16 provided there.
  • this relates to a relief 26 with recesses and/or protrusions which correspond to the print 12.
  • the impressions 27 realized by means of the press element may manifest themselves in one or more of the material layers 6-9-11-16 provided on the board 1.
  • the substrate 2 itself is not deformed, although this is not excluded.
  • the larger boards 1 can be subdivided into a plurality of smaller panels 5, which approximately show the dimensions of the final panels 15. This may take place, for example, by means of a multirip saw.
  • Figure 3 shows that the obtained rectangular panels 5, at least on two opposite edges 28-29 and in this case on both pairs of opposite edges 28-29-30-31 , possibly can be provided with profiled edge regions 32, which comprise, for example, coupling means 33 with which two of such panels 5 can be coupled to each other.
  • the treatment step in which the possible profiled edge regions 32 are realized is not represented here. Such treatment step may take place at any time after performing said dividing step.
  • the invention is of particular importance with such panels. As the adherence of the top layer now is improved, the risk of damaging the top layer when realizing the coupling means 33 is minimized.
  • Figure 4 represents an example of such coupling means 33.
EP14726412.1A 2013-04-12 2014-04-04 Verfahren zum herstellen von paneelen Active EP2983923B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14726412T PL2983923T3 (pl) 2013-04-12 2014-04-04 Sposób wytwarzania paneli

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE2013/0279A BE1021674B1 (nl) 2013-04-12 2013-04-12 Werkwijze voor het vervaardigen van panalen en paneel hierbij bekomen.
PCT/IB2014/060433 WO2014167472A1 (en) 2013-04-12 2014-04-04 Method for manufacturing panels

Publications (2)

Publication Number Publication Date
EP2983923A1 true EP2983923A1 (de) 2016-02-17
EP2983923B1 EP2983923B1 (de) 2020-02-12

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EP14726412.1A Active EP2983923B1 (de) 2013-04-12 2014-04-04 Verfahren zum herstellen von paneelen

Country Status (5)

Country Link
EP (1) EP2983923B1 (de)
BE (1) BE1021674B1 (de)
ES (1) ES2787358T3 (de)
PL (1) PL2983923T3 (de)
WO (1) WO2014167472A1 (de)

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Publication number Publication date
PL2983923T3 (pl) 2020-10-19
BE1021674B1 (nl) 2016-01-05
WO2014167472A1 (en) 2014-10-16
EP2983923B1 (de) 2020-02-12
ES2787358T3 (es) 2020-10-15

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