EP3375934B1 - Verfahren zur herstellung eines flockenbasierten thermischen und / oder akustischen isoliermaterials - Google Patents

Verfahren zur herstellung eines flockenbasierten thermischen und / oder akustischen isoliermaterials Download PDF

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Publication number
EP3375934B1
EP3375934B1 EP18162261.4A EP18162261A EP3375934B1 EP 3375934 B1 EP3375934 B1 EP 3375934B1 EP 18162261 A EP18162261 A EP 18162261A EP 3375934 B1 EP3375934 B1 EP 3375934B1
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Prior art keywords
mixture
substance
web
process according
property
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English (en)
French (fr)
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EP3375934A1 (de
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Ruggero RE
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Enerpaper SRL
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Enerpaper SRL
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/06—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods
    • D21B1/066—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by dry methods the raw material being pulp sheets
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00—Fibreboard
    • D21J1/16—Special fibreboard
    • D21J1/20—Insulating board

Definitions

  • the present invention refers to a process of making a flocks-based, cellulose-based thermal and/or acoustic insulating material.
  • the majority of the known processes for manufacturing insulating flocks of the present type comprise using waste paper or paperboard as a raw material, and usually comprise a series of steps in which such material is firstly mechanically treated for being shredded and reduced in flocks, and then is treated by a series of additives for sanitizing the material, for example biologic inhibitors (boric acid, borax, etc.).
  • biologic inhibitors for sanitizing the material, for example biologic inhibitors (boric acid, borax, etc.).
  • the insulating materials obtained by such processes have the inconvenience of containing undesired substances (e. g. magazines, newspapers, etc.), optical whitening inks, coats, etc., and boron salts considered toxic by the latest European updates regarding in general the health protection.
  • Some boron compounds were reclassified as mutagens and/or toxic for the reproduction system, according to what was established by the European Commission (No. 790/2009). The present limits for boric acid, borates, and tetraborates, were set by the SCCNFP in 1998.
  • the CSSC were required to do an evaluation about the safety, based on the same scientific data by which the classification of the present compounds, listed in the CSSC original document, was modified.
  • the CSSC is in the opinion of that all the substances listed in the tables attached to the document, apart from dibutyl hydrogen borate, are effectively regulated by number 1a of Annex III, while tetraborates are regulated both by number 1a and number 1b in the same Annex.
  • dibutyl hydrogen borate no limit was set by the European Commission (No. 790/2009) and no evaluation was produced with reference to the risk thereof.
  • the CSSC is in the opinion that the toxicity threshold of these substances is similar to the one of other boron compounds, and therefore they are considered safe if used under the conditions by which are used these latter.
  • the CSSC observes that the octaborates are not classified as toxic for the reproduction system, and that does not exist a specific concentration limit set for them.
  • Such process comprises introducing a group of additives, for example, fungicides, fire-retardant agents, dyes, etc., in the containing vat and/or in a pipe transporting the cellulose sludge pulp to a sludge press.
  • a group of additives for example, fungicides, fire-retardant agents, dyes, etc.
  • the Applicants have provided a new type of process of manufacturing a flocks-based, cellulose-based, insulating material, enabling to obtain a plurality of advantages, both with reference to the provision of the process and with reference to the quality of the manufactured product.
  • the described process has the object of manufacturing a flocks-based, cellulose-based material.
  • such process is characterized by the fact of providing the following steps:
  • such process is characterized by the fact of providing the following steps:
  • such process is characterized by the fact of providing the following steps:
  • such process is characterized by the fact of providing the following steps:
  • the step of applying a coating is made by a "size-press” station or a "film-press” station, or a coater, or a mill-finishing machine, or a spraying bar predisposed to apply, on both sides of said web, a mixture containing said first substance and said second substance.
  • the mixture further contains a third substance having an anti-dusting property.
  • the coating on the web with a determined density, preferably comprised between 5 and 30 g/m 2 .
  • the substance is selected between one or more in the group comprising rosin salts, water-repellent resins, and water-repellent paraffins.
  • An independent aspect of the invention provides to use a paper making line for manufacturing a flocks-based insulating material, wherein said line comprises a "size-press” station, or a "film-press” station, or a coater, or a mill-finishing machine, or a spraying bar, such use comprising the steps of:
  • said mixture comprises also a third substance having an anti-dusting property.
  • the process of making the present cellulose-based thermal and/or acoustic insulating material comprises making an actual paper web, optionally, by adding to the cellulose-based pulp, from which it is desired to obtain such web, a mixture (A) and/or by subjecting such web to a specific treatment of the surface by a mixture (B) for providing the insulating material with determined properties.
  • the web As soon as the web has taken a final configuration from the point of view of its composition and structure, it is mechanically processed for obtaining flocks forming the final product.
  • making flocks by obtaining an intermediate product consisting in an actual paper web enables to be capable of precisely and repeatably controlling the thickness and density of the final flocks; further, it enables to always precisely and repeatably control the quantity of additives introduced to them.
  • mixture (A) means a mixture which can be added by mass to the cellulose-based pulp before forming the paper web or sheet.
  • mixture (B) means a mixture which can be used for treating the surface of a paper web or sheet obtained by the cellulose-based pulp.
  • the substances with a fireproof property useable both in mixture (A) and in mixture (B) can be ammonium phosphate salts, urea, or aluminum salts.
  • ammonium phosphate salts urea
  • aluminum salts aluminum sulfate and/or aluminum polychloride both directly reacted during the manufacturing step can be used.
  • the substances with an anti-mould property useable both in mixture (A) and in mixture (B) can be cupric salts, such as for example copper sulfate, copper oxychloride, Bordeaux slurry.
  • mixture (A) and mixture (B) can have the same or a different composition from each other.
  • the mixture (A) comprises at least one substance having an anti-mould property
  • the mixture (A) comprises at least one substance having an anti-mould property
  • the cupric salt such as calcium and/or magnesium hydroxides, can be in a powder state and liquid state.
  • the weight percentage of said combination is comprised between 0.01% and 10% by the total weight of the final cellulose-based product (flocks) to be obtained.
  • the percentage by weight of the cupric salt is comprised between 2% and 40%, by the total weight of said combination.
  • the mixture (A) comprises the combination of cupric salt and calcium hydroxide, magnesium hydroxide or a mixture thereof (substances capable of making basic the product); the percentage by weight of calcium hydroxide, magnesium hydroxide, or a mixture thereof, is comprised between 60% and 98% by weight with respect to the total weight of said combination.
  • such salt is present in a percentage comprised between 0.1% and 1% by weight with respect to the total weight of the final cellulose-based product to be obtained.
  • the weight ratio of the cupric salt to the fireproof substance is comprised between 1:2 and 1:50 in the cellulose-based final product obtained by applying the process of the present invention.
  • mixture (A) and/or mixture (B) can comprise at least one substance having an anti-dusting property.
  • the substances capable of imparting an anti-dusting property can be amide-based organic polymers, carboxymethylcellulose; cold-soluble polyvinyl alcohols, and also monomers of mono-disaccharide sugars (glucose, mannose, saccharose, etc.); preferably, mixtures (A) and/or (B) comprise such elements as ligands and with an anti-dusting property.
  • the anti-dusting property consists in more bonding cellulose fibrils and several fillers together, contained in the paper web, in order to reduce the dispersion thereof in air as an aerosol of fine particulate.
  • Such property enables to avoid to form dust during the steps of flocking and blowing the insulating material, improving in this way from one side the safety of the working environment - due to the smaller amount of suspended dusts - and, on the other side, by making more uniform and time constant the average size of a cellulose flock.
  • the herein described process can be directly executed in a standard line for manufacturing paper, as will be shown in the following, suitably adapted for being capable of reproducing the present process.
  • the raw materials of the process can be unaltered raw materials, particularly wood, or can be secondary materials, for example waste paper, paper making sludge, or a combination thereof.
  • the process comprises making a pulp for manufacturing the paper web, which generally speaking, can have the same characteristics as a standard pulp for producing paper (step 10 of the diagram in Fig. 1 ).
  • a mixture (A) comprising at least one substance having a fireproof property and at least one substance having an anti-mould property, can be added to the cellulose-based pulp (step 10 of the diagram in Fig. 1 - in which additives by mass are added).
  • the mixture (A) further comprises also an additional substance having the anti-dusting property.
  • the mixture (A) comprises at least one substance having an anti-mould property
  • such mixture comprises also calcium hydroxide, magnesium hydroxide, or a mixture thereof.
  • such pulp comprising said additives
  • the headbox of the line which in turn, supplies the pulp on a forming wire, on which the pulp is evenly distributed and starts moving along the line until a sheet is formed.
  • the water content in the pulp is gradually decreased by passing the pulp through a series of cylinders groups, particularly - as an example of the main cylinders groups of the line: drainer cylinders, press cylinders, and drying cylinders.
  • the grammage and thickness of the sheet is suitably adjusted as a function of particular applications to which the insulating material is destined, the sheet thickness being comprised between 0.1 and 0.5 mm.
  • Preferred grammage values are comprised between 5 and 200 g/m 2 .
  • Such adjustment is performed by acting on the same parameters on which it is possible to act, for adjusting density and thickness, in the field of a standard process for making paper.
  • the density is controlled at the headbox by adjusting the distribution of the pulp on the forming wire.
  • the sheet thickness is controlled by the above-mentioned press cylinders, by adjusting the height development in the formed nip through such cylinders.
  • the surface of the obtained web or sheet could be treated by a mixture (B) comprising at least one substance having a fireproof property and/or at least one substance having an anti-mould property, downstream the drying cylinders, when the sheet has already a stable defined structure (step 30 in Fig. 1 ).
  • the mixture (B) further comprises a substance having an anti-dusting property.
  • such treatment provides to cover the sheet, preferably on both sides, with a group of substances adapted to impart it determined properties in view of the final use of the material as insulating material.
  • a coating material a mixture (B) comprising at least one substance having a fireproof property, and at least one further substance having an anti-mould property.
  • such surface treatment of the sheet is obtained by a so-called “size-press” station or by a “film-press” station, such stations are usually used for apply a coat to the paper.
  • Fig. 2 which schematically illustrates a "size-press" station
  • such station usually comprises two squeezing cylinders 101 through which the sheet moves and, above such cylinders, there is a kind of well 103 containing the mixture for coating the paper.
  • the sheet is completely dipped in the mixture before arriving to the two cylinders, and in this way, the paper is completely deeply impregnated by the mixture.
  • the mixture quantity which remains applied on the sheet depends on the pressure between the two cylinders.
  • the sheet moves to an infrared oven for being dried.
  • a film-press station is different from the above described size-press station or coater, or mill-finishing machine because the mixture is not directly applied on the sheet, but on one of the two squeezing cylinders, which then transfers it on the sheet.
  • the present treatment enables to completely coat the surface of the paper web and, further, to accurately control the density and thickness of the coating. Also, in this case, the parameters used for performing such kind of adjustment can be the same as those used for adjusting the density and thickness of the coating made in the scope of a standard coating process.
  • the values of the density of the deposited coating are comprised between 5 and 20 g/m 2 .
  • hydrophobic the paper web by treating the surface of the web itself by at least one or more particular substances adapted for this purpose.
  • the surface treatment will be a spreading; the substance can be selected among one or more in a group comprising rosin salts, water-repellent resins, and water-repellent paraffins.
  • the so-formed paper web can be subjected to a directly in-line step for grinding it into flocks, so that downstream the web manufacturing line, it is possible to provide a grinding station adapted to perform such step.
  • the web after being possibly cut-to-size along the opposite longitudinal edges, can be also wound in a reel and then can be stored in such format.
  • This option clearly enables to substantially reduce the occupied space in a warehouse and enables to make easier to transport the material.
  • the web instead of being wound in a reel, can be cut in single sheets which are stored as packs.
  • it also foreseeable to transform the paper web in flocks only when the insulating material is installed, so that the web is directly subjected to the grinding step on the field.
  • grinding and making the flocks can be done in a factory and the produced flocks are in this case packaged inside bags for being transported.
  • the grinding step is performed by a hammer mill.
  • FIG. 3 illustrates an example of a movable machine adapted to perform such step. As illustrated, this machine is preferably provided with wheels.
  • Such machine is adapted to directly house the reel, and is also capable, according to a continuous process, to blow the formed flocks on the field.
  • such machine comprises a chamber 201 containing one or more grinding tools (a micro mill), in which the sheet unwound from the reel, is shredded for reducing it to the desired dimensions.
  • a chamber 201 containing one or more grinding tools (a micro mill), in which the sheet unwound from the reel, is shredded for reducing it to the desired dimensions.
  • Such chamber communicates with a second chamber 206 in which the formed flocks are gathered.
  • the machine comprises a fan 208 for suctioning the formed flocks and supplying them, through a tube 212, directly on the field.
  • a partitioning membrane provided with openings (for example a mesh - not illustrated), such openings have predetermined dimensions for only enabling the passage of flocks having dimensions less than a given threshold value.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Paper (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (14)

  1. Verfahren zur Herstellung eines thermischen und/oder akustischen Isoliermaterials auf Flockenbasis und Zellulosebasis, dadurch gekennzeichnet, dass es die folgenden Schritte umfasst:
    - Herstellen einer Pulpe auf Zellulosebasis;
    - Zugeben einer Mischung (A) zu der Pulpe, umfassend mindestens eine Substanz mit feuerfesten Eigenschaften und mindestens eine Substanz mit schimmelhemmenden Eigenschaften;
    - Herstellen einer Papierbahn mit einer bestimmten Dicke und einem bestimmten Flächengewicht aus der Pulpe, der die Mischung zugesetzt wird;
    - Unterziehen der Bahn einem Mahlvorgang, um Flocken zu erhalten, die das Isoliermaterial auf Flockenbasis bilden,
    wobei das Verfahren eingestellt wird, um eine Bahn zu erhalten, deren Dicke zwischen 0,1 und 0,5 mm liegt.
  2. Verfahren nach Anspruch 1, wobei die Substanz mit feuerfesten Eigenschaften ausgewählt ist aus Ammoniumphosphatsalzen, Harnstoff und Aluminiumsalzen und/oder die Substanz mit schimmelhemmenden Eigenschaften ausgewählt ist aus Kupfersalzen, vorzugsweise aus Kupfersulfat, Kupferoxychlorid und Bordeaux-Schlamm.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Mischung (A) die Substanz mit schimmelhemmenden Eigenschaften umfasst, einschließlich einer Verbindung auf Kupferbasis, wie ein Kupfersalz, und insbesondere auch Calciumhydroxid, Magnesiumhydroxid oder eine Mischung aus Calciumhydroxid und Magnesiumhydroxid.
  4. Verfahren nach Anspruch 3, wobei der Gewichtsprozentsatz der Kombination aus Kupfersalz und Calciumhydroxid, Magnesiumhydroxid oder einer Mischung davon zwischen 0,01 % und 10 %, bezogen auf das Gesamtgewicht des Endprodukts auf Flockenbasis und Cellulosebasis, liegt.
  5. Verfahren nach Anspruch 3 oder 4, wobei der Gewichtsprozentsatz des Kupfersalzes zwischen 2 % und 40 %, bezogen auf das Gesamtgewicht der Kombination aus Kupfersalz und Calciumhydroxid, Magnesiumhydroxid und einer Mischung davon, liegt.
  6. Verfahren nach Anspruch 3 oder 4 oder 5, wobei der Gewichtsprozentsatz von Calciumhydroxid, Magnesiumhydroxid und einer Mischung davon zwischen 60 % und 98 %, bezogen auf das Gesamtgewicht der Kombination aus Kupfersalz und Calciumhydroxid, Magnesiumhydroxid und einer Mischung davon, liegt.
  7. Verfahren nach einem der vorstehenden Ansprüche, wobei die Mischung (A) ferner mindestens eine Substanz mit Anti-Staub-Eigenschaften umfasst, vorzugsweise ausgewählt aus organischen Polymeren auf Stärkebasis; Carboxymethylcellulose; kaltlöslichen Polyvinylalkoholen; Monomeren von Mono-Disaccharid-Zuckern, vorzugsweise Glucose, Mannose, Saccharose.
  8. Verfahren nach einem der vorstehenden Ansprüche, angepasst, um eine Bahn zu erhalten, deren Dicke zwischen 0,1 und 0,5 mm liegt und die ein Flächengewicht zwischen 50 und 200 g/m2 aufweist.
  9. Verfahren nach einem der vorstehenden Ansprüche, umfassend die folgenden Schritte:
    - Hydrophobieren der Papierbahn durch Behandlung der Oberfläche der Bahn mit mindestens einer Substanz, die geeignet ist, sie hydrophob zu machen, wobei die Oberflächenbehandlung insbesondere in einem optionalen Ausbreiten der Substanz besteht, ausgewählt aus einem oder mehreren aus der Gruppe bestehend aus Kolophoniumsalzen, wasserabweisenden Harzen und wasserabweisenden Paraffinen;
    - optionales Aufwickeln der Papierbahn auf eine Rolle und anschließendes Abwickeln der Bahn von der Rolle und Unterziehen der Bahn dem Mahlvorgang.
  10. Verfahren nach einem der vorstehenden Ansprüche, umfassend den Schritt des Aufbringens einer Beschichtung auf die Bahn, bestehend aus einer Mischung (B), umfassend mindestens eine Substanz mit feuerfesten Eigenschaften und/oder mindestens eine Substanz mit schimmelhemmenden Eigenschaften, wobei die Substanz mit feuerfesten Eigenschaften ausgewählt ist aus Ammoniumphosphatsalzen, Harnstoff und Aluminiumsalzen und/oder die Substanz mit schimmelhemmenden Eigenschaften ausgewählt ist aus Kupfersalzen, vorzugsweise aus Kupfersulfat, Kupferoxychlorid und Bordeaux-Schlamm.
  11. Verfahren nach dem vorstehenden Anspruch, wobei die Mischung (B) Kupfersalz umfasst, wobei dieses Salz in einem Prozentsatz zwischen 0,1 und 1 Gew.-%, bezogen auf das Gesamtgewicht des zu erhaltenden Endprodukts auf Cellulosebasis, vorhanden ist.
  12. Verfahren nach einem der vorstehenden Ansprüche 10 oder 11, wobei die Mischung (B) ferner mindestens eine Substanz mit Anti-Staub-Eigenschaften umfasst, vorzugsweise ausgewählt aus organischen Polymeren auf Stärkebasis; Carboxymethylcellulose; kaltlöslichen Polyvinylalkoholen; Monomeren von Mono-Disaccharid-Zuckern, vorzugsweise Glucose, Mannose, Saccharose.
  13. Verfahren nach einem der vorstehenden Ansprüche 10 oder 11, wobei der Schritt des Aufbringens einer aus einer Mischung (B) bestehenden Beschichtung auf die Bahn das Beschichten des Bogens vorzugsweise auf beiden Seiten umfasst:
    - durch eine "Auftragspress"-Station, in der der Bogen in die Mischung (B) getaucht wird, bevor er zwei Zylinder erreicht, und das Papier mit der Mischung (B) imprägniert wird; stromabwärts der beiden Zylinder durchläuft der Bogen eine Trockenstation, wie z. B. einen Infrarotofen; oder
    - durch eine Film-Press-Station, wobei die Mischung (B) auf mindestens einen von zwei Presszylindern aufgebracht wird, von denen sie auf den Bogen übertragen wird.
  14. Verfahren nach dem vorstehenden Anspruch, wobei die Dichte der aus der Mischung (B) erhaltenen Beschichtung Werte zwischen 5 und 20 g/m2 aufweist.
EP18162261.4A 2017-03-16 2018-03-16 Verfahren zur herstellung eines flockenbasierten thermischen und / oder akustischen isoliermaterials Active EP3375934B1 (de)

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SI201830881T SI3375934T1 (sl) 2017-03-16 2018-03-16 Postopek izdelave toplotno in/ali zvočno izolacijskega materiala na osnovi kosmičev

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Application Number Priority Date Filing Date Title
IT102017000029362A IT201700029362A1 (it) 2017-03-16 2017-03-16 Procedimento per realizzare un materiale isolante termico e/o acustico in fiocchi

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EP3375934A1 EP3375934A1 (de) 2018-09-19
EP3375934B1 true EP3375934B1 (de) 2023-01-11

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EP (1) EP3375934B1 (de)
ES (1) ES2941487T3 (de)
HU (1) HUE061712T2 (de)
IT (1) IT201700029362A1 (de)
PL (1) PL3375934T3 (de)
SI (1) SI3375934T1 (de)

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Publication number Priority date Publication date Assignee Title
WO2024100087A1 (en) 2022-11-09 2024-05-16 Circusol Holding B.V. Method and system for manufacturing cellulose-based insulation
EP4650052A1 (de) 2024-05-15 2025-11-19 CircuSol Holding B.V. Zerfaserungsschleifer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4184311A (en) * 1977-03-25 1980-01-22 Rood Leonard D Fire retardant insulation
AU676553B2 (en) * 1993-06-16 1997-03-13 Aaltje Elisabeth Maude Method and apparatus for producing insulation materials
FI104476B (fi) * 1997-10-27 2000-02-15 Aislo Oy Menetelmä eristemateriaalin valmistamiseksi, orgaaninen kuitumateriaali sekä puhalluseristysmenetelmä eristyksen suorittamiseksi
WO2006014426A1 (en) * 2004-07-06 2006-02-09 Thilmany, Llc Insulation paper facing containing an antimicotic of fungicide and methods of making and using the same
IT1400884B1 (it) * 2010-07-07 2013-07-02 Nesocell S R L Procedimento per realizzare materiale isolante.
US8388807B2 (en) * 2011-02-08 2013-03-05 International Paper Company Partially fire resistant insulation material comprising unrefined virgin pulp fibers and wood ash fire retardant component

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HUE061712T2 (hu) 2023-08-28
SI3375934T1 (sl) 2023-06-30
PL3375934T3 (pl) 2023-05-22
EP3375934A1 (de) 2018-09-19
ES2941487T3 (es) 2023-05-23
IT201700029362A1 (it) 2018-09-16

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