EP4168474A1

EP4168474A1 - Method for recycling filtering facepiece respirators

Info

Publication number: EP4168474A1
Application number: EP21740140.5A
Authority: EP
Inventors: Anthony Bonnet; Salima BOUTTI
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2020-06-19
Filing date: 2021-06-18
Publication date: 2023-04-26
Also published as: JP2023534128A; CN115702190A; WO2021255402A1; FR3106135A1; FR3106135B1; US20230219262A1

Abstract

The invention relates to a method for recycling filtering facepiece respirators comprising a plurality of layers made from a single thermoplastic polymer selected from among polypropylene, polyethylene terephthalate, polylactic acid, polyamide 6 (PA6) homopolymers and copolymers and long chain polyamides such as PA11 or PA12, and comprising a polyvinylidene fluoride filtration layer.

Description

PROCESS FOR RECYCLING RESPIRATORY PROTECTIVE MASKS

FIELD OF THE INVENTION

The present invention relates to a process for recycling respiratory protective masks comprising several layers made from a single thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6) and long chain polyamides such as PA11 or PA12, and comprising a filtration layer of polyvinylidene fluoride.

TECHNICAL BACKGROUND

Particle masks are respiratory protection devices capable of filtering out particles and fine dust. Among these masks, we find personal protective equipment such as FFP masks (for "Filtering Facepiece Particles"). Their protection perimeter is determined by European standard EN 149 which specifies the minimum characteristics to be required of filtering half-masks used as respiratory protection devices against particles except for evacuation. This standard defines three classes of devices, namely FFP1, FFP2 and FFP3, on the basis of three criteria: the maximum penetration of the filter material of aerosols of average diameter by mass of 0.6 μm, the respiratory resistance and the rate of leakage inward.

The FFP1 dust mask has an aerosol filtration rate of at least 80% and an inward leakage rate of 22% or less.

The FFP2 mask has an aerosol filtration rate of at least 94% and an inward leakage rate of 8% or less. This mask protects against powdered chemicals and can also serve as protection against aerosols carrying viral particles and / or bacteria.

The FFP3 mask has an aerosol filtration rate of at least 99% and an inward leakage rate of 2% at most. It protects against very fine particles of asbestos (asbestosis) or silica (silicosis).

There are also masks for medical use (surgical masks) developed according to standard EN 14683, intended to prevent the projection towards the environment of the droplets emitted by the person wearing the mask. These masks also protect the wearer against the projections of droplets emitted by a person opposite. However, depending on the circumstances, they do not protect against the inhalation of very small particles suspended in the air and potentially carrying viruses.

Respiratory protection masks are generally composed of fibers, or combinations of synthetic fibers, obtained from thermoplastic polymers such as: polyolefins, polyamides, polyvinyls, polyimides, polyacrylates, poly-methacrylates, polyurethanes or also fluoropolymers, and in particular polyvinylidene fluoride (PVDF).

Among the many types of known masks, some include at least one layer of nanofibers which are particularly suitable for providing the barrier properties required for at least FFP2 type respiratory protection. The electrospinning of polymers in solution makes it possible, under certain conditions, to obtain fibers of sufficiently small diameters for good breathability and good mechanical filtration efficiency, and possibly electrostatic, of the membrane for air filtration.

Document EP 2517607 describes the advantages of masks comprising at least one layer of nanofibers, and the manufacture thereof by electrospinning. The masks have sandwich-type structures since they include several superimposed layers, for example a three-layer type: non-woven layer - nanofibrous layer - non-woven layer.

Document US2019 / 0314746 describes the production of a porous nonwoven PVDF membrane by an electrospinning process, suitable for air filtration. Nanofibers are electrospun onto the surface of a drum covered with a polypropylene nonwoven substrate.

The increasing use of respiratory masks, whether they are single-use (disposable) or reusable, leads to a major environmental problem of management of this waste and of the reuse of the polymer material used for the manufacture of these masks. Worn masks are potentially loaded with particles and / or soiled by pathogenic microorganisms (bacteria and / or viruses). There are several methods of cleaning reusable masks: washing with detergent at 60 or 95 ° C, sterilization at 121 ° C for 50 minutes, irradiation with gamma or beta radiation, exposure to ethylene oxide, heating at 70 ° C in dry heat or in water, use of hydrogen peroxide vapors.

However, even when the cleaning is effective and allows the elimination of dust particles and / or microorganisms deposited on the mask, the latter can only undergo a limited number of cleaning cycles, at the end of which the problem of the treatment of used masks and that of the desired recovery of all or part of the raw materials used in their manufacture. There is therefore a need to develop a method for recycling used masks making it possible to prevent their accumulation and possible G pollution of the environment, and the recovery of the raw materials used in their manufacture.

It has now been found that used masks containing layers made from a predominantly thermoplastic polymer chosen from among polypropylene, polyethylene terephthalate, polylactic acid and certain polyamides, and PVDF in the form of nanofibres, can feed a recycling process leading to the production of a masterbatch suitable for use as an extrusion aid agent (in English: polymer processing aid or PPA), that is to say an additive which allows, among others: to reduce or eliminate the surface defects which appear when the said thermoplastic resin is extruded, to reduce the pressure at the head of the extrusion die, thus making it possible to increase the throughput of the extrusion line, to limit the frequency of cleaning the extrusion die, limit the formation of surface defects on the extruded film.

SUMMARY OF THE INVENTION

The invention aims to provide a method for recycling respiratory protection masks containing from 98.5 to 99.5% by weight of a major thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6) and long chain polyamides such as PA11 or PA12, and from 0.05 to 1.5% of poly (vinylidene fluoride) or PVDF, in particular in the form of nanofibers, said process comprising the steps following: a) grinding of the masks leading to the production of flakes, b) granulation (extrusion) of said flakes leading to the production of a masterbatch in the form of granules.

Advantageously, said masterbatch obtained by the recycling process according to the invention can be used as an extrusion aid agent (or extrusion agent) in the molten process of the predominant thermoplastic for the manufacture of any type of material. 'objects, especially in the form of film, fiber, cable or molded part.

According to one embodiment, the masks subjected to the recycling process according to the invention comprise a layer of PVDF nanofibers obtained by an electrospinning process, said layer being deposited on a substrate of predominantly thermoplastic polymer. The present invention relates to a process for regenerating worn respiratory protective masks allowing the recovery of the polymer raw materials entering into their composition. More particularly, the method according to the invention applies to masks comprising several layers made from a predominant thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6). and long chain polyamides such as PA11 or PA12, and comprising a filtration layer made of polyvinylidene fluoride, and results in the manufacture of a masterbatch, which can be used directly as an aid agent for the extrusion of said polymer majority thermoplastic.

The use of this masterbatch in a processing line for the majority thermoplastic polymer leads to an increase of up to 10% in the productivity of the line, and to a reduction in the extrusion pressure of 10 to 20%, compared to extrusion of the same thermoplastic polymer in the absence of extrusion agent. Furthermore, an increased persistence of electrets on the surface of said thermoplastic polymer, obtained using the extrusion agent produced according to the process of the invention, has been observed compared to the same unmodified polymer.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in more detail and in a nonlimiting manner in the description which follows.

The invention is based on the discovery of the capacity of respiratory protective masks, in particular masks of the FFP1 to FFP3 type and surgical masks, comprising a major thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6) and long chain polyamides such as PA11 or PA12, and a filtration layer of polyvinylidene fluoride nanofibers, to be subjected to a recycling process to provide a playable masterbatch , in the molten state, the role of an extrusion aid agent during the transformation of said predominantly thermoplastic polymer, leading to a reduction in the head pressure in the extruder, allowing an increase in the flow rate during the 'extrusion and reducing the material which deposits at the head of the die, which can create defects on the fibers, rods or extruded films. This makes it possible to reduce the frequency of cleaning the equipment and therefore machine downtime. According to a first aspect, the subject of the invention is a process for recycling respiratory protection masks containing from 98.5 to 99.5% by weight of a predominant thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, acid polylactic, homopolymers and copolymers of polyamide 6 (PA6) and of long-chain polyamides such as PA11 or PA12, and from 0.05 to 1.5% of poly (vinylidene fluoride) or PVDF, in particular in the form of nanofibers, said method comprising a step of grinding the masks leading to the production of flakes, and a step of granulation (extrusion) of said flakes, leading to the production of a masterbatch in the form of granules.

According to various embodiments, said method comprises the following characters, if necessary combined.

The masks used in this recycling process are used masks containing exclusively a single thermoplastic polymer, called “majority”, chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6) and long chain polyamides such as PA11 or PA12, and PVDF. More particularly, these masks contain from 98.5 to 99.5% by weight of the majority thermoplastic polymer and from 0.05 to 1.5% of poly (vinylidene fluoride) or PVDF, in particular in the form of nanofibers.

According to one embodiment, the recycling process uses surgical masks complying with standard EN 14683.

According to one embodiment, the recycling process uses masks of the FFP type complying with standard EN 149.

According to one embodiment, the recycling process uses a mixture of surgical and FFP-type masks, provided that they have the composition indicated above.

The term “worn mask” used here includes both masks that have been used (used), as well as unused masks that would have expired because they have exceeded the warranty period provided by the manufacturer, or even material scraps (in particular of polymer thermoplastic) recovered during the manufacture of the masks, which can represent from 15 to 16% of the total material used.

According to one embodiment, the mask used in the recycling process is a breathing mask consisting of a body and retaining straps, said body being composed of at least two and preferably three layers, including a layer of PVDF filter material, said body comprising a nose bar, said retaining straps being fixed to the body of the mask without adding material, preferably by welding. In this mask, all layers, except PVDF fibers, of materials constituting the body and the retaining straps are composed of nonwovens of the same predominantly thermoplastic polymer material. The majority thermoplastic polymer is chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6) and of long chain polyamides such as PA11 or PA12.

Long chain polyamides are aliphatic polyamides having an average number of carbon atoms per nitrogen atom greater than 8.5, preferably greater than 9, in particular greater than 10.

The PVDF used in the context of the invention is also a thermoplastic polymer. The fluoropolymer used in the invention, generically designated by the abbreviation "PVDF", is a vinylidene difluoride-based polymer.

By “thermoplastic” is meant here a non-elastomeric polymer. An elastomeric polymer is defined as a polymer which can be stretched, at room temperature, to twice its initial length and which, after stress relief, rapidly returns to its initial length, to within 10%, as indicated by ASTM in Special Technical Publication No. 184.

According to one embodiment, the mask to be recycled contains an inner layer of non-woven thermoplastic polymer, with a basis weight of between 20 and 100 g / m ² and having a permeability of between 500 and 1500 l / m ² / s measured at 100 Pa. Said thermoplastic polymer exhibits a melt flow index (MFR) of 34 g / 10 min at 230 ° C. under 2.16 kg.

According to one embodiment, the mask to be recycled comprises a central layer comprising a nonwoven substrate, with a basis weight of between 20 and 100 g / m ² and having a permeability of between 500 and 2500 Fm ² / s measured at 100 Pa.

According to one embodiment, said substrate is manufactured by spinning-lapping from a thermoplastic polymer which has a hot melt index of 34 g / 10 min at 230 ° C and 2.16 kg.

The support layer (the substrate) can, according to another embodiment, be made by extrusion blow molding from a thermoplastic polymer which has a melt flow index of 34 g / 10 min at 230 ° C and 2, 16 kg.

According to one embodiment, on this substrate is deposited, by an electro-spinning process, a layer of PVDF nanofibers. According to one embodiment, the PVDF comprises, and preferably consists of: i. a homopolymeric PVDF; ii. a mixture of two PVDF homopolymers having different viscosities, or different molar masses, or different architectures, for example different degrees of branching; iii. a copolymer comprising vinylidene difluoride (VDF) units and one or more types of comonomer units compatible with vinylidene difluoride (hereinafter referred to as "VDF copolymer"); iv. a blend of a PVDF homopolymer and a VDF copolymer; v. a blend of two VDF copolymers.

The comonomers compatible with vinylidene difluoride can be halogenated (fluorinated, chlorinated or brominated) or non-halogenated. By “compatible comonomer” is meant here the capacity of said comonomer to copolymerize with VDF and thus to form a copolymer.

Examples of suitable fluorinated comonomers are: vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, trifluoropropenes and in particular 3,3,3-trifluoropropene, tetrafluoropropenes and in particular 2,3,3,3-tetrafluoropropene or 1 , 3,3,3- tetrafluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropenes and in particular 1,1,3,3,3-pentafluoropropene or 1,2,3,3,3-pentafluoropropene, perfluoroalkylvinylethers and in particular those of general formula Rf-0-CF-CF2, Rf being an alkyl group, preferably C1 to C4 (preferred examples being perfluoropropylvinylether and perfluoromethylvinylether). The fluorinated monomer can contain a chlorine or bromine atom. It can in particular be chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene. Chlorofluoroethylene can denote either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene. The 1-chloro-1-fluoroethylene isomer is preferred. The chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.

The VDF copolymer can also include nonhalogenated monomers such as ethylene, and / or acrylic or methacrylic comonomers.

When the layer of nanofibers is composed of a mixture of two constituents among those mentioned above (ii., Iv. And v.), The mass proportion between the constituents of the mixture varies from 1:99 to 99: 1.

According to one embodiment, said PVDF nanofibers have an average Dv50 fiber diameter of between 30 and 500 nm, preferably from 30 to 300 nm. The Dv50 is the volume median diameter which corresponds to the value of the particle size which divides the population of particles examined exactly in half. The Dv50 is measured according to the ISO 9276 standard - parts 1 to 6. According to one embodiment, said electrospun PVDF layer has a basis weight of between 0.03 g / m ² and 3 g / m ² .

The average thickness of this PVDF nanofiber layer is 0.1 µm to 100 µm. The diameter of the fibers, their thickness and their distribution can be estimated by scanning electron microscopy (SEM).

The solvent used in the electrospinning to dissolve the PVDF is chosen from cyclopentanone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, acetone, ethyl methyl ketone, tetrahydrofuran, g- butyrolactone, hexafluoroisopropanol or their mixtures in all proportions.

The PVDF layer deposited by electrospinning can be electrically charged by a corona treatment in order to improve its filtration properties and obtain an aerosol filtration rate of at least 80%, preferably greater than 94%, or even greater than 98. %, and a pressure drop much less than 70 Pa.s for a flow rate of 95L / min of air on inspiration.

According to one embodiment, the used masks to be recycled comprise an outer layer of thermoplastic polymer, having a melt flow index (MFR) of 34 g / 10 min at 230 ° C under 2.16 kg; this nonwoven layer has a basis weight of between 20 and 100 g / m ² and a permeability of between 500 and 1500 l / m ² / s measured at 100 Pa.

According to one embodiment, the retaining straps of the mask to be recycled, made of thermoplastic polymer, are adjustable buckles produced by injection or 3D printing or elastics (non-woven or wrapped filaments), made from said thermoplastic polymer with a grammage of between 10 and 100 gr / m ² having a hot melt index of 34 g / 10 min at 230 ° C and 2.16 kg.

According to one embodiment, the nasal bar is made from a mixture of 50% by weight of a PVDF homopolymer having a hot melt index of 32 g / 10 min at 230 ° C and 2.16 kg, and 50% by mass of a major thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 (PA6) and of long chain polyamides such as PA11 or PA12, and having a hot melt index of 34 g / 10 min at 230 ° C under 2.16 kg.

The recycling process according to the invention comprises a first step of grinding the masks resulting in the production of flakes.

According to one embodiment, the used masks are passed through a knife mill to transform them into fibers of a few millimeters, for example from 1 to 10 mm, preferably from 1 to 5 mm. A grid makes it possible to calibrate the fiber pulp according to the desired length. The grinding is carried out at a temperature which is at least 30 ° C lower than the melting point Tf of the material to be transformed, in the case of semi-crystalline thermoplastic polymers, and at least 30 ° C lower than the glass transition temperature Tg for the case of amorphous thermoplastic polymers.

According to one embodiment, the mask is ground in an extruder, which may be of the single screw or twin screw type, or in a BUS S co-mixer.

If the crushed masks have metal parts, such as the nosepiece, these can be removed with a magnet.

The recycling process according to the invention then comprises a step of granulating said flakes, resulting in the production of a masterbatch in the form of granules.

According to one embodiment, the granulation is carried out in the molten state by extrusion through a die with circular holes, then cutting chilled and drying beads to make granules of 1 to 5 millimeters in diameter.

According to another embodiment, the molten granulation takes place in a BUS S type co-mixer with cutting under water and production of lenticular granules.

According to a second aspect, the invention relates to the use of said masterbatch as an extrusion agent during the extrusion of the same majority thermoplastic polymer as that constituting the recycled mask, apart from the PVDF.

The extrusion agent obtained by the recycling process according to the invention is used to reduce or eliminate surface defects which appear during the extrusion of the majority thermoplastic resin. It significantly reduces the time to achieve a stable and flawless extrusion over a range of extrusion parameters that normally exhibit significant extrusion instabilities.

The extrusion agent and the thermoplastic resin are contacted in a solid state prior to extrusion. They can be premixed in a solid state or simply introduced into the hopper of the extruder. The extrusion agent can also be introduced in the molten state at any point on the extruder which serves to extrude the thermoplastic resin, for example using a side extruder.

According to one embodiment, the proportion by weight of the extrusion agent is from 1 to 30%, preferably from 1 to 10%, preferably from 1.5 to 10%, even more preferably from 2 to 10% for respectively from 70 to 99%, preferably from 90 to 99%, preferably from 90 to 98.5%, even more preferably from 90 to 98% of thermoplastic resin to be extruded. The masterbatch is particularly useful for the extrusion of thermoplastic polymers in the form of a film or else in the form of a tube, a section or a hollow body. In addition to the advantages already mentioned, it facilitates obtaining a smooth and flawless surface, which is particularly important in the case of a film in order to obtain good optical properties. The extrusion agent also makes it possible to reduce the pressure at the level of the air gap of the die as well as the rate of gels. It also makes it possible to a certain extent to reduce deposits at the outlet of the die.

EXAMPLES

The following examples illustrate the invention without limiting it.

Example 1: Production of electro-spun fibers on spunbond polypropylene (spunbond PP) 18 g / m ²

A mixture of homopolymer (Kynar®761 A) and of copolymer of VF2 (Kynar®2801-00) is dissolved with stirring for 2 hours at 55 ° C and according to the composition shown in Table 1.

Table 1

This solution is then fed into an electro-spinning process on a spunbond PP 18 g / m ^{2 support} . Such nonwovens are sold, for example, by the company Mogul. An electro-spun fiber-based filtration membrane was thus produced with a width of 480 mm using the conditions given in Table 2.

Table 2

Example 2: Production of electro-spun fibers on spunbond polyester (Spunbond PET) 28 g / m ²

The electrospinning solution prepared as described in Example 1 is fed into an electrospinning process on a 28 g / m ² PET spunbond support. Such nonwovens are for example marketed by the company Mogul under the name Buffalo. An electro-spun fiber-based filtration membrane was thus produced with a width of 480 mm using the conditions given in Table 3.

Table 3 Example 3: Nasal bar production

The nasal support bar is made of a rod 1.5 mm in diameter and 10 cm long. This rod is obtained by mixing / extrusion at 230 ° C in a single-screw extruder of a 50/50 mixture by mass of PVDF homopolymer having a melt index of 32 g / 10 min at 230 ° C and 2.16 kg and of polypropylene with a flow rate of 35 g / 10 min at 230 ° C under 2.16 kg.

Example 4: Assembly of masaue from the elements produced in examples 1 to 3

A mask is produced using the elements obtained in the preceding examples with the following structure: spunbond PP 1 - Espun PP membrane 1- spunbond PP 2. The non-woven “spunbond PP 1” (40 g / m ² ) forms the outer layer and improves the mechanical strength of the mask body. The “Espun PP 1” intermediate layer filters the aerosols. Finally, the “spunbond 2” nonwoven (18 g / m ² ) placed inside the mask is intended to be in contact with the face of the user, it protects the filtration layer from possible degradation. The elastics are round polypropylene cords, such products are marketed for example by the company Liasa.

Assembly follows the steps described below:

The cohesion between the layers of nonwovens is obtained by lamination.

The nasal bar produced in Example 3 is inserted into a space created by the folding of the nonwoven material over a width of 5 ± 2 mm near the periphery of the mask. The bar is held in place by welding points arranged regularly along the length of the fold.

The elastics are attached to each side of the mask so as to form a loop and are attached without adding material by ultrasonic welding.

Example 6: Grinding / granulation & extrusion of recycled material

After decontamination by passing in an oven at 70 ° C. for one hour, the masks are ground in a knife mill. The flakes obtained are fed into a BUSS type twin-screw extruder at 230 ° C. in order to produce granules. The granules obtained are composed of approximately 0.9 wt% of PVDF and used as a masterbatch to achieve a concentration of 500 ppm of PVDF in the PP then used in a process for the manufacture of multifilaments by extrusion-spinning. The pressure at the head of the extruder reached during the production of PP multi-flakes in the presence of 500 ppm of PVDF is of the order of 4.8 MPa, that is to say approximately 20% lower than that conventionally obtained during the setting. work of PP alone. Also, the impact of the presence of PVDF is visually observed by less fouling of the dies after several hours of extrusion.

Claims

1. Process for recycling respiratory protection masks containing from 98.5 to 99.5% by weight of a major thermoplastic polymer chosen from polypropylene, polyethylene terephthalate, polylactic acid, homopolymers and copolymers of polyamide 6 ( PA6) and long chain polyamides such as PA11 or PA12, and from 0.05 to 1.5% of poly (vinylidene fluoride) or PVDF in the form of nanofibers, said process comprising a step of grinding the masks leading to the 'obtaining flakes, and a step of granulating said flakes, leading to obtaining a masterbatch in the form of granules.

2. The recycling method according to claim 1, wherein the mask used consists of a body and retaining straps, said body being composed of at least two layers, including a layer of PVDF filter material, said retaining straps being fixed to the body of the mask without adding material.

3. Recycling method according to one of claims 1 and 2, wherein said mask comprises a nonwoven inner layer with a basis weight of between 20 and 100 g / m ² of thermoplastic polymer having a hot melt index of 34 g / m. 10 min at 230 ° C under 2.16 kg.

4. Recycling method according to one of claims 1 to 3, wherein said mask comprises a central layer comprising a nonwoven substrate, with a basis weight of between 20 and 100 g / m ² and having a permeability of between 500 and 2500. l / m ² / s measured at 100 Pa.

5. The recycling process according to claim 4, wherein said substrate is manufactured by extrusion blow molding or spun-lapping from a thermoplastic polymer which exhibits a melt flow index of 34 g / 10 min at 230 ° C and 2.16 kg.

6. Recycling method according to one of claims 4 and 5, wherein said central layer comprises an electrospun layer of PVDF nanofibers.

7. The recycling method according to one of the preceding claims, wherein said PVDF comprises a PVDF homopolymer; a mixture of two PVDF homopolymers; a copolymer comprising vinylidene difluoride (VDF) units and one or more types of comonomer units compatible with vinylidene difluoride; a mixture of a PVDF homopolymer and a copolymer of VDF; or a blend of two VDF copolymers.

8. The recycling process according to one of the preceding claims, wherein said PVDF nanofibers have an average D50 fiber diameter of between 30 and 500 nm, preferably 30 to 300 nm.

9. The recycling method according to one of the preceding claims, wherein the average thickness of said PVDF nanofiber layer is 0.1 µm to 100 µm.

10. The recycling method according to one of the preceding claims, wherein said mask comprises a nonwoven outer layer with a basis weight of between 20 and 100 g / m ² of thermoplastic polymer having a hot melt index of 34 g / 10 min. at 230 ° C under 2.16 kg.

11. The recycling method according to one of claims 2 to 10, wherein said retaining straps are adjustable buckles produced by injection or 3D printing or elastics, made from said majority thermoplastic polymer.

12. Use of the masterbatch obtained by the mask recycling process according to one of claims 1 to 11 as an extrusion agent during the extrusion of said thermoplastic polymer.