Solventless method for manufacturing a film

Abstract

The present invention relates to the production of porous polymer membranes as follows: (a) providing a granulate comprising a polymer matrix and particles in a ratio of 90:10 to 10:90, (b) converting the granulate into a non-porous film by a solvent-free process; (c) removing the particles from the film with an aqueous composition, thereby obtaining the membrane. The present invention also relates to granulates that can be used in such a production process, and to porous polymer membranes obtained or obtainable by such a production process, and to textile materials and articles containing such membranes; and to the use of such granulates, membranes and articles.

Description

[0001] The present invention relates to a novel method for obtaining polymer membranes and the polymer membranes as defined herein. The present invention further relates to starting materials suitable for such a manufacturing method, and to textiles containing such membranes; and to the use of such membranes, textiles and intermediates.

[0002] (The manufacture of) (porous) membranes per se is known. CN102432946 describes the manufacture of polyolefin membranes by extruding granular starting materials followed by longitudinal and transverse stretching. In many cases, obtaining a porous structure by stretching is considered an adverse process step. EP3178873 describes the manufacture of membranes starting from a polymer dispersion followed by removal of the solvent; this method avoids stretching. However, in many cases, the use of solvents is also considered adverse. JP2006287176 describes the manufacture of membranes by removing a plasticizer using an organic solvent. Again, the use of organic solvents is considered adverse on a commercial scale. EP0811479 describes the manufacture of microporous polyolefin composite membranes. This manufacture includes a stretching step and an extraction step using an organic solvent and is thus adverse for the reasons given above.

[0003] US2011 / 0151259 describes the manufacture of medical implants, in particular acetabular cups having pores of 100 to 1000 microns. These implants are manufactured starting from a polymer containing uncoated sodium chloride (“pharmaceutical grade”) as a filler. The target use as an implant requires a relatively thick material and a small area. While suitable, it has been found impossible to transfer this method to continuous production or to large-sized membranes.

[0004] Therefore, there is a need to provide an additional / improved method for manufacturing polymer membranes. There is also a need for additional / improved materials for manufacturing polymer membranes and additional / improved textiles containing such membranes.

[0005] Therefore, an object of the present invention is to alleviate at least some of these drawbacks of the prior art. In embodiments of the present invention, an improved method for manufacturing porous polymer membranes is provided. In other embodiments of the present invention, porous polymer membranes suitable for advanced applications, such as for waterproof and breathable textile materials, are provided. In further embodiments of the present invention, novel materials suitable for, for example, carrying out the manufacturing method of the present invention are provided.

[0006] The present invention will be described in more detail below. It should be understood that the different embodiments, preferences and scopes provided / disclosed in this specification can be combined arbitrarily. In addition, depending on the specific embodiment, the selected definitions, embodiments or scopes may not be applicable. It is further to be understood that all references indicated herein are incorporated herein by reference in their entirety.

[0007] The above object is achieved by providing the manufacturing method defined in claim 1. Further aspects of the invention are disclosed in the description and the independent claims, and the preferred embodiments are disclosed in the description and the dependent claims. The method for manufacturing a solvent-free hydrophobic or hydrophilic porous polymer membrane described herein has proven to be very versatile, reliable, and easy to control. This method is particularly suitable for the rapid and low-cost production of large-area membranes. The polymer membranes described herein have been demonstrated to be useful for the applications defined below and are further capable of fabricating improved articles and / or facilitating the fabrication of the articles defined below.

[0008] As will be apparent upon reading this specification, the present invention specifically relates to a method for manufacturing a polymer membrane and the corresponding membrane (first aspect); to a shaped article suitable for manufacturing such a polymer membrane (second aspect); and to an article (including textiles, containers, filters) comprising (i.e., containing or consisting of) such a polymer membrane (third aspect).

[0009] Furthermore, the present invention will be better understood with reference to the accompanying drawings.

[0010] Figure 1 A schematic diagram of the method of the present invention is shown, wherein:

[0011] (1) represents a shaped article ("pellet", second aspect of the present invention)

[0012] (2) represents a non-porous thin film, an intermediate material

[0013] (3) represents the porous polymer membrane of the present invention (unsupported; free-standing);

[0014] (4) represents particles ("fillers"; including uncoated and coated particles);

[0015] (5) represents the polymer matrix of the pellet;

[0016] (51) represents a polymer;

[0017] (52) represents an optional additive;

[0018] (6) represents an aqueous composition;

[0019] (7) represents a textile material (fourth aspect of the present invention)

[0020] (8) represents an article (commercial product, fourth aspect of the present invention); and

[0021] (a)…(f), (f’) are process steps (see the first aspect of the present invention).

[0022] Unless otherwise indicated, the following definitions shall apply to this specification:

[0023] The term "particle" is known in the art and includes crystalline or amorphous materials. This term includes uncoated particles and coated particles. Additionally, in the context of the present invention, particles are also referred to as "fillers", thereby indicating their purpose.

[0024] It is known that particles can aggregate. In the context of the present invention, suitable particles have a diameter in the sub-micron size range, and thus the particle size is preferably from 5 to 10,000 nm, for example from 5 to 4,000 nm.

[0025] Suitable particles can be obtained from a number of preparation methods, including high-temperature gas-phase methods (such as flame synthesis, laser methods, and plasma methods), and liquid-phase chemical methods (such as precipitation and sol-gel methods), and grinding of particles. Particles that are particularly suitable in the context of the present invention can be obtained by precipitation methods or by grinding of naturally occurring materials. In the context of the present invention, the particles are prefabricated to distinguish them from in-situ synthesized particles.

[0026] The terms "salt" and "oxide" are known in the art. A salt is defined as the product formed by the neutralization reaction of an acid and a base. A salt is an ionic compound containing a cation and an anion, such that the product is electrically neutral. Examples of salt types are halides (chlorides, fluorides, bromides, iodides), sulfates, phosphates, carbonates, nitrates, especially phosphates, carbonates, and halides. In the context of the present invention, metal oxides (i.e., products formed by the oxidation of metals) are not considered salts. Metal oxides include stoichiometric and non-stoichiometric oxides. Examples of salts are NaCl, CaCO3, and examples of oxides are ZnO.

[0027] The term "polymer" is known in the art. This term refers to materials in which structural units ("monomers") are repeated, especially synthetic polymers (comprising synthetic monomers). Thus, this term includes homopolymers, copolymers, and their blends. This term further includes oligomers. Polymers can be crosslinked. Suitable polymers in the context of the present invention include thermoplastic polymers and thermosetting polymers.

[0028] The terms "membrane" and "film" are known in the art. The term membrane refers to a shaped article in the form of a permeable film. Thus, a membrane is distinguished from a film by its permeability.

[0029] The "permeability" of the materials described herein is defined as the flux of a fluid (i.e., a liquid medium or a gaseous medium) through the interconnected pores of the material. Permeability is achieved through pores in a direction perpendicular to the plane of the membrane. Permeability can be determined by measuring the volume of liquid or gas passing through a specified membrane area under an applied pressure over a specified time. A typical measure of such a flux is liters per square meter per bar and hour ([L / (m 2 × bar × h)]).

[0030] For gaseous media, the water vapor transmission rate (WVTR) is a suitable parameter for determining permeability. The WVTR is measured in accordance with ASTM standard E96, with the unit of grams per square meter per day (g / (m 2 ×d)), as further specified in the Examples section below (also known as the upright cup method). Briefly, it is a cup with water covered by the sample to be tested. The sample thus prepared is weighed before being placed in an oven that controls the temperature (23 °C), relative humidity (50% RH), and ventilation (1 m / s). Two phenomena contribute to vapor transport through the porous membrane: solid-state diffusion (minor effect) and pore diffusion (the main transport mechanism). In a non-porous (or dense, defect-free) layer, only solid-state diffusion occurs.

[0031] Solid-state diffusion can be described with the following terms as per E.L. Cussler (Cussler, E.L. Diffusion. (Cambridge University Press, 1997, page 21)):

[0032]

[0033] where j describes the efflux flux of the covered cup, in grams per square meter per day (g / (m 2 d)), D is the diffusion coefficient of water molecules in the membrane material, in square meters per second (m 2 / s), H is the partition coefficient of the solubility of water molecules in the membrane material (dimensionless), and c in and c out are the concentrations of water molecules inside and outside the cup, in moles per cubic meter (mol / m 3 ).

[0034] In a porous medium, water molecules diffuse freely through the pores, which is described by the flux and uses a corrected diffusion coefficient:

[0035]

[0036] where ε is the void fraction of the porous membrane (a dimensionless number between 0 and 1), and τ represents the curvature of the porous system (a dimensionless number between 0 and 1).

[0037] For small pore diffusion based on the interaction of molecules with each other, it is restricted because water molecules not only interact with themselves but also interact significantly more frequently with the pore walls. In air, the mean free path is about 60 nm, which means that pores with a smaller diameter exhibit Knudsen diffusion, where the diffusion coefficient is adjusted as follows 1 :

[0038]

[0039] where d is the pore diameter in meters (m), k B is the Boltzmann constant in joules per kelvin (J / K), T is the temperature in kelvin (K), and m is the particle mass in grams (g).

[0040] For a liquid medium, water repellency is a relevant parameter. In the determination of water repellency, the relevant driving force is pressure. The water column (WC) in meters (m) is determined in accordance with ISO 811. Briefly, water is pressed onto the sample at a constant pressure increase over time (600 mm WC / min). The dry side of the sample is visually observed, and the third penetrating water drop is defined as the breakthrough of the sample, and the pressure is expressed as the water column (WC). A theoretical approximation can be made using the Hagen-Poiseuille equation:

[0041]

[0042] where the pressure difference (Δp in bar) is calculated by: V the volumetric flow rate in cubic meters per second (m 3 / s), η is the viscosity in bar multiplied by seconds (bar×s), t is the layer thickness in meters (m), A is the layer area in square meters (m 2 ), is the areal porosity, which is a dimensionless value between 0 and 1, and the pore diameter (d) in meters (m) (Kellenberger et al., J. Membr. Sci. 387 - 388, 76 - 82 (2012)).

[0043] As described herein, the "porosity" of a material is the volume percentage of pores in the entire material. Porosity can be determined by porosimetry, by measuring the apparent density of the material, BET analysis, or by microscopic images. Preferably, porosity is determined by microscopic image analysis. In the context of the present invention, a membrane or film is considered "porous" if the porosity is 10 - 90%, preferably 50 - 90%, for example 55 - 60%, and "non-porous" if the porosity is less than 10%, preferably less than 5%. The pore size can vary over a wide range, typically in the range of 5 nm to 2000 nm.

[0044] The "specific surface area" is a known parameter and can be determined by the nitrogen adsorption method using the BET method (according to: Janssen et al., Journal of Applied Polymer Science 52, 1913, 1994). The BET method is widely used in surface science to calculate the surface area of solids by the physical adsorption of gas molecules (such as nitrogen molecules).

[0045] In general, in a first aspect, the present invention relates to a method for manufacturing a porous polymer membrane (3) having pore sizes from 5 nm to 15,000 nm, the method comprising the steps of: (a) first providing a shaped article (1) comprising a polymer matrix (5) and particles (4) by solventless provision, (b) subsequently converting the shaped article (1) into a non-porous polymer film (2) by a solventless process, and then (c) removing the particles (4) from the film (2) by contacting the film with an aqueous composition (6), thereby obtaining the porous polymer membrane (3). This method is shown in Figure 1 and is further explained below.

[0046] It is believed that the use of the solventless process step provides a significant improvement over known methods for preparing porous polymer membranes. Specifically, the method of the present invention does not require organic solvents, thereby having a positive impact on the ecological balance sheet and cost considerations. The method for manufacturing a porous polymer membrane of the present invention has proven to be very versatile, reliable, and easy to control. The method is particularly suitable for the rapid and low-cost production of large-area membranes.

[0047] In another embodiment, the method of the present invention provides a method for manufacturing a porous polymer membrane (3) without using a stretching method / stretching step. Such stretching is limited to specific polymers and is usually applied to foils to obtain membranes. This additional step is difficult to control and is therefore disadvantageous for commercial manufacturing. Thus, the present invention also provides the method described herein which does not include a stretching step.

[0048] This aspect of the present invention will be explained in more detail below, first describing the process steps and subsequently the starting materials and particularly suitable embodiments:

[0049] Process steps:

[0050] The manufacturing method described herein is considered advantageous because the individual steps are known in the industry and have been used for commercial applications. Additionally, the method is very fast and can be implemented in a continuous process.

[0051] Step a: The manufacture of pellets (1) comprising a polymer matrix, optional additives, and fillers is known per se.

[0052] In one embodiment, step (a) comprises co-extruding a polymer (51) and particles (4), which polymer is optionally blended with an additive (52).

[0053] In one embodiment, a synthesis step (d) precedes step (a). In such a synthesis step, the polymer can be formed or blended together with an additive (51) (step d1) and / or the particles (4) can be coated with a coating (41) (step d2). Such an additional synthesis step (d) is known per se and can be carried out in the presence or absence of a solvent. In one embodiment, step (d2) is solvent-free.

[0054] In one embodiment, step (a) is carried out with the shaped article (1), wherein the ratio of the polymer matrix (5) to the particles (4) in the article (1) is from 10:90 to 90:10, preferably from 50:50 to 20:80 (matrix: particles, wt%), and wherein the particles (4) are dispersed in the matrix (5).

[0055] Step b: The conversion of the shaped article / pellet (1) into a non-porous film is known per se and is applied on a commercial scale.

[0056] In one embodiment, step (b) is selected from film extrusion, calendering, injection molding, compression molding, blow molding, die coating, and meltblowing. In a preferred embodiment, step (b) is selected from film extrusion, calendering. This is particularly suitable for large-area films.

[0057] In one embodiment, step (b) is supplemented with a crosslinking step (step b1)

[0058] In one embodiment, step (b) is supplemented with coating the film (2) onto a substrate (7) (step b2).

[0059] In one embodiment, step (b) provides a film having a thickness of from 5 to 200 μm, preferably from 30 to 80 μm. In one embodiment, step (b) provides a film having a thickness of from 0.01 μm to 1000 μm, preferably from 2 μm to 60 μm.

[0060] Step c: Dissolving the continuous salt phase / oxide phase in such a nanocomposite film, which results in a nanoporous polymer film (porous polymer film (3)). This single step is known and is described, for example, in EP3178873. Without being bound by theory, it is believed that the coating remains within the polymer structure when present and is located on the surface of the pores. Suitable are aqueous solvents such as water or acidic aqueous solutions (such as acetic acid or hydrochloric acid). The choice of solvent depends specifically on the type of particles (metal salt / metal oxide) used.

[0061] In one embodiment, step (c) is carried out for 90 minutes or less, for example 5 minutes.

[0062] It is believed that the dissolution step (c) is a key element of the manufacturing method and also a key element for obtaining the porous polymer film (3) of the present invention.

[0063] In another embodiment, the process step (c) can be repeated. This measure ensures the complete removal of the particles (4). Thus, step (c) also includes multiple washings and drying. When using a multi-step scheme, the same or different aqueous compositions can be used, for example, first with a dilute aqueous acid solution and subsequently with water.

[0064] General method features: In one embodiment, the method of the present invention does not include a phase separation step. This phase separation is limited to specific polymers, and the corresponding pore formation is highly sensitive to different process parameters (such as temperature, humidity, time), which requires careful control simultaneously. Obviously, this method is disadvantageous for rapid and large-scale commercial manufacturing. Therefore, the present invention also provides the method described herein, which does not include a phase separation step. In the context of the present invention, the phase separation step is considered a separate step in the manufacturing method, which requires specialized equipment. It should also be noted that phase inversion is only observed in a limited number of polymer / polymer combinations. The present invention is not limited to such specific polymers or their combinations and is thus considered to be significantly more general.

[0065] In one embodiment, no organic solvents are used in steps a) to c).

[0066] In one embodiment, steps b) and c) are carried out without the aid of a substrate. Thus, the thin film (2) and the film (3) of the present invention can be obtained directly without the need to provide and remove a carrier material. This direct scheme is beneficial compared to the above-known methods.

[0067] In one embodiment, steps a) and b) are combined into a single step. In this embodiment, the co-compounding step is omitted. Instead, the polymer matrix (5) and the particles (4) are directly mixed in a suitable device such as a film extruder. This embodiment is considered beneficial in the case of coating particles. This embodiment is further considered beneficial in the case of polymers having good fluidity (which is usually indicated by a low melting point of the polymer). Thus, the particles (4) containing the coating (41) are combined with a thermosetting polymer (51) such as PCL and optional additives (52) and fed into the inlet of a film extruder. This embodiment avoids the separate preparation of the shaped article (1). Instead, the starting materials are directly converted into a non-porous polymer film (2). This embodiment is particularly beneficial because it simplifies the manufacturing process in one step and thus simplifies large-scale production.

[0068] In another embodiment, the present invention provides the method as described herein, wherein one or more of the steps, such as steps b) and c), preferably steps a) to c), more preferably all steps are adapted to a continuous process. Such continuous processes can be film extrusion, calendering, injection molding, compression molding, blow molding, die coating, melt blowing. These processes are also capable of producing multi-layer materials that include the porous membrane of the present invention as one of the layers. The thickness of such multi-layer materials can be 1 mm or even greater. Such multi-layer materials can naturally have more complex functions than single-layer materials. This can be advantageous in many applications, including both textiles and non-textiles.

[0069] The manufacturing method provides a porous polymer membrane of substantially unlimited size. Since the manufacturing steps do not provide a limitation on the size of the material (except for the apparatus used), it is possible to obtain large sheets of material in terms of length and width. Accordingly, the present invention also provides the method as disclosed herein, wherein the area of the porous polymer membrane is greater than 100 cm 2 , preferably greater than 1000 cm 2 , most preferably greater than 1 m 2 . When using a roll-to-roll apparatus, a single-piece porous polymer membrane of 100 m 2 or even greater can be prepared. In an embodiment, the width of the membrane of the present invention per roll is 1.4 to 1.6 m and the length is 500 to 1000 m.

[0070] Starting materials:

[0071] The manufacturing method as described herein is considered advantageous because the single starting material is commercially available or can be obtained according to known methods.

[0072] Particles (4): The particles as described herein are also referred to in the art as "fillers" or "porogens". The particles can be uncoated or coated, as described below. The present invention relates to the use of one type of particle (e.g., unimodal size, and / or the same material) or more than one type of particle (e.g., bimodal size distribution, different materials, coated and uncoated).

[0073] Suitably, the particles (4) are prefabricated. By prefabricated it is meant that the particles are not formed in situ during process step (a). Typically, the uncoated particles (4) are obtained from a supplier with the required quality. The coated particles (4) can be obtained from a supplier or coated by combining the coating (41) and the particles (4), optionally in the presence of a diluent, according to known methods.

[0074] Suitably, the particle size of the particles (4) is 5 to 10000 nm, preferably 5 to 4000 nm.

[0075] Suitably, the particles (4) are selected from organic salts, metal salts, metal oxides; and are optionally coated with a coating (41). As is apparent from above, suitable particles (4) are soluble in an aqueous medium, for example having a solubility of at least 1 g at pH 1 to 14 / 20 °C, preferably having a solubility of 10 g at pH 1 to 14 / 20 °C.

[0076] In one embodiment, the particles (4) consist of a salt selected from carbonates, bicarbonates, sulfates, halides, nitrates and phosphates. In one embodiment, the particles (4) consist of oxides selected from ZnO and MgO.

[0077] In one embodiment, the particles (4) consist of a salt and a coating (41), the salt being selected from carbonates, bicarbonates, sulfates, halides, nitrates and phosphates, the coating (41) being selected from carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes. In one embodiment, the particles (4) consist of an oxide and a coating (41), the oxide being selected from ZnO and MgO, the coating (41) being selected from carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes.

[0078] A particularly preferred type of particles is CaCO3 particles. Typically, CaCO3 particles are obtained by a precipitation method or by extraction from ore and grinding to the desired size.

[0079] A particularly preferred type of particles is NaCl. Typically, NaCl particles are obtained by evaporating brine or by mining rock salt and then grinding to the desired size.

[0080] Flame synthesis is an alternative route for obtaining the particles as defined herein.

[0081] Coating (41): As described above, the particles can be coated or uncoated.

[0082] Suitable coatings (41) can be selected from hydrophobic or hydrophilic materials. Such materials are commercial products or can be prepared according to known methods; they are selected to improve compatibility with the polymer (51). It has been found that the coating (41) beneficially affects the manufacture of the membrane and the properties of the membrane.

[0083] Hydrophobic coatings are suitable, for example in cases where water repellency is a relevant membrane property. By way of example, mention can be made of membranes for clothing. Suitable hydrophobic coatings can be selected from:

[0084] · C6-C 24 Carboxylic acids, preferably C6-C 24 Monocarboxylic acids, including saturated and unsaturated fatty acids, particularly preferably stearic acid;

[0085] · C 15 -C 40 Alkanes, preferably paraffinic oils and paraffinic waxes;

[0086] · Vegetable oils, preferably castor oil;

[0087] · Polyesters or polyamides having a melting point of 50 to 70 °C, preferably polycaprolactone; and

[0088] · Polymaleic anhydride derivatives having linear or branched C6-C 40 alkyl chains, preferably poly(maleic anhydride-alt-1-octadecene); and

[0089] · Siloxanes in the form of nanoparticles or filaments; and

[0090] · C6-C 24 alkyl-C1-C4 alkoxy-silanes, preferably C6-C 24 alkyl-methoxy-silanes.

[0091] Hydrophilic coatings are suitable for preparing membrane filters. Suitable hydrophilic coatings can be selected from:

[0092] · Polyol derivatives, preferably propan-1,2,3-triol, polyethylene glycol (Mn = 200 to 50000), polyethylene oxide (Mw = 100000 to 1000000) and polypropylene glycol;

[0093] · Polyvinylpyrrolidone (Mw = 50000 to 1000000); and

[0094] · Chitosan.

[0095] A particularly suitable type of coating is polyol derivatives, such as glycerol and C6-C 24 monocarboxylic acids such as stearic acid, and alkanes.

[0096] Suitably, the average size of the core of the coated particles is 5 to 10000 nm, and the coating is in total 0.1 to 10 wt% of the coated particles, preferably 1 to 4 wt%. It has been found that such coatings can produce large membranes with high WVTR and high WC. So far, it has been impossible to produce membranes on a commercial scale and obtain membranes of substantially infinite size, and meeting the WVTR and WC requirements, based on solvent-free methods.

[0097] In an embodiment, the particles are uncoated particles selected from CaCO3 (preferably with a particle size of 0.3 to 10 μm, such as 0.5 μm to 6 μm), NaCl (preferably with a particle size of 0.3 μm to 10 μm, such as 0.5 μm to 6 μm), and ZnO (preferably with a particle size of 0.005 μm to 2 μm, such as 0.05 μm to 1 μm).

[0098] In an embodiment, the particles are coated particles, the particles comprising a CaCO3 core and a coating (the coating preferably containing C6-C 24 carboxylic acid, C6-C 24 hydrocarbons, linear or branched bulky organic molecules selected from short-chain polymers, zwitterionic surfactants, alkyl-silane derivatives, polyol derivatives, particularly preferably polyol derivatives); the core of the coated particles has an average size of 5 to 10,000 nm, and the coating amount is 0.1 to 10 wt% (preferably 1 to 4 wt%) of the coated particles.

[0099] In an embodiment, the particles are coated particles, the particles comprising an NaCl core and a coating (the coating preferably containing C6-C 24 carboxylic acid, C6-C 24 hydrocarbons, linear or branched bulky organic molecules selected from short-chain polymers, zwitterionic surfactants, alkyl-silane derivatives, polyol derivatives, particularly preferably polyol derivatives; the core of the coated particles has an average size of 5 to 10,000 nm, and the coating amount is 0.1 to 10 wt% (preferably 1 to 4 wt%) of the coated particles.

[0100] The coated particles are prepared in a separate method before step (a) as described above. The present invention thus relates to the method described herein, wherein the particles are not prepared in situ, i.e., they are prefabricated.

[0101] Polymer (51): The term polymer is known in the art and includes homopolymers, copolymers, and blends of polymers. Suitable polymers are selected from the group of thermoplastic polymers and thermosetting polymers.

[0102] A thermoplastic polymer is a polymer that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling; this process is reversible. Such polymers include polyesters (which include PCL, PLA, and PET), polyolefins (which include PE and PP), polystyrene, polyethers, polyamides, polyurethanes. Polycaprolactone (PCL), polyurethane (TPU), and polylactic acid (PLA) are preferred polymers.

[0103] A thermosetting polymer is a polymer that will only melt and harden once. Typically, such thermosetting polymers are crosslinked. Thus, thermosetting polymers include polymers of the types defined above that are crosslinked.

[0104] Additives (52): Additives are well-known in the field of polymer chemistry. They are used to improve product quality and / or improve processing performance. Suitable additives can be selected from a wide range of known additives and their mixtures and are known in the art. The term additives includes film flow agents, film homogenizers, anti-orange peel agents, and wetting agents. These additives are commercially available, for example, from Byk Additives and Instruments, Evonik Industries, CRODA International, and include compounds selected from fatty acids, C6-C 24 hydrocarbons, polyethylene glycols, and glycerols.

[0105] Aqueous composition (6): A solvent (6) is selected to ensure the dissolution of the particles / coated particles without dissolving the polymer. Surprisingly, not only the non-coated particles described herein, but also the coated particles can be easily dissolved in an aqueous solution.

[0106] Shaped article (1): The shaped article described in the context of step (a) is also referred to in the art as a "granule" or "powder". The typical size range for granules is 0.5 to 5 cm; for powders it is 0.1 mm to less than 5 mm. The powder can be obtained by grinding the polymer (5) and the co-compounded particles (1), thereby obtaining such a shaped article (1) in powder form.

[0107] A suitable article (1) comprises a matrix (5) and particles (4) dispersed in the matrix, and the ratio of the two is 90:10 to 10:90 (matrix: particles, wt%), preferably 50:50 to 10:90 (wt%). Compared with traditional methods, the particle loading in the granules is considered to be high.

[0108] The matrix comprises a polymer (51) and optionally additives (52). In one embodiment, the matrix consists of a polymer (51). In another embodiment, the matrix (5) consists of a polymer (51) and one or more additives (52).

[0109] Porous polymer membrane (3): Obviously, the method of the present invention can be used to obtain a wide range of porous polymer membranes.

[0110] By suitably selecting the particles (e.g., size, coating, and amount) and by selecting process parameters (e.g., extrusion parameters), the porosity and pore size distribution can vary over a wide range. Accordingly, the present invention also provides the method described herein, wherein the porous polymer membrane (3) conforms to one or more of the following:

[0111] · Thickness: The film (3) obtained according to the method of the present invention exhibits a thickness that varies within a wide range and depends on its target application. Suitable values are from 0.01 μm to 1000 μm for a single-layer film, preferably from 2 μm to 60 μm, and up to 180 μm for a three-layer film. For the selected application, very thin or very thick films can also be manufactured, such as from 0.01 μm to 1000 μm. For such extreme ranges, the WC and WVTR properties do not remain the same. Thick films (several hundred microns or more) are particularly suitable for applications in multi-layer form.

[0112] · Porosity: Suitably it is 10 to 90%, preferably 50 to 90%, for example 55 to 60%.

[0113] · Pore size: In the case of hydrophobic polymers, suitably it is 5 nm to 15000 nm; preferably 200 nm to 4000 nm; or in the case of hydrophilic polymers, preferably 5 nm to 500 nm.

[0114] · Water column (WC): Suitable values are at least 4.8 m, preferably at least 9 m, particularly preferably at least 18 m.

[0115] · Water vapor transmission rate (WVTR): Suitable values are at least 500 g / m 2 / day, preferably at least 700 g / m 2 / day.

[0116] · Water contact angle: Suitable values are at least 50°, preferably at least 95°. This shows the hydrophobicity of the polymer film (3).

[0117] · Stress: Measured for porous samples to be about 3 to 5 MPa, thus about 7 to 10 MPa if porosity is included.

[0118] It can be seen that the method of the present invention is capable of manufacturing films with very high porosity. This high porosity is beneficial for high water vapor transmission rates and can also provide significant thermal insulation. Both are significant advantages for textile applications, buildings, and when used in multi-layers.

[0119] Furthermore, by suitably selecting the polymer (51) and additive (52), a wide range of films can be obtained, especially those in which

[0120] · The film (3) is free of halogenated polymers, and / or

[0121] · The film (3) is composed of biodegradable polymers according to ISO 16929 and ISO 20200 (decomposition test methods for industrial composting), ISO 14853 and EN 14995 (anaerobic digestion environment) or EN 13432 (composting and biodegradation). They generally involve the measurement of CO2 emissions.

[0122] Similarly, the applicability to a wide range of polymeric materials is a significant advantage.

[0123] Particular combinations of materials have been found to be particularly suitable.

[0124] In one embodiment, the polymer (51) is hydrophilic and the particles (4) are coated or uncoated, preferably uncoated.

[0125] In one embodiment, the polymer (51) is hydrophobic and the particles (4) are coated or uncoated, preferably the particles (4) comprise a coating (41).

[0126] In one embodiment, the polymer (51) is hydrophobic and the particles (4) are coated, and the coating is selected from the above C6-C 24 carboxylic acids, preferably stearic acid. This embodiment provides a membrane (3) having hydrophobicity.

[0127] In one embodiment, the polymer (51) is hydrophobic and the particles (4) are coated, and the coating is selected from C6-C 24 hydrocarbons and paraffins, preferably paraffins. This embodiment provides a membrane (3) having hydrophobicity.

[0128] In one embodiment, the polymer (51) is hydrophilic or hydrophobic and the particles (4) are coated, and the coating is selected from the above polyol derivatives, preferably glycerol-coated. This embodiment provides a membrane (3) having hydrophilicity.

[0129] In one embodiment, the polymer (51) is hydrophilic or hydrophobic and the particles (4) are coated, and the coating is selected from the above PVP. This embodiment provides a membrane (3) having hydrophilicity.

[0130] The present invention in a second aspect relates to a shaped article (1). Such articles, particularly in the form of pellets or powders, are useful starting materials for the manufacturing methods described herein. Such articles can be utilized according to step (a) above, particularly by coextrusion or co-blending. This aspect of the invention will be further explained in detail below:

[0131] In an embodiment, the present invention provides a shaped article component (1) (“granules” or “powder”), wherein each element of the component comprises a polymer matrix (5) and particles (4) dispersed therein; and the matrix (5) comprises a thermoplastic or thermosetting polymer (51) as described herein (especially in the first aspect and the claims) and optionally additives (52); and the particles (4) are as defined herein (especially in the first aspect and the claims); characterized in that the ratio of the matrix (5): particles (4) is 1:1 to 1:9 (wt%). These shaped articles are suitable as starting materials in the method of the present invention. The amount of particles (4) (“fillers”) in the shaped articles (1) (“granules”, “powder”) is relatively high.

[0132] In an embodiment, the shaped article comprises a hydrophilic polymer (51) and uncoated particles (4).

[0133] In an embodiment, the shaped article comprises a hydrophobic polymer (51), and particles (4) comprising a coating (41).

[0134] In an embodiment, the granule size is 0.5 to 5 cm, and / or the average particle size of the powder is 0.1 mm to less than 5 mm.

[0135] In an embodiment, the present invention provides the use of the shaped article (1) as described in this aspect of the present invention in the method as described in the first aspect of the present invention.

[0136] In an embodiment, the present invention provides the use of the shaped article (1) as described in this aspect of the present invention for manufacturing the film (3) as described in the third aspect of the present invention.

[0137] Broadly speaking, any (coated or uncoated) salt or metal oxide particles can be used, and the preferred types of particles and coatings are those disclosed in the first aspect of the present invention above. The manufacture of suitable coated particles (4) is known in the art. It has been found advantageous to use prefabricated coated particles.

[0138] The additives (52) can be selected, as described above, from, for example, surfactants, polymerization initiators, stabilizers, crosslinking agents, wetting agents.

[0139] The present invention relates in a third aspect to a novel polymer film (3). In this aspect, in particular, the advantageous polymers and the properties of the films of the present invention are described below.

[0140] In one embodiment, the present invention provides a porous polymer film (3) which can be obtained or has been obtained by the method according to the first aspect of the present invention, wherein the film complies with all the properties (i) to (iii) and optionally complies with one, two or three of the properties (iv) to (vi):

[0141] (i) The water column (WC) is at least 4.8 m;

[0142] (ii) The WVTR is at least 500 g / m 2 / day;

[0143] (iii) The flux is at least 1 L×m -2 ×h -1 ;

[0144] (iv) The thickness is from 0.01 μm to 1000 μm, preferably from 10 μm to 100 μm;

[0145] (v) The orifice size is from 5 nm to 2000 nm;

[0146] (vi) The porosity is from 10 to 90%.

[0147] In one embodiment, the present invention provides a porous polymer membrane (3) comprising, in particular consisting of, a polymer (51), wherein the membrane complies with all the properties (i) to (v) and (vii) and optionally complies with (vi):

[0148] (i) The water column (WC) is at least 4.8 m;

[0149] (ii) The WVTR is at least 500 g / m 2 / day;

[0150] (iii) The flux is at least 1 L×m -2 ×h -1 ;

[0151] (iv) The thickness is from 0.01 μm to 1000 μm, preferably from 10 μm to 100 μm;

[0152] (v) The orifice size is from 5 nm to 2000 nm;

[0153] (vi) The porosity is from 10 to 90%;

[0154] (vii) The polymer (51) is selected from the thermoplastic polymers described herein (in particular in the first aspect of the present invention and in the claims) or the thermosetting polymers described herein (in particular in the first aspect of the present invention and in the claims).

[0155] Membrane: In one embodiment, the present invention relates to a polymer membrane having (i) thickness and / or (ii) porosity; and / or (iii) pore size; and / or (iv) tensile properties and / or (iv) water column; and / or (v) water vapor transmission rate; and / or (vi) water contact angle, as described in the first aspect of the present invention above. Due to the unique manufacturing method as described herein, the present invention provides a porous membrane (or even a nanoporous membrane) that combines specific properties of organic polymers. Advantageously, due to the specific application of the membrane of the present invention, the above parameters can be adjusted.

[0156] In one embodiment, the membrane of the present invention can consist of a single layer. This embodiment is advantageous for jackets and outdoor clothing, building roof coverings in construction (to manage water and steam in buildings), packaging materials (such as for food, consumer goods, and pharmaceuticals), agricultural tarpaulins, and sensors.

[0157] In another embodiment, the membrane of the present invention can consist of two or more layers, such as 2 or 3 layers. This embodiment is advantageously used for outdoor clothing (due to better sweat management, especially by transporting sweat within the jacket layer from inaccessible areas of the clothing to more accessible areas, thereby providing increased comfort), cool textiles (i.e., materials that provide a cooling effect to the user by evaporating water from a multi-layer material), packaging of living organisms, packaging of food, pharmaceuticals, and sensitive consumer goods, cooling curtains (allowing passive cooling in and around buildings and public transportation), air humidification in air conditioning units. Additional applications are for flexible gas absorbers, air cleaning devices, personal hygiene products, and personal protection devices.

[0158] Polymer: As described above, a wide variety of polymers can be used for the membrane of the present invention. In one embodiment, the polymer is selected from the polymers of the first aspect of the present invention listed above.

[0159] Advantageously, this polymer is halogen-free, especially fluorine-free. This is considered advantageous because the membrane is environmentally friendly.

[0160] Advantageously, this polymer is biodegradable. This is considered advantageous because the membrane is environmentally friendly and desirable in certain industrial applications. Poly(lactic acid) (PLA) is a preferred polymer.

[0161] In another embodiment, polycaprolactam (PCL) is a preferred polymer.

[0162] Pores: As described above, the material of the present invention is porous. The material of the present invention is characterized by the pore size, type, and amount present. The pore size, type, and amount are affected by the coating type, coating amount, starting materials, particle:polymer ratio, manufacturing method, and coating type.

[0163] The pore size of the film of the present invention (defined by the diameter of the coated particles) is in the nanometer size range, typically 5 nm to 15,000 nm, preferably 200 nm to 4,000 nm for hydrophobic membranes, and 5 nm to 500 nm for hydrophilic membranes. The pore size can be determined by microscopy. In addition, the pore size distribution can be precisely adjusted due to the starting materials used.

[0164] The porosity, i.e., the ratio of the pore volume to the entire film volume, can vary within a wide range. The materials of the present invention exhibit a porosity of 10 to 90 vol%, preferably 20 to 90 vol%, more preferably 50 to 90 vol%, for example 55 to 60 vol%. The porosity can be determined by micrograph analysis.

[0165] The pores of the material can be arranged in such a way that the material is permeable, partially permeable, or impermeable. The pores are mainly perpendicular to the plane of the film. If substantially all the pores of the material have closed ends, the material is impermeable. Conversely, if substantially all the pores of the material have open ends, the material is considered permeable. Thus, if a portion of the pores has closed ends, the material is considered partially permeable. In an advantageous embodiment, the present invention provides a polymer film in which at least 50%, preferably at least 80% of the pores are interconnected.

[0166] Thickness: The thickness of the film of the present invention can vary within a wide range, for example 0.01 μm to 1000 μm. In the case where the film of the present invention exists in a single layer form, a suitable thickness is 0.01 to 1000 μm; preferably 1 to 500 μm, most preferably 20 μm to 60 μm. In the case where the film of the present invention exists in a multilayer structure form, a suitable thickness is 1 μm to 1000 μm; preferably 30 μm to 250 μm. Such a film can also be referred to as a "sheet" or "porous foil"; these terms indicate that the material has a length and width that are at least one order of magnitude (preferably at least two orders of magnitude) greater than the thickness of the material.

[0167] The water repellency (measured as WC) and breathability (measured as WVTR) of the film of the present invention are as described in the first aspect of the present invention above.

[0168] The mechanical properties of the film of the present invention, such as tensile strength and flexibility, are as described in the first aspect of the present invention above, which makes them suitable for many applications such as textile applications.

[0169] The present invention in a fourth aspect relates to textile materials and articles comprising the porous polymer membranes (3) described herein. In many cases, the membranes (3) will not be commercial products, but important intermediates for such commercial products. A wide variety of commercial products, including textile materials and articles, can be equipped with the porous polymer membranes (3) of the present invention. This aspect of the invention will be explained in further detail below:

[0170] Textile materials: In an embodiment, the present invention relates to a woven or non-woven textile material (7) comprising the polymer membranes (third aspect of the present invention) described herein. The membrane is laminated to the textile, or the membrane is self-supporting and is connected to the textile membrane, for example, by gluing, welding, stitching, and / or extrusion. It is considered beneficial that the membranes (3) of the present invention can be easily used in existing manufacturing devices, such as those used in the textile industry.

[0171] Commercial products: The present invention further provides articles (8), particularly selected from clothing (such as coats, jackets, trousers, underwear); and containers (such as bags, backpacks); and separation devices (particularly filtration devices, such as water filters), said articles comprising the above-mentioned woven or non-woven textile materials (7) or the polymer membranes (3) described in the third aspect of the present invention.

[0172] Clothing comprising the membranes of the present invention meets consumer expectations, particularly with regard to WC and WVTR performance. Such textiles are fluorine-free and optionally silicone-free. Therefore, the product can be treated in a nature-friendly manner, such as non-hazardous incineration. In addition, a biodegradable chemical composition of such clothing can be ensured. The enabling technology is more versatile and eco-friendly when compared with existing methods; this is particularly due to the solvent-free process steps and the options of hydrophilic and hydrophobic membranes.

[0173] The membranes of the present invention are self - supporting ("free - standing"). Thus, they are distinct from known membranes of similar thickness and porosity on a carrier. However, the materials of the present invention are suitable for coating a suitable carrier. The possibility of the membrane being independent of a specific carrier makes it very versatile. In an embodiment, the membrane of the present invention is applied to a substrate. Suitable substrates can be selected from a wide range of known substrates. The substrate can be any carrier compatible with the manufacturing method. It is more beneficial if the membrane (3) and the film (2) adhere to the substrate during manufacturing and can be removed after manufacturing. Suitable materials for the substrate include polymeric materials, glass, metals (such as aluminum), ceramics, and paper (coated or uncoated in each case). In the case of textile manufacturing, it is advantageous to directly coat the films described herein onto a tightly woven fabric. In this embodiment, it is advantageous if the polymer matrix adheres sufficiently to the type of polymer or biopolymer used in the textile substrate. For outdoor clothing, suitable substrates are tightly woven polyamides, polyolefins, or polyesters.

[0174] The present invention further relates to the uses / methods of using the membranes, textiles, and intermediates described herein.

[0175] To further illustrate the present invention, the following examples are provided. The purpose of providing these examples is not intended to limit the scope of the present invention.

[0176] I General procedures

[0177] The general procedures for the following small - scale experiments are as follows:

[0178] 1. Co - extrude the particles (4) and the polymer pellets (5) into shaped particles (1)

[0179] 2. Use a hot press to produce a non - porous film (2), generating a circular sample with a diameter of about 10 cm and a thickness of 70 to 150 microns.

[0180] 3. Wash the non - porous film (2) in a water bath (6) to produce a porous membrane (3).

[0181] The general procedures for large - scale experiments are similar, except that a film extruder is used instead of a press, which produces samples with a length > 100 m, a width of 20 to 30 cm, and a thickness of 20 to 500 microns.

[0182] The general analysis procedures are as follows:

[0183] · The membrane thickness is determined by magnetic induction method and SEM micrograph analysis.

[0184] · The water column of the obtained membrane is determined in accordance with ISO 811 as described above.

[0185] · The gas permeability / WVTR of the obtained membrane was measured in accordance with ASTM E96 described above.

[0186] · The LMH of the obtained membrane was determined by measuring the volume of liquid that passed through a specified membrane area within a specified time under a specified applied pressure. LMH represents the flux and the unit is liters per square meter per bar and hour ([L / (m 2 × bar × h)].

[0187] · The retention rate of the obtained membrane was determined by the concentration of fluorescent nanoparticles (50 to 250 nm) before filtration (feed solution) and after filtration (permeate). It was calculated by the following formula:

[0188]

[0189] II Examples of testing hydrophobic membranes:

[0190] A. Small scale:

[0191] 1. Scale: 35 g for each loading and each type of additive

[0192] Polymer: Polylactic acid (PLA)

[0193] Loading: 60 / 40, 70 / 30, 80 / 20 filler / polymer

[0194] Additives: TBC, castor oil, paraffin wax (each having 3 loadings: 19 wt%, 27 wt%, 38 wt%) (relative to the polymer)

[0195] Filler: CaCO3

[0196] Functionalization: 4% stearic acid

[0197] Results: Coextrusion produced shaped articles (1). All the membranes (3) achieved relatively high gas permeability (the higher the filler loading, the higher), and some had greater hydrophobicity than others.

[0198] 2. Scale: 35 g for each loading and each type of additive

[0199] Polymer: Polyester

[0200] Loading: 60 / 40, 70 / 30, 80 / 20 filler / polymer

[0201] Additives: TBC, castor oil, paraffin wax (each having 3 loadings: 19 wt%, 27 wt%, 38 wt%) (relative to the polymer)

[0202] Filler: CaCO3

[0203] Functionalization: 4% stearic acid

[0204] Results: Co - extrusion produced shaped articles (1). All of the membranes (3) achieved a relatively high gas permeability (higher with higher filler loadings), and some were more hydrophobic than others.

[0205] 3. Scale: 5 g for each polymer

[0206] Polymers: Polyester (PE), PLA, Polycaprolactam (PCL), Polyamide (PA), Polytrimethylene terephthalate (PTT), Polypropylene (PP)

[0207] Loadings: 60 / 40, 67 / 33, 70 / 30, 80 / 20 filler / polymer

[0208] Additives: Tributyl citrate (only for PE)

[0209] Fillers: CaCO3

[0210] Functionalization: 4% stearic acid

[0211] Results: See Table 1

[0212] Table 1: Examples of properties obtained for porous hydrophobic membranes made using a solvent - free method (see small - scale 3. description)

[0213]

[0214] * The presence of pores in the porous membrane (3) explains the low water column results.

[0215] ** PE, containing tributyl citrate, 5:1 wt / wt.

[0216] Without being limited to theory, it is believed that adding a plasticizer (52) will improve the flowability of brittle polymers and thus facilitate the extrusion process.

[0217] 4. Scale: 5 g

[0218] Polymers: PLA

[0219] Loadings: 60 / 40 filler / polymer

[0220] Additives: None

[0221] Fillers: NaCl

[0222] Functionalization: None

[0223] Results: Co - extrusion produced shaped articles (1). The rough surface of the pellets (1) and subsequent films (2) is believed to be attributed to large NaCl particles (4). Without being bound by theory, it is believed that reducing the particle size and coating of the NaCl filler particles will improve the process.

[0224] B. Large scale

[0225] 1. Scale: 5 kg

[0226] Polymer: PLA

[0227] Loading: 60 / 40 filler / polymer

[0228] Additive: TBC 20 wt% (relative to polymer)

[0229] Filler: CaCO3

[0230] Functionalization: None

[0231] Results: Co - extrusion produced a shaped article (1). The film (2) produced by the experimental setup at ETH performed well, but the formed thickness was too high (>300 microns). It was difficult to completely dissolve CaCO3 (6) from the polymer throughout the thickness. Without being bound by theory, it is believed that reducing the thickness will improve the method.

[0232] 2. Scale: 20 kg

[0233] Polymer: PLA

[0234] Loading: 60 / 40 filler / polymer

[0235] Additive: TBC 20 wt% (relative to polymer)

[0236] Filler: CaCO3

[0237] Functionalization: 4% stearic acid

[0238] Results: Co - extrusion produced a shaped article (1). The film (2) produced by the experimental setup performed well, and the thickness was achieved from 20 μm to 200 μm by changing the roller speed. The film (3) had good gas permeability and hydrophobicity.

[0239] 3. Scale: 100 kg (for each loading type)

[0240] Polymer: PLA + TBAT

[0241] Loading: 50 / 50, 60 / 40, 65 / 35, 70 / 30 filler / polymer

[0242] Additive: None

[0243] Filler: CaCO3

[0244] Functionalization: 1% stearic acid

[0245] Results: Coextrusion produced a shaped article (1), and films (2) were manufactured by a meltblown test apparatus (thickness 20 to 50 μm) and a film extrusion test apparatus (thickness 70 to 200 μm). The film (3) exhibited good gas permeability and hydrophobicity.

[0246] 4. Scale: 100 kg (for each loading type)

[0247] Polymer: Hydrophobic TPU

[0248] Loading: 50 / 50, 60 / 40, 65 / 35 filler / polymer

[0249] Additive: None

[0250] Filler: CaCO3

[0251] Functionalization: 1% stearic acid

[0252] Results: Coextrusion produced a shaped article (1), and films (2) were manufactured by a meltblown test apparatus (thickness 20 to 50 μm) and a film extrusion test apparatus (thickness 70 to 200 μm). The film (3) exhibited good gas permeability and hydrophobicity.

[0253] III. Examples of testing hydrophilic membranes:

[0254] A. Small scale

[0255] 1. Scale: 15 g

[0256] Polymers: PLA, PESU, EVOH, PE / PVAc copolymer, PET, PA

[0257] Loading: 60 / 40, 70 / 30, 80 / 20 filler / polymer

[0258] Additives: PVP, TEC, polyol plasticizer

[0259] Fillers: CaCO3, ZnO nanoparticles

[0260] Functionalization: PEG, PVP

[0261] Results: Coextrusion produced a shaped article (1). Most of the films (3) achieved a relatively high retention rate and water flux. Some of them produced very brittle results and thus could not be properly tested. It is believed that changing the polymer chain length will improve the method. See Table 2.

[0262] Table 2: Examples of properties obtained using a solvent-free method to manufacture hydrophilic porous membranes (see Small scale 1 description)

[0263]

[0264] B. Large scale

[0265] 1. Scale: 2 kg

[0266] Polymer: PLA

[0267] Loading: 80 / 20 filler / polymer

[0268] Additives: PVP, polyol plasticizer

[0269] Filler: CaCO3

[0270] Functionalization: None

[0271] Results: Co - extrusion produced a shaped article (1) with well - dispersed CaCO3 particles (4). The formed film achieved a relatively high retention rate and water flux.

[0272] 2. Scale: 20 kg

[0273] Polymer: PLA

[0274] Loading: 80 / 20 filler / polymer

[0275] Additives: PVP, polyol plasticizer

[0276] Filler: CaCO3

[0277] Functionalization: None

[0278] Results: Co - extrusion (1) produced a shaped article with well - dispersed CaCO3 particles (4). The film (2) was produced using a flat film extruder and was directly pressed between two non - woven fabrics (7). The formed loaded film (3)(7) exhibited high stability, flux, and particle retention rate.

Claims

1. A method for manufacturing a porous polymer membrane (3) for woven or non-woven textile materials, the method comprising the steps of: a) providing a shaped article (1) comprising a polymer matrix (5) and particles (4) dispersed within the matrix through a solvent-free process; b) converting the shaped article (1) into a non-porous polymer film (2) through a solvent-free process; c) removing the particles (4) from the film (2) by contacting the film with an aqueous composition (6), thereby obtaining the porous polymer membrane (3); characterized in that: ● The membrane (3) has: ● >1m 2 Area; ● A pore size of 0.005 μm to 15 μm; ● At least 4.8 m of water column (WC), measured according to ISO 811; ● WVTR of at least 500 g / m 2 / day, measured according to ASTM standard E96, and ● The shaped article (1) comprises a matrix (5) and particles (4) in a wt% ratio of 90:10 to 10:90, and ● The matrix (5) comprises a thermoplastic or thermosetting polymer (51) and optionally additives (52), ● The particles (4) are prefabricated; the particle size is 0.005 μm to 10 μm; selected from organic salts, metal salts, metal oxides; and coated with a coating (41), ● The coating (41) is selected from ● A hydrophobic coating; or ● A hydrophilic coating.

2. The method according to claim 1, wherein the membrane (3) ● Has a thickness of 5 to 200 microns; and / or ● Size > 100m 2 .

3. The method according to claim 1, wherein ● The polymer (51) is hydrophobic, and the particle (4) comprises a coating (41) selected from C6-C 24 carboxylic acids, C6-C 24 hydrocarbons and alkanes; or ● The polymer (51) is hydrophilic or hydrophobic, and the particles (4) comprise a coating (41) selected from polyol derivatives and PVP.

4. The method according to any one of claims 1-3, characterized in that ● The particles (4) ○ Consist of a salt and the coating (41) defined in claim 1, the salt being selected from carbonates, bicarbonates, sulfates, halides, nitrates and phosphates; or ○ Consist of an oxide and the coating (41) defined in claim 1, the oxide being selected from ZnO and MgO; and / or ● The polymer (51) ○ Is selected from thermoplastic polymers; or ○ Is selected from thermosetting polymers; ● The additive (52) is selected from fatty acids and C6-C 24 hydrocarbons, polyethylene glycols and glycerol; and / or ● The aqueous composition (6) is selected from ○ Water, ○ Water containing a pH regulator selected from weak bases, weak acids, strong bases, strong acids, buffers.

5. The method according to claim 1, characterized in that the porous polymer membrane (3) ● Has a porosity of 10 to 90%, determined by micrograph analysis; and / or ● The pore size is 0.2 μm to 4 μm in the case of a hydrophobic polymer or 5 nm to 500 nm in the case of a hydrophilic polymer; and / or ● Does not contain halogenated polymers; and / or ● Is biodegradable according to ISO 16929, ISO 20200 or ISO 14853.

6. The method according to claim 1, characterized in that: ● The step a) ○ Includes co-extruding the polymer (51) and particles (4) optionally blended with additives (52) to obtain a shaped article (1) in the form of pellets; and / or ○ grinding a polymer (51), optionally blended with an additive (52), and blending it with the particles (4) to obtain a shaped article (1) in powder form; and / or ○ preceded by a synthesis step d); and / or ○ carried out on the shaped article (1), wherein the wt% ratio of the polymer matrix (5) to the particles (4) is from 50:50 to 20:80; and / or ● said step b) ○ selected from film extrusion, calendering, injection molding, compression molding, blow molding, die coating, melt blowing; and / or ○ supplemented with a crosslinking step b1); and / or ○ supplemented with step b2): coating the film (2) onto a substrate (7); and / or ○ said step b) provides a film with a thickness of 5 to 200 microns; and / or ● said step c) ○ carried out for 90 minutes or less.

7. The method according to claim 1, characterized in that: ● the method does not include a phase separation step; and / or ● the method does not include a stretching step; and / or ● said steps a) to c) do not use organic solvents; and / or ● one or more of said steps a) to c) are carried out continuously.

8. The method according to claim 1, wherein said steps a) and b) are combined into a single step.

9. The method according to claim 1, wherein the particles (4) are coated particles, the particles: ● comprise a CaCO3 or NaCl core, and ● comprise the coating defined in claim 1; ● have an average core size of 0.005 to 10 microns; and / or ● have a coating (41) accounting for 0.1 to 10 wt% of the coated particles.

10. The method according to claim 1, wherein the hydrophobic coating is selected from C6-C 24 carboxylic acids, C 15 -C 40 alkanes, vegetable oils, polyesters and polyamides with a melting point of 50 to 70 °C, polymaleic anhydride derivatives of linear or branched C6-C 40 alkyl chain siloxanes, C6-C 24 alkyl-C1-C4 alkoxy-silanes; or the hydrophilic coating is selected from polyol derivatives, PVP and chitosan.

11. The method according to claim 4, wherein ● said particles (4) ○ consist of a salt and a coating (41), the salt being selected from carbonates, bicarbonates, sulfates, halides, nitrates and phosphates, and the coating (41) being selected from carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes; or ○ consist of an oxide and a coating (41), the oxide being selected from ZnO and MgO, the coating (41) being selected from carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes; and / or ● the thermoplastic polymer is selected from polyesters including PLA and PET, polyolefins including PE and PP, polystyrene, polyethers, polyamides including PCL, and polyurethanes; ● the thermosetting polymer is selected from polyesters, polyolefins including PP, polystyrene, polyethers, polyamides, polyurethanes, and they are crosslinked.

12. The method according to claim 7, wherein steps b) and c) are carried out continuously.

13. The method according to claim 9, wherein the coating (41) accounts for 1 to 4 wt% of the coated particles.

14. The method according to claim 4, wherein the pH regulator is HCl.

15. The method according to claim 8, wherein said steps b) and c) are carried out without the aid of a substrate.

16. A component for forming an article (1) for a porous polymer membrane (3) for a woven or non-woven textile material as defined in claim 1, wherein: ● Each said formed article comprises a polymer matrix (5) and particles (4) dispersed therein; and ● The matrix (5) comprises a thermoplastic or thermosetting polymer (51) and optionally additives (52), the thermoplastic polymers being selected from polyesters including PLA and PET, polyolefins including PE and PP, polystyrene, polyethers, polyamides including PCL, and polyurethanes, the thermosetting polymers being selected from polyesters, polyolefins including PP, polystyrene, polyethers, polyamides, polyurethanes, and being crosslinked as defined in claim 1 or 4; and ● The particles (4) are CaCO3 particles and the coating (41) contains C6-C 24 carboxylic acid; It is characterized in that ● The wt% ratio of matrix (5):particles (4) is from 90:10 to 10:90, and ● The coating (41) accounts for 0.1 to 10 wt% of the coated particles, ● The coated particles have an average core size of 5 to 10,000 nm.

17. The formed article component (1) according to claim 16, wherein the polymer (51) is hydrophobic.

18. A porous polymer membrane (3) for a woven or non-woven textile material obtained by the method according to any one of claims 1 - 15.

19. The membrane according to claim 18, wherein the membrane: ● The water column (WC) is at least 4.8 m, measured according to ISO 811; and ● WVTR is at least 500 g / m 2 / day, measured according to ASTM standard E96; and ● The thickness is 2 to 60 microns; and / or ● The orifice size is 5 nm to 2000 nm; and / or ● The porosity is 10 to 90%.

20. A porous polymer membrane (3) for a woven or non-woven textile material obtained by the method according to any one of claims 1 - 15, which comprises a polymer (51), in particular consists of a polymer (51), characterized in that: ● The polymer (51) ○ is a thermoplastic polymer, the thermoplastic polymers being selected from polyesters including PLA and PET, polyolefins including PE and PP, polystyrene, polyethers, polyamides including PCL, and polyurethanes; or ○ is a thermosetting polymer selected from polyester, polyolefins including PP, polystyrene, polyethers, polyamides, polyurethanes, and they are crosslinked; and ● Optionally the thickness of the membrane (3) is 2 to 60 microns; and ● Optionally the orifice size of the membrane (3) is 5 nm to 2000 nm; and ● Optionally the porosity of the membrane (3) is 10 to 90%; and wherein said film (3) has a WC of at least 4.8 m, as determined according to ISO 811, and a WVTR of at least 500 g / m 2 / day, as determined according to ASTM standard E96.

21. A woven or non-woven textile material (7) comprising a porous polymer membrane (3) according to any one of claims 18 - 20 and a fabric material, characterized in that the membrane (3) ● Is laminated to the fabric material, or ● Is self-supporting and is connected to the fabric material by gluing, welding, stitching and / or pressing.

22. The woven or non-woven textile material (7) according to claim 21, characterized in that the membrane ● Comprises a polymer biodegradable according to ISO 16929, ISO 20200, ISO 14853, EN 13432 or EN 14995, and ● Is connected / laminated to a biodegradable fabric with a biodegradable glue.

23. An article (8) selected from clothing, containers and filtration devices, said article comprising the textile material (7) according to claim 21 or 22, or the porous polymer membrane (3) according to claim 18 or 20.

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