Solvent-free membrane manufacturing process

Abstract

The present invention relates to a method for producing a porous polymer membrane by (a) providing pellets containing a polymer matrix and particles in a ratio of 90:10 to 10:90, (b) converting the pellets into a non-porous film by a solvent-free process, and (c) removing the particles from the film with an aqueous composition to thereby obtain a membrane. The present invention also relates to pellets useful in such a production process, porous polymeric membranes obtained by such a production process, and fibrous materials and molded articles containing such membranes, as well as uses of such pellets, membranes, and molded articles.

Description

[Technical Field]

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

[0002] The production of (porous) membranes is known per se. CN 102432946 describes the production of polyolefin membranes by extrusion of granular starting materials followed by longitudinal and transverse stretching. Obtaining a porous structure by stretching is often considered a disadvantageous process step. EP 3178873 describes the production of membranes starting from a polymer dispersion and removing the solvent, a process that avoids stretching. However, the use of solvents is also often considered a disadvantage. JP 2006287176 describes the production of membranes by removing plasticizers using organic solvents. Here too, the use of organic solvents is considered a disadvantage on a commercial scale. EP 0811479 describes the production of microporous polyolefin composite membranes. This production involves stretching and extraction steps using organic solvents and is therefore disadvantageous for the reasons mentioned above. US2011 / 0151259 describes the production of medical implants, specifically acetabular cups with pores between 100 and 1000 microns. These implants are manufactured starting from a polymer containing uncoated sodium chloride ("pharmaceutical grade") as a filler. For their intended use as implants, a fairly thick material and a small surface area are required. However, it has proven impossible to transfer this process to continuous production or large-scale membranes.

[0003] As a result, there is a need to provide additional / improved manufacturing processes for polymeric membranes, as well as additional / improved materials for making polymeric membranes and additional / improved textiles that include such membranes. Summary of the Invention

[0004] It is therefore an object of the present invention to alleviate at least some of these drawbacks of the prior art. In embodiments of the present invention, an improved manufacturing process for porous polymer membranes is provided. In further embodiments of the present invention, porous polymer membranes suitable for advanced applications such as in waterproof and breathable textile materials are provided. In further embodiments of the present invention, novel materials are provided that are suitable, for example, for carrying out the manufacturing methods of the present invention.

[0005] The present invention will be described in more detail below. It is understood that the various embodiments, preferences, and ranges provided / disclosed herein can be combined in some cases. Furthermore, depending on the specific embodiment, the selected definition, embodiment, or range may not be applicable. Furthermore, it is understood that all references identified herein are incorporated by reference in their entirety.

[0006] The above object is achieved by providing a manufacturing process as defined in claim 1. Further aspects of the invention are disclosed in the description and independent claims, and preferred embodiments are disclosed in the description and dependent claims. The manufacturing process for solvent-free hydrophobic or hydrophilic porous polymer membranes as described herein proves to be highly versatile, reliable, and simple to control. The process is particularly suitable for the fast, low-cost production of large-area membranes. The polymer membranes as described herein prove useful in applications as defined below and further enable the production of improved articles and / or facilitate the production of articles as defined below.

[0007] As will become apparent from reading this specification, the present invention relates in particular to polymeric membranes and corresponding methods for producing the membranes (a first aspect); to shaped articles suitable for producing such polymeric membranes (a second aspect); and to articles (including textiles, containers, filters) comprising (i.e. containing or consisting of) such polymeric membranes (a third aspect). [Brief explanation of the drawings]

[0008] Furthermore, the present invention will be better understood with reference to the drawings. [Figure 1] FIG. 1 is a schematic diagram of the process of the present invention, in which:

[0009] (1) represents a molded article ("pellet", second aspect of the invention). (2) represents non-porous film and intermediate material. (3) represents a porous polymer membrane of the present invention (unsupported; freestanding). (4) represents particles ("fillers"; including uncoated and coated particles). (5) represents the polymer matrix of the pellet. (51) represents a polymer (52) indicates an optional additive. (6) represents an aqueous composition (7) represents a fibrous material (fourth aspect of the invention). (8) represents an item (a commercial product, the fourth aspect of the invention); and (a)...(f), (f') indicate process steps (ie, the first aspect of the present invention).

[0010] In this specification, unless otherwise specified, definition applies.

[0011] The term "particle" is known in the art and includes crystalline or amorphous materials. This term includes uncoated and coated particles. Furthermore, in the context of the present invention, particles are also referred to as "fillers," thereby indicating their purpose. It is known that particles may aggregate. In the context of the present invention, suitable particles have diameters in the submicron size range, whereby the particle size is preferably between 5 and 10,000 nm, for example between 5 and 4,000 nm.

[0012] Suitable particles can be obtained from a variety of preparation methods, including high-temperature gas-phase processes (such as flame synthesis, laser processes, and plasma processes), and liquid-phase chemical methods (such as precipitation and sol-gel processes), as well as particle milling. Particularly suitable particles in the context of the present invention can be obtained by precipitation processes or by milling of naturally occurring materials. Particles in the context of the present invention are pre-manufactured, to distinguish them from in situ synthesis of particles.

[0013] The terms "salt" and "oxide" are known in the art. A salt is defined as a product formed from 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 salts include halides (chloride, fluoride, bromide, iodide), sulfates, phosphates, carbonates, and nitrates, particularly phosphates, carbonates, and halides. In the context of the present invention, metal oxides (i.e., products formed by the oxidation of a metal) are not considered salts. Metal oxides include stoichiometric and non-stoichiometric oxides. Examples of salts are NaCl and CaCO3, and an example of an oxide is ZnO.

[0014] The term "polymer" is known in the art. This term refers to a material of repeating structural units ("monomers"), in particular synthetic polymers (including synthetic monomers). Thus, this term includes homopolymers, copolymers, and blends thereof. This term also includes oligomers. Polymers may be crosslinked. Suitable polymers in the context of the present invention include thermoplastic and thermosetting polymers.

[0015] The terms "membrane" and "film" are known in the art. The term membrane refers to a shaped article in the form of a permeable membrane. Thus, membranes are distinguished from films by their permeability.

[0016] The "permeability" of a material described herein is defined as the flux of a fluid (i.e., a liquid or gaseous medium) through the interconnected pores of the material. Permeability is achieved by pores oriented perpendicular to the plane of the membrane. Permeability can be determined by measuring the volume of liquid or gas that passes through a defined membrane area under applied pressure in a defined time. It is generally measured in liters per square meter, atmosphere, and hour ([l / (m2 * bar * hour).

[0017] For gaseous media, the water vapor transmission rate (WVTR) is a suitable parameter for determining water permeability. WVTR is measured in grams per square meter per day (g / (m)), in accordance with ASTM standard E96, as further defined in the Examples section below. 2* d)) (also known as the upright cup method). Briefly, it is a cup of water in which the test specimen is covered. The specimen thus prepared is weighed before being placed in an oven controlled for temperature (23°C), relative humidity (50% RH), and ventilation (1 m / s). Two phenomena contribute to the transport of vapors through porous membranes: solid-state diffusion (a small effect) and pore diffusion (the primary means of transport). In non-porous (or dense, defect-free) layers, only solid-state diffusion occurs. Solid-state diffusion can be explained in the following terms according to EL Cussler (Cussler, EL Diffusion. (Cambridge University Press, 1997, p. 21)):

number

[0018] j = grams / square meter·day (g / (m 2 Let D be the outflow from the covered cup in square meters per second (m 2 / sec), H is the distribution coefficient (dimensionless) for the solubility of water molecules in the membrane material, and c is the diffusion coefficient of water molecules in the membrane material. in and c out to moles per cubic meter (mol / m 3 ) is the concentration of water molecules inside and outside the cup. In porous media, water molecules diffuse freely through the pores and this is described by a flux with a corrected diffusion coefficient:

number

[0019] where ε is the void fraction of the porous membrane (a dimensionless number between 0 and 1), and τ is the tortuosity of the porous system (a dimensionless number between 0 and 1). In small pores, diffusion based on molecular interactions is limited because water molecules interact not only with themselves but also more frequently with the pore walls. The mean free diameter in air is about 60 nm, and Knudsen diffusion occurs in small diameter pores, with the diffusion coefficient scaled as follows: 1 :

number

[0020] where d is the pore diameter (meters), k B is Boltzmann's constant (joules / kelvin), T is the temperature (kelvin), and m is the mass of the particle (grams).

[0021] For liquid media, waterproofness is a relevant parameter. In determining waterproofness, the relevant driving force is pressure. The water column (WC) in metres (m) is determined according to ISO 811. Briefly, water is forced onto the sample over time with a constant pressure increase (600 mmWC per minute). The dry surface of the sample is observed optically, and the third penetrating drop is defined as the sample break, the pressure of which represents the water column (WC). A theoretical approximation can be made by the Hagen-Poiseuille equation:

number

[0022] Using the pressure difference (Δp (bar)), V is the volumetric flow rate in cubic metres per second (m 3 / s), η is bar times seconds (bar * s), t is the layer thickness (m), A is square meters (m 2 ) is the layer area, φ is the areal porosity as a dimensionless number with values ​​between 0 and 1, and pore diameter (d) is in meters (m) (Kellenberger et al. J. Membr. Sci. 387-388, 76-82 (2012)).

[0023] The "porosity" of a material described herein is the volume percentage of pores in the total material. Porosity can be determined by porosimetry, measurement of apparent material density, BET analysis, or microscopic imaging. Preferably, porosity is determined by micrograph analysis. In the context of the present invention, a membrane or film is considered "porous" if it has a porosity of 10-90%, preferably 50-90%, e.g., 55-60%, and "non-porous" if it has a porosity of less than 10%, preferably less than 5%. Pore diameters may vary widely, typically within the range of 5 nm to 2,000 nm.

[0024] "Specific surface area" is a known parameter and can be determined by nitrogen adsorption 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 for the calculation of the surface area of ​​a solid by physical adsorption of gas molecules (e.g., nitrogen molecules).

[0025] In general terms, the present invention provides First aspect The present invention relates to a method for producing a porous polymer membrane (3) having a pore size of 5 nm to 15,000 nm, the method comprising the steps of: (a) first providing a molded article (1) comprising a polymer matrix (5) and particles (4) by a solventless process; (b) subsequently converting the molded article (1) into a non-porous polymer film (2) by a solventless process; and (c) contacting the film with an aqueous composition (6) to remove the particles (4) from the film (2), thereby obtaining a porous polymer membrane (3). This process is shown in Figure 1 and further described below.

[0026] The use of solvent-free process steps is believed to provide a significant improvement over known processes for preparing porous polymer membranes. Specifically, the process of the present invention does not require organic solvents, thereby positively impacting the ecological balance sheet and cost considerations. The method for producing porous membranes of the present invention has proven to be highly versatile, reliable, and easy to control. It is particularly suitable for producing large-area membranes at high speed and low cost.

[0027] In a further embodiment, the present invention provides a process for producing a porous polymer membrane (3) without using a stretching / orientation step. Such stretching is limited to certain polymers and is typically applied to foils to obtain membranes. Such additional steps are difficult to control and therefore disadvantageous for commercial production. Therefore, the present invention also provides a method as described herein that does not involve a stretching step.

[0028] This aspect of the invention will be described in further detail below, first describing the process steps, followed by a description of the starting materials and particularly preferred embodiments.

[0029] Process steps: The manufacturing process as described herein is believed to be advantageous because the individual steps are known in the industry and are already in commercial use. Furthermore, the described process is very fast and can be carried out in a continuous process.

[0030] Step a: The production of pellets (1) comprising a polymer matrix, optional additives and fillers is known per se.

[0031] In an embodiment, step (a) comprises co-extrusion of a polymer (51), optionally blended with additives (52), and particles (4). In an embodiment, step (a) is preceded by a synthesis step (d). In such a synthesis step, the polymer may be formed or blended with an additive (51) (step d1) and / or the particles (4) may be coated with a coating material (41) (step d2). Such additional synthesis steps (d) are known per se and may be carried out in the presence or absence of a solvent. In an embodiment, step (d2) is solvent-free. In an embodiment, the step (a) is carried out using the molded article (1) in which the ratio of the polymer matrix (5) to the particles (4) is 10:90 to 90:10, preferably 50:50 to 20:80 (matrix:particles, wt %), and the particles (4) are dispersed in the matrix (5).

[0032] Step b: The conversion of extrusions / pellets (1) into non-porous films is known per se and has been applied on a commercial scale. In an embodiment, the step (b) is selected from film extrusion, calendering, injection molding, compression molding, blow molding, mold coating, and melt blowing. In a preferred embodiment, the step (b) is selected from film extrusion and calendering, which are particularly suitable for large-area membranes.

[0033] In an embodiment, said step (b) is complemented by a cross-linking step (step b1).

[0034] In an embodiment, said step (b) is complemented by coating a film (2) on a substrate (7) (step b2).

[0035] In an embodiment, step (b) provides a membrane having a thickness of 5 to 200 μm, preferably 30 to 80 μm. In an embodiment, step (b) provides a membrane having a thickness of 0.01 μm to 1000 μm, preferably 2 μm to 60 μm.

[0036] Step c: The continuous salt / oxide phase in such a nanocomposite membrane is dissolved to give a nanoporous polymer membrane (porous polymer membrane (3)). This individual process is known and is described, for example, in EP 3178873. Without being bound by theory, it is believed that the coating material, if present, remains within the polymer structure and is located on the surface of the pores. Aqueous solvents are suitable, such as water or aqueous acid solutions (e.g., acetic acid or hydrochloric acid). The choice of solvent depends, inter alia, on the type of particles (metal salt / metal oxide) used. In an embodiment, step (c) is carried out for 90 minutes or less, for example 5 minutes. The dissolution step (c) is a critical element of the manufacturing process and is considered to be a key element for obtaining the porous polymer membrane (3) of the present invention. In a further embodiment, process step (c) may be repeated. This procedure ensures complete removal of particles (4). Process step (c) therefore also includes multiple washings and dryings. When a multi-step protocol is used, either the same or different aqueous compositions may be used, for example, first using a dilute aqueous acid, followed by water.

[0037] General process characteristics: In embodiments, the method of the present invention does not involve a phase separation step. Such phase separation is limited to specific polymers, and the corresponding pore formation is highly sensitive to various process parameters (e.g., temperature, humidity, time) that must simultaneously be carefully controlled. Such a process is clearly disadvantageous for high-speed, large-scale commercial manufacturing. Therefore, the present invention also provides a method as described herein that does not involve a phase separation step. In the context of the present invention, the phase separation step is considered a separate step in the manufacturing process that requires specific equipment. It should also be noted that phase inversion is observed only for a limited number of polymer / polymer combinations. The present invention is not limited to such specific polymers or combinations and is therefore considered to be much more versatile.

[0038] In an embodiment, no organic solvent is used in the steps a) to c).

[0039] In an embodiment, steps b) and c) are carried out without the aid of a substrate.Therefore, it is possible to directly obtain the film (2) and the membrane (3) of the present invention without the need to provide and remove a support material.Such a direct approach is advantageous compared to the known methods mentioned above.

[0040] In an embodiment, steps a) and b) are combined into one single step. In such an embodiment, the co-mixing step is omitted. Rather, the polymer matrix (5) and particles (4) are directly mixed in a suitable device, such as a film extruder. This embodiment is considered advantageous for coated particles. This embodiment is also considered advantageous for polymers with good flowability, typically indicated by a low melting point of the polymer. Thus, particles (4) including a coating (41) are combined with a thermosetting polymer (51), such as PCL, and optional additives (52), and then fed to the inlet of a film extruder. In this embodiment, the separate preparation of a molded article (1) can be avoided. Rather, the starting material is directly converted into a non-porous polymer film (2). This embodiment is particularly advantageous because it requires only one manufacturing step, thus simplifying large-scale production.

[0041] In a further embodiment, the present invention provides a method as described herein, wherein one or more of steps b) and c), preferably steps a) through c), more preferably all steps, are adapted for a continuous process. Such continuous processes may be film extrusion, calendaring, injection molding, compression molding, blow molding, mold coating, or melt-blowing. These processes also allow for the production of multilayer materials, including the porous membrane of the present invention as one of the layers. Such multilayer materials may have thicknesses on the order of 1 mm or even greater. Such multilayer materials can, of course, be more functionally complex than monolayer materials. This can be advantageous in many applications, both woven and nonwoven.

[0042] The described manufacturing process provides porous polymeric membranes of virtually unlimited size. Because the manufacturing process imposes no limitations on the size of the material (except for the equipment used), large sheets of material can be obtained in terms of length and width. Thus, the present invention provides a method for manufacturing porous polymeric membranes of 100 cm 2 More than 1000 cm 2 More than 1 m, most preferably 2The process as disclosed herein also provides for areas greater than 100 m when using roll-to-roll equipment. 2 Porous polymer membranes having an area of ​​1000 to 1500 m or larger can be prepared at one time. In an embodiment, the membranes of the present invention are 1.4-1.6 m wide and 500-1000 m long per roll.

[0043] Starting materials: The processes described herein are considered advantageous because the individual starting materials are commercially available or can be obtained according to known methods.

[0044] Particle (4): The particles described herein are also known in the art as "fillers" or "pore-forming agents." The particles may be uncoated or coated, as described below. The present invention contemplates using one type of particle (e.g., unimodal size and / or same material) or two or more types of particles (e.g., bimodal size distribution, different materials, coated and uncoated). Preferably, the particles (4) are pre-manufactured. Pre-manufactured means that the particles are not formed in situ during process step (a). Typically, the uncoated particles (4) are obtained from a supplier in the required quality. The coated particles (4) may be obtained from a supplier or may be coated according to known methods by combining the coating material (41) with the particles (4), optionally in the presence of a diluent.

[0045] Suitably, the particles (4) have a particle size in the range of 5 to 10,000 nm, preferably 5 to 4,000 nm. Preferably, the particles (4) are selected from the group consisting of organic salts, metal salts, and metal oxides, and are optionally coated with a coating (41). As is clear from the above, preferred particles (4) are soluble in aqueous media, e.g., have a solubility of at least 1 g at pH 1-14 / 20°C, preferably at least 10 g at pH 1-14 / 20°C.

[0046] In one embodiment, the particles (4) comprise a salt selected from the group consisting of carbonates, bicarbonates, sulfates, halides, nitrates, and phosphates, hi one embodiment, the particles (4) comprise an oxide selected from the group consisting of ZnO and MgO. In one embodiment, the particles (4) are comprised of a salt selected from the group consisting of carbonates, bicarbonates, sulfates, halides, nitrates, and phosphates, and a coating material (41) selected from the group consisting of carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes, and alkyl-alkoxy-silanes. In one embodiment, the particles (4) are comprised of an oxide selected from the group consisting of ZnO and MgO, and a coating material (41) selected from the group consisting of carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxysilanes, and alkylalkoxysilanes.

[0047] A particularly preferred class of particles is CaCO3 particles. Typically, CaCO3 particles are obtained by a precipitation process or by extraction from mines and ground to the desired size. A particularly preferred class of particles is NaCl. Typically, NaCl particles are obtained by evaporation of brine or by mining rock salt and then crushed to the desired size. Flame synthesis is an alternative route to obtain the particles defined herein.

[0048] Coating(41): As noted above, the particles may be coated or uncoated. Suitable coating materials (41) can be selected from hydrophobic or hydrophilic materials. Such materials are commercially available or can be prepared according to known methods; they are selected to improve compatibility with the polymer (51). Coatings (41) have been found to beneficially affect membrane fabrication and membrane properties.

[0049] Hydrophobic coating materials are suitable, for example, when water repellency is a relevant membrane property, such as membranes for clothing. Suitable hydrophobic coating materials may be selected from the group consisting of: C6-C24 carboxylic acids, preferably C6-C24 monocarboxylic acids, including saturated and unsaturated fatty acids, particularly preferably stearic acid; C15-C40 alkanes, preferably paraffin oil, paraffin wax; ● vegetable oil, preferably castor oil; polyester or polyamide, preferably polycaprolactone, having an MP of 50 to 70 ° C; and Poly(maleic anhydride) derivatives with linear or branched C6-C40 alkyl chains, preferably poly(maleic anhydride-alt-1-octadecene); and Siloxanes in the form of nanoparticles or filaments; and • C6-C24 alkyl-C1-C4 alkoxy-silanes, preferably C6-C24 alkyl-methoxy-silanes. Hydrophilic coating materials are suitable for preparing membrane filters. Suitable hydrophilic coating materials can be selected from the group consisting of: Polyol derivatives, preferably propane-1,2,3-triol, polyethylene glycol (Mn=200-50,000), polyethylene oxide (Mw=100,000-100,000) and polypropylene glycol; Polyvinylpyrrolidone (Mw=50,000~1,000,000); and ●Chitosan.

[0050] A particularly suitable class of coating materials are polyol derivatives such as glycerin and C6-C24 monocarboxylic acids such as stearic acid, and paraffins. Preferably, the coated particles have an average core size of 5 to 10,000 nm, and the coating is present in an amount of 0.1 to 10 wt %, preferably 1 to 4 wt %, of the coated particles. It has been found that such coatings enable the production of large membranes with high WVTR and high WC. Until now, it has not been possible to produce membranes on a commercial scale based on solventless processes and obtain membranes of virtually unlimited size that meet WVTR and WC requirements.

[0051] In an embodiment, the particles are uncoated particles selected from the group consisting of CaCO3 (preferably having a particle size of 0.3 to 10 μm, e.g., 0.5 to 6 μm), NaCl (preferably having a particle size of 0.3 to 10 μm, e.g., 0.5 to 6 μm), and ZnO (preferably having a particle size of 0.005 to 2 μm, e.g., 0.05 to 1 μm).

[0052] In an embodiment, the particles are coated particles, which comprise a CaCO3 core and a coating (the coating preferably comprises linear or branched bulky organic molecules selected from the group consisting of C6-C24 carboxylic acids, C6-C24 hydrocarbons, short-chain polymers, amphiphilic surfactants, alkylsilane derivatives, and polyol derivatives, particularly preferably polyol derivatives); the coated particles have an average core size of 5-10,000 nm and the coating weighs 0.1-10 wt% (preferably 1-4 wt%) of the coated particle.

[0053] In an embodiment, the particles are coated particles, which comprise a NaCl core and a coating (the coating preferably comprises linear or branched bulky organic molecules selected from the group consisting of C6-C24 carboxylic acids, C6-C24 hydrocarbons, short-chain polymers, amphoteric surfactants, alkylsilane derivatives, and polyol derivatives, particularly preferably polyol derivatives); the coated particles have an average core size of 5-10,000 nm and the coating weighs 0.1-10 wt% (preferably 1-4 wt%) of the coated particle.

[0054] The coated particles are prepared prior to step (a) in a separate process, as outlined above. Thus, the present invention relates to methods described herein, wherein the particles are not prepared in situ, i.e., are pre-manufactured.

[0055] Polymer (51): The term polymer is known in the art and includes homopolymers, copolymers, and blends of polymers. Suitable polymers are selected from the classes of thermoplastic and thermoset polymers. Thermoplastic polymers are polymers that are flexible and moldable at a certain temperature and solidify upon cooling, a process that is reversible. Such polymers include polyesters (including PCL, PLA, and PET), polyolefins (PE, PP, etc.), polystyrene, polyethers, polyamides, and polyurethanes. Polycaprolactone (PCL), polyurethane (TPU), and polylactic acid (PLA) are preferred polymers.

[0056] Thermosetting polymers are polymers that can be melted and cured only once. Typically, such thermosetting polymers are crosslinked. Thus, thermosetting polymers include the class of polymers as defined above that are crosslinked.

[0057] Additives (52): Additives are widely known in the field of polymer chemistry. They are used to improve product quality and / or processing characteristics. Suitable additives can be selected from a wide range of known additives and mixtures thereof and are well known in the art. The term additives includes film flow agents, film uniformity agents, anti-orange peel agents, and humectants. Such additives are commercially available from, for example, Byk Additives and Instruments, Evonik Industries, and CRODA International, and include compounds selected from the group consisting of fatty acids, C6-C24 hydrocarbons, polyethylene glycol, and glycerin.

[0058] Aqueous composition (6): The solvent (6) is selected to ensure dissolution of the particles / coated particles without dissolving the polymer. It is surprising that not only uncoated particles but also coated particles as discussed herein can be readily dissolved in aqueous solution.

[0059] Molded products (1): The molded articles described in the context of step (a) are also known in the art as "pellets" or "powders." Typical size ranges for pellets are 0.5-5 cm, and for powders are between 0.1 mm and 5 mm or less. Powders can be obtained by grinding polymer (5) and co-blending particles (1), thereby obtaining such molded articles (1) in powder form. A suitable article (1) comprises a matrix (5) and particles (4) dispersed within the matrix in a ratio of 90:10 to 10:90 (matrix:particles, wt%), preferably 50:50 to 10:90 (wt%). This is believed to result in a higher particle loading within the pellet compared to conventional methods. The matrix comprises a polymer (51) and optionally an additive (52). In one embodiment, the matrix comprises a polymer (51). In a further embodiment, the matrix (5) comprises a polymer (51) and one or more additives (52).

[0060] Porous polymer membrane (3): It is clear that a wide range of porous polymeric membranes can be obtained using the process of the present invention.

[0061] By appropriate selection of particles (such as size, coating material and amount) and process parameters (such as extrusion parameters), the porosity and pore size distribution can be varied over a wide range. Thus, the present invention also provides a process as disclosed herein, wherein the porous polymer membrane (3) complies with one or more of the following: Thickness: The membranes (3) obtained according to the process of the present invention exhibit thicknesses that vary over a wide range and depend on their intended use. Suitable values ​​are 0.01 μm to 1000 μm, preferably 2 μm to 60 μm for single-layer membranes and up to 180 μm for triple-layer membranes. For specific applications, very thin or very thick membranes, such as those between 0.01 μm and 1000 μm, can also be produced. At these extremes, the performance of WC and WVTR is not the same. Thick membranes (several hundred μm or more) are particularly suitable for use in multilayer configurations. Porosity: 10 to 90%, preferably 50 to 90%, for example, 55 to 60% is appropriate. Pore ​​size: In the case of hydrophobic polymers, 5 nm to 15,000 nm is appropriate; preferably 200 nm to 4,000 nm; in the case of hydrophilic polymers, 5 nm to 500 nm is appropriate. Water column (WC): 4.8 m or more, preferably 9 m or more, and particularly preferably 18 m or more. ●Water vapor transmission rate (WVTR): 500 g / m2 / day or more, preferably 700 g / m2 / day or more. Water contact angle: suitably a value of at least 50°, preferably at least 95°, which indicates the hydrophobicity of the polymer membrane (3). ●Stress: Measured values ​​are around 3 to 5 MPa for porous samples, and around 7 to 10 MPa when porosity is included.

[0062] As can be seen, the process of the present invention allows for the production of membranes with very high porosity. Such high porosity is advantageous for high water vapor transport rates and can also provide significant thermal insulation. Both are clearly advantageous in textile applications, in buildings, and when used in multiple layers.

[0063] Furthermore, by appropriate selection of polymers (51) and additives (52), a wide range of membranes can be obtained, in particular: The membrane (3) does not contain halogenated polymers, and / or The membrane (3) is made of a biodegradable polymer according to ISO 16929 and ISO 20200 (disintegration test methods for industrial composting), ISO 14853 and EN 14995 (anaerobic digestion environments) or EN 13432 (composting and biodegradation), which usually involve measuring CO2 emissions. Again, applicability to a wide range of polymeric materials is a clear advantage.

[0064] Certain combinations of materials have been found to be particularly suitable. In an embodiment, the polymer (51) is hydrophilic and the particles (4) are coated or uncoated, preferably uncoated.

[0065] In an embodiment, the polymer (51) is hydrophobic and the particles (4) are coated or uncoated, preferably the particles (4) include a coating (41). In an embodiment, the polymer (51) is hydrophobic and the particles (4) are coated with a C6-C24 carboxylic acid as defined above, preferably stearic acid, providing a membrane (3) with hydrophobic properties. In an embodiment, the polymer (51) is hydrophobic and the particles (4) are coated, the coating being selected from C6-C24 hydrocarbons and paraffins, preferably paraffins, providing a membrane (3) with hydrophobic properties. In an embodiment, the polymer (51) is hydrophilic or hydrophobic and the particles (4) are coated, the coating being selected from the polyol derivatives defined above, preferably glycerol coatings, providing a membrane (3) with hydrophilic properties. In an embodiment, the polymer (51) is hydrophilic or hydrophobic and the particles (4) are coated, the coating being selected from PVP as defined above. This embodiment provides the membrane (3) with hydrophilic properties.

[0066] The present invention provides Second aspect The present invention relates to a molded article (1). Such articles, especially in the form of pellets or powder, are useful starting materials for the manufacturing process described herein. Such articles can be used according to step (a) above, especially by coextrusion or cocompounding. This aspect of the invention will be explained in more detail below.

[0067] In an embodiment, the present invention provides an assembly of molded articles (1) ("pellets" or "powder"), each of which comprises a polymer matrix (5) and particles (4) dispersed therein; the matrix (5) comprises a thermoplastic or thermosetting polymer (51) as defined herein (particularly in the first aspect and claims) and optionally an additive (52); and the particles (4) are as defined herein (particularly in the first aspect and claims), characterized in that the ratio matrix (5):particles (4) is 1:1 to 1:9 (wt%). These molded articles are suitable as starting materials for the method of the present invention. The amount of particles (4) ("filler") in the molded article (1) ("pellets", "powder") is relatively high.

[0068] In an embodiment, the molded article comprises a polymer (51) that is hydrophilic and uncoated particles (4).

[0069] In an embodiment, the molded article comprises a polymer (51) that is hydrophobic and particles (4) that make up the coating (41).

[0070] In an embodiment, the pellets are 0.5 to 5 cm in size and / or the powder has an average particle size of 0.1 mm to less than 5 mm.

[0071] In an embodiment, the present invention provides the use of a shaped article (1) as described in this aspect of the invention in a method as described in the first aspect of the invention.

[0072] In an embodiment, the present invention provides the use of a shaped article (1) as described in this aspect of the invention for producing a membrane (3) according to the third aspect of the invention.

[0073] In a broad sense, any (coated or uncoated) salt or metal oxide particle can be used, and preferred classes of particles and coating materials are disclosed above in the first aspect of the invention. The preparation of suitable coated particles (4) is known in the art. It has been found advantageous to use pre-prepared coated particles.

[0074] The additives (52) can be selected from the group consisting of, for example, surfactants, polymerization initiators, stabilizers, crosslinkers, and wetting agents, as described above.

[0075] The present invention provides The third aspect This aspect, particularly advantageous polymers and properties of the membranes of the invention are outlined below.

[0076] In an embodiment, the present invention provides a porous polymeric membrane (3) obtainable by or obtainable by a process according to the first aspect of the present invention, said membrane complying with all properties (i) to (iii) and optionally one, two or three properties (iv) to (vi): (i) The water column (WC) must be at least 4.8 m. (ii) Daily WVTR is 500 g / m2 or more. (iii) Flux is at least 1 L * m-2 * It must be h-1. (iv) It has a thickness of 0.01 μm to 1,000 μm, preferably 10 μm to 100 μm. (v) Pore diameters of 5 nm to 2,000 nm. (vi) Porosity is 10 to 90%.

[0077] In an embodiment, the present invention provides a porous polymeric membrane (3) comprising, in particular, a polymer (51), said membrane meeting all of the properties (i) to (v) and (vii), and optionally (vi): (i) The water column (WC) must be at least 4.8 m. (ii) Daily WVTR is 500 g / m2 or more. (iii) Flux is at least 1 L * m-2 * It must be h-1. (iv) It has a thickness of 0.01 μm to 1000 μm, preferably 10 μm to 100 μm. (v) Pore diameter: 5 nm to 2,000 nm. (vi) Porosity is 10 to 90%. (vii) Polymer (51) is selected from the group of thermoplastic polymers as defined herein (especially the first aspect of the invention and claims), or is selected from the group of thermosetting polymers as defined herein (especially the first aspect of the invention and claims).

[0078] film: In one embodiment, the present invention relates to a polymeric membrane, as described above for the first aspect of the present invention, having (i) thickness and / or (ii) porosity; and / or (iii) pore size; and / or (iv) tensile properties and / or water column; and / or (v) water vapor transmission rate; and / or (vi) water contact angle. Due to the unique manufacturing process outlined herein, the present invention provides porous (or even nanoporous) membranes that combine specific properties for organic polymers. Depending on the specific application of the membrane of the present invention, it may be advantageous to be able to adjust the above parameters.

[0079] In one embodiment, the membrane of the present invention may consist of one single layer, which is advantageous for jackets and outdoor garments, architectural house wraps (to manage water and vapor within buildings), packaging materials (e.g., for food, consumer goods, and pharmaceuticals), agricultural tarps, and sensors.

[0080] In a further embodiment, the membrane of the present invention may consist of two or more layers, such as two or three layers. This embodiment has advantageous applications in outdoor clothing (thereby providing improved comfort through better sweat management, particularly by transporting sweat in the jacket layer from less accessible to more accessible areas of the garment), cooling textiles (i.e., materials that provide a cooling effect to the user through the evaporation of water from the multilayer material), packaging for biological products, packaging for food, medicines, and sensitive consumer goods, cooling curtains (allowing passive cooling around buildings and public transport), and air humidification in air conditioning units. Further applications include flexible gas absorbers, air purifiers, and personal hygiene and protective equipment.

[0081] polymer: As outlined above, a wide variety of polymers can be used in the membranes of the invention, hi one embodiment, the polymer is selected from the group of polymers described in the first aspect of the invention above.

[0082] Advantageously, such polymers are halogen-free, and in particular fluorine-free, which is considered advantageous as the membranes are environmentally benign. Advantageously, such polymers are biodegradable, which is considered advantageous because the membranes are environmentally friendly, which is desirable in certain industrial applications. Polylactic acid (PLA) is a preferred polymer. In a further embodiment, polycaprolactam (PCL) is the preferred polymer.

[0083] pore: As outlined above, the materials of the present invention are porous. They are characterized by the size, type, and amount of pores present. The size, type, and amount of pores can be influenced by the type of coating, the amount of coating material, the starting material, the particle:polymer ratio, the manufacturing process, and the type of coating material. The pore size (defined as the diameter of the coated particles) of the membrane of the present invention is in the nanoscale 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 microscopic observation. Furthermore, the pore size distribution can be precisely adjusted depending on the starting material used. The porosity, i.e., the volume of pores relative to the total volume of the membrane, can vary within wide limits. The inventive material exhibits a porosity in the range of 10-90 vol-%, preferably 20-90 vol-%, highly preferably 50-90 vol-%, for example 55-60 vol-%. The porosity can be determined by photomicrographic analysis. The pores of a material may be arranged so that the material is permeable, partially permeable, or impermeable. The pores are primarily perpendicular to the plane of the membrane. If essentially all of the pores of a material have dead ends, the material is impermeable. Conversely, if essentially all of the pores are open-ended, the material is considered permeable. Consequently, if some of the pores have dead ends, the material is considered partially permeable. In an advantageous embodiment, the present invention provides a polymer membrane in which at least 50%, preferably at least 80%, of the pores are interconnected.

[0084] Thickness: The thickness of the membrane of the present invention may vary over a wide range, for example, from 0.01 μm to 1,000 μm. When the membrane of the present invention is in the form of a single layer, the preferred thickness is in the range of 0.01 to 1,000 μm, preferably 1 to 500 μm, and most preferably 20 to 60 μm. When the membrane of the present invention is in the form of a multilayer structure, the preferred thickness is in the range of 1 μm to 1,000 μm; preferably 30 to 250 μm. Such membranes may also be referred to as "sheet materials" or "porous foils"; these terms indicate that the material has a length and width that are at least one-fold greater (preferably at least two-fold greater) than the thickness of the material.

[0085] Waterproof: The waterproofness (measured as WC) and moisture permeability (measured as WVTR) of the membranes of the present invention are described above in the first aspect of the present invention.

[0086] Mechanical properties: The mechanical properties of the membranes of the present invention, such as tensile strength and flexibility, make them suitable for many applications, such as the first aspect of the present invention, textile applications, as discussed above.

[0087] The present invention provides The fourth aspectThe present invention relates to textile materials and articles comprising a porous polymeric membrane (3) as described herein. In many cases, the membrane (3) will not be a commercial product, but rather an important intermediate for such a commercial product. A wide variety of commercial products, including textile materials and articles, may comprise the porous polymeric membrane (3) of the present invention. This aspect of the invention is described in more detail below.

[0088] Fiber material: In an embodiment, the present invention relates to a woven or nonwoven textile material (7) comprising a polymeric membrane as described herein (the third aspect of the present invention). The membrane is laminated onto the textile or the membrane is self-supportingly connected to the textile membrane, for example by gluing, welding, sewing and / or pressing. Advantageously, the membrane of the present invention (3) can be easily adapted to existing manufacturing equipment, such as those used in the textile industry.

[0089] Commercially available: The present invention further provides an item (8) selected in particular from the group of clothing (coats, jackets, trousers, underwear, etc.); and containers (bags, backpacks, etc.); and separation devices (particularly filter devices, water filters, etc.), said item comprising the above-mentioned woven or nonwoven material (7) or the polymer membrane (3) discussed in the third aspect of the invention.

[0090] Garments containing the membranes of the present invention meet customer expectations, particularly with regard to performance in WC and WVTR. Such textiles contain fluorine-free and, optionally, silicone-free materials. Therefore, the products can be disposed of in environmentally friendly ways, such as non-hazardous incineration. Furthermore, the biodegradable chemical composition of such garments can be ensured. This technology is more versatile and environmentally friendly than existing processes, particularly due to the solvent-free process steps and the option for hydrophilic and hydrophobic membranes.

[0091] The membranes of the present invention are self-supporting ("free-standing"). Therefore, they are distinguishable from known membranes of similar thickness and porosity on a support. However, the materials of the present invention are suitable for coating any suitable support. The ability to manufacture such membranes independently of a specific support makes them highly versatile. In an embodiment, the membranes of the present invention are applied to a substrate. Suitable substrates can be selected from a wide range of known substrates. The substrate may also be a support compatible with the manufacturing process. It would be even more beneficial if the membranes (3) and films (2) could be attached to the substrate during manufacturing and removed afterward. Suitable substrate materials include polymeric materials, glass, metals (such as aluminum), ceramics, and paper (whether coated or uncoated). In textile manufacturing, it may be advantageous to coat the films described herein directly onto tightly woven fabrics. In this embodiment, it is advantageous if the polymer matrix adheres well to the type of polymer or biopolymer used in the textile substrate. For outdoor clothing, suitable substrates are tightly woven polyamides, polyolefins, or polyesters. The present invention further relates to uses / methods of use of the films, textiles and intermediates described herein.

[0092] To further illustrate the present invention, the following example These examples are not intended to limit the scope of the invention.

[0093] I. General Procedure below Small-scale experiments The general procedure is as follows: 1. Preparation of molded particles (1) by co-extrusion of particles (4) and polymer pellets (5). 2. Production of non-porous film (2) by heat pressing. Circular samples with a diameter of approximately 10 cm and a thickness of 70 to 150 microns were obtained. 3. Manufacture of porous membrane (3) by washing non-porous membrane (2) in aqueous bath (6).

[0094] Larger scale experiments The general procedure is similar, but a film extruder is employed instead of a press, resulting in samples over 100 m long, 20-30 cm wide, and 20-500 microns thick.

[0095] General Analysis procedure is as follows: • The film thickness is determined by magnetic induction processing and analysis of SEM micrographs. ●The water column of the obtained membrane is measured in accordance with the aforementioned ISO811. The moisture permeability / WVTR of the obtained membrane was measured in accordance with the aforementioned ASTM E96. The LMH of a given membrane is determined by measuring the volume of liquid passing through a defined membrane area at a defined pressure in a defined time. LMH is expressed in liters per square meter, per atmosphere, per hour ([l / (m2 * bar * hour). The retention of the resulting membrane is determined by measuring the concentration of fluorescent nanoparticles (50-250 nm) before filtration (feed solution) and after filtration (permeate). It is calculated using the following formula:

number

[0096] II. Hydrophobic membrane test example A. Small scale: 1. Scale: 35g for each weight and each additive. Polymer: Polylactic acid (PLA). Loading: 60 / 40, 70 / 30, 80 / 20 filler / polymer. Additives: TBC, castor oil, paraffin wax (added in three portions, 19 wt%, 27 wt%, 38 wt%) (relative to polymer). Filler: Calcium carbonate. Functionalization: 4% stearic acid. Results: Co-extrusion yielded molded articles (1). All membranes (3) exhibited relatively high breathability (the higher the filler loading, the higher the breathability), but some were more hydrophobic than others.

[0097] 2. Scale: 35g for each weight and type of additive. Polymer: Polyester. Loading: 60 / 40, 70 / 30, 80 / 20 filler / polymer. Additives: TBC, castor oil, paraffin wax (three different amounts of each: 19wt%, 27wt%, 38wt%, based on polymer). Filler: Calcium carbonate. Functionalization: 4% stearic acid. Results: Co-extrusion yielded molded articles (1). All membranes (3) exhibited relatively high breathability (the higher the filler loading, the higher the breathability), but some were more hydrophobic than others.

[0098] 3. Scale: 5g of each polymer Polymers: Polyester (PE), PLA, Polycaprolactam (PCL), Polyamide (PA), Polytrimethylene terephthalate (PTT), Polypropylene (PP). Loading: 60 / 40, 67 / 33, 70 / 30, 80 / 20 filler / polymer. Additive: Tributyl citrate (for PE only). Filler: Calcium carbonate. Functionalization: 4% stearic acid. Results: See Table 1.

[0099] [Table 1]

[0100] Without being bound by theory, it is believed that the addition of plasticizer (52) improves the flowability of otherwise brittle polymers, thus facilitating the extrusion process.

[0101] 4.Scale: 5g. Polymer: PLA. Loading: 60 / 40 filler / polymer. Additives: None. Filler: NaCl. Functionalization: None. Results: Coextrusion resulted in a molded part (1). The rough surface of the pellets (1) and subsequent film (2) is believed to be due to the large NaCl particles (4). Without being bound by theory, it is believed that reducing the size of the NaCl filler particles and coating them may improve the process.

[0102] B. Large scale 1.Scale: 5kg. Polymer: PLA. Loading: 60 / 40 filler / polymer. Additive: TBC 20wt% (based on polymer). Filler: Calcium carbonate. Functionalization: None. Results: Coextrusion yielded molded parts (1), and filming (2) was successful in the ETH pilot machine, but the thickness achieved was too high (>300 microns). Complete dissolution of the CaCO3 (6) from the polymer was difficult throughout the thickness. Without being bound by theory, it is believed that a reduction in thickness would improve the process.

[0103] 2. Scale: 20kg Polymer: PLA Loading: 60 / 40 filler / polymer Additive: TBC 20wt% (based on polymer) Filler: Calcium carbonate Functionalization: stearic acid 4% Results: Molded products (1) were obtained by coextrusion, and film production (2) by a pilot machine worked well at thicknesses of 20 to 200 μm by changing the roll speed. Film (3) had good breathability and hydrophobicity.

[0104] 3. Scale: 100kg (each loading type) Polymer: PLA + TBAT Loading: Filler / Polymer: 50 / 50, 60 / 40, 65 / 35, 70 / 30 Additives: None Filler: Calcium carbonate Functionalization: 1% stearic acid Results: Molded products (1) were obtained by coextrusion, films (2) with a thickness of 20 to 50 μm were produced by a melt-blowing pilot machine, and films (3) with a thickness of 70 to 200 μm were produced by a film extrusion pilot machine. Film (3) had good breathability and hydrophobicity.

[0105] 4. Scale: 100kg (each loading type) Polymer: Hydrophobic TPU Loading: Filler / Polymer: 50 / 50, 60 / 40, 65 / 35 Additives: None Filler: Calcium carbonate Functionalization: 1% stearic acid Results: Molded products (1) were obtained by coextrusion, films (2) of 20-50 μm thickness were obtained by melt-blowing pilot machines, and films (3) of 70-200 μm thickness were obtained by film extrusion pilot machines. The membranes (3) had good breathability and hydrophobicity.

[0106] III. Hydrophilic membrane test example A. Small scale 1. Scale 15g Polymer: PLA, PESU, EVOH, PE / PVAc copolymer, PET, PA Loading: 60 / 40, 70 / 30, 80 / 20 filler / polymer Additives: PVP, TEC, polyol plasticizer Filler: CaCO3, ZnO nanoparticles Functionalization: PEG, PVP Results: Coextrusion yielded molded articles (1). Most of the membranes (3) achieved relatively high retention and water flux. Some were too brittle to be properly tested. It appears that the process can be improved by varying the polymer chain length. See Table 2.

[0107] [Table 2]

[0108] B. Large scale 1. Scale: 2kg Polymer: PLA Loading: 80 / 20 filler / polymer Additives: PVP, polyol plasticizer Filler: Calcium carbonate Functionalization: None Results: Co-extrusion produced molded articles (1) with well-dispersed CaCO3 particles (4). The resulting thin films exhibited relatively high retention and water flux.

[0109] 2. Scale: 20kg Polymer: PLA Loading: 80 / 20 filler / polymer Additives: PVP, polyol plasticizer Filler: Calcium carbonate Functionalization: None Results: Coextrusion (1) yielded molded articles (4) with well-dispersed CaCO3 particles. Films (2) were produced using a flat-film extruder and directly pressed between two sheets of nonwoven fabric (7). The resulting supported membranes (3) (7) exhibited high stability, flux, and particle retention. The following is further disclosed in relation to the present invention. [1] A method for producing a porous polymer membrane (3), comprising the following steps: a) providing a molded article (1) comprising a polymer matrix (5) and particles (4) dispersed within said matrix by a solvent-free process; b) converting said molded article (1) into a non-porous polymer film (2) by a solvent-free process; c) removing the particles (4) from the film (2) by contacting the film (2) with an aqueous composition (6), thereby obtaining a porous polymer membrane (3); Includes The membrane (3) is ●1m 2 Area exceeding ●The pore size is 0.005 μm to 15 μm, and The molded article (1) contains a matrix (5) and particles (4) in a ratio of 90:10 to 10:90 (matrix:particles, wt%), and the matrix (5) comprises a thermoplastic or thermosetting polymer (51) and optionally an additive (52); the particles (4) are pre-manufactured; have a particle size in the range of 0.005 μm to 10 μm; are selected from the group consisting of organic salts, metal salts, and metal oxides; and are coated with a coating (41); ●Coating (41) is as follows: hydrophobic coatings, preferably selected from C6-C24 carboxylic acids, C15-C40 alkanes, vegetable oils, polyesters and polyamides (mp 50-70°C), poly(maleic anhydride) derivatives with linear or branched C6-C40 alkyl chain siloxanes in the form of nanoparticles or filaments, C6-C24 alkyl-C1-C4 alkoxy-silanes; or a hydrophilic coating, preferably selected from polyol derivatives, PVP and chitosan; The above method, characterized in that the compound is selected from the group consisting of: [2] The membrane (3) • 5 to 200 microns thick; and / or ●100m 2 It is larger than [1] The method described in [1]. [3] the polymer (51) is hydrophobic and the particles (4) comprise a coating (41) selected from the group consisting of C6-C24 carboxylic acids, C6-C24 hydrocarbons and paraffins; or the polymer (51) is hydrophilic or hydrophobic, and the particles (4) comprise a coating (41) selected from polyol derivatives and PVPs; [1] The method described in [1]. [4] The particles (4) are a salt selected from the group consisting of carbonates, hydrogen carbonates, sulfates, halides, nitrates and phosphates, and a coating material (41) as defined in [1], preferably selected from the group consisting of carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes; or an oxide selected from ZnO and MgO and a coating material (41) as defined in [1], preferably selected from the group of carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes; and / or The polymer (51) is selected from the group of thermoplastic polymers, preferably selected from the group consisting of polyesters (including PLA and PET), polyolefins (including PE and PP), polystyrene, polyethers, polyamides (including PCL), and polyurethanes; or selected from the group of thermosetting polymers, preferably from the group consisting of polyesters, polyolefins (including PP), polystyrene, polyethers, polyamides, crosslinked polyurethanes; the additive (52) is selected from the group consisting of fatty acids and C6-C24 hydrocarbons, polyethylene glycol, and glycerin; and / or The aqueous solution (6) is 〇Water, Water containing a pH adjuster selected from weak bases, weak acids, strong bases, strong acids, and buffers, preferably HCl; The method according to any one of [1] to [3], characterized in that the method is selected from the following: [5] The porous polymer membrane (3) ● have a porosity of 10 to 90%; and / or having a pore size of 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 be biodegradable according to ISO 16929, ISO 20200, or ISO 14853, The method according to any one of [1] to [4], [6] The step (a) co-extruding the particles (4) with a polymer (51), optionally blended with additives (52), to obtain a molded article (1) in the form of pellets; and / or grinding the polymer (51), optionally blended with additives (51), and co-compounding it with the particles (4) to obtain a molded article (1) in powder form; and / or precedes synthesis step (d); and / or The molding (1) is carried out in a ratio of the polymer matrix (5) and the particles (4) of 50:50 to 20:80 (matrix:particles, wt%); and / or The step (b) selected from film extrusion, calendering, injection molding, compression molding, blow molding, mold coating, melt blowing; and / or Complemented by a cross-linking step (step b1); and / or completed by coating a film (2) on a substrate (7) (step b2); and / or step (b) provides a film having a thickness of 5 to 200 microns; and / or The step (c) 〇It will be carried out within 90 minutes, The method according to any one of [1] to [5], [7] the method does not involve a phase separation step; and / or the method does not involve a stretching step; and / or the steps a) to c) do not involve organic solvents; and / or One or more of steps a) to c), preferably steps b) and c), are carried out consecutively; 3. The method according to claim 1, wherein the [8] said steps a) and b) are combined into one single step; and Preferably, steps b) and c) are carried out without the aid of a substrate; and Preferably, no organic solvent is used in steps a) to c). The method according to any of the preceding claims. [9] The particles (4) are coated particles, the particles comprising: Contains a core of CaCO3 or NaCl, and ●Contains a coating as described in [1]; having an average core size of 0.005 to 10 micrometers; and / or - having a coating (41) that accounts for 0.1 to 10 wt %, preferably 1 to 4 wt %, of the coated particles; The method according to any of the preceding claims.

[10] An assembly of molded articles (1) ("pellets"), wherein each of said pellets comprises a polymer matrix (5) and particles (4) dispersed therein; and the matrix (5) comprises a thermoplastic or thermosetting polymer (51) as defined in [1] or [4] and optionally an additive (52); and the particles (4) and coating (41) are as defined in [1] or [4]; The ratio of matrix (5):particle (4) is 90:10 to 10:90 (wt%), and The coating (41) represents 0.1 to 10 wt %, preferably 1 to 4 wt %, of the coated particles; 2. The assembly as described above.

[11] the polymer (51) is hydrophobic and the particles (4) comprise a coating (41) preferably selected from the group of C6-C24 carboxylic acids, C6-C24 hydrocarbons and paraffins; or the polymer (51) is hydrophilic or hydrophobic, and the particles (4) comprise a coating (41) selected from polyol derivatives and PVPs; An assembly of a molded article (1) according to

[10] .

[12] A porous polymer membrane (3) obtainable or obtainable by the method according to any one of [1] to [9], wherein the membrane comprises: • have a water column (WC) of at least 4.8 m; and • Have a WVTR of at least 500 g / m2 per day; and optionally having a thickness of 2 to 60 μm; and / or optionally having pore diameters of 5 nm to 2,000 nm; and / or • Have a porosity of 10 to 90%; or The membrane comprises: At least 1L * m-2 * h-1; and optionally having a thickness of 2 to 60 microns; and / or optionally having pore diameters of 5 nm to 2,000 nm; and / or ●Porosity of 10 to 90% The membrane.

[13] A porous polymer membrane (3) comprising, in particular consisting of, a polymer (51): the polymer (51) is selected from the group of thermoplastic polymers as defined in [4] or thermosetting polymers as defined in [4]; and Optionally, the membrane (3) has a thickness of 2 to 60 microns; and Optionally, the membrane (3) has a pore size of 5 nm to 2,000 nm; and Optionally, the membrane (3) has a porosity of 10 to 90%; And the membrane (3) At least 4.8m of WC and at least 500g / m per day 2 or At least 1L * m-2 * h-1, The porous polymer membrane (3) is characterized by:

[14] A woven or nonwoven textile material (7) comprising a porous polymer membrane (3) according to any one of

[12] to

[13] and a fabric material, wherein the membrane (3) comprises: - laminated onto said fabric material, or - self-supporting and connected to said fabric material by gluing, welding, sewing, and / or pressing; The woven or nonwoven fiber material as described above.

[15] The membrane is Contains biodegradable polymers that comply with ISO16929, ISO20200, ISO14853, EN13432 or EN14995, and -Connected / laminated to biodegradable fabric with biodegradable adhesive,

[14] A woven or nonwoven textile material (7).

[16] An item (8) selected from the group consisting of clothing, containers, and filter devices, the item comprising the textile material (7) described in

[14] or

[15] , or the porous polymer membrane (3) described in

[12] or

[13] .

Claims

1. A method for producing a porous polymer membrane (3) for woven or nonwoven textile materials, comprising the following steps: a) providing a molded article (1) comprising a polymer matrix (5) and particles (4) dispersed within said matrix by a solvent-free process; b) converting said molded article (1) into a non-porous polymer film (2) by a solvent-free process; c) removing said particles (4) from said film (2) by contacting said film (2) with an aqueous composition (6), thereby obtaining a porous polymer membrane (3); Includes The membrane (3) is ●1m ２ Area exceeding having a pore size of 0.005 μm to 15 μm, and At least 500g / m per day ２ WVTR, and The molded article (1) contains a matrix (5) and particles (4) in a ratio of 90:10 to 10:90 (matrix:particles, wt%), and said matrix (5) comprises a thermoplastic or thermosetting polymer (51); the particles (4) are pre-manufactured; have a particle size ranging from 0.005 μm to 10 μm; are selected from the group consisting of organic salts, metal salts, and metal oxides; and are coated with a coating (41); The coating (41) is: Hydrophobic coating, or ●Hydrophilic coating, is selected from The polymer (51) is a thermoplastic polymer selected from the group consisting of polyesters, including PLA and PET, polypropylene, polystyrene, polyethers, polyamides, including PCL, and polyurethanes; or a thermosetting polymer selected from the group consisting of polyester, polypropylene, polystyrene, polyether, polyamide, crosslinked polyurethane and The method as described above, characterized in that it does not involve a stretching step.

2. The membrane (3) is between 5 and 200 microns thick; and / or ●100m ２ It is larger than The method of claim 1.

3. the polymer (51) is hydrophobic and the particles (4) comprise a coating (41) selected from the group of C6-C24 carboxylic acids, C6-C24 hydrocarbons and paraffins; or the polymer (51) is hydrophilic or hydrophobic, and the particles (4) comprise a coating (41) chosen from polyol derivatives and PVPs; The method of claim 1.

4. The particles (4) are a coating material (41) and a salt selected from the group consisting of carbonates, bicarbonates, sulfates, halides, nitrates and phosphates; or consisting of an oxide selected from ZnO and MgO and a coating material (41); and / or the matrix (5) further comprises an additive (52) selected from the group consisting of fatty acids and C6-C24 hydrocarbons, polyethylene glycol, and glycerin; and / or The aqueous composition (6) is 〇Water, Water containing a pH adjuster selected from a weak base, a weak acid, a strong base, a strong acid, and a buffer; The method according to any one of claims 1 to 3, characterized in that the compound is selected from the group consisting of:

5. The porous polymer membrane (3) having a porosity of 10 to 90%; and / or having a pore size of 0.2 μm to 4 μm in the case of a hydrophobic polymer, or pore size of 5 nm to 500 nm in the case of a hydrophilic polymer; and / or does not contain halogenated polymers; and / or are biodegradable according to ISO 16929, ISO 20200, or ISO 14853, and / or having a thickness of 2 to 60 microns, and / or - has a pore diameter of 5 nm to 2000 nm, and / or • Have a WC of at least 4.8 m, determined in accordance with ISO 811 2. The method of claim 1.

6. The step (a) co-extruding the polymer (51) or a blend of the polymer (51) and the additive (52) with the particles (4) to obtain a molded article (1) in the form of pellets; and / or It comprises grinding the polymer (51) or a blend of the polymer (51) and the additive (52) and co-compounding it with the particles (4) to obtain a molded article (1) in the form of a powder; and / or precedes synthesis step (d); and / or carried out on said molded article (1) in which the ratio of polymer matrix (5) and particles (4) is between 50:50 and 20:80 (matrix:particles, wt%); and / or The step (b) selected from film extrusion, calendering, injection molding, compression molding, blow molding, mold coating, and meltblowing; and / or complemented by a cross-linking step (step b1); and / or completed by coating a film (2) on a substrate (7) (step b2); and / or step (b) provides a film having a thickness of 5 to 200 microns; and / or The step (c) 〇It will be carried out within 90 minutes, 2. The method of claim 1 .

7. the method does not involve a phase separation step; and / or said steps a) to c) do not involve organic solvents; and / or one or more of steps a) to c) are performed sequentially; 2. The method of claim 1.

8. said steps a) and b) are combined into one single step; The method of claim 1.

9. The particles (4) are coated with a coating (41): and CaCO ３ or containing a core of NaCl; having an average core size of 0.005 to 10 micrometers; and / or - having a coating (41) that amounts to 0.1 to 10 wt% of the coated particles; The method of claim 1.

10. 2. The method of claim 1, wherein the hydrophobic coating is selected from C6-C24 carboxylic acids, C15-C40 alkanes, vegetable oils, polyesters and polyamides with m.p. of 50-70°C, poly(maleic anhydride) derivatives with linear or branched C6-C40 alkyl chain siloxanes in the form of nanoparticles or filaments, and C6-C24 alkyl-C1-C4 alkoxy-silanes.

11. The method of claim 1 , wherein the hydrophilic coating is selected from polyol derivatives, PVP, and chitosan.

12. The method of claim 4, wherein the pH adjuster is HCl.

13. 9. The method of claim 8, wherein steps b) and c) are performed without the aid of a substrate.

14. The woven or nonwoven textile material (7) comprises the porous polymer membrane (3) and a textile material; The membrane (3) comprises: laminated onto said fabric material; or self-supporting and connected to the fabric by gluing, welding, sewing, and / or pressing; The method of claim 1.

15. The method described in claim 7, wherein steps b) and c) are carried out continuously.

16. The method of claim 9, wherein the coating (41) comprises 1 to 4 wt% of the coated particle.

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