3D modeling of porous waterproof membrane

Abstract

The present invention relates to a seamless manufacturing process for three-dimensional waterproof and breathable porous polymer membranes by spraying, dip-coating, or painting a dispersion containing a polymer, coated or uncoated particles, and a diluent onto a substrate. The particles are mobilized by dissolution, creating porosity after 3D painting / molding. The invention further relates to dispersions for obtaining such membranes, the resulting polymer membranes, and shaped articles containing such membranes. The invention also relates to uses of such membranes, shaped articles, and intermediates.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a three-dimensionally shaped microporous, waterproof and breathable polymeric membrane, to intermediates suitable for obtaining such membranes, to the polymeric membranes described herein, their seamless application to different substrates, in particular textiles, to textiles comprising such membranes, and to the use of such membranes, textiles and intermediates. [Background technology]

[0002] The membranes, as they are known, separate the compartments. In clothing, rain and weather are kept out, but sweat needs to travel through the membrane to get out.

[0003] Current porous membrane systems for clothing are manufactured using two-dimensional (2D) methods, such as Gore-Tex®, eVent®, Xpore®, or phase inversion (Porelle®). Thus, no solution has been found for producing truly 100% seamless microporous membranes. Instead, constructing "three-dimensional" (3D) objects, such as textiles, from membranes requires the use of stitching, gluing, welding, bonding, and / or pressing. These boundaries are the primary cause of textile failure and typically require additional steps to ensure full performance and consistent stability. This means that seam taping is required in the case of stitching. Therefore, the present invention addresses this shortcoming.

[0004] Furthermore, the production of textiles using known 2D techniques generates significant waste, and in embodiments, the present invention addresses this drawback.

[0005] Furthermore, the choice of polymers used in the manufacturing process of such 3D microporous membranes also defines their environmental impact. Materials that can be harmlessly incinerated after use are needed. The inventors identified a particular need for materials that are useful for partially or fully biodegradable clothing, or for easily recyclable materials with typical high protective properties. For example, fluorine-containing hydrocarbons are highly persistent and considered a threat to nature.

[0006] Patent Document 1 and its family members Patent Documents 2 and 3 disclose waterproof and breathable porous membranes and their manufacture, but the manufacturing methods disclosed therein relate only to two-dimensional microporous membranes.

[0007] Patent Document 4 discloses a waterproof, water-vapor-permeable shoe that includes an upper, a sock-shaped functional layer, a lining, and a sole. Its manufacture still requires stitching to secure the functional layer to the upper opening. The sole can also be secured to the bottom of the shoe by gluing or sewing, and the seams can be resealed by applying additional waterproof, water-vapor-permeable polymer, or the sole can be injection-molded to avoid further sealing. This complicates the process. To adapt the functional layer to the shoe size, the layer can be adapted by cutting a slit in the bottom of the layer and joining the edges. Therefore, the shoes disclosed in that document are not completely seamless.

[0008] Patent Document 5 discloses a waterproof, breathable garment and a method for manufacturing the same. The garment may include a laminate of a seamless ePTFE membrane and at least one woven fabric. The seamless membrane may shrink or expand to fit multiple sizes of garments. A breathable continuous or discontinuous adhesive must be used to bond the textile to the membrane.

[0009] Patent Document 6 discloses waterproof, breathable socks, boots, shoe inserts, and footwear assemblies including the shoe inserts. The boots and shoe inserts may include a laminate including a seamless stretch film, such as a polyurethane film, and at least one textile. Again, a breathable continuous or discontinuous adhesive must be used to bond the textile to the membrane.

[0010] Patent Document 7 discloses a method for manufacturing a breathable waterproof garment. The method includes the steps of: forming a first garment layer in a stretched configuration on an oversized three-dimensional garment former; covering the first garment layer with an intermediate garment layer that is resistant to penetration by liquid water but permeable to water vapor; and covering the intermediate garment layer with a second garment layer. A non-porous functional layer is attached to the first and second garment layers at a plurality of discrete, fixed locations.

[0011] Patent Document 8 discloses a method for producing preformed membranes for clothing. According to this document, a 3D substrate is (a) immersed in a liquid, (b) the resulting intermediate material is polymerized, and (c) the non-reactive material is removed. The non-reactive material used in this document is dissolved in the remaining components; that is, it is not particulate. The pores obtained according to this protocol cover a very wide range. Precise control of the pore size and pore size distribution is almost impossible and depends on the process parameters and the materials used. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Patent Publication No. 2017 / 097778 [Patent Document 2] European Patent Publication No. 3368598 [Patent Document 3] European Patent Publication No. 3178873 [Patent Document 4] European Patent Publication No. 1212953 [Patent Document 5] International Patent Publication No. 2017 / 0031432 [Patent Document 6] International Patent Publication No. 2017 / 027826 [Patent Document 7] International Patent Publication No. 2014 / 167288 [Patent Document 8] International Patent Publication No. 2010 / 046118 Summary of the Invention [Problem to be solved by the invention]

[0013] Therefore, there is a need to add and / or improve the manufacturing process for seamless 3D porous polymer membranes that can be used in a wide variety of applications, including not only the design but also the materials used (a wide variety of polymers, including durable solutions) and / or support materials. New 3D polymer membranes with beneficial properties, especially with regard to water vapor permeability, are also needed. Another area for improvement is the use of adhesives between fabrics and 3D-shaped functional membranes (e.g., socks, gloves, etc.). This includes not only in terms of structure and performance, but more specifically, the adhesives and their environmental impact in downstream processes such as recycling and (biodegradation). [Means for solving the problem]

[0014] The present invention is described in further detail below with reference to the following specific embodiments. First aspect: Fabrication of 3D microporous membranes Second aspect: Intermediate suitable for the first aspect Third side: 3D seamless membrane Fourth aspect: Special applications in textiles

[0015] Unless otherwise stated, the following definitions apply in this specification:

[0016] Polymer: The term "polymer" is known in the art. This term refers to a material of repeating structural units ("monomers"), especially synthetic polymers (including synthetic monomers). Thus, the term includes homopolymers, copolymers, and blends thereof. Polymers may be crosslinked.

[0017] Particles / Molds / Fillers: The term "particles" is known in the art and includes crystalline or amorphous materials. This term includes uncoated and coated particles, as well as treated and untreated particles. In this work, "particles" can also be referred to as "molds," since they are removed to obtain the final product. It is known that particles may aggregate. In the context of the present invention, suitable particles have a diameter in the submicron size range, preferably with a particle size of 5 to 15,000 nm, for example 2000 to 8,000 nm. Suitable particles can be obtained from a range of preparation methods, including high-temperature gas-phase processes (such as flame synthesis, laser processes, plasma processes, etc.), and liquid-phase chemical methods (such as precipitation and sol-gel processes), and particle milling. Particularly suitable particles in the context of the present invention can be obtained by precipitation processes or by grinding of natural materials.

[0018] Salt: The term "salt" is known in the art. A salt is defined as the product formed from the neutralization reaction of an acid and a base. A salt is an ionic compound composed of a cation and an anion such that the product is electrically neutral. Examples of salts are halides (chloride, fluoride, bromide, iodide), sulfates, phosphates, carbonates, and nitrates, particularly phosphates, carbonates, and halides. In inorganic salts, the cation is a metal ion and the anion is a nonmetallic ion. Specific examples of inorganic salts include calcium phosphate, calcium carbonate, magnesium sulfate, sodium chloride, ammonium chloride, and ammonium carbonate. In the context of this invention, metal oxides (i.e., products formed by the oxidation of metals) are not considered salts. In organic salts, the cation or anion is an organic ion. Examples of organic salts may be selected from the group consisting of alkylammonium salts and metal carboxylates.

[0019] Viscosity: The "viscosity" of a fluid is a measure of its resistance to mixing at a given stirring rate. The more viscous a liquid is, the more difficult it is to move. More specifically, this measurement describes the internal friction of a moving fluid and determines the energy required to make it flow. Viscosity is measured with a HAAKE ViscoTester iQ. A rotating cylinder is immersed in the liquid (18.5 g) and the resistance of the liquid is measured. Several parameters influence the results, including the temperature of the fluid and the shear rate of the cylinder. To understand the behavior of the fluid, it is common to plot viscosity as a function of shear rate at a specific temperature. Porosity: The "porosity" of a material described herein is the volume percentage of pores in the total material. Porosity can be determined by porosimetry, measuring the apparent material density, BET analysis, or microscopic imaging.

[0020] Pore ​​size: The "pore size" of the materials described herein is the median size of the pore size distribution throughout the membrane. A particularly suitable method in the context of the present invention is optical analysis of the membrane's surface, which provides information about pore opening size.

[0021] Permeability: 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 can be determined by measuring the volume of liquid or gas that passes through a defined membrane area in a defined time at an applied pressure. i) For gaseous media, the water vapor transmission rate (WVTR) is the appropriate parameter for determining permeability, also referred to as "breathability" in this work. WVTR is expressed in grams per square meter and per day (g / (m)), according to ASTM standard E96 B. 2 d)). This method, also known as the upright cup method, involves covering a cup filled with water with the test specimen. The prepared sample was weighed before being placed in an oven controlled for temperature (23°C), relative humidity (50% RH), and ventilation (1 m / s). Alternative methods are covered by the inverted cup standard ASTM E96 BW, or the sweating hot plate method ISO 11092. The desiccant method of the upright cup test is also described in the ASTM E96 standard. ii) For liquid media, waterproofness is a relevant parameter. When determining waterproofness, the relevant driving force is pressure. The water column (WC) in meters (m) is determined in accordance with ISO 811. Briefly, water is forced onto the sample with a constant pressure increase (600 mmWC per minute). The dry side of the sample is observed optically, and the third penetrating drop is defined as the breakthrough of the sample, with the pressure representing the water column (WC). iii) Windproofing: Airflow through a structure is characterized by the volume of air (cm) passing through a defined area of ​​the structure at a particular applied pressure over time. 3 / cm 2 / min, or cm 3 / ft / min, abbreviated "cfm"). Appropriate measurements are described in standards ISO 9237 or ASTM D737. A test specimen is considered windproof if the material or substrate does not show any appreciable air movement throughout its structure.

[0022] Seamless: A "seamless" membrane is defined as an uninterrupted membrane in 3D shape (x, y, z coordinates). That is, there are no visible seams and / or cuts on one or both sides of two or more initially separated membranes, and no attachments or connections (glues, presses, and similar artifacts). The seamless phase must be continuous throughout the object, except for "working" openings that provide access to enclosed voids, such as holes for inserting a foot into a sock or a hand into a glove. If necessary, the edges of "working" openings are free of seam tape, as this is where the membrane phase stops and can be attached to the final object, i.e., shoe structure, by gluing, presses, and similar artifacts.

[0023] Three-dimensional and two-dimensional: these geometric configurations are known as spatial and planar structures, respectively, and are used in their usual context. Therefore, 3D structures are described herein as non-planar structures, thus excluding flat structures (2D structures). To avoid misunderstanding, curved 2D structures, such as cylinders, are still considered 2D. A 3D object is composed of three unique coordinates, e.g., y, z, and x. More specifically, a 3D membrane may adapt to the shape of a flexible or rigid object. In the context of the present invention, a 3D substrate can take the shape of a human body or a part of it, such as a hand or foot, or can be a tailored, finished textile product. Therefore, a 3D membrane is a membrane created in a continuous phase on these 3D substrates. Depending on the final application, it can be removed or remain on the substrate.

[0024] Body Mapping: Body mapping is described herein as the ability to purposefully place different membrane performance levels and / or colors on specific areas of the human body to maximize membrane use. For example, a jacket may be more waterproof but less breathable in the shoulders, and more breathable but less waterproof in the back and underarms, tailored to the individual's needs.

[0025] Generally speaking, the present invention relates in a first aspect to a method for producing a 3D seamless porous polymeric membrane (4) having a pore size of 5 nm to 10,000 nm, for example 500 to 2,000 nm, comprising the following subsequent process steps (a) to (g):

[0026] Step (a): Preparation of a liquid film dispersion (1) and optionally one or more dyes (9) by a milling process that combines a polymer matrix (5), coated or uncoated particles (6), a solvent (7), and optionally one or more additives (8) dissolved therein.

[0027] Step (b): 3D application, such as direct spraying, dip coating, painting, printing, or 3D printing of the liquid film dispersion (1) onto the substrate (2.2). If necessary, the substrate (2.2) can be chemically, physically, or thermally pretreated or charged to facilitate uniform application of the liquid film dispersion (1). If necessary, when the substrate (2.2) is a finished textile product, a specific mounting structure, such as a mannequin, shape-changing mannequin, or inflatable mannequin, can be used to control the shape, state, and positioning of the substrate.

[0028] Step (c): Drying of the wet layer and substrate resulting in a non-porous multiphase (polymer, template and possibly coating) dry film (2.1) on the substrate (2.2), thus forming one single object (2).

[0029] Optional repetition of steps b and c: Optionally, multiple repetitions of steps b and c can be applied in the following order. Following such a protocol results in a multilayer film. Such repetition is referred to as step (d).

[0030] Step (e): If necessary, a polymerization or crosslinking step is added.

[0031] Step (f): A step of removing particles (6) from the non-porous polymer film (2.1) by contacting the single object (2) comprising the non-porous polymer film (2.1) and the substrate (2.2) with an aqueous composition (10). After a washing step (3.1), a porous polymer membrane (3.1) is obtained together with the substrate. Thus, the final product (3) after step (d) is a 3D microporous membrane (3.1) and a substrate (3.2).

[0032] Step (g): Optionally, the 3D microporous membrane (3.1) can be removed from the support (3.2), resulting in a so-called "free-standing membrane" or "self-supporting structure" (4). [Effects of the Invention]

[0033] This process is illustrated in Figure 1 and described in more detail below. As will become apparent from review of this specification, the present invention provides many advantages:

[0034] First, the 3D application of a protective polymer layer does not require any changes to the initial manufacturing process, making it useful for already molded objects. Simply adding a membrane by spraying, dipping, painting, or coating the polymer dispersion is sufficient. By creating a porous system after the membrane has been molded, the process described herein provides access to beneficial performance in multiple dimensions. Adding membrane performance to this polymer layer provides added value, such as weather protection and humidity control. Finally, microporosity offers additional benefits in terms of breathability thanks to its open, porous structure. This opens up new design freedom for functional 3D molded parts, as no existing 3D application solution can deliver that level of performance while maintaining a seamless appearance.

[0035] Second, the current 3D application of microporous membranes offers significant improvements in terms of waste and avoids performance loss. An example of this is their use in finished textiles. Typically, the membrane would have been present in the initial laminate prior to construction / conditioning of the object. Therefore, all cuts required during production are membrane waste. This is avoided by the present invention. Furthermore, sewing the laminate creates holes in the membrane, which must later be covered with seam taping to provide the necessary waterproofing. This process is tedious, time-consuming, expensive, and prevents breathability (tape does not work / is not breathable). In this invention, the seams are directly covered with the 3D microporous membrane, maintaining breathability in the presence of the seams.

[0036] Third, the present invention allows for the production of halogen-free 3D microporous membranes, which are particularly believed to be superior to known membranes for apparel applications.

[0037] Fourth, the performance of 3D microporous membranes can be further enhanced by several parameters, including the initial chemical recipe of such membrane dispersions, which is published in WO 2017 / 097778. The following parameters can influence the final design and performance of the object: thickness (can be from one to multiple layers), hierarchical pore structure (pore volume and size), mapping of different local performances (e.g., body mapping of an outdoor jacket), and optical representations such as coloring or molding to allow for differentiation of the regions.

[0038] In one embodiment, the membrane is three-dimensional (3D) and seamless and attached to a substrate. In a further embodiment, the membrane is three-dimensional (3D) and seamless and free-standing (4). [Brief explanation of the drawings]

[0039] [Figure 1] FIG. 1 is a diagram outlining the process steps of the manufacturing process for a 3D waterproof breathable membrane shown as a sock.

[0040] The pore size of the membrane can vary over a wide range. Suitable pore sizes are 5 to 10,000 nm, preferably 100 to 5,000 nm, and most preferably 300 to 1,000 nm. In an embodiment, the pore size is 400 to 4,000 nm. In a preferred embodiment, the pore size is 500 to 2,000 nm. It is considered advantageous to be able to fine-tune the pore size of the membrane by selecting the appropriate particles (6). Preferably, the pore size distribution is unimodal. The pore size may be influenced by the selection of particle size. Thus, compared to known methods for forming 3D membranes, such as those discussed in WO 2010 / 046118, the pore size is primarily influenced by the selection of starting materials rather than the selection of process parameters. This is considered a major advantage, as it makes fabrication more robust and simplifies scale-up. DETAILED DESCRIPTION OF THE INVENTION

[0041] In one embodiment, a dispersion suitable for step (a) meets one or more of the following parameters: (i) Composition: a. 40 to 99 wt. % diluent; b. 1 to 20 wt. % of a polymer; c. 0.5 to 40% by weight of coated or uncoated particles; d. 0-6 wt. %, preferably 2-4 wt. % of a coating material; e. 0-5 wt. % additives; f. 0-5% by weight of a dye: ii) Particle size: 5-15,000 nm, preferably 2,000-8,000 nm. iii) Polymer / particle weight ratio: 10 / 90 to 90 / 10, preferably 50 / 50 to 20 / 80. iv) Viscosity: 50-2000 mPas, preferably 100-800 mPas, at 25°C, 200 rpm.

[0042] In a further embodiment, the dispersion suitable for step (a) meets one or more of the following parameters: (i) Composition: a. 40 to 99 wt. % diluent; b. 1 to 20 wt. % of a polymer; c. 0.5 to 40% by weight of coated or uncoated particles; d. 0-6 wt. %, preferably 2-4 wt. % of a coating material; e. 0-5 wt. % additives; f. 0-5% by weight of a dye; ii) Particle size: 5-15,000 nm, preferably 2,000-8,000 nm. iii) Polymer / particle weight ratio: 10 / 90 to 90 / 10, preferably 50 / 50 to 20 / 80. iv) Viscosity: 50-2000mPas, preferably 400-1500mPas, at 25°C, 200 rpm.

[0043] In further embodiments, the 3D membranes (3), (4) of the present invention comply with one or more of the following parameters: i) Pore size: 5 to 10,000 nm, preferably 100 to 5000 nm, most preferably 300 to 1000 nm. ii) Porosity: 30 to 80%, preferably 55 to 65%. iii) Thickness: 0.01 to 1000 microns, preferably 1 to 120 microns, most preferably 15 to 50 microns. iv) Waterproof (ISO811):>4.8m. v) Contact angle: >50°. vi) Breathability (ASTM E96 B):>500g / m 2 / day. vii) Number of layers: 1 to 20, preferably 1 to 4.

[0044] Additional details about the process:

[0045] Step (a) can be divided into sub-steps: preparation of the coated particles (a1) and preparation of the solution before milling (a2). Step (a1): In one embodiment, suitable methods for producing the coated particles (6) are known per se and include mixing, ball milling or pug milling of the respective starting materials (uncoated particles and coating material), optionally in the presence of an inert diluent. In a further embodiment, the uncoated particles are not pre-prepared but are selected to meet the same size requirements, i.e., in the range of 5 to 15,000 nm, preferably 2000 to 8000 nm.

[0046] Step (a2): In one embodiment, suitable methods for preparing the dispersion (1) are known per se and involve preparing a solution of one or more polymers, one or more solvents, and optionally additives (8) and dyes (9). This solution is combined with one or more coated and / or uncoated particles (6) of step (a1). A vigorous stirring / grinding step produces the final membrane dispersion (1). The solvent (7) is selected to ensure dissolution of the polymer (5) without dissolving the particles (6). Alternatively, the polymer / solvent mixture can be readily purchased from a supplier.

[0047] In further embodiments, the following sections list suitable candidates for each of the raw materials: Suitable solvents (7) can be selected from a wide range of known solvents and combinations thereof, preferably solvents with a temperature below 200°C. Examples of solvents include water or organic solvents selected from the group consisting of alcohols, ethers, ketones, esters, halogenated alkanes, alkanes, cycloalkanes, sulfoxides, amides, pyrrolidones, and lactams.

[0048] Suitable polymers (5) can be selected from a wide range of known polymers and combinations thereof, including crosslinkable polymers. The present invention also encompasses the use of copolymers, such as rubber, and mixtures ("blends") of polymers. Furthermore, the polymer is selected from the group of soluble polymers. In the context of the present invention, a polymer is considered soluble if 1 g of the polymer, preferably 10 g of the polymer, dissolves in 1 liter of organic solvent or 1 liter of water, and the resulting solution follows the standard behavior of a polymer solution (viscosity as a function of concentration and temperature, change in solvent vapor pressure, solution clarity, etc.). Typically, such soluble polymers exhibit little or no crosslinking. Such polymers are known to those skilled in the art and can be easily identified. Soluble polymers can be selected from the group consisting of polyurethanes (including thermoplastic polyurethanes, TPUs), ethyl vinyl acetate, polycarbonates, synthetic rubbers, polyesters, polyethers, polyaryletherketones, polyamides, polyacrylates, polyarylates, polystyrenes, cycloolefin copolymers, and polyolefins.

[0049] In embodiments, the polymer is selected from a group of prepolymers that are crosslinked in a subsequent step. The crosslinked polymer is typically insoluble, whereas the corresponding starting material is. Again, such polymers are known to those skilled in the art and can be easily identified. The crosslinked polymer may be selected from the group consisting of natural and artificial rubbers, polysiloxanes, epoxide resins, and specially modified crosslinkable forms of the above polymers. In embodiments, the polymer is selected from the group of prepolymers that are polymerized in a subsequent step. Such polymers may or may not be soluble depending on their molecular structure. Suitable prepolymers to be polymerized may be selected from the group of polyesters and polyamides, whose corresponding starting materials are lactones and lactams, respectively, and polyurethanes, whose corresponding starting materials are diisocyanates and diols or / and amines.

[0050] Particularly preferred polymers according to the invention are selected from the group of polysulfones, polyethersulfones, polycarbonates, polystyrenes, polyacrylates, polysiloxanes, polyarylates, polyurethanes (including thermoplastic polyurethanes, TPU), ethyl vinyl acetate, artificial and natural rubbers, polyesters, polyethers, polyaryletherketones, polyamides, cycloolefin copolymers and polyolefins. Very particularly preferred polymers according to the invention are selected from the group of polyurethanes (including thermoplastic polyurethanes, TPU), polyesters, polyamides and polyolefins.

[0051] Suitable coated or uncoated particles (6) may have a particle size of 5 to 15,000 nm, preferably 2,000 to 8,000 nm. Suitable materials for the particles include inorganic pore templates selected from the group consisting of crystalline organic compounds, metal salts, and metal oxides, as well as organic salts, and combinations thereof. Preferably, the metal salt particles are selected from the group consisting of carbonates (including bicarbonates), sulfates, halides, nitrates, and phosphates, preferably carbonates. Examples of metal salts include MgCO3, CaCO3, SrCO3, BaCO3, Na2CO3, K2CO3, and NaCl. Examples of metal oxides include ZnO and MgO. Preferably, the crystalline organic compounds are selected from the group consisting of sugars, such as glucose and fructose, or a combination of both. Preferably, the organic salt particles are selected from the group consisting of solid alkylammonium compounds and alkali metal carboxylates. Examples of organic salts include tetramethylammonium chloride and sodium citrate. The pore templates can be obtained from known synthetic methods, such as wet or dry methods, or can be obtained from naturally occurring sources.

[0052] Suitable coating materials for the particles can be selected from surface functionalization reagents known to those skilled in the art. Suitable coating materials for the particles include anhydrides such as polymaleic anhydride (PMAH), its homopolymers as well as copolymers containing PMAH, and mixtures of PMAH, or C6-34 The PMAH may be selected from carboxylic acids, such as carboxylic acids and mixtures of carboxylic acids. In the context of the present invention, the PMAH may be linear or branched. Furthermore, copolymers containing PMAH may also contain other functional groups, such as alkane or alkene functional groups. In the context of the present invention, the carboxylic acid may be linear or branched. Furthermore, carbocyclic acids may contain one or more double bonds. The term carboxylic acid further includes monocarboxylic and dicarboxylic acids. Suitable carboxylic acids are selected from the group of naturally occurring fatty acids, such as stearic acid, and naturally occurring dicarboxylic acids, such as pimelic acid and sebacic acid.

[0053] They may further be selected from the group of alkyl-aryl-alkoxy-silanes, aryl-alkoxy-silanes, alkyl-alkoxy-silanes, and mixtures of such silanes. In the context of the present invention, these silanes may be selected from the group of trialkoxysilane derivatives, dialkoxysilane derivatives, and monoalkoxysilane derivatives. These silane derivatives may also be cyclic or linear. Suitable silanes include ((C 2-16 ) alkyl) Si(OMe)3, ((C 2-16 ) alkyl) Si(OEt)3, ((C 2-16 ) alkyl)2-Si(OMe)2, ((C 2-16 ) alkyl)2Si(OEt)2 and, for example, (C 2-16 and corresponding optionally substituted phenyl-containing derivatives such as arylsilanes, wherein one or more of the alkyl groups are replaced by at least one phenyl or substituted phenyl group.

[0054] 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 thickeners, hardeners, leveling agents, film flow agents, film uniformity agents, defoamers, orange peel inhibitors, and wetting agents.Such additives are commercially available from, for example, Byk Additives and Instruments, Evonik Industries, and CRODA International.

[0055] Suitable dyes can be selected from a wide range of dyes known in the art, preferably sustainable dyes from natural sources such as plants, invertebrates, minerals, etc.

[0056] Suitable dispersions can be prepared from the starting materials described above using known techniques. It has been found suitable to combine the starting materials by vigorously stirring the components, subjecting them to sonication, and / or subjecting the mixture to a ball milling process. The dispersion can be maintained at an elevated temperature, e.g., 40-100°C. Such temperatures increase the solubility of the polymer and reduce viscosity, facilitating the process described herein. If a more viscous dispersion is preferred, i.e., for spraying, the temperature can be maintained at room temperature (18-28°C). The appropriate viscosity range can be determined by routine experimentation and depends, among other things, on the application method. Generally speaking, a suitable range is 50 to 2000 mPas. In an embodiment, the viscosity is in the range of 50 to 1000 mPas, preferably 200 to 600 mPas. This range is typically used for application. In an embodiment, the viscosity is in the range of 500 to 2000 mPas, preferably 400 to 1500 mPas, which is the range typically used for spraying. It was found that a proper viscosity match improved membrane properties such as pore size.

[0057] Step (b): In one embodiment, this step involves applying the liquid film dispersion (1) of step (a) onto a three-dimensional substrate. The substrate can be either a rigid or flexible object. The application method can be various, such as spraying, dip coating, printing, or painting. If the substrate is not standing, it is placed on a standing support to facilitate 3D application. Furthermore, the substrate is usually preheated before the liquid film dispersion (1) is applied.

[0058] Step (c): In one embodiment, the formed, wet-coated substrate is subjected to a heat treatment (e.g., drying) to expedite solvent evaporation. The temperature and treatment time vary depending on the starting materials (e.g., solvent (7)), but are typically between 25 and 200°C, preferably below the melting point of the film and support polymer. This heat treatment can be performed from the outside of the film (e.g., ovens with or without ventilation, heat guns, etc.) or from the inside (e.g., thermally inflatable structures). Typical drying times are between 10 seconds and 2 hours, preferably 30 seconds to 10 minutes, and most preferably 1 hour, depending on the final desired result of the film (i.e., thickness, performance, etc.).

[0059] Step (d): Steps (b) and (c) can be repeated as many times as necessary (usually less than four times) depending on the final desired result of the membrane (ie, thickness, performance, etc.).

[0060] Step (e) In a further embodiment, the obtained material is optionally subjected to a polymerization or crosslinking step.

[0061] Step (f): In one embodiment, the removal of template particles is performed on a non-porous 3D film (2.1), while the washing is performed on said film attached to a substrate (2.2). Optionally, the non-porous 3D film (2.1), especially in the case of "simple" structures, can be removed / peeled off from the substrate (2.2) before the washing step (step (f)). The washing material (10) is selected to ensure dissolution of the coated particles without dissolving the polymer. Suitable materials (10) for this washing step are aqueous solvents, in particular water or aqueous acid solutions (e.g., formic acid, acetic acid, or hydrochloric acid). The choice of solvent depends, in particular, on the type of template material (metal salt / metal oxide) used. After complete removal of the template, the object (3) is washed again with water to remove any residual washing agent, i.e., acid, and finally dried at room temperature or using a drying / heating device to expedite the process.

[0062] Suitable cleaning agents (10) can be prepared from water, acidic aqueous solutions containing, for example, formic acid, acetic acid, citric acid, or hydrochloric acid, with a pH of less than 7, or basic aqueous solutions containing, for example, sodium hydroxide or potassium hydroxide, with a pH of greater than 7.

[0063] Step (g): In a further embodiment, the 3D microporous membrane (3.1) can be optionally removed from the 3D support (3.2) after the washing step (f) while maintaining the 3D shape of the support. The membrane at this stage is soft and elastic, allowing for smooth peeling. The resulting membrane (4) is seamless and hole-free, thus becoming a so-called "freestanding membrane" or "self-supporting structure." It can then be attached to an already finished product of similar shape, for example, but not limited to, between two layers of a finished textile product. Seam tape is not required.

[0064] In a further embodiment, the manufacture of the membranes of the present invention does not involve any bonding, sewing, welding, gluing, knitting, stitching, or other "closure" steps that are detectable in the final product.

[0065] In a further embodiment, the production of the membranes of the present invention does not involve phase separation.

[0066] In a further embodiment, the porosity of the membrane of the present invention is introduced only after application of the liquid membrane precursor (1) onto the substrate and thus after assembly into a 3D-shaped product. This dissolution step (f) is carried out for 90 minutes or less.

[0067] In a further embodiment, the coating step (b) is selected from the group consisting of spraying, painting, printing (including 3D printing), and dip coating.

[0068] Generally speaking, the present invention provides: Second Aspect relates to the use and properties of a substrate (2.1) for obtaining a 3D microporous membrane (3) or (4) and thus a so-called "seamless membrane".

[0069] i. Type of substrate: material, shape A suitable substrate (2.1) in terms of material can be selected from a wide range of known substrates. The substrate can be any support compatible with the manufacturing process. It must be inert to solvents, especially to enable step (g). In certain cases, it is even more beneficial if the coating adheres to the substrate during manufacturing and can be removed after manufacturing. In certain cases where the final product includes a membrane and a substrate (i.e., without step (g)), the bond between the membrane and the substrate is strong and difficult to remove.

[0070] In one embodiment, materials suitable for the substrate include polymeric materials, leather, silicone, glass, metals (such as aluminum), ceramics, concrete, cement, wood, and paper (in either case, painted or unpainted). In textile manufacturing, it may be advantageous to coat the dispersions (1) described herein directly onto tightly woven, knitted, or nonwoven fabrics. This embodiment is advantageous if the membrane polymer adheres well to the type of polymer or biopolymer used in the textile substrate. Potential additives (8) in or on the substrate surface, as well as in the dispersion, can provide the necessary adhesion enhancement.

[0071] For outdoor wear, suitable materials are tightly woven polyamide, polyester, or polypropylene. The present invention is particularly advantageous when the dispersion is applied directly to the finished textile to cover the seams with a membrane. The membrane can be placed on the inside or outside of the textile. The membrane can be further covered by an additional layer of membrane with different properties or by a layer of fabric. In one embodiment, the substrate or textile product can be maintained at an elevated temperature, e.g., 40-100°C. Such temperatures help to evaporate the solvent more quickly and facilitate the methods described herein. In another embodiment, the textile product should be placed on a mannequin, e.g., inflatable to facilitate the methods described herein.

[0072] In terms of shape, suitable substrates (2.1) can be selected from a wide range of known substrates for hands (gloves), feet (socks), torsos (pullovers), legs (stockings), heads (caps) or general clothing types. Furthermore, all types of molded leather and textile products can be coated with the liquid film dispersion (1). Furthermore, this technology allows the creation of complex 3D geometries (designs, styles). The application of the liquid film precursor (1) adapts to the shape of the substrate, i.e., special patterns are covered by the film, creating complex shapes that are waterproof and breathable.

[0073] ii. Direct to substrate: no removal step After step (f), the final product is obtained. The final membrane is placed on a substrate with a certain adhesive force to provide a breathable, waterproof protective layer. This membrane is widely applicable, suitable for all applications, including but not limited to textiles, where it replaces two-dimensional membranes.

[0074] iii. Self-supporting structure: Use of a manikin with a removable step Step (e): If necessary, the porous film (3.1) can be removed from the substrate (2.2), for example by peeling or transferring it to another substrate as a multilayer material. This removal step can be carried out after, or optionally before, the washing step (f). Step (g) can be carried out using processes known per se. The purpose of this removal step (g) is to remove the substrate (2.2) to obtain an unsupported, seamless porous polymer membrane (4), for example, in the form of a glove or sock. This free-standing, three-dimensional membrane is then transferred to a support material of another shape to achieve a finished textile product, for example, a glove or sock with the membrane of the present invention. Again, this membrane (4) is suitable for all applications where it replaces a two-dimensional membrane, including, but not limited to, textiles.

[0075] iv.Manufacturing The described manufacturing process provides porous materials limited in size by the substrate. Single-part manufacturing processes can be achieved by in-line assembly using spray robots or surface printing or 3D printing. Alternatively, mannequins can be dipped into the dispersion, similar to the manufacturing of laboratory gloves.

[0076] The present invention provides Third Aspect This aspect, particularly advantageous polymers, features of the membranes of the invention, and examples are outlined below.

[0077] Membrane: In one embodiment, the present invention relates to a seamless polymeric membrane, said membrane having thickness and / or porosity; and / or pore size; and / or tensile properties and / or water column; and / or water vapor transmission rate; and / or water contact angle; and / or air permeability and / or a three-dimensional shape encompassing a structure without seams, cuts, bonds, or similar assembly artifacts as described in the first aspect of the invention above. Through the unique manufacturing process outlined herein, the present invention provides porous membranes (or even nanoporous membranes) that combine specific properties with the three-dimensional shape of the polymeric membrane. Advantageously, such shaped membranes may be constructed from a single piece with the required functionality, without seams, cuts, bonds, or similar assembly artifacts.

[0078] 3D Shape: In one embodiment, the materials of the present invention are characterized by their three-dimensional shape, which distinguishes them from two-dimensional ("flat," "sheet-like") materials. The materials of the present invention are essentially free of assembly artifacts such as seams, cuts, and joins.

[0079] In one embodiment, the final shape of the membrane is congruent with the final product, regardless of the product's initial shape, whether two-dimensional or three-dimensional. This embodiment is advantageous for jackets and outdoor clothing, house wraps in construction (to manage water and vapor within buildings), packaging materials (e.g., for food, consumer goods, and pharmaceuticals), and sensors.

[0080] In a further embodiment, the membrane coatings described herein are located on specific areas of a garment to provide localized functionality, rather than on all parts of the garment. As previously mentioned, this also eliminates the need for seams, cuts, glues, or similar assembly techniques. This has advantages in assembly, performance, and optics. The coated parts can be modified without the added special cutting and assembly required currently for localized performance.

[0081] Polymer: As outlined above, a wide variety of polymers can be used in the membranes of the present invention. In one embodiment, the polymer is selected from the group consisting of polymers soluble in organic solvents and cross-linked polymers thereof. This is considered advantageous because currently known polymer membranes are limited in terms of suitable materials and / or their pore characteristics. Suitable polymers can be selected from the group of polymers soluble in organic solvents. Furthermore, suitable polymers can be selected from the group of polymers soluble in organic solvents, including polyurethane, ethyl vinyl acetate, polycarbonate, synthetic rubber, polyester, polyether, polyaryletherketone, polyamide, polyacrylate, polyarylate, polystyrene, cycloolefin copolymer, polyolefin, cross-linkable polymer (natural rubber, synthetic rubber, polysiloxane, epoxide resin, etc.). Particularly preferably, the polymer is selected from the group consisting of polyurethane, polyamide, polyester, and polyolefin. Advantageously, such polymers are halogen-free, and in particular fluorine-free, which is considered advantageous as the membranes are environmentally friendly. Advantageously, such polymers are cyclic in nature, either by virtue of being reversible in the recycling stream or being biodegradable. Advantageously, flexible polymers can be used as the basis for membranes that provide the necessary tactile, optical, and mechanical properties for membranes used in clothing, and it is also possible to combine the properties of multiple layers of different polymers.

[0082] In a further embodiment, the seamless membrane has the following features: Porosity: As outlined above, the materials of the present invention are porous. They are characterized by their three-dimensional shape, which is free of seams, discontinuities, bonds, or similar assembly artifacts, as well as the size, type, and quantity of pores present. The size, type, and quantity of pores can be affected 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.

[0083] Size: The pore size of the membrane of the present invention (defined by the diameter of the coated particles; 5 to 15,000 nm, preferably 2,000 to 8,000 nm) can be determined by microscopic examination. Furthermore, the pore size distribution can be precisely adjusted depending on the starting material used.

[0084] Amount: Porosity, i.e., the volume of pores relative to the total volume of the membrane, can vary over a wide range. The materials of the present invention exhibit a porosity in the range of 30-80% by volume, preferably 55-65% by volume. Porosity can be determined by photomicrographic analysis.

[0085] Type: The pores of a material may be arranged so that the material is permeable, partially permeable, or impermeable. If substantially all of the pores of a material have dead ends, the material is impermeable. Conversely, if substantially all of the pores of a material have open ends, the material is considered permeable. Thus, if some of the pores are dead ends, the material is considered partially permeable. In an advantageous embodiment, the invention provides a polymeric membrane in which at least 50%, preferably at least 80%, of the pores are interconnected.

[0086] Thickness: The thickness of the membrane of the present invention can vary over a wide range, such as from 0.01 to 1000 μm. When the membrane of the present invention exists in the form of a single layer, a suitable thickness is in the range of 0.01 to 500 μm, preferably 1 to 120 μm, and most preferably 15 to 50 μm. When the membrane of the present invention exists in the form of a multilayer structure, a suitable thickness is in the range of 1 to 1000 μm, preferably 30 to 250 μm. Such membranes are sometimes referred to as "sheet materials" or "porous foils." These terms indicate that the material has a length and width that are at least one order of magnitude greater (preferably at least two orders of magnitude greater) than the thickness of the material.

[0087] The waterproofness (measured as WC and contact angle) and moisture vapor permeability (measured as WVTR) of the membranes of the present invention are described above in the first aspect of the present invention.

[0088] The mechanical properties of the membranes of the present invention, such as tensile strength and flexibility, make them suitable for many applications, including textile applications.

[0089] The possibility of producing silicone-free membranes is attracting more attention in OEM production lines, as silicones are considered a risk in all industries that rely on painting and adhesives and where goods are given a final coating (e.g., auto body paint shops; silicones cause defects such as in the exterior paint finish).

[0090] Layer: In one embodiment, the membrane of the present invention consists of a single layer. This embodiment is advantageous for jackets and outdoor clothing, house wraps in construction (to manage water and vapor within buildings), packaging materials (e.g., for food, consumer goods, and pharmaceuticals), and sensors.

[0091] In a further embodiment, the membrane of the present invention comprises two or more layers, such as two or three or up to 20 layers. This embodiment is advantageous for outdoor clothing (thereby providing improved comfort through better sweat management, particularly by moving sweat from less accessible areas in the jacket layer to more accessible areas of the garment), cooling textiles (i.e., materials that provide a cooling effect to the user through evaporation of moisture from the multilayer material), packaging for biological products, packaging for food, medicines, and sensitive consumer goods, cooling curtains (allowing passive cooling in and around buildings and public transportation), and air humidification units in air acclimation. Other applications include flexible gas absorbers, air purification devices, personal hygiene, and personal protective equipment.

[0092] Generally speaking, the present invention provides: Fourth Aspect relates to the specific use of 3D microporous membranes in textile applications and textile products comprising the 3D polymer membranes of the present invention, thus providing performance to clothing.

[0093] Generally, the textiles of the present invention retain the beneficial properties of 3D polymeric membranes, particularly waterproofness and breathability, and are therefore suitable for all applications applicable to such membranes, including, in particular, use in textile materials, such as those disclosed herein.

[0094] i. Direct application to 2D textile products In a further embodiment, simple 2D textiles can be directly coated with functional membranes without the use of adhesives / lamination. These textiles can be selected from the group of woven, nonwoven, or knitted textiles, for example, using specific patterns that are difficult to laminate.

[0095] ii. Direct application to 3D textile products (finished textile products) In a further embodiment, the functional garments comprising the seamless membrane are particularly selected from the group of garments (coats, jackets, trousers, underwear, etc.), containers (bags, backpacks, etc.) and others (gloves, hats and shoes, etc.). These garments are made of textiles which can be selected from the group of woven, nonwoven or knitted. The 3D membrane is sprayed, dip coated or painted directly onto the finished textile product, covering even the seams.

[0096] These substrates are considered "flexible" substrates, see below for more information on 3D applications on flexible substrates.

[0097] 1. Direct application to flexible textile products The finished textile product (e.g., a jacket) is placed on a heat-expandable support. Before proceeding to step (c), the substrate is covered with as uniform a layer as possible using spraying, dipping, or painting. Additional layers of the dispersion can be applied to critical areas of the substrate to enhance the performance and / or stability and durability of the resulting film.

[0098] 2. Freestanding membrane transferred to a flexible finished textile product Another technique for coating flexible substrates involves first applying the dispersion from step (a) to a rigid object according to the previous procedure described in step (g) to produce a free-standing film (4), and then attaching a flexible substrate to the same object / mannequin and immersing this substrate in the dispersion's solvent (7). Substrate immersion can be achieved by spraying the solvent onto the substrate, adhering the interior of the flexible substrate to the molded dispersion without the use of adhesives.

[0099] In certain embodiments, the method of applying the film directly or by transfer to a finished textile product can be applied to sports apparel, such as jackets and / or pants, shoes and / or socks, and gloves.

[0100] iii.Seamless freestanding membrane In a further embodiment, the 3D membrane is self-supporting and is connected to said textile membrane by gluing, welding, etc. These structures function in 3D shapes in general, but in particular:

[0101] a. Gloves In a further embodiment, the functional garment comprising the 3D shaped seamless self-supporting membrane is a glove, where the 3D shaped membrane is attached between an outer (oversized) and inner (undersized) glove-shaped tailored textile, for example, but not limited to, by specific points of three-dimensionally applied adhesive.

[0102] b.Socks In a further embodiment, the functional garment comprising the 3D shaped seamless self-supporting structural membrane is a sock, where the 3D shaped membrane is attached between an outer (oversized) and inner (undersized) sock-shaped custom-tailored textile, for example, but not limited to, by specific points of three-dimensionally applied adhesive.

[0103] iv. Body Mapping In further embodiments, 3D membranes can be applied in predetermined locations, such as by body mapping for performance control. Colors (dyes) can be added to the design as needed to accommodate different performance areas. Furthermore, the membrane can cover the entire surface of the garment or only selected areas.

[0104] Furthermore, the present invention provides Figure 1 This will be better understood by reference to the diagram, which outlines the process steps of the invention described herein, specifically the manufacturing process of a 3D waterproof and breathable membrane, shown here as a sock. Steps (a)-(g) and materials (1)-(10) are described in the specification and claims. The invention is further illustrated by the following non-limiting examples: Example is further explained by

[0105] I.Synthesis Polymer mixtures of commercial polymers were obtained by dissolving them in a solvent using an external stirrer (IKA® RW 20 Digital). Coated or uncoated particles were added to the mixture, and the resulting solution was passed through a ball mill (WAB Dyno®-Mill Multi Lab, pump speed 10 rpm, milling speed 3800 U / min with 1 mm ZrO2 milling beads) once to obtain the final polymer solution.

[0106] I.1 Example 1: Ether-based polyurethane and CaCO3: A 600 kg dispersion (1) was synthesized by dissolving two different ether-based polyurethanes in N,N-dimethylacetamide. Specially coated CaCO3 particles were added to the mixture, and the dispersion was milled to the required particle size. The final dispersion needed to be degassed under vacuum.

[0107] I.2 Example 2: Ether-based polyurethane and NaCl: Two kg of dispersion (1) was synthesized by dissolving two different ether-based polyurethanes in N,N-dimethylacetamide. NaCl particles were added to the mixture, and the dispersion was milled until the required particle size was achieved. The final dispersion needed to be degassed under vacuum.

[0108] I.3 Example 3: Water-based polyurethane and CaCO3: 0.5 kg of dispersion (1) was synthesized using commercially available aqueous PU (as dispersion). Specially coated CaCO3 particles were added to the mixture, and the dispersion was milled to the required particle size. The final dispersion had to be degassed under vacuum.

[0109] I.4 Example 4: Polylactic acid (PLA): A 2 kg dispersion (1) was synthesized by dissolving PLA in tetrahydrofuran (THF). Specially coated CaCO3 particles were added to the mixture, and the dispersion was milled to the required particle size. The final dispersion needed to be degassed under vacuum.

[0110] II. Application After synthesis of the dispersion (1) as described in I, the liquid film is sprayed, dip coated or painted onto the substrate (above).

[0111] II.1 Spraying General procedure: The substrate (2.2) was placed on a support and the spray area was demarcated using paper tape. It was then preheated in an oven at 110°C for at least 5 minutes. A few tens of milliliters of room temperature liquid film dispersion (1) was added to the spray gun tank. The spray gun was connected to a pressure-controllable airflow. When the gun trigger was fully pulled, the pressure was set to 2.5 bar.

[0112] The heated substrate (2.2) was then removed from the oven and the liquid film dispersion (1) was sprayed onto it to completely cover the desired area. The distance from the gun nozzle to the substrate (2.2) was 5 to 25 cm, and the gun advance speed could be varied from 5 to 500 mm / s. After applying the first single layer of the sprayed liquid film (2.1), the coated substrate (2) was again placed in a 110 °C oven to completely evaporate the solvent. The dried, coated substrate (3) was then removed from the oven, and a second layer was applied using the same procedure. This step can be repeated several times until the desired film thickness is reached. If the dried, non-porous film (3.1) is not easily removed from the substrate (3.2), the dried film on the substrate (3) is then placed in a bath to wash off the template particles (6). This bath can be acidic, depending on the particles (6) used.

[0113] Depending on the end use of the product, the 3D membrane is removed from the substrate (step e)) after washing step d), as described in more detail below.

[0114] Mannequin (Freestanding Film): Tests were performed on a mannequin wearing shoes and gloves. The spray parameters of distance to the sample and speed were fairly close (5-15 cm) and fast (250-500 mm / s). The manually created spray pattern appeared to have uniform film thickness across the entire sample, including 3D corners (+ / - 5 microns). After following the remaining general procedure, the resulting sample was gently removed from the mannequin, leaving a freestanding film.

[0115] Regarding 2D textiles: Textile tests were carried out on various types of fabrics, e.g., polyester, cotton, polyamide, and polypropylene. The procedure was adapted to the behavior of the fabric, including its thickness, weave, and liquid film absorption. The textile was fixed to a 2D support plate and preheated before the spraying process. At this stage, the support was kept vertical. The distance and speed parameters were fairly far (approximately 15-20 cm) and slow (approximately 5-10 mm / s). The spray pattern was more of a vertical and horizontal line to cover the entire surface. The rest of the general procedure was followed.

[0116] For finished textile products (including seams): Two techniques were experimented with to achieve membrane coverage of finished textile products including seams. i) Using the same technique as 2D spraying on fabrics, but by heating the sample beforehand. For samples too large to fit inside the oven, a heated blow-up support structure could be used to spray and dry simultaneously. ii) As explained in the previous part, first spray the mannequin and pass the sample through the membrane while it is still supported. Next, spray the solvent onto the fabric sample and submerge it with an airflow pressure of about 1 bar, then return the sample to the oven at 110 °C to dry the solvent. The rest of the general procedure was followed. This was used, for example, as a possibility to transfer the seamless membrane onto a finished textile-based sock.

[0117] II.2 Immersion General procedure: The substrate (2.2) was placed on a support and the immersion area was delimited with paper tape. The immersion test was performed without preheating (note that preheating the substrate is also effective). The liquid film dispersion (1) was kept at room temperature. The substrate (2.2) was immersed in the liquid film and dried in an oven at 110 °C. This step can be repeated several times until the desired film thickness is reached. If the dried non-porous film (3.1) was not easily removed from the substrate (3.2), the dried coated object (3) was placed in a bath to wash off the template particles (6). This bath can be acidic depending on the particles (6) used. Depending on the end use of the product, the 3D film is removed from the substrate (step (g)) after the washing step (f). More details are provided below:

[0118] Mannequin (freestanding membrane): A mannequin with a hand and shoe was immersed in a bucket of liquid membrane dispersion (1), then removed and left on top of the bucket for a while to allow the excess to drain back into the bucket, and placed in an oven at 110°C. The thickness of the sample was not consistent for all shapes because the liquid film accumulated at the bottom due to gravity. This could be avoided by moving the sample during drying. The remaining general procedure was as follows:

[0119] Finished textile (including seams): The finished textile was placed in a container and the liquid membrane dispersion (1) was poured over all desired areas. The coated object (2) was then removed and placed over a container for a short time to allow excess film to flow back into the container, before being placed in a 110°C oven. For example, a full men's size sock required approximately 200 mL of liquid film. The rest of the general procedure was followed.

[0120] II.3 Painting General procedure: The substrate (2.2) was placed on the support, and paper tape was used to demarcate the paint area. The coating test was performed without preheating (note that preheating the substrate also works). A paintbrush was dipped into a bath of the film dispersion (1) and a layer was applied to the sample with the brush. After this layer of paint film, the coated object (2) was placed in an oven at 110 °C. The sample was then removed from the oven, and a second layer was applied using the same procedure. This step can be repeated several times until the desired film thickness is reached. If the dried, non-porous film (3.1) is not easily removed from the substrate (3.2), the dried coated object (3) was placed in a bath to wash off the template particles (6). This bath can be acidic depending on the particles (6) used. Depending on the end use of the product, the 3D film is removed from the substrate (step (g)) after the washing step (f). More details are provided below:

[0121] 2D textile products: The liquid film was applied according to the instructions with a brush in one layer, leaving as few brush marks as possible. Even after passing through the oven, visible marks were still visible. A second layer was applied in a perpendicular direction and the painted sample (2) was again placed in the oven at 110°C. The rest of the general procedure was followed.

[0122] Finished textile product (including seams): The same procedure was applied as for 2D textiles. For example, the seams of a jacket were painted with the liquid film dispersion (1) not only along the direction of the seam but also perpendicular to it for uniform coverage. A second layer was applied using the same direction, and the painted object (2) was again placed in a 110°C oven. The rest of the general procedure was followed.

[0123] III.Analysis: The obtained product was discarded to allow for subsequent analytical measurements.

[0124] [Table 1]

[0125] [Table 2]

[0126] IV. Viscosity In two sets of experiments, 3D films were prepared in accordance with the present invention by spray coating with the dispersions described herein and compared to 3D films prepared by spray coating with known dispersions. Set 1: Three different viscosity dispersions (high, medium, low) were sprayed onto polyester fabric. The visual rating of the sprayed film was visually analyzed and rated from 1 to 6, with 6 representing no defects, no unevenness, and no intrusions in the film on the opposite, unsprayed side of the fabric. The experiment was repeated three times for each viscosity and standard. The standard deviation was determined. The success of the sprayed membranes was analyzed by their pore size and whether they could be measured. The results are summarized in Table 3 below.

[0127] [Table 3]

[0128] Conclusion: The results clearly show the influence of the viscosity of the starting material on the membrane performance. High viscosity dispersions give excellent results, while low viscosity dispersions fail to spray coat polyester fabric because the membrane layer is uneven and shows large uncontrolled holes. Therefore, the pore size required to achieve the target performance cannot be determined.

[0129] Set 2: Dispersions of the present invention and known dispersions are sprayed onto 3D objects and the results are compared in Table 4.

[0130] [Table 4]

[0131] Conclusion: We found that by adjusting the viscosity, it is possible to reliably produce 3D membranes with the appropriate pore size and monomodal size distribution. Previously known dispersions failed under similar conditions.

Claims

1. A method for producing a polymer membrane, comprising: The polymer membrane is ・It is a three-dimensional membrane with no seams a membrane (3.1) attached to a substrate (2.2) or a free-standing membrane (4), - Porous, with a pore size of 500 to 2,000 nm; The method includes the following steps: a. By milling: one or more diluents (7) in an amount of at least 40% by weight; one or more polymers (5) dissolved in said diluent (7), one or more coated or uncoated particles (6, 6', 6'') dispersed in said diluent (7), Optionally, one or more additives (8) dissolved in said diluent (7), Optionally, one or more dyes (9) dispersed in said diluent (7), providing a liquid membrane dispersion (1) having a viscosity of 400-1500 mPas at 25°C and 200 rpm; b. Coating a three-dimensional substrate (2.2) with said liquid film dispersion (1), thereby obtaining a layer (2.1) that partially or completely covers said substrate (2.2); c. subjecting the obtained material (2) to a drying process to obtain a dried material (3); d. Optionally, repeating steps (b) and (c), thereby obtaining a multi-coated material (3'); e. Optionally, subjecting the material thus obtained to a polymerization or crosslinking step; f. removing said particle or particles (6, 6', 6'') by a dissolution step, thereby obtaining a porous polymer membrane (3.1) attached to the substrate (2.2); and g. Optionally, removing the resulting polymeric porous membrane (3.1) from said substrate (2.2) without destroying its three-dimensional shape, thereby obtaining a free-standing 3D membrane (4); wherein said 3D membrane comprises three distinct coordinates y, z, and x, thereby excluding 2D membranes and curved 2D membranes; wherein said polymer (5) has a solubility of at least 1 g / l in the diluent (7); Here, the coated particles (6') are It is pre-manufactured, selected from the group consisting of organic salts, metal salts, metal oxides and combinations thereof, or organic crystals; The coating material of the coated particles (6') is selected from the group consisting of polymaleic anhydride, carboxylic acids, aryl-alkoxy-silanes, alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes. - has a particle size in the range of 5 to 15,000 nm; and wherein the uncoated particles (6'') are selected from the group consisting of organic salts, metal salts, metal oxides and combinations thereof, or organic crystals; -having a particle size in the range of 5 to 15,000 nm; method.

2. The method of claim 1 , wherein the coating is a spray coating.

3. 10. The method of claim 1, characterized by the following steps: the method does not include a closing step that is detectable in the textile or that modifies the polymeric membrane; the closing step is in particular selected from bonding, sewing, welding, gluing, knitting, stitching, and / or the method does not include a phase separation step; and / or the application method does not include a two-dimensional pore formation step before assembly into a three-dimensional product; and / or - said application generates pores (step (f)) into the final shape after application of the liquid membrane precursor (step (b)); and / or said coating step (b) is selected from the group consisting of spraying, painting, printing (including 3D printing), and dip coating; and / or The dissolution (f) is carried out within 90 minutes.

4. 2. The method according to claim 1, wherein the polymeric membrane completely or in a predetermined area covers the outer or inner surface of the garment (2.2).

5. 10. The method of claim 1, characterized by the following steps: the metal salts are selected from the group consisting of carbonates, bicarbonates, sulfates, halides, nitrates and phosphates, and the metal oxides are selected from ZnO and MgO; and / or the organic crystal is selected from the group consisting of sugars; and / or the coating material is selected from the group of natural fatty acids, acid anhydrides such as polymaleic anhydride (PMAH), their homopolymers as well as copolymers containing PMAH, and mixtures of PMAH, or carboxylic acids; and / or the diluent is selected from the group consisting of solvents with a boiling point of 200°C or less; and / or the substrate is selected from the group consisting of polymer, metal, leather, ceramic, concrete, and paper, each painted or unpainted; The three-dimensional substrate is (i) clothing; (ii) any type of molded leather object; (iii) Specialized electronic components, furniture, or construction It has the shape of

6. 5. The method according to claim 1, wherein the polymer is selected from the group consisting of polyurethanes, polyesters, polyamides, and polyolefins.

7. 10. The method of claim 1, The polymer membrane is: - has a thickness of 0.01 to 1000 microns; and / or - has a porosity of 30-80%; and / or - pore opening size between 5 and 10,000 nm; and / or There is at least 4.8m of water column (WC), and / or Water vapor transmission rate (WVTR) of at least 500 g / m ２ and / or - The water contact angle is 50° or more, ・It consists of 1 to 20 layers.

8. 10. The method of claim 1, The liquid membrane dispersion (1) comprises: 40 to 99% by weight of a diluent (7); 1 to 20% by weight of polymer (5); 0.5 to 40% by weight of coated and / or uncoated particles (6); 0 to 6% by weight of a coating material; 0 to 5% by weight of additive (8); 0 to 5% by weight of dye (9).

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