Polymer composition for waterproof and breathable membrane

Abstract

This invention relates to compositions comprising: 75 to 98 wt% of at least one hydrophilic elastomer thermoplastic polymer (TPE) A, selected from (a1) copolymers containing polyester and polyether blocks, and (a2) copolymers containing polyurethane and polyether blocks or polyester blocks and / or mixtures thereof; 2 to 15 wt% of at least one copolymer B, comprising units derived from ethylene, alkyl (meth)acrylate, and a comonomer containing at least one acid, anhydride, or epoxide functional group; and 0 to 10 wt% of at least one additive. The invention further relates to a process for manufacturing a membrane and the membrane thereof.

Description

Technical Field

[0001] This invention relates to polymer compositions and waterproof and breathable membranes obtained using said compositions. Background Technology

[0002] Membranes that are impermeable to liquid water but permeable to water vapor are used in various fields such as textiles, construction, agriculture, and packaging. For example, these membranes can be used as packaging to cover products or as coatings that adhere to the surface of products.

[0003] Generally, breathable membranes must meet certain requirements, such as a uniform appearance, wind resistance, high permeability to water vapor, a certain degree of elasticity, and the ability to adhere to different substrates. Furthermore, these membranes must be easy to process during production (especially by extrusion) without causing deformation within the membrane. Poor processability is reflected in defects on the membrane, such as pores or irregular edges.

[0004] It is known practice to form such membranes using components containing polyamide and polyether blocks. However, despite their high permeability to water vapor, the resulting membranes are rarely stretchable, which causes problems when they are manufactured by extrusion (especially by extrusion coating).

[0005] Furthermore, the use of terpolymer compositions, especially terpolymers derived from olefinic, acrylic, and butene monomers, makes it possible to obtain films that can be easily processed by extrusion. However, these films have very low air permeability.

[0006] US 2004 / 0 029 467 relates to a breathable membrane comprising at least one polymer (a) selected from ethylene / (meth)acrylate alkyl copolymer (a1), optionally neutralized ethylene / (meth)acrylate copolymer (a2), ethylene / vinyl monomer copolymer (a3), mixtures (a1) / (a2), mixtures (a1) / (a3), mixtures (a2) / (a3) and mixtures (a1) / (a2) / (a3), and / or the breathable membrane comprising at least one functionalized polyethylene (b); and at least one copolymer (c) containing copolyamide blocks or polyester blocks and polyether blocks.

[0007] US 5,614,588 relates to a polymer blend comprising a polyether block amide consisting of: 30 wt% to 60 wt% polyamide-12, polyamide-11, and / or polyamide-12,12 blocks and 70 wt% to 40 wt% polyethylene glycol blocks; a polyether block amide consisting of: 65 wt% to 85 wt% polyamide-12, polyamide-11, and / or polyamide-12,12 blocks and 35 wt% to 15 wt% polyethylene glycol blocks; and a poly(ethylene-co-vinyl acetate-g-maleic anhydride) polymer consisting of: 75 wt% to 95 wt% ethylene, 5 wt% to 25 wt% vinyl acetate, and 0.1 wt% to 2 wt% maleic anhydride. The compositions described in this document are used to manufacture membranes permeable to water vapor.

[0008] US 5 506 024 relates to a membrane permeable to water vapor, which is made of a thermoplastic elastomer based on polyether ester amide (and preferably based on polyether block amide).

[0009] US 5,800,928 relates to a membrane permeable to water vapor, comprising at least one thermoplastic elastomer comprising a polyether block and at least one copolymer comprising ethylene and at least one (meth)acrylate alkyl ester.

[0010] A composition is required that allows the manufacture of such a membrane, which has good permeability to water vapor and good processability during the manufacture of the membrane. Summary of the Invention

[0011] This invention relates first to a composition comprising:

[0012] -75% to 98% by weight of at least one hydrophilic thermoplastic elastomer (hereinafter referred to as TPE) polymer A, selected from: (a1) copolymers containing polyester blocks and polyether blocks (COPE), (a2) copolymers containing polyurethane blocks and polyether or polyester blocks (TPU) and / or mixtures thereof, relative to the weight of the composition.

[0013] -2% to 15% by weight of at least one copolymer B, comprising units derived from ethylene, alkyl (meth)acrylates, and a comonomer comprising at least one acid, anhydride, or epoxide functional group, relative to the weight of the composition; and

[0014] - 0% to 10% by weight of at least one additive, relative to the weight of the composition.

[0015] For the purposes of this invention, copolymers containing polyester and polyether blocks (hereinafter referred to as COPE or copolyether ester) are copolymers containing polyester and polyether blocks. They consist of flexible polyether blocks and rigid polyester blocks, the flexible polyether blocks being derived from polyether glycols, and the rigid polyester blocks being derived from the reaction of at least one dicarboxylic acid with at least one short-chain extended diol unit. The polyester and polyether blocks are linked by ester bonds through the reaction of the acid functional group derived from the dicarboxylic acid with the OH functional group of the polyether glycol. The connection between the polyether and the diacid forms the flexible block, while the connection between ethylene glycol or butanediol and the diacid forms the rigid block of the copolyether ester. The short-chain extended diol may be selected from neopentyl glycol, cyclohexanediol, and the formula HO(CH2). n OH aliphatic diols, where n is an integer from 2 to 10.

[0016] Advantageously, the diacid is an aromatic dicarboxylic acid containing 8 to 14 carbon atoms. Up to 50 mol% of the said aromatic dicarboxylic acid may be replaced by at least one other aromatic dicarboxylic acid containing 8 to 14 carbon atoms, and / or up to 20 mol% may be replaced by an aliphatic dicarboxylic acid containing 2 to 14 carbon atoms.

[0017] Examples of aromatic dicarboxylic acids include: terephthalic acid, isophthalic acid, biphenylic acid, naphthalenedicarboxylic acid, 4,4'-biphenylic acid, bis(p-carboxyphenyl)methane, ethylenebis(p-benzoic acid), 1,4-tetramethylenebis(p-oxybenzoic acid), ethylenebis(p-oxybenzoic acid), and 1,3-trimethylenebis(p-oxybenzoic acid).

[0018] Examples of diols include: ethylene glycol, 1,3-trimethylenediol, 1,4-tetramethylenediol, 1,6-hexamethylenediol, 1,3-propanediol, 1,8-octamethylenediol, 1,10-decamethylenediol, and 1,4-cyclohexylenediethanol. Copolymers containing polyester and polyether blocks are, for example, polyether units derived from polyether diols (such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylenediol (PO3G), or polytetramethylenediol (PTMG)), dicarboxylic acid units such as terephthalic acid, and ethylene glycol (ethanediol) or 1,4-butanediol units. Such copolyether esters are described in patents EP402883 and EP 405 227. These polyether esters are thermoplastic elastomers. They may contain plasticizers. Examples that may be mentioned include those from DSM under the name... Commercially available products sold, or products sold by DuPont.

[0019] For the purposes of this invention, copolymers containing polyurethane blocks and polyether or polyester blocks (hereinafter referred to as TPU) are polyether urethanes derived from the condensation of flexible polyether blocks (which are polyether diols) and rigid polyurethane blocks, wherein the polyurethane blocks are derived from the reaction of at least one diisocyanate with at least one short-chain diol, wherein the diisocyanate may be selected from aromatic diisocyanates (e.g., MDI, TDI) and aliphatic diisocyanates (e.g., HDI or hexamethylene diisocyanate). The short-chain extended diol may be selected from the diols mentioned in the description of copolyether esters above.

[0020] The polyurethane and polyether blocks are linked by bonds derived from the reaction of isocyanate functional groups with the OH functional groups of polyether diols.

[0021] Also mentioned are polyester urethanes, derived from the condensation of flexible polyester blocks (which are polyester diols) and rigid polyurethane blocks (derived from the reaction of at least one diisocyanate with at least one short-chain diol). The polyester diol is derived from the condensation of a dicarboxylic acid and a diol, wherein the dicarboxylic acid is advantageously selected from aliphatic dicarboxylic acids containing 2 to 14 carbon atoms, and the diol is a short-chain extended diol selected from the diols mentioned in the description of copolyether esters above. They may contain plasticizers.

[0022] According to one embodiment, the hydrophilic TPE contains at least 10% by weight, preferably at least 20% by weight, preferably at least 30% by weight, preferably at least 40% by weight, and preferably at least 50% by weight of polyethylene glycol (PEG), relative to the weight of the TPE.

[0023] According to some embodiments, (meth)acrylate alkyl esters include alkyl groups comprising 1 to 24 carbon atoms, preferably 1 to 5 carbon atoms.

[0024] According to certain embodiments, the alkyl methacrylate is selected from methyl methacrylate, ethyl methacrylate, and butyl methacrylate and combinations thereof.

[0025] According to some embodiments, the molar content of units derived from (meth)acrylate in copolymer B is 5% to 35%.

[0026] According to some embodiments, the molar content of the comonomer comprising at least one acid, anhydride, or epoxide functional group in copolymer B is from 0.1% to 15%.

[0027] According to some embodiments, the comonomer comprising at least one acid, anhydride, or epoxide functional group is selected from unsaturated carboxylic anhydrides, and is preferably maleic anhydride.

[0028] According to some embodiments, the comonomer comprising at least one acid, anhydride, or epoxide functional group has an unsaturated epoxide functional group, and is preferably glycidyl methacrylate.

[0029] According to some embodiments, copolymer B does not contain units derived from vinyl acetate.

[0030] According to some embodiments, the additives are selected from inert dyes such as titanium dioxide, fillers, surfactants, crosslinking agents, nucleating agents, reactive compounds, mineral or organic flame retardants, ultraviolet (UV) or infrared (IR) light absorbers, UV or IR fluorescent agents, and combinations thereof.

[0031] The present invention also relates to a process for manufacturing membranes using the compositions described above.

[0032] The membrane according to the invention can be prepared by any method that yields a close or homogeneous mixture (e.g., melt blending, extrusion, pressing or roller milling), the mixture containing the hydrophilic TPE and copolymer B according to the invention, and optionally one or more additives.

[0033] According to one embodiment, the TPE in granular form and copolymer B can be dry-blended before being processed into a film.

[0034] It is advantageous to use common mixing and kneading equipment in the thermoplastics industry, such as extruders, twin-screw extruders, especially self-cleaning gear co-rotating twin-screw extruders, and kneaders, such as Buss co-kneaders or internal mixers.

[0035] According to a preferred embodiment, the process for manufacturing the film is an extrusion process. According to some embodiments, the extrusion is carried out at a temperature of 100 to 300°C, and preferably 150 to 280°C.

[0036] This process generally includes a step of traction composition. The traction step can be carried out by extrusion blow molding.

[0037] According to one embodiment, the traction step is carried out by extrusion coating.

[0038] According to one implementation, the traction step is carried out by flat extrusion.

[0039] The present invention also relates to membranes obtained by the processes described above.

[0040] This invention overcomes the shortcomings of the prior art. More specifically, it provides a composition that allows the manufacture of a membrane having both good permeability to water vapor and good processability during the manufacture of the membrane.

[0041] This is achieved by a composition comprising: polymer A as described above and at least one copolymer B, wherein copolymer B comprises units derived from: at least three comonomers: a first ethylene comonomer, a second (meth)acrylate alkyl comonomer, and a third comonomer comprising at least one reactive functional group in the form of an acid, anhydride, or epoxide group; and optionally one or more additives.

[0042] More specifically, this composition comprises: 75% to 98% by weight of polymer A, 2% to 15% by weight of copolymer B, and 0% to 10% by weight of at least one additive, which makes it possible to obtain a film with good permeability to water vapor and very good processability (especially by extrusion, and particularly by hot extrusion).

[0043] The invention will now be described in more detail in a non-limiting manner in the following description.

[0044] Composition

[0045] The composition according to the present invention comprises the following:

[0046] - At least one polymer A, selected from: (a1) copolymers containing polyester blocks and polyether blocks and (a2) copolymers containing polyurethane blocks and polyether or polyester blocks;

[0047] - At least one copolymer B, comprising units derived from: at least three comonomers: a first ethylene comonomer, a second (meth)acrylate alkyl ester comonomer, and a third comonomer, the third comonomer comprising at least one reactive functional group in the form of an acid, anhydride, or epoxide group; and

[0048] -At least one optional additive.

[0049] Polymer A is present in the composition in the following amounts: 75% to 98% by weight, and preferably 75% to 95% by weight, relative to the weight of the composition. For example, polymer A may be present in the composition in the following amounts: 75% to 78% by weight; or 78% to 80% by weight; or 80% to 82% by weight; or 82% to 84% by weight; or 84% to 86% by weight; or 86% to 88% by weight; or 88% to 90% by weight; or 90% to 92% by weight; or 92% to 94% by weight; or 94% to 96% by weight; or 96% to 98% by weight, relative to the weight of the composition.

[0050] Regarding copolymer B comprising units derived from at least three comonomers, it is present in an amount of 2% to 15% by weight, and preferably 5% to 15% by weight, relative to the weight of the composition. For example, this copolymer B may be present in the composition in an amount of 2% to 3% by weight; or 3% to 4% by weight; or 4% to 5% by weight; or 5% to 6% by weight; or 6% to 7% by weight; or 7% to 8% by weight; or 8% to 9% by weight; or 9% to 10% by weight; or 10% to 11% by weight; or 11% to 12% by weight; or 12% to 13% by weight; or 13% to 14% by weight; or 14% to 15% by weight, relative to the weight of the composition.

[0051] The first comonomer used to manufacture this copolymer B is ethylene. The ethylene-derived units in copolymer B may have the following molar content: 50% to 94.9%, and preferably 58% to 79%. This molar content may be particularly 50% to 55%; or 55% to 60%; or 60% to 65%; or 65% to 70%; or 70% to 75%; or 75% to 80%; or 80% to 85%; or 85% to 90%; or 90% to 94.9%.

[0052] The second comonomer used to manufacture copolymer B is an alkyl (meth)acrylate. The term "alkyl (meth)acrylate" refers to both alkyl acrylate and alkyl methacrylate. Preferably, the alkyl group of the alkyl (meth)acrylate contains 1 to 24 carbon atoms, and more preferably 1 to 5 carbon atoms. For example, it may contain 1 to 2; or 2 to 4; or 4 to 6; or 6 to 8; or 8 to 10; or 10 to 12; or 12 to 14; or 14 to 16; or 16 to 18; or 18 to 20; or 20 to 22; or 22 to 24 carbon atoms.

[0053] According to certain preferred embodiments, the second comonomer is selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and combinations thereof. Preferably, the second comonomer is selected from methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

[0054] According to some implementations, only one second (meth)acrylate alkyl comonomer is used to manufacture copolymer B.

[0055] According to other embodiments, copolymer B can be manufactured from more than one second alkyl methacrylate comonomer (e.g., two or three second comonomers). For example, copolymer B can be manufactured from ethyl methacrylate and / or methyl methacrylate and / or butyl methacrylate.

[0056] The units derived from one or more second comonomers may have the following molar content in copolymer B: 5% to 35%, and preferably 20% to 30%. This molar content may be particularly 5% to 10%; or 10% to 15%; or 15% to 20%; or 20% to 25%; or 25% to 30%; or 30% to 35%.

[0057] The third comonomer includes at least one reactive functional group in the form of an acid, anhydride, or epoxide group.

[0058] According to some embodiments, the third comonomer is selected from unsaturated carboxylic acids or their carboxylic anhydride derivatives, and preferably from unsaturated dicarboxylic acids or their dicarboxylic anhydride derivatives.

[0059] Examples of unsaturated dicarboxylic anhydrides include, in particular, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. Maleic anhydride is preferred.

[0060] Unsaturated monocarboxylic or dicarboxylic acid monomers, such as (meth)acrylic acid, can also be used.

[0061] Alternatively, the third comonomer may contain unsaturated epoxide-type functional groups.

[0062] Notable examples include:

[0063] - Aliphatic glycidyl esters and ethers, such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconic acid glycidyl ester, glycidyl methacrylate (GMA) and glycidyl acrylate; and

[0064] - Alicyclic glycidyl esters and ethers, such as glycidyl-2-cyclohexyl-1-ene ether, 4,5-cyclohexene carboxylic acid diglycidyl ester, 4-cyclohexene carboxylic acid glycidyl ester, 5-norbornene-2-methyl-2-carboxylic acid glycidyl ester and cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid diglycidyl ester.

[0065] The units derived from the third comonomer may be present in copolymer B in the following molar amounts: 0.1% to 15%, and preferably 1% to 12%. This molar amount may be particularly 0.1% to 1%; or 1% to 3%; or 3% to 5%; or 5% to 7%; or 7% to 9%; or 9% to 11%; or 11% to 13%; or 13% to 15%.

[0066] According to some embodiments, only one third (meth)acrylate comonomer is used to manufacture copolymer B.

[0067] According to other embodiments, copolymer B may contain units derived from more than one third comonomer (e.g., two or three third comonomers). For example, the composition according to the invention may contain units derived from maleic anhydride and glycidyl methacrylate.

[0068] In this case, the content of units derived from the third comonomer is provided relative to the total amount of various third comonomers.

[0069] Preferably, copolymer B does not contain any units derived from comonomers other than the first, second, and third comonomers described above.

[0070] Preferably, copolymer B is a terpolymer, meaning it comprises units derived from only three comonomers.

[0071] Examples of preferred copolymer B are: terpolymers derived from ethylene, methyl acrylate and maleic anhydride; terpolymers derived from ethylene, ethyl acrylate and maleic anhydride; terpolymers derived from ethylene, butyl acrylate and maleic anhydride; terpolymers derived from ethylene, methyl acrylate and glycidyl methacrylate; terpolymers derived from ethylene, ethyl acrylate and glycidyl methacrylate; and terpolymers derived from ethylene, butyl acrylate and glycidyl methacrylate.

[0072] Copolymer B is preferably manufactured by copolymerization of various comonomers, especially by high-pressure free radical polymerization. For example, the second and third comonomers can be copolymerized directly with ethylene, especially by high-pressure free radical polymerization.

[0073] According to certain preferred embodiments, the compositions according to the invention, and more particularly copolymer B, do not contain units derived from vinyl acetate. This is because the monomer can have toxic properties. Furthermore, it is unsuitable for hot extrusion, which makes it difficult or even impossible to form films from compositions containing units derived from this monomer.

[0074] Regarding additives, they are optionally present in the following weight percentages: 0 to 10%, preferably 0 to 5%. For example, one or more additives may be present in the following weight percentages: 0 to 0.5%; or 0.5% to 1%; or 1% to 2%; or 2% to 3%; or 3% to 4%; or 4% to 5%; or 5% to 6%; or 6% to 7%; or 7% to 8%; or 8% to 9%; or 9% to 10%.

[0075] These additives may include, for example, inert dyes such as titanium dioxide, fillers, surfactants, crosslinking agents, nucleating agents, reactive compounds, mineral or organic flame retardants, ultraviolet (UV) or infrared (IR) light absorbers, and UV or IR fluorescent agents. Typical fillers include talc, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, and wood flour.

[0076] These additives allow for the alteration of one or more physical properties of the composition.

[0077] membrane

[0078] The present invention also relates to membranes obtained using the compositions described above.

[0079] This film can preferably be manufactured by extrusion. Preferably, the extrusion is carried out thermally at a temperature in the range of 100 to 300°C, preferably 150 to 300°C, for example 180 to 280°C.

[0080] According to some embodiments, the membrane is manufactured by extruding and coating a composition according to the invention onto a substrate. In this case, the extrusion temperature may be, for example, 250 to 300°C. The substrate may be selected from aluminum, paper, board, cellophane, membranes based on polyethylene, polypropylene, polyamide, polyester, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), or polyacrylonitrile (PAN) resins, which may optionally be oriented, optionally metallized, optionally treated by physical or chemical means, and membranes coated with a thin inorganic barrier layer, such as polyester (PET SiOx or AlOx) and woven or nonwoven fabrics. When the membrane is not a woven or nonwoven fabric, it is preferably perforated, especially microperforated.

[0081] According to other embodiments, the film can be manufactured by flat film extrusion (“extrusion casting”) of the composition according to the invention. In this case, the extrusion temperature can be, for example, 180 to 230°C.

[0082] The membrane according to the present invention is a waterproof and breathable membrane. The term "waterproof and breathable" means that it is permeable to water vapor and impermeable to liquid water.

[0083] The membrane according to the invention may have a thickness of 2 to 100 μm, and preferably 10 to 50 μm.

[0084] According to one embodiment, the waterproof and breathable membrane has a thickness of less than or equal to 50 mm, preferably less than or equal to 40 mm, 30 mm, or 25 mm, and preferably between 5 and 25 mm.

[0085] The thickness described above provides good properties in terms of water vapor permeability.

[0086] Preferably, the membrane according to the invention, for a membrane thickness of 30 μm, has a strength of at least 700 g / m³ at 23°C and 50% relative humidity. 2 / 24-hour water vapor permeability (MVTR, representing "moisture permeability"). More preferably, for a membrane thickness of 30 μm at 23°C and 50% relative humidity, the membrane water vapor permeability is at least 800 g / m. 2 / 24h. Specifically, for a membrane thickness of 30 μm at 23°C and 50% relative humidity, the permeability of the MVTR membrane can range from 700 to 800 g / m². 2 / 24h, or 800 to 900g / m 2 / 24h, or 900 to 1000 g / m 2 / 24h, or 1000 to 1200 g / m 2 / 24h, or 1200 to 1500 g / m 2 / 24h, or 1500 to 2000 g / m 2 / 24h, or 2000 to 2500 g / m 2 / 24h, or 2500 to 3000 g / m 2 / 24h, or 3000 to 3500 g / m 2 / 24h, or 3500 to 4000 g / m 2 / 24h, or 4000 to 4500 g / m 2 / 24h, or 4500 to 5000 g / m 2 / 24h. At 23°C, with 50% relative humidity, and a membrane thickness of 30 μm, the membrane's water vapor permeability (MVTR) can be measured according to standard ASTM E96 A.

[0087] The present invention also relates to the use of the membranes described herein in the fields of medical, hygiene, luggage, manufacturing, clothing, household or home appliances, furniture, blankets, automobiles, industry, especially industrial filtration, agriculture and / or construction.

[0088] The present invention also relates to laminated products (hereinafter referred to as laminates) comprising at least one material and at least one waterproof and breathable membrane according to the present invention, wherein the material may be selected, for example, from textiles, building materials, packaging or coatings.

[0089] According to a particular embodiment, the material is a textile material, and the film is adhered to at least one surface of the textile material, wherein the peel force is in the range of 0.5 to 50 N, preferably 0.5 to 10 N.

[0090] Advantageously, the film according to the invention is applied to textile materials by any known process, preferably without the use of any adhesive between the film and the textile.

[0091] Examples that may be mentioned include extruding and coating the composition film onto textiles, or hot-pressing (thermal lamination or lamination bonding) the film onto or between textiles at a temperature sufficient to impregnate and wrap the textile fibers.

[0092] According to alternative embodiments or embodiments in combination with the foregoing embodiments (one or more), the use of adhesive sealant bonding may be mentioned, which is preferably an aqueous adhesive sealant, i.e., the adhesive sealant composition contains less than 5% by weight of solvent.

[0093] Preferably, the film has a thickness between 5 and 50 mm, and more preferably between about 5 and 10 mm. Advantageously, in extrusion-coating applications, a thermoplastic film of 10 to 50 g / m² is applied to textiles.

[0094] In this specification of the invention, the following definitions apply:

[0095] - The term "textile material" or "textile" means any material made of fibers or filaments, and any material forming a porous membrane layer characterized by a length-to-thickness ratio of at least 300, including paper and cardboard.

[0096] - The term "fiber" refers to any synthetic or natural material characterized by a length-to-diameter ratio of at least 300;

[0097] The term "silk" refers to any fiber of infinite length.

[0098] In textiles, especially fiber splices (dressings, filter membranes, felts), rovings (dressings), yarns (for sewing, weaving or weaving), woven fabrics (straight, circular, fully formed), fabrics (traditional, jacquard, multiple, double-sided, multi-axis, 2.5D, 3D) and many others.

[0099] According to a preferred embodiment of the present invention, the at least one textile material is a porous membrane layer, in the form of woven textiles or nonwoven textiles.

[0100] Advantageously, the at least one textile material comprises synthetic fibers, especially synthetic fibers obtained from bio-based raw materials, natural fibers, artificial fibers made from natural raw materials, mineral fibers and / or metal fibers.

[0101] Advantageously, the textile comprises synthetic fibers derived from bio-based raw materials, such as polyamide fibers, especially polyamide 11. Advantageously, the textile also comprises natural fibers, such as cotton, wool and / or silk, artificial fibers made from natural raw materials, and mineral fibers, such as carbon, glass, silica and / or magnesium fibers.

[0102] Textiles are particularly selected from fabrics or textile surfaces, such as woven, braided, nonwoven, or blanket surfaces. These articles may include, for example, blankets, carpets, upholstery, surface coverings, sofas, curtains, bedding, mattresses and pillows, clothing, and medical textile materials.

[0103] The textiles according to the invention advantageously constitute felts, filter membranes, membranes, gauze, cloth, dressings, layers, fabrics, woven fabrics, garment articles, clothing, bedding articles, furnishing articles, curtains, passenger cabin coverings, functional technical textiles, geotextiles and / or agricultural textiles. Example

[0104] The following examples illustrate, but do not limit, the present invention.

[0105] Membranes were prepared from different compositions (A to G) in the following two ways to evaluate water vapor permeability and membrane stability limits (processability).

[0106] To assess the permeability to water vapor:

[0107] Films are prepared from various compositions (A to G) using an extruder with the following parameters via a flat film extrusion process (“extrusion casting”):

[0108] - Screw diameter: 30mm;

[0109] -L / D ratio: 25

[0110] - Shape: Screw-Barrier;

[0111] - Mold head: T-shaped, 250μm wide and 300μm air gap.

[0112] The extrusion temperature is between 180°C and 230°C and varies depending on the grade of the copolymer.

[0113] The water vapor permeability MVTR was measured at 23°C and 50% relative humidity according to standard ASTM E96A.

[0114] The obtained membrane has a thickness of 50 μm.

[0115] To assess processability:

[0116] Films were prepared by extruding and coating various compositions (A to G) onto an aluminum (37 μm) / polymer support using a Collin extrusion coating line with the following parameters:

[0117] - Air gap: 70mm;

[0118] - Screw speed: 80 rpm;

[0119] -Die head gap: 300μm.

[0120] The extrusion temperature is 280℃.

[0121] The membrane has an initial thickness of 50 μm (which decreases as the linear velocity increases).

[0122] Therefore, to assess the stability limits of the membrane, the linear velocity was gradually increased from 5 m / min until an instability was observed. This instability could be membrane rupture, the formation of one or more pores on the membrane, or instability in the membrane width. These observations were performed three times to confirm the results, and the average value was taken.

[0123] The membrane stability limit corresponds to a velocity at or above which instability occurs.

[0124] In both cases:

[0125] The terpolymers used (polymers comprising units derived from at least three comonomers) are as follows:

[0126] [Table 1]

[0127] terpolymer First Single Unit Second monomer (molar content) Third monomer (molar content) Terpo1 ethylene Ethyl acrylate (29%) Maleic anhydride (1.3%) Terpo2 ethylene Butyl acrylate (25%) Glycidyl methacrylate (8%) Terpo3 ethylene Butyl acrylate (25%) Glycidyl methacrylate (5%)

[0128] The copolymers used for comparison purposes are as follows:

[0129] [Table 2]

[0130] copolymer First Single Unit Second monomer (molar content) Copo1 ethylene Methyl acrylate (25%) Copo2 ethylene Methyl acrylate (30%)

[0131] The characteristics of compositions A to G are provided in the following table:

[0132] [Table 3]

[0133] Composition TPE polymer (%) terpolymers or copolymers (%) A (Invention) 90％ Terpo1 (10%) B (Invention) 90％ Terpo2 (10%) C (Invention) 90％ Terpo3 (10%) D (Comparison) 80％ Terpo1 (20%) E (Comparison) 90％ Copo1 (10%) F (Contrast) 90％ Copo2 (10%) G (contrast) 100％ - H (Invention) 90％ Terpo1 10% I (Comparison) 100％ -

[0134] The TPE polymer used in Example (AG) is a commercially available COPE product, manufactured by DSM under the brand name... VT3108 for sale.

[0135] The TPE polymer used in Examples H and I is a commercially available aromatic polyether polyurethane product, marketed by Covestro under the brand name... Sale.

[0136] Compositions A to C and H are according to the invention, and D to G correspond to comparative examples (composition D contains copolymer B according to the invention, but in a higher amount than claimed, and composition G contains only Arnitel copolymer).

[0137] The results regarding the water vapor permeability and stability limits of the membranes (A to G) obtained using compositions A to G are shown below:

[0138] [Table 4]

[0139] membrane Stability limit (m / min) Permeability to water vapor A (Invention) 35 325 B (Invention) 41 330 C (Invention) 38 322 D (Comparison) 50 245 E (Comparison) 22 320 F (Contrast) 23 315 G (contrast) 17 360 H (Invention) 40 300 I (Comparison) 25 310

[0140] The membranes (A to C, H) according to the present invention are observed to have both high water vapor permeability and good processability (membrane stability limit).

Claims

1. A composition comprising the following: - 75% to 98% by weight of at least one hydrophilic thermoplastic elastomer (TPE) polymer A, selected from (a2) copolymers containing polyurethane blocks and polyether or polyester blocks and / or (a1) copolymers containing polyester blocks and polyether blocks and (a2) copolymers containing polyurethane blocks and polyether or polyester blocks, relative to the weight of the composition. - 2% to 15% by weight of at least one copolymer B, comprising units derived from ethylene, alkyl (meth)acrylate and a comonomer comprising at least one acid, anhydride or epoxide functional group, relative to the weight of the composition, wherein the ethylene-derived units have a molar content of 50% to 94.9% in copolymer B, the alkyl (meth)acrylate-derived units have a molar content of 20% to 30% in copolymer B, and the units derived from the comonomer comprising at least one acid, anhydride or epoxide functional group are present in copolymer B at a molar content of 0.1% to 15%; and - At least one additive, from 0% to 10% by weight, relative to the weight of the composition.

2. The composition of claim 1, wherein the (meth)acrylate alkyl ester comprises an alkyl group containing 1 to 24 carbon atoms.

3. The composition of claim 2, wherein the (meth)acrylate alkyl ester comprises an alkyl group containing 1 to 5 carbon atoms.

4. The composition according to any one of claims 1 to 3, wherein the alkyl methacrylate is selected from methyl methacrylate, ethyl methacrylate, and butyl methacrylate and combinations thereof.

5. The composition according to any one of claims 1 to 3, wherein the molar content of the units derived from (meth)acrylate in copolymer B is 5% to 35%.

6. The composition according to any one of claims 1 to 3, wherein the molar content of the comonomer comprising at least one acid, anhydride or epoxide functional group in copolymer B is from 0.1% to 15%.

7. The composition according to any one of claims 1 to 3, wherein the comonomer comprising at least one acid, anhydride, or epoxide functional group is selected from unsaturated carboxylic anhydrides.

8. The composition of claim 7, wherein the comonomer comprising at least one acid, anhydride, or epoxide functional group is selected from maleic anhydride.

9. The composition according to any one of claims 1 to 3, wherein the comonomer comprising at least one acid, anhydride, or epoxide functional group has an unsaturated epoxide functional group.

10. The composition of claim 9, wherein the comonomer comprising at least one acid, anhydride, or epoxide functional group is glycidyl methacrylate.

11. The composition according to any one of claims 1 to 3, wherein copolymer B does not contain units derived from vinyl acetate.

12. The composition according to any one of claims 1 to 3, wherein the additive is selected from inert dyes, fillers, surfactants, crosslinking agents, nucleating agents, reactive compounds, mineral or organic flame retardants, ultraviolet (UV) or infrared (IR) light absorbers, UV or IR fluorescent agents, and combinations thereof.

13. The composition of claim 12, wherein the inert dye is titanium dioxide.

14. A process for manufacturing a film, comprising extruding the composition as described in any one of claims 1 to 13.

15. The process as described in claim 14, wherein the membrane is a waterproof and breathable membrane.

16. The process of claim 14, wherein the extrusion is carried out at a temperature of 100 to 300°C.

17. The process of any one of claims 14 to 16, wherein the extrusion is extrusion coating or extrusion casting.

18. A membrane obtained by the process described in any one of claims 14 to 17.

19. The membrane as described in claim 18, having a thickness of 2 to 100 µm.

20. The membrane as described in claim 19, having a thickness of 10 to 50 µm.

21. Use of the membrane as described in any one of claims 19 and 20 in the fields of medical, hygiene, luggage, manufacturing, clothing, household or home appliances, furniture, blankets, automobiles, industry, agriculture and / or construction.

22. The use as described in claim 21, wherein it is in industrial filtration.