Block copolymer-based stretchable, flexible, waterproof, and breathable film

Abstract

The present invention relates to a flexible, stretchable, waterproof, breathable film based on a block copolymer comprising at least one rigid polyamide PA block and at least one flexible block, characterized in that the copolymer comprises at least one carboxylic acid chain end blocked with a polycarbodiimide.The present invention also relates to the use of a polycarbodiimide in a process for the production of a film based on a copolymer comprising a polyamide block and a flexible block, the copolymer comprising at least one carboxylic acid chain end, to simultaneously improve the extrudability of the copolymer, the stretchability of the copolymer in film form, and / or the extrusion rate of the copolymer, and to improve the stretchability of the film, its flexibility, its abrasion resistance, and its tear strength. [Selection diagram] None

Description

[Technical Field]

[0001] Field of the present invention The present invention relates to waterproof and breathable films based on block copolymers that are permeable to water vapor and impermeable to water. These films can be used particularly in the food, packaging, or sporting goods sectors, or in construction, particularly as insulation under building roofs and as insulation for walls.

[0002] In these sectors, it is important to have films that are flexible, stretchable, strong—that is, tear-resistant, abrasion-resistant, and recyclable—while also having sufficient permeability to water vapor.

[0003] The permeability to water vapor is evaluated by the MVTR parameter (moisture vapor transmission rate). In particular, for waterproof and breathable films, it is desirable that the MVTR value measured according to ASTM standard E96 is at least 100 g / m2 per 24 hours at 23°C with a relative humidity of 50% and a sample thickness of 30 μm. For certain block copolymers, it is possible to increase the permeability to water vapor of these copolymers by increasing the polyether group content.

[0004] The objective of the present invention is to improve the flexibility, elasticity, and strength of these films, as well as their abrasion resistance, without altering their permeability to water vapor.

[0005] Flexibility is evaluated by the following coefficients: the tensile modulus according to ISO standard 527 1A:2012, and the flexural modulus at 23°C according to ISO standard 178:2010. A decrease in these modulus values ​​tends to improve the flexibility of the film.

[0006] The elasticity is evaluated by an elongation rheology test, as defined below in the embodiments of this patent application.

[0007] Abrasion resistance is evaluated by mass loss according to ISO standard 527-1A:2012: the less mass loss of the material, the better the abrasion resistance of the film made from this material.

[0008] The tear strength of that portion is evaluated according to ISO standard 34-1:2015.

[0009] Among the block copolymers known for their use in the manufacture of waterproof and breathable films, copolymers containing polyamide blocks and polyether blocks (PEBAs) can be cited. These PEBAs, when resulting from the co-condensation of a polyamide block having a reactive carboxyl terminus and a polyether block having a reactive terminus (polyether polyol (polyether diol)), have an ester bond between the polyamide block and the flexible polyether block, and belong to a specific type of polyether ester amide.

[0010] PEBA is known for its physical properties, such as its flexibility, impact strength, and ease of implementation by injection molding. However, these copolymers are difficult to convert into film form by extrusion molding, particularly due to their low melt viscosity and the resulting low melt strength.

[0011] Various methods exist for adjusting the melt viscosity of polymers.

[0012] Therefore, it may be conceivable to increase the polyamide content, which tends to increase viscosity. Furthermore, extrudeable polymer compositions can be obtained by compounding block copolymers with other polymers, particularly polyolefins. However, in both cases, this leads to a decrease in the overall PEG content present in the polymer composition, resulting in reduced permeability to water vapor.

[0013] Furthermore, it is possible to increase the melt viscosity by lengthening the polymer chain, for example, by extending the polymerization. This approach was measured according to ISO standard 1621-10:2015 and proved disappointing, as it failed to achieve the desired level of melt viscosity of at least 300 Pa.s and also caused degradation of the PEG block, resulting in yellowing of the material.

[0014] Finally, it is conceivable to increase the melt viscosity by simultaneously increasing the size of various polymer blocks, for example, in the case of PEBA, by increasing the size of both the polyamide and polyether blocks. For example, for PEBA PA6-PEG, transitioning from 1500-1500 to 2000-2000 should allow for an increase in melt viscosity of a similar degree of polymerization without degrading properties in terms of water vapor permeability. However, tests conducted along these lines were not conclusive: the reactivity between the PA and PEG blocks decreased significantly.

[0015] Therefore, an object of the present invention is also to provide an improved method for producing stretchable and flexible waterproof and breathable films based on block copolymers, which facilitates extrusion molding and increases the maximum achievable extrusion rate.

[0016] The applicant has found that, in a method for producing a film based on a copolymer comprising a polyamide block and a flexible block, each containing at least one carboxylic acid chain end, the use of polycarbodiimide under certain conditions significantly improves the stretchability of the copolymer in film form and / or increases the extrusion rate of the copolymer, while simultaneously improving the elasticity, flexibility, abrasion resistance and tear strength of the thus obtained film without sacrificing the water vapor permeability or recyclability of the resulting film. [Brief explanation of the drawing]

[0017] [Figure 1]Figure 1 shows the results of extensional rheology measurements at 180°C for PEBA 3 (lower curve) and Copo 3 (upper curve). [Figure 2] Figure 2 shows the results of extensional rheology measurements at 150°C for PEBA 4 (lower curve) and Copo 4 (upper curve).

Mode for Carrying Out the Invention

[0018] Description of Embodiments of the Present Invention In this specification, when referring to a range, it is pointed out that expressions of the type "from... to..." or "including / comprising... to..." include the limits of the range. Conversely, expressions of the type "between... and..." exclude the limits of the range.

[0019] Unless otherwise specified, the percentages shown are mass percentages. Unless otherwise stated, the reference parameters are measured at atmospheric pressure and at room temperature (20 - 25°C, usually 23°C).

[0020] The present invention is described in detail and non - limiting in the following description.

[0021] Thus, one subject of the present invention is a flexible and stretchable waterproof breathable film based on a block copolymer comprising at least one hard polyamide PA block and at least one flexible block, wherein the copolymer comprises at least one carboxylic acid chain end blocked with a polycarbodiimide.

[0022] In this specification, it is pointed out that a "copolymer - based" film means that the film contains at least 51% by weight of the copolymer based on the total weight of the film.

[0023] Preferably, the film according to the present invention contains at least 60% by weight of the copolymer as defined by the present invention. Preferably, it contains at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight, and more preferably at least 95% by weight of the copolymer as defined below by the present invention, based on the total weight of the film.

[0024] Copolymers comprising rigid polyamide PA blocks and flexible blocks as defined in accordance with the present invention fall under the category of thermoplastic elastomer polymers. The term "thermoplastic elastomer polymer," abbreviated as "TPE," refers to a polymer constituting a multiphase material having at least two transitions, namely a first transition at temperature T1 (generally this is the glass transition temperature) and a second transition at temperature T2 above T1 (generally this is the melting point). Below T1, the material is rigid, exhibits elastic behavior between T1 and T2, and melts above T2. Such polymers combine the elastic behavior of rubber-type materials with the deformability of thermoplastics.

[0025] Polyamide-based thermoplastic elastomers (TPE-A) for the purposes of the present invention, such as PEBA, are block copolymers comprising alternating arrangements of rigid or hard blocks (HB) and flexible or soft blocks (SB) according to the following general formula: -[HB-SB]n- During the ceremony: • HB or Hard Block or Rigid Block: Refers to a block containing polyamide (homopolyamide or copolyamide), or a mixture of blocks containing polyamide (homopolyamide or copolyamide), and will be independently abbreviated as PA or HB block below; · SB or soft block or flexible block: Represents a block or mixture thereof based on polyether (PE block), polyester (PES block), polydimethylsiloxane (PDMS block), polyolefin (PO block), polycarbonate (PC block) and / or any other polymer having a low glass transition temperature, in the form of alternating, statistical or block copolymers. Preferably, SB is a block that is entirely or partially based on a polyether containing alkylene oxide units. n represents the number of repeating units within the copolymer unit -HB-SB-. n is in the range of 1 to 60, preferably 5 to 30, or more preferably 6 to 20.

[0026] For the purposes of the present invention, the expression "low glass transition temperature" for a polymer contained in the SB composition means a glass transition temperature Tg of less than 15°C, preferably less than 0°C, preferably less than -15°C, and more preferably less than -30°C. For example, the soft block may be based on PEG having a number average molecular weight equal to 1500 g / mol and a Tg of about -35°C. The glass transition temperature Tg may be less than -50°C, especially when the soft block is based on PTMG.

[0027] Copolyether block amides, abbreviated as "PEBA" and also known as copolymers containing polyether blocks and polyamide blocks, are particularly derived from the polycondensation of a polyamide block with reactive ends and a polyether block with reactive ends, as follows: 1) Polyamide blocks having diamine chain ends and polyoxyalkylene blocks having dicarboxyl chain ends; 2) A polyamide block having a dicarboxyl chain terminus and a polyoxyalkylene block having a diamine chain terminus, obtained by cyanoethylation and hydrogenation of an α,ω-dihydroxylated aliphatic polyoxyalkylene block known as a polyetherdiol; 3) A polyamide block having a dicarboxyl chain terminus and a polyetherdiol (in particular, the product obtained in this case is a polyether esteramide).

[0028] Polyamide blocks having dicarboxyl chain ends are obtained, for example, from the condensation of polyamide precursors in the presence of chain-restricted dicarboxylic acids. Polyamide blocks having diamine chain ends are obtained, for example, from the condensation of polyamide precursors in the presence of chain-restricted diamines.

[0029] The molar mass Mn of the polyamide block is between 400 g / mol and 20,000 g / mol, preferably between 500 g / mol and 10,000 g / mol.

[0030] Polymers containing polyamide blocks and polyether blocks may also contain randomly distributed units.

[0031] Three types of polyamide blocks may be advantageously used.

[0032] According to the first type, the polyamide block is obtained by condensation of a dicarboxylic acid, particularly one containing 4 to 20 carbon atoms, preferably one containing 6 to 18 carbon atoms, with an aliphatic or aromatic diamine, particularly one containing 2 to 20 carbon atoms, preferably one containing 6 to 14 carbon atoms.

[0033] Examples of dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, butanediic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, terephthalic acid, and isophthalic acid, as well as dimerized fatty acids.

[0034] Examples of diamines include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, isomers of bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), and 2-2-bis-(3-methyl-4-aminocyclohexyl)propane (BMACP), as well as para-aminodicyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN), and piperazine (Pip).

[0035] With respect to polyamide rigid blocks, the standard NF EN ISO 1874-1:2011 defines the nomenclature for polyamides. In this specification, the term “monomer” should be interpreted as meaning “repeating unit.” A special case exists when the repeating unit of a polyamide consists of a combination of diacid and diamine. It is considered that the combination of diamine and diacid, i.e., the monomer, is a diamine diacid (also called an equimolar “XY” pair). This is explained, individually, by the fact that diacid or diamine is merely a structural unit and is not sufficient on its own to polymerize.

[0036] Examples include blocks PA412, PA414, PA418, PA610, PA612, PA614, PA618, PA912, PA1010, PA1012, PA1014, and PA1018.

[0037] According to the second type, the polyamide block is produced from the condensation of one or more lactams and / or one or more α,ω-aminocarboxylic acids containing 6 to 12 carbon atoms in the presence of a diamine or a dicarboxylic acid containing 4 to 12 carbon atoms. Examples of lactams include caprolactam, oenantholactam, and lauryllactam. Examples of α,ω-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminodecanoic acid.

[0038] Advantageously, the second type of polyamide block is made from polyamide-11, polyamide-12, or polyamide-6.

[0039] According to the third type, the polyamide block arises from the condensation of at least one α,ω-aminocarboxylic acid (or lactam), at least one diamine, and at least one dicarboxylic acid.

[0040] In this case, the polyamide PA block is - A linear aliphatic or aromatic diamine (or multiple diamines) containing X carbon atoms, - A dicarboxylic acid (or multiple dicarboxylic acid) containing Y carbon atoms, - Comonomers {Z} (plural) selected from α,ω-aminocarboxylic acids and lactams containing Z carbon atoms, and equimolar mixtures of at least one diamine containing X1 carbon atoms and at least one dicarboxylic acid containing Y1 carbon atoms (where (X1, Y1) is different from (X, Y)). It is a polycondensation of; - The comonomer {Z}(or more) is introduced in a weight proportion of up to 50%, preferably up to 20%, and more favorably up to 10%, relative to the total amount of the polyamide-precursor monomer; - The above polycondensation occurs in the presence of a chain restricting agent selected from dicarboxylic acids. It is prepared by polycondensation.

[0041] Advantageously, a dicarboxylic acid containing Y carbon atoms is used as a chain limiting agent and is introduced in excess relative to the stoichiometry of the diamine(s).

[0042] According to one variation of this third type, the polyamide block is obtained from the condensation of at least two α,ω-aminocarboxylic acids or at least two lactams containing 6 to 12 carbon atoms, or from the condensation of one lactam and one aminocarboxylic acid that do not have the same number of carbon atoms, in the presence of a chain restrictor as needed. Examples of aliphatic α,ω-aminocarboxylic acids include aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminodecanoic acid. Examples of lactams include caprolactam, oenantholactam, and lauryllactam. Examples of aliphatic diamines include hexamethylenediamine, dodecamethylenediamine, and trimethylhexamethylenediamine. An example of an alicyclic diacid that can be given is 1,4-cyclohexyldicarboxylic acid. Examples of aliphatic diacids include butanediic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, dimerized fatty acids (these dimerized fatty acids preferably have a dimer content of at least 98%; they are preferably hydrogenated; they are commercially available from Uniqema under the trademark name Pripol® or from Henkel under the trademark name Empol®), and α,ω-diacid polyoxyalkylenes. Examples of aromatic diacids include terephthalic acid (T) and isophthalic acid (I). Examples of alicyclic diamines include isomers of bis(4-aminocyclohexyl)methane (BACM), bis(3-methyl-4-aminocyclohexyl)methane (BMACM), 2-2-bis(3-methyl-4-aminocyclohexyl)propane (BMACP), and para-aminodicyclohexylmethane (PACM). Other commonly used diamines include isophoronediamine (IPDA), 2,6-bis(aminomethyl)norbornane (BAMN), and piperazine.

[0043] If the PA block of PEBA according to the present invention contains at least two different monomers called "comonomers," namely at least one monomer and at least one comonomer (a monomer other than the first monomer), then they contain a copolymer such as a copolyamide, abbreviated as CoPA.

[0044] Examples of the third type of polyamide block include the following: - 66 / 6 (66 represents the hexamethylenediamine unit formed by condensation with adipic acid, and 6 represents the unit resulting from the condensation of caprolactam.) - 66 / 610 / 11 / 12 (66 represents hexamethylenediamine condensed with adipic acid. 610 represents hexamethylenediamine condensed with sebacic acid. 11 represents a unit resulting from the condensation of aminoundecanonic acid. 12 represents a unit resulting from the condensation of lauryl lactam.)

[0045] The mass Mn of the flexible block is between 100 and 6000 g / mol, preferably between 200 and 3000 g / mol.

[0046] Preferably, the polymer comprises 1% to 80% by mass of flexible blocks and 20% to 99% by mass of polyamide blocks, preferably 4% to 80% by mass of flexible blocks and 20% to 96% by mass of polyamide blocks.

[0047] According to a preferred embodiment, the rigid polyamide block in the copolymer containing the rigid PA block and the flexible block according to the present invention comprises at least one of the following polyamide units: 11, 12, 6, 610, 612, 1010, 1012, and mixtures thereof or copolyamide.

[0048] Polyether blocks PE are formed from alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide units, or tetrahydrofuran (which form a polytetramethylene glycol sequence). Thus, PEG (polyethylene glycol) blocks, i.e., blocks formed from ethylene oxide units, PPG (propylene glycol) blocks, i.e., blocks formed from propylene oxide units, PO3G (polytrimethylene glycol) blocks, i.e., blocks formed from polytrimethylene glycol ether units (such copolymers having polytrimethylene ether blocks are described in U.S. Patent No. 6590065), and PTMG blocks, i.e., blocks formed from tetramethylene glycol units, also known as polytetrahydrofuran, are used. PEBA copolymers may contain several types of polyethers in their chains, and the copolyethers may be in block form or statistical form.

[0049] A block obtained by oxyethylation of bisphenol, such as bisphenol A, can also be used. The latter product is described in patent EP613919.

[0050] Polyether blocks can also be formed from ethoxylated primary amines. Examples of ethoxylated primary amines include the products of the following formulas: TIFF0007851685000001.tif36170 (wherein m and n are between 1 and 20, and x is between 8 and 18). These products are marketed by CECA under the trademark Noramox® and by Clariant under the trademark Genamin®.

[0051] Flexible polyether blocks may include polyoxyalkylene blocks having NH2 chain ends, and such blocks can be obtained by cyanoacetylation of α,ω-dihydroxylated aliphatic polyoxyalkylene blocks called polyetherdiols. More specifically, Jeffamine products (e.g., Jeffamine® D400, D2000, ED 2003, XTJ 542, which are commercial products from Huntsman, and are also described in patents JP2004346274, JP2004352794 and EP1482011) can be used.

[0052] The polyetherdiol block is used in its unmodified form and copolymerized with a polyamide block having a carboxyl-terminated group, or they are aminated to a polyetherdiamine and then condensed with a polyamide block having a carboxyl-terminated group. A general method for the two-step preparation of a PEBA copolymer containing an ester bond between the PA block and the PE block is known, for example, described in French Patent FR2846332. A general method for the preparation of the PEBA copolymer of the present invention containing an amide bond between the PA block and the PE block is known, for example, described in European Patent (EP) 1482011. The polyether block can also be mixed with a polyamide precursor and a chain-restricting diacitor to produce a polymer containing polyamide and polyether blocks with randomly distributed units (one-step method).

[0053] In this specification, the term "PEBA" in this invention refers not only to the Pebax® products sold by Arkema, the Vestamid® products sold by Evonik, and the Grilamid® products sold by EMS, but also to the Kellaflex® products sold by DSM, or any other PEBA from other suppliers.

[0054] Advantageously, the PEBA copolymer comprises the PA block as PA 6, as PA 11, as PA 12, as PA 612, as PA 66 / 6, as PA 1010, and / or as PA 614, preferably as PA 11 and / or PA 12 blocks; and the PE block as PTMG, as PPG, and / or as PO3G. A PEBA based on a PE block mainly composed of PEG is classified within the range of hydrophilic PEBA. A PEBA based on a PE block mainly composed of PTMG is classified within the range of hydrophobic PEBA.

[0055] Advantageously, the PEBA used in the composition of the present invention is at least partially obtained from raw materials derived from organisms.

[0056] The term "raw material from renewable origin" or "raw material from biological origin" means a material containing carbon from biological origin or carbon from renewable origin. Specifically, unlike materials derived from fossil raw materials, materials consisting of renewable starting materials 12 , 14 , -12 , 12 contain C. The "content of carbon from renewable origin" or "content of carbon from biological origin" is determined by the application of ASTM standard D 6866 (ASTM D 6866-06) and ASTM standard D 7026 (ASTM D 7026-04). For example, a PEBA based on polyamide 11 is at least partially derived from raw materials from biological origin and has a content of carbon from biological origin of at least 1%, which corresponds to an isotope ratio of at least 1.2×10 -14 of 12 C / 14 C. Preferably, the PEBA according to the present invention contains at least 50% by mass of carbon from biological origin based on the total mass of carbon, which corresponds to an isotope ratio of at least 0.6×10 -12 of 12 C / 14 C. In the case of a PEBA containing a PA11 block and a PE block containing PO3G, PTMG and / or PPG resulting from starting materials from renewable origin, this content is advantageously high, especially up to 100%, which corresponds to an isotope ratio of 1.2×10 -12 of 12 C / 14 This corresponds to the 14C isotope ratio.

[0057] Polyester blocks (PES) are typically produced by polycondensation between dicarboxylic acids and diols. Suitable carboxylic acids include those listed above used to form polyamide blocks, with the exception of terephthalic acid and isophthalic acid. Suitable diols include linear aliphatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,6-hexylene glycol; branched diols such as neopentyl glycol, 3-methylpentane glycol, and 1,2-propylene glycol; and cyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane and 1,4-cyclohexanedimethanol.

[0058] The term "polyester" also refers to poly(caprolactone) and PES based on fatty acid dimers, particularly products of Croda or Uniqema's Priplast®.

[0059] It is also possible to consider alternating, statistical, or block "copolyester" type PES blocks containing sequences of at least two of the above types of PES.

[0060] For the purposes of the present invention, the term polysiloxane block (hereinafter abbreviated as PSi) means an organosilicon polymer or oligomer having a linear, cyclic, branched, or crosslinked structure, obtained by polymerization of functionalized silanes, and essentially consisting of repeating main units (siloxane bonds -Si-O-Si-) in which silicon atoms are linked via oxygen atoms, and optionally substituted hydrocarbon-based radicals are directly linked to the silicon atoms via carbon atoms. The most common hydrocarbon-based radicals are alkyl radicals, particularly C1-C10, especially methyl, fluoroalkyl, aryl radicals, and especially phenyl, alkenyl radicals, and especially vinyl; other types of radicals that can be bonded to siloxane chains directly or via hydrocarbon-based radicals include hydrogen, halogens, especially chlorine, bromine, or fluorine, thiols, alkoxy radicals, polyoxyalkylene (or polyether) radicals, especially polyoxyethylene and / or polyoxypropylene, hydroxyl or hydroxyalkyl radicals, substituted or unsubstituted amine groups, amide groups, acyloxy or acyloxyalkyl radicals, hydroxyalkylamino or aminoalkyl radicals, quaternary ammonium groups, amphoteric or betaine groups, anionic groups, e.g., carboxylates, thioglycolates, sulfosuccinates, thiosulfates, phosphates, and sulfates, and mixtures thereof. This list is clearly not limiting ("organically modified" silicones).

[0061] Preferably, the polysiloxane block comprises polydimethylsiloxane (hereinafter abbreviated as PDMS block), polymethylphenylsiloxane, and / or polyvinylsiloxane.

[0062] For the purposes of the present invention, the term polyolefin block (hereinafter abbreviated as PO block) means any polymer containing α-olefin as a monomer, i.e., a homopolymer of olefins or a copolymer of at least one α-olefin and at least one other copolymerizable monomer, wherein the α-olefin preferably contains 2 to 30 carbon atoms.

[0063] Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacocene, 1-octacosene, and 1-triacontene. These α-olefins can be used individually or as mixtures of two or more types.

[0064] Examples that can be mentioned include: - Ethylene homopolymers and copolymers, particularly low-density polyethylene (LDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), and polyethylene obtained by metallocene catalysts. - Propylene homopolymers and copolymers, - Essentially amorphous or atactic poly-α-olefins (APAOs), - Ethylene / α-olefin copolymers, such as ethylene / propylene, EPR (ethylene-propylene-rubber) elastomers and EPDM (ethylene-propylene-diene) elastomers, as well as mixtures of polyethylene with EPR or EPDM. - Styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), and styrene / ethylene-propylene / styrene (SEPS) block copolymers; - Copolymers of ethylene with at least one product selected from salts or esters of unsaturated carboxylic acids, such as alkyl (meth)acrylates, possibly alkyls containing up to 24 carbon atoms, vinyl esters of saturated carboxylic acids, such as vinyl acetate or propionic acid, and dienes, such as 1,4-hexadiene or polybutadiene.

[0065] According to an advantageous embodiment of the present invention, the at least one polyolefin block comprises polyisobutylene and / or polybutadiene.

[0066] In a particularly advantageous embodiment, the block copolymer according to the present invention comprises at least one flexible polyolefin block (PO block) and at least one hard hydrophilic block (hereinafter abbreviated as hHB) containing both polyamide and polyether, such as a polyetheramide block, a polyether esteramide block and / or a polyetheramide imide block. The PO block preferably contains a polyolefin containing an acid, alcohol, or amine-terminated group. Preferably, the PO block is obtained by thermally decomposing a high molecular weight polyolefin to form a functionalized polyolefin at a lower mass (Reference method: Japanese Patent Application Publication No. 03-62804). As for the hHB block, it may also contain at least one polymer selected from: a quaternary amine-type cationic polymer and / or a phosphorus derivative; and / or a modified diacid-type anionic polymer containing a sulfonic acid group and capable of reacting with a polyol. The addition of an organic salt may then be considered in the preparation of the hHB block or during the reaction between the PO block and the hHB block. U.S. Patent No. 6,552,131 describes the synthesis of copolymers containing PO blocks and hHB blocks and various possible structures, the latter of which is certainly conceivable in the method according to the present invention.

[0067] For the purposes of the present invention, the term polycarbonate block (hereinafter abbreviated as PC block) means, more specifically, any aliphatic polycarbonate. Aliphatic polycarbonates are described, for example, DE2546534 and JP1009225. Such polycarbonate homopolymers or copolymers are also described in U.S. Patent No. 471203. International Publication Nos. 92 / 22600 and 95 / 12629 describe copolymers containing polycarbonate blocks and methods for synthesizing them. The blocks (and their synthesis) described in the said documents can be fully assumed for the synthesis of PC block copolymers according to the present invention. Preferably, the polycarbonate block of the copolymer according to the present invention has the following formula: In formula TIFF0007851685000002.tif29170, a is an integer from 2 to 300; R1 and R2 may be the same or different, and represent a linear or branched aliphatic or alicyclic chain containing 2 to 18 carbon atoms, or a polyoxyalkylene group, or a polyester group.

[0068] A polycarbonate in which R1 and R2 are selected from hexylene, decylene, dodecylene, 1,4-cyclohexylene, 2,2-dimethyl-1,3-propylene, 2,5-dimethyl-2,5-hexylene, or polyoxyethylene groups is preferred.

[0069] If the block copolymers described above generally include at least one rigid polyamide block and at least one flexible block, then, provided that at least one of these blocks is a polyamide block, it is clear that the present invention actually covers all copolymers containing two, three, four (or more) different blocks selected from those described herein.

[0070] Advantageously, the copolymer according to the present invention comprises a block-segmented copolymer comprising three different types of blocks (referred to herein as “triblocks” in this specification) resulting from the condensation of several of the blocks described above. The triblocks are preferably selected from copolyether ester amides and copolyether amide urethanes, where relative to the total mass of the triblocks, - The mass percentage of rigid polyamide blocks exceeds 10%; - The mass percentage of the flexible block exceeds 20%.

[0071] According to a preferred embodiment, in a film based on a copolymer comprising a rigid PA block and a flexible block according to the present invention, the flexible block preferably comprises a polyether PE block selected from PTMG, PPG, PO3G and / or PEG (preferably a polyether PE block).

[0072] According to another advantageous embodiment, the flexible block in the copolymer comprising a rigid PA block and a flexible block of the film according to the present invention comprises a polyester PES block selected from polyester diols, poly(caprolactone), and fatty acid dimer-based polyesters (preferably a polyester PES block).

[0073] Advantageously, in the copolymer according to the present invention, the weight ratio of the PA block to the flexible block is in the range of 0.3 to 10, preferably 0.3 to 6, preferably 0.3 to 3, and preferably 0.3 to 2.

[0074] Preferably, the copolymer based on the film according to the present invention comprises 45% to 75% by weight of flexible polyethylene glycol (PEG) blocks, preferably 50% to 70% by weight of PEG blocks, based on the total weight of the copolymer.

[0075] Preferably, the rigid polyamide PA block of the copolymer used in the film of the present invention comprises at least one of the following polyamide units: 6, 66, 610, 612, PA1010, PA1012, PA11, PA12, PA6 / 12, PA6 / 66, and mixtures thereof or copolyamides.

[0076] Advantageously, the copolymer comprises a copolymer containing rigid polyamide blocks and flexible polyether blocks (PEBA), and mixtures thereof, preferably selected from the following PEBA:PA6-PEG, PA1010-PEG, PA1012-PEG, PA11-PEG, PA12-PEG, PA6 / 12-PEG, PA66-PEG, PA6 / 66-PEG.

[0077] A polycarbodiimide suitable for the present invention is represented by the following general formula: R-[-N=C=N-R'] n - In the formula, R is monovalent, R' is divalent, and n is from 2 to 50, preferably from 2 to 45, preferably from 2 to 20, and preferably from 5 to 20.

[0078] R may be, for example, a C1-C20 alkyl, C3-C10 cycloalkyl, or C1-C20 alkenyl group, and may be cyclic or branched, or may contain a C8-C16 aromatic nucleus, or may be substituted with a functional group.

[0079] R' may be a divalent group corresponding to all of the above, such as a C1-C20 alkylene or a C3-C10 cycloalkylene. Examples of functional groups, but not limited to these, include cyanates and isocyanates, halos, amides, carboxamides, aminos, imides, iminos, silyls, and the like. This list is for illustrative purposes only and is not intended to limit the scope of the present invention.

[0080] Examples of polycarbodiimides that can be used in the present invention include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, 4,4'-dicyclohexylmethanecarbodiimide, tetramethylxylylenecarbodiimide (aromatic carbodiimide), N,N-dimethylphenylcarbodiimide, N,N'-bis(2,6-diisopropylphenyl)carbodiimide, repeating units of 2,2',6,6'-tetraisopropyldiphenylcarbodiimide (aromatic carbodiimide), aromatic homopolymers of 1,3,5-triisopropyl-2,4-diisocyanatobenzene, aromatic heteropolymers of 1,3,5-triisopropyl-2,4-diisocyanatobenzene, and 2,6-diisopropylphenyl isocyanate, or combinations thereof.

[0081] Specific examples of R' include, but are not limited to, 2,6-diisopropylbenzene, naphthalene, 3,5-diethyltoluene, 4,4'-methylenebis(2,6-diethylenephenyl), 4,4'-methylenebis(2-ethyl-6-methylphenyl), 4,4'-methylenebis(2,6-diisopropylphenyl), 4,4'-methylenebis(2-ethyl-5-methylcyclohexyl), 2,4,6-triisopropylphenyl, divalent radicals and analogs derived from n-hexane, cyclohexane, dicyclohexylmethane and methylcyclohexane.

[0082] U.S. Patents No. 5,130,360, 5,859,166, 368,493, 7,456,137, U.S. Patent Application Publication No. 2007 / 0278452, U.S. Patent Application Publication No. 2009 / 0176938, and in particular U.S. Patent No. 5,360,888, describe more examples of polycarbodiimides.

[0083] Suitable polycarbodiimides can be obtained from commercially available sources such as the Stabaxol P series from Rhein Chemie, the Stabilizer series from Raschig, and others from Ziko or Teijin, for example.

[0084] Advantageously, the polycarbodiimide is selected from Stabilizer products, particularly Stabilizer® 9000 corresponding to poly(1,3,5-triisopropylphenylene-2,4-carbodiimide), Stabaxol® products, particularly Stabaxol® P products, particularly Stabaxol® P100 or Stabaxol® P400, or mixtures thereof.

[0085] Preferably, the polycarbodiimide has a weight-average molecular weight greater than 10,000 g / mol.

[0086] Advantageously, the weight-average molecular weight of the polycarbodiimide is in the range of 10,000 to 40,000 g / mol, preferably 15,000 to 30,000 g / mol.

[0087] The weight content of polycarbodiimide is advantageously 0.5 to 10% by weight, preferably 0.5 to 7% by weight, preferably 0.5 to 3% by weight, preferably 0.5 to 2.5% by weight, and preferably 0.5 to 2% by weight, based on the total weight of the copolymer according to the present invention.

[0088] According to an advantageous embodiment of the present invention, in the film according to the present invention, the carboxylic acid of the copolymer forms a urea bond by reaction with the carbodiimide of the polycarbodiimide.

[0089] One advantage of the blocked copolymer having blocked acid chain ends based on the film of the present invention is that it remains in a non-crosslinked linear form and the copolymer dispersion Mw / Mn is less than 3. This is surprising, insofar as carbodiimides are used in the prior art to increase the viscosity of polyamides (see, for example, Japanese Patent FR3027907) and to improve their resistance to hydrolysis, as described in U.S. Patent No. 5360888, particularly by crosslinking them.

[0090] The subject of the present invention is also the use of polycarbodiimide in a method for producing a film based on a copolymer comprising a polyamide block and a flexible block, each containing at least one carboxylic acid chain end, for improving the extrudeability and / or stretchability of the copolymer in film form and / or for improving the extruder rate of the copolymer, wherein at least one carboxylic acid chain end of the copolymer is blocked by a carbodiimide functional group of the polycarbodiimide.

[0091] The subject of the present invention is also the use of polycarbodiimide in a film based on a copolymer comprising a polyamide block and a flexible block, comprising at least one carboxylic acid chain end, for improving the stretchability, flexibility, abrasion resistance and tear strength of the film, wherein at least one carboxylic acid chain end of the copolymer is blocked by a carbodiimide functional group of the polycarbodiimide.

[0092] Preferably, for use according to the present invention, the polycarbodiimide has a weight-average molecular weight greater than 10,000 g / mol, preferably in the range of 10,000 to 40,000 g / mol, and preferably 15,000 to 30,000 g / mol.

[0093] Preferably, the weight-average molecular weight of the polycarbodiimide used in the present invention is measured by gel permeation chromatography (GPC) in tetrahydrofuran (THF).

[0094] Advantageously, at least one carboxylic acid chain terminus of the copolymer is blocked by a urea functional group formed by reaction with polycarbodiimide.

[0095] The subject of the present invention is also a copolymer-based film composition according to the present invention, characterized by comprising the following: In relation to the total weight of the composition, - 51% to 99.9% by weight of the block copolymer as defined above, - 0.1% to 49% by weight of at least one other component selected from polyamides, functional polyolefins, copolyether esters, thermoplastic polyurethanes (TPUs), copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylates, and copolymers of ethylene and alkyl (meth)acrylates. and / or - Additives selected from 0.1% to 10% by weight of nucleating agents, fillers, especially inorganic fillers such as talc, reinforcing fibers, especially glass fibers or carbon fibers, dyes, UV absorbers, antioxidants, especially phenolic, phosphorus-based or sulfur-based antioxidants, hindered amine light stabilizers (HALS), and mixtures thereof.

[0096] Advantageously, the film according to the present invention comprises a functional polyolefin comprising grafting with monomers selected from the group including unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, vinyl monomers, acrylic monomers, and mixtures thereof.

[0097] Preferably, the functional polyolefin is selected from the group comprising ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer-maleic acid anhydride copolymer, and ethylene-acrylic acid copolymer-glycidyl methacrylate copolymer.

[0098] Advantageously, the film according to the present invention has a thickness of 100 μm or less, preferably 50 μm or less, preferably 30 μm or less, preferably 25 μm or less, and preferably within the range of 5 to 25 μm.

[0099] The subject of the present invention is also a method for producing a film according to the present invention, comprising the following steps: a) A step of providing a copolymer comprising at least one carboxylic acid chain end blocked by polycarbodiimide, optionally as a mixture with other components of the film as described above. b) A step of extruding the copolymer or the mixture from step a), c) A step of stretching the copolymer or the mixture to form a film.

[0100] According to a particular embodiment, the method of the present invention comprises, prior to step a), mixing a block copolymer comprising at least one rigid polyamide PA block and at least one flexible block with a polycarbodiimide, so that at least one carboxylic acid chain terminus of the block copolymer reacts with a carbodiimide functional group of the polycarbodiimide. Preferably, the mixing is carried out using a single-screw or twin-screw extruder, or by adding the polycarbodiimide during the synthesis of the block copolymer.

[0101] Advantageously, the stretching process c) is carried out by extrusion blow molding, inflation film molding, pultrusion, overjacket extrusion, extrusion calendering, flat die extrusion, extrusion coating, lamination and / or co-extrusion.

[0102] Advantageously, step b) is carried out at a temperature in the range of 80 to 350°C, preferably 100 to 300°C, and preferably 150 to 250°C.

[0103] The use of polycarbodiimide-blocked copolymers according to the present invention allows for a wider window of processability, particularly in terms of temperature, and exhibits less extrusion instability than the corresponding unblocked copolymers, as well as a higher achievable maximum extrusion rate.

[0104] The subject matter of the present invention is also a laminated product comprising at least one textile material and at least one film according to the present invention, wherein the film is adhered to at least one surface of the textile material with a peel force in the range of 0.5 to 50 N, preferably 0.5 to 10 N, as measured according to ISO standard 11339.

[0105] Preferably, the at least one woven material is in the form of a porous membrane, a woven fabric, or a nonwoven fabric.

[0106] Preferably, the at least one textile material includes synthetic fibers, particularly synthetic fibers obtained from biological raw materials, natural fibers, artificial fibers manufactured from natural raw materials, mineral fibers and / or metallic fibers.

[0107] Advantageously, the at least one textile material constitutes felt, filter, film, gauze, cloth, bandage, layer, fabric, knit fabric, clothing, garment items, bedding, furniture, curtains, room covers, functional industrial textiles, geotextiles and / or agrotextiles.

[0108] The subject matter of the present invention is also the use of the film of the present invention in the following fields: medical, sanitation, luggage, manufacturing, clothing, domestic or household equipment, furniture, carpets, automobiles, industry, especially industrial filtration, agriculture and / or construction.

[0109] The film according to the present invention is advantageous in packaging components, particularly in the agricultural and food sectors. Packaging components, comprising food packaging films, packaging films for cooking and / or smoking, especially for sausages, waterproof and breathable films, particularly waterproof and breathable films used in architecture, textiles, sporting goods, shoes, athletic shoes, soles, ornaments, luggage, eyeglasses, furniture, audiovisual equipment, information technology, automotive or aerospace equipment components, and / or medical equipment components. [Examples]

[0110] Examples The following examples are illustrative and not limiting to the present invention. The standards used in the examples also correspond to those more commonly used to characterize the present invention in this specification or in the claims.

[0111] Materials used: In the following embodiment, PEBA 1:PA 12-PTMG(Mn:600-2000) PEBA 1 is a copolymer containing PA 12 blocks and PTMG blocks, with each having a number-average molecular weight (Mn) of 600-2000. Copo 1:98.5% PEBA 1 + 1.5% PCDI PEBA 2:PA 12-PTMG(Mn:850-2000) PEBA 2 is a copolymer according to the present invention, comprising PA 12 blocks and PTMG blocks, each having a number-average molecular weight (Mn) of 850-2000. Copo 2: 98% PEBA 2 + 2% PCDI PEBA 3:PA 12-PTMG(Mn:2000-1000) PEBA 3 is a copolymer according to the present invention, comprising PA 12 blocks and PTMG blocks, each having a number-average molecular weight (Mn) of 2000-1000. Copo 3:98.5% PEBA 3 + 1.5% PCDI PEBA 4:PA11-PTMG (600-1000) PEBA 4 is a copolymer containing PA 11 blocks and PTMG blocks, with each having a number-average molecular weight (Mn) of 600-1000. Copo 4:98% PEBA 4 + 2% PCDI PCDI: Polycarbodiimide used in the examples: Poly(1,3,5-triisopropylphenylene-2,4-carbodiimide)

[0112] A waterproof and breathable film was fabricated from the materials described above. The moisture permeability (or MVTR) of various films of the above materials (PEBA and Copo) is measured. In all cases, the MVTR of the PEBA film and the corresponding Copo film are substantially identical: the measured moisture permeability (MVTR) is greater than 100 g / m² per 24 hours at 23°C for a relative humidity of 50% and a sample thickness of 30 μm.

[0113] The adhesion of the film is directly related to the peel strength value. The peel test is preferably performed within a period of 2 to 48 hours after the laminate containing a 25 μm PEBA or Copo film adhesive is manufactured on a nonwoven polypropylene fabric by extrusion coating. The peel test was performed on each test laminate (according to ISO standard 11339), starting with a 15 mm strip of the laminate and then pulled at a speed of 200 mm / min.

[0114] For all laminates, the peel force of the PEBA film and the corresponding Copo film remained substantially the same; in all cases, the measured value was greater than 0.5 N.

[0115] Example 1: Measurement of extrusion properties of PEBA and Copo materials Table 1 below shows the melt viscosity measured at 220°C as a function of angular frequency (rad / s) in accordance with ISO standard 6721-10:2015. * The results are shown in Pascal units. TIFF0007851685000003.tif129170

[0116] The Copo material according to the present invention is observed to have a higher melt viscosity than comparative PEBA.

[0117] Therefore, the Copo material according to the present invention can be extruded into film more easily than the comparative PEBA material.

[0118] Example 2: Measurement of the stretchability of PEBA and Copo using Rheotens

[0119] Explanation of the extension rheology test: Principle: A rod is extruded through a die of a capillary rheometer; it is gripped in a molten state by two pairs of wheels driven by a variable-speed motor. The first pair of wheels and motor are mounted on the free and deflectable ends of a support body directly connected to a sensor, which represents a restoring force.

[0120] A second pair of wheels (connected to the first pair) allows for the guidance and restriction of the rod wrapping around the upper wheels. Small pads soaked in a surfactant solution (a mixture of water, ethanol, and surfactant) are also applied to the wheels to cool them and thereby limit the sticky effect.

[0121] The melting strength curves in Figures 1 and 2 represent the tensile stress on the y-axis as a function of the elongation coefficient on the x-axis. TIFF0007851685000004.tif15170TIFF0007851685000005.tif14170 TIFF0007851685000006.tif42170

[0122] Operating conditions: - Capillary rheometer: Equipment: Gottfert Rheotester 2000 capillary rheometer Die: 30mm x 1mm die L / d = 30 / 1 Sensor: 0-1400 bar (Reference 131055) Preheating time: 300 seconds (5 minutes) 150°C or 180°C depending on the test temperature grade. Shear rate: 50s -1 - Rheotens: Wheels: Stainless steel with notches Winding height: 105mm Gap: Approximately 0.6 mm Vo (initial velocity)≒6mm / s Acceleration:a * t,a = 2.4 mm / s 2 Lubricant: A mixture of water and surfactant. Piston diameter: 12mm Piston speed: 0.043 mm / s

[0123] Figure 1 shows the results of extensional rheology measurements at 180°C for PEBA 3 (lower curve) and Copo 3 (upper curve).

[0124] Figure 2 shows the results of extensional rheology measurements at 150°C for PEBA 4 (lower curve) and Copo 4 (upper curve).

[0125] The copolymers Copo 3 and Copo 4 used in the film according to the present invention have improved stretchability compared to that of the respective control PEBA 3 and PEBA 4.

[0126] Films according to the present invention, based on a blocked copolymer containing at least one carboxylic acid chain end blocked with polycarbodiimide, have improved stretchability compared to films based on the same non-blocked copolymer.

[0127] Example 3 - Comparison of tensile modulus and flexural modulus values ​​of various PEBAs and Copo The results of these tests are shown in Table 2 below. TIFF0007851685000007.tif87170

[0128] Copolymers Copo 1 and Copo 4 used in the textile material according to the present invention have lower tensile modulus and flexural modulus values ​​than those of their respective control PEBA 1 to 4.

[0129] Films according to the present invention, based on a blocked copolymer containing at least one carboxylic acid chain end blocked with polycarbodiimide, have improved flexibility compared to films based on the same non-blocked copolymer.

[0130] Example 4 - Comparison of abrasion resistance and tear strength of various PEBAs and Copo The results of these tests are shown in Table 3 below. TIFF0007851685000008.tif106170

[0131] In the case of the copolymer according to the present invention, the mass loss is smaller, and the copolymer-based film according to the present invention therefore has better abrasion resistance than the respective control PEBA-based film. Similarly, films based on the copolymer according to the present invention have better tear strength than their respective control PEBA-based films.

[0132] Example 5 - Measurement of the dispersion of various PEBAs and Copo The measured weight-average molecular weight and number-average molecular weight, Mw and Mn, increased, respectively, upon migration from PEBA to the corresponding Copo used in the film according to the present invention. This indicates that a reaction occurred between the carbodiimide functional group of the polycarbodiimide and the acid functional group of PEBA, forming a Copo with blocked acid chain ends used according to the present invention.

[0133] The degree of dispersion is considered to be equal to the ratio of weight-average molecular weight to number-average molecular weight, Mw / Mn. The measurement accuracy is within 5%.

[0134] The number-average molecular weight (or molar mass) is determined by the amount of chain-limiting agent present. It can be calculated according to the following formula: Mn=(n モノマー / n 制限剤 ) * M 繰り返し単位 +M 制限剤 n モノマー = Number of moles of monomer n 制限剤 = number of moles of excess diacitate M 繰り返し単位 = Molar mass of repeating units M 制限剤 = Molar mass of excess diacid

[0135] Furthermore, the dispersion ratio Mw / Mn was preserved in each copolymer according to the present invention compared to the corresponding initial PEBA, and the measured value was less than 3 in all copolymers, which demonstrates that the copolymers according to the present invention remained in a non-crosslinked linear form. Therefore, films based on these copolymers remain fully recyclable.

[0136] In summary, the polycarbodiimide used in this manner in the film according to the present invention improves the extrudeability, stretchability, flexibility, abrasion resistance, and tear strength properties of the film while preserving its moisture permeability, adhesiveness, and recyclability.

[0137] These advantageous properties were not observed with the monomer carbodiimides because, due to their volatility, they could not react with or effectively block the carboxylic acids of the block copolymers used in the films of the present invention.

Claims

1. A flexible, stretchable, waterproof, and breathable film based on a block copolymer comprising at least one rigid polyamide PA block and at least one flexible block, wherein the copolymer comprises at least one carboxylic acid chain end blocked with polycarbodiimide, and the copolymer is in a non-crosslinked linear form with a dispersion degree Mw / Mn of less than 3.

2. The film according to claim 1, wherein the weight-average molecular weight of the polycarbodiimide exceeds 10,000 g / mol.

3. The film according to either claim 1 or 2, wherein the weight content of polycarbodiimide accounts for 0.5 to 10% by weight relative to the total weight of the copolymer.

4. The film according to any one of claims 1 to 3, wherein the carboxylic acid forms a urea bond through a reaction with the carbodiimide of the polycarbodiimide.

5. The film according to any one of claims 1 to 4, wherein the flexible block comprises at least one block selected from polyether, polyester, polydimethylsiloxane, polyolefin, polycarbonate, and mixtures or copolymers thereof.

6. The film according to any one of claims 1 to 5, wherein the flexible block comprises at least one polyether PE.

7. The film according to any one of claims 1 to 6, wherein the flexible block comprises at least one polyester PES.

8. The film according to any one of claims 1 to 7, wherein the at least one copolymer comprises 45% to 75% by weight of flexible polyethylene glycol (PEG) blocks relative to the total weight of the copolymer.

9. The film according to any one of claims 1 to 8, wherein the polyamide PA block comprises at least one of the following polyamide units: 6, 66, 610, 612, PA1010, PA1012, PA11, PA12, PA6 / 12, PA6 / 66, and mixtures thereof or copolyamides.

10. The film according to any one of claims 1 to 9, wherein the at least one copolymer comprises a copolymer comprising a rigid polyamide block and a flexible polyether (PEBA) block.

11. The film according to any one of claims 1 to 10, wherein the at least one copolymer is selected from the following PEBAs: PA6-PEG, PA1010-PEG, PA1012-PEG, PA11-PEG, PA12-PEG, PA6 / 12-PEG, PA66-PEG, PA6 / 66-PEG, and mixtures thereof.

12. The film according to any one of claims 1 to 7, wherein the weight ratio of PA blocks to flexible blocks is in the range of 0.3 to 10.

13. In relation to the total weight of the composition, - 51% to 99.9% by weight of the block copolymer, - 0.1% to 49% by weight of at least one other component selected from polyamides, functional polyolefins, copolyether esters, thermoplastic polyurethanes (TPUs), copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylates, and copolymers of ethylene and alkyl (meth)acrylates. and / or - Additives selected from nucleating agents, fillers, reinforcing fibers, dyes, UV absorbers, antioxidants, hindered amine light stabilizers (HALS), and mixtures thereof, in an amount of 0.1% to 10% by weight. A copolymer-based film according to any one of claims 1 to 12, characterized by containing the following:

14. The film according to claim 13, characterized by comprising a functional polyolefin comprising grafting with a monomer selected from the group comprising unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, vinyl monomers, acrylic monomers, and mixtures thereof.

15. The film according to claim 14, wherein the functional polyolefin is selected from the group comprising ethylene-acrylic acid copolymer, ethylene-acrylic acid copolymer-maleic anhydride copolymer, and ethylene-acrylic acid copolymer-glycidyl methacrylate copolymer.

16. The film according to any one of claims 1 to 15, wherein the film has a thickness in the range of 25 μm or less.

17. Use of polycarbodiimide in a method for producing a film based on a copolymer comprising a polyamide block and a flexible block, each containing at least one carboxylic acid chain end, for improving the extrudeability and / or stretchability of the copolymer in film form and / or increasing the extruder rate of the copolymer, wherein at least one carboxylic acid chain end of the copolymer is blocked by a carbodiimide functional group of the polycarbodiimide.

18. Use of polycarbodiimide in a film based on a copolymer comprising a polyamide block and a flexible block, each containing at least one carboxylic acid chain end, for improving the stretchability, flexibility, abrasion resistance, and tear strength of the film, wherein at least one carboxylic acid chain end of the copolymer is blocked by a carbodiimide functional group of the polycarbodiimide.

19. The use according to claim 17 or 18, wherein the polycarbodiimide has a weight-average molecular weight greater than 10,000 g / mol.

20. a) A step of providing the copolymer according to claim 1, comprising at least one carboxylic acid chain end blocked by polycarbodiimide, b) A step of extruding the copolymer provided in step a), c) A process of stretching the copolymer to form a film. A method for producing the film according to any one of claims 1 to 16, including the method described in any one of claims 1 to 16.

21. The method according to claim 20, characterized in that step a) is to provide the copolymer according to claim 1, which includes at least one carboxylic acid chain end blocked with polycarbodiimide, as a mixture with other components of the film according to any one of claims 13 to 16.

22. The method according to claim 20 or 21, comprising, prior to step a), a step of mixing a block copolymer comprising at least one rigid polyamide PA block and at least one flexible block with polycarbodiimide, thereby obtaining a copolymer comprising at least one carboxylic acid chain end of the block copolymer reacting with a carbodiimide functional group of polycarbodiimide to obtain a copolymer comprising at least one carboxylic acid chain end blocked by polycarbodiimide.

23. The method according to claim 22, characterized in that the mixing is carried out using a single-screw or twin-screw extruder, or by adding polycarbodiimide during the synthesis of a block copolymer.

24. The method according to any one of claims 20 to 23, wherein the stretching step c) is carried out by extrusion blow molding, inflation film molding, pultrusion, overjacket extrusion, extrusion calender molding, flat die extrusion, extrusion coating, lamination and / or co-extrusion.

25. The method according to any one of claims 20 to 24, wherein step b) is performed at a temperature in the range of 100°C to 300°C.

26. A laminated product comprising at least one textile material and at least one film according to any one of claims 1 to 16, wherein the film is adhered to at least one surface of the textile material with a peel force in the range of 0.5 to 50 N.

27. The laminate according to claim 26, wherein the at least one woven material is in the form of a porous membrane, a woven fabric, or a nonwoven fabric.

28. The laminate according to claim 26 or 27, wherein the at least one textile material comprises synthetic fibers, natural fibers, artificial fibers made from natural raw materials, mineral fibers and / or metal fibers.

29. The laminate according to any one of claims 26 to 28, wherein the at least one textile material constitutes felt, filter, film, gauze, cloth, bandage, layer, fabric, knit fabric, clothing, garment item, bedding, furniture, curtain, room cover, functional industrial textile, geotextile and / or agrotextile.

30. Use of the film according to any one of claims 1 to 16 in the following sectors: medical, sanitation, baggage, manufacturing, clothing, domestic or household equipment, furniture, carpets, automobiles, industry, industrial filtration, agriculture and / or construction.

31. The film according to any one of claims 1 to 16, wherein the film is a packaging component, a food packaging film, a packaging film for cooking and / or smoking, or a waterproof and breathable film.

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