EP4237240A1

EP4237240A1 - Waterproof and breathable multilayer structure

Info

Publication number: EP4237240A1
Application number: EP21815557.0A
Authority: EP
Inventors: Quentin Pineau; Charlotte HERDT; Sébastien Jun MOUGNIER
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2020-10-27
Filing date: 2021-10-27
Publication date: 2023-09-06
Also published as: WO2022090665A1; JP2023546496A; FR3115491B1; FR3115491A1; CN116490349A; US20230391059A1

Abstract

The invention relates to a multilayer structure comprising a textile layer which comprises at least one polymer chosen from a polyamide and a copolymer with polyamide blocks and polyether blocks as well as combinations thereof; and a film comprising at least one copolymer with polyamide blocks and polyether blocks, the polyether blocks comprising polyethylene glycol blocks, the polyethylene glycol blocks representing at least 40% by mass relative to the mass of the film, the film adhering to the textile layer via a copolyamide. The invention also relates to a method for producing the multilayer structure, a method for recycling the multilayer structure and an article comprising the multilayer structure.

Description

Title: Waterproof-breathable multilayer structure

Field of invention

The present invention relates to a waterproof-breathable multilayer structure comprising a textile layer, a film comprising at least one copolymer with polyamide blocks and with polyether blocks and optionally a hot-melt adhesive composition.

Technical background

There are many technical fields that require textiles with improved and prolonged waterproof-breathable properties. Mention may in particular be made of the medical field, medical equipment, surgical gowns, mats, mattresses, dressings, protective clothing; agriculture, agricultural films; wrapping, packaging; military equipment, maritime equipment, in particular marine covers; transport, aeronautics, automotive; the sport ; leisure (“warm clothing”, “casual clothing”); IT, electronics, furniture; the decoration ; baby or child equipment; outdoor equipment; the insulation of the walls of a building, the under-roof films.

In these various fields, it is important to have protective barrier films against liquids, in particular against water, in particular waterproof-breathable films, which nevertheless ensure the transmission of water vapour. For example, in the case of sports clothing such as hiking jackets, it is important to protect the hiker against the rain, while promoting breathability, in order to allow the evaporation of perspiration and thus ensure the comfort of the hiker. hiker. It is also desirable to provide this same comfort to surgeons, nurses, or even to patients, who, during surgical operations, must be protected from any contact with bodily fluids, infectious agents or chemical products. Examples of corresponding protective clothing include gowns worn by surgeons and nurses, and surgical drapes placed on patients during operations.

It is known to use micro-perforated membranes in polytetrafluoroethylene (PTFE) or in thermoplastic polyurethane (TPU) so as to form this type of film on a textile, using an adhesive of the type isocyanate or polyurethane. However, the recycling of structures comprising PTFE can pose problems given the environmental impact linked to the destruction of a textile comprising PTFE. In general, this type of structure can be recycled by separating the PTFE membrane from the textile. In addition, the recycling of structures comprising TPU can have drawbacks, since this type of film can be incompatible with the textile (such as polyamide for example), which leads to recycled products of lower quality.

Furthermore, the presence of adhesive incompatible with the textile also makes it difficult to recycle the structure and leads to recycled products with deteriorated properties compared to those of the initial product.

JP 2011037101 relates to a waterproof-breathable textile widely applicable for cold protective clothing, sportswear, casual wear and the like, while maintaining excellent moisture-proof performance and reusable after recycling.

Document JP 2011073141 relates to a waterproof-breathable polyamide-based textile, advantageous in terms of cost and waterproof-breathable performance.

Document US 2019/0099989 relates to a composite textile product comprising a polyamide textile layer and a polyamide film bonded to the polyamide textile layer.

Document US 6420045 relates to a multilayer structure comprising a material covered with a copolymer with polyamide blocks and hydrophilic blocks, the copolymer having a melting point below 135°C.

US 5533210 relates to a fully recyclable jacket, the components of which consist of thermoplastic synthetic polymers which can be homogeneously mixed with each other in the molten state.

Document US 2005/0020161 describes a waterproof-breathable, recyclable and extensible multilayer composite textile which comprises at least one layer a woven, knitted or non-woven fabric of stretchable bicomponent fibers and an elastomeric film or coating of the same polymer.

Document US 2002/0160674 relates to a process for producing a wash-resistant binder between a waterproof breathable copolyetherester-based film and a polyester-based substrate.

US 2005/0208854 discloses a laminated fabric with a structure in which a first fabric is laminated to one side of a durable film with a temporary adhesive layer interposed therebetween and a second fabric is laminated to the other side of the durable film. with a durable adhesive layer interposed between them.

Document WO 2019/097184 relates to a stretchable, flexible, waterproof film based on a block copolymer comprising at least one rigid polyamide block and at least one flexible block, characterized in that the copolymer comprises at least one acid chain end carboxylic acid blocked by a polycarbodiimide.

Document WO 2012/089977 describes a waterproof-breathable film comprising an amide block copolyether and/or an ester block copolyether and/or a functionalized polyolefin, and starch. This film can be used as an under-roof film or wall insulation film for a home.

Document WO 2014/001674 describes the use of thermoplastic starch for the manufacture of an ultra-thin waterproof-breathable and adhesive film, said starch being in the form of an alloy with hydrophilic TPE. This film can be used in a textile product.

Document WO 2018/087501 relates to an extrudable polymer composition comprising at least one copolymer with flexible blocks and rigid blocks and at least one polyol comprising at least three hydroxyl groups, the composition being used in extrusion processes for manufacturing objects permeable to water vapor.

Document WO 2019/072755 relates to a functional product comprising a waterproof-breathable film without any additional layer, such as a textile layer. There is a need to provide an impermeable, breathable and recyclable structure, with performances that exhibit good resistance over time. In addition, there is a need to provide a breathable and recyclable structure, the properties of which are preserved after recycling.

Summary of the invention

The invention relates firstly to a multilayer structure, comprising:

- a textile layer comprising at least one polymer chosen from a polyamide and a copolymer with polyamide blocks and with polyether blocks as well as their combinations; and

- a film comprising at least one copolymer with polyamide blocks and with polyether blocks (also called PEBA copolymer), the polyether blocks comprising blocks of polyethylene glycol, the blocks of polyethylene glycol representing at least 40% by mass relative to the mass of the film ; wherein the film adheres to the textile layer via a copolyamide.

According to certain embodiments, the PEBA copolymer of the film comprises blocks of copolyamide.

According to a particular embodiment, the film whose PEBA copolymer comprises blocks of copolyamide adheres directly to the textile layer.

According to certain embodiments, the film is fixed to the textile layer by a hot-melt adhesive composition comprising the copolyamide, the copolyamide preferably comprising units derived from polyethylene glycol monomers representing at least 20% by mass relative to the mass of the copolyamide.

According to certain embodiments, the copolyamide of the hot-melt adhesive composition is chosen from PA 6/6.6/12, PA 6/6.6/11, PA 6/6.10/11, PA 6/6.10/12, PA 6/6.12/11, PA 6/6.12/12, PA 6/6.12/11/PEG.12, PA 6/11/PEG.6, PA 6/6.6/11/12 and PA 6/ Pip.12/12. According to some embodiments, the hot melt adhesive composition has a melting temperature that is lower than the melting temperature of the textile layer.

According to certain embodiments, the hot-melt adhesive composition has a melting point less than or equal to 150° C., and preferably less than or equal to 130° C.; and/or an MVR volumetric fluidity index of 2 to 200 cm ³ /10 min, and preferably 5 to 70 cm ³ /10 min.

According to certain embodiments, the polymer of the textile layer is polyamide and preferably the textile layer consists of at least one polyamide.

According to certain embodiments, the polyamide blocks of the copolymer with polyamide blocks and with polyether blocks in the film are chosen from blocks of polyamide 11, blocks of polyamide 12, blocks of polyamide 6, blocks of polyamide 6.10, blocks of polyamide 6.12, blocks of polyamide 10.10, blocks of polyamide 10.12, blocks of polyamide 10.14 and their combinations and again preferably blocks of polyamide 11, blocks of polyamide 12, their combinations and their copolymers.

According to certain embodiments, the film has a thickness of 1 to 50 μm, and preferably of 10 to 30 μm, even more preferably of 10 to 20 μm.

According to certain embodiments, the film consists of the PEBA copolymer and optionally of one or more additives chosen from inert dyes, fillers, surfactants, crosslinking agents, nucleating agents, reactive compounds, mineral agents or organic flame retardants, ultraviolet or infrared light absorbers, waxes, heat stabilizers, anti-blocking agents, antifoaming agents and ultraviolet or infrared fluorescent agents.

According to certain embodiments, the film is obtained by recycling a multilayer structure, preferably by recycling a multilayer structure as described above.

The invention also relates to a method of manufacturing the multilayer structure as described above, comprising: - supply of the textile layer;

- the supply of the film;

- optionally the application of the hot-melt adhesive composition on a surface of the textile layer or of the film; and

- Bringing the film into contact with the textile layer, the hot-melt adhesive composition being, if present in the multilayer structure, between the film and the textile layer.

The invention also relates to a process for recycling the multilayer structure as described above comprising:

- grinding the multilayer structure to obtain particles;

- the melting of the particles to obtain a molten mixture; and

- the formation of granules from the molten mixture.

The invention also relates to an article comprising the multilayer structure as described above, which can be chosen from a dressing, a gauze, a canvas, a carpet, a rug, an upholstery covering, a surface covering, a covering cockpit, a sofa, a curtain, bedding, a mattress, a pillow, clothing, in particular sports clothing or medical clothing.

The present invention makes it possible to meet the need expressed above. More particularly, it provides a waterproof, breathable and recyclable structure, with performances that show good resistance over time. In addition, it provides a waterproof, breathable and recyclable structure, whose properties are preserved after recycling.

This is accomplished through the multi-layered structure of the present invention. More particularly, the multilayer structure of the invention comprises a textile layer and a film which adheres to the textile layer via a copolyamide. Thus, the film can adhere directly to the textile layer or indirectly, that is to say via a hot-melt adhesive composition being in contact with the textile layer and the film. In other words, the copolyamide can either be part of the film or belong to a separate composition. The film comprises at least 40% by mass of the polyethylene glycol blocks relative to the mass of the film. This makes it possible to form a waterproof-breathable film by avoiding films made from fluorinated polymers (such as PTFE for example) which facilitates and improves recycling of the entire structure, without negative impact on the environment. This also makes it possible to form a waterproof-breathable film compatible with the textile layer (comprising polyamide or PEBA), which again facilitates recycling and makes it possible to obtain recycled products with properties and performance comparable to those of produced before recycling.

In the case where the multilayer structure is devoid of hot-melt adhesive composition, the copolymer with polyamide blocks and with polyether blocks of the film comprises copolyamide blocks. This allows the film to have a satisfactory adhesion allowing its direct adhesion to the textile layer.

In the case where the multilayer structure also comprises a hot-melt adhesive composition, this composition preferably comprises at least one copolyamide comprising units derived from polyethylene glycol monomers representing at least 20% by mass relative to the mass of the copolyamide. This allows the hot melt adhesive composition to adhere the film to the textile layer, without unacceptably degrading the waterproof-breathable properties of the structure.

Furthermore, the use of a hot-melt adhesive composition comprising polyamide also makes it possible to maintain this compatibility with the textile layer in order to increase the efficiency and quality of recycling.

detailed description

The invention is now described in more detail and in a non-limiting manner in the description which follows.

The multilayer structure according to the invention comprises a textile layer, a film and optionally a hot-melt adhesive composition between the textile layer and the film. In other words, the film is adhered directly to the textile layer or the hot-melt adhesive composition makes it possible to adhere the film to the textile layer.

Textile layer The textile layer comprises at least one polymer which can be chosen from a polyamide, a copolymer with polyamide blocks and polyether blocks, as well as their combinations. Typically, the textile layer comprises polyamide fibers and/or block copolymer fibers. polyamide and polyether blocks.

The polyamide can be a homopolyamide or a copolyamide.

Preferably, the polyamide included in the textile layer is chosen from PA 6, PA 6.6, PA 11 and PA 12.

According to certain embodiments, the polymer of the textile layer is a copolymer with polyamide blocks and with polyether blocks.

According to preferred embodiments, the polymer of the textile layer is a polyamide, as described above.

According to other embodiments, the polymer of the textile layer is a mixture of polyamide and of copolymer with polyamide blocks and with polyether blocks.

According to certain embodiments, the textile layer comprises a single polymer according to the invention. In this case, it is preferable for this polymer to be a polyamide and preferably one of the preferred polyamides mentioned above.

Alternatively, the textile layer can comprise more than one polymer according to the invention, for example two, or three, or four, or five, or more than five polymers. In this case, it is preferable for at least one of these polymers (and preferably all the polyamides) to be one of the polyamides and preferably of the preferred polyamides mentioned above.

According to certain preferred embodiments, the textile layer consists essentially, or even consists, of one or more polyamides.

The fibers of the textile layer can be mono or multi-filament, textured or not, and are chosen in terms of cost, texture, and this type Fiber is preferably formed using polyamide fibers having a count of 15 to 2000 dtex and preferably 15 to 1000 dtex.

According to certain embodiments, the fibers of the textile layer can be bi- or multi-component fibers, that is to say fibers in which two polymers of the same general class are in an eccentric or side-to-side sheath-core relationship. coast.

The textile layer may have a melting temperature of 150 to 300°C, and preferably 180 to 270°C. The melting temperature can be determined according to ISO 11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.

The textile layer can be a woven, non-woven or knitted fabric. Thus, the textile layer according to the invention can be a woven, knitted, nonwoven or carpet layer (surface). This layer can be, for example, a layer of a dressing, a gauze, a canvas, a carpet, a rug, an upholstery covering, a surface covering, a passenger compartment covering, a sofa, a curtain, bedding, a mattress, a pillow, an item of clothing such as sports clothing or medical clothing.

Preferably, the textile layer comprises fibers obtained from bio-resourced raw materials.

Preferably, the textile layer further comprises natural fibers, artificial fibers made from natural raw materials, mineral fibers and/or metal fibers.

Film

The film according to the invention comprises at least one copolymer with polyamide blocks and with polyether blocks. This is a waterproof breathable film. By “waterproof-breathable”, we mean permeable to water vapor and impermeable to liquid water.

PEBA copolymers result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, among others:

1) polyamide blocks with diamine chain ends with blocks polyoxyalkylenes with dicarboxylic chain ends;

2) polyamide blocks at the ends of dicarboxylic chains with polyoxyalkylene blocks at the ends of diamine chains, obtained for example by cyanoethylation and hydrogenation of polyoxyalkylene a,oo-dihydroxylated aliphatic blocks called polyetherdiols;

3) polyamide blocks with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.

Polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid. Polyamide blocks with diamine chain ends come, for example, from the condensation of polyamide precursors in the presence of a diamine chain limiter.

The polymers containing polyamide blocks and polyether blocks can also comprise randomly distributed units.

Three types of polyamide blocks can advantageously be used.

According to a first type, the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms and an aliphatic, cycloaliphatic or aromatic, in particular those having 2 to 20 carbon atoms, preferably those having 5 to 14 carbon atoms.

Examples of dicarboxylic acids include the acid

1.4-cyclohexyldicarboxylic acids, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids.

Examples of diamines include tetramethylene diamine,

1.5-pentanediamine, 2-methylpentane-1,5-diamine hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, isomers of bis-(4-aminocyclohexyl)-methane (BACM), bis- (3-methyl-4- ammocyclohexyl)methane (BMACM), and 2-2-bis-(3-methyl-4- aminocyclohexyl)-propane (BMACP), and paraamino-di-cyclo-hexyl-methane (PACM), and isophoronediamine (IPDA) , 2,6-bis-(aminomethyl)-norbornane (BAMN) and piperazine (Pip).

Advantageously, PA 4.12, PA 4.14, PA 4.18, PA 5.10, PA 5.12, PA 5.14, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 blocks are used . In the notation PA X.Y, X represents the number of carbon atoms resulting from the diamine residues, and Y represents the number of carbon atoms resulting from the diacid residues, in the conventional way.

According to a second type, the polyamide blocks result from the condensation of one or more a,oo-aminocarboxylic acids and/or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 with 12 carbon atoms or a diamine. Examples of lactams include caprolactam, oenantholactam and lauryllactam. As examples of α,oo-amino carboxylic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids.

Advantageously, the polyamide blocks of the second type are made of polyamide 11, of polyamide 12 or of polyamide 6. In the notation PA X, X represents the number of carbon atoms resulting from the amino acid residues.

According to a third type, the polyamide blocks result from the condensation of at least one a,oo-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.

In this case, the polyamide PA blocks are prepared by polycondensation:

- linear aliphatic, cycloaliphatic or aromatic diamine(s) having X carbon atoms;

- dicarboxylic acid(s) having Y carbon atoms; and

- co-monomer(s) {Z}, chosen from lactams and a,oo-aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X1 carbon atoms and at least one diacid carboxylic acid having Y1 carbon atoms, (X1 , Y1 ) being different from (X, Y), - said {Z} comonomer(s) being introduced in a proportion by weight ranging up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all of the polyamide precursor monomers ;

- in the presence of a chain limiter chosen from dicarboxylic acids; advantageously, the dicarboxylic acid having Y carbon atoms is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine(s).

According to a variant of this third type, the polyamide blocks result from the condensation of at least two a,oo-aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or of a lactam and of a aminocarboxylic acid not having the same number of carbon atoms in the optional presence of a chain limiter. By way of example of an aliphatic α,oo-amino carboxylic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids. By way of example of lactam, mention may be made of caprolactam, oenantholactam and lauryllactam. By way of example of aliphatic diamines, mention may be made of 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine. As an example of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid. By way of example of aliphatic diacids, mention may be made of butane-dioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, dimerized fatty acids (these dimerized fatty acids preferably have a dimer content of at least 98% they are preferably hydrogenated; they are marketed under the trademark "PRIPOL" by the company "CRODA", or under the trademark RADIACID by the company OLEON) and polyoxyalkylene a,oo-diacids. By way of example of aromatic diacids, mention may be made of terephthalic (T) and isophthalic (I) acids. By way of example of cycloaliphatic diamines, mention may be made of the isomers of bis-(4-aminocyclohexyl)-methane (BACM), bis-(3-methyl-4-aminocyclohexyl)methane (BMACM), and 2-2-bis -(3-methyl-4-aminocyclohexyl)-propane (BMACP), and para-amino-di-cyclo-hexyl-methane (PACM). Other commonly used diamines may be isophoronediamine (IPDA), 2,6-bis-(aminomethyl)-norbornane (BAMN), and piperazine. By way of examples of polyamide blocks of the third type, the following may be mentioned:

- PA 6.6/6 in which 6.6 designates hexamethylenediamine units condensed with adipic acid and 6 designates units resulting from the condensation of caprolactam,

- PA 6.6/6.10/11/12 in which 6.6 denotes hexamethylenediamine condensed with adipic acid; 6.10 denotes hexamethylenediamine condensed with sebacic acid; 11 denotes units resulting from the condensation of aminoundecanoic acid; and 12 denotes units resulting from the condensation of lauryllactam.

The notations PA X/Y, PA X/Y/Z, etc. refer to copolyamides in which X, Y, Z, etc. represent homopolyamide units as described above.

Advantageously, said at least one polyamide block of the copolymer(s) used in the film of the invention comprises at least one of the following polyamide monomers: 6, 11, 12, 5.4, 5.9, 5.10, 5.12 , 5.13, 5.14, 5.16, 5.18, 5.36, 6.4, 6.9, 6.10, 6.12, 6.13, 6.14, 6.16, 6.18, 6.36, 10.4, 10.9, 10.10,

10.12, 10.13, 10.14, 10.16, 10.18, 10.36, 10.T, 12.4, 12.9, 12.10, 12.12,

12.13, 12.14, 12.16, 12.18, 12.36, 12.T and their mixtures or copolymers; and preferably chosen from the following polyamide monomers: 6, 11, 12, 6.10, 10.10, 10.12, and mixtures or copolymers thereof.

According to preferred embodiments, the polyamide blocks of the PEBA copolymer are chosen from blocks of polyamide 6, blocks of polyamide 11, blocks of polyamide 6.10, blocks of polyamide 6.12, blocks of polyamide 10.10, blocks of polyamide 10.12, polyamide blocks

10.14, polyamide 12 blocks, polyamide 11/12 blocks, their combinations and their copolymers.

The polyether blocks of the PEBA copolymer of the invention comprise blocks derived from polyethylene glycol (PEG) representing at least 40% by weight relative to the weight of the film. For example, the polyether blocks of the PEBA copolymer can comprise from 40 to 45%; or 45 to 50%; or 50 to 55%; or 55 to 60%; or 60 to 65%; or 65 to 70%; or 70 to 75%; or 75 to 80%; or from 80 to 85% by mass of PEG blocks relative to the mass of the film. The mass proportion of PEG in the film can be determined by NMR spectroscopy or infrared spectroscopy.

The polyether blocks may further comprise blocks derived from PPG (propylene glycol), and/or blocks derived from PO3G (polytrimethylene glycol), and/or blocks derived from PTMG (polytetramethylene glycol or polytetrahydrofuran). The PEBA copolymers can comprise in their chain several types of polyethers, the copolyethers possibly being block or random.

According to certain embodiments, the polyether blocks of the PEBA copolymer consist of PEG blocks.

It is also possible to use blocks obtained by oxyethylation of bisphenols, such as for example bisphenol A. These latter products are described in patent EP613919.

The polyether blocks can also consist of ethoxylated primary amines. By way of example of ethoxylated primary amines, mention may be made of the products of formula: [Chem in which m and n are between 1 and 20 and x between 8 and 18. These products are commercially available under the brand NORAMOX® from the company ARKEMA and under the brand GENAMIN® from the company CLARIANT.

The flexible polyether blocks can comprise polyoxyalkylene blocks with ends of NH2 chains, such blocks being able to be obtained by cyanoacetylation of aliphatic polyoxyalkylene a,oo-dihydroxylated blocks called polyether diols. More particularly, Jeffamines can be used (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from the company Huntsman, also described in the patent documents JP2004346274, JP2004352794 and EP1482011). Some of these products (notably Jeffamine® ED2003) include PEG blocks.

The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or they are transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends. The general method for the two-step preparation of PEBA copolymers having ester bonds between the PA blocks and the PE blocks is known and is described, for example, in French patent FR2846332. The general method for preparing the PEBA copolymers of the invention having amide bonds between the PA blocks and the PE blocks is known and described, for example in European patent EP1482011. The polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to make polymers with polyamide blocks and polyether blocks having randomly distributed units (one-step process).

Of course, the designation PEBA in the present description of the invention relates both to PEBAX® marketed by Arkema, to Vestamid® marketed by Evonik®, to Grilamid® marketed by EMS, and to Pelestat® type PEBA marketed by Sanyo or any other PEBA from other providers.

Advantageously, the PEBA copolymers can have polyamide blocks made of PA 6, PA 11, PA 12, PA 6.10, PA 6.12, PA 6.6/6, PA 10.10, PA 10.12 and/or PA 6.14, preferably PA 11 and/or PA 12 blocks; and polyether blocks in PEG.

Particularly preferred PEBA copolymers in the context of the invention are copolymers comprising blocks: PA 11 and derived from PEG; PA 12 and derived from PEG; PA 6.10 and derived from PEG; PA 10.10 and derived from PEG; PA 10.12 and derived from PEG; PA 6.12 and derived from PEG; PA 6 and derived from PEG; PA 11/12 and derived from PEG.

The PEBA copolymer can also comprise compounds with a functionality greater than 2. By “functionality” is meant the number of reactive functions present in the monomers and capable of participating in the growth of the chain. These compounds can be, for example, tri- or tetra-functional polyethers or compounds such as trimethylolpropane, dimethylolpropane, pentaerythritol.

If the block copolymers described above generally comprise at least one polyamide block and at least one polyether block, the present invention also covers all the copolymers comprising two, three, four (or even more) different blocks chosen from those described in the present invention. description, since these blocks comprise at least polyamide and polyether blocks.

Advantageously, the copolymer is a segmented block copolymer comprising three different types of blocks (called “triblock” in the present description of the invention), which result from the condensation of several of the blocks described above.

The number-average molar mass of the polyamide blocks in the PEBA copolymer is preferably from 400 to 20,000 g/mol, more preferably from 500 to 10,000 g/mol, preferably from 500 to 2,000 g/mol, and even more preferably from 1,000 to 1500 g/mol. In some embodiments, the number-average molar mass of the polyamide blocks in the PEBA copolymer is from 400 to 1000 g/mol, or from 1000 to 1500 g/mol, or from 1500 to 2000 g/mol, or from 2000 to 2500 g/mol, or from 2500 to 3000 g/mol, or from 3000 to 3500 g/mol, or from 3500 to 4000 g/mol, or from 4000 to 5000 g/mol, or from 5000 to 6000 g/mol, or from 6000 to 7000 g/mol, or from 7000 to 8000 g/mol, or from 8000 to 9000 g/mol, or from 9000 to 10000 g/mol, or from 10000 to 11000 g/mol, or from 11000 to 12000 g/mol, or from 12000 to 13000 g/mol, or from 13000 to 14000 g/mol, or from 14000 to 15000 g/mol, or from 15000 to 16000 g/mol, or from 16000 to 17000 g/mol, or from 17,000 to 18,000 g/mol, or from 18,000 to 19,000 g/mol, or from 19,000 to 20,000 g/mol.

The number-average molar mass of the polyether blocks is preferably from 100 to 6000 g/mol, more preferably from 200 to 3000 g/mol, and even more preferably from 200 to 2000 g/mol. In some embodiments, the number average molar mass of the polyether blocks is from 100 to 200 g/mol, or from 200 to 500 g/mol, or from 500 to 800 g/mol, or from 800 to 1000 g/mol , or from 1000 to 1500 g/mol, or from 1500 to 2000 g/mol, or from 2000 to 2500 g/mol, or from 2500 to 3000 g/mol, or from 3000 to 3500 g/mol, or 3500 to 4000 g/mol, or 4000 to 4500 g/mol, or 4500 to 5000 g/mol, or 5000 to 5500 g/mol, or 5500 to 6000 g/mol.

The number-average molar mass is fixed by the content of chain limiter. It can be calculated according to the relationship:

Mn ⁼ H monomer X MW repeat pattern / H chain limiter + MW chain limiter

In this formula, nmonomer represents the number of moles of monomer, nchain-limiter represents the number of excess moles of limiter (e.g., diacid), MWrepeat unit represents the molar mass of the repeating unit, and MWchain-limiter represents the mass excess molar of the limiter (eg diacid).

The number-average molar mass of the polyamide blocks and of the polyether blocks can be measured before the copolymerization of the blocks by gel permeation chromatography (GPC).

The mass proportion of polyether blocks in the copolymer can be from 40 to 85% relative to the total weight of the copolymer, and preferably from 50 to 60% relative to the total weight of the copolymer. The mass proportions of blocks in the copolymer can be determined from the number-average molar masses of the blocks.

The film according to the invention adheres to the textile layer via a copolyamide. According to certain embodiments, this copolyamide is part of the PEBA copolymer. In other words, the PEBA copolymer comprises copolyamide blocks. In this case, the film adheres directly to the textile layer.

Thus, in the case where the copolyamide is part of the PEBA copolymer, the polyamide blocks of the PEBA copolymer comprise at least two distinct repeating units, these distinct units being formed from at least two different monomers. In other words, in this case, the polyamide blocks of the PEBA copolymer are copolyamide blocks. The various monomers for forming the copolyamide blocks are as detailed above. Preferred copolyamide blocks can be chosen from PA 6/12; AP 6/11; PA 6/10.10; PA 6/10.12; AP 6/10.14; AP 11/12; PA 11/10.10; AP 11/10.12; AP 11/10.14; PA 12/10.10; PA 12/10.12; AP 12/10.14; PA 6/6.6/12; PA 6/6.10/12; PA 6/6.12/12; PA 6/6.6/11; PA 6/6.10/11 and PA 6/6.12/11.

According to certain embodiments, the film comprises a single PEBA copolymer. In this case, the PEBA included in the film is as described above.

Alternatively, the film may comprise more than one PEBA copolymer, for example two, or three, or four, or five, or more than five PEBA copolymers. In this case, it is preferable for at least one of these PEBA copolymers to be a PEBA copolymer according to the invention. It is even more preferred that all PEBA copolymers are according to the invention.

According to certain embodiments, the film of the invention consists essentially, or even consists of one or more PEBA copolymers according to the invention and optionally of one or more additives.

For example, the film of the invention may include one or more additives, which may include inert dyes such as titanium dioxide, fillers, surfactants, crosslinking agents, nucleating agents, reactive compounds, inorganic or organic flame retardants, ultraviolet (UV) or infrared (IR) light absorbers and UV or IR fluorescent agents, waxes, heat stabilizers (phenolic or phosphorus-based for example), anti- blocking agents, anti-foaming agents. Typical fillers include talc, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass microspheres, microspheres ceramic, thermoplastic microspheres, barite and wood flour.

The additives are optionally present at a content by weight of 0 to 10% and preferably of 0 to 5%. For example, one or more additives may be present at a content by weight of 0 to 0.5%; or from 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%. These additives make it possible to modify one or more physical properties of the film.

According to other embodiments, the film may comprise other components apart from the PEBA copolymer(s) according to the invention and the additives mentioned above.

In this case, the film may comprise one or more additional polymers (other than PEBAs) chosen, for example, from ethylene and vinyl acetate (EVA) polymers and/or ionomers (that is to say copolymers ionically cross-linked thermoplastics). For example, the film may comprise additional polymers at a content by weight of less than or equal to 30%.

The film of the invention can be manufactured in particular by extrusion. Preferably the extrusion is carried out hot at a temperature ranging from 170 to 280°C, and preferably from 180 to 280°C.

Alternatively, the film of the invention can be manufactured by sheath blowing, by lamination or by extrusion-coating.

Preferably, the film is a monolithic film. In other words, the film according to the invention has no perforations (such as microperforations). This prevents clogging or tearing of the perforations and thus achieves better hold of the properties of the film over time.

The film can have a thickness of 1 to 50 μm, and preferably 10 to 20 μm.

Preferably, the material constituting the film has a permeability to water vapor (MVTR, for “Moisture Vapor Transmission Rate”) of at least 700 g/m ² per 24 hours, at 23° C., at a rate of relative humidity of 50%, for a reference thickness of 30 μm. More preferably, the water vapor permeability MVTR of the film is at least 800 g/m ² /24 h, at 23° C., at a relative humidity level of 50%, for a film thickness of 30 p.m. In particular, the MVTR permeability of the membrane can be worth 700 to 800 g/m ² /24 h, or from 800 to 900 g/m ² /24 h, or from 900 to 1000 g/m ² /24 h, or from 1000 to 1200 g/m ² /24 h, or 1200 to 1500 g/m ² /24 h, or from 1500 to 2000 g/m ² /24 h, or from 2000 to 2500 g/m ² /24 h, or from 2500 to 3000 g/m ² /24 h , or from 3000 to 3500 g/m ² /24 h, or from 3500 to 4000 g/m ² /24 h, or from 4000 to 4500 g/m ² /24 h, or from 4500 to 5000 g/m ² / 24 h, 23°C, 50% relative humidity, 30 µm film thickness. The water vapor permeability (MVTR) of the film, at 23°C, for a relative humidity of 50%, for a film thickness of 30 μm, can be measured according to the ASTM E96 B standard.

Hot melt adhesive composition

As mentioned above, the film according to the invention adheres to the textile layer via a copolyamide. According to certain embodiments, this copolyamide is part of a separate hot melt adhesive composition which is located between the textile layer and the film and allows the adhesion of the film to the textile layer.

By “hot melt adhesive composition” is meant an adhesive deposited in the molten state on a surface to be bonded, the adhesion then being obtained by cooling, by the return to the solid state of the composition.

The hot melt adhesive composition is (when present) in contact with the textile layer and the film.

The hot-melt adhesive composition according to the invention comprises at least one copolyamide. The “copolyamides” abbreviated “COPA” comprise at least two distinct repeating units, these distinct units being formed from at least two different monomers. The copolyamides are therefore prepared from two or more comonomers chosen from an amino acid, a lactam and/or a dicarboxylic acid with a diamine.

Thus, by copolyamide (abbreviated CoPA), we mean the polymerization products of at least two different monomers chosen from:

- monomers of the amino acid or aminocarboxylic acid type, and preferably α,α-aminocarboxylic acids;

- monomers of the lactam type having from 3 to 18 carbon atoms on the main ring and which may be substituted; - monomers of the “diamme.diacide” type resulting from the reaction between an aliphatic diamine having 4 and 36 carbon atoms and a dicarboxylic acid having 4 and 36 carbon atoms; and

- their mixtures, with monomers with different carbon numbers in the case of mixtures between an amino acid type monomer and a lactam type monomer.

As examples of a,oo-amino acids, mention may be made of those having from 4 to 18 carbon atoms, such as aminocaproic, 7-aminoheptanoic, 11-aminoundecanoic, n-heptyl-11-aminoundecanoic and 12-aminoundecanoic acids. aminododecanoic.

Mention may be made, as examples of lactams, of those having from 3 to 18 carbon atoms on the main ring and which may be substituted. Mention may be made, for example, of P,p-dimethylpropriolactam, α,α-dimethylpropriolactam, amylolactam, caprolactam also called lactam 6, capryllactam also called lactam 8, oenantholactam, 2-pyrrolidone and lauryllactam also called lactam 12.

Regarding monomers of the “diamine. diacid”:

As examples of dicarboxylic acid, mention may be made of acids having 4 and 36 carbon carbon atoms. Mention may be made, for example, of adipic acid, sebacic acid, azelaic acid, suberic acid, dodecanedioic acid, tetradecanedioic acid, isophthalic acid, butanedioic acid, 1 ,4 cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salt of sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and l dodecanedioic acid HOOC-(CH ₂ )IO-COOH.

By way of example of a diamine, mention may be made of aliphatic diamines having from 4 to 18 atoms, which may be aryl and/or saturated cyclic. By way of example, mention may be made of pentanediamine, hexamethylenediamine, piperazine (abbreviated "Pip"), tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl- 1,6-diamino-hexane, diamine polyols, isophorone diamine (IPD), 2-methyl-1,5-pentamethylenediamine (MPDM), bis(aminocyclohexyl) methane (BACM), bis(3-methyl -4 aminocyclohexyl) methane (BMACM), methoxylyenediamme, bis-p aminocyclohexylmethane and trimethylhexamethylene diamine.

As examples of monomers of the "diamine, diacid" type, mention may be made of those resulting from the condensation of hexamethylene diamine with a C6 to C36 diacid, in particular the monomers: 6.6, 6.10, 6.11, 6.12, 6.14, 6.18 . Mention may be made of the monomers resulting from the condensation of decanediamine with a C6 to C36 diacid, in particular the monomers: 10.10, 10.12, 10.14, 10.18.

As examples of copolyamides formed from the various types of monomers described above, mention may be made of the copolyamides resulting from the condensation of at least two α,ε-aminocarboxylic acids or of two lactams or of a lactam and of an α,α-aminocarboxylic acid. Mention may also be made of the copolyamides resulting from the condensation of at least one a,oo-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid. Mention may also be made of the copolyamides resulting from the condensation of an aliphatic diamine with an aliphatic dicarboxylic acid and at least one other monomer chosen from aliphatic diamines different from the previous one and aliphatic diacids different from the previous one.

Examples of copolyamides include copolymers of caprolactam and lauryllactam (PA 6/12), copolymers of caprolactam, hexamethylene diamine and adipic acid (PA 6/6.6), copolymers of caprolactam , lauryllactam, hexamethylene diamine and adipic acid (PA 6/12/6.6), copolymers of caprolactam, hexamethylene diamine and azelaic acid, 11-aminoundecanoic acid, and lauryllactam, ( PA 6/6.9/11/12), copolymers of caprolactam, adipic acid and hexamethylene diamine, amino-11-undecanoic acid, lauryllactam (PA 6/6.6/11/12), copolymers of hexamethylene diamine, azelaic acid, and lauryllactam (PA 6.9/12), copolymers of 2-pyrrolidone and caprolactam (PA 4/6), copolymers of 2-pyrrolidone and lauryllactam (PA 4/12) , copolymers of caprolactam and 11-amino-undecanoic acid (PA 6/11), copolymers of lauryllactam and capryllactam (PA 12/8), copolymers of 11-amino acid -undecanoic acid and 2-pyrrolidone (PA 11/4), copolymers of capryllactam and caprolactam (PA 8/6), copolymers of capryllactam and 2-pyrrolidone (PA 8/4), copolymers of lauryllactam and capryllactam (PA 12/8), copolymers of lauryllactam and 11-amino-undecanoic acid (PA 12/11).

The copolyamide of the hot-melt adhesive composition according to the invention preferably also comprises units derived from polyethylene glycol (PEG) monomers. In other words, apart from the units forming the copolyamide, this polymer also preferably comprises blocks derived from PEG monomers, that is to say it is a particular type of PEBA polymer such as as described above, with copolyamide blocks and PEG blocks.

The PEG blocks preferably represent at least 20% by mass relative to the mass of the copolyamide. For example, the copolyamide can comprise from 20 to 25%; or 25 to 30%; or 30 to 35%; or 35 to 40%; or 40 to 45%; or 45 to 50%; or 50 to 55%; or from 55 to 60% by mass of PEG blocks relative to the mass of the copolyamide.

According to certain embodiments, the copolyamide can also comprise blocks other than PEG blocks, for example PPG blocks, PTMG blocks, polyetheramines of the Jeffamine® type marketed by the company HUNTSMAN and aliphatic amines of the Baxxodur™ type marketed by the BASF company.

The PEG blocks can be used as such and copolycondensed with copolyamide blocks (for example with carboxylic ends), or transformed into polyether diamines and condensed with polyamide blocks (with carboxylic ends).

Advantageously, the copolyamide used in the composition according to the invention is obtained at least partially from bio-resourced raw materials.

By “raw materials of renewable origin” or “bio-resourced raw materials”, is meant materials which comprise bio-resourced carbon or carbon of renewable origin. Indeed, unlike materials derived from fossil materials, materials made from renewable raw materials contain ¹⁴ C. The “carbon content of renewable origin” or “bio-resource carbon content” is determined in application of the ASTM D 6866 (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04) standards. For example, COPAs based on polyamide 11 come at least in part from bio-resourced raw materials and have a bio-resourced carbon content of at least 1%, which corresponds to an isotopic ratio of ¹² C / ¹⁴ C of at least 1.2 x 10' ¹⁴ . Preferably, the COPAs according to the invention comprise at least 50% by mass of bio-based carbon on the total mass of carbon, which corresponds to a ¹² C/ ¹⁴ C isotopic ratio of at least 0.6. X 10' ¹² . This content is advantageously higher, in particular up to 100%, which corresponds to a ¹² C/ ¹⁴ C isotopic ratio of approximately 1.2 x 10 ^-12 , in the case of COPAs derived entirely from raw materials of renewable.

Examples of amino acids of renewable origin include: 11-aminoundecanoic acid produced from castor oil, for example, 12-aminododecanoic acid produced from castor oil, for example , 10-aminodecanoic acid produced from decylenic acid obtained by metathesis of oleic acid for example, 9-aminononanoic acid produced from oleic acid for example.

As examples of diacids of renewable origin, mention may be made, depending on the number x of carbons of the molecule (Cx): C4: succinic acid from glucose for example; C6: adipic acid from glucose for example; C7: heptanedioic acid from castor oil; C9: azelaic acid from oleic acid (ozonolysis) for example; C10: sebacic acid from castor oil for example; C11: undecanedioic acid from castor oil; C12: dodecanedioic acid from biofermentation of dodecanoic acid = lauric acid (rich oil: palm kernel oil and coconut) for example; C13: brassylic acid from erucic acid (ozonolysis) found in rapeseed for example; C14: tetradecanedioic acid by biofermentation of myristic acid (rich oil: palm kernel oil and coconut) for example; C16: hexadecanedioic acid by biofermentation of palmitic acid (mainly palm oil) for example; C18: octadecanedioic acid obtained by biofermentation of stearic acid (a little in all vegetable oils but majority in animal fats) for example; C20: eicosanedioic acid obtained by biofermentation of arachidic acid (predominant in rapeseed oil), for example; C22: docosanedioic acid obtained by metathesis of undecyl acid (castor oil) for example; C36: fatty acid dimer derived from softwood by-products transformed by the Kraft process.

As examples of diamines of renewable origin, mention may be made, depending on the number x of carbons of the molecule (Cx): C4: butanediamine obtained by amination of succinic acid; C5: pentamethylene diamine (from lysine); and so on for the diamines obtained by amination of the diacids of renewable origin seen previously.

Thus, the copolyamide blocks of the copolyamide can be of totally renewable origin, i.e. resulting from the polymerization of various monomers (renewable, non-renewable or mixed) such as those mentioned above. This is the case for example of the copolyamide 6.6/10.10 in which the “6.6” monomer is of non-renewable origin while the “10.10” monomer is of renewable origin.

By copolyamide blocks of totally renewable origin entering into the composition according to the invention, is meant the copolyamides resulting from the polymerization of various monomers, such as those mentioned above, such as for example the following copolyamides: PA 11/10.10, PA 11/10.36, PA 10.10/10.36, amino-11-undecanoic/n-heptyl-11-aminoundecanoic copolyamide.

The copolyamide of the hot-melt adhesive composition may in particular be chosen from the following copolyamides:

- PA 6/6.6/12, whose corresponding mass ratios of monomers can be for example (in percentage): 40/20/40, 35/20/45, 45/35/20, 30/30/40, 22/ 18/60, 40/25/35;

- PA 6/6.6/11;

- PA 6/6.10/11;

- PA 6/6.10/12;

- PA 6/6.6/11/12, whose corresponding mass ratios of monomers can be for example (in percentage): 30/15/10/45, 30/20/20/30, or 15/25/25/35 ; ;

- PA 6/12, for example with a mass ratio of 70/30;

- PA 6.9/12, for example with a mass ratio of 30/70;

- PA Pip.9/Pip.12/11, for example with a mass ratio of 15/70/15; - PA 6/IPD.6/12, for example with a mass ratio of 20/15/65;

- PA IPD.9/12, for example with a mass ratio of 20/80;

- PA 6/6.12/11;

- PA 6/6.12/12, for example with a mass ratio of 30/30/40;

- PA 6/Pip.12/12, for example with a mass ratio of 30/20/50;

- PA 6/6.12/11/PEG.12, for example with a mass ratio of 25/21/25/30;

- PA 6/11 /PEG.6;

- PA 6/6.6/6.10/6.1, for example with a mass ratio of 40/10/40/10;

- PA 6.10/Pip.10/Pip.12, for example with a mass ratio of 20/40/40;

- PA 6/11/12, for example with a mass ratio of 10/36/54;

- PA Pip.12/12, for example with a mass ratio of 35/65;

- PA IPD.10/12, for example with a mass ratio of 80/20;

- PA Pip.10/12, for example with a mass ratio of 72/28;

- PA 6/11, for example with a mass ratio of 50/50;

- PA Pip.10/11/Pip.9, for example with a mass ratio of 65/30/5;

- PA 6/6.6/6.10, for example with a mass ratio of 35/30/35.

The PEG.6 notation designates a PEG block with a C6 diacid chain limiter, and the PEG.12 notation designates a PEG block with a C12 diacid chain limiter.

According to preferred embodiments, the copolyamide can be chosen from the copolyamides PA 6/6.6/12, PA 6/6.6/11, PA 6/6.10/11, PA 6/6.10/12, PA 6/6.12/11, PA 6/6.12/12, PA 6/6.12/11/PEG.12, PA 6/11/PEG.6, PA 6/6.6/11/12, and PA 6/Pip.12/12.

According to certain embodiments, the hot melt adhesive composition comprises a single copolyamide above.

According to other embodiments, the hot melt adhesive composition may comprise more than one copolyamide above, for example two, or three, or four, or five, or more than five copolyamides above.

The hot-melt adhesive composition may, in addition to the copolyamide, comprise additional polymers such as polymers of ethylene and vinyl acetate (EVA) and/or polymers of ethylene and acrylic acid (EAA) and/or ionomers. Alternatively and preferably, the hot-melt adhesive composition consists essentially, or even consists, of the copolyamide(s) according to the invention and optionally of one or more additives.

For example the hot melt adhesive composition may include one or more additives, which may include waxes, heat stabilizers and ultraviolet stabilizers, anti-foaming agents, anti-caking agents (such as zinc stearate, calcium stearate , N,N-ethylene-bis(stearamide)) and optical brighteners.

The hot melt adhesive composition may have a melting temperature of 85 to 150°C, and preferably 95 to 130°C. The melting temperature can be determined according to ISO 11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.

Preferably, the hot melt adhesive composition has a melting temperature lower than the melting temperature of the textile layer. The difference between the melting temperature of the hot melt adhesive composition and the textile layer can be 15°C to 100°C, and preferably 30°C to 70°C.

The melt flow index by volume or MVR (abbreviation of Melt Volume Rate) at 160° C./2.16 kg of the hot-melt adhesive composition can be from 2 to 200 cm ³ /10 min, and from preferably 5 to 70 cm ³ /10 min. It is measured according to the ISO 1133 standard.

Multi-layer structure

The multilayer structure according to the invention comprises:

- the textile layer as described above;

- the film as described above; and optionally (as detailed above)

- the hot-melt adhesive composition as described above between the textile layer and the film.

According to certain embodiments, the multilayer structure according to the invention consists of the textile layer, the film, and optionally the hot-melt adhesive composition. According to other preferred embodiments, the multilayer structure may comprise, apart from these two (or three) elements, other components and/or layers and/or films.

For example, the multilayer structure may comprise a film as described above, and two layers of textile as described above on either side, the adhesion on either side taking place as described below. above and below. Or the multilayer structure may comprise a layer of textile as described above, and two films as described above on either side, the adhesion on either side taking place as described above. and below.

For example again, the multilayer structure according to the invention can comprise additional textile layers such as layers comprising fibers made of polyester, polyurethane, polyolefins, polyvinylidene chloride, and polyacrylics or any other functional or structural layer known to man. of career.

In certain embodiments, the multilayer structure according to the invention comprises a fluorinated polymer. It can be a separate layer comprising at least one fluoropolymer or, preferably, a modification (by reaction) of one of the surfaces of the multilayer structure (for example of the surface of the textile layer) to form a fluorinated polymer in situ.

In other embodiments, the multilayer structure according to the invention is devoid of a fluorinated layer, which makes it possible to improve and facilitate the recycling of this structure.

The multilayer structure is manufactured according to a process comprising:

- providing the textile layer as described above;

- the supply of the film as described above;

- optionally the application of the hot-melt adhesive composition (as described above) on a surface of the textile layer or of the film; and

- Bringing the film into contact with the textile layer, the hot-melt adhesive composition being, if present in the multilayer structure, between the film and the textile layer. The manufacture without adhesive composition can for example be carried out by extrusion coating, cast extrusion (“extrusion-cast”) or blown extrusion (“extrusion-blown”) of the film on the textile, or by hot pressing (thermo-lamination), at a sufficient temperature for the film to impregnate and coat the fibers of the textile.

The manufacture with adhesive composition can for example be carried out by applying the adhesive composition in the molten state or in a solvent on one of the two surfaces intended to be bonded (for example at a temperature of 180 to 230° C.), then application and pressing of the other surface on this one.

Manufacturing with the adhesive composition can alternatively be carried out by manufacturing a film of the adhesive composition which is then applied to the surface of the film or of the textile layer. This is followed by applying and pressing the other surface onto the film of the adhesive composition.

Still alternatively, the manufacture with adhesive composition can be carried out by depositing a powder of the adhesive composition on the surface of the film or of the textile layer (preferably the surface of the textile layer) and the heating of this structure to melt the adhesive composition. This is followed by applying and pressing the other surface onto the adhesive composition. Alternatively, the adhesive composition can be applied by coating with a solvent or in the melt.

According to some embodiments, the hot melt adhesive composition is applied to the surface of the textile layer.

According to other embodiments, the hot melt adhesive composition is applied to the surface of the film.

According to some embodiments, the hot melt adhesive composition is applied over the entire surface of the textile layer or of the film. Alternatively, the hot melt adhesive composition is applied to part of this surface, for example in a pattern such as a dot pattern, a linear pattern, a checkered pattern, a hexagonal pattern or the like.

The multilayer structure according to the invention can be used in particular in the medical field, the sports field, hygiene, luggage, clothing, clothing, household or household equipment, furnishings, carpets , automobile, industry, in particular industrial filtration, agriculture and/or construction.

Recycling of the multilayer structure

The multilayer structure according to the invention can be recycled in its entirety, that is to say without separating the film from the textile layer. This is possible due to the nature of the multilayer structure. In other words, the components of this structure are compatible with each other, which facilitates and improves the recycling process and allows the recycling of the entire multilayer structure.

The method for recycling the multilayer structure is preferably mechanical recycling. It therefore includes the following steps:

- grinding the multilayer structure to obtain particles;

- the melting of the particles to obtain a molten mixture;

- the formation of granules from the molten mixture.

Before these steps, the recycling process may include a step of separating (detaching) the multilayer structure from another structure (for example a metal or polymeric structure) attached to the multilayer structure.

The grinding step is carried out in order to reduce the size of the multilayer structure according to the invention. Thus, after grinding particles of the multilayer structure are obtained. These particles may for example have a Dv50 size of 0.1 to 10 mm.

Preferably, the grinding step is carried out without separating the film from the textile layer. In other words, the grinding step is performed on the entire multilayer structure. The grinding step can be carried out in a counter-rotating pin mill, that is to say the mill comprises a first series of brushes rotating in one direction and a second series of brushes rotating in the opposite direction. Alternatively, the grinding step can be carried out in a hammer mill (hammer mill) or in a whirl mill (whirl mill).

The particles obtained after the grinding step are then melted in order to obtain a molten mixture of the multilayer structure. According to certain embodiments, particles are fused in the presence of one or more additives which may include, inert colorants such as titanium dioxide, fillers, surfactants, crosslinking agents, nucleating agents, compounds reagents, inorganic or organic flame retardants, ultraviolet (UV) or infrared (IR) light absorbers, UV or IR fluorescent agents, waxes, heat stabilizers (phenolic or phosphorus-based for example), anti-blocking agents, anti-foaming agents. Typical fillers include talc, calcium carbonate, clay, silica, mica, wollastonite, feldspar, aluminum silicate, alumina, hydrated alumina, glass microspheres, microspheres ceramic, thermoplastic microspheres, barite and wood flour.

The particles can be melted at a temperature of 150 to 300°C, and preferably 180 to 280°C.

Optionally, this process can comprise a stage of filtration of the molten mixture in order to remove the impurities having for example a particle size of 5 μm to 1 mm.

Finally, the molten mixture (filtered or not) is then used to form recycled granules of the multilayer structure. More particularly, the granules can be formed by extrusion.

According to certain embodiments, the recycled granules can be used for the manufacture of a multilayer structure according to the invention and more particularly for the manufacture of film according to the invention. In this case, the recycled granules can be used as such or by adding a quantity of PEBA copolymer according to the invention. According to other embodiments, the recycled granules can be used in other applications such as the manufacture of buttons, the manufacture of zippers, as well as the manufacture of articles injected in any other field such as the automobile, the sports, household goods, packaging, clothing and electronics. The recycled granules can in particular be introduced into an extruder or an injection press to manufacture an extruded or injected article.

Example

The examples below illustrate the present invention without limiting its scope.

Film A composed of PA11/PEG.6 (40/60 by weight) where Mn (PA11): 1000 g/mol and Mn (PEG): 1500 g/mol, Tf = 150°C

Film B composed of PA 6/6.12/11/PEG.12 (24.5/20.9/24.5/30.1/by weight respectively) where Mn (PA): 2000 g/mol, and Mn (PEG): 600 g/mol , Tf= 100°C

A/B bilayer films are also produced while maintaining a total thickness of 25 μm.

The water vapor permeability is measured according to the ASTM E96B standard - 38°C/50%RH and given by the MVTR:

MVTR (Film A) = 3000 g/m ² /24h

MVTR (Movie B) = 1600 g/m ² /24h The films are then heat-sealed onto a 107 g/m ² nylon textile at 130° C. under a pressure of 1 bar for 30 s. Membership is evaluated manually:

It has been observed that film A has good permeability to water vapor but poor adhesion capacity on a nylon textile, whereas the use of film B alone or in combination with film A makes it possible to improve the adhesion capacity while maintaining good water vapor permeability.

Claims

34 Claims

1. Multi-layered structure, including:

- a film comprising at least one copolymer with polyamide blocks and with polyether blocks, the polyether blocks comprising blocks of polyethylene glycol, the blocks of polyethylene glycol representing at least 40% by mass relative to the mass of the film; wherein the film adheres to the textile layer via a copolyamide.

2. Multilayer structure according to claim 1, in which the copolymer with polyamide blocks and with polyether blocks of the film comprises copolyamide blocks.

3. Multilayer structure according to claim 2, in which the film adheres directly to the textile layer.

4. Multilayer structure according to claim 1 or 2, in which the film is fixed to the textile layer by a hot-melt adhesive composition comprising the copolyamide, the copolyamide preferably comprising units derived from polyethylene glycol monomers representing at least 20% by mass relative to the mass of the copolyamide.

5. Multilayer structure according to claim 4, in which the copolyamide of the hot-melt adhesive composition is chosen from PA 6/6.6/12, PA 6/6.6/11, PA 6/6.10/11, PA 6/6.10 /12, the AP 6/6.12/11, the AP 6/6.12/12, the

PA 6/6.12/11/PEG.12, PA 6/11/PEG.6, PA 6/6.6/11/12 and PA 6/Pip.12/12.

6. Multilayer structure according to one of Claims 4 or 5, in which the hot-melt adhesive composition has a 35 melting temperature which is lower than the melting temperature of the textile layer. Multilayer structure according to one of Claims 4 to 6, in which the hot-melt adhesive composition has a melting point less than or equal to 150°C, and preferably less than or equal to 130°C; and/or an MVR volumetric fluidity index of 2 to 200 cm ³ /10 min, and preferably 5 to 70 cm ³ /10 min. Multilayer structure according to one of Claims 1 to 7, in which the polymer of the textile layer is polyamide and preferably in which the textile layer consists of at least one polyamide. Multilayer structure according to one of Claims 1 to 8, in which the polyamide blocks of the copolymer with polyamide blocks and polyether blocks in the film are chosen from polyamide 11 blocks, polyamide 12 blocks, polyamide 6 blocks, blocks of polyamide 6.10, blocks of polyamide 6.12, blocks of polyamide 10.10, blocks of polyamide 10.12, blocks of polyamide 10.14 and their combinations and again preferably blocks of polyamide 11, blocks of polyamide 12, their combinations and their copolymers. Multilayer structure according to one of Claims 1 to 9, in which the film has a thickness of 1 to 50 µm, and preferably of 10 to 20 µm. Multilayer structure according to one of Claims 1 to 10, in which the film consists of the copolymer with polyamide blocks and with polyether blocks and optionally in one or more additives chosen from inert dyes, fillers, surfactants, crosslinking agents , nucleating agents, reactive compounds, inorganic or organic flame retardants, ultraviolet or infrared light absorbers, waxes, heat stabilizers, anti-blocking agents, anti-foaming agents and ultraviolet fluorescent agents or infrared. Multilayer structure according to one of Claims 1 to 11, in which the film is obtained by recycling a multilayer structure, preferably by recycling a multilayer structure according to one of Claims 1 to 11. Process for manufacturing the multilayer structure according to one of Claims 1 to 12, comprising:

- supply of the textile layer;

- the supply of the film;

- optionally the application of the hot-melt adhesive composition on a surface of the textile layer or of the film; and bringing the film into contact with the textile layer, the hot-melt adhesive composition being, if present in the multilayer structure, between the film and the textile layer. Process for recycling the multilayer structure according to one of Claims 1 to 13 comprising:

- grinding the multilayer structure to obtain particles;

- the melting of the particles to obtain a molten mixture; and

- the formation of granules from the molten mixture. Article comprising the multilayer structure according to one of claims 1 to 12, selected from a dressing, a gauze, a canvas, a carpet, a rug, an upholstery covering, a surface covering, an interior covering, a sofa, curtain, bedding, mattress, pillow, clothing, in particular sports clothing or medical clothing.