WASH-RESISTANT COPOLYMER

Abstract

The invention relates to an amide-polyether copolymer comprising at least one motif A, at least one motif B and at least one motif C, wherein: - motif A is a specific aliphatic amide repeating motif comprising 10 or more carbon atoms, - motif B is an aliphatic amide repeating motif selected from a motif obtained from at least one amino acid, a motif obtained from at least one lactam, and an X2.Y2 motif, motif B comprising from 6 to 36 carbon atoms, advantageously from 6 to 20 carbon atoms; motif A being different from motif B, - motif C is a repeating motif of formula X3.Y3 is obtained from the polycondensation of at least one polyethylene glycol diamine and / or at least one polypropylene glycol diamine, denoted X3, with a molecular weight between 200 and 1000, and a linear aliphatic dicarboxylic acid, denoted Y3, with motif A representing at least 30% by weight relative to the total weight of the copolymer; the melting temperature being between 75 and 130°C; the melt flow index being between 5 and 200 cm³ / 10 min, measured at 160°C under a determined load of 2.16 kg; and the tensile modulus on film being less than 200 MPa. The invention also relates to its use as an adhesive.

Description

Title of the invention: WASH-RESISTANT COPOLYMER

[0001] The present invention relates to a copolymer for the manufacture of a heat-sensitive adhesive, in particular a web, a film, granules, a filament, a grid, a powder or a suspension.

[0002] It also relates to said heat-sensitive adhesives and their use in the textile industry, in particular for the manufacture and assembly of flexible materials.

[0003] In the textile field, and in particular for sportswear, it is thus known to stick or flock inscriptions or shapes onto clothing. Flocking can be defined as the application of a thin film onto a textile surface. The film can be made of polyurethane, polyvinyl or polyester and the textile can be made of nylon, polyester, cotton or lycra. The film is coated with an adhesive, then transferred using heat onto the textile surface. This transfer can be done using a press or an iron at temperatures between 150°C and 200°C.

[0004] There is a constant search for adhesives that can be used at temperatures below 150°C in order to reduce energy costs. The aim is also to be able to flock delicate textiles and to be able to use less temperature-resistant films, for example polyurethane.

[0005] Furthermore, it is expected that the flocked garment can withstand several washing cycles at 40°C, or even 60°C.

[0006] In order not to stiffen the flocked garment, the adhesive used must also be flexible. Ideally, it is characterized by a modulus close to that of the textile to be flocked.

[0007] These adhesives can also be used to assemble shoe soles, particularly sports shoes. In this technical field, great flexibility is required and the adhesive must not stiffen the sole once assembled.

[0008] Thermoplastic polyurethanes (TPU) are used in the textile industry as heat-sensitive adhesives for seamless assembly. They have, in particular, flexibility or suppleness properties. However, they have the disadvantage of not being resistant to washing, particularly in a machine, especially above 60°C. In addition, they are difficult to implement.

[0009] Some copolyamides can be resistant to washing up to 90°C and easy to process. However, they are not sufficiently flexible or are too rigid.

[0010] PEBAs are copolymers with amide units and polyether units but without thermo-adhesive properties.

[0011] Thus, there is a real need for adhesives having the aforementioned properties.

[0012] The inventors have discovered a new copolymer, which meets each of these requirements. Brief description of the invention

[0013] Thus, the subject of the present invention is a copolymer with amide units and polyether units comprising at least one unit A, at least one unit B and at least one unit C, in which: - the unit A is an aliphatic repeating unit chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam, and a unit X1.Y1 obtained from the polycondensation of at least one linear aliphatic diamine denoted XI and at least one linear aliphatic dicarboxylic acid denoted Yl, and their mixture, motif A having 10 or more carbon atoms, - motif B is a repeating aliphatic motif chosen from a motif obtained from an amino acid, a motif obtained from a lactam, and an X2.Y2 motif obtained from polycondensation: - at least one diamine denoted X2, said diamine being chosen from a linear or branched aliphatic diamine, a cycloaliphatic diamine and a mixture thereof and - at least one dicarboxylic acid noted Y2, said diacid being chosen from an aliphatic diacid and a cycloaliphatic diacid, the motif B comprising from 6 to 36 carbon atoms, advantageously from 6 to 20 carbon atoms; pattern A being different from pattern B, - unit C is a repeating unit of formula X3.Y3 obtained from the polycondensation of at least one polyethylene glycol diamine or polypropylene glycol diamine denoted X3 with a molecular mass of between 200 and 1000 g.mol1 and a linear aliphatic dicarboxylic acid denoted Y3, unit A representing at least 30% by weight of the copolymer, the melting temperature being between 75 and 130°C as measured by DSC (differential scanning calorimetry) according to standard 11357-3 (2013), the melt flow index (MFI), being between 5 and 200 cmVIO min, measured at 160°C under a load of 2.16 kg as determined according to standard ISO 1133-1 (2011), and the film tensile modulus being less than 200MPa, as determined according to the ISO 178 (2010) standard. Detailed description of the invention

[0014] Other characteristics, aspects, objects and advantages of the present invention will appear even more clearly on reading the description which follows.

[0015] It is specified that the expressions “from .. .to ...” and “between ... and ...” used in the present description must be understood as including each of the limits mentioned.

[0016] The nomenclature used to define polyamides is described in the ISO 1874-1:1992 standard "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2).

[0017] The covopolymer

[0018] By polyamide (homopolyamide or copolyamide) within the meaning of the invention, we mean the condensation products of lactams, amino acids and / or diacids with diamines.

[0019] The copolymer according to the invention results from the polycondensation of at least one precursor of unit A with at least one precursor of unit B and with at least one precursor of unit C.

[0020] Unit A is an aliphatic repeating unit chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam, and a unit X1.Y1 obtained from the polycondensation of at least one linear aliphatic diamine denoted XI and at least one linear aliphatic dicarboxylic acid denoted Yl, and their mixture, unit A comprising 10 or more carbon atoms.

[0021] When the aliphatic repeating unit A is obtained from a unit derived from an amino acid, it may be chosen from 10-aminodecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, as well as its derivatives, in particular N-heptyl-11-aminoundecanoic acid.

[0022] When the aliphatic repeating unit A is a unit derived from a lactam, it may be chosen from decanolactam, undecanolactam, and lauryllactam.

[0023] When the repeating unit A corresponds to the formula X1.Y1, the precursor of XI can be chosen from linear aliphatic diamines of formula H2N-(CH2)a-NH2 chosen from decanediamine (a=10), undecanediamine (a=11), dodecanediamine (a=12), tridecanediamine (a=13), tetradecanediamine (a=14), hexadecanediamine (a=16), octadecanediamine (a=18) and octadecenediamine (a=18).

[0024] The precursor of Yl can be chosen from linear aliphatic diacids of formula HOOC-(CH2)b-COOH chosen from sebacic acid (b=10), undecanedioic acid (b=11), dodecanedioic acid (b=12), brassylic acid (b=13), tetradecanedioic acid (b=14), hexadecanedioic acid (b=16), octadecanedioic acid (b=18) and octadecenedioic acid (b=18).

[0025] Preferably, the unit A is obtained from a unit chosen from decanolactam, 11-aminoundecanoic acid, lauryllactam, the unit noted 10.10 obtained from decanediamine and sebacic acid and the unit noted 10.12 obtained from decanediamine and dodecanedioic acid.

[0026] Unit B is an aliphatic repeating unit chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam, and an X2.Y2 unit obtained from polycondensation: -at least one diamine denoted X2, said diamine being chosen from a linear or branched aliphatic diamine, a cycloaliphatic diamine and a mixture thereof and -at least one dicarboxylic acid denoted Y2, said diacid being chosen from an aliphatic diacid, a cycloaliphatic diacid and a mixture thereof, the unit B comprising from 6 to 36 carbon atoms, advantageously from 6 to 20 carbon atoms.

[0027] When the repeating unit B is obtained from an amino acid, the latter may be chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, as well as its derivatives, in particular N-heptyl-11-aminoundecanoic acid.

[0028] When the repeating unit B is obtained from a lactam, the latter can be chosen from pyrrolidinone, 2-piperidinone, caprolactam, enantholactam, capry-lolactam, pelargolactam, decanolactam, undecanolactam, and lauryllactam.

[0029] When the repeating unit B corresponds to the formula X2.Y2, the precursor of X2 can be chosen from linear or branched aliphatic diamines and cycloaliphatic diamines.

[0030] When the diamine is aliphatic and linear, it may in particular be of formula H2 N-(CH2)d-NH2, the diamine is chosen from butanediamine (d=4), pentanediamine (d=5), hexanediamine (d=6), heptanediamine (d=7), octanediamine (d=8), no-nanediamine (d=9), decanediamine (d=10), undecanediamine (d=11), dodeca-nediamine (d=12), tridecanediamine (d=13), tetradecanediamine (d=14), hexadecanediamine (d=16), octadecanediamine (d=18) and octadecenediamine (d=18).

[0031] When the diamine is aliphatic and branched, it may have one or more methyl or ethyl substituents on the main chain. For example, it may be chosen from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-l,6-hexanediamine, 1,3-diaminopentane, 2-methyl-l,5-pentanediamine, 2-methyl-l,8-octanediamine.

[0032] When the diamine is cycloaliphatic, it is preferably chosen from piperazine, an aminoalkylpiperazine, bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, bis-(3-methyl-4-aminocyclohexyl)-methane (BMACM or MACM), p-bis(aminocyclohexyl)-methane (PACM) and isopropylidenedi(cyclohexylamine) (PACP). It may also comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), di(methylcyclohexyl) propane. A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

[0033] When the repeating unit B corresponds to the formula X2.Y2, the precursor of Y2 can be chosen from linear or branched aliphatic diacids and cycloaliphatic diacids.

[0034] When the diacid of formula HOOC-(CH2)e-COOH is aliphatic and linear, it is preferentially chosen from succinic acid (e=4), pentanedioic acid (e=5), adipic acid (e=6), heptanedioic acid (e=7), octanedioic acid (e=8), azelaic acid (e=9), sebacic acid (e=10), undecanedioic acid (e=111), dodecanedioic acid (e=12), brassylic acid (e=13), tetradecanedioic acid (e=14), hexadecanedioic acid (e=16), octadecanedioic acid (e=18) and octadecenedioic acid (e=18).

[0035] When the diacid is cycloaliphatic, it can comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl), di(methylcyclohexyl)propane.

[0036] Regarding the calculation of the number of carbon atoms in unit B, this carbon number is the sum of the carbon number of the units constituting the unit. For example, for unit 6, i.e. the unit resulting from the polycondensation of ca-prolactam, the carbon number is 6. For unit 66, for example, i.e. the unit resulting from the polycondensation of hexanediamine and adipic acid, the carbon number is 12.

[0037] Preferably, the unit B is obtained from a unit chosen from caprolactam, the unit noted 6.6 obtained from hexanediamine and adipic acid and the unit noted 10.10 obtained from decanediamine and sebacic acid.

[0038] Patterns A and B are different from each other.

[0039] Unit C is of formula X3.Y3 and is obtained from the polycondensation of at least less one polyethylene glycol diamine or polypropylene glycol diamine noted X3 with a molecular mass between 200 and 1000 and a linear aliphatic dicarboxylic acid noted Y3.

[0040] The precursor of unit X3 is a polyethylene glycol or polypropylene glycol with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic alpha-omega dihydroxylated polyethylene or polypropylene sequences called polyethylene ether diol or polypropylene ether diol.

[0041] The precursor of the X3 unit has a molecular mass of between 200 and 1000 g.mol *, preferably between 300 and 600 g.mol *.

[0042] The list of dicarboxylic acids mentioned above for the Y2 unit of the B unit also applies to the Y3 unit.

[0043] Advantageously, the polyalkylene ether diamine of the copolymer according to the invention is chosen from diamines derived from PPG, PEG or a PEG-PPG mixture. The polyalkylene ether diamines may in particular be chosen from commercial products sold under the brands Elastamine® or Jeffamine® by Huntsman, or Baxxodur® by BASF.

[0044] The copolymer according to the invention can be obtained by reacting polyalkylene ether diamine precursor of the unit X3, the polyamide precursors of the units A and B and a chain-limiting diacid precursor of the unit Y3. A polymer is obtained having essentially polyether blocks, polyamide blocks of variable length, but also units resulting from the random reaction between the different precursors distributed randomly (statistically) along the polymer chain.

[0045] Unit A represents at least 30% by weight of the copolymer according to the invention, preferably between 30 and 70%, and more particularly between 30 and 50% by weight relative to the total weight of the copolymer.

[0046] Preferably, the unit B represents between 10 and 40% and in particular between 15 and 30% by weight relative to the total weight of the copolymer.

[0047] Preferably, the unit C represents at least 30% by weight of the copolymer relative to the total weight of the copolymer according to the invention, preferably between 30 and 70%, and more particularly between 30 and 50% by weight relative to the total weight of the copolymer.

[0048] In a particularly preferred manner, the copolymer according to the invention comprises between 30 and 50% by weight of unit A, between 10% and 40% by weight of unit B, and between 30% and 50% by weight of unit C relative to the total weight of the copolymer, the sum of the contents of units A, B and C representing 100%.

[0049] The copolymer according to the invention can consist of 3 monomers A, B and C, and thus be a terpolymer.

[0050] The copolymer can also be a tetrapolymer and contain 4 different units, with for example 2 different B patterns, according to the following formula A / B1 / B2 / C or with for example 2 different A patterns according to the following formula A1 / A2 / B1 / C.

[0051] The copolymer can also be a pentapolymer and contain 5 different units, with for example 2 different A units and 2 different B units, according to the following formula A1 / A2 / B1 / B2 / C.

[0052] Preferably, the copolymer according to the invention is chosen from 10.12 / 6 / PPG400.12; 11 / 6 / PPG400.6; 12 / 6 / PPG400.6; 10.10 / 6 / PPG400.10; 11 / 6 / 6.6 / PPG400.6, 11 / 12 / 6 / 6.6 / PPG400.6; .11 / 10.10 / PPG400.10.

[0053] The melting temperature of the copolymer according to the invention is between 75 and 130°C, preferably between 90 and 120°C. The melting temperature is measured by DSC (differential scanning calorimetry) according to standard 11357-3 (2013).

[0054] The melt flow index, called in English Melt Flow Index (MFI) is between 5 and 200 cmVIO min, measured at 160°C under a load of 2.16 kg determined according to the ISO 1133-1 (2011) standard, preferably between 10 and 100 cm3 / 10 min, in particular between 15 and 50 cmVIO min, at 160°C under a load of 2.16 kg as determined according to the ISO 1133-2 (2011) standard.

[0055] The film tensile modulus of the copolymer according to the invention is less than 200 MPa, as determined according to ISO 178(2010). Preferably, the modulus is between 50 and 180 MPa, and more particularly between 90 and 160 MPa. The process of preparing the copolymer

[0056] The copolymer with amide units and polyether units can be prepared by the following process: -in a first step, the precursors of the amide units are prepared by polycondensation: -diamine(s); -dicarboxylic acid(s); and - where appropriate, one or more comonomers chosen from lactams and alpha-omega aminocarboxylic acids; in the presence of a chain limiter Y3 chosen from dicarboxylic acids; then - in a second step, the precursors of the amide units obtained are reacted with the polyalkylene ether diamine(s), in the presence of a catalyst.

[0057] The general method for preparing the copolymers of the invention in two stages is known and is described, for example, in French patent FR 2 846 332 and in European patent EP 1 482 011.

[0058] The reaction for the formation of the precursors of the amide units usually takes place between 180 and 300°C, preferably between 200 and 290°C, the pressure in the reactor is established between 5 and 30 bars, and is maintained for approximately 2 to 3 hours. The pressure is then slowly reduced, and the excess water is distilled off.

[0059] Once the polyamide with carboxylic acid ends has been prepared, the polyetherdiamine and a catalyst are then added. The polyether can be added in one or more steps, as can the catalyst. According to an advantageous form, the polyetherdiamine is first added, the reaction of the NH2 ends of the polyether and the COOH ends of the polyamide begins with the formation of amide bonds and the elimination of water. As much water as possible is removed from the reaction medium by distillation, and then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks. This second step is carried out with stirring, preferably under a vacuum of at least 15 mm Hg (2000 Pa) at a temperature such that the reactants and the copolymers obtained are in the molten state. For example, this temperature can be between 100 and 400°C and most often 200 and 300°C.The reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the target torque or power value.

[0060] One or more antioxidant agents may be added during the synthesis, for example those commercially available under the name Irganox® 1010, Irganox® 245 or Irganox 1098®.

[0061] We can also consider the process for preparing the copolymer such that all the monomers are added to water at the beginning, i.e. in a single step, to carry out the polycondensation: - diamine(s); - dicarboxylic acid(s); and - where applicable, of the other polyamide comonomer(s); - a chain limiter Y3 chosen from dicarboxylic acids; - polyalkylene ether diamine(s); - in the presence of a catalyst for the reaction between the amide units and the amide units.

[0062] Advantageously, said dicarboxylic acid is used as chain limiter Y3, which is introduced in excess relative to the stoichiometry of the diamine(s).

[0063] Advantageously, a strong acid such as phosphoric acid, hypophosphorous acid or phosphorous acid is used as catalyst.

[0064] The reaction medium is heated to a temperature of 270°C, then expanded. The polycondensation is then carried out under nitrogen scavenging. The reaction is completed under vacuum, at a pressure between 20 and 50 mbar. The polycondensation temperature must be adapted according to the melting temperature of the monomers used. The composition

[0065] The invention also relates to a composition comprising predominantly at at least one copolymer according to the invention and at least one additive.

[0066] Preferably, the additives are present in the composition in a content of between 0.10 and 5%, preferably between 0.25 and 2% by weight relative to the total weight of the composition.

[0067] The additives are chosen in particular from stabilizers and colorants.

[0068] For example, the stabilizer may be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of Irganox® 245 or 1098 or 1010 from the company Ciba-BASF), a phosphite-type antioxidant (for example Irgaphos® 126 from the company Ciba-BASF) and possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or hindered amine light stabilizer (for example Tinuvin® 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin® 312 from the company Ciba), a phosphorus-based stabilizer. It is also possible to use amine-type antioxidants such as Naugard® 445 from Crompton or polyfunctional stabilizers such as Nylostab S-EED® from Clariant.

[0069] This stabilizer may also be a mineral stabilizer, such as a copper-based stabilizer. Examples of such mineral stabilizers include copper halides and acetates or those of other metals such as silver. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.

[0070] Preferably, the colorants are present in a proportion of 0 to 1.5%, in particular 0.5 to 1% by weight relative to the total weight of the composition. Preferably, the stabilizers are present in a proportion of 0 to 2%, in particular 0.5 to 1% by weight relative to the total weight of the composition.

[0071] Advantageously, the composition of the invention is free of plasticizer and in particular BBSA.

[0072] Advantageously, the composition according to the invention comprises: - predominantly at least one copolymer as defined above and between 0 and 2% by weight of at least one additive chosen from a stabilizer, a colorant, and a mixture thereof, relative to the total weight of the composition.

[0073] The composition may also comprise a second polymer, preferably chosen from a polyester, a polyurethane, or a polyamide. Preferably, the composition comprises between 0.25 and 15% by weight at least one polymer chosen from a polyester, a polyurethane, a polyamide, relative to the total weight of the composition.

[0074] The composition according to the invention can be manufactured by methods known to those skilled in the art. In particular, it is possible to add the additives to the copolymer of the invention during or after synthesis. When the addition is carried out after synthesis, it can be done in particular by melt mixing (in an extruder for example).

[0075] The copolymer as defined above or the composition according to the invention as defined above is useful as a heat-sensitive adhesive of the HMA (or hot melt adhesives) type.

[0076] HMAs are thermoplastic adhesives which are made to be melted by heating and which when applied to two parts of a textile allow, after cooling, an edge-to-edge bonding of the two parts, thus avoiding a seam to connect the two parts.

[0077] Advantageously, the heat-sensitive adhesive as defined above is used in the form of a veil, a film, granules, a filament, a grid, a powder or even a suspension. The copolymer or the composition of the invention can thus be easily shaped using methods known for this purpose.

[0078] The thickness of the heat-sensitive adhesive is preferably from 5 to 200 μm (equivalent to 5 to 200 g / m2 which corresponds to another unit of measurement), in particular from 5 to 100 μm. Depending on the form in which the adhesive is used, the preferred thickness may vary. Thus, for example, the thickness of a veil is preferably from 5 to 30 μm, the thickness of a film is preferably from 10 to 100 μm, and the thickness of a grid is preferably from 10 to 50 μm.

[0079] The heat-sensitive adhesive in powder form can be used in different types of powders, characterized by a particle diameter ranging from: • more than 0 to 80 microns; • more than 0 to 120 microns; • from 80 to 180 microns; • from 80 to 200 microns; or • from 200 to 500 microns.

[0080] As regards the suspension, the above powder is suspended, in particular in water, in particular at a concentration of 40% to 50%.

[0081] Advantageously, said adhesive as defined above, in particular in film form, has a thickness of from 10 to 200 μm, preferably a thickness of from 20 to 100 μm, and more particularly between 30 and 60 μm.

[0082] Said heat-sensitive adhesive as defined above, when in film form, may consist of a single layer or in multi-layer form, i.e. comprising at least two layers.

[0083] By way of example, said adhesive in the form of a film with a thickness of 40 μm may be a film consisting of a layer of 40 μm or of 2 layers of 20 μm, i.e. as many layers as the thickness of the film divided by the thickness of one layer.

[0084] According to another aspect, the present invention relates to the use of the copolymer or the composition as defined above, as a heat-sensitive adhesive.

[0085] According to another aspect, the present invention relates to the use of the copolymer or the composition as defined above for the manufacture of a heat-sensitive adhesive, in particular a web, a film, granules, a filament, a grid, a powder or a suspension.

[0086] Advantageously, the heat-sensitive adhesive as defined above is used in the textile industry, in particular for the manufacture of flexible materials, in particular the bonding or flocking of textiles, in particular sports textiles.

[0087] The adhesive according to the invention is preferably used for flocking clothing.

[0088] According to another aspect of the invention, the adhesive according to the invention can be used for assembling shoe soles, in particular sports shoe soles.

[0089] The examples which follow illustrate the present invention, but are in no way limiting. Example

[0090] Sample preparation

[0091] The exemplified copolymers are prepared according to a one-step process.

[0092] Regarding copolymer 1, the monomers and the additive were mixed with water, and with phosphoric acid as a catalyst. The reaction medium was heated to 230°C, then pressure was reduced. Polycondensation then continued under nitrogen sparging. The reaction medium was then placed under vacuum at a pressure between 20 and 50 mbar.

[0093] Polymers 2 to 4 were prepared according to a similar method.

[0094] The formulation of the copolymers is detailed in Table 1 below. [Tables 1] Ex 1 Ex2 Ex3 Ex4 Caprolactam 20 30 - 12 11-Amino unde-cylcarboxylic acid 40 - - - Lactam 12 - 50 - 27.9 Ethylenediamine - - 4.2 - Piperazine - 5.5 15.1 - Adipic acid 9.9 - - - Sebacic acid - - 9.8 10.3 Dodecanedioic acid - 14.5 - - Pripol 1013' - - 67.9 - D4002 30.1 - - - PTMG 1000 - - - 49.8 Stearic acid - - 3 - Irganox 1098 0.1 0.1 - - Irganox 1010 - - - 0.2 Tego antifoam N - - 0.05 -

[0095] 1 Pripol 1013 designates a fatty acid dimer sold by the company CRODA.

[0096] 2 D400 denotes a polypropylene glycol diamine with a molecular mass of 400 g.mol1 sold under the brand name Jeffamine D400 by the Huntsman company. Measurement of sample properties

[0097] The following physicochemical properties of these copolymers and compositions were measured.

[0098] The melting temperature is measured by DSC (differential scanning calorimetry) according to standard 11357-3 (2013).

[0099] The melt flow index (MFI) is measured according to ISO 1133-1 (2011), at 160°C under a load of 2.16 kg.

[0100] The film tensile modulus is measured according to ISO 178(2010).

[0101] The physicochemical properties of the tested copolymers are gathered in the table 2 below.

[0102] [Tables2] Ex 1 inv Ex 2 Ex 3 Ex 4 Tf (°C) 105 106 85 112 MFI (cm3 / 10 min) 26 30 250 15 Modulus (MPa) 140 330 44 80

[0103] Copolymer 2 does not meet the modulus condition. It is too rigid and does not allow a flexible flocked textile to be obtained.

[0104] Copolymer 3 does not meet the MFI condition. It is too fluid. Sample Evaluation

[0105] The copolymers are transformed into 45 μm film by extrusion blow molding.

[0106] The film thus obtained is placed between a nylon textile fabric and a polyurethane film, the assembly is then assembled at 147°C, for 5 seconds under a pressure of 1.5 bars.

[0107] The samples are evaluated using two separate tests:

[0108] In a first test, the samples are subjected to 15 washing cycles in a washing machine at 40°C then drying at 80°C, and the adhesion of the film is visually assessed between each cycle.

[0109] The results are collected in Table 3.

[0110] [Tables3] Ex 1 inv Ex 3 Ex 4 Resistance to washing Resistant Delamination after 5 cycles Delamination after 10 cycles

[0111] In the second test, the samples are subjected to 10 machine wash cycles at 60°C followed by drying at 80°C, and the adhesion of the film is visually assessed between each cycle.

[0112] The results are collected in Table 4.

[0113] [T ables 4] Ex 1 inv Ex 3 Ex 4 Resistance to washing Resistant Delamination after 2 cycles Delamination after 5 cycles

[0114] The results show that the copolymer according to the invention makes it possible to resist washing, even at 60°C.

Claims

Claims

1. Copolymer with amide units and polyether units comprising at least one unit A, at least one unit B and at least one unit C, in which - unit A is a repeating aliphatic amide unit chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam, and a unit X1.Y1 obtained from the polycondensation of at least one linear aliphatic diamine denoted XI and at least one linear aliphatic dicarboxylic acid denoted Yl, unit A comprising 10 carbon atoms or more, - unit B is a repeating aliphatic amide unit chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam, and an X2.Y2 unit obtained from polycondensation: -at least one diamine denoted X2, said diamine being chosen from a linear or branched aliphatic diamine, a cycloaliphatic diamine and a mixture thereof and -at least one dicarboxylic acid noted Y2, said diacid being chosen from an aliphatic diacid, a cycloaliphatic diacid, the motif B comprising from 6 to 36 carbon atoms, advantageously from 6 to 20 carbon atoms; pattern A being different from pattern B, - unit C is a repeating unit of formula X3.Y3 obtained from the polycondensation of at least one polyethylene glycol diamine and / or at least one polypropylene glycol diamine denoted X3 with a molecular weight of between 200 and 1000 g.mol1 and a linear aliphatic dicarboxylic acid denoted Y3, unit A representing at least 30% by weight relative to the total weight of the copolymer, - the melting temperature being between 75 and 130°C as measured by DSC (differential scanning calorimetry) according to standard 11357-3 (2013), - the melt flow index, called in English Melt Flow Index being between 5 and 200 cmVIO min, measured at 160°C under a load of 2.16 kg determined according to standard ISO 1133-1 (2011), and - the film tensile modulus being less than 200 MPa, as determined according to standard ISO 178 (2010).

2. Copolymer according to claim 1, characterized in that it comprises at least 30% by weight relative to the total weight of the copolymer of C units.

3. Copolymer according to claim 1 or 2, characterized in that it comprises between 30% and 50% by weight of unit A, between 10% and 40% by weight of unit B, and between 30% and 50% by weight of unit C relative to the total weight of the copolymer, the sum of the contents of units A, B and C representing 100%.

4. Copolymer according to any one of claims 1 to 3, characterized in that the unit A is obtained from a unit chosen from decanolactam, 11-aminoundecanoic acid, lauryllactam, the unit noted 10.10 obtained from decanediamine and sebacic acid and the unit noted 10.12 obtained from decanediamine and do-decanedioic acid.

5. Copolymer according to any one of claims 1 to 4, characterized in that the unit B is obtained from a unit chosen from ca-prolactam, the unit noted 6.6 obtained from hexanediamine and adipic acid and the unit noted 10.10 obtained from decanediamine and sebacic acid.

6. Copolymer according to any one of claims 1 to 5, characterized in that it is chosen from 10.12 / 6 / PPG400.12; 11 / 6 / PPG400.6; 12 / 6 / PPG400.6; 10.10 / 6 / PPG400.10; 11 / 6 / 6.6 / PPG400.6, 11 / 12 / 6 / 6.6 / PPG400.6; .11 / 10.10 / PPG400.

10.

7. Adhesive composition characterized in that it comprises - predominantly at least one copolymer as defined in any one of the preceding claims and - between 0 and 2% by weight of at least one additive chosen from a stabilizer, a colorant, and a mixture thereof, relative to the total weight of the composition.

8. Composition according to claim 7, characterized in that it comprises between 0.25 and 15% by weight at least one polymer chosen from a polyester, a polyurethane, a polyamide, relative to the total weight of the composition.

9. Composition according to claim 7 or 8, characterized in that it is in the form of a veil, a film, granules, a filament, a grid, a powder or a suspension.

10. Use of the copolymer as defined in any one of claims 1 to 6 or of the composition as defined in any one of claims 7 to 9, as a heat-sensitive adhesive.

11. Use according to claim 10, in the textile industry, in particular for the manufacture and assembly of flexible materials and in the shoe industry, in particular for the assembly of shoe soles.