Shoe cleats

Abstract

The invention relates mainly to a shoe cleat, particularly for sports shoes, made of a composition comprising, by weight relative to the total weight of the composition: 50 to 100% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, in which the polyether blocks comprise on average more than 50% of ether motifs having at least 3 carbon atoms per oxygen atom; 0 to 50% of fillers; and 0 to 5% of additives in which the composition has a Shore hardness of less than 100A.

Description

Title of the invention: Shoe cleats technical field

[0001] This patent application relates to shoe cleats, their manufacturing process and their use for the manufacture of shoes, in particular sports shoes, said shoes, their manufacturing process and their recycling process. Previous technique

[0002] It has long been known to equip shoes, particularly sports shoes, with cleats to improve grip on the ground and provide better support. These cleats have been made of various materials, for example metal, leather or plastic.

[0003] Utility model CN ​​212368440 U describes a football boot comprising thermoplastic polyurethane (TPU) studs with a replaceable end piece made of polyether block amide (PEBA). Utility model CN ​​215737221 U describes a stud that retains elasticity at low temperatures, comprising an elastic base made of PEBA with a Shore hardness of less than 55D, and an end piece, intended to be in contact with the ground, made of TPU with a Shore hardness of 90 to 95A. These composite studs are, however, complex to manufacture and also difficult to recycle.

[0004] EP patent application 3 939 465 A1 describes a cleated shoe comprising an outsole in two rigid parts, each capable of being fitted with cleats. One part extends over most of the length of the shoe, while the other is shorter. The latter can be made of TPU, PU, ​​or PEBA. CN patent application 112741394 A describes a football boot sole comprising a PEBA sole body to which cleats made of TPU reinforced with modified glass fibers are attached by overmolding. However, these cleats have low abrasion resistance, which reduces their lifespan and necessitates replacement at short intervals.

[0005] These cleats may have insufficient mechanical properties, particularly in terms of abrasion resistance and slip resistance on smooth, wet surfaces such as locker room floors or lawns in the rain. They may also be uncomfortable to use, especially on uneven ground, deform in wet conditions, or produce unwanted noise. Summary of the invention

[0006] The invention therefore aims to provide cleats that overcome at least some of the aforementioned drawbacks. In particular, it aims to provide cleats with satisfactory mechanical properties, especially in terms of abrasion resistance and slip resistance on smooth or wet surfaces. Furthermore, it aims to provide cleats that are easy to manufacture and allow, in particular, automated assembly with the sole. Finally, it aims to provide cleats designed to facilitate the recycling of the shoe when it is no longer usable.

[0007] Indeed, the present invention is based on the observation that the choice of PEBA appropriate for the cleat makes it possible to optimize its properties.

[0008] Also, according to a first aspect, the invention relates to a shoe cleat, in particular for sports shoes, made of a composition comprising, by weight relative to the total weight of the composition: a. 50 to 100% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, in which the polyether blocks comprise on average more than 50% ether motifs having at least 3 carbon atoms per oxygen atom; b. 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of charges; and c. 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives

[0009] wherein the composition has a Shore hardness of less than 100A.

[0010] Preferably, the composition further comprises (d) 0 to 40%, preferably 5 to 30% and in particular 10 to 20% by weight of polymer different from (a).

[0011] Advantageously, the composition further comprises (e) 0 to 30%, preferably 2 to 25% and in particular 5 to 20% by weight of rubber.

[0012] According to a preferred embodiment, the PEBA comprises 30 to 80%, in particular 35 to 70% and especially 40 to 65% by weight of polyether blocks.

[0013] Preferably, PEBA comprises 20 to 70%, in particular 30 to 65% and especially 35 to 60% by weight of polyamide blocks. Advantageously, PEBA comprises polyamide blocks having 9 or more carbon atoms per amide group, in particular selected from PA 10, PA 11, PA 12, PA 513, PA 514, PA 516, PA 518, PA 536, PA 612, PA 613, PA 614, PA 616, PA 618, PA 636, PA 912, PA 104, PA 109, PA 1010, PA 1012, PA 1013, PA 1014, PA 1016, PA 1018, PA 1036, PA 129, PA 1210, PA 1212, PA 1213, PA 1214, PA 1216, PA 1218, PA 1236, PA 12T, and their copolymers. Preferably, the polyether blocks comprise on average more than 50% by weight of PTMG motifs. Advantageously, PEBA has a ratio between the number-average molar mass of the polyamide blocks and the number-average molar mass of the polyether blocks of 0.1 to 3.0, preferably 0.2 to 2.5 and in particular 0.3 to 2.0.

[0014] Preferably, the composition has a Shore hardness of less than 95A, preferably 90A and in particular 85A.

[0015] According to a second aspect, the invention relates to a method for manufacturing such a crampon, comprising the steps of:

[0016] (i) mix in the molten state, by weight relative to the total weight of the composition:

[0017] a. 50 to 100% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, wherein the polyether blocks comprise on average more than 50% of ether motifs having at least 3 carbon atoms per oxygen atom;

[0018] b. 0 to 50% of charges; and

[0019] c. 0 to 5% additives,

[0020] wherein the composition has a Shore hardness of less than 100A; and

[0021] (ii) shape the resulting composition to form a crampon.

[0022] Advantageously, step (ii) is carried out by injection.

[0023] According to a third aspect, the invention aims at the use of such a cleat for the manufacture of shoes, in particular sports shoes.

[0024] According to a fourth aspect, the invention relates to a shoe, in particular a sports shoe, comprising such a cleat. Preferably, the shoe also comprises a sole made of polyamide or PEBA. Advantageously, it relates to a shoe for soccer, American football, rugby, baseball, lacrosse, track and field, or golf.

[0025] According to a fifth aspect, the invention relates to a method for manufacturing such a shoe, comprising the steps of: I. assembly of one or more cleats as described with a sole, in particular by gluing, heat bonding, overmolding of the sole onto the cleats, overmolding of the cleats onto the sole, heat compression, screwing or clipping; and II. Assembly of the sole fitted with cleats obtained with a shoe upper.

[0026] According to a sixth and final aspect, the invention relates to a method for recycling such a shoe, comprising the steps of: 1. separation of the sole from the shoe, if applicable; 2. crushing the sole with the cleats to obtain a pulverized material; 3. heating the ground material obtained in step (a) until melted to obtain a molten mass; and 4. Extrusion of the molten mass obtained in step (b) to obtain granules. Description of implementation methods Definition of terms

[0027] The term "cleat" refers to a protruding part, generally cylindrical in shape, fixed to the bottom of a shoe sole, particularly a sports shoe, which, by engaging with the ground, improves grip and reduces slippage on the ground.

[0028] The term "thermoplastic elastomer" refers to a polymer comprising rigid and flexible blocks, in the form of a block copolymer, in which the rigid blocks, generally semi-crystalline or having a high glass transition temperature, melt or soften as the temperature increases. Above the melting temperature or the glass transition temperature of the rigid block domains, the material can be processed using conventional thermoplastic polymer processing techniques. Below the melting temperature of the rigid block domains, the thermoplastic elastomer exhibits elastic properties close to those of cross-linked elastomers. PEBAs are explicitly excluded from this definition of thermoplastic elastomers.

[0029] The term “PEBA” is meant to designate a sequenced copolymer comprising rigid blocks and flexible blocks, the rigid blocks being polyamide blocks and the flexible blocks being polyether blocks.

[0030] The term "polyamide" or "PA" refers to a homopolyamide or a copolyamide, such as those obtained from the polycondensation of suitable monomers, in particular lactam, α,co-aminocarboxylic acid and / or dicarboxylic acid and diamine. The nomenclature used to define polyamides is described in ISO 1874-1:1992 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (Tables 1 and 2).

[0031] By "alloy", we mean a homogeneous mixture of polymers (macroscopically, i.e., visible to the naked eye). In one embodiment, the different components of the alloy are linked by one or more covalent bonds.

[0032] In what follows, physical quantities are, unless otherwise stated, measured under normal temperature and pressure conditions, specifically at 23°C and atmospheric pressure. It is further specified that the expressions "between... and..." and "from... to..." used in this description shall be understood as including each of the limits mentioned. Finally, unless otherwise stated, percentages are expressed as weight relative to the total weight of the composition. A. Crampon

[0033] According to a first aspect, the invention relates to a shoe cleat, in particular for sports shoes, made of a composition comprising a specific PEBA and having a particular hardness.

[0034] The crampon can be of any shape, provided that it is compatible with its main function of improving grip on the ground and support.

[0035] The crampon generally comprises two parts: a base for assembly with the sole of the shoe, and a tip for penetration into the ground. Preferably, both parts of the crampon can be made of thermoplastic material, and more preferably of thermoplastic material of the same polymer class, for example, PEBA. It is particularly preferable that both parts be made of the same material and formed as a single piece. This greatly simplifies both manufacturing and subsequent recycling.

[0036] Most often, the crampon will have a rotationally symmetrical shape, for example conical, pyramidal or cylindrical. But it is also possible to consider other shapes, for example lamellae, parallelepipeds, or even circumflex accents.

[0037] Generally, the crampon has a maximum width of between 2 and 30 mm, by reference 5 to 20 mm and in particular 5 and 15 mm and a maximum length of between 2 and 50 mm, preferably 4 to 30 mm and in particular 5 to 20 mm.

[0038] According to the invention, the crampon is made of a composition comprising, by weight relative to the total weight of the composition: a. 50 to 100%, preferably 60 to 95%, and in particular 70 to 90% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, wherein the polyether blocks comprise on average more than 50% of ether motifs having at least 3 carbon atoms per oxygen atom; b. 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of charges; and c. 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives,

[0039] in which the PEBA has a Shore hardness of less than 100A. PEBA

[0040] The composition according to the invention therefore comprises, as a main component, a particular polyether block amide (PEBA).

[0041] PEBAs result from the polycondensation of reactive-end polyamide blocks with reactive-end polyether blocks. In particular, PEBAs can result from the polycondensation of:

[0042] (a) diamine-ended polyamide blocks with polyoxyalkylene blocks dicarboxylic ends; or of

[0043] (b) dicarboxylic end polyamide blocks with polyetherdiols (blocks polyoxyalkylene a,co-dihydroxylated), the products obtained in this case being polyetheresteramides.

[0044] Preferably, the PEBA in the composition comprises 30 to 80%, in particular 35 to 70% and especially 40 to 65% by weight of polyether blocks.

[0045] These polyether blocks essentially comprise or are made up of alkylene oxide motifs.

[0046] The polyether blocks comprise on average more than 50%, in particular more than 60%, especially more than 70%, more specifically more than 80%, particularly more than 90%, and particularly preferably 100% by weight of ether units comprising at least 3, and in particular at least 4, carbon atoms per oxygen atom. Preferably, a PEBA is one in which 80 to 100%, preferably 90 to 100%, and advantageously 95 to 100% by weight of the polyether blocks comprise at least 3, and in particular 4, carbon atoms per oxygen atom. Indeed, a PEBA with such polyether blocks exhibits reduced hydrophilicity and therefore a low affinity for water, reducing water absorption and improving dimensional stability over time.

[0047] These may include PPG (polypropylene glycol) blocks, consisting of propylene oxide motifs, PO3G (polytrimethylene glycol) blocks, consisting of trimethylene glycol ether motifs, and / or PTMG (polytetrahydrofuran) blocks, consisting of tetramethylene glycol motifs, PRMG blocks being preferred.

[0048] PEBAs may comprise polyether blocks comprising several distinct polyether motifs, these copolyethers being block or statistical.

[0049] Preferably, the PEBA in the composition comprises up to 80%, in particular 20 to 70%, in particular 30 to 65%, and in particular 35 to 60% by weight of polyamide blocks. Indeed, when the polyamide block content in the PEBA is higher, the PEBA does not adapt sufficiently to the surface irregularities and therefore does not create the necessary grip with the substrate to achieve a coefficient of friction required for slip resistance, particularly on wet surfaces. Such PEBA also results in discomfort during use, especially on uneven ground.

[0050] Polyamide blocks with dicarboxylic acid ends are obtained, for example, from the condensation of polyamide precursors in the presence of a dicarboxylic acid acting as a chain limiter. Polyamide blocks with diamine ends are obtained, for example, from the condensation of polyamide precursors in the presence of a diamine acting as a chain limiter.

[0051] Three types of polyamide blocks can be used advantageously.

[0052] According to a first type, the polyamide blocks are obtained from the condensation of a dicarboxylic acid preferably having 4 to 36, in particular 4 to 20, and especially 6 with 18 carbon atoms, and a diamine preferably having 2 to 20, in particular 6 to 14 carbon atoms.

[0053] The dicarboxylic acid may be, in particular, an aliphatic, cycloaliphatic or aromatic dicarboxylic acid. Examples of dicarboxylic acids include butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, brassylic acid, thapsic acid, octadecanedicarboxylic acid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid (T), isophthalic acid (I) and dimerized fatty acids.

[0054] Dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are for example the products marketed under the brand "PRIPOL" by the company "CRODA", or under the brand EMPOL by the company BASF, or under the brand Radiacid by the company OLEON, and polyoxyalkylenes α,co-diacids.

[0055] The diamine may be, in particular, an aliphatic, cycloaliphatic or aromatic diamine. By way of examples, tetramethylenediamine, cadaverine, rhexamethylenediamine, 1,10-decamethylenediamine, 1,12-dodecamethylenediamine, trimethylhexamethylenediamine, 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), p-amino-di-cyclohexylmethane (PACM), isophoronediamine (IPDA), 2,6-bis-(aminomethyl)norbomane (BAMN) and piperazine (Pip).

[0056] The polyamide block of the first type is preferably chosen from PA 412, PA 414, PA 418, PA 513, PA 516, PA 610, PA 612, PA 613, PA 614, PA 618, PA 912, PA 1010, PA 1012, PA 1014 and PA 1018.

[0057] According to a second type, the polyamide blocks result from the condensation of one or more α,co-aminocarboxylic acids and / or one or more lactams in the presence of a dicarboxylic acid having from 4 to 18 carbon atoms or a diamine.

[0058] Examples of α,co-amino carboxylic acids include aminocaproic, amino-7-heptanoic, amino-10-decanoic, amino-11-undecanoic and amino-12-dodecanoic acids.

[0059] The lactams are preferably chosen from those which preferably comprise 6 to 12 carbon atoms, in particular caprolactam, oenantholactam and lauryllactam.

[0060] Advantageously, the polyamide blocks of the second type are chosen from the PA 10, PA 11 and PA 12 blocks.

[0061] According to a third type, the polyamide blocks result from the condensation of monomers of the first and second types as described above respectively, for example of at least one α,co-aminocarboxylic acid or lactam with at least one diamine and at least one dicarboxylic acid.

[0062] Examples of third-type polyamide blocks include PA 66 / 6 and PA 66 / 610 / 11 / 12.

[0063] Advantageously, the PEBA thus comprises one or more polyamide blocks selected from PA 10, PA 11, PA 12, PA 54, PA 59, PA 510, PA 512, PA 513, PA 514, PA 516, PA 518, PA 536, PA 64, PA 66, PA 69, PA 610, PA 612, PA 613, PA 614, PA 616, PA 618, PA 636, PA 912, PA 104, PA 109, PA 1010, PA 1012, PA 1013, PA 1014, PA 1016, PA 1018, PA 1036, PA 10T, PA 124, PA 129, PA 1210, PA 1212, PA 1213, PA 1214, PA 1216, PA 1218, PA 1236, PA 12T, and their copolymers.

[0064] Particularly preferred are polyamide blocks comprising 7 or more, in particular 9 or more carbon atoms per amide group. These polyamides can notably be chosen from PA 10, PA 11, PA 12, PA 513, PA 514, PA 516, PA 518, PA 536, PA 612, PA 613, PA 614, PA 616, PA 618, PA 636, PA 912, PA 104, PA 109, PA 1010, PA 1012, PA 1013, PA 1014, PA 1016, PA 1018, PA 1036, PA 129, PA 1210, PA 1212, PA 1213, PA 1214, PA 1216, PA 1218, PA 1236, PA 12T, and their copolymers.

[0065] Particularly preferred are the polyamide blocks of PEBA selected from the PA 11, PA 12, PA 10, PA 1010 and PA 1012 blocks, especially PA 11 and PA 12, and the polyether blocks of PEBA selected from the polyethylene glycol and polytetrahydrofuran blocks. The particularly preferred PEBAs comprise blocks of PA 11 and PTMG or of PA 12 and PTMG.

[0066] PEBAs can be obtained, in particular, by copolycondensation of polyetherdiol with carboxyl-terminated polyamides. The general two-step method for preparing PEBA copolymers having ester bonds between the PA and PE blocks is described, for example, in document FR 2846332. The general method for preparing PEBA copolymers having amide bonds between the PA and PE blocks is described, for example, in document EP 1482011. The polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to prepare polymers with polyamide and polyether blocks having statistically distributed motifs (one-step process).

[0067] In addition to polyamide and polyether blocks, PEBAs may include other additional blocks. For example, PEBA may comprise three different types of blocks ("triblock"). This triblock may, for example, comprise a polyamide block, a polyether block, and a polyester block. Alternatively, it may comprise a polyamide block and two different polyether blocks, for example, a PPG block and a PTMG block. Preferred triblock PEBAs are copolyetheresteramides.

[0068] The number-average molar mass (Mn) of the polyamide blocks in the PEBA is preferably 400 to 20,000 g / mol, in particular 500 to 10,000 g / mol. Preferably, the number-average molar mass of the polyamide blocks in the PEBA is less than 4,000 g / mol, and in particular less than 3,000 g / mol. In embodiments, the number-average molar mass of polyamide blocks in PEBA is 600 to 700 g / mol, or 700 to 800 g / mol, or 800 to 900 g / mol, or 900 to 1000 g / mol, or 1000 to 1100 g / mol, or 1100 to 1200 g / mol, or 1200 to 1300 g / mol, or 1300 to 1400 g / mol, or 1400 to 1500 g / mol, or 1500 to 1600 g / mol, or 1600 to 1700 g / mol, or 1700 to 1800 g / mol, or 1800 to 1900 g / mol, or 1900 to 2000 g / mol.

[0069] The number-average molar mass Mn of the polyether blocks is preferably 100 to 6000 g / mol, in particular 500 to 3000 g / mol. Preferably, the number-average molar mass of the polyether blocks is greater than 900 g / mol. In some embodiments, the number-average molar mass of the polyether blocks is 1000 to 1200 g / mol, or 1200 to 1400 g / mol, or 1400 to 1600 g / mol, or 1600 to 1800 g / mol, or 1800 to 2000 g / mol.

[0070] The number-average molar mass (Mn) of the respective blocks can be adjusted by the chain limiter content. It can be calculated according to the following relationship:

[0071] [Math.l]

[0072] In this formula, nmonomer represents the number of moles of monomer, ni chain imitator represents the number of moles of excess diacid limiter, MWrepeater represents the molar mass of the repeating motif, and MWichainimitator represents the molar mass of the excess diacid.

[0073] The number-average molar mass of the polyamide blocks and the polyether blocks can be measured before copolymerization of the blocks by gel permeation chromatography (GPC), according to ISO 16014-1:2019.

[0074] Preferably, the ratio of the number-average molar mass of the polyamide blocks and the polyether blocks is 0.1 to 3, preferably 0.2 to 2.5 and in particular 0.3 to 2.0. This ratio can be calculated by dividing the number-average molar mass of the polyamide blocks by the number-average molar mass of the polyether blocks.

[0075] In particular, the mass ratio of the polyamide blocks to the polyether blocks of the PEBA can be from 0.1 to 0.5, or from 0.5 to 0.7, or from 0.7 to 1.0, or from 1.0 to 1.5, or from 1.5 to 2.0, or from 2.0 to 2.5, or from 2.5 to 3.0. Indeed, when this ratio is too high, the material is too rigid, resulting in poor slip resistance on smooth and wet surfaces, and also discomfort when walking, particularly on uneven ground. Conversely, when this ratio is too low, the material is too flexible and It then no longer resists abrasion sufficiently, thus often reducing the lifespan of the shoe.

[0076] The PEBA in the composition preferably has an average number molar mass Mn as measured by size exclusion chromatography according to ISO 16014-1:2019 of between 10,000 and 70,000 g / mol, preferably between 20,000 and 70,000 g / mol, advantageously between 30,000 and 70,000 g / mol.

[0077] PEBAs are commercially available, and sold in particular by Arkema under the name PEBAX®, by Evonik under the name Vestamid®, by EMS under the name Grilamid® and by Sanyo under the name Pelestat®. Other polymers

[0078] Advantageously, the composition constituting the crampon of the invention may comprise, in addition to the PEBA(s), one or more other different thermoplastic polymers.

[0079] Thus, according to a preferred embodiment, the composition further comprises (d) 0 to 40%, preferably 5 to 30% and in particular 10 to 20% by weight of one or more thermoplastic polymers different from (a), in particular thermoplastic elastomers.

[0080] The thermoplastic polymer (d) may in particular be selected from polyolefins, in particular polypropylene (PP) and polyethylene (PE) and functionalized polyolefins, polyamides, polyesters such as polyethylene terephthalate (PET), polylactic acid (PLA) and poly(butylene succinate (PBS), polystyrene, acrylonitrile butadiene styrene (ABS), polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA).

[0081] Preferably, the thermoplastic polymer (d) has a Shore hardness of less than 100A, in particular less than 90A and especially less than 80A.

[0082] Preferably, the thermoplastic polymer (d) is a thermoplastic elastomer. The thermoplastic elastomer can be chosen in particular from a thermoplastic polyurethane (TPU), a styrene copolymer, a polyester elastomer, with thermoplastic polyurethane (TPU) and styrene copolymer being preferred.

[0083] In the thermoplastic elastomer, the soft blocks and the rigid blocks can be covalently linked by functions chosen from among the CC bonds, amides, esters, methanes, or ureas.

[0084] This may include a thermoplastic polyurethane (TPU). It generally results from the reaction of at least one polyisocyanate (X) with at least one compound reactive with the isocyanate, preferably having two functional groups reactive with the isocyanate, more preferably a polyol, and optionally with a chain extender, optionally in the presence of a catalyst.

[0085] The rigid blocks of the TPU can be blocks of motifs derived from polyisocyanates and chain extenders while the flexible blocks mainly comprise motifs derived from compounds reactive with isocyanate, preferably polyols.

[0086] The polyisocyanate may be aliphatic, cycloaliphatic, araliphatic and / or aromatic. Preferably, the polyisocyanate is a diisocyanate. Advantageously, the polyisocyanate is selected from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-butylene diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylenexylene diisocyanate (TMXDI), 4,4'-, 2,4'- and / or 2,2'-Dicyclohexylmethane diisocyanate (H12 MDI), 1,4-cyclohexane diisocyanate, l-methyl-2,4- and / or l-methyl-2,6-cyclohexane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI),2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate, phenylene diisocyanate, methylene bis(4-cyclohexylisocyanate) (HMDI), and mixtures thereof. Preferably, the polyisocyanate is selected from the group consisting of diphenylmethane diisocyanates (MDI), toluene diisocyanates (TDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), methylene bis(4-cyclohexylisocyanate) (HMDI), and mixtures thereof. Even more preferably, the polyisocyanate is 4,4'-MDI (4,4'-diphenylmethane diisocyanate), 1,6-HDI (1,6-hexamethylene diisocyanate), or a mixture thereof. Advantageously, it does not comprise cycloaliphatic diisocyanate. Preferably, the polyisocyanate is aliphatic.

[0087] The compound(s) reactive with isocyanate preferably have an average functionality between 1.8 and 3, more preferably between 1.8 and 2.6, and even more preferably between 1.8 and 2.2. The average functionality of the compound(s) reactive with isocyanate corresponds to the number of isocyanate-reactive functions of the molecules, calculated theoretically for one molecule from a quantity of compounds. Preferably, the compound reactive with isocyanate has, according to a statistical average, a number of active Zerewitinoff hydrogens in the above ranges.

[0088] Advantageously, the compound that reacts with the isocyanate has at least one reactive group selected from among the hydroxyl group, the amine group, the thiol group, and the carboxylic acid group. Preferably, the compound that reacts with the isocyanate has at least one hydroxyl reactive group, and more preferably several hydroxyl groups. Thus, in a particularly advantageous way, the compound reactive with the isocyanate comprises or consists of a polyol.

[0089] Preferably, the compound reactive with the isocyanate has a number-average molar mass, as determined by GPC, according to ISO 16014-1:2012, of 500 to 100000 g / mol, in particular of 500 to 8000 g / mol, preferably still of 700 to 6000 g / mol, in particular of 800 to 4000 g / mol.

[0090] Preferably, the polyol is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate diols, polyalkylene diols, and mixtures thereof. More preferably, the polyol is a polyether polyol, a polyester polyol, and / or a polycarbonate diol, such that the flexible blocks of the thermoplastic polyurethane are polyether blocks, polyester blocks, and / or polycarbonate blocks, respectively. Even more preferably, the flexible blocks of the thermoplastic polyurethane are polyether blocks and / or polyester blocks (the polyol being a polyether polyol and / or a polyester polyol).

[0091] Examples of polyester polyols include polycaprolactone polyols and / or copolyesters based on one or more carboxylic acids selected from adipic acid, succinic acid, pentanedioic acid and / or sebacic acid and one or more alcohols selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and / or polytetrahydrofuran. Preferably, the polyol is not a cycloaliphatic diol.

[0092] More particularly, the copolyester may be based on adipic acid and a mixture of 1,2-ethanediol and 1,4-butanediol, or the copolyester may be based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof, and polytetrahydrofuran (tetramethylene glycol), or the copolyester may be a mixture of these copolyesters.

[0093] As a polyether polyol, polyetherdiols (i.e., aliphatic α,co-dihydroxylated polyoxyalkylene blocks) are preferably used. Preferably, the polyether polyol is a polyetherdiol based on ethylene oxide, propylene oxide, and / or butylene oxide, a block copolymer based on ethylene oxide and propylene oxide, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetrahydrofuran, polybutane diol, or a mixture thereof.

[0094] The polyether polyol is preferably a polytetrahydrofuran (flexible blocks of thermoplastic polyurethane are therefore polytetrahydrofuran blocks) and / or a polypropylene glycol (flexible blocks of thermoplastic polyurethane are therefore polypropylene glycol blocks) and / or a polyethylene glycol (flexible blocks of thermoplastic polyurethane are therefore polyethylene glycol blocks), of preferably a polytetrahydrofuran having a number average molar mass of 500 to 15000 g / mol, preferably of 1000 to 3000 g / mol.

[0095] The polyalkylene diols usable in the invention are preferably butadiene-based.

[0096] One or more polyols can be used as a reactive compound with the isocyanate.

[0097] In a particularly preferred manner, the flexible blocks of the TPU are blocks of polytetrahydrofuran, polypropylene glycol and / or polyethylene glycol.

[0098] Preferably, a chain extender (Y) is used for the preparation of the thermoplastic polyurethane, in addition to the isocyanate and the compound reactive with the isocyanate.

[0099] The chain extender may be aliphatic, araliphatic, aromatic and / or cycloaliphatic.

[0100] It advantageously has a number-average molar mass of 50 to 499 g / mol. The number-average molar mass can be determined by GPC, preferably according to ISO 16014-1:2012. The chain extender preferably has two reactive groups with the isocyanate (also called "functional groups").

[0101] A single chain extender or a mixture of at least two chain extenders can be used.

[0102] The chain extender is preferably bifunctional. Examples of extenders The chains are diamines and alkanediols having from 2 to 10 carbon atoms. In particular, the chain extender can be chosen from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanol cyclohexane, neopentyl glycol, hydroquinone bis(beta-hydroxyethyl) ether (HQEE), di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or deca-alkylene glycol, their respective oligomers, polypropylene glycol and mixtures thereof. More preferably, the chain extender is chosen from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and mixtures thereof, and more preferably it is chosen from 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol.Even more preferably, the chain extender is a mixture of 1,4-butanediol and 1,6-hexanediol, more preferably in a molar ratio of 6:1 to 10:1.

[0103] Preferably, the TPU is semi-crystalline. Its melting temperature Tf is preferably between 100°C and 230°C, more preferably between 120°C and 160°C. The melting temperature can be measured according to ISO 11357-3 Plastics - Differential scanning calorimetry (DSC) Part 3.

[0104] Advantageously, the TPU can be recycled TPU and / or partially or completely bio-based TPU.

[0105] Advantageously, the rigid polyurethane block is composed of a diisocyanate selected from 4,4'-MDI, HDI or PDI and / or a diol selected from butanediol, propanediol, pentanediol and hexanediol.

[0106] The mass ratio between the rigid polyurethane blocks and the flexible polyol blocks of the TPU is preferably less than or equal to 1.0, in particular less than 0.9, and in particular less than 0.8. According to one embodiment, this mass ratio is from 0.1 to 1.0, preferably from 0.2 to 0.8 and in particular from 0.3 to 0.5.

[0107] According to one embodiment, PEBA forms an alloy with the thermoplastic elastomer.

[0108] Thus, TPU and PEBA can be linked by one or more covalent bonds, for example by a urethane function. Up to 10% by weight, in particular up to 5% by weight, of PEBA can thus be covalently linked to the thermoplastic polyurethane, preferably by a urethane function. Rubber

[0109] According to one embodiment, the composition further comprises (e) 0 to 30%, preferably 2 to 25% and in particular 5 to 20% by weight of rubber.

[0110] The rubber may in particular be a synthetic rubber selected from the group consisting of bromobutyl rubber, butyl rubber, polyisoprene rubber, polynorbomene rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), nitrile rubber (NBR), carboxylated nitrile rubber, polychloroprene rubber (neoprene rubber), polysulfide rubber, polyacrylic rubber, silicone rubber, chlorosulfonated polyethylene rubber, polybutadiene rubber, styrene-butadiene rubber (SBR), butyl rubbers (isobutylene-isoprene) or one of their mixtures.

[0111] Among these, polyisoprene rubber, ethylene-propylene-diene rubber (EPDM), nitrile rubber (NBR), polybutadiene rubber, styrene-butadiene rubber (SBR), butyl rubber (isobutylene-isoprene), styrene-butadiene rubber, and mixtures thereof are particularly preferred. Butadiene rubber is particularly preferred. Charges

[0112] According to the invention, the composition of the crampon also comprises 0 to 50% by weight, preferably 5 to 40% by weight, in particular 10 to 30% by weight of fillers relative to the total weight of the composition.

[0113] These may include mineral or organic fillers. Mineral fillers include, in particular, metal oxides and carbonates such as silica, calcium carbonate and zinc oxide, aluminum oxides, calcium carbonate and aluminosilicates, as well as carbon black or molybdenum disulfide. Organic fillers include, in particular, PTFE powder and aramid powder. Mineral fillers are preferred.

[0114] These fillers are generally in powder form but can also be in other forms, particularly in the form of fibers. Preferably, the composition is free of glass fibers. Additives

[0115] According to the invention, the composition of the crampon also comprises 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% by weight of additives relative to the total weight of the composition.

[0116] The additive(s) may be chosen in particular from among catalysts, antioxidants, thermal stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, crosslinking agents, anti-abrasion agents, chain extenders, pigments and dyes.

[0117] According to a preferred embodiment, the composition comprises 0.05 to 0.2% by weight of one or more antioxidant and / or UV-stabilizing agents. In particular, a phenolic agent combined with a phosphite compound may be used for this purpose.

[0118] According to a preferred embodiment, the composition comprises less than 10% by weight, preferably less than 5% by weight, in particular less than 1% by weight of carbon black. It is particularly preferred that the composition be free of carbon black. Composition

[0119] Advantageously, the PEBA composition is homogeneous when examined with the naked eye, and forms a non-heterogeneous, for example non-porous, medium. Nevertheless, the crampon may, for reasons of weight reduction or aesthetics, for example, have one or more recesses.

[0120] Generally, the density of the crampon composition, as measured according to ISO 1183-1, is less than 1.1, and in particular it is from 0.7 to 1.1 and especially from 0.8 to 1.0.

[0121] Due to its particular constitution, the crampon of the invention has a set of interesting properties.

[0122] First, it has excellent mechanical properties, in particular excellent abrasion resistance, as measured according to ISO 4649:2010, which is preferably less than 100 mm³, in particular less than 90 mm³, and in particular less than 80 mm3. It also ensures high resistance to slipping on smooth and wet surfaces and thus greatly improves grip on wet grass for example.

[0123] The cleat also advantageously exhibits high responsiveness (elastic rebound), as demonstrated by the measurement of a low damping factor, tangent delta. The tangent delta is measured on a film approximately 250 µm thick obtained by pressing the granules in a mold above their melting temperature under a 2T load. The test is performed by DMA (Dynamic Mechanical Analysis) in tension according to ISO 6721, carrying out a temperature sweep from -100 to 180°C at a rate of 2°C / min and at a frequency of 1 Hz and an amplitude of 20 µm. The value of tan delta then corresponds to the maximum of the curve obtained. The value of the tangent delta over the measurement range remains below 0.3, advantageously below 0.2.

[0124] The crampon also has a Shore hardness, as measured according to ISO 7619-1 after 3s, of 50A to 100A, preferably 60A to 95A and in particular 75A to 95A.

[0125] Finally, it advantageously exhibits an elongation at break as measured according to ISO 527 greater than 400%.

[0126] The cleats of the invention also provide great comfort in use. First, the flexibility of the material, even at low temperatures, makes it more comfortable, particularly on uneven ground, and reduces unwanted squeaking noises. In addition, its low water absorption means it deforms very little or not at all in wet conditions, also contributing to comfort and safety. Preferably, the cleats of the invention have a water absorption rate when immersed at 23°C and at equilibrium, as measured according to ISO 62, of less than 2%, advantageously less than 1.5%. The cleats also do not leave marks on the ground. The composition of the cleats of the invention is also lighter than rubber and aromatic TPU, which makes the shoe lighter.

[0127] Finally, the essentially thermoplastic composition of the crampon facilitates its manufacture as well as its recycling.

[0128] According to a preferred embodiment, the crampon is made of a composition comprising, by weight relative to the total weight of the composition: a. 50 to 100%, preferably 60 to 95%, and in particular 70 to 90% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, wherein the polyether blocks comprise on average more than 50% of ether motifs having at least 3 carbon atoms per oxygen atom; b. 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of charges; c. 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives; d. 5 to 30% and in particular 10 to 20% by weight of one or more elastomers thermoplastics other than (a); and e. 2 to 25% and in particular 5 to 20% by weight of rubber,

[0129] in which PEBA has a Shore hardness of less than 100A. B. Cleat manufacturing process

[0130] According to a second aspect, the invention relates to a method for manufacturing the crampon according to the invention, comprising the steps of:

[0131] (i) mix in the molten state, by weight relative to the total weight of the composition:

[0132] (a) 50 to 100% of at least one polyether block amide (PEBA) comprising blocks polyamide and polyether blocks, in which the polyether blocks comprise on average more than 50% ether motifs having at least 3 carbon atoms per oxygen atom;

[0133] (b) 0 to 50% charges; and

[0134] (c) 0 to 5% additives,

[0135] the composition having a Shore hardness of less than 100A; and

[0136] (ii) shape the resulting composition to form a crampon.

[0137] Step (i) of the process can in particular be carried out by heating under shear raised, for example in an extruder, so as to allow good dispersion of the molten components and the obtaining of a homogeneous mixture.

[0138] The crampon of the invention can be manufactured by any means known to a person skilled in the art. Preferably, it is manufactured by injection molding. Therefore, step (ii) can advantageously be carried out by injection molding. C. Usage

[0139] According to a third aspect, the invention relates to the use of the crampon for the manufacture of a crampon shoe.

[0140] The crampon thus manufactured can then be attached to the shoe. Generally, it is fixed to the sole of the shoe by one of the methods known to those skilled in the art, for example by gluing, heat-bonding, overmolding, heat compression, screwing, or clipping. It may be advantageous to provide a detachable fastening for the crampons, since this allows a worn crampon to be replaced without replacing the sole or even the entire shoe.

[0141] According to a preferred embodiment, the cleat is assembled to the sole by overmolding the sole. In this case, the sole is preferably made of a similar material, for example PEBA or polyamide, preferably PA11 or PA12. This embodiment ensures the shaping of the cleat and its assembly with the sole in a single step; it thus allows a considerable gain in productivity compared to a conventional manual assembly.

[0142] Such a sole and cleat assembly is also easily recyclable, unlike an assembly with cleats comprising or made of non-recyclable materials such as rubber. D. Shoe

[0143] According to a fourth aspect, the invention relates to a shoe, in particular a sports shoe, comprising one or more cleats as described above.

[0144] Preferably, it is a football, American football, rugby, baseball, lacrosse, track and field or golf shoe.

[0145] The shoe generally comprises an upper surrounding the foot and a sole.

[0146] The sole and / or the upper may advantageously comprise or be made of polyamide and / or PEBA. This choice makes recycling easier since polyamide and PEBA are compatible with the material of the cleats.

[0147] Preferably, the polyamide is a polyamide with at least 7, in particular at least 9 carbon atoms per polyamide motif, and in particular it is PA 11 or PA 12.

[0148] The PEBA used for manufacturing the sole and / or upper preferably comprises, relative to the total polyamide blocks, at least 80 to 100%, in particular 90 to 100% and especially 95 to 100% by weight of polyamide blocks with at least 7, in particular at least 9 carbon atoms per polyamide unit, preferably PA11 or PA12 blocks. Furthermore, the PEBA preferably comprises, relative to the total polyether blocks, at least 80 to 100%, in particular 90 to 100% and especially 95 to 100% by weight of polyether blocks with at least 3, in particular at least 4 carbon atoms per ether oxygen, preferably PTMG blocks. A PEBA comprising PA11 and PTMG blocks or comprising PA12 and PTMG blocks is particularly preferred.

[0149] According to one embodiment, the polyamide and / or PEBA may contain 10 to 60% by weight of fillers to increase its rigidity. The fillers may, in particular, be chosen from those indicated above concerning the composition of the cleats.

[0150] Most often, the cleat(s) will be assembled with the sole. According to one embodiment, however, they can be manufactured as a single unit with the sole.

[0151] Generally, a shoe will have several studs. A shoe may thus typically have 4 to 60, in particular 6 to 40, and especially 8 to 25 studs. The studs may be evenly distributed over the outsole, or placed only in certain areas, for example at the front of the foot and the heel. According to one embodiment, the sole may thus have 4 to 17 studs at the front of the foot and 2 to 8 studs at the heel. of the heel. The cleats can also be located entirely at the front of the foot, for example in the case of athletic shoes.

[0152] The sole of the shoe generally has a total length of 9 to 40 cm.

[0153] The shoes of the invention have, in addition to their good performance and excellent comfort, the advantage of having a long lifespan. E. Shoe manufacturing process

[0154] According to a fifth aspect, the invention relates to a method for manufacturing a shoe as described above, comprising the steps of: I. assembly of one or more cleats as described with a sole, in particular an outsole; and IL assembly of the sole fitted with cleats obtained with a shoe upper.

[0155] Step (I) can be carried out in particular by gluing, heat bonding, overmolding of the sole onto the studs, overmolding of the studs onto the sole, heat compression, screwing or clipping, preferably it is carried out by overmolding.

[0156] Step (II) can be carried out by gluing or any of the processes mentioned above or known for this purpose. F. Shoe recycling process

[0157] The shoes thus obtained have, in addition to the advantages mentioned, also that of being easily recyclable.

[0158] Also, according to a sixth aspect, the invention relates to a method for recycling such a shoe, comprising the steps of: a. Separation of the sole from the shoe, if applicable; b. Grinding the sole with the cleats to obtain a mulch; c. Heating the ground material obtained in step (a) until melted to obtain a molten mass; and d. Extrusion of the molten mass obtained in step (b) to obtain granules.

[0159] The invention will be explained in more detail in the examples that follow. Examples

[0160] In order to evaluate the properties of interest for the manufacture of crampons, the following thermoplastic elastomer compositions were prepared and tested.

[0161] PEBA 1: PA11 (Mn=1000 g / mol) and PTMG (1000 g / mol) block copolymer with 50% PTMG.

[0162] PEBA 2: PA6 (Mn=1500 g / mol) and PEG (1500 g / mol) block copolymer with 50% PEG.

[0163] PEBA 3: PA11 (Mn=6000 g / mol) and PTMG (Mn=650 g / mol) block copolymer with 9.8% PTMG.

[0164] PEBA 4: PA12 (Mn=850 g / mol) and PTMG (Mn=2000 g / mol) block copolymer with 70.2% PTMG.

[0165] PEBA 5: PA12 (Mn=600 g / mol) and PTMG (Mn=2000 g / mol) block copolymer with 76.9% PTMG.

[0166] TPU1: Elastollan 1185A thermoplastic aromatic polyether-urethane available from BASF.

[0167] PB: Europrene® NEOCIS BR 60 polybutadiene sold by Eni Versalis.

[0168] Compositions EI3 and EI4 were manufactured by molten-state mixing (compounding) using a co-rotating twin-screw extruder.

[0169] For the purpose of their evaluation, plates of 100mm x 100mm x 100mm and 100mm x 100mm x 2mm and studs of a diameter of 16mm and a thickness of 6mm were prepared by injection molding using unpolished molds.

[0170] After drying the granules in a desiccator at 70°C for a minimum of 4 hours, they were injected under the following conditions (for examples EU and EC2 and EC3): - Barrel temperature: 220-240°C - Nozzle temperature: 240°C - Mold temperature: 30°C - Cycle time 60 seconds.

[0171] [Table 1]: Compositions of thermoplastic elastomers studied (in % by weight) EU EI2 EI3 EI4 EC1 EC2 EC3 PEBA 1 100 - - - - - - PEBA 2 - - - - 100 - PEBA 3 - - - - - - 100 PEBA 4 - 100 - - - - - PEBA 5 - - 60 70 - - - TPU 1 - - 30 25 100 - - PB - - 10 5 - - - Total 100 100 100 100 100 100 100

[0172] The injection was carried out under slightly different conditions for examples EI2 to EI4 and EC1: - Sheath temperature: 180-200°C - Nozzle temperature: 200°C - Mold temperature: 30°C - Cycle time 60 seconds.

[0173] The plates were then evaluated in terms of hardness, water absorption, abrasion resistance and slip resistance as explained below. (a) Shore hardness

[0174] Shore A hardness is measured according to ISO 48-4:2008 using a durometer at 23°C. The results are summarized in Table 2 below. (b) Water absorption

[0175] The measurement is carried out on the 100x100x1 mm³ plate according to ISO 62:2008 (<5%) after immersion in water at 23°C until equilibrium is reached. Absorption is expressed as a percentage of the difference in mass before and after exposure to water relative to the initial mass. The results are summarized in Table 2 below, (c) Abrasion resistance

[0176] The abrasion resistance of the compositions is measured according to DIN ISO 4649:2017 (method B with rotating test specimen holder) on injected pads with a diameter of 16 mm and a thickness of 6 mm. Abrasion resistance is expressed as the volume change before and after the test. A composition is considered satisfactory when the volume change is less than 100 mm³. The results are summarized in Table 2 below. (d) Slip resistance

[0177] The coefficient of friction is measured on 100 mm x 00 mm x 2 mm plates according to the SATRA TM 144 evaluation method on a wet STM 603AC quarry tile standard coating at 23°C, using SATRA STM 603 measuring equipment. The resistance to sliding is expressed as a coefficient of friction. The higher this coefficient, the higher the resistance to sliding. The results are summarized in Table 2 below.

[0178] [Table 2]: Properties of the thermoplastic elastomer compositions studied EU EI2 EI3 EI4 EC1 EC2 EC3 Shore A Hardness 94A 83A 74A 76A 89A 94A >100A Water absorption [%] 1.3 1.2 1.5 1.5 ND >50 1.5 AV after abrasion [mm3] 38 83 70 67 183 ND <30 Dynamic friction coefficient 0.2 0.33 0.21 0.2 NDND 0.1

[0179] The results show that the compositions of the cleats of the invention exhibit better abrasion resistance compared to those made of TPU (comparative example EC1). Furthermore, these compositions exhibit less water absorption. Compared to PEBA with polyethylene glycol polyether blocks (comparative example EC2), high water absorption leads to cleat deformation and reduced comfort. Finally, these compositions offer better slip resistance on wet surfaces compared to PEBA with a low PTMG group content (comparative example EC3). List of documents cited

[0180] CN 215737221 U

[0181] CN 112741394

[0182] CN 212368440 U

[0183] EP 3 939 465 Al

Claims

Demands

1. Shoe cleat, in particular for sports footwear, made of a composition comprising, by weight relative to the total weight of the composition: a. 50 to 100% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, wherein the polyether blocks comprise on average more than 50% of ether motifs having at least 3 carbon atoms per oxygen atom; b. 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of fillers; and c. 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives, wherein the composition has a Shore hardness of less than 100A.

2. Cleat according to claim 1, wherein the composition further comprises (d) 0 to 40%, preferably 5 to 30% and in particular 10 to 20% by weight of polymer different from (a).

3. Crampon according to claim 1 or 2, wherein the composition further comprises (e) 0 to 30%, preferably 2 to 25% and in particular 5 to 20% by weight of rubber.

4. Crampon according to any one of claims 1 to 3, wherein the PEBA comprises 30 to 80%, in particular 35 to 70% and especially 40 to 65% by weight of polyether blocks.

5. Crampon according to any one of claims 1 to 4, wherein PEBA comprises 20 to 70%, in particular 30 to 65% and especially 35 to 60% by weight of polyamide blocks.

6. Crampon according to any one of claims 1 to 5, wherein the PEBA comprises polyamide blocks having 9 or more carbon atoms per amide group, in particular selected from PA 10, PA 11, PA 12, PA 513, PA 514, PA 516, PA 518, PA 536, PA 612, PA 613, PA 614, PA 616, PA 618, PA 636, PA 912, PA 104, PA 109, PA 1010, PA 1012, PA 1013, PA 1014, PA 1016, PA 1018, PA 1036, PA 129, PA 1210, PA 1212, PA 1213, PA 1214, PA 1216, PA 1218, PA 1236, PA 12T, and their copolymers.

7. Cleat according to any one of claims 1 to 6, wherein the polyether blocks comprise on average more than 50% by weight of PTMG motifs.

8. Crampon according to any one of claims 1 to 7, wherein the PEBA has a ratio between the number-average molar mass of the polyamide blocks and the number-average molar mass of the polyether blocks of 0.1 to 3.0, preferably from 0.2 to 2.5 and in particular from 0.3 to 2.

0.

9. Crampon according to any one of claims 1 to 8, wherein the composition has a Shore hardness of less than 95A, preferably 90A and in particular 85A.

10. A method for manufacturing a crampon according to any one of claims 1 to 9, comprising the steps of: (i) mixing in a molten state, by weight relative to the total weight of the composition: a. 50 to 100% of at least one polyether block amide (PEBA) comprising polyamide blocks and polyether blocks, wherein the polyether blocks comprise on average more than 50% of ether motifs having at least 3 carbon atoms per oxygen atom; b. 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of fillers; and c. 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives, wherein the composition has a Shore hardness of less than 100A; and (ii) shaping the resulting composition to form a crampon.

11. A manufacturing method according to claim 10, wherein step (ii) is carried out by injection.

12. Use of a cleat according to any one of claims 1 to 9 for the manufacture of footwear, in particular sports footwear.

13. Footwear, in particular sports footwear, comprising a cleat according to any one of claims 1 to 9.

14. Shoe according to claim 13, further comprising a sole made of polyamide or PEBA.

15. Shoe according to claim 13 or 14, characterized in that it is a football, American football, rugby, baseball, lacrosse, athletics or golf shoe.

16. A method for manufacturing a shoe according to any one of claims 13 to 15, comprising the steps of: (I) assembling one or more cleats according to any one of claims 1 to 9 with a sole, in particular by gluing, heat bonding, overmolding the sole onto the cleats, overmolding the cleats onto the sole, heat compression, screwing or clipping; and (II) assembling the sole with cleats obtained with a shoe upper.

17. A method for recycling a shoe according to any one of claims 1 to 9, comprising the steps of: (1) separating the sole from the shoe, if applicable; (2) grinding the sole with the cleats to obtain a ground material; (3) heating the ground material obtained in step (a) until melting to obtain a molten mass; and (4) extruding the molten mass obtained in step (b) to obtain granules.