Footwear cleats

Abstract

The invention mainly relates to a footwear 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 units comprising at least 3 carbon atoms per oxygen atom; (b) 0 to 50% of fillers; and (c) 0 to 5% of additives, wherein the composition has a Shore hardness of less than 100A.

Description

[0001] SHOE CLEATS

[0002] [Technical field]

[0003] 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.

[0004] [Previous technique]

[0005] It has long been known to equip shoes, especially sports shoes, with cleats to improve grip and provide better support. These cleats have been made from various materials, such as metal, leather, or plastic.

[0006] Utility model CN ​​212368440 U describes a football boot comprising thermoplastic polyurethane (TPU) studs with a replaceable apex section made of polyether block amide (PEBA). Utility model CN ​​215737221 U describes a stud that retains elasticity at low temperatures, comprising an elastic PEBA base with a Shore hardness of less than 55D, and a TPU apex section, intended to be in contact with the ground, with a Shore hardness of 90 to 95A. These composite studs are, however, complex to manufacture and difficult to recycle.

[0007] Patent application EP 3 939 465 A1 describes a cleated shoe comprising a two-part rigid outsole that can be fitted with cleats, one part extending along most of the shoe's length and the other shorter, the latter being made of TPU, PU, ​​or PEBA. Patent application CN 112741394 A describes a football boot sole comprising a PEBA sole body to which cleats made of modified glass fiber reinforced TPU are overmolded. These cleats, however, have low abrasion resistance, which reduces their lifespan and necessitates frequent replacement. These cleats may also have insufficient mechanical properties, particularly in terms of abrasion resistance and slip resistance on smooth, wet surfaces such as locker room floors or grass pitches in the rain.They can also be uncomfortable to use, especially on uneven ground, deform in wet conditions or produce unwanted noise.

[0008] [Summary of the invention]

[0009] The invention aims to provide cleats that overcome at least some of the aforementioned drawbacks. Specifically, it aims to provide cleats with satisfactory mechanical properties, particularly 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 for automated assembly with the sole. Finally, it aims to provide cleats designed to facilitate the recycling of footwear when it is no longer usable.

[0010] Indeed, the present invention is based on the observation that the choice of appropriate PEBA for the cleat allows its properties to be optimized.

[0011] Also, according to a first aspect, the invention relates to a shoe cleat, particularly for sports shoes, made of a composition comprising, by weight relative to the total weight of the composition:

[0012] (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% ether motifs having at least 3 carbon atoms per oxygen atom;

[0013] (b) 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of charges; and

[0014] (c) 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives in which the composition has a Shore hardness of less than 100A.

[0015] 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).

[0016] Advantageously, the composition further comprises (e) 0 to 30%, preferably 2 to 25% and in particular 5 to 20% by weight of rubber.

[0017] According to a preferred embodiment, PEBA comprises 30 to 90%, in particular 35 to 85% and especially 40 to 80% by weight of polyether blocks.

[0018] Preferably, PEBA comprises 10 to 70%, in particular 15 to 65% and especially 20 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.

[0019] Preferably, the composition has a Shore hardness of less than 95A, preferably 90A, and particularly 85A. According to a second aspect, the invention relates to a method for manufacturing such a crampon, comprising the steps of:

[0020] (i) mix in the 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% ether motifs having at least 3 carbon atoms per oxygen atom; b. 0 to 50% of fillers; and c. 0 to 5% of additives, 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, particularly a sports shoe, comprising such a stud. 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:

[0026] (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

[0027] (II) assembly of the sole equipped with cleats obtained with a shoe upper. According to a sixth and final aspect, the invention relates to a method for recycling such a shoe, comprising the steps of:

[0028] (1) separation of the sole from the shoe, if applicable;

[0029] (2) grinding the sole with the cleats to obtain a mulch;

[0030] (3) heating the ground material obtained in step (a) until melted to obtain a molten mass; and

[0031] (4) Extrusion of the molten mass obtained in step (b) to obtain granules. [Description of embodiments]

[0032] Definition of terms

[0033] 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.

[0034] 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 or 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 similar to those of cross-linked elastomers. PEBA (polyethylene deposition modeling alloys) are explicitly excluded from this definition of thermoplastic elastomers.

[0035] The term “PEBA” refers to a sequenced copolymer comprising rigid blocks and flexible blocks, the rigid blocks being polyamide blocks and the flexible blocks being polyether blocks.

[0036] The term "polyamide" or "PA" refers to a homopolyamide or copolyamide, such as those obtained by 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).

[0037] The term "alloy" refers to 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.

[0038] In what follows, physical quantities are, unless otherwise stated, measured under standard temperature and pressure conditions, specifically at 23°C and atmospheric pressure. Furthermore, the expressions "between... and..." and "from... to..." used in this description should be understood as including each of the specified limits. Finally, unless otherwise stated, percentages are expressed as a percentage of the total weight of the composition.

[0039] A. Crampon

[0040] According to a first aspect, the invention relates to a shoe cleat, particularly for sports shoes, made of a composition comprising a specific PEBA and exhibiting a particular hardness. The cleat can be of any shape, provided it is compatible with its main function of improving grip and support.

[0041] The crampon generally consists of two parts: a base for attaching to the shoe sole, and a tip for digging into the ground. Preferably, both parts of the crampon can be made of thermoplastic material, and ideally of the same polymer class, such as PEBA. It is particularly desirable for both parts to be made of the same material and formed as a single piece. This greatly simplifies both manufacturing and subsequent recycling. Most often, the crampon will have a rotationally symmetrical shape, such as conical, pyramidal, or cylindrical. However, other shapes are also possible, such as a blade, a parallelepiped, or even a circumflex accent.

[0042] Preferably, the entire crampon is made of the composition according to the invention. Alternatively, when the crampon has several parts, in particular two parts, made of different materials, at least the terminal part (the part intended to engage in the ground) is made of the composition according to the invention.

[0043] Generally, the crampon has a maximum width of between 2 and 30 mm, with a reference of 5 to 20 mm and in particular 5 to 15 mm and a maximum length of between 2 and 50 mm, preferably 4 to 30 mm and in particular 5 to 20 mm.

[0044] According to the invention, the crampon is made of a composition comprising, by weight relative to the total weight of the composition:

[0045] (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;

[0046] (b) 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of charges; and

[0047] (c) 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives, wherein the PEBA has a Shore hardness of less than 100A.

[0048] PEBA

[0049] The composition according to the invention therefore comprises, as a main component, a particular polyether block amide (PEBA).

[0050] PEBAs result from the polycondensation of reactive-end polyamide blocks with reactive-end polyether blocks. Specifically, PEBAs can result from the polycondensation of:

[0051] (a) diamine-ended polyamide blocks with dicarboxylic-ended polyoxyalkylene blocks; or (b) dicarboxylic-ended polyamide blocks with polyetherdiols (ct,cü-dihydroxylated polyoxyalkylene blocks), the products obtained in this case being polyetheresteramides.

[0052] Preferably, the PEBA in the composition comprises 30 to 90%, preferably 35 to 85%, and more preferably 40 to 80% by weight of polyether blocks. Alternatively, the PEBA in the composition may advantageously comprise 30 to 80%, in particular 35 to 70%, and especially 40 to 65% by weight of polyether blocks.

[0053] These polyether blocks essentially comprise or are made up of alkylene oxide motifs.

[0054] Polyether blocks comprise on average more than 50%, particularly more than 60%, especially more than 70%, more specifically more than 80%, particularly more than 90%, and especially preferably 100% by weight of ether units having at least 3, and especially at least 4, carbon atoms per oxygen atom. A PEBA is preferred in which 80 to 100%, preferably 90 to 100%, and advantageously 95 to 100% by weight of polyether blocks have at least 3, and especially 4, carbon atoms per oxygen atom. Indeed, a PEBA with such polyether blocks exhibits reduced hydrophilicity and therefore low affinity for water, reducing water absorption and improving dimensional stability over time.

[0055] These may include PPG (polypropylene glycol) blocks, made up of propylene oxide motifs, PO3G (polytrimethylene glycol) blocks, made up of trimethylene glycol ether motifs, and / or PTMG (polytetrahydrofuran) blocks, made up of tetramethylene glycol motifs, with PRMG blocks being preferred.

[0056] PEBAs can include polyether blocks comprising several distinct polyether motifs, these copolyethers being block or statistical.

[0057] Preferably, the PEBA in the composition comprises up to 80%, preferably 10 to 70%, more preferably 15 to 65%, and even more preferably 20 to 60% by weight of polyamide blocks. Alternatively, the PEBA in the composition may comprise, in particular, 20 to 70%, especially 30 to 65%, and especially 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.

[0058] Polyamide blocks with dicarboxylic acid ends are obtained, for example, by 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, by the condensation of polyamide precursors in the presence of a diamine acting as a chain limiter.

[0059] Three types of polyamide blocks can be advantageously used. According to a first type, the polyamide blocks come from the condensation of a dicarboxylic acid preferably having 4 to 36, in particular 4 to 20, and in particular 6 to 18 carbon atoms, and a diamine preferably having 2 to 20, in particular 6 to 14 carbon atoms.

[0060] Dicarboxylic acids can be, in particular, aliphatic, cycloaliphatic, or aromatic. 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. Dimerized fatty acids preferably have a dimer content of at least 98%; preferably, they are hydrogenated. This includes, for example, products marketed under the brand name "PRIPOL" by the company "CRODA", or under the brand name EMPOL by the company BASF, or under the brand name Radiacid by the company OLEON, and polyoxyalkylenes α, co-diacids.

[0061] The diamine can be, in particular, an aliphatic, cycloaliphatic, or aromatic diamine. Examples include tetramethylenediamine, cadaverine, hexamethylenediamine, 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)norbornane (BAMN), and piperazine (Pip).

[0062] 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.

[0063] According to a second type, polyamide blocks result from the condensation of one or more ct,(jo-aminocarboxylic acids and / or one or more lactams in the presence of a dicarboxylic acid having 4 to 18 carbon atoms or a diamine.

[0064] Examples of α,co-amino carboxylic acids include aminocaproic, amino-7-heptanoic, amino-10-decanoic, amino-11-undecanoic and amino-12-dodecanoic acids.

[0065] Lactams are preferably chosen from those which preferably have 6 to 12 carbon atoms, in particular caprolactam, oenantholactam and lauryllactam.

[0066] Advantageously, the second type polyamide blocks are chosen from PA 10, PA 11 and PA 12 blocks.

[0067] According to a third type, polyamide blocks result from the condensation of monomers of the first and second type 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.

[0068] Examples of third-type polyamide blocks include PA 66 / 6 and PA 66 / 610 / 11 / 12. Advantageously, 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.

[0069] Polyamide blocks with 7 or more, especially 9 or more carbon atoms per amide group, are particularly preferred. 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.

[0070] 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 include blocks of PA 11 and PTMG or of PA 12 and PTMG.

[0071] PEBAs can be obtained, in particular, by copolycondensation of polyetherdiol with carboxyl-terminated polyamides. The general two-step method for preparing PEBA copolymers with ester linkages between PA and PE blocks is described, for example, in document FR 2846332. The general method for preparing PEBA copolymers with amide linkages between PA and PE blocks is described, for example, in document EP 1482011. 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).

[0072] In addition to polyamide and polyether blocks, PEBAs may contain other additional blocks. For example, a PEBA may comprise three different types of blocks ("triblock"). This triblock may, for instance, include a polyamide block, a polyether block, and a polyester block. Alternatively, it may include a polyamide block and two different polyether blocks, for example, a PPG block and a PTMG block. Preferred triblock PEBAs are copolyetheresteramides.

[0073] The number-average molar mass (Mn) of the polyamide blocks in 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 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. 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.

[0074] 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:

[0075] [Math 1]

[0076] In this formula, n monO mother represents the number of moles of monomer, chain limiter represents the number of moles of excess diacid limiter, MW mot if of repetition represents the molar mass of the repeating motif, and MW| im The chain length represents the molar mass of the excess diacid.

[0077] The number-average molar mass of polyamide blocks and polyether blocks can be measured before copolymerization of the blocks by gel permeation chromatography (GPC), according to ISO 16014-1:2019.

[0078] 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.

[0079] Specifically, the mass ratio of polyamide blocks to polyether blocks in PEBA can be 0.1 to 0.5, 0.5 to 0.7, 0.7 to 1.0, 1.0 to 1.5, 1.5 to 2.0, 2.0 to 2.5, or 2.5 to 3.0. When this ratio is too high, the material is too rigid, resulting in poor slip resistance on smooth, wet surfaces and discomfort when walking, especially on uneven ground. Conversely, when this ratio is too low, the material is too flexible and therefore lacks sufficient abrasion resistance, thus often reducing the shoe's lifespan.

[0080] 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 10000 and 70,000 g / mol, preferably between 20,000 and 70,000 g / mol, advantageously between 30,000 and 70,000 g / mol.

[0081] PEBAs are commercially available and sold, notably 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

[0082] Advantageously, the composition constituting the crampon of the invention may comprise, in addition to the PEBA(s), one or more other different thermoplastic polymers.

[0083] 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.

[0084] The thermoplastic polymer (d) may in particular be selected from polyolefins, including polypropylene (PP) and polyethylene (PE) and functionalized polyolefins, polyamides, polyesters such as polyethylene terephthalate (PET), polylactic acid (PLA) and poly(butylene succinate (PBS), polystyrene, acryonitrile butadiene styrene (ABS), polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA).

[0085] Preferably, the thermoplastic polymer (d) has a Shore hardness of less than 100A, in particular less than 90A and especially less than 80A.

[0086] Preferably, the thermoplastic polymer (d) is a thermoplastic elastomer. The thermoplastic elastomer may be chosen in particular from a thermoplastic polyurethane (TPU), a styrene copolymer, a polyester elastomer, with thermoplastic polyurethane (TPU) and styrene copolymer being preferred.

[0087] In thermoplastic elastomer, soft blocks and rigid blocks can be covalently linked by functions chosen from CC bonds, amides, esters, urethanes, or ureas.

[0088] This can include thermoplastic polyurethane (TPU). It generally results from the reaction of at least one polyisocyanate (X) with at least one compound reactive with isocyanate, preferably having two functional groups reactive with isocyanate, more preferably a polyol, and optionally with a chain extender, optionally in the presence of a catalyst. The rigid blocks of 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.

[0089] Polyisocyanate can be aliphatic, cycloaliphatic, araliphatic, and / or aromatic. Preferably, polyisocyanate is a diisocyanate. Advantageously, the polyisocyanate is chosen 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, l,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, 1-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.

[0090] 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 in 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 Zerewitinoff number of active hydrogens within the above ranges.

[0091] 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, particularly advantageously, the compound that reacts with the isocyanate comprises or consists of a polyol.

[0092] 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.

[0093] 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).

[0094] 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.

[0095] More specifically, 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.

[0096] 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.

[0097] The polyether polyol is preferably a polytetrahydrofuran (flexible blocks of thermoplastic polyurethane are therefore blocks of polytetrahydrofuran) and / or a polypropylene glycol (flexible blocks of thermoplastic polyurethane are therefore blocks of polypropylene glycol) and / or a polyethylene glycol (flexible blocks of thermoplastic polyurethane are therefore blocks of polyethylene glycol), preferably a polytetrahydrofuran having a number-average molar mass of 500 to 15000 g / mol, preferably of 1000 to 3000 g / mol.

[0098] The polyalkylene diols usable in the invention are preferably butadiene-based.

[0099] One or more polyols can be used as a reactive compound with the isocyanate.

[0100] In a particularly preferred manner, the flexible blocks of TPU are blocks of polytetrahydrofuran, polypropylene glycol and / or polyethylene glycol.

[0101] Preferably, a chain extender (Y) is used for the preparation of thermoplastic polyurethane, in addition to the isocyanate and the compound reactive with the isocyanate.

[0102] The chain extender can be aliphatic, araliphatic, aromatic and / or cycloaliphatic.

[0103] 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").

[0104] You can use a single chain extender or a mixture of at least two chain extenders.

[0105] The chain extender is preferably bifunctional. Examples of chain extenders are diamines and alkanediols having from 2 to 10 carbon atoms. In particular, the chain extender may be selected 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 selected 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 even more preferably 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.

[0106] Preferably, TPU is semi-crystalline. Its melting temperature (Tf) is preferably between 100°C and 230°C, and even 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.

[0107] Advantageously, TPU can be recycled TPU and / or partially or completely bio-based TPU.

[0108] 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.

[0109] 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.

[0110] According to one embodiment, PEBA forms an alloy with the thermoplastic elastomer.

[0111] Thus, TPU and PEBA can be bonded by one or more covalent bonds, for example, via a urethane group. Up to 10% by weight, and in particular up to 5% by weight, of PEBA can be covalently bonded to the thermoplastic polyurethane, preferably via a urethane group.

[0112] Rubber

[0113] 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.

[0114] Rubber may in particular be a synthetic rubber selected from the group consisting of bromobutyl rubber, butyl rubber, polyisoprene rubber, polynorbornene 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.

[0115] 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 their blends are particularly preferred. Butadiene rubber is especially preferred.

[0116] Charges

[0117] According to the invention, the crampon composition also comprises 0 to 50% by weight, preferably 5 to 40% by weight, and in particular 10 to 30% by weight of fillers relative to the total weight of the composition. These fillers 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.

[0118] These fillers are generally in powder form but can also be in other forms, particularly as fibers. Preferably, the composition is free of glass fibers.

[0119] Additives

[0120] 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.

[0121] The additive(s) may be chosen from among the following: catalysts, antioxidants, thermal stabilizers, UV stabilizers, light stabilizers, lubricants, flame retardants, nucleating agents, crosslinking agents, anti-abrasion agents, chain extenders, pigments and dyes.

[0122] In 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.

[0123] According to a preferred embodiment, the composition comprises less than 10% by weight, preferably less than 5% by weight, and in particular less than 1% by weight, of carbon black. It is particularly preferred that the composition be free of carbon black. Composition

[0124] Advantageously, PEBA's composition is homogeneous when examined with the naked eye, forming a non-heterogeneous, i.e., non-porous medium. Nevertheless, the crampon may, for reasons of weight reduction or aesthetics, for example, have one or more recesses.

[0125] 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.

[0126] Due to its particular constitution, the crampon of the invention presents a set of interesting properties.

[0127] Firstly, it has excellent mechanical properties, including excellent abrasion resistance, as measured according to ISO 4649:2010, which is preferably less than 100 mm 3 , in particular less than 90 mm 3 and in particular less than 80 mm 3 It also provides high resistance to slipping on smooth and wet surfaces, thus greatly improving grip on wet grass, for example.

[0128] The cleat also advantageously exhibits high responsiveness (elastic rebound), as evidenced by the measurement of a low damping factor, tangent delta. 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 using Dynamic Mechanical Analysis (DMA) in tension according to ISO 6721, with a temperature sweep from -100 to 180°C at a rate of 2°C / min, a frequency of 1 Hz, and an amplitude of 20 µm. The tangent delta value then corresponds to the maximum of the resulting curve. The tangent delta value over the measurement range remains below 0.3, and advantageously below 0.2.

[0129] 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.

[0130] Finally, it advantageously exhibits an elongation at break as measured according to ISO 527 greater than 400%.

[0131] 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. Furthermore, 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. Finally, the cleat's predominantly thermoplastic composition facilitates its manufacture and recycling.

[0132] According to a preferred embodiment, the crampon is made of a composition comprising, by weight relative to the total weight of the composition:

[0133] (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;

[0134] (b) 0 to 50%, preferably 5 to 40% and in particular 10 to 30% of charges;

[0135] (c) 0 to 5%, preferably 0.1 to 4% and in particular 1 to 3% of additives;

[0136] (d) 5 to 30% and in particular 10 to 20% by weight of one or more thermoplastic elastomers different from (a); and

[0137] (e) 2 to 25% and in particular 5 to 20% by weight of rubber, in which PEBA has a Shore hardness of less than 100A.

[0138] B. Cleat manufacturing process

[0139] According to a second aspect, the invention relates to a method for manufacturing the crampon according to the invention, comprising the steps of:

[0140] (i) mix in the molten state, by weight relative to the total weight of the composition:

[0141] (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% ether motifs having at least 3 carbon atoms per oxygen atom;

[0142] (b) 0 to 50% charges; and

[0143] (c) 0 to 5% additives, the composition having a Shore hardness of less than 100A; and

[0144] (ii) shape the resulting composition to form a crampon.

[0145] Step (i) of the process can in particular be carried out by heating under high shear, for example in an extruder, so as to allow good dispersion of the molten components and the obtaining of a homogeneous mixture.

[0146] 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. Use

[0147] According to a third aspect, the invention aims at the use of the crampon for the manufacture of a cramponed shoe.

[0148] The manufactured crampon can then be attached to the shoe. Generally, it is fixed to the sole of the shoe using one of the methods known to those skilled in the art, such as gluing, heat bonding, overmolding, heat compression, screwing, or clipping. It can be advantageous to provide a detachable crampon attachment, as this allows a worn crampon to be replaced without replacing the sole or even the entire shoe.

[0149] 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 PAU or PA12. This embodiment ensures that the cleat is shaped and assembled with the sole in a single step; it thus allows for a considerable gain in productivity compared to conventional manual assembly.

[0150] Such a sole and cleat set is also easily recyclable, unlike a set with cleats comprising or made of non-recyclable materials such as rubber.

[0151] D. Shoe

[0152] According to a fourth aspect, the invention relates to a shoe, in particular a sports shoe, comprising one or more cleats as described above.

[0153] Preferably, it should be a football, American football, rugby, baseball, lacrosse, track and field or golf shoe.

[0154] The shoe typically consists of an upper surrounding the foot and a sole.

[0155] The sole and / or upper may advantageously include 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.

[0156] 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.

[0157] 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 PAU 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.

[0158] Depending on the embodiment, the polyamide and / or PEBA may contain 10 to 60% by weight of fillers to increase its rigidity. These fillers may be selected from those listed above regarding the composition of the cleats.

[0159] Most often, the stud(s) will be assembled with the sole. However, depending on the manufacturing method, they can be made as a single unit with the sole.

[0160] Generally, a shoe will have several studs. A shoe can typically have from 4 to 60 studs, notably from 6 to 40, and particularly from 8 to 25 studs. The studs can be evenly distributed across the outsole, or placed only in certain areas, for example, at the front of the foot and the heel. In one embodiment, the sole can thus have from 4 to 17 studs at the front of the foot and from 2 to 8 studs at the heel. The studs can also be located entirely at the front of the foot, for example, in athletic shoes.

[0161] The sole of the shoe typically has a total length of 9 to 40 cm.

[0162] In addition to their good performance and excellent comfort, the shoes of the invention have the advantage of a long lifespan.

[0163] E. Shoe manufacturing process

[0164] According to a fifth aspect, the invention relates to a method for manufacturing a shoe as described above, comprising the steps of:

[0165] (I) assembly of one or more cleats as described with a sole, in particular an outsole; and

[0166] (II) assembly of the sole fitted with cleats obtained with a shoe upper.

[0167] Step (I) can be carried out in particular by gluing, heat gluing, overmolding the sole onto the studs, overmolding the studs onto the sole, heat compression, screwing or clipping, preferably it is carried out by overmolding.

[0168] Step (II) can be carried out by gluing or any of the processes mentioned above or known for this purpose.

[0169] F. Shoe recycling process

[0170] The shoes thus obtained have, in addition to the advantages mentioned, also the advantage of being easily recyclable.

[0171] Finally, according to a sixth aspect, the invention relates to a recycling process for such a shoe, comprising the steps of: (a) Separating the sole from the shoe, if necessary;

[0172] (b) Grinding the sole with the cleats to obtain a mulch;

[0173] (c) Heating the ground material obtained in step (a) until melted to obtain a molten mass; and

[0174] (d) Extrusion of the molten mass obtained in step (b) to obtain granules.

[0175] The invention will be explained in more detail in the examples that follow.

[0176] [EXAMPLES]

[0177] In order to evaluate the properties of interest for the manufacture of crampons, the following thermoplastic elastomer compositions were prepared and tested.

[0178] PEBA 1: PAU (Mn=1000 g / mol) and PTMG (1000 g / mol) block copolymer with 50% PTMG.

[0179] PEBA 2: PA6 (Mn=1500 g / mol) and PEG (1500 g / mol) block copolymer with 50% PEG.

[0180] PEBA 3: PAU (Mn=6000 g / mol) and PTMG (Mn=650 g / mol) block copolymer with 9.8% PTMG.

[0181] PEBA 4: Block copolymer PA12 (Mn=850 g / mol) and PTMG (Mn=2000 g / mol) with 70.2% PTMG.

[0182] PEBA 5: Block copolymer PA12 (Mn=600 g / mol) and PTMG (Mn=2000 g / mol) with 76.9% PTMG.

[0183] TPU1: Elastollan 1185A thermoplastic aromatic polyether-urethane available from BASF.

[0184] PB: Polybutadiene Europrene® NEOCIS BR 60 sold by Eni Versalis.

[0185] Compositions EI3 and EI4 were manufactured by molten-state mixing (compounding) using a co-rotating twin-screw extruder.

[0186] 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.

[0187] 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 Eli and EC2 and EC3):

[0188] Sheath temperature: 220-240°C

[0189] Nozzle temperature: 240°C

[0190] Mold temperature: 30°C

[0191] Cycle time 60 seconds. [Table 1]: Compositions of thermoplastic elastomers studied (in wt%)

[0192] The injection molding was carried out under slightly different conditions for examples El 2 to EI4 and EC1: Barrel temperature: 180-200°C; Nozzle temperature: 200°C; Mold temperature: 30°C

[0193] Cycle time 60 seconds.

[0194] The plates were then evaluated in terms of hardness, water absorption, abrasion resistance and slip resistance as explained below.

[0195] (a) Shore hardness

[0196] 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.

[0197] (b) Water absorption

[0198] The measurement is taken on the 100x100x1 mm plate 3 According to ISO 62:2008 (<5%), absorption was measured after immersion in water at 23°C until equilibrium was 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.

[0199] (c) Abrasion resistance

[0200] The abrasion resistance of the compositions is measured according to DIN ISO 4649:2017 (method B with rotating specimen holder) on injection-molded 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 mm 3 The results are summarized in Table 2 below. (d) Sliding resistance

[0201] The coefficient of friction was measured on 100mm x 00mm x 2mm plates according to the SATRATM144 evaluation method on a wet STM 603AC quarry tile standard coating at 23°C, using SATRA STM 603 measuring equipment. Slip resistance is expressed as a coefficient of friction. The higher this coefficient, the greater the slip resistance. The results are summarized in Table 2 below.

[0202] [Table 2]: Properties of the thermoplastic elastomer compositions studied

[0203] The results demonstrate that the cleat compositions of the invention exhibit better abrasion resistance compared to TPU cleats (comparative example EC1). Furthermore, these compositions exhibit less water absorption compared to PEBA with polyethylene glycol polyether blocks (comparative example EC2). Excessive water absorption leads to cleat deformation and reduces comfort. Finally, these compositions offer better slip resistance on wet surfaces compared to PEBA with a low PTMG group content (comparative example EC3).

[0204] [List of documents cited]

[0205] CN 215737221 U

[0206] CN 112741394

[0207] CN 212368440 U

[0208] EP 3 939 465 Al

Claims

DEMANDS 1. Shoe cleat, particularly 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, wherein 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 in which the composition has a Shore hardness of less than 100A.

2. Crampon 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 90%, in particular 35 to 85% and especially 40 to 80% by weight of polyether blocks.

5. Crampon according to any one of claims 1 to 4, wherein PEBA comprises 10 to 70%, in particular 15 to 65% and especially 20 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. Crampon 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 number of polyether blocks from 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) mix in the 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) shape the resulting composition to form a crampon.

11. 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. Footwear 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: (1) assembly of one or more cleats according to any one of claims 1 to 9 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.

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 mulch; (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.

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