Process for realizing e-TPU midsole / TPU sole in one single molding step

Abstract

The present invention relates to a molded body comprising particles of an expanded thermoplastic elastomer at least partly coated with a thermoplastic polymeric surface coating-and a shaped body, wherein the thermoplastic polymeric surface coating is homogeneously distributed between the particles of an expanded thermoplastic elastomer in the molded body. The present invention further relates to a process for preparing a molded body comprising the steps of providing at least partly coated particles of an expanded thermoplastic elastomer with a polymeric coating,; bringing the coated particles in contact with a shaped body, and fusing the coated particles and the shaped to obtain a molded body. The present invention also relates to the use of a molded body according to the invention in shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors.

Description

[0001] Process for realizing E-TPU Midsole / TPU Sole in one single molding step

[0002] The present invention relates to a molded body comprising particles of an expanded thermoplastic elastomer at least partly coated with a thermoplastic polymeric surface coating-and a shaped body, wherein the thermoplastic polymeric surface coating is homogeneously distributed between the particles of an expanded thermoplastic elastomer in the molded body . The present invention further relates to a process for preparing a molded body comprising the steps of providing at least partly coated particles of an expanded thermoplastic elastomer with a polymeric coating, bringing the coated particles in contact with a shaped body, and fusing the coated particles and the shaped body to obtain a molded body. The present invention also relates to the use of a molded body according to the invention in shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors.

[0003] The preparation of expanded thermoplastic elastomer bead foam is for example described within WO2014 / 198779 A1 using the extrusion technology while the preparation of parts out of the expanded thermoplastic elastomer beads is not explained.

[0004] WO2015 / 052265 also describes the preparation of thermoplastic elastomer foam particles out of thermoplastic elastic polymers using an autoclave to impregnate the compact particles also referred to as granules.

[0005] Foam particles also referred to as bead foams, such as polypropylene or polystyrene bead foams, typically are fused together with superheated water vapor in automatic molding machines to form shaped foam moldings for the packaging industry for example. The manufacturing of moldings with foam particles of thermoplastic polyurethane by means of steam chest molding is described for example in DE102013110242 A1. Here, different variations on filling the mold are explained all with the intention to have a fully filled cavity.

[0006] Since superheated steam fusion has very high energy requirements, in recent years, there has been increasing search for alternatives. One alternative possibility to fuse the foam particles is to supply the required energy through an electromagnetic field. Using electromagnetic radiation or an electromagnetic field to provide the energy required for the molding process is described in general in EP3698949 A1 and W02017 / 125410 A1 for different foam particles. Especially in W02017 / 125410 A1 it is shown that a foam molding with homogeneously fused foam particles can be achieved by using an electromagnetic field to apply the energy.

[0007] However, fusing foam particles through an electromagnetic field requires a certain excitability of the particle foams regarding electromagnetic radiation which results from their specific dielectric properties. A low material specific excitability regarding electromagnetic radiation will lead to high cycle times and, therefore, result in inefficient molding processes.

[0008] W02017 / 125410 A1 relates to a method for producing a particle foam molding wherein foam particles are heated in a mold such that they weld together. This foam particles are made from polyurethane (Pll), polylactate (PLA), polyethylene block amide (PEBA) or from polyethylene terephthalate (PET) which are inherent excitable by electromagnetic radiation. In contrast to processing with steam, which is characterized by the fact that the steam acts only on the surface, the electromagnetic field causes heating of the entire foam particle. Depending on the component thickness, a longer cooling time may therefore be required before demolding, which in turn affects the overall cycle time. Furthermore, due to the fact that the foam has an insulating effect and therefore, tends to retain heat inside the particles, which in turn might cause a damage of the cellular foam structure.

[0009] An alternative approach is the use of a coating to fuse the particles. One approach is the coating of foam particles with a water-based binder which can be reactivated by suitable solvents or heat as described in WO 2022 / 223438. The European patent application with application number EP22202204.8 relates to storage stable coated particles and shaped bodies comprising said coated particles as well as a process for the preparation for the preparation of storage-stable coated particles of a moldable thermoplastic particle foam.

[0010] It was therefore an object of the present invention to provide a method for the energy-efficient preparation of a molding comprising foamed particles with simple apparatuses. Furthermore, it was an object of the present invention to control the molding process in such a way that, on the one hand, the surfaces of the foam particles weld together sufficiently but at the same time the foam structure of the particles does not collapse leading for example to an unfavorable density increase.

[0011] According to the present invention, this problem was solved by a molded body comprising particles of an expanded thermoplastic elastomer at least partly coated with a thermoplastic polymeric surface coating and a shaped body, wherein the thermoplastic polymeric surface coating is homogeneously distributed between the particles of an expanded thermoplastic elastomer in the molded body.

[0012] Homogeneous in the context of the present invention means that the thermoplastic polymeric coating is evenly distributed between the particles of an expanded thermoplastic elastomer in the molded body and also over the cross section of the part of the molded body which is formed by the particles of an expanded thermoplastic elastomer in the molded body. The distribution might for example be determined using optical methods, such as microscopic methods.

[0013] According to the present invention, preferably the bonding strength between the particles and the shaped body is equal or greater than 1 N / mm measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm.

[0014] Surprisingly, it was found that the new method allows the processing of particle foam in the presence of at least one bulky, shaped body, which would be hardly or not processible by steam chest molding as it would reduce the hot air penetrate the particle foam e.g. during crack steaming.

[0015] Surprisingly, it was found that the method according to the present invention is associated with lower energy consumption compared to the methods of the state of the art. The use of foam particles with a thermoplastic polymeric surface coating for the preparation of a molded part allows to use thermo-pressing to fuse the particles. The coating allows by heat press the realization of 3D parts with excellent mechanical values, which are comparable and even superior to 3D parts made by using standard steam chest molding processes. In particular when a thick part is fused with foamed particles, it is often difficult to obtain suitable temperatures for fusing the parts when steam molding is used. The steamless processes can drastically reduce costs. Furthermore, it is possible to integrate moisture-sensitive components (e.g. electronics) in to the molded part.

[0016] Due to the fact, that the foam particles are exposed to lower energy, the foam structure of the particles is preserved. Thus, the risk of obtaining particle foam molded parts with increased density and stiffness due to a damaged foam structure can be significantly reduced.

[0017] Since the particle foam molded body is exposed to lower temperatures, also the stabilization time (in case of passive cooling) or cooling effort in the case of active tool cooling can be reduced. This generally translates in shorter cycle time. Furthermore, the use of the coated particles according to the present invention allows for simple recycling of the molded body using mild conditions.

[0018] The bonding strength between the particles and the shaped body is equal or greater than 1 N / mm measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm in the molded body according to the present invention.

[0019] Preferably, the bonding layer between the foamed particles and the shaped body essentially consist of the thermoplastic polymeric coating. Preferably, no further adhesive is used to fuse the coated particles and the shaped body.

[0020] The molded body according to the present invention comprises particles of an expanded thermoplastic elastomer which are at least partly coated with a thermoplastic polymeric surface coating.

[0021] In general, all kind of particles can be used, such as for example shredded foam parts. Preferably, foamed beads are used in the context of the present invention.

[0022] Foam particles or also foam beads or foam granules in the sense of the present invention refers to a foam in the form of a lot of loose particles of the same chemical nature, the average length of the particles preferably being in the range of 1 to 20 mm. In the case of non-spherical, e.g., oval particles average length means the longest dimension by length, (determined by 3D evaluation of the granules, for example by means of dynamic image analysis with an optical measuring device named “PartAn 3D”, Microtrac). According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the particles of the expanded thermoplastic elastomer are foam beads with an average length of the particles in the range of 1 to 20 mm.

[0023] The single foam granules according to the present invention preferably have an average mass in the range of 0,1 to 50 mg, preferable in the range between 0,5 and 45 mg. The average mass means in this context the arithmetic mean based on a sample size of 10 different particles wherein each particle is weighted three times. The foam particles according to the invention usually have a bulk density of 20 g / l to 350 g / l, preferably 30 g / l to 250 g / l, more preferably 40 g / l to 200 g / l. The bulk density is measured analogously to DIN ISO 60:1999, wherein the determination of the above values in contrast to the standard, a vessel with 10 I volume is used instead of a vessel with 0,1 I volume, since especially for the foam particles with low density and large mass a measurement with only 0,1 I volume is too inaccurate.

[0024] Useful thermoplastic elastomers for foam particles include, for example, thermoplastic polyurethanes (TPU), thermoplastic polyester elastomers (e.g., polyether esters and polyester esters), thermoplastic copolyamides (e.g., polyether copolyamides) or thermoplastic styrene-butadiene block copolymers.

[0025] In a preferred embodiment the foam particles are thermoplastic polyurethane foam particles. Thermoplastic polyurethane foam particles according to the present invention are expanded foam particles and belong to the group of particle foams, which are also referred to as foamed pellets (or bead foams, particle foam, expanded thermoplastic elastomer particles or expanded thermoplastic polyurethane beads). Particle foams and moldings (also referred to as molded article) made therefrom, based on thermoplastic polyurethanes or other thermoplastic elastomers, are known (for example WO 94 / 20568A1 , WO 2007 / 082838 A1 , WO2017 / 030835 A1 , WO 2013 / 153190 A1 , WO 2010 / 010010 A1 , WO 2019 / 202095, WO2018 / 087362) and can be used in many ways.

[0026] It is also possible in accordance with the invention to use mixtures of different foam particles. In a preferred embodiment the foam particles comprise at least two foam particles based on different polymers or different particle size.

[0027] Two or more foam particles in the sense of the present invention refers to a mixture of different lots of loose foam particles, wherein the lots differ in their chemical nature.

[0028] In principle, all types of foam particles can be mixed regardless of their thermal properties such as melting point or glass transition.

[0029] It is for example possible that the foam particles comprise at least two thermoplastic foam particles selected from the group consisting of styrene polymer foam particles, polyamide foam particles, thermoplastic elastomer foam particles, polyolefin foam particles and mixtures thereof. A thermoplastic polymeric surface coating in the sense of the present invention refers to a coating with a polymeric composition, also referred to as coating material, which is bound to the particle surface as a distributed powder, patches, or a continuous shell-like layer, wherein the surface of the foam particles may be completely or partially covered with the thermoplastic polymeric composition.

[0030] In a preferred embodiment of the present invention the thermoplastic polymeric surface coating is selected from the group consisting of acrylic polymers, styrene-acrylic polymers, vinylester polymers, ethylene vinylester polymers, styrene butadiene polymers, polyester polymers, polyamide polymers, polyolefin polymers, polyurethane polymers, polyurethane-polyacrylate hybrid polymers and polyurethane-polystyrene-butadiene hybrid polymers.

[0031] In a preferred embodiment the thermoplastic polymeric surface coating is in the solid state at ambient conditions.

[0032] Different methods are available to achieve the coating of the foam particles, wherein the polymeric composition which forms the coating can be applied to the particle surface in form of a melt, a powder, a polymeric solution or a liquid polymer dispersion.

[0033] In general, common methods for coating, like spray coating, e.g., as described in EP0009727A1 can be used. In a preferred embodiment, the particles are spray coated keeping them in motion via blowing them with e.g., air or mixtures of different gases.

[0034] In case of the powder coating, the foam particles are brought into contact with the powdered polymer composition in the solid state. Powder coating is a well-known method and a person skilled in the art is able to conduct said powder coating.

[0035] In a preferred embodiment the coating of the particle foams is achieved by bringing the foam particles into contact with the polymeric coating material in its molten state. To obtain a sufficient surface coating, preferably, the foam particles are kept in motion while applying the molten coating material by devices known to the person skilled in the art, such as for example kitchen mixer, cement mixer, conveyor belt, vibrating channel, or spray coating drum.

[0036] In a preferred embodiment the coating of the particle foams is achieved by, in a first step, bringing the foam particles into contact with a polymeric solution, wherein the coating material is dissolved in an organic solvent. In a second step, the organic solvent is removed by drying the foam particles at a temperature below the melting point of the coating material to obtain the surface-coated foam particles. The first step can be carried out by methods known to the person skilled in the art, such as mixing the foam particles with the polymeric solution by drum mixers or rotor-stator mixers. For the drying step in principle, all suitable methods are possible, like convective drying, contact drying, infrared drying and, also microwave technology.

[0037] Suitable solvents are organic solvents, like acetone, acetonitrile, butanol, t-butyl alcohol, buta- none (MEK), chlorobenzene, chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethoxy ethane, dimethylformamide, dioxane, ethanol, ethyl acetate, ethylene glycol, glycerin, heptane, hexane, methanol, methyl t-butyl ether, N-methyl-2-pyrrolidinone, methylene chloride, pentane, propanol, pyridine, tetrahydrofuran, toluene, triethyl amine, xylene. A preferred organic solvent is MEK.

[0038] In a preferred embodiment the composition of the thermoplastic polymeric surface coating may also comprise functional additives and fillers in suitable amounts. Preferably the content of thermoplastic polymer of the thermoplastic polymeric surface coating is in the range between 60% and 100% related to the total mass of the polymeric surface coating.

[0039] Suitable fillers for thermoplastic polymeric coatings are in principle known to the person skilled in the art.

[0040] Functional additives are preferably selected from the group consisting of heat conductive additives, electrically conductive additives, antistatic aids, flame retardants, dyes, UV stabilizers, plasticizers, viscosity modifiers, hydrophobic agents, and mixtures thereof.

[0041] Hydrophobic agents or additives, such as waxes, silanes, polysiloxanes, silicone resins, can avoid uncontrolled water uptake of the foam particles, and therefore serve for an improved process control at electromagnetic-induced fusing processes.

[0042] Stabilizers are additives which protect a plastic material or in particular the foam particle from damaging environmental effects. Examples are primary and secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis stabilizers, quenchers, and flame retardants.

[0043] Heat conductive and electrically conductive additives can be additionally used to increase the response of the surface-coated foam particle to electromagnetic irradiation. Preferably heat and electrically conductive additives are selected from the group consisting of metal nitride, metal oxide, metal carbide, metal sulfide, metal silicate, silicon carbide, silicon nitride, boron nitride, carbon fibers, glassy carbon, carbon nanotubes, carbon nanobuds, aero graphite, linear acetylenic carbon, q-carbon, graphene, a salt, a monocrystalline powder, a polycrystalline powder, an amorphous powder, a glass fiber, and mixtures thereof.

[0044] The surface-coating of the foam particles may comprise an amorphous or a semi-crystalline polymer.

[0045] In a preferred embodiment of the present invention the thermoplastic polymeric surface coating has a glass transition temperature lower than the melting temperature of the foam particles.

[0046] Glass transition temperature and melting temperature of the thermoplastic polymeric surface coating means in the sense of the present invention that the thermoplastic polymer comprised in the polymeric surface coating has these values.

[0047] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the polyurethane coating has a glass transition temperature Tg measured according to DIN EN ISO 11357-2 2018 from -10°C to -80°C and a melting temperature Tm1 in the range of 30° to 100° C, and preferentially 40° to 80° C.

[0048] The glass transition temperature of the thermoplastic polymeric coating can be determined by differential scanning calorimetry according to DIN EN ISO 11357-2 (2014), as so-called midpoint temperature. The glass transition temperature of the thermoplastic polymeric surface coating is the glass transition temperature obtained when evaluating the second heating curve (heating rate 20 K / min) after heating the polymeric coating material to 130 °C (holding time 1 min) and cooling it with 20 K / min to -80°C.

[0049] Preferably, the thermoplastic polymeric surface coating has at least a first glass transition temperature Tg1 and a second glass transition temperature Tg2, wherein Tg1 is below 0°C and Tg2 is higher than 25 °C. Preferably, Tg1 is below -10 °C. Preferably, Tg2 is higher than 40 °C, more preferably higher than 50 °C, even more preferably higher than 60 °C. Preferably, the thermoplastic polymeric coating has exactly two Tg.

[0050] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the polyurethane coating comprises a polyurethane having at least a first glass transition temperature Tg1 and a second glass transition temperature Tg2, wherein

[0051] Tg1 is below 0°C and Tg2 is higher than 25 C

[0052] If the coating is formed from a liquid dispersion, a drying step and preconditioning is required before the glass transition can be measured. The drying step is conducted by filling the dispersions into a heatable mold and keeping the dispersions there for 3 days at a temperature of 40°C (within the mold-cavity). Usually, the dispersions form a film. For preconditioning the dried dispersion film are stored at 23°C for 7 days.

[0053] The melting temperature of the foam particles is determined according to DIN EN ISO 11357-3 (2018) (melting point = peak temperature) by heating with 20 K / min after cooling to -80°C. In case of the foam particles the first heating run is evaluated. In the presence of more than one endothermal melting peaks the maximum of the peak having the largest melting endotherm was used to define the melting temperature.

[0054] In a preferred embodiment of the present invention the thermoplastic polymeric surface coating has a melting temperature Tm1 lower than the melting temperature of the foam particles.

[0055] Melting temperature and enthalpy of fusion of the thermoplastic polymeric surface coating are determined according to DIN EN ISO 11357-3 (2018) (melting point = peak temperature) by heating with 20 K / min after cooling to -80°C, while enthalpy of fusion of the second run (Delta H2) is calculated from the area of second melting only.

[0056] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the thermoplastic polymeric surface coating preferably is a thermoplastic polyurethane coating.

[0057] In a preferred embodiment the thermoplastic polymeric surface coating comprises a polyurethane with a K-value in the range from 5 to 100 determined according to DIN EN ISO 1628-1 2021.

[0058] The K-value is a relative viscosity number, which is determined in analogy to DIN EN ISO 1628- 1 2021 at 25°C. It comprises the flow rate of a 1 weight-% strength solution of the polyurethane in DMF, relative to the flow rate of pure DMF, and characterizes the average molecular weight of the polyurethane. In a preferred embodiment the thermoplastic polymeric surface coating has a mass fraction in the range from 0.5% to 40 % based on the total mass of the coated foam particles.

[0059] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the thermoplastic polymeric surface coating has a glass transition temperature lower than the melting temperature of the foam particles, in particular wherein the thermoplastic polymeric surface coating has a glass transition temperature higher than room temperature and lower than the melting temperature of the foam particles.

[0060] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the thermoplastic polymeric surface coating has a melting temperature lower than the melting temperature of the foam particles.

[0061] In a preferred embodiment the foam particles are coated with a polymer dispersion. According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the coating is applied as a dispersion.

[0062] Preferably the polymer dispersion comprises at least one polymer as polymeric binder dispersed in a liquid dispersion medium, such as water, and optionally additives. Preferred additives are selected from the group consisting of ionic surfactants, non-ionic surfactants, rheology modifiers (including thickeners), anti-blocking additives, other dispersions, cross-linkers, plasticizers, stabilizers against hydrolytic degradation, biocides, fillers, additives that are excitable by electromagnetic radiation and antifoam agents.

[0063] More preferably the thermoplastic polymeric surface coating is applied as aqueous polymer dispersion.

[0064] The term “aqueous” means that the liquid in which the polymer is dispersed or solved is a mixture of liquids with a water content of more than 50% by weight based on the total weight of the mixture of liquids or the polymer is dispersed or dissolved in water as such. Suitable mixtures are mixtures or water with alcohol or the like. Mixtures are preferably mixtures of water with water-miscible solvents, for example alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol; glycols, such as ethylene glycol, propylene glycol and butylene glycol; the methyl or ethyl ethers of dihydric alcohols, diethylene glycol, triethylene glycol, polyethylene glycols having number-average molecular weights up to about 3000 g / mol, glycerol and dioxane, and ketones, such as acetone in particular. In one specific embodiment the aqueous dispersion or solution is substantially free from organic solvents. “Substantially free from organic solvents” is to be understood as meaning that the proportion of organic solvents is not more than 5% by weight, particularly preferably not more than 1 % by weight, in particular not more than 0.1 % by weight, based on the total weight of the solvent.

[0065] A method to prepare an aqueous polymer dispersion that can be applied to obtain surface- coated foam particles are described in WO 2022 / 223438.

[0066] Polymers suitable for aqueous polymer dispersions can be all film forming polymer dispersions from the product classes well known in the art, i.e. , acrylic dispersions, styrene-acrylic dispersions, vinylester dispersions, ethylene vinylester dispersions, styrene butadiene dispersions, which are all prepared by free radical emulsion polymerization. Suitable polymers are also the well-known polyurethane dispersions, prepared by polyaddition reaction of isocyanates and polyols and subsequent dispersion in water, as well as the polyurethane-polyacrylate hybrid dispersions and polyurethane-polystyrene-butadiene hybrid dispersions. In each of these product classes, a large variety of monomers can be used in order tailor e.g., the glass transition temperature (Tg), the colloidal stability and other properties. Preferred polymers for water-based aqueous polymeric dispersions are aqueous polystyrene acrylic dispersions, aqueous acrylic dispersions, aqueous butadiene / styrene dispersions or aqueous polyurethane dispersions. More preferably, the water-based aqueous polymeric dispersion is an aqueous acrylic dispersion or an aqueous polyurethane dispersion. Even more preferably, the water-based aqueous polymeric dispersion is an aqueous polyurethane dispersion.

[0067] Especially, preferred dispersions used for the process of the present invention can have high solid content (>35%), but still show low viscosity. This allows an easy application of the dispersions to the particles. The particles are homogenously coated with a transparent coating, which is tack free at room temperature. On the other hand, when the particles are heated under compression, such as in a hot press process, the coating melts and allows bridging of beads upon cooling. Only moderate heat is required.

[0068] Preferably, the aqueous polymer dispersion used in the process of the present invention has a solid content of at least 30 wt.-% based on the total weight of the dispersion, more preferably in the range of from 35 wt.-% to 60 wt.-% based on the total weight of the dispersion.

[0069] Preferably, the polyurethane of the aqueous polymer dispersion and comprised in the at least partly coated particle and shaped body according to the present invention has a viscosity of less than 300 mPas at 23 °C, preferably less than 200 mPas at 23 °C, measured according to DIN EN ISO 3219-2:2021 at 23°C and a shear rate of 250 s-1.

[0070] In general, the aqueous polyurethane dispersion used in the process of the present invention can be prepared by methods known in the art. Exemplary methods are described in WO 2021 / 249749 A 1

[0071] Preferably the aqueous polymer dispersion is selected from the group consisting of acrylic dispersions, styrene-acrylic dispersions, vinylester dispersions, ethylene vinylester dispersions, styrene butadiene dispersions, polyurethane dispersions, polyurethane-polyacrylate hybrid dispersions and polyurethane-polystyrene-butadiene hybrid dispersions.

[0072] In a preferred embodiment the aqueous polymer dispersion is a polyurethane dispersion, and the polyurethane has a K-value in the range from 40 to 100 determined according to DIN EN ISO 1628-1 2021. According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the polyurethane coating comprises a polyurethane having a K-value according to DIN EN ISO 1628-1 2021 in the range from higher than 5 to lower than 100, preferably from 40 to 100, in particular from 50 to 95.

[0073] The molded body further comprises a shaped body. The shape and size of the shaped body may vary as long as it allows for the bonding between the coated particles and the shaped body to be equal or greater than 1 N / mm measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm.

[0074] According to the present invention it is also possible that the molded body comprises two or more shaped bodies which may have different size and shape and may consist of the same or different materials.

[0075] Preferably, the shaped body may be selected from the group consisting of synthetic or natural textiles, chopped textiles, leather, paper, thermoplastic films, thermoplastic tapes, organo- sheets, in mold coating, pieces of fiber composites, rubber sheets, rubber crumbs, pieces of wood, thermosetting films, plastic agglomerates, chopped foamed materials, and mixtures thereof. Additional materials can be virgin or of recycled nature. The shaped body can be fused together with the coated foam particles in one step or in a separate processing step. The shaped body may consist of a foamed material or a compact material. According to the present invention, the shaped body may be prepared separately. Processes for preparing shaped bodies, in particular shaped bodies comprising polymer materials, are in principle known and include shaping processes such as extrusion or molding processes as well as 3D printing.

[0076] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the shaped body comprises a material selected from thermoplastic polymers, thermoset polymers, elastomers, in particular thermoplastic elastomers, leather, rubber, cork, wood, metal, textile fabrics, and ceramic or mixtures thereof or recycled materials thereof.

[0077] The shaped body may for example comprise polymers selected from the group consisting of styrene polymers, polyurethanes, polyamides, thermoplastic elastomers, polyolefines, ethylenevinyl acetates and mixtures thereof.

[0078] According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the shaped body is a compact thermoplastic body, in particular a compact thermoplastic polyurethane. Suitable thermoplastic polyurethanes are in principle known to the person skilled in the art. The thermoplastic polyurethane may for example be selected from polyether based thermoplastic polyurethanes and polyester based polyurethanes.

[0079] Preferably, in case the foamed particles comprise a thermoplastic polyurethane based on a polyether polyol, also the shaped body comprises a thermoplastic polyurethane based on a polyether polyol and in case the foamed particles comprise a thermoplastic polyurethane based on a polyester polyol, also the shaped body comprises a thermoplastic polyurethane based on a polyester polyol. This is particularly advantageous for recycling the molded body.

[0080] According to the present invention, it is also possible that one or more surfaces of the molded body may be structured, in particular one or more surfaces formed by the fused foamed particles. Embossing or structuring of the surface may for example be achieved by using a suitable mold or additives for impregnating the mold in the preparation process of the molded body.

[0081] The molded body according to the present invention can have a wide variety of sizes and shapes. It is for example possible to combine different elements to adjust the properties or the appearance of the molded body. The molded body may for example be a shoe sole or part of a shoe sole. According to a preferred embodiment, the present invention is also directed to the molded body as disclosed above, wherein the molded body is a shoe sole or part of a shoe sole.

[0082] According to a preferred embodiment, the shaped body is the outer part of a shoe sole and the midsole is formed of the coated particles. It is also possible to include further parts such as for example films which cover part or all of the shoe sole or are embedded or partly embedded in the molded body such as polymer films to adjust the properties of the molded body. It is for example possible to add colored elements or elements to adjust the stiffness of the molded body for example to adjust the stiffness in one dimension only.

[0083] The molded body may for example be a sports and or a casual shoe sole or part of a sports and or casual shoe sole or a safety shoe sole or part of a safety shoe sole.

[0084] Soles of safety shoes or sports shoes typically comprise several layers and inmolds. Typically, the layered sole comprises an insert made of elastic material capable of making it more comfortable to rest the foot on the floor during walking. This elastic part typically forms a midsole and is joined with the outer sole. The elastic insert extends substantially at the entirety of the user's foot sole. The sole may comprise an upper part which may be equipped, at the shoe toe, with a safety toe cap. The layered sole which is connected with the upper typically comprises a lower layer adapted to come into contact with the ground, and an intermediate layer associated with the upper and with the lower layer, respectively.

[0085] Further functional parts may be inserted in the layers, in particular in the intermediate layer, such as for example an elastic insert. Preferably, an elastic insert may be embedded that extends exclusively at the rear zone of the shoe on a surface less than 55% of the overall surface of the layered sole.

[0086] Advantageously, the elastic insert extends on a surface comprised between 30% and 50% of the overall surface of the layered sole. In particular, the elastic insert typically has a length equal at most to 55% of the total length of the layered sole and a width slightly smaller than, if not substantially equal to, the total width of the layered sole.

[0087] The lower layer is preferably made of polyurethane or nitrile material, or a combination of these two elements. The molded body may also be a part of functional wear or protective gear such as body protection or helmets. The molded body may also be a sports article or part thereof, for example a ball or a racket, for example a table tennis racket.

[0088] According to the present invention, the parts of the molded body, i.e. the particles of an expanded thermoplastic elastomer at least partly coated with a thermoplastic polymeric surface coating and the shaped body, preferably are fused using thermo-pressing. According to a further embodiment, the present invention is also directed to the molded body as disclosed above, wherein the shaped body is prepared using thermo-pressing.

[0089] It is also possible in the context of the present invention that the molded body comprises further parts which are joined using thermos-pressing or also using radiation or steam molding.

[0090] According to a further aspect, the present invention is also directed to a process for preparing a molded body comprising the steps of a) providing at least partly coated particles of an expanded thermoplastic elastomer with a thermoplastic polymeric coating; b) bringing the particles in contact with a shaped body, c) fusing the particles obtained from step a) and the shaped body to obtain a molded body.

[0091] The process allows realization of 3D parts of very complex geometries. The 3D parts can still have empty spaces among the particles (allowing water penetration) or can have no empty spaces among the beads, which is high desirable for the fabrication of shoe soles.

[0092] The process of the present invention comprises steps a), b), and c) but may also comprise further steps, in particular heating or cooling steps.

[0093] According to step a), at least partly coated particles of an expanded thermoplastic elastomer with a polymeric coating are provided. With respect to the particles, reference is made to the disclosure above.

[0094] In the context of the present invention, step a) may also comprise further steps, in particular steps a1) and a2). a1) wetting the surface of the foam particles, in particular wetting the surface of the foam particles with an aqueous polymer dispersion, a2) obtaining surface-coated foam particles by drying the wetted foam particles.

[0095] According to step b), the particles are brought in contact with a shaped body. Typically, the particles are brought in contact with the shaped body in a suitable apparatus, such as a mold. A preferred method for the preparation of a molded body includes inserting the foam particles and the shaped body in a corresponding mold.

[0096] According to step c), the particles and the shaped body are fused to obtain a molded body.

[0097] The fusion in step c) preferably takes place in a closed mold, wherein the fusion can for example be induced by steam, hot air or energetic radiation such as microwaves, radio waves or infrared waves. Preferably, steam-less molding is used. Preferably, fusing according to step c) is at least partially achieved using thermo pressing. Suitable temperatures for thermos pressing preferably are in the range of from 80 to 180°C, more preferable from 100 to 160°C, for example ion the range of from 130°C to 160°C, more preferably in the range of from 135°C to 160°C, in particular in the range of from 140°C to 155°C.

[0098] The temperature at the fusion of the surface-coated foam particles preferably is at least 10K higher than the softening temperature Tsoft of the thermoplastic polymeric surface coating. Preferably the temperature at the fusion of the surface coated foam particles is in the range from Tsoft+30K to Tsoft+40K. The softening temperature is in case of a semi-crystalline polymeric coating the melting temperature Tm1 or in case of an amorphous polymeric coating a glass transition appearing above room temperature (25°C) determined by differential scanning calorimetry according to DIN EN ISO 11357-2 (2014) in the first heating run. Temperature at the fusion is the mass temperature in the mold cavity measured for example by means of an optical temperature sensor.

[0099] The molded body can be produced by means of molding machines. For this purpose, the surface-coated foam particles are conveyed into the shaping tool manually or automated by using pressurized air. The shaping tool also referred to as mold or molding tool comprises two primary components, the injection mold-plate with the filling nozzles, and a counterpart-plate. To generate the particle-foam molded part, both mold-plates are pressed together so that a cavity in the shape of the molding part is formed. The filling of the mold-cavity can be conducted either by crack filling method or by the pressure filling method. Typically, the shaped body is inserted in the mold before the coated particles are inserted. The particles may be inserted manual or fully automated.

[0100] The crack-filling method comprises the following steps:

[0101] (i) injecting the expanded foam particles into the mold-cavity without a backpressure of the counterpart-plate,

[0102] (ii) fusing the particles while closing the plates of the mold mechanically,

[0103] (iii) cool down the molding part and

[0104] (iv) demold the produced part, wherein in step (i) a gap between the injection mold-plate and the counterpart-plate is adjusted which is also referred to as crack-height. The mold-cavity is filled with a predetermined amount of the expanded beads in step (i). In step (ii) the volume of the mold-cavity is reduced compared to step (i), because the two parts of the molding tool are closed tightly and the intermediate gap is, thus, disappeared. This leads to a pressure increase within the mold-cavity. The expanded foam particles are thus pressed against one another and can therefore become fused to give the molding.

[0105] The pressure filling method comprises the following steps:

[0106] (i*) injecting the foam particles into the mold-cavity by pneumatic pressure while compressing both plates of the mold tightly together,

[0107] (ii*) fusing the particles,

[0108] (iii*) cool down the particle-foam molded part, (iv*) demold the produced part.

[0109] Since the exerted injection pressure in step (i) is ceased in step (ii) the inserted foam particles may further expand and as a result be pressed against one and another and, therefore, become fused and give the molding.

[0110] According to the present invention, it is also possible to fuse further layers or parts in one step or also stepwise, i.e. prepare a first molded part in a first fusing step and then add one or more further parts or layers to obtain a second molded part.

[0111] It is for example possible to fuse a shaped body which is moisture sensitive with the coated particles using steam-less thermo-pressing to obtain a first molded part. It is for example possible that the coated particles form a layer around the shaped body thus protecting it. This first molded body can then be subjected to further fusing steps which might also include stem molding.

[0112] Depending on the size of the molded body to be prepared and the nature of the coated particles and the shaped body, the time, temperature and pressure applied for step c) might vary. Typically, the fusing is carried out at a temperature in the range of from 80 to 180°C, preferably from 80 to 160°C or 100 to 160°C.

[0113] It is also possible to pretreat or activate the shaped body prior to the fusing step, for example using radiation, such as IR radiation. A pretreatment includes for example a treatment of the surface to improve the fusing step. Activation includes for example a heat treatment.

[0114] According to a further embodiment, the present invention is also directed to the process as disclosed above, wherein the fusing is carried out at a temperature in the range of from 80 to 180°C, preferably from 100 to 160°C.

[0115] Typically, the temperature and pressure are applied for a time of 30 seconds to 30 minutes.

[0116] Preferably, the thermo-pressing (also called hot press or heat press) is carried out at a temperature of from 80 °C to 160 °C, more preferably from 90 °C to 150 °C, even more preferably from 90 °C to 140 °C. Preferably, after shaping by thermo-pressing the resulting molded bodies are cooled down to room temperature, which can improve mechanical properties.

[0117] The process according to the present invention may also comprise step d) d) cooling the molded body to room temperature.

[0118] Preferably, the demolding temperature is lower than the softening temperature or the polymeric coating. Suitable processes and conditions for cooling are in principle known to the person skilled in the art.

[0119] According to a further aspect, the present invention is also directed to a molded body obtained or obtainable according to a process as disclosed above. Typically, the molded density of the fused particles in the molded body is in the range of from 15 to 500 g / l, more preferable in the range of from 20 to 300 g / l in particular in the range of from 25 to 200 g / l.

[0120] Preferably, the molded body is a composite material of the particles with other materials, like textile, leather, a thermoplastic film or parts containing metals, especially electronic parts.

[0121] Another aspect of the present invention relates to a method for disposing a shaped body comprising the steps of

[0122] I) disassembling the particles by subjecting the molded body to a temperature in the range of 80 to 180°C.

[0123] Disassembling according to step I) is preferably possible using mild conditions. Preferably, a temperature in the range of from 80 to 180°C is applied. Additionally, alkaline wash solution may be used to support the disassembling.

[0124] The debonding may be supported by mechanical pulling or wetting with solvents, for example solvents such as N,N-Dimethyllactamide and gamma-valerolactone. Moreover, the disassembly may be facilitated by hot wash in water at a temperature above 60°C, for example in the range of from 60°C to 80°C, at a pH > 7, preferably >8.

[0125] According to the present invention, it is possible to separate the parts of the molded body which may be individually be reused. It is for example possible to separate the foamed particles and the shaped body and reuse only the foamed particles.

[0126] The molded body according to the present invention can be used for different applications.

[0127] The molded body may for example be used as parts for industrial, consumer, transportation, and construction-application used solely or as a component for sealing, insolation of e.g. houses, pipelines or gas-tanks, part of a shoe, shoe midsole, shoe insert, shoe combi sole, bicycle seats, bicycle tires, dampening element, shock protection, sound and vibration dampers, decoration, furniture, upholstery, mattress, yoga matts, underlayment, railway pads, handles, protective sheet, packaging, fall protection, automotive interior and exterior, headliner, arm rest, door lining, seats, battery housing, sport equipment, balls, tennis-racket, base-ball club, treadmill, toys, flooring, running tracks, artificial turf, play-grounds, sport halls, and sidewalks. According to a further aspect, the present invention is also directed to the use of a molded body according to the present invention in shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, underlays, grips, flooring, mattresses, sporting goods, protective gear, protective helmets bicycle saddles, running tracks, construction applications, tires and in automotive interiors and exteriors.

[0128] The molded body according to the present invention allows to combine particles of different sizes and chemistry (e.g. thermoplastic polyurethanes, thermoplastic polyester elastomers (e.g., polyether esters and polyester esters), thermoplastic copolyamides (e.g., polyether copolyamides) or thermoplastic styrene-butadiene block copolymers) with stable bonding. Also particles with high melting point can be fused at a temperature of, e.g. 100 °C into in a steam-less process due to the polymeric coating.

[0129] The molded body can be built stepwise and different layers can be combined, for example to adjust the properties for a given application or to include colored layers.

[0130] Furthermore, the bonding layer which essentially consists of the polymeric coating allows to disassemble the molded body by applying a temperature in the range of the melting temperature of the polymeric coating.

[0131] “Essentially consists” in the context of the invention means that more than 60% of the bonding layer are formed of the thermoplastic polymeric coting, in particular more than 80%.

[0132] Further embodiments of the present invention can be found in the claims and the examples. It will be appreciated that the features of the subject matter / processes / uses according to the invention that are mentioned above and elucidated below are usable not only in the combination specified in each case but also in other combinations without departing from the scope of the invention. For example, the combination of a preferred feature with a particularly preferred feature or of a feature not characterized further with a particularly preferred feature etc. is thus also encompassed im-plicitly even if this combination is not mentioned explicitly.

[0133] Illustrative embodiments of the present invention are listed below, but these do not restrict the present invention. In particular, the present invention also encompasses those embodiments which result from the dependency references and hence combinations specified hereinafter. 1 . A molded body comprising particles of an expanded thermoplastic elastomer at least partly coated with a thermoplastic polymeric surface coating and a shaped body, wherein the thermoplastic polymeric surface coating is homogeneously distributed between the particles of an expanded thermoplastic elastomer in the molded body .

[0134] 2. The molded body according to embodiment 1 , wherein the bonding strength between the particles and the shaped body equal or greater than 1 N / mm measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm.

[0135] 3. The molded body according to any one of embodiments 1 or 2, wherein the particles of the expanded thermoplastic elastomer are foam beads with an average length of the particles in the range of 1 to 20 mm.

[0136] 4. The molded body according to any one of embodiments 1 to 3, wherein the shaped body comprises a material selected from thermoplastic polymers, thermoset polymers, elastomers, in particular thermoplastic elastomers, leather, rubber, cork, wood metal, textile fabrics, and ceramic or mixtures thereof or recycled materials thereof.

[0137] 5. The molded body according to any one of embodiments 1 to 4, wherein the shaped body is a compact thermoplastic body, in particular a compact thermoplastic polyurethane.

[0138] 6. The molded body according to any one of embodiments 1 to 5, wherein the molded body is a shoe sole or part of a shoe sole.

[0139] 7. The molded body according to any one of embodiments 1 to 6, wherein the thermoplastic polymeric surface coating has a glass transition temperature higher than room temperature, but lower than the melting temperature of the foam particles.

[0140] 8. The molded body according to any one of embodiments 1 to 7, wherein the thermoplastic polymeric surface coating has a melting temperature higher than room temperature, but lower than the melting temperature of the foam particles.

[0141] 9. The molded body according to any one of embodiments 1 to 8, wherein the thermoplastic polymeric surface coating is a thermoplastic coating, preferably a thermoplastic polyurethane coating. 10. The molded body according to any one of embodiments 1 to 9, wherein the polyurethane coating comprises a polyurethane having a K-value according to DIN EN ISO 1628-1 2021 in the range from higher than 5 to lower than 100, preferably from 50 to 95.

[0142] 11. The molded body according to any one of embodiments 1 to 10, wherein the coating is applied as a dispersion.

[0143] 12. The molded body according to any one of embodiments 1 to 11 , wherein the polyurethane coating has a glass transition temperature Tg measured according to DIN EN ISO 11357-2 2018 from -10°C to -80°C and a melting temp (Tm1) in the range of from 30 to 100°C, preferentially in the range from 40 to 80°C.

[0144] 13. The molded body according to any one of embodiments 1 to 11 , wherein the polyurethane coating comprises a polyurethane having at least a first glass transition temperature Tg1 and a second glass transition temperature Tg2, wherein Tg1 is below 0°C and Tg2 is higher than 25 °C

[0145] 14. The molded body according to any one of embodiments 1 to 13, wherein the shaped body is prepared using thermo-pressing.

[0146] 15. A process for preparing a molded body comprising the steps of a) providing at least partly coated particles of an expanded thermoplastic elastomer with a polymeric coating; b) bringing the particles in contact with a shaped body, c) fusing the particles obtained from step a) and the shaped body to obtain a molded body.

[0147] 16. The process according to embodiment 15, wherein the fusing according to step c) is carried out by steam-less thermo-pressing.

[0148] 17. The process according to any one of embodiments 15 or 16, wherein the fusing is carried out at a temperature in the range of from 80 to 180, preferably 100 to 160°C. The process according to any one of embodiments 15 to 17, wherein the bonding strength between the particles and the shaped body equal or greater than 1 N / mm measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm. The process according to any one of embodiments 15 to 18, wherein the particles of the expanded thermoplastic elastomer are foam beads with an average length of the particles in the range of 1 to 20 mm. The process according to any one of embodiments 15 to 19, wherein the shaped body comprises a material selected from thermoplastic polymers, thermoset polymers, elastomers, in particular thermoplastic elastomers, leather, rubber, cork, wood metal, textile fabrics, and ceramic or mixtures thereof or recycled materials thereof. The process according to any one of embodiments 15 to 20, wherein the shaped body is a compact thermoplastic body, in particular a compact thermoplastic polyurethane. The process according to any one of embodiments 15 to 21 , wherein the molded body is a shoe sole or part of a shoe sole. The process according to any one of embodiments 15 to 22, wherein the thermoplastic polymeric surface coating has a glass transition temperature higher than room temperature, but lower than the melting temperature of the foam particles. The process according to any one of embodiments 15 to 23, wherein the thermoplastic polymeric surface coating has a melting temperature higher than room temperature, but lower than the melting temperature of the foam particles. The process according to any one of embodiments 15 to 24, wherein the thermoplastic polymeric surface coating is a thermoplastic coating, preferably a thermoplastic polyurethane coating. The process according to any one of embodiments 15 to 25, wherein the polyurethane coating comprises a polyurethane having a K-value according to DIN EN ISO 1628-1 2021 in the range from higher than 5 to lower than 100, preferably from 50 to 95. The process according to any one of embodiments 15 to 26, wherein the coating is applied as a dispersion. The process according to any one of embodiments 15 to 27, wherein the polyurethane coating has a glass transition temperature Tg measured according to DIN EN ISO 11357- 2 2018 from -10°C to -80°C and a melting temp (Tm1) in the range of from 30 to 100°C, preferentially in the range from 40 to 80°C. The process according to any one of embodiments 15 to 27, wherein the polyurethane coating comprises a polyurethane having at least a first glass transition temperature Tg1 and a second glass transition temperature Tg2, wherein Tg1 is below 0°C and Tg2 is higher than 25 °C The process according to any one of embodiments 15 to 27, wherein the molded body obtained is selected from shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, protective gear, protective helmets, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors. The process according to any one of embodiments 15 to 27, wherein the process further comprises a step of preparing an article selected from shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, protective gear, protective helmets, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors. A molded body obtained or obtainable according to a process according to any one of embodiments 15 to 31. Use of a molded body according to any one of embodiments 1 to 14 or 32 in shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, protective gear, protective helmets, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors.

[0149] 34. Use of a molded body obtained or obtainable according to a process according to any one of embodiments 15 to 31 in shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, protective gear, protective helmets, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors.

[0150] Examples

[0151] Viscosity is measured according to DIN EN ISO 3219-2:2021 (at 23°C and a shear rate of 250 s1).

[0152] The dispersions are dried in a mold at 40°C for 3 days and then at 23°C for 7 days. Thermal properties are measured by differential scanning calorimetry.

[0153] Glass-transition temperature (as the midpoint temperature of the second heating curve at a heating rate of 20 K / min), melting-points and enthalpy of fusion are determined according to DIN ISO 11357 (2018) (melting point = peak temperature) by heating with 20 K / min after cooling to -80°C; while enthalpy of fusion of the second run (Delta H2) is calculated from the area of second melting only; a) from a film at its untreated state (drying see above) -> Tm1 , Delta H1 b) after heating the polyurethane films to 130 °C, cooling with 20 K / min to -80°C; reheating with 20k / min-> Tm2 delta H2

[0154] The K-value was determined according to DIN EN ISO 1628-1 :2021

[0155] Example EX1 : used dispersions

[0156] Example EX1.1 : Dispersion with two Tgs. The highest Tg is higher than RT (allowing storage-stable coated E-TPU single beads) 1039 g of a polyesterdiol from Adipic acid and Isophthalic acid (molar 1 :1) and 1 ,6 Hexanediol (molecular weight 2000 g / mol; monomer b1)), 104,6 g of Dimethylolpropionic acid (DM PA, monomer c)), 186.8 g Butanediol-1 ,4 (monomer b2) were reacted with 900 g IPDI (monomer a)) in 530 g dry acetone in a pressurized reactor; starting at 50°C, increasing the temperature in 30 min to 90°C, then at 90°C for 8 h at 2.9 bar. The mixture was diluted with 1852 g acetone and cooled to 40°C and expanded to atmospheric pressure. The NCO-value was determined to 1.2%. Then 10.2 g of Isophoronediamine (monomer d) were added in a shot, followed by 81 g Diethylethanolamine (neutralization agent) in 5 min. After 5 min stirring, the dispersion step was continued with 3567 g deionized water in 37 min at 30°C, followed by an addition of 19.8 Diethylenetriamine (monomer d) in 340 g deionized water in 30min. The acetone was removed by vacuum distillation with the help of 0.23 g of defoamer (FoamStar PB 2724, BASF) and the solids content was 37.4%.

[0157] Example EX1.2: Semicrystalline dispersion

[0158] 676 g of a polyesterdiol with a molecular weight of 2493 g / mol (based on adipic acid and 1 ,4- butanediol, monomer b1)) were reacted with 0.11 g titaniumtetrabutylate, 40 g isophorone diisocyanate (IPDI, monomer a)), 0.77 g NCO-terminated polycarbodiimid (Elastostab H02, BASF, monomer d)) at 60°C in 153 g dry acetone for 60 min. Then, 37.8 g 1 ,6-hexane diisocyanate (HDI, monomer a)) was added and the temperature raised to 74°C. The reaction was continued until the NCO-value was lower than 1.25%. The mixture was diluted with 539 g acetone and cooled to 35-40°C. Then 22.4 g of aminoethyl aminoethansulfonate sodium salt (50% in water, monomer c)) diluted with 22 g demineralized water was added within a period of 3 min, followed by 4.6 g isophorone diamine, (monomer d) diluted in 23 g demineralized water also added within a period of 3 min. Before dispergation, 38.7 g of a 20% aqueous solution of alkyl polyethylene glycol ether made from a linear, saturated C16C18 fatty alcohol with 18 moles of ethylene oxide, 20% active (e.g., Lutensol AT18 from BASF) was added. In the next step, the dispergation of the produced compound with 463 g demineralized water was carried out by using an anchor stirrer over a period of 15 min. Immediately after the water feed, additionally 4 g of N-(2- aminoethyl)-ethanolamine (monomer d)) solved in 30 g water was added during the dispergation. During dispergation an additional amount of 200 g demineralized water was added. After the dispergation step, the acetone was removed by vacuum distillation with the help of two drops of defoamer (FoamStar PB 2724, BASF) and the solids content of the obtained semicrystalline dispersion adjusted to 50% by addition of controlled amount of water. The properties of the obtained dispersion are shown in Table 1.

[0159] Table 1

[0160] Example 2: Used e-TPU

[0161] Ex 2.1 E-TPU beads with bulk density of 130g / l

[0162] E-TPU beads (particles), made according to example 1 of WO 2013 / 153190 A1 having a bulk density 130 g / l and a particle weight of 27 mg.

[0163] Ex 2.2 E-TPU beads with bulk density of 95g / l

[0164] The TPU precursor synthesis was carried out in a twin-screw extruder, ZSK58 MC, of the company Coperion with a process length of 48D (12 housings). The melt discharge from the extruder was carried out by a gear pump. After melt filtration, the polymer melt was processed by underwater granulation into granules, which were continuously dried in a heating vortex bed, at 40 - 90 °C.

[0165] Polyols, chain extender and diisocyanate (Table 2) were dosed into the first zone. The housing temperatures are in the range 150 - 230 °C. The melt discharge and underwater pelletizing are carried out at melt temperatures of 210 - 245°C. The screw speed was between 180 and 240 1 / min. The throughput was in the range of 180 - 220 kg / h.

[0166] Table 2: TPU formulation

[0167] The dried TPU and further raw materials listed in table 3 were fed into a twin screw extruder (ZE40, KraussMaffei Berstorff) and melted in a temperature range of 160 °C to 220 °C.

[0168] As blowing agents, 1.12 wt.% CO2 (based on the weight of the polymer composition) and 0.194 wt.% N2 (based on the weight of the polymer composition) were injected into the melt in the extruder and mixed with the thermoplastic polyurethane and the other additives to form a ho- mogenic melt.

[0169] The melting mixture was then pressed via a gear pump at 160-200 ° C into a perforated plate having a temperature of 180 - 200 ° C and cut in the cutting chamber of the underwater granulating (having a temperature of 49 °C and a pressure of 8.7 bar) to granules, which subsequently expanded under water.

[0170] After separating the expanded granules from the water via a centrifugal dryer, the expanded granules were dried at 60 °C for 2 h.

[0171] Table 3: Examples and references TPU blends

[0172] The obtained E-TPLI beads have a bulk density of 95 g / L and a particle weight of 20 mg EX3.1 coated e-TPU beads by using a Vollrath dissolver

[0173] 10g of the polyurethane dispersion described in example Ex1.2 was mixed with 90 g of E-TPU beads (particles), made according to example 1 of WO 2013 / 153190 A1 having a bulk density 130 g / l and a particle weight of 27 mg with a Vollrath dissolver for 60 second at room temperature. Later the beads were let drying at RT on a Teflon foil, keeping attention to isolate them from each other. After a time of around 10 minutes the beads were collected. The coated beads are non- sticky, storage stable and can be collected without agglomeration.

[0174] Ex.3.2 coated e-TPU beads (low density) by using a Vollrath dissolver

[0175] 13,5 g of the polyurethane dispersion, described in Ex1.1 was mixed with 86.5 g of E-TPU beads (particles), made according to Ex2.2 with a Vollrath dissolver for 60 second at room temperature. Later the beads were let drying at RT on a Teflon foil, keeping attention to isolate them from each other. After a time of around 10 minutes the beads were collected. The coated beads are non- sticky, storage stable and can be collected without agglomeration.

[0176] Ex.3.3 coated e-TPU beads (low density) by using a Vollrath dissolver

[0177] 10g of the polyurethane dispersion described in example Ex1.2 was mixed with 90 g of E-TPU beads (particles), made according to Ex2.2 with a Vollrath dissolver for 60 second at room temperature. Later the beads were let drying at RT on a Teflon foil, keeping attention to isolate them from each other. After a time of around 10 minutes the beads were collected. The coated beads are non-sticky, storage stable and can be collected without agglomeration.

[0178] Ex. 4.1 : Hotpress plates with E-TPU beads according to experiment 3.3

[0179] A TPU injection molded sole, based on the recipe described in table 4, was placed in his aluminum mold, which was preheated to 135C. After two minutes, 65 g of coated beads according to experiment 3.1 were placed in it. The filled mold was covered with a mold lid (which was sprayed with a release agent Indrosil 2000), which allows a compression / compactaction of 50%. The time in the heated press was 6 minutes. After that the mold was actively cooled (water cooling) until a temperature of 40 C was reached.

[0180] The whole shoe part (midsole plus sole) has a weight of 155.7 g and a very good adhesion between sole and midsole. Table 4: Composition of TPU ester based molded sole:

[0181] Parts

[0182] The results of the separation test, measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm, are summarized in table 5

[0183] Table 5: Result separation test

[0184] Ex. 4.2: Hotpress plates with E-TPU beads according to experiment 3.3

[0185] A TPU injection molded sole, based on the recipe described in table 6, was placed in his aluminum mold, which was preheated to 130C. After two minutes, 65 g of coated beads according to experiment 3.1 were placed in it. The filled mold was covered with a mold lid (which was sprayed with a release agent Indrosil 2000), which allows a compression / compactaction of 50%. The time in the heated press was 6 minutes. After that the mold was actively cooled (water cooling) until a temperature of 40 C was reached.

[0186] The whole shoe part (midsole plus sole) has a weight of 155.7 g and a very good adhesion between sole and midsole.

[0187] Ex. 4.3: Hotpress plates with E-TPU beads according to experiment 3.3 A TPU injection molded sole, based on the recipe described in table 6, was placed in his aluminum mold, which was preheated to 135C. After two minutes, 65 g of coated beads according to experiment 3.1 were placed in it. The filled mold was covered with a mold lid (which was sprayed with a release agent Indrosil 2000), which allows a compression / compactaction of 50%. The time in the heated press was 6 minutes. After that the mold was actively cooled (water cooling) until a temperature of 40 C was reached.

[0188] The whole shoe part (midsole plus sole) has a weight of 155.7 g and a very good adhesion between sole and midsole.

[0189] Table 6: Composition of TPU ether based molded sole:

[0190] The results of the separation test for ex. 4.2 and 4.3, measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm, are summarized in table 7

[0191] Table 7: Result separation test

[0192] Literature cited

[0193] WO20 14 / 198779 A 1

[0194] WO20 15 / 052265 DE102013110242 A1

[0195] EP3698949 A1

[0196] W02017 / 125410 A1 W02017 / 125410 A1 WO2017 / 125410 A1

[0197] WO 2022 / 223438

[0198] EP22202204.8

[0199] WO 94 / 20568A1

[0200] WO 2007 / 082838 A1 WO20 17 / 030835 A 1

[0201] WO 2013 / 153190 A1

[0202] WO 2010 / 010010 A1

[0203] WO 2019 / 202095 WO20 18 / 087362 WO 2022 / 223438

Claims

Claims1 . A molded body comprising particles of an expanded thermoplastic elastomer at least partly coated with a thermoplastic polymeric surface coating and a shaped body, wherein the thermoplastic polymeric surface coating is homogeneously distributed between the particles of an expanded thermoplastic elastomer in the molded body .

2. The molded body according to claim 1 , wherein the bonding strength between the particles and the shaped body equal or greater than 1 N / mm measured according to ISO 20344:2021 (Chapter 5.2, Macharttyp f und g) at 23°C differentiating by using grippers with a width of 27.5 mm (according to DIN EN ISO 20344:2012) and a test specimen width of 20 mm.

3. The molded body according to any one of claims 1 or 2, wherein the particles of the expanded thermoplastic elastomer are foam beads with an average length of the particles in the range of 1 to 20 mm.

4. The molded body according to any one of claims 1 to 3, wherein the shaped body comprises a material selected from thermoplastic polymers, thermoset polymers, elastomers, in particular thermoplastic elastomers, leather, rubber, cork, wood metal, textile fabrics, and ceramic or mixtures thereof or recycled materials thereof.

5. The molded body according to any one of claims 1 to 4, wherein the shaped body is a compact thermoplastic body, in particular a compact thermoplastic polyurethane.

6. The molded body according to any one of claims 1 to 5, wherein the molded body is a shoe sole or part of a shoe sole.

7. The molded body according to any one of claims 1 to 6, wherein the thermoplastic polymeric surface coating has a glass transition temperature higher than room temperature, but lower than the melting temperature of the foam particles.

8. The molded body according to any one of claims 1 to 7, wherein the thermoplastic polymeric surface coating has a melting temperature higher than room temperature, but lower than the melting temperature of the foam particles.

9. The molded body according to any one of claims 1 to 8, wherein the thermoplastic polymeric surface coating is a thermoplastic coating, preferably a thermoplastic polyurethane coating.

10. The molded body according to any one of claims 1 to 9, wherein the polyurethane coating comprises a polyurethane having a K-value according to DIN EN ISO 1628-1 2021 in the range from higher than 5 to lower than 100, preferably from 50 to 95.

11. The molded body according to any one of claims 1 to 10, wherein the coating is applied as a dispersion.

12. The molded body according to any one of claims 1 to 11 , wherein the polyurethane coating has a glass transition temperature Tg measured according to DIN EN ISO 11357-2 2018 from -10°C to -80°C and a melting temp (Tm1) in the range of from 30 to 100°C, preferentially in the range from 40 to 80°C.

13. The molded body according to any one of claims 1 to 11 , wherein the polyurethane coating comprises a polyurethane having at least a first glass transition temperature Tg1 and a second glass transition temperature Tg2, wherein Tg1 is below 0°C and Tg2 is higher than 25 °C14. The molded body according to any one of claims 1 to 13, wherein the shaped body is prepared using thermo-pressing.

15. A process for preparing a molded body comprising the steps of a) providing at least partly coated particles of an expanded thermoplastic elastomer with a polymeric coating; b) bringing the particles in contact with a shaped body, c) fusing the particles obtained from step a) and the shaped body to obtain a molded body.

16. The process according to claim 15, wherein the fusing according to step c) is carried out by steam-less thermo-pressing.

17. The process according to any one of claims 15 or 16, wherein the fusing is carried out at a temperature in the range of from 80 to 180, preferably 100 to 160°C.

18. A molded body obtained or obtainable according to a process according to any one of claims 15 to 17.

19. Use of a molded body according to any one of claims 1 to 14 or 18 in shoe soles, part of shoe soles, shoe intermediate soles shoe insoles, damping elements, cushioning elements, protective devices, protective gear, protective helmets, underlays, grips, flooring, mattresses, sporting goods, bicycle saddles, running tracks, construction applications, functional wear, helmets, isolation, battery casing, prostheses, sport mats, balls, rackets, furniture, seats, tires and in automotive interiors and exteriors.

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