Processes for the preparation of stable particles and for the preparation of a molded body, particle, molded body and use of a particle

Description

1 / 42 “PROCESSES FOR THE PREPARATION OF STABLE PARTICLES AND FOR THE PREPARATION OF A MOLDED BODY, PARTICLE, MOLDED BODY AND USE OF A PARTICLE” Description

[001] The present invention relates to a process for preparing storage-stable particles (also referred to herein as “spheres”) of a moldable thermoplastic particle foam, at least partially coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, comprising the steps of: a1) placing the particles in contact with the hot melt adhesive to obtain the coated particles; a2) moving the coated particles until they are free of stickiness.The invention also relates to a storage-stable particle, at least partially coated, of a moldable thermoplastic particle foam that is at least partially coated with a hot-melt adhesive, preferably a non-reactive hot-melt adhesive, wherein the coated particle is free from stickiness, preferably obtained by said process, as well as to a process for preparing molded bodies and molded bodies obtained by said process and to the use of said particles and molded bodies.

[002] Moldable thermoplastic particle foams are used, for example, for the production of any solid foam bodies, for example, for gym mats, car body protectors, lining elements in car construction, sound and vibration dampers, packaging or shoe soles.

[003] Traditionally, a mold is filled with foam particles, followed by the fusion of the individual foam particles on its surface by the action of heat, thus joining them to form a piece of foam particles. Thus, in addition to simple products, products can be produced. Petition 870250087664, dated 09 / 26 / 2025, pp. 131 / 177 2 / 42 complex semi-finished parts or molded parts with recesses.

[004] Moldable thermoplastic particle foams are known in the art and described, for example, in Robin Britton (Author), Update on Moldable Particle Foam Technology, Rapra technology Ltd, 2009. Expanded thermoplastic elastomers, especially expanded thermoplastic polyurethanes (eTPU), represent specific moldable thermoplastic particle foams.

[005] Expanded thermoplastic elastomers are known in the art. For example, WO 2018 / 082984 A1 describes particle foams based on expanded thermoplastic elastomers. WO 2008 / 087078 A1 describes hybrid systems consisting of expanded thermoplastic elastomers and polyurethanes. Hybrid eTPU systems are also described in CN 109337343 A, CN 110240795 A and CN 109080061 A.

[006] An exemplary thermoplastic polymer is expanded thermoplastic polyurethane (eTPU), which is commercially available, for example, marketed by BASF under the name Infinergy®. eTPU particles mainly represent particle foam with mostly closed to fully closed cells. Thermoplastic polyurethane (e.g., Elastollan®) is expanded, resulting in particle foam, and can be processed on standard molding machines. Thanks to its closed particle surface and the chemical nature of the TPU used, standard eTPU grades also absorb only small amounts of water. Like the TPU on which it is based, it can also be characterized by high elongation at break, tensile strength, and abrasion resistance, combined with good chemical resistance.

[007] Rapid prototyping of 3D objects made from expanded thermoplastic elastomers is not easy to do nowadays. Typically, Petition 870250087664, dated 09 / 26 / 2025, pp. 132 / 177 3 / 42 Isocyanate-containing binders are used to bond the particles, or water vapor and appropriate machines, such as a steam box molder, are used. Both approaches are not readily accessible due to health and safety reasons, energy costs, or the lack of availability of appropriate machines (steam box molder). Furthermore, the use of water vapor only allows the molding of particles of the same type, whereas a coating on an eTPU particle or the use of a water-based binder can allow the bonding of eTPU particles of different types (glass transition temperature, melting point) and sizes, but also the bonding of different TPUs or even different particle foams, for example, different mixtures of eTPS, ePS, ePP, eTPA, eTPC, eTPO, and the like.The application of a coating also allows for the adjustment of mechanical performance and applicability through the incorporation of additives, such as pigments or dyes, flame retardants, or antistatic agents, directly onto the particle surface. Fillers, for example, allow for increased rigidity of the final part, while the use of additives that are, for example, excitable by an electromagnetic field, allows for moldability of the coating, thus reducing the energy required for molding.

[008] Additives may include pigments, dyes, odors, fillers, bio-based and / or biodegradable additives, UV and heat stabilizers, flame retardants such as expandable graphite, additives that generate antistatic properties, electrical conductivity, additives that reduce dirt absorption, antimicrobial additives, wax, crosslinking agents, functionalized surface fillers, foaming additives such as Expancell®, additives that can be irradiated by an electromagnetic field and / or radio frequency and / or microwaves.

[009] Document WO 2022 / 223 438 A1 and the patent application Petition 870250087664, dated 09 / 26 / 2025, pp. 133 / 177 European patent application number EP 22 202 204.8 describes various water-based binders for coating particles that can be molded into the aforementioned 3D parts.

[0010] US patent 6,616,797 B1 describes the formation of adhesive bonds by a process that includes applying a dispersion containing a polyurethane with structural units of formula (I) to a surface. The dispersion is first applied to the surface to form a coating. The coating is dried to form an essentially anhydrous coating. The dried coating is then subjected to heat activation. The adhesive bond is formed by the bonding of the heat-activated coating to itself or to another surface. However, particle coating is not described.

[0011] WO 2012 / 13506 A1 describes the use of an aqueous polyurethane dispersion adhesive for the production of biologically disintegrating composite films with at least two substrates bonded together using the polyurethane dispersion adhesive, at least one of the substrates being a biologically disintegrating polymeric film. At least 60% by weight of the polyurethane is made of diisocyanates, polyester diols and at least one bifunctional carboxylic acid selected from dihydroxycarboxylic acids and diaminocarboxylic acids.

[0012] Document WO 2005 / 003247 A1 refers to a method for joining substrates with different surface energies. The adhesive used for the bonding consists of at least 15% by weight of a polyurethane (water or other organic solvents with a boiling point below 150 °C at 1 bar are not counted), the adhesive is applied to the substrate with the lower surface energy and the substrate coated with the resulting adhesive is bonded to the substrate with the higher surface energy.

[0013] Document WO 2021 / 249749 A1 describes recycling Petition 870250087664, dated 09 / 26 / 2025, pp. 134 / 177 5 / 42 of articles bonded, including foam substrates - TPU, using aqueous dispersions of polyurethane with specific molecular weights as adhesives. It is not mentioned whether the foam particles are coated.

[0014] US patent 2019 / 367698 A1 describes methods for preparing expanded thermoplastic polyurethane elastomer products using hot-melt adhesives such as Mirathane® H306. However, the coated particles are not moved until they are free of tackiness, but rather inserted directly into a product mold for vulcanization. The vulcanization process involves cross-linking between the particles, leading to the formation of a three-dimensional material that loses its thermoplastic characteristics, such as remeltability and recyclability.

[0015] Document WO 2019 / 073607 A1 describes a shoe sole element, part or all of which is formed by a resin composite body comprising an unexpanded elastic matrix composed of an elastomer and a plurality of resin foam particles dispersed in the elastic matrix. Furthermore, a shoe provided with this shoe sole element is disclosed.

[0016] Although different binders are described, generally useful for bonding particles, there is a need to prepare coated particles that are stable during storage, preventing the clumping of stored particles. This includes particles with better flowability, lower electrostatic charge due to friction, and that allow for much easier production of 3D parts through a simple molding process (e.g., standard convection oven or heat press).

[0017] Thus, there is a need for a material that combines the following advantages: Different eTPE spheres, or even other classes of materials, can be mixed; Petition 870250087664, dated 09 / 26 / 2025, pp. 135 / 177 6 / 42 - The hot melt can be used as a vehicle for, for example, stabilizers, pigments, etc.; The thermal fuse can be recycled along with the eTPU; - Particle foam bodies, made of particles coated with a heat-fusible compound, can be detached and the eTPU parts can be recovered; - Beads coated with heat-fusible material can be easily fused by hot pressing or by using other molding technologies such as radio frequency and vapor box molding.

[0018] A non-stick coating on the particles allows for easy filling, for example, in molds or cavities during processing due to improved flowability and lower electrostatic charge from friction.

[0019] Furthermore, the particles can be processed in different ways, for example, by a standard convection oven or thermal press, but also by an electromagnetic field. Thus, the spheres can be filled, for example, in intermediate spaces and glued together by a trigger.

[0020] Thus, an objective of the present invention is to provide a process for the preparation of storage-stable coated particles.

[0021] The objective is achieved by a process for preparing storage-stable particles of a moldable thermoplastic particle foam, at least partially coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, comprising the steps of: a1) Place the particles in contact with the hot melt adhesive to obtain coated particles; a2) move the coated particles until they are free of stickiness. Petition 870250087664, dated 09 / 26 / 2025, pp. 136 / 177 7 / 42

[0022] The objective is also achieved by a process of preparing a molded body which comprises the following steps: b1) coating particles according to the process for preparing storage-stable particles according to the present invention; b2) mold the particles obtained in step b1).

[0023] The objective is also achieved by a storage-stable particle, at least partially coated, of a moldable thermoplastic particle foam that is at least partially coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, wherein the coated particle is free of stickiness, preferably obtained by a process for preparing storage-stable particles according to the present invention.

[0024] The objective is also achieved by a molded body obtained from a process for preparing a molded body according to the present invention or obtained by molding particle foams according to the present invention.

[0025] Surprisingly, it has been found that the use of hot-melt adhesives results in stickiness-free coatings, which can be used for the production of 3D parts without the need for steam, even if compatibility with the steam box is still ensured. Given the low melting point of the hot-melt adhesive, the energy used in the processes according to the present invention is low, even when steam box molding is used and the cycle time is short. The coating allows for the hot-pressing of 3D parts with excellent mechanical values, which are comparable to and even superior to 3D parts made using standard steam box molding processes. Furthermore, shorter cycle times during processing are possible. Especially, the use of hot-melt adhesive... Petition 870250087664, dated 09 / 26 / 2025, pp. 137 / 177 8 / 42 cast is advantageous because solvent removal, especially aqueous solvent removal, which is costly and energy-intensive, can be avoided.

[0026] To prepare storage-stable particles of a moldable thermoplastic particle foam that are at least partially coated with a hot melt adhesive, the particles are brought into contact with the hot melt adhesive to obtain the coated particles in one step ai).

[0027] There are different methods available to obtain the coating.

[0028] In a first aspect, the hot melt adhesive is placed in contact in its molten state. A typical temperature used is in the range of 60 °C to 200 °C, preferably 60 °C to 180 °C, more preferably 80 °C to 180 °C.

[0029] Preferably, the hot melt adhesive in its molten state has a viscosity in the range of 0.1 mPas to 800,000 mPas, more preferably from 1 mPas to 600,000 mPas, even more preferably from 10 mPas to 500,000 mPas, measured at 160 °C. Preferably, the viscosity is measured using a Brookfield viscometer. The Brookfield viscometer measures the torque required to rotate the selected spindle in a fluid. This torque value is directly related to the viscosity of a fluid. More specifically, a Brookfield / Ametek rotational viscometer (HB DV2T Extra) can be used, which measures the torque required to rotate the spindle (SC427) in a fluid at 0.4 rpm.

[0030] Preferably, the particles are kept under agitation (kitchen mixer, concrete mixer or spray coating drum). The mixer is preferably kept at a temperature of 15 °C to 100 °C, preferably 30 °C to 100 °C, and even more preferably 60 °C to 100 °C. Petition 870250087664, dated 09 / 26 / 2025, pp. 138 / 177 9 / 42

[0031] Thus, in a preferred embodiment, the particles are tempered before step ai), so that the temperature of the particles, at least at the beginning of step ai), preferably throughout step ai), is from 15 °C to 100 °C, preferably from 30 °C to 100 °C, even more preferably from 60 °C to 100 °C.

[0032] In a second aspect, the hot melt adhesive is brought into contact in its solid state by means of powder coating. Powder coating is a well-known method and a person skilled in the art is capable of performing such powder coating.

[0033] In a third aspect, the hot melt adhesive is brought into contact in the form of a solution, where the hot melt adhesive is dissolved in an organic solvent, followed by the step of: ae) remove the organic solvent and / or dry the particles after step a2) at a temperature below the melting point of the hot melt adhesive to obtain the coated particles.

[0034] Suitable organic solvents are organic solvents such as acetone, acetonitrile, butanol, t-butyl alcohol, butanone (MEK), chlorobenzene, chloroform, cyclohexane, diethylene glycol, diethyl ether, dimethoxyethane, 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, triethylamine, xylene. A preferred organic solvent is MEK. Drying in step a3) can be carried out by conventional methods.

[0035] A more preferred embodiment is the use of the hot melt adhesive in its molten state.

[0036] The processes of the present invention relate to the preparation of coated particles of a moldable thermoplastic particle foam. Such foams are known in the art (see, for example). Petition 870250087664, dated 09 / 26 / 2025, pp. 139 / 177 10 / 42 example, Robin Britton (Author), Update on Moldable Particle Foam Technology, Rapra Technology Ltd, 2009). Preferably, the moldable thermoplastic particle foam is an expanded thermoplastic elastomer.

[0037] Expanded thermoplastic elastomer particles are known in the art. Suitable thermoplastic elastomers are, for example, thermoplastic polyurethanes (TPU), thermoplastic polyester elastomers (e.g., polyetherester and polyesterester) (TPC), thermoplastic copolyamides (e.g., polyether copolyamides) (TPA), thermoplastic polyolefins (TPO), or thermoplastic styrene-butadiene block copolymers (TPS). Thermoplastic polyurethane (TPU)-based foam particles are particularly preferred. Thus, preferably, the expanded thermoplastic elastomer is eTPU.

[0038] Examples of methods for preparing expanded thermoplastic elastomer particles are described in WO 2008 / 087078 A1, WO 2018 / 082984 A1, US 10 005 218 B2 and WO 2007 / 082838 A1.

[0039] Preferably, the glass transition temperature (Tg) of the moldable thermoplastic particle foam, as well as of the expanded thermoplastic polymer particles, is, according to the aforementioned patents, < 100 °C and is measured by DSC, in accordance with the standard DIN EN ISO 113573:2013, preferably with a heating rate of 20 °C / min after a first pre-drying step at 100 °C for 10 min. The Tg of the soft phase can be measured in the first heating step.

[0040] Preferably, in step a-1), contact is achieved by mixing the foam beads with the hot melt adhesive using kitchen or cement mixers or by spraying, such as mixing with a Vollrath mixer or spray drying. The amount of liquid / solution relative to the weight of the product can be in the range of 1 ml / kg / min to 1000 ml / g / min. The droplet size can vary from 1 mm to 1000 mm. Petition 870250087664, dated 09 / 26 / 2025, pp. 140 / 177 1 1 / 42 mm in diameter. Suitable nozzles would be hollow cone nozzles, full cone nozzles, or flat jet nozzles, as well as spray discs that produce droplets through rotational motion and centrifugal force. A suitable mixer that can be used is an EMT 30 L. The EMT L 30 is a discontinuous paddle mixer. It is suitable for mixing, agglomeration, and coating experiments. It consists of a rigid container with rotating mixing tools. Depending on the field of application, there are several nozzle installation possibilities available. The mixer is heatable due to a double jacket. The rotation speed is adjustable by means of a mechanical variator. Melting vessels and pressure vessels are used to add liquids.

[0041] In general, common coating methods, such as spray coating, for example, as described in document EP 0 009 727 A1, can be used. In a preferred embodiment of coating, the particles are coated by spraying, keeping them in motion by means of blowing with, for example, air or mixtures of different gases.

[0042] The at least partially coated particles are coated in an amount of 0.1% by weight to 40% by weight, preferably 5% by weight to 25% by weight, based on the total weight of the particle and the coating. Preferably, the at least partially coated particles are coated in an amount of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably fully coated based on the total surface area of ​​the particle.

[0043] Step a3) refers to the drying of the coated particles, if the hot melt adhesive is applied in the form of a solution, where the hot melt adhesive is dissolved in an organic solvent. In principle, all suitable methods are possible, such as convective drying, Petition 870250087664, dated 09 / 26 / 2025, pp. 141 / 177 12 / 42 Contact drying, infrared drying, and microwave technology are also available. When using a molten melt-resistant coating, it is only necessary to bring the coated particles to room temperature.

[0044] In the case of contact drying, the temperature difference between the product and the wall should be limited to 1 - 100 K; in the case of convective drying, the gas composition can be N2 or air. The gas quantity is preferably 1-1000 liters / min per 1 kg of product and the product temperature in the mixer should be between 1 °C and 100 °C, preferably between 10 °C and 60 °C.

[0045] In step as), the coated particles are moved until they are free of stickiness. The term “free of stickiness” refers to obtaining a non-sticky surface at room temperature, preferably in the range of 20 °C to 25 °C. This occurs when the coated particles do not agglomerate upon contact with each other and do not adhere to a second surface at room temperature. This translates to a Tfb (described in more detail below) of the melt above 40 °C, preferably above 60 °C. Non-sticky particles are important to provide stable particles during storage.

[0046] The movement of the coated particles in step a2) may occur simultaneously with step a1) or after or both, beginning with or during step a1) and continuing after the completion of step ai).

[0047] Preferably, after step a1) and before step a2), the particles are separated from each other. This can be achieved, for example, by using a vibrating belt or similar. In addition, this option prevents the particles from clumping together.

[0048] Preferably, the hot melt adhesive is a composition comprising a thermoplastic polymer, preferably a thermoplastic polyurethane. Petition 870250087664, dated 09 / 26 / 2025, pp. 142 / 177 13 / 42

[0049] A hot melt adhesive is typically solid at room temperature, solvent-free, and meltable above room temperature. Hot melt adhesives are generally non-reactive thermoplastics. Hot melt adhesives (HMAs) are adhesive systems that are solid at room temperature, become tacky or sticky when heated, and melt into a liquid or fluid state. They typically solidify rapidly upon cooling to room temperature to develop internal strength and cohesion. Hot melt adhesives are single-component, solvent-free thermoplastic adhesives characterized by low to medium viscosity when applied at the required distribution temperature. Once applied, hot melt adhesives cool and solidify to form a strong bond between items. The bonds formed with thermoplastic hot melt adhesives are reversible.Under sufficiently high thermal stress, thermoplastic hot melt adhesives liquefy and lose their cohesive strength.

[0050] The melting point, measured by differential scanning calorimetry (DSC), of the composition comprising the thermoplastic polymer, in particular thermoplastic polyurethane, is preferably between about 50 °C and about 180 °C, or between about 50 °C and about 160 °C. The test method refers to ASTM D 3418-12 (Standard Test Method for Polymer Melting and Crystallization Transition Temperatures and Enthalpies by Differential Scanning Calorimetry), using Hitachi High-Tech Co., DSC7000X, with a heating rate of 10 °C / min and a cooling rate of 10 °C / min.

[0051] It has been surprisingly discovered that the flow start temperature (Tfb) of the composition comprising the thermoplastic polymer influences the coating properties of the composition. Adjusting the flow start temperature within a suitable range can be used to Petition 870250087664, dated 09 / 26 / 2025, pp. 143 / 177 14 / 42 influence the temperature behavior of the adhesive strength to obtain good coating properties under conditions of use, but also to allow easy recycling. It was surprisingly discovered that an advantageous combination of good coating using mild conditions can be achieved using a composition comprising a thermoplastic polymer that has a flow start temperature (Tfb) of at least 50 °C, preferably at least 60 °C, more preferably at least 70 °C, as measured according to Example 1 referring to JSI K7311-1995 and K7210-1999 and using the Shimadzu Flowtester CFT-500D Capillary Rheometer.

[0052] According to another embodiment, the present invention is also directed to the process according to the present invention, wherein the thermoplastic polymer composition has a flow start temperature (Tfb) measured according to Example 1 in the range of 50 °C to 160 °C, preferably 60 °C to 160 °C, more preferably 70 °C to 160 °C, most preferably 70 °C to 150 °C.

[0053] Preferably, the composition comprising the thermoplastic polymer, used in accordance with the present invention, has a relatively low softening temperature and also a low flow start temperature.

[0054] The composition comprising the thermoplastic polymer may include a variety of polymers commonly used in adhesives. For example, the composition may include at least one polymer selected from polyurethane, polychloroprene, latex, polystyrene, polyamide, polyolefin, polyacrylate, polyester, polyether, a copolymer thereof, and any combination thereof. In some respects, the polystyrene is or includes a polystyrene block copolymer. Suitable polystyrenes may include poly(styrene-isoprene-styrene), poly(styrene-butadiene-styrene), poly(styrene-ethylene-butene-styrene), and a poly(styrene-ethylene-propene). Petition 870250087664, dated 09 / 26 / 2025, pp. 144 / 177 15 / 42

[0055] In some respects, the composition comprising the thermoplastic polymer includes at least one thermoplastic selected from a thermoplastic polyurethane, a thermoplastic polyamide, a thermoplastic polyolefin, a thermoplastic polyester, a thermoplastic polyether, a thermoplastic copolymer thereof, and any combination thereof. In some respects, the composition includes a polyolefin, such as a polyethylene, a polypropylene, a copolymer thereof, or any combination thereof. The polyolefin may be an ethylene copolymer. In some respects, the composition includes a thermoplastic polyolefin. The thermoplastic polyolefin, in some respects, includes a thermoplastic polyethylene, a thermoplastic polypropylene, a thermoplastic copolymer thereof, or any combination thereof. The thermoplastic polyolefin may include a thermoplastic ethylene copolymer. In some respects, the thermoplastic ethylene copolymer is ethylene vinyl acetate (EVA).

[0056] In some respects, the composition includes at least one thermoplastic polymer that is a polymer or copolymer including a plurality of functional groups in its chemical structure, wherein the plurality of functional groups is selected from hydroxyl groups, carboxyl groups, amine groups, amide groups, urethane groups and combinations thereof.

[0057] According to another embodiment, the present invention is also directed to the processes disclosed herein, wherein the thermoplastic polymer composition comprises at least one polymer selected from a thermoplastic polyurethane, a polychloroprene, a polystyrene, a polyamide, a polyolefin, a polyacrylate or a mixture thereof.

[0058] The composition is typically applied at elevated temperatures to produce adhesive coatings. The composition can, for example, be applied as a molten mass at temperatures of, Petition 870250087664, dated 09 / 26 / 2025, pp. 145 / 177 16 / 42 preferably, 60 °C to 220 °C, more preferably 80 °C to 200 °C, and even more preferably 80 °C to 200 °C, in the foam to be coated, the surface being coated at least partially with the composition comprising the thermoplastic polymer.

[0059] The application amount of the composition comprising the thermoplastic polymer is preferably in the range of 1% by weight to 30% by weight, more preferably 5% by weight to 20% by weight based on the total weight of the coated particle.

[0060] Preferably, the composition comprises a thermoplastic polyurethane. According to a further embodiment, the present invention also relates to a process as disclosed herein, in which the thermoplastic polymer is a thermoplastic polyurethane.

[0061] Suitable thermoplastic polyurethanes typically comprise the reaction product of: a) a polyisocyanate component; b) a polyol component; and c) optionally a current extender component.

[0062] The reaction may or may not be carried out in the presence of a catalyst. According to another embodiment, the present invention also relates to a process such as that disclosed herein, in which thermoplastic polyurethane is the product of the reaction of the construction components: a polyol, an isocyanate and, optionally, a chain extender.

[0063] Starting materials are preferably selected to adjust the initial flow temperature of the thermoplastic polyurethane. The initial flow temperature can, for example, be adjusted by reducing the content of hard segments in the thermoplastic polyurethane.

[0064] According to the present invention, mixtures of polyols or mixtures of chain extenders can also be used to adjust the Petition 870250087664, dated 09 / 26 / 2025, pp. 146 / 177 17 / 42 initial flow temperature. Furthermore, the polyol structure can be adjusted by choosing suitable monomers or monomer mixtures to influence the initial flow temperature. Additionally, the molecular weight and / or chain length of the chain extender used can be adjusted to influence the initial flow temperature.

[0065] Adjusting the molecular weight of thermoplastic polyurethane by choosing an appropriate molar ratio of NCO / OH groups also influences the initial flow temperature. According to the present invention, two or more of these adjustments can also be used to obtain an ideal combination of hardness, initial flow temperature, and other properties.

[0066] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the isocyanate is an aromatic isocyanate, an aliphatic isocyanate, an alicyclic isocyanate and combinations thereof.

[0067] The isocyanate component may comprise one or more polyisocyanates. In some useful embodiments, the polyisocyanate component includes one or more diisocyanates. Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, cycloaliphatic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component includes one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is essentially free of, or even completely free of, aliphatic diisocyanates. In other embodiments, the polyisocyanate component includes one or more aliphatic diisocyanates and / or cycloaliphatic diisocyanates.

[0068] In some embodiments, the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates. In some embodiments, mixtures of aliphatic and aromatic diisocyanates may be useful. Examples of Petition 870250087664, dated 09 / 26 / 2025, pp. 147 / 177 Useful polyisocyanates include aromatic diisocyanates such as 4,4'-methylenebis(phenylisocyanate) (4,4'-MDI), 2,4-diphenylmethane diisocyanate (2,4-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), m-xylene diisocyanate (XDI), phenylene 1,4-diisocyanate (1,4-PDI), naphthalene-1,5-diisocyanate (NDI), 4,4'-diisocyanate-1,2-diphenylethane, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), and toluene diisocyanate (TDI); as well as aliphatic diisocyanates such as ethylene diisocyanate (EDI), 1,4-butane diisocyanate (BDI), and 1,6-hexamethylene diisocyanate (HDI), decane-1,10-diisocyanate, 1,12-dodecane diisocyanate (DDI), lysine diisocyanate (LDI); and cycloaliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI) and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). Isomers of these diisocyanates may also be useful. Mixtures of two or more polyisocyanates may be used. In some embodiments, the polyisocyanate is MDI and / or H12MDI.In some embodiments, the polyisocyanate consists essentially of MDI. In some embodiments, the polyisocyanate consists essentially of H12MDI.

[0069] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the aromatic isocyanate is more preferably selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-diphenylmethane diisocyanate and / or 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanate-1,2-diphenylethane, 1,5-naphthalene diisocyanate and combinations thereof.

[0070] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the aromatic isocyanate is more preferably 4,4'-diphenylmethane diisocyanate (4,4'-MDI).

[0071] According to another embodiment, the present Petition 870250087664, dated 09 / 26 / 2025, pp. 148 / 177 19 / 42 The invention is also directed to a process as disclosed herein, wherein the aliphatic isocyanate is more preferably selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-docecane diisocyanate and combinations thereof.

[0072] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the aliphatic isocyanate is more preferably 1,6-hexamethylene diisocyanate (HDI).

[0073] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the alicyclic isocyanate is more preferably selected from the group consisting of isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate and their corresponding isomer mixtures, 4,4'-, 2,4- and 2,2'-dicyclohexylmethane diisocyanate and their corresponding isomer mixtures and combinations thereof.

[0074] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the alicyclic isocyanate is more preferably 4,4'-dicyclohexylmethane diisocyanate (H12MDI).

[0075] Thermoplastic polyurethanes are also made using b) a polyol component. Polyols, which can be described as hydroxyl-terminated intermediates, useful in the present invention include polyester polyols, polyether polyols, polycarbonate polyols and combinations thereof. Polyester polyols are preferably linear polyesters. Hydroxyl-terminated polymeric intermediates having a number average molecular weight (Mn) preferably of about 300 to about 10,000, for example about 400 to about 8,000 Daltons, or for example about 500 to about 6,000 Daltons. The molecular weight is determined by assaying the functional groups. Petition 870250087664, dated 09 / 26 / 2025, pp. 149 / 177 20 / 42 terminals and is related to the number-average molecular weight. Unless otherwise indicated, the molecular weight can be determined by quantifying the terminal group or can be calculated from the OH number according to EN ISO 4629-1:2016 in the context of the present invention.

[0076] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the polyol is a polyol with a number average molecular weight between 0.4 x 103 g / mol and 6 x 103 g / mol, measured according to the quantification of the terminal group.

[0077] Suitable polyester intermediates can be produced by (1) an esterification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides, or (2) by transesterification reaction, i.e., the reaction of one or more glycols with dicarboxylic acid esters, or (3) ring-opening polymerization, for example, polycaprolactone diol (PCL-diol), polylactide diol (PLA-diol), etc. Molar ratios generally greater than one mole of glycol to acid are preferred in order to obtain linear chains with a preponderance of terminal hydroxyl groups. The dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or combinations thereof.Suitable dicarboxylic acids that can be used alone or in mixtures generally have a total of 4 to 44 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, isophthalic, terephthalic, cyclohexane dicarboxylic acid, fatty acid dimers, and the like. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used. The glycols that react to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of 2 to 44 or 2 to 36 carbon atoms. Suitable examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl Petition 870250087664, dated 09 / 26 / 2025, page 150 / 177. 21 / 42 1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, fatty diol dimer and mixtures thereof.

[0078] Suitable hydroxyl-terminated polyether intermediates include polyether polyols derived from a diol or polyol with a total of 2 to 15 carbon atoms. In some embodiments, the hydroxyl-terminated polyether is an alkyl diol or glycol that reacts with an ether comprising an alkylene oxide with 2 to 6 carbon atoms, typically ethylene oxide or propylene oxide or mixtures thereof. For example, the polyether with hydroxyl functionality can be produced by first reacting propylene glycol with propylene oxide, followed by subsequent reaction with ethylene oxide.

[0079] Primary hydroxyl groups resulting from ethylene oxide are more reactive than secondary hydroxyl groups and are therefore preferred. Useful commercial polyether polyols include poly(ethylene glycol) comprising ethylene oxide reacted with ethylene glycol, poly(propylene glycol) comprising propylene oxide reacted with propylene glycol, poly(tetramethylene glycol) comprising water reacted with tetrahydrofuran, which may be described as polymerized tetrahydrofuran and commonly referred to as PTMEG.

[0080] The suitable polyurethanes described herein are produced using, optionally, c) a chain extender component. Suitable chain extenders include low molecular weight diols (molecular weight less than 500 g / mol), diamines and combinations thereof. Suitable chain extenders include relatively small polyhydroxylated compounds, for example, lower aliphatic or short-chain glycols with 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol (EDO), diethylene glycol (DEG), propylene glycol (PDO), dipropylene glycol (DPG), 1,4-butanediol (BDO), 2-methyl-1,3-propanediol (MPO), 1,6-hexanediol (HDO), 1,3 Petition 870250087664, dated 09 / 26 / 2025, pp. 151 / 177 22 / 42 butanediol (1,3-BDO), 1,5-pentanediol (1,5-PDO), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyethoxy)phenylpropane (HEPP)], hexamethylenediol (HDO), heptanediol, nonanediol (NDO), dodecanediol (DDO), 3-methyl-1,5-pentanediol (MPD), hydroquinone bis(2-hydroxyethyl) ether (HQEE), ethylenediamine (EDA), butanediamine (BDA), hexamethylenediamine (HDA) and hydroxyethyl resorcinol (HER), and the like, as well as mixtures thereof. In some embodiments, the chain extender includes BDO, HDO, 3-methyl-1,5-pentanediol or a combination thereof. In some embodiments, the chain extender includes BDO. Other glycols, such as aromatic glycols, may be used.In some embodiments, the composition is formed using less than 40% by weight, for example, only less than 30% by weight, preferably less than 25%, for example, less than 15%, or even, for example, less than 12%, in particular less than 8% by weight of the total reagents of a chain extender. In some embodiments, the thermoplastic polyurethanes are essentially free or even completely free of chain extender.

[0081] According to another embodiment, the present invention is also directed to a process as disclosed herein, wherein the chain extender is selected from ethylene glycol, propanediol, butanediol, pentanediol, hexanediol or is a mixture thereof, more preferably the chain extender is butanediol, hexanediol, cyclohexane dimethanol (CHDM), hydroquinone bis(2-hydroxyethyl)ether (HQEE) or is a mixture thereof.

[0082] The thermoplastic polyurethanes used according to the present invention typically have a hard segment content of less than 50% by weight, preferably less than 40% by weight. Optionally, one or more polymerization catalysts may be present during the polymerization reaction. Generally, any conventional catalyst can be used. Petition 870250087664, dated 09 / 26 / 2025, pp. 152 / 177 23 / 42 is used to react the diisocyanate with polyol intermediates or the chain extender. Examples of suitable catalysts that particularly accelerate the reaction between the NCO groups of diisocyanates and the hydroxyl groups of polyols and chain extenders are conventional tertiary amines known in the prior art, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane and the like, and also in particular organometallic compounds, such as titanic esters, iron compounds, for example, ferric acetylacetonate, tin compounds, for example, stannous diacetate, stannous octoate, stannous dilaurate, bismuth compounds, for example, bismuth trineodecanoate, or dialkyltin salts of aliphatic carboxylic acids, for example, dibutyltin diacetate, dibutyltin dilaurate or the like.The commonly used amounts of catalysts are from 0.001 to 0.1 parts by weight per 100 parts by weight of the polyol component. In some embodiments, the reaction to form the thermoplastic PU used according to the present invention is substantially free or completely free of catalyst.

[0083] Various types of optional components may be present during the polymerization reaction and / or incorporated into the composition comprising the thermoplastic polymer described above to improve processing and other properties. These additives include, but are not limited to, antioxidants, such as phenolic types, rheology modifiers, such as hydrophobic or hydrophilic pyrogenic silica, and adhesion promoters, such as malonic acid, fumaric acid, chlorinated rubber, vinyl chloride / vinyl acetate copolymers, vinyl chloride / vinyl acetate / maleic acid terpolymers. Other additives may be used to improve the performance of the composition or the blended product, such as other resins, including, but not limited to, coumarone-indene or terpene-phenolic, which may help to increase the Petition 870250087664, dated 09 / 26 / 2025, pp. 153 / 177 24 / 42 tackiness of the hot melt adhesive and retard recrystallization time. All additives described above can be used in an effective amount typical for these substances.

[0084] Other additives may be used, including pigments, dyes, odors, fillers, bio-based and / or biodegradable additives, UV and heat stabilizers, flame retardants such as expandable graphite, additives that generate antistatic properties, electrical conductivity, additives that reduce dirt absorption, antimicrobial additives, wax, crosslinking agents, functionalized surface fillers, foaming additives such as Expancell®, heat-conducting additives and additives that can be irradiated by an electromagnetic field and / or radio frequency and / or microwaves.

[0085] Exemplary additives are mentioned in DE 10 2021 205 928 A1, such as heat-conducting additives, for example, a metal nitride, a metal oxide, a metal carbide, a metal sulfide, a metal silicate, a silicon carbide and silicon nitride, particularly preferably boron nitride, BN, SILATHERM® (a mixture of Al2O3 and SiO2) or SILATHERM®Advance. Exemplary electrically conductive additives are a mixture of a carbon material and an inorganic material, carbon fiber, glassy carbon, carbon nanotubes, carbon nanobuttons, aerographite, linear acetylenic carbon, q-carbon, graphene, a salt, a monocrystalline powder, a polycrystalline powder, an amorphous powder, a glass fiber.

[0086] Additives can be incorporated into the components or reaction mixture for the preparation of the thermoplastic polymer and then melted, or they can be incorporated directly into the thermoplastic polymer melt.

[0087] Thermoplastic polyurethane can be manufactured by any method known to those skilled in the art, such as, for example, Petition 870250087664, dated 09 / 26 / 2025, pp. 154 / 177 25 / 42 batch processes, REX line procedure or Belt line procedure. For example, the components: (a) the diisocyanate component, (b) the polyol component and (c) the optional chain extender component react with each other to form the thermoplastic PU useful in this invention. Any known processes for reacting the reagents can be used to produce the thermoplastic PU. In one embodiment, the process is termed “oneshot”, in which all reagents are added, mixed and reacted. The weight equivalent of the diisocyanate relative to the total weight equivalent of the hydroxyl-containing components, i.e., the polyol intermediate and, if included, the glycol chain extender, can be from about 0.5 to about 1.30, or from about 0.6 to about 1.20, or from about 0.7 to about 1.10.Reaction temperatures using a urethane catalyst can be from about 175 °C to about 245 °C, preferably from 180 °C to 220 °C in the reaction zone of a twin-screw reactive extruder (REX line) procedure; or from about 80 °C to about 160 °C, preferably from 90 °C to 150 °C in the reaction zone of a belt line procedure.

[0088] As another example, thermoplastic PU can also be prepared using a prepolymer process.

[0089] In the prepolymer route, the polyol component is reacted with a generally equivalent excess of one or more diisocyanates to form a prepolymer solution with free or unreacted diisocyanate in the presence of a suitable urethane catalyst. Subsequently, a chain extender, as noted above, is added in an equivalent amount, generally equal to the terminal isocyanate groups, as well as any free or unreacted diisocyanate compounds. The overall equivalent ratio between the total diisocyanate and the total equivalent of the polyol intermediate and the chain extender is therefore from about 0.5 to about 1.30, or about Petition 870250087664, dated 09 / 26 / 2025, pp. 155 / 177 26 / 42 0.6 to about 1.20, or from about 0.7 to about 1.10. Typically, the prepolymer route can be carried out in any conventional device.

[0090] The process described for the preparation of thermoplastic PU includes both the “pre-polymer” process and the “one-shot” process, in batch or continuous form. That is, in some embodiments, thermoplastic PU can be produced by the reaction of the components in a “one-shot” polymerization process, in which all components, including the reagents, are added simultaneously or substantially simultaneously to a mixer and react to form the thermoplastic PU. While in other embodiments, thermoplastic PU can be produced by the initial reaction of the polyisocyanate component with part of the polyol component, forming a pre-polymer, and then completing the reaction by the reaction of the pre-polymer with the remaining reagents, resulting in the thermoplastic PU.After exiting the extruder, the composition can be pelletized and stored, eventually being sold in pellet form; or it can be extruded directly from the reaction extruder through a die, forming a final product profile.

[0091] For better recycling reasons, it is preferable that the chemical nature of the particles and the coating be the same, especially a PU hot melt adhesive and eTPU particles.

[0092] Another aspect of the present invention is a process for preparing a molded body comprising the steps of: b1) coating particles according to the process of the present invention; b2) mold the particles obtained in step bi).

[0093] Preferably, the shaping in step b2) is carried out by steam-free thermopressing, steam box molding and / or by means of an electromagnetic field, especially radio frequency, preferably by Petition 870250087664, dated 09 / 26 / 2025, pages 156 / 177 27 / 42 steam-free heat pressing.

[0094] Preferably, thermopressing (also called hot pressing or thermal pressing) is carried out at a temperature of 60 °C to 160 °C, more preferably 80 °C to 160 °C, even more preferably 90 °C to 140 °C, even more preferably 100 °C to 140 °C.

[0095] Preferably, after thermopress molding, the resulting molded bodies are cooled to room temperature, which can improve mechanical properties.

[0096] Preferably, the molded body is a composite material of the particles with other materials, such as textiles, leather, a thermoplastic film, or parts containing metals, especially electronic parts.

[0097] Another aspect of the present invention relates to a method for arranging a molded body comprising the steps of: (ci) prepare a molded body according to the process of the present invention; c2) disassemble the particles by subjecting the molded body to heat, preferably placing the particles in contact with hot water, which may optionally contain a surfactant.

[0098] The particles at least partially coated according to the present invention can be used pure, as a mixture of different particles and / or other materials to obtain 3D parts, such as the molded bodies of the present invention, for various uses, including industrial, consumer, transport and construction applications, used alone or as a component for sealing, insulation of, for example, houses, ducts or gas tanks, part of a shoe, shoe midsole, shoe insole, combined shoe sole, bicycle seats, bicycle tires, damping element, shock protection, Petition 870250087664, dated 09 / 26 / 2025, pages 157 / 177 28 / 42 sound and vibration dampers, decoration, furniture, upholstery, mattresses, yoga mats, lining, rail pads, handles, protective sheet, packaging, fall protection, automotive interior and exterior, headliner, armrest, door lining, seats, battery compartment, sporting equipment, balls, tennis racket, baseball bat, treadmill, toys, flooring, running tracks, synthetic grass, playgrounds, sports gyms and sidewalks.

[0099] Consequently, another aspect of the present invention is the use of a storage-stable particle, at least partially coated, or a molded body of the present invention for industrial, consumer, transport and / or construction applications, especially for the uses mentioned above. Brief Description of the Figures

[00100] Figure 1 shows a structural drawing of the Shimadzu. Flowtester CFT-500EX: 1. stopper die hole; 2. cylinder; 3. heater; 4. matrix; 5. die press; 6. piston; 7. pressure joint; 8. Load axle; 9. Temperature detector; 10. Potentiometer (for stroke detection); 11. Load lever; 12. air cylinder for weight lifting; 13. solenoid valve; 14. equilibrium weight; Petition 870250087664, dated 09 / 26 / 2025, pp. 158 / 177 29 / 42 15. wheel assembly; 16. Control unit (CPU); 17. weight; and 18. fulcrum of the movement.

[00101] It consists of the main unit that heats and pressurizes the sample inserted into the cylinder, extrudes the molten sample through the die orifice for testing, and the control unit that calculates the shear rate and viscosity based on measured data relating to cylinder temperature and piston travel distance.

[00102] The sample is loaded into the cylinder and heated by the external heater. The force generated by the weight is multiplied by the loading lever, applied to the piston via the loading shaft, and extrudes the sample through the die orifice. The piston stroke is detected by the potentiometer.

[00103] The potentiometer value is read by the instrument's control unit. The flow rate is then calculated from the relationship between the extrusion time and the piston stroke to obtain the shear rate and viscosity.

[00104] The load mechanism generates a load force 10 times greater than that of the weights, combining the wheel assembly with a 1:2 lever ratio and the load lever with a 1:5 lever ratio. The wheel assembly and the load lever operate in unison via the connecting steel strip. As the upper and lower parts of the load shaft are fixed with guide bearings, the load shaft moves vertically, but its horizontal movement is restricted. When the weight-lifting cylinder is going up or down, the load force is not generated by the weights. However, when the cylinder is going down, the load force is generated on the load shaft, which extrudes the sample. When the load shaft goes up and down, the fulcrum of the weight lever moves horizontally about the point of Petition 870250087664, dated 09 / 26 / 2025, pp. 159 / 177 30 / 42 flat support to prevent any force other than horizontal from being applied to the load axis.

[00105] Figure 2 shows a schematic view of the cylinder unit. The cylinder (c) comprises the die holder (dh) and the heater (h). The sample(s) is / are placed between the die (d) and the piston (p).

[00106] Figure 3 shows a schematic view of the die. The die (d) has a length (dl), a die hole diameter (ddi) and a die width (do).

[00107] Figure 4 shows a schematic flow test curve using a constant heating rate method. The piston stroke (PS, y-axis) is plotted as a function of temperature (T, x-axis). Points A and B mark the preheating period. B and C determine the softening region. Between points C and D, there is a non-flow region. Starting at D and continuing to point E, a flow region is shown. The softening temperature (Ts) and the initial flow temperature (Tfb) are also marked.

[00108] Figure 5 shows a configuration involving a more direct coating unit, consisting of a jacketed thermofuse container (19) of up to 170 ml and 4 bar, connected to a Schlick atomizing nozzle (20), which is heated by a gas heater (21) and process air (arrows). A plowshare (22) was chosen to allow complete mixing properties until the granules are free of stickiness. The setting temperature is controlled by a thermostat (23). Examples Materials used: 1) Polyurethane-based hot melts:

[00109] All selected PU hot melts are non-sticky at room temperature; they remain stable under conditions of Petition 870250087664, dated 09 / 26 / 2025, pp. 160 / 177 31 / 42 storage and are activated with increasing temperature. Unlike cross-linked TPU, the mechanical properties (hardness, tensile strength...) are determined by hydrogen bonds (or other intermolecular forces, such as VDW and π-π interaction) between the polymer chains, which are reversible. The following properties are specified for the selected hot melts: Thermal fuse 1: • It consists of polyester made from adipic acid and butanediol with F = 2 and Mn : 3000 g / mol, 1,4-butanediol (BDO) and methylene diphenyl diisocyanate (4-4'-MDI); • Hardness: 96A / 45D; • Hard segment: ~6%; • Lamination temperature: 100 - 110 °C; • Melting point: ~50 °C; • Tfb: 80 °C; Thermal fuse 2: • It consists of polyester made from adipic acid and butanediol with F = 2 and Mn: 1000 g / mol, HDO and 4,4'-MDI; • Hardness: 80A; • Hard segment: ~15%; • Lamination temperature: 110 - 150 °C; • Tfb: 105 °C; Thermal fuse 3: • It consists of a polyester made of adipic acid and butanediol with F = 2 and Mn: 1000 g / mol, PTHF 1000 g / mol and F = 2, BDO and a 50 / 50 mixture of 4,4'-MDI and 2,4'-MDI; • Hardness: 60A; • Hard segment: ~26%; Petition 870250087664, dated 09 / 26 / 2025, pp. 161 / 177 32 / 42 • Lamination temperature: 110 - 120 °C; • Tfb: 95 °C; Thermal fuse 4: • It consists of polyethylene glycol with Mn: 3400 g / mol and F=2, BDO and 4,4'-MDI; • Hardness: 96A / 45D; • Hard segment: ~9%; • Melting point: ~50 °C; Thermal fuse 5: • It consists of polyester made from adipic acid and butanediol with F = 2 and Mn: 5000 g / mol and 4,4'-MDI; • Hardness: 97A / 50D; • Hard segment: 0%; • Melting point: ~60 °C; • Tfb: 60 °C; Thermal fuse 6: • It consists of polyester made from adipic acid and butanediol with F = 2 and Mn: 1000 g / mol, BDO and hexamethylene diisocyanate (1,6-HDI); • Hardness: 90A; • Hard segment: ~7%; • Melting point: ~110 °C; • Tfb: 110 °C.

[00110] The hardness of the PU hot melts was measured according to the ASTM D2240-15 standard test method for rubber properties - Durometer hardness.

[00111] The amount of hard segments (HS) in % by weight was calculated according to the following equation, where m(CE) is the mass in g / mol of the chain extender, m(iso) is the mass in g / mol of the isocyanate in (polyol) Petition 870250087664, dated 09 / 26 / 2025, pp. 162 / 177 33 / 42 the mass in g / mol of the polyol: Equation 1: m(CE) + m(iso reacted with CE) m(polyol) + m(CE) + m(iso)

[00112] The melting point was measured via DSC according to ASTM. D3418 - 12 Standard test method for transition temperatures and enthalpies of fusion and crystallization of polymers by differential scanning calorimetry, heating rate: 10 °C / min, cooling rate: 10 °C / min.

[00113] The molecular weight of the polyols was calculated from their hydroxyl number, which was measured according to the ASTM E1899-16 standard test method for hydroxyl groups using reaction with p-toluenesulfonyl isocyanate (TSI) and potentiometric titration with tetrabutylammonium hydroxide: Equation 2: , (V2 -V1 )*N* 56.1 number of hydroxyl groups (OH#) =---------------sample, g with N = concentration of Bu4NOH in meq / mL, Vi = mL of Bu4NOH for the first potentiometric endpoint, V2 = mL of Bu4NOH for the second potentiometric endpoint, and sample, g = sample mass in grams. Equation 3: / g\ 56100 *number of OH groups per mole is molecular weight (mol) =-----------------Oh#----------------Preparation of PU thermofuses

[00114] A mixture of each component was heated to 80 °C, under stirring, using a paddle mixer (SHIN KWANG GR-150R) for 1 to 5 minutes at a rotation speed of 500 to 1,000 revolutions per minute (rpm). The TPU HMA was then discharged. The TPU HMA was subjected to post-heat treatment at 100 °C for 1 to 5 hours and then pelletized. Petition 870250087664, dated 09 / 26 / 2025, pp. 163 / 177 34 / 42 Polyester heat-fusible adhesive

[00115] Dynacoll® 7130 hot melt adhesive: Solid, amorphous, saturated copolymer. Chemical structure according to WO 2009 / 010324 A1; Temperature: 30 °C; OH count: 35 mg KOH / g Example 1 - Measurement of the initial flow temperature (Tfb)

[00116] The initial flow temperature (Tfb) of a sample is measured by placing one or more samples in a hollow cylinder with a die comprising a channel, allowing the molten sample to flow through this channel, placing the sample under a piston in the hollow cylinder with a load, heating the sample until it melts and flows through the channel, and determining the temperature at which the sample begins to flow (= initial flow temperature (Tfb)).

[00117] The experimental setup is described in JIS K 7311 and JIS K 7210 standards. The general configuration of the apparatus used is shown in Figure 1. A concentric hollow heatable cylinder with a piston in this hole as shown in Figure 2. The cylinder hole is closed at the bottom with a die comprising a channel as described in detail in Figure 3. This cylinder is placed in a device to determine Tfb. The device is constructed to allow the die channel to be closed by screwing the die presser into the bottom of the cylinder and pressing the die to fit perfectly to the bottom of the cylinder. Closing the die channel is important to remove air from the sample before the start of the experiment. Air removal is done by compressing the sample in the cylinder hole with a piston being pressed towards the die with a specific load without increasing the cylinder temperature.After removing the air, the piston with a specific load is placed in the sample, and the sample is heated by heating the cylinder with a constant increase in temperature. Petition 870250087664, dated 09 / 26 / 2025, pp. 164 / 177 35 / 42 parallel tracing the temperature around the sample. As soon as the sample reaches the initial flow temperature (Tfb), the melt begins to flow through the die channel by the pressure of the piston loaded with the specific charge. The temperature at which the piston begins to move is detected by a suitable motion detection means. The temperature at which the piston begins to move is the initial flow temperature (Tfb).

[00118] The device used in all experiments is the Shimadzu CFT-500D, from Shimadzu Corporation, Tokyo, Japan. The sample was collected and cut into pieces with a maximum diameter not exceeding the diameter of the cylinder, preferably not exceeding 5 mm and, more preferably, not exceeding 2 mm. The temperature of the cylinder with the piston was conditioned to 30 °C + / - 2 °C well before the measurement.

[00119] 1.9 g of cut pieces of the sample were placed in the hole of the preheated cylinder closed with a die with a 1 mm channel (details see Figure 1). A plunger rod was used to bring the sample to the bottom of the hole. The hole with the sample was then closed with the piston. The die used in this measurement has Di = 1 mm, Dl = 10 mm, as shown in Figure 3.

[00120] The die channel was then closed with the means to close the channel and the air was removed from the sample by repeatedly pressing the piston 3 times towards the sample with a load of 100 kg. Then, the channel closing means was removed to reopen it.

[00121] The sample under the piston with a load of 100 kg was then held at a temperature of 30 °C for 240 seconds. Subsequently, under a continuous load of 100 kg, the sample was heated at a heating rate of 3 °C / min and the temperature near the sample was continuously plotted.

[00122] The initial flow temperature (Tfb) is the temperature at which the piston began to move under load when the molten sample began to Petition 870250087664, dated 09 / 26 / 2025, pages 165 / 177 36 / 42 pass through the matrix channel. A typical diagram for determining the initial flow temperature (Tfb) can be obtained in Figure 4.

[00123] It is not mandatory to use the Shimadzu CFT-500D, from Shimadzu Corporation, Tokyo, Japan, to measure the initial flow temperature (Tfb). Other devices with similar cylinder geometry will lead to the same initial flow temperature (Tfb) results within the scope of this invention. Example 2 - Experiments with hot melt adhesive solutions Preparation of a polyurethane hot melt adhesive solution

[00124] Dissolve the selected polyurethane melting compound in the MEK solution, adjust the amount of PU melting compound to achieve a solution viscosity of 50-100 (cps, 25°C), using a Brookfield viscometer to measure the solution viscosity (the TPU melting compound is already dissolved in the MEK solution), with a 61 LV spindle at 30 rpm, the solids content of this solution is 5-15% w / w Hot melt coating on eTPU spheres by means of solution coating

[00125] The selected PU hot melt adhesive was dissolved in MEK solution, the viscosity of which should be less than 100 cps (25 °C), which can be achieved by adjusting the solids content. The above solution was mixed with eTPU spheres (manufactured according to WO 2013 / 153190 A1, Infinergy 230 based on diisocyanate 4, BDO and polyol 1, BASF SE) using a mechanical stirrer for 30 seconds at room temperature. The spheres were dried on a Teflon-coated plate at room temperature (RT), taking care to isolate them from each other. After 5 to 20 minutes of drying, the coated spheres are free of stickiness and stable for storage. The amount of hot melt coating was 7% to 12% for the spheres. Heat press molding

[00126] Place the coated eTPU spheres on the plate of Petition 870250087664, dated 09 / 26 / 2025, pages 166 / 177 37 / 42 shoe cavity and then mold with a heat press under the specified conditions: • Temperature: 120, 130, 140, 150 °C; • Warm-up time: 10-15 minutes; • Cooling time: 5 - 15 min.

[00127] eTPU spheres coated with hot melt adhesive 1 and 2, according to the procedure described in experiment 2, were hot-pressed (15 minutes, heating at 140 °C and 15 minutes of cooling, mold temperature of 140 °C). The mechanical properties are presented in the table below. For comparison, an eTPU plate manufactured by steam immersion molding is presented. Table 1 Forming Process Coating Agent Tensile Strength (MPa)* Elongation at Break (%)* Hot Press Molding Hot Melt Melt 1 7.7% w / w in sphere 2.6 360 Hot Press Molding Hot Melt 2 11% w / w in sphere 2.3 340 Steam Box Molding - 1.2 211 * in accordance with ASTM D412-16 (2021): “Standard test methods for vulcanized rubber and thermoplastic elastomers, and using an eTPU strip with dimensions: 10.5x2.5x1.5 cm3 (length, width, depth). Example 3 - Experiment with melted hot melt adhesive and spray coating

[00128] The configuration shown in Figure 4 was used and successfully tested with the non-reactive commercial hot melt adhesive Dynacoll®7130. The configuration operates at a maximum temperature of 200 °C and a viscosity of 10 mPas. The thermoplastic particle foams (eTPU foam particles) were tempered at 80 °C before the coating step. The following conditions were used: Petition 870250087664, dated 09 / 26 / 2025, pages 167 / 177 38 / 42 Final product: eTPU coated with Dynacoll® 7130; Apparent density: 0.120 kg / l; Product quantity: 2000 g; Coating quantity: 113.0 g (5.65%); Transfer rate: 5 g / min.; Atomized air absorption rate: 70%; Atomized air pressure: 3.3 bar; Outlet temperature of gas heater T1: 165 °C; Gas control for T2 nozzle: 168 °C; Gas pressure from T3 nozzle in front of the nozzle: 166 °C; Temperature of the hot melting vessel: 165 °C; Hot melt vessel under pressure: 2.5 bar; Mixer: plow mixer; Mixer revolutions per minute: 50 rpm.

[00129] Coated eTPU spheres were obtained.

[00130] The same experiment was repeated with a coating quantity of 7%. Experiment 4 - Coating eTPU spheres using a SPRAY GUN AND KITCHEN MIXER

[00131] The 5-point thermal fuse in granular form was placed in the cartridge unit (TR 80 LCD cartridge) of a spray gun (Reka Klebetechnik). The 5-point thermal fuse was melted at a temperature of 160 °C and then sprayed using a pressure of 6 bar.

[00132] 100 g of eTPU spheres (manufactured according to WO 2013 / 153190 A1, Infinergy 230 based on diisocyanate 4, BDO and polyol 1, BASF SE) were placed in a food processor (Cooking Chef XL KCL95) and kept at room temperature, under movement, with the aid of a paddle mixer. The molten melt was sprayed onto the Petition 870250087664, dated 09 / 26 / 2025, pp. 168 / 177 39 / 42 spheres, which remained in motion for a period of two minutes. A coating quantity of 10% w / w was obtained.

[00133] The same procedure was repeated while maintaining the temperature of the spheres during the spraying process at 70 °C, which led to a better distribution of the hot-melt coating on the eTPU spheres.

[00134] The same procedure, maintaining the eTPU spheres at 70 °C during the spraying process, was repeated using the thermal fuse 6 Experiment 5 - Making plates using eTPU spheres COATED

[00135] 65 g of eTPU spheres, coated with thermofusible 6, according to experiment 4, were placed in a preheated mold with dimensions (16.3 x 9.6 x 3.3 cm3 (length, width, depth)). The filled mold was covered with a mold lid, which allows for 50% compression / compaction. The time in the heated press and the residual time for cooling the 3D parts before demolding are summarized in the following table.

[00136] For reference, 65 g of eTPU spheres, as per WO 2013 / 153190 A1, were placed in a preheated mold with dimensions of 16.3 x 9.6 x 3.3 cm3 (length, width, depth). The filled mold was covered with a mold lid, which allows for 50% compression / compaction. This results in a plate with the following dimensions: 16 x 9.5 x 1.6 cm3. Three-dimensional hot-pressed molded parts obtained from uncoated eTPU spheres are reported respectively.

[00137] Tensile strength and elongation measured according to ASTM D 5035:2011, where instead of fabric strips (150 x 25.4 x 1.6) mm3 eTPU strips were used, rebonding measured according to DIN 53512:2000-4 and the density of the 3D parts obtained, measured according to DIN Petition 870250087664, dated 09 / 26 / 2025, pp. 169 / 177 40 / 42 EN ISO 845:2009-10, are also reported below. Table 2 Thermofusible Experiment 6 Temperature [°C] Heating Time [min] Cooling Time [min] Tensile Strength [MPa] Elongation [%] Re-bonding [%] Density [g / cm3] 5.1 10% 140 10 5 1.54 289 71 0.29 5.1-C 0% 140 10 5 0.7 100 73 0.29 Experiment 6 - Coating of eTPU spheres by means of powder coating with THERMOFUSIBLE PU POWDER

[00138] The selected PU 6 hot melt adhesive was ground to a fine powder (100 to 600 µm). The powder was mixed with eTPU spheres (manufactured according to WO 2013 / 153190 A1, Infinergy 230 based on diisocyanate 4, BDO and polyol 1, BASF SE) in a defined weight ratio to achieve a coating quantity of 5% w / w, 10% w / w and 15% w / w, respectively. The eTPU spheres were preheated to at least 120 °C. After homogeneous mixing, residual powder was removed by filtration. The coated spheres are residue-free and stable during storage. The hot melt coating quantity was 5% to 15% for the spheres.

[00139] Using eTPU coated spheres with hot melt 6 (10.8% w / w coating on the sphere), plates were produced by heat press molding according to the procedure described in experiment 2. The mold temperature was maintained at 110 °C for 15 minutes with a cooling time of 9 minutes.

[00140] The following mechanical data were obtained: Table 3 Forming process Coating agent Tensile strength (MPa)* Elongation at break (%)* Hot pressing molding Thermofusible 6 10.8% w / w in the sphere 2.2 515 Petition 870250087664, dated 09 / 26 / 2025, pages 170 / 177 41 / 42 Forming process Coating agent Tensile strength (MPa)* Elongation at break (%)* Steam box molding - 1.2 211 * in accordance with ASTM D412-16 (2021): “Standard test methods for vulcanized rubber and thermoplastic elastomers, and using an eTPU strip of dimension: 10.5x2.5x1.5 cm3 (length, width, depth). Experiment 7. Production of heat-fusible coated spheres with a different chemical nature than ETPU.

[00141] In additional coating experiments, according to the procedure described in Examples 2, 3 and 4, other spheres different from eTPU were used. The same experimental setup was used for the coating: loose ePA spheres (produced by the procedure described in WO 2021 / 052881 A1), loose expanded ePP spheres (Neopor, BASF), eTPO (Argilix-O, JSP), loose expanded ePS spheres (Styropor) and loose eTPA spheres (produced by the procedure described in WO 2017 / 220671 A1).

[00142] Coated sphere plates were produced according to experiment 5, using the same sphere art or mixing spheres of different chemistry coated with the same hot melt. Experiment 8 - Making a composite (plate / textile) using eTPU spheres coated with hot melt adhesive.

[00143] A piece (16.3x9.6cm2) of cotton canvas (0.45 mm thick, standard cotton fabric, Type 10A from Fa. Rocholl) was placed in the mold described in experiment 5. Then, the coated eTPU spheres were inserted into the mold preheated to 140 °C and a plate was made according to the procedure described in experiment 5. A plate, glued to the cotton canvas fabric, was made. Petition 870250087664, dated 09 / 26 / 2025, pp. 171 / 177 42 / 42 Experiment 9 - Detachment of eTPU coated with spheres coated with THERMO-FUSIBLE

[00144] An eTPU board bonded with cotton canvas, according to experiment 7, was placed in a preheated oven at a temperature of 30 minutes. The board remained in the oven for 30 minutes. After removing it from the oven, the cotton canvas was easily delaminated manually from the eTPU board.

[00145] Alternatively, an eTPU plate, bonded to cotton canvas fabric, as in experiment 7, was placed in a water bath maintained at a temperature of 80 °C under agitation (650 rpm). After 30 minutes, delamination of the plate from the fabric was observed.

[00146] The same procedure was repeated, maintaining the temperature of the batch of water at 90 °C. After 30 minutes, not only was the tissue delaminated from the plate, but also the spheres of the plates were separated from each other and recovered.

[00147] The same procedure, repeated while maintaining the water batch temperature at or below 60°C, did not result in delamination or disassembly of the spheres. This ensures the stability of the assembly throughout its service life, including in washing cycles at temperatures equal to or below 60°C. Petition 870250087664, dated 09 / 26 / 2025, pp. 172 / 177

Claims

1 / 4 Claims 1. PROCESS FOR PREPARING STABLE PARTICLES in storage of a moldable thermoplastic particle foam, at least partially coated with a hot melt adhesive, characterized by comprising the steps of a1) placing the moldable thermoplastic particle foam particles in contact with the hot melt adhesive, wherein the hot melt adhesive is a composition comprising a thermoplastic polymer, to obtain the coated particles of the moldable thermoplastic particle foam; a2) moving the coated particles of the moldable thermoplastic particle foam until they become free of stickiness.

2. PROCESS, according to claim 1, characterized in that the moldable thermoplastic particle foam has a glass transition temperature (Tg) below 100 °C, measured via DSC in accordance with DIN EN ISO 11357-3:2013.

3. PROCESS, according to any one of claims 1 to 2, characterized in that the fusible adhesive is a non-reactive fusible adhesive.

4. PROCESS, according to any one of claims 1 to 3, characterized by the hot-melt adhesive being placed in contact in the form of its molten state.

5. PROCESS, according to any one of claims 1 to 4, characterized in that the melt-melt adhesive in its molten state has a viscosity in the range of 0.1 mPas to 800,000 mPas, preferably in the range of 1 mPas to 600,000 mPas, more preferably in the range of 10 mPas to 500,000 mPas, measured at 160 °C using a Brookfield viscometer. Petition 870250087664, dated 09 / 26 / 2025, pp. 173 / 177 2 / 4 6. PROCESS, according to any one of claims 1 to 3, 5, characterized in the hot-melt adhesive being brought into contact in the form of its solid state by powder coating.

7. PROCESS, according to any one of claims 1 to 3, 5, characterized in that the hot melt adhesive is placed in contact in the form of a solution, in which the hot melt adhesive is dissolved in an organic solvent, followed by the step of: a3) removing the organic solvent and / or drying the moldable thermoplastic foam particles after step a2) at a temperature below the softening point of the hot melt adhesive to obtain the coated particles of moldable thermoplastic foam particles.

8. PROCESS, according to any one of claims 1 to 7, characterized in that the moldable thermoplastic particle foam is an expanded thermoplastic elastomer, preferably an expanded thermoplastic polyurethane.

9. PROCESS, according to any one of claims 1 to 8, characterized in that in step a1) the contact is made by mixing or spraying.

10. PROCESS, according to any one of claims 1 to 9, characterized in that the particles of the moldable thermoplastic particle foam are at least partially coated with a coating in an amount of 0.1% by weight to 40% by weight based on the total weight of the moldable thermoplastic particle foam and the coating.

11. PROCESS, according to any one of claims 1 to 10, characterized in that after step a1) and before step a2) the particles of the moldable thermoplastic particle foam are separated from each other. Petition 870250087664, dated 09 / 26 / 2025, p. 174 / 177 3 / 4 12. PROCESS, according to any one of claims 1 to 11, characterized by the thermoplastic polymer serum thermoplastic polyurethane.

13. PROCESS, according to any one of claims 1 to 12, characterized in that the composition comprises the thermoplastic polymer having an initial flow temperature (Tfb) in the range of 50 °C to 160 °C, preferably in the range of 60 °C to 160 °C, more preferably in the range of 70 °C to 160 °C, most preferably in the range of 70 °C to 150 °C.

14. PROCESS FOR PREPARING A MOLDED BODY, characterized by comprising the steps of b1) coating particles of a moldable thermoplastic particle foam according to the process as defined in any one of claims 1 to 13; b2) molding the particles obtained in step b1).

15. PROCESS, according to claim 14, characterized in that the shaping in step b2) is carried out by steam-free thermopressing, steam box molding and / or by means of an electromagnetic field, especially radio frequency, preferably by steam-free thermopressing.

16. PROCESS, according to any one of claims 14 to 15, characterized in that the thermopressing is carried out at a temperature of 60 °C to 160 °C, preferably 80 °C to 160 °C, more preferably 90 °C to 140 °C, most preferably 100 °C to 140 °C.

17. PROCESS, according to any of claims 14 to 16, characterized in that the molded body is a composite material of moldable thermoplastic foam particles with other materials, such as textiles, leather, a thermoplastic film or parts containing metals, especially electronic parts.

18. A moldable thermoplastic foam particle, at least partially coated and stable during storage, which is at least partially coated with a hot melt adhesive, characterized in that the hot melt adhesive is a composition comprising a thermoplastic polymer and in which the coated particle of the moldable thermoplastic foam particle is free from stickiness, preferably a non-reactive hot melt adhesive.

19. MOLDED BODY, characterized by being obtained from a process as defined in any one of claims 14 to 17, or obtained by molding particle foams as defined in claim 18.

20. USE OF A stable particle in storage, at least partially coated with a moldable thermoplastic particle foam, as defined in claim 18, or a molded body, as defined in claim 19, characterized by being for industrial, consumer, transportation and / or construction applications. Petition 870250087664, dated 09 / 26 / 2025, pp. 176 / 177

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