Fabrication of moldable thermoplastic particle foams with storage stability, particles and molded objects, and the use of the same.

Abstract

The present invention relates to a method for producing moldable thermoplastic particle foam particles with storage stability, which are at least partially coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, the method comprising: a1) contacting particles with a hot melt adhesive to obtain coated particles; and a2) moving the coated particles until the particles lose their adhesive properties. The present invention also relates to a method for producing moldable thermoplastic particle foam particles with storage stability, which are at least partially coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive, wherein the coated particles do not have adhesive properties, as well as molded bodies that can be obtained by the above method, and the use of the above particles and molded bodies.

Description

Technical Field

[0001] The present invention relates to a method for producing storage-stable particles (also referred to herein as "beads") of a moldable thermoplastic particle foam, at least partially coated with a hot-melt adhesive, preferably a non-reactive hot-melt adhesive, comprising: a1) contacting the particles with the hot-melt adhesive to obtain coated particles; and a2) moving the coated particles until the particles lose their adhesiveness. The present invention also relates to particles of a moldable thermoplastic particle foam, at least partially coated with a hot-melt adhesive, preferably a non-reactive hot-melt adhesive, wherein the coated particles have no adhesiveness and can preferably be obtained by the above method, and to a method for producing a shaped body, and to a shaped body obtainable by the above method, and to the use of the above particles and shaped bodies.

[0002] The moldable thermoplastic particle foam is used, for example, in the production of any solid foam body, such as a sports mat, a body protector, a lining element in an automotive structure, an acoustic and vibration damper, a packaging or a shoe sole.

[0003] In conventional methods, foam particles are filled into a mold, and subsequently, the surfaces of the individual foam particles are melted by heat action to bond the particles together and form a particle foam part. Thus, in addition to simple products, it is possible to produce complex semi-finished products or molded articles having undercuts.

[0004] Moldable thermoplastic particle foams are known in the art and are described, for example, in Robin Britton (Author), Update on Moldable Particle Foam Technology, Rapra Technology Ltd, 2009. Foamed thermoplastic elastomers, in particular foamed thermoplastic polyurethanes (eTPUs), are representative of certain moldable thermoplastic particle foams.

[0005] Foamed thermoplastic elastomers are known in the art. For example, International Publication No. 2018 / 082984 describes a particle foam based on a foamed thermoplastic elastomer. International Publication No. 2008 / 087078 describes a hybrid system consisting of a foamed thermoplastic elastomer and polyurethane. Hybrid eTPU systems are also described in Chinese Patent Application Publication No. 109337343, Chinese Patent Application Publication No. 110240795, and Chinese Patent Application Publication No. 109080061.

[0006] An exemplary thermoplastic polymer is foamed thermoplastic polyurethane (eTPU), which is commercially available, for example, sold by BASF under the name Infinergy®. eTPU particles primarily represent closed-cell or fully closed-cell particle foams. Thermoplastic polyurethane (e.g., Elastollan®) can be foamed to produce particle foams that can be processed using standard molding machines. Standard eTPU grades absorb only small amounts of water due to their closed particle surface and the chemical properties of the TPU used. Like the base TPU, eTPU can also feature high elongation at break, tensile strength, and abrasion resistance, along with good chemical resistance.

[0007] Rapid prototyping of 3D objects made from foamed thermoplastic elastomers is currently not easily achievable. Typically, isocyanate-containing binders or appropriate machinery such as steam and steam chest molding machines are used to bond particles together. Neither approach is readily available due to health and safety concerns, energy costs, or the difficulty in obtaining appropriate machinery (steam chest molding machines). Furthermore, while the use of steam only allows for the molding of particles of the same type, coating eTPU particles or using aqueous binders can enable the bonding of eTPU particles of different types (glass transition temperature, melting point) and sizes, as well as different TPUs or different particle forms, such as different mixtures of eTPS, ePS, ePP, eTPA, eTPC, eTPO, etc. By applying coatings, it is also possible to adjust mechanical properties and applicability by directly incorporating additives, such as pigments or dyes, flame retardants or antistatic agents, into the particle surface. For example, fillers can increase the rigidity of the final part, and the use of additives that can be excited by an electromagnetic field, for instance, enables the moldability of the coating, thereby reducing the energy required for molding.

[0008] As additives, pigments, dyes, odors, fillers, bio-based and / or biodegradable additives, UV stabilizers, heat stabilizers, flame retardants such as expandable graphite, additives that provide antistatic properties and electrical conductivity, additives that reduce dirt adsorption, antimicrobial additives, waxes, crosslinking agents, surface functionalizing fillers, foaming additives such as Expansell®, and additives that can withstand irradiation from electromagnetic fields and / or high-frequency and / or microwaves may be used.

[0009] International Publication No. 2022 / 223438 and European Patent Application No. 22202204.8 describe various aqueous binders for coating particles that can be shaped into the above-mentioned 3D parts.

[0010] U.S. Patent No. 6,616,797 describes the formation of adhesive bonds by a process involving the application of a dispersion containing a polyurethane having structural units of formula (I) to a surface. The dispersion is first coated onto the surface to form a coating. The coating is dried to obtain a substantially anhydrous coating. The dried coating is then subjected to thermal activation. Adhesive bonds are formed by bonding the thermally activated coating to itself or another surface. However, particulate coatings are not described.

[0011] International Publication No. 2012 / 13506 describes the use of an aqueous polyurethane dispersion adhesive for producing a biodegradable composite film, wherein at least two substrates are bonded together, and at least one of the substrates is a biodegradable polymer film. At least 60% by weight of the polyurethane is composed of diisocyanates, polyester diols, and at least one bifunctional carboxylic acid selected from dihydroxycarboxylic acids and diaminocarboxylic acids.

[0012] International Publication No. 2005 / 003247 relates to a method for bonding substrates having different surface energies. The adhesive used for bonding consists of at least 15% by weight of polyurethane (water or other organic solvents with a boiling point less than 150°C at 1 bar are not counted), the adhesive is applied to the substrate with the lower surface energy, and the resulting adhesive-coated substrate is bonded to the substrate with the higher surface energy.

[0013] International Publication No. 2021 / 249749 describes the recycling of bonded articles containing TPU foam substrates by using an aqueous polyurethane dispersion of a specified molecular weight as an adhesive. Coating of foam particles is not mentioned.

[0014] U.S. Patent Application Publication 2019 / 367698 describes a method for producing foamed thermoplastic polyurethane elastomer products using a hot-melt adhesive such as Mirathane® H306. However, the coated particles are not moved until they lose their adhesive properties; instead, they are directly filled into a product mold and vulcanized. The vulcanization process involves crosslinking between particles, resulting in a 3D material, but this leads to the loss of thermoplastic properties such as remeltable and recyclable properties.

[0015] International Publication No. 2019 / 073607 describes a shoe sole component, which is formed in part or in whole from a resin composite comprising a non-foamed elastic matrix made of an elastomer and a plurality of resin foam particles dispersed in the elastic matrix. Furthermore, a shoe comprising this shoe sole component is disclosed.

[0016] While various binders generally useful for bonding particles together have been described, there is a need to create coated particles with storage stability and prevent aggregation of stored particles. This includes particles that have better fluidity, less electrostatic charging due to friction, and enable the creation of much easier 3D parts using simpler molding processes (e.g., standard convection ovens or hot presses).

[0017] Therefore, a material is needed that possesses the following advantages: • Different eTPE beads or even other material classes can be mixed; • Hot melt adhesives can be used as a support for stabilizers, pigments, etc. • Hot melt can be recycled together with eTPU; • The particle foam, made from particles coated with hot melt, can be separated, and the eTPU components can be recovered; Beads coated with hot melt can be fused together by simple hot pressing or using other molding techniques such as high-frequency and steam chest molding.

[0018] In coatings with non-adherent particles, fluidity is better and electrostatic charging due to friction is reduced, allowing for easier filling into molds or cavities during processing.

[0019] Furthermore, the particles can be processed in various ways, not only by standard convection ovens or hot presses, but also by electromagnetic fields. This allows the beads to be used, for example, to fill gaps and bond them with a trigger.

[0020] Therefore, an object of the present invention is to provide a method for producing coated particles with storage stability.

[0021] The above objective is a method for producing moldable thermoplastic particle foam particles with storage stability, which are at least partially coated with a hot melt adhesive, preferably a non-reactive hot melt adhesive. a1) A step of bringing particles into contact with a hot melt adhesive to obtain coated particles, a2) A process of moving the coated particles until the particles lose their adhesive properties. This is achieved by methods including,

[0022] The above objective is a method for producing a molded object, b1) A step of coating particles according to a method for producing storage-stable particles according to the present invention, b2) Process for forming particles obtained from process b1) This can also be achieved by methods including those mentioned above.

[0023] The above object is also achieved by particles of a storage-stable, formable thermoplastic particle foam, at least partially coated with a hot-melt adhesive, preferably a non-reactive hot-melt adhesive, wherein the coated particles have no adhesiveness and can preferably be obtained by a method for producing storage-stable particles according to the invention.

[0024] The above object can also be achieved by a method for producing a shaped body according to the invention or by a shaped body obtained by shaping a particle foam according to the invention.

[0025] Surprisingly, it has been found that the use of a hot-melt adhesive results in a non-adhesive coating that can be used for the realization of 3D parts that do not require steam, even when steam chest compatibility is still obtained. Considering the low melting point of the hot-melt adhesive, even when steam chest molding is used, the energy used in the method according to the invention is low and the cycle time is short. This coating enables the realization of 3D parts with excellent mechanical values equal to, and even exceeding, those of 3D parts produced using a standard steam chest molding process by means of a hot press. In addition, shorter cycle times during processing become possible. In particular, the use of molten hot-melt is advantageous because it can avoid the removal of solvents, especially aqueous solvents, which require large amounts of cost and energy.

[0026] In order to produce storage-stable particles of a formable thermoplastic particle foam, at least partially coated with a hot-melt adhesive, in step a1), the particles are brought into contact with the hot-melt adhesive to obtain coated particles.

[0027] Various methods are available to achieve the coating.

[0028] In the first embodiment, the hot melt adhesive is brought into contact in a molten state. The typical temperature used is in the range of 60°C to 200°C, preferably 60°C to 180°C, and more preferably 80°C to 180°C.

[0029] Preferably, the molten hot-melt adhesive has a viscosity in the range of 0.1 mPas to 800,000 mPas, more preferably 1 mPas to 600,000 mPas, and even more preferably 10 mPas to 500,000 mPas, as measured at 160°C. Preferably, the viscosity is measured using a Brookfield viscometer. The Brookfield viscometer measures the torque required to rotate a selected spindle in the fluid. This torque value is directly related to the viscosity of the fluid. More specifically, a Brookfield / Ametek rotational viscometer (HB DV2T Extra) can be used to measure the torque required to rotate a spindle (SC4-27) at 0.4 rpm in the fluid.

[0030] Preferably, the particles are kept under agitation (cooking mixer, cement 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 more preferably 60°C to 100°C.

[0031] Therefore, in a preferred embodiment, the particles are heated before step a1) so that their temperature is at least at the start of step a1) and preferably 15°C to 100°C, preferably 30°C to 100°C, and more preferably 60°C to 100°C throughout step a1).

[0032] In a second embodiment, the hot melt adhesive is brought into contact in a solid state by powder coating. Powder coating is a known method, and those skilled in the art can perform the powder coating.

[0033] In the third embodiment, the hot melt adhesive is brought into contact in solution form, the hot melt adhesive is dissolved in an organic solvent, and then, a3) After step a2), remove the organic solvent and / or dry the particles at a temperature below the melting point of the hot melt adhesive to obtain coated particles. To do so.

[0034] Suitable organic solvents include 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, and xylene. MEK is a preferred organic solvent. Drying in step a3) can be carried out by conventional methods.

[0035] The most preferred embodiment involves using the hot-melt adhesive in a molten state.

[0036] The present invention relates to a method for producing coated particles of a moldable thermoplastic particle foam. Such foams are known in the art (see, for example, Robin Britton (Author), Update on Mouldable Particle Foam Technology, Rapra Technology Ltd, 2009). Preferably, the moldable thermoplastic particle foam is a foamed thermoplastic elastomer.

[0037] Foamed thermoplastic elastomer particles are known in the art. Suitable thermoplastic elastomers include, for example, thermoplastic polyurethane (TPU), thermoplastic polyester elastomer (e.g., polyether esters and polyester esters) (TPC), thermoplastic copolyamide (e.g., polyether copolyamide) (TPA), thermoplastic polyolefin (TPO), or thermoplastic styrene-butadiene block copolymer (TPS). Foam particles based on thermoplastic polyurethane (TPU) are particularly preferred. For this reason, the foamed thermoplastic elastomer is preferably eTPU.

[0038] Examples of methods for producing foamed thermoplastic elastomer particles are described in International Publication No. 2008 / 087078, International Publication No. 2018 / 082984, U.S. Patent No. 10005218, and International Publication No. 2007 / 082838.

[0039] Preferably, the glass transition temperature (Tg) of a moldable thermoplastic particle foam, such as foamed thermoplastic polymer particles, is less than 100°C, according to the aforementioned patent, and is measured by DSC in accordance with DIN EN ISO 11357-3:2013, preferably at a heating rate of 20°C / min, after an initial pre-drying step of 10 minutes at 100°C. The Tg of the soft phase can be measured during the initial heating run.

[0040] Preferably, in step a1), contact is achieved by mixing the foam beads with the hot melt adhesive using a cooking mixer or cement mixer, or by spraying, such as mixing or spray drying with a Vollrath mixer. The amount of liquid / solution relative to the weight of the product can range from 1 ml / kg / min to 1000 ml / g / min. The droplet size can vary from 1 mm to 1000 mm in diameter. Suitable nozzles are hollow cone nozzles, full cone nozzles or flat jet nozzles, as well as spray discs that generate droplets by rotational motion and centrifugal force. A suitable mixer that can be used is the 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 vessel with a rotatable mixing tool. Depending on the application, various configurable nozzles are available. The mixer is heatable by a double jacket. The rotation speed is adjustable by a mechanical variator. A melting vessel and a pressure vessel are used for adding the liquid.

[0041] In general, common coating methods can be used, such as the spray coating described in European Patent Application Publication No. 0009727. In a preferred embodiment of the coating, the particles are spray-coated while they are in motion, for example by spraying air or a mixture of different gases.

[0042] Particles that are at least partially coated are coated in an amount of 0.1% to 40% by weight, preferably 5% to 25% by weight, based on the total weight of the particles and the coating. Preferably, particles that are at least partially coated are coated in an amount of at least 90%, preferably at least 95%, more preferably at least 99%, based on the entire surface of the particles, and more preferably completely coated.

[0043] Step a3) involves drying the coated particles when the hot melt adhesive is applied in the form of a solution obtained by dissolving the hot melt adhesive in an organic solvent. In principle, all suitable methods are possible, such as convection drying, contact drying, infrared drying, and even microwave technology. When using molten hot melt, the coated particles only need to be allowed to come to room temperature.

[0044] In contact drying, the temperature difference between the product and the wall is preferably limited to 1-100K, and in convection drying, the gas composition may be N2 or air. The gas flow rate is preferably 1-1000 liters / minute per kg of product, and the product temperature in the mixer is preferably 1°C-100°C, preferably 10°C-60°C.

[0045] In step a2), the coated particles are moved until they are no longer adhesive. The term "no adhesive" means that a non-sticky surface is achieved at room temperature, preferably in the range of 20°C to 25°C. This means that the coated particles do not come into contact with each other and aggregate, and do not adhere to the second surface at room temperature. This means that the Tfb (explained further below) of the hot melt is higher than 40°C, preferably higher than 60°C. Non-adhesive particles are important for obtaining particles with storage stability.

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

[0047] Preferably, the particles are separated from each other after step a1) and before step a2). This can be achieved, for example, by using a vibrating belt. This option also prevents particle aggregation.

[0048] Preferably, the hot melt adhesive is a composition comprising a thermoplastic polymer, preferably a thermoplastic polyurethane.

[0049] Hot melt adhesives are typically solid at room temperature, solvent-free, and meltable above room temperature. Hot melt adhesives are generally non-reactive thermoplastic resins. Hot melt adhesives (HMAs) are adhesive systems that are solid at room temperature, become adhesive or tacky when heated, and melt into a liquid or fluid state. They typically solidify rapidly upon cooling to ambient temperature, exhibiting internal strength and cohesive force. Hot melt adhesives are solvent-free, one-component thermoplastic adhesives characterized by low to moderate viscosity when applied at the required distribution temperature. Upon application, hot melt adhesives cool and solidify, forming strong bonds between articles. Bonds formed by thermoplastic hot melt adhesives are reversible. Under sufficiently high thermal stress, thermoplastic hot melt adhesives liquefy and lose cohesive strength.

[0050] The melting point of compositions containing thermoplastic polymers, particularly thermoplastic polyurethanes, as measured by differential scanning calorimetry (DSC), is preferably about 50°C to about 180°C or about 50°C to about 160°C. The test method conforms to ASTM D 3418-12 (Standard test method for transition temperature and enthalpy of melting and crystallization of polymers by differential scanning calorimetry) using Hitachi High-Tech Corporation's DSC7000X at a heating rate of 10°C / min and a cooling rate of 10°C / min. Surprisingly, it was found that the flow onset temperature (Tfb) of compositions containing thermoplastic polymers affects the coating properties of the composition. By adjusting the flow onset temperature to a suitable range, it is possible to influence the temperature behavior of adhesive strength, obtain good coating properties under usage conditions, and enable easy recycling. Surprisingly, it was found that using compositions comprising thermoplastic polymers having a flow onset temperature (Tfb) of at least 50°C, preferably at least 60°C, and more preferably at least 70°C, as measured according to Example 1 using a Shimadzu Flowtester Capillary Rheometer CFT-500D in accordance with JSI K7311-1995 and K7210-1999, can achieve a favorable combination of good coating under mild conditions.

[0051] In a further embodiment, the present invention also relates to a method according to the present invention in which the thermoplastic polymer composition has a flow onset 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, and more preferably 70°C to 150°C.

[0052] Preferably, the composition containing the thermoplastic polymer used according to the present invention has a relatively low softening temperature, and even a low flow initiation temperature.

[0053] Compositions containing thermoplastic polymers may include a variety of polymers commonly used in adhesives. For example, a composition may include at least one polymer selected from polyurethane, polychloroprene, latex, polystyrene, polyamide, polyolefin, polyacrylate, polyester, polyether, copolymers thereof, and any combination thereof. In some embodiments, polystyrene may be or contain polystyrene block copolymers. Suitable polystyrenes include poly(styrene-isoprene-styrene), poly(styrene-butadiene-styrene), poly(styrene-ethylene-butene-styrene), and poly(styrene-ethylene-propene).

[0054] In some embodiments, the composition comprising a thermoplastic polymer comprises at least one thermoplastic polymer selected from thermoplastic polyurethanes, thermoplastic polyamides, thermoplastic polyolefins, thermoplastic polyesters, thermoplastic polyethers, their thermoplastic copolymers, and any combination thereof. In some embodiments, the composition comprises polyolefins such as polyethylene, polypropylene, their copolymers, or any combination thereof. The polyolefin may be an ethylene copolymer. In some embodiments, the composition comprises a thermoplastic polyolefin. In some embodiments, the thermoplastic polyolefin comprises thermoplastic polyethylene, thermoplastic polypropylene, their thermoplastic copolymers, or any combination thereof. The thermoplastic polyolefin may also comprise a thermoplastic ethylene copolymer. In some embodiments, the thermoplastic ethylene copolymer is ethylene vinyl acetate (EVA).

[0055] In some embodiments, the composition comprises at least one thermoplastic polymer, which is a polymer or copolymer containing multiple functional groups in its chemical structure, wherein the multiple functional groups are selected from hydroxyl groups, carboxyl groups, amine groups, amide groups, urethane groups, and combinations thereof.

[0056] In further embodiments, the present invention also relates to methods disclosed herein in which the thermoplastic polymer composition comprises at least one polymer selected from thermoplastic polyurethanes, polychloroprene, polystyrene, polyamides, polyolefins, polyacrylates, or mixtures thereof.

[0057] The composition is typically applied at an elevated temperature to produce an adhesive coating. The composition can be applied as a molten material, for example, at a temperature preferably 60°C to 220°C, more preferably 80°C to 200°C, and even more preferably 80°C to 200°C, to coat the foam, and the surface to be coated is at least partially coated with the composition containing a thermoplastic polymer.

[0058] The amount of the composition containing the thermoplastic polymer applied is preferably in the range of 1% to 30% by weight, and more preferably 5% to 20% by weight, based on the total weight of the coated particles.

[0059] Preferably, the composition comprises a thermoplastic polyurethane. In further embodiments, the present invention also relates to a method disclosed herein in which the thermoplastic polymer is a thermoplastic polyurethane.

[0060] Suitable thermoplastic polyurethanes are typically, a) Polyisocyanate components, b) Polyol component, and c) Optional chain extender component It contains the reaction products.

[0061] The reaction may or may not be carried out in the presence of a catalyst. In further embodiments, the present invention also relates to a method disclosed herein in which the thermoplastic polyurethane is a reaction product of components of a polyol, an isocyanate, and finally a chain extender.

[0062] The starting material is preferably selected to adjust the flow initiation temperature of the thermoplastic polyurethane. The flow initiation temperature can be adjusted, for example, by reducing the hard segment content of the thermoplastic polyurethane.

[0063] According to the present invention, a mixture of polyols or a mixture of chain extenders can also be used to adjust the flow initiation temperature. Furthermore, the structure of the polyol can be adjusted by selecting a suitable monomer or mixture of monomers that affects the flow initiation temperature. Additionally, the flow initiation temperature can be influenced by adjusting the molecular weight and / or chain length of the chain extender used.

[0064] The molecular weight of the thermoplastic polyurethane can also be adjusted by selecting a suitable molar ratio of NCO / OH groups, which affects the flow initiation temperature. According to the present invention, an ideal combination of hardness, flow initiation temperature, and other properties can be achieved by using two or more of these adjustments.

[0065] In further embodiments, the present invention also relates to methods disclosed herein in which the isocyanate is an aromatic isocyanate, an aliphatic isocyanate, an alicyclic isocyanate, or a combination thereof.

[0066] The isocyanate component may comprise one or more polyisocyanates. In some useful embodiments, the polyisocyanate component comprises one or more diisocyanates. Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, or combinations thereof. In some embodiments, the polyisocyanate component comprises one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is substantially or completely free of aliphatic diisocyanates. In other embodiments, the polyisocyanate component comprises one or more aliphatic diisocyanates and / or alicyclic diisocyanates.

[0067] In some embodiments, the polyisocyanate component is substantially or completely free of aromatic diisocyanates. In some embodiments, a mixture of aliphatic and aromatic diisocyanates may be useful. Examples of useful polyisocyanates include 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'-diisocyanato-1,2-diphenylethane, 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI), and toluene diisocyanate. Examples include aromatic diisocyanates such as (TDI); aliphatic diisocyanates such as ethylene diisocyanate (EDI), 1,4-butane diisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), decane-1,10-diisocyanate, 1,12-dodecane diisocyanate (DDI), and lysine diisocyanate (LDI); and alicyclic 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. A mixture of two or more polyisocyanates may be used. In some embodiments, the polyisocyanate is MDI and / or H12MDI. In some embodiments, the polyisocyanate consists substantially of MDI. In some embodiments, the polyisocyanate is substantially composed of H12MDI.

[0068] In further embodiments, the present invention also relates to methods disclosed herein in which 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'-diisocyanato-1,2-diphenylethane, 1,5-naphthalene diisocyanate, and combinations thereof.

[0069] In further embodiments, the present invention also relates to a method disclosed herein in which the aromatic isocyanate is most preferably 4,4'-diphenylmethane diisocyanate (4,4'-MDI).

[0070] In further embodiments, the present invention also relates to a method disclosed herein in which the aliphatic isocyanate is more preferably selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-docecandiisocyanate and combinations thereof.

[0071] In further embodiments, the present invention also relates to a method disclosed herein in which the aliphatic isocyanate is most preferably 1,6-hexamethylene diisocyanate (HDI).

[0072] In further embodiments, the present invention also relates to a method disclosed herein in which 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 mixtures of their corresponding isomers, 4,4'-, 2,4-, and 2,2'-dicyclohexylmethane diisocyanate, and mixtures of their corresponding isomers and combinations thereof.

[0073] In further embodiments, the present invention also relates to a method disclosed herein in which the alicyclic isocyanate is most preferably 4,4'-dicyclohexyl-methanediisocyanate (H12MDI).

[0074] Thermoplastic polyurethanes are also produced using (b) polyol components. Polyols, which may also 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 polymer intermediates preferably have a number-average molecular weight (Mn) of about 300 to about 10,000, for example, about 400 to about 8,000 daltons, and even, for example, about 500 to about 6,000 daltons. The molecular weight is determined by assay of the terminal functional groups and is related to the number-average molecular weight. Unless otherwise specified, in the context of the present invention, the molecular weight can be determined by the terminal group weight or calculated from the OH value in accordance with EN ISO 4629-1:2016.

[0075] According to a further embodiment, the present invention provides a polyol that is measured according to the amount of end groups to 0.4 × 10 3 g / mol ~ 6 × 10 3 The present invention also relates to a method disclosed herein, which involves a polyol having a number-average molecular weight of g / mol.

[0076] Suitable polyester intermediates can be produced by (1) esterification of one or more glycols with one or more dicarboxylic acids or anhydrides, (2) transesterification, i.e., reaction of one or more glycols with esters of dicarboxylic acids, or (3) ring-opening polymerization, such as polycaprolactone diol (PCL-diol), polylactide diol (PLA-diol), etc. Generally, a molar ratio of more than 1 mole of glycol to acid is preferred to obtain linear chains with a predominance of terminal hydroxyl groups. The desired polyester dicarboxylic acid can be aliphatic, alicyclic, aromatic, or a combination 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 acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, dimer fatty acids, etc. Anhydrides of the above dicarboxylic acids, such as phthalic anhydride and tetrahydrophthalic anhydride, can also be used. The glycols that react to form the desired polyester intermediates are aliphatic, aromatic, or a combination thereof, and may have a total of 2 to 44 or 2 to 36 carbon atoms. Preferred 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-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, dimer fatty diols, and mixtures thereof.

[0077] Suitable hydroxyl-terminated polyether intermediates include polyether polyols derived from diols or polyols having a total of 2 to 15 carbon atoms. In some embodiments, the hydroxyl-terminated polyether is an alkyldiol or glycol and is reacted with an ether containing an alkylene oxide, typically ethylene oxide or propylene oxide, or a mixture thereof, having 2 to 6 carbon atoms. For example, a hydroxyl-functionalized polyether can be produced by first reacting propylene glycol with propylene oxide, followed by a subsequent reaction with ethylene oxide.

[0078] Primary hydroxyl groups derived from ethylene oxide are preferred over secondary hydroxyl groups due to their higher reactivity. Useful commercially available polyether polyols include poly(ethylene glycol) containing ethylene oxide obtained by reaction with ethylene glycol, poly(propylene glycol) containing propylene oxide obtained by reaction with propylene glycol, and poly(tetramethylene glycol) containing water obtained by reaction with tetrahydrofuran. These are sometimes described as polymerized tetrahydrofuran and are generally referred to as PTMEG.

[0079] The preferred polyurethanes described herein are optionally prepared using c) chain extender components. Preferred chain extenders include low molecular weight diols (molecular weight less than 500 g / mol), diamines, and combinations thereof. Preferred chain extenders include relatively small polyhydroxy compounds, e.g., lower aliphatic or short-chain glycols having 2 to 20 or 2 to 12 or 2 to 10 carbon atoms. Preferred 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-butanediol (1,3-BDO), 1,5-pentanediol (1,5-PDO), neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), and 2,2-bis[4] Examples include -(2-hydroxyethoxy)phenyl]propane (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), as well as mixtures thereof. In some embodiments, the chain extender comprises BDO, HDO, 3-methyl-1,5-pentanediol, or a combination thereof. In some embodiments, the chain extender comprises 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 less than 30% by weight, preferably less than 25% by weight, for example less than 15% by weight, and even more, for example less than 12% by weight, particularly less than 8% by weight of the total reactant of the chain extender. In some embodiments, the thermoplastic polyurethane is substantially or completely free of chain extenders.

[0080] In further embodiments, the present invention also relates to methods disclosed herein in which the chain extender is selected from ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, or a mixture thereof, and more preferably, the chain extender is butanediol, hexanediol, cyclohexanedimethanol (CHDM), hydroquinone bis(2-hydroxyethyl) ether (HQEE), or a mixture thereof.

[0081] The thermoplastic polyurethane used in accordance with the present invention typically has 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 to react the diisocyanate with the polyol intermediate or chain extender. Examples of suitable catalysts for particularly accelerating the reaction between the NCO group of the diisocyanate and the hydroxyl group of the polyol and chain extender include conventional tertiary amines known from the prior art, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane, and especially organometallic compounds, such as titanates, iron compounds, such as iron acetylacetonate, tin compounds, such as stannous acetate, stannous octanoate, stannous dilaurate, bismuth compounds, such as bismuth trineodecanoate, or dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate and dibutyltin dilaurate. The usual amount of catalyst used is 0.001 to 0.1 parts by weight per 100 parts by weight of the polyol component. In some embodiments, the reaction for forming the thermoplastic PU used according to the present invention is substantially or completely catalyst-free.

[0082] Various types of arbitrary components may be present during the polymerization reaction and / or incorporated into the composition containing the thermoplastic polymer to improve processing properties and other properties. These additives include, but are not limited to, antioxidants such as phenols, rheology modifiers such as hydrophobic or hydrophilic fumed silica, and adhesion promoters such as malonic acid, fumaric acid, chlorinated rubber, vinyl chloride / vinyl acetate copolymer, and vinyl chloride / vinyl acetate / maleate terpolymer. Other additives, such as coumarone-indene or terpene-phenol resins, which may help increase the tackiness of hot-melt adhesives at high temperatures and delay recrystallization time, can be used to improve the performance of the composition or mixed product. All of the above additives may be used in conventional effective amounts relative to these substances.

[0083] Further additives may be used, including pigments, dyes, fragrances, fillers, bio-based and / or biodegradable additives, UV stabilizers, heat stabilizers, flame retardants such as expandable graphite, additives that provide antistatic properties and electrical conductivity, additives that reduce dirt adsorption, antimicrobial additives, waxes, crosslinking agents, surface functionalizing fillers, foaming additives such as Expansell®, thermal conductive additives, and additives that can withstand irradiation from electromagnetic fields and / or high-frequency and / or microwaves.

[0084] Exemplary thermally conductive additives, such as metal nitrides, metal oxides, metal carbides, metal sulfides, metal silicates, silicon carbides and silicon nitride, particularly preferably boron nitride, BN, SILATHERM® (a mixture of Al2O3 and SiO2), or SILATHERM® Advance, are mentioned in German Patent Application Publication No. 102021205928. Exemplary conductive additives include mixtures of carbon and inorganic materials, carbon fibers, glassy carbon, carbon nanotubes, carbon nanobuds, aerographite, linear acetylene carbon, q-carbon, graphene, salts, single-crystal powders, polycrystalline powders, amorphous powders, and glass fibers.

[0085] The additive may be incorporated into the components of the thermoplastic polymer or the reaction mixture for the preparation of the thermoplastic polymer and melted, or it may be incorporated directly into the molten thermoplastic polymer.

[0086] Thermoplastic polyurethanes can be produced by any means known to those skilled in the art, such as a batch process, the REX line method, or the belt line method. For example, components (a) a diisocyanate component, (b) a polyol component, and (c) an optional chain extender component are reacted with each other to form a thermoplastic PU useful for the present invention. The thermoplastic PU can be produced using any known process for reacting the reactants. In one embodiment, the process is a so-called "one-shot" process in which all reactants are added together, mixed, and reacted. The equivalent amount of diisocyanate relative to the total equivalent amount of the hydroxyl-containing component, i.e., the polyol intermediate, and, if present, the chain extender glycol, can be about 0.5 to about 1.30, or about 0.6 to about 1.20, or about 0.7 to about 1.10. The reaction temperature when using a urethane catalyst may be approximately 175°C to 245°C, preferably 180°C to 220°C, in the reaction zone of the twin-screw reaction extruder (REX line) method, or approximately 80°C to 160°C, preferably 90°C to 150°C, in the reaction zone of the belt line method.

[0087] As another example, thermoplastic PUs can also be prepared using a prepolymerization process.

[0088] In the prepolymer route, the polyol component is reacted with one or more diisocyanates, generally in an equivalent excess, in the presence of a suitable urethane catalyst to form a prepolymer solution containing free or unreacted diisocyanates. Subsequently, as described above, a chain extender is added in an equivalent amount generally equal to the isocyanate end groups and any free or unreacted diisocyanate compounds. Thus, the total equivalent ratio of all diisocyanates to the total equivalents of the polyol intermediate and chain extender is about 0.5 to about 1.30, or about 0.6 to about 1.20, or about 0.7 to about 1.10. Typically, the prepolymer route can be carried out with any conventional device.

[0089] The described method for producing thermoplastic PU includes both a “prepolymer” process and a “one-shot” process, either in a batch or continuous manner. That is, in some embodiments, the thermoplastic PU can be produced by reacting the components together in a “one-shot” polymerization process, where all components, including the reactants, are added to a mixer simultaneously or substantially simultaneously and reacted to form the thermoplastic PU. On the other hand, in other embodiments, the thermoplastic PU can be produced by first reacting a polyisocyanate component with a portion of the polyol component to form a prepolymer, and then reacting the prepolymer with the remaining reactants to complete the reaction and obtain the thermoplastic PU. After being removed from the extruder, the composition can be pelletized, stored, and ultimately sold in pellet form, or it can be extruded directly from the reaction extruder through a die to form a profile of the final product.

[0090] For better recycling, it is preferable that the chemical properties of the particles and coatings, particularly the PU hot melt adhesive and eTPU particles, are the same.

[0091] Another aspect of the present invention is a method for producing a molded body, b1) A step of coating particles according to the method of the present invention, b2) Process for forming particles obtained from process b1) This method includes [something].

[0092] Preferably, the molding in step b2) is carried out by steam-less thermo-pressing, steam chest molding, and / or by an electromagnetic field, particularly high frequency, preferably steam-less thermo-pressing.

[0093] Preferably, the thermopress (also called hot press or thermal press) is performed at a temperature of 60°C to 160°C, more preferably 80°C to 160°C, even more preferably 90°C to 140°C, and even more preferably 100°C to 140°C.

[0094] Preferably, after molding by thermopress, the resulting molded body is cooled to room temperature, thereby improving its mechanical properties.

[0095] Preferably, the molded body is a composite material of particles and other materials such as textiles, leather, thermoplastic films, or metals, particularly electronic components.

[0096] Another aspect of the present invention is a method for processing a molded body, c1) A step of producing a molded body according to the method of the present invention, c2) Preferably, a step of heating the molded body to decompose the particles by bringing the particles into contact with hot water which may optionally contain a surfactant. This includes methods.

[0097] The at least partially coated particles according to the present invention can be used in their pure form or as a mixture of different particles and / or other materials to obtain 3D parts such as the molded bodies of the present invention for a variety of applications, including industrial, consumer, transportation and construction uses, used alone or as a component for industrial, consumer, transportation and construction uses, such as sealing and insulation of houses, pipelines or gas tanks, shoe parts, shoe midsoles, shoe inserts, shoe combi soles, bicycle saddles, bicycle tires, damping elements, shock protection, acoustic and vibration dampers, decoration, furniture, upholstery, mattresses, yoga mats, underlays, railway pads, handles, protective sheets, packaging, drop protection, automotive interiors and exteriors, headliners, armrests, door upholstery, seats, battery cases, sporting goods, balls, tennis rackets, baseball clubs, treadmills, toys, flooring, running tracks, artificial turf, playgrounds, sports halls and walkways.

[0098] Therefore, another aspect of the present invention is the use of at least partially coated storage-stable particles or molded bodies of the present invention for industrial, consumer, transportation and / or construction applications, particularly for the aforementioned applications. [Brief explanation of the drawing]

[0099] [Figure 1] This is a structural diagram of the Shimadzu Flowtester CFT-500EX. [Figure 2] This is a schematic diagram of the cylinder unit. [Figure 3] This is a schematic diagram of the die. [Figure 4] This is a schematic diagram of the flow test curve using the constant heating rate method. [Figure 5] This figure shows a setup including a more direct coating unit, consisting of a jacketed hot melt container (19) with a capacity of up to 170 ml and 4 bar, connected to a Schlick atomizing nozzle (20) heated by a gas heater unit (21) and processing air (arrow).

[0100] Figure 1 shows the structure of the Shimadzu Flowtester CFT-500EX. (1) Die opening stopper (2) Cylinder (3) Heater (4) Die (5) Die press (6) Piston (7) Press joint (8) Load axis (9) Temperature detector (10) Potentiometer (for stroke detection) (11) Load lever (12) Weight lifting air cylinder (13) Solenoid valve (14) Balance weight (15) Wheelset (16) Control Unit (CPU) (17) Weights (18) Movable pivot point

[0101] This system consists of a main unit that heats and pressurizes a sample inserted into a cylinder and extrudes the molten sample through a test die opening, and a control unit that calculates the shear rate and viscosity based on measurement data regarding cylinder temperature and piston travel distance.

[0102] The sample is loaded into the cylinder and heated by a heater outside the cylinder. The force generated by the weight is amplified by a load lever and applied to the piston via a load shaft, pushing the sample out through the die opening. The piston stroke is detected by a potentiometer.

[0103] The potentiometer value is read by the device control unit. Then, the flow rate is calculated from the relationship between the extrusion time and piston stroke, and the shear rate and viscosity are obtained.

[0104] The load mechanism generates a load force 10 times that of the weight by combining a wheelset with a lever ratio of 1:2 and a load lever with a lever ratio of 1:5. The wheelset and load lever operate as a single unit via a connecting steel strip. The load shaft moves vertically, but its horizontal movement is limited, as the upper and lower parts of the load shaft are fixed with guide bearings. No load force is generated by the weight when the weight lifting cylinder is raised or lowered. However, when the cylinder is lowered, a load force is generated on the load shaft, pushing the sample out. When the load shaft is raised or lowered, the pivot point of the weight lever moves horizontally on a flat pivot bearing, preventing forces other than horizontal forces from being applied to the load shaft.

[0105] Figure 2 shows a schematic diagram of the cylinder unit. The cylinder (c) comprises a die holder (dh) and a heater (h). The sample (s) is placed between the die (d) and the piston (p).

[0106] Figure 3 shows a schematic diagram of the die. The die (d) has a die length (dl), a die opening diameter (ddi), and a die width (do).

[0107] Figure 4 shows a schematic flow test curve using the constant heating rate method. The piston stroke (PS, y-axis) is plotted against temperature (T, x-axis). Points A and B indicate the preheating period. Points B and C determine the softening region. There is a non-flowing region between points C and D. The flowing region, starting from D and continuing beyond point E, is shown. The softening temperature (Ts) and the flow onset temperature (Tfb) are also shown.

[0108] Figure 5 shows a setup including a more direct coating unit, consisting of a jacketed hot melt container (19) with a capacity of up to 170 ml and 4 bar, connected to a Schlick atomizing nozzle (20) heated by a gas heater unit (21) and processing air (arrow). A plow shear (22) was selected to allow sufficient mixing characteristics until the beads lost their adhesive properties. The setup temperature is controlled by a thermostat (23). [Examples]

[0109] Materials used: 1) Polyurethane-based hot melt adhesive: All selected PU hot melts are non-tacky at room temperature, stable under storage conditions, and activated when the temperature rises. Unlike cross-linked TPUs, their mechanical properties (hardness, tensile strength, etc.) are determined by reversible hydrogen bonding between polymer chains (or other intermolecular forces such as VDW and π-π interactions). The following are the properties specified for the selected hot melts:

[0110] Hot melt 1: It consists of a polyester made from adipic acid and butanediol with F=2 and Mn:3000g / mol, 1,4-butanediol (BDO), and methylenediphenyl diisocyanate (4-4'-MDI). ·Hardness: 96A / 45D • Hard segment: approximately 6% • Laminating temperature: 100-110℃ Melting point: Approximately 50°C Tfb: 80℃

[0111] Hot Melt 2: It consists of a polyester made from adipic acid and butanediol with F=2 and Mn:1000g / mol, HDO, and 4,4'-MDI. ·Hardness: 80A • Hard segment: approximately 15% • Laminating temperature: 110~150℃ Tfb: 105℃

[0112] Hot Melt 3: It consists of a polyester made from adipic acid and butanediol with F=2 and Mn:1000g / mol, PTHF with 1000g / mol and F=2, BDO, and a 50 / 50 mixture of 4,4'-MDI and 2,4'-MDI. Hardness: 60A • Hard segment: approximately 26% • Laminating temperature: 110~120℃ Tfb: 95℃

[0113] Hot melt 4: It consists of polyethylene glycol with Mn: 3400 g / mol and F=2, BDO, and 4,4'-MDI. ·Hardness: 96A / 45D • Hard segment: approximately 9% Melting point: Approximately 50°C

[0114] Hot melt 5: It consists of a polyester made from adipic acid and butanediol with F=2 and Mn:5000g / mol, and 4,4'-MDI. ·Hardness: 97A / 50D • Hard segment: 0% Melting point: Approximately 60°C Tfb: 60℃

[0115] Hot melt 6: It consists of a polyester made from adipic acid and butanediol with F=2 and Mn:1000g / mol, BDO, and hexamethylene diisocyanate (1,6-HDI). ·Hardness: 90A • Hard segment: approximately 7% Melting point: Approximately 110°C Tfb: 110℃

[0116] The hardness of the PU hot melt was measured in accordance with ASTM D2240-15 Standard Test Methods for the Properties of Rubber - Durometer Hardness.

[0117] The amount of hard segment (HS) in weight percentage is given by the following formula: HS = {m(CE) + m(iso reacted with CE)} / {m(polyol) + m(CE) + m(iso)} The calculation was performed according to the following formula. Here, m(CE) is the mass of the chain extender in g / mol units, m(iso) is the mass of the isocyanate in g / mol units, and m(polyol) is the mass of the polyol in g / mol units.

[0118] The melting point was measured by DSC in accordance with ASTM D3418-12, the standard test method for differential scanning calorimetry to determine the transition temperature and enthalpy of melting and crystallization of polymers. Heating rate: 10°C / min, cooling rate: 10°C / min.

[0119] The molecular weight of the polyol was calculated from the hydroxyl value, measured according to the standard test method for hydroxyl groups using reaction with p-toluenesulfonyl isocyanate (TSI) and potentiometric titration with tetrabutylammonium hydroxide, as defined by ASTM E1899-16. Hydroxyl value (OH#) = {(V2-V1) × N × 56.1} / sample, g Here, the concentration of Bu4NOH in units of N = meq / mL, V1 = mL of Bu4NOH up to the first potentiometric titration endpoint. V2 = mL of Bu4NOH up to the second potentiometric titration endpoint. Sample, g = mass of the sample in grams. Molecular weight (g / mol) = (56100 × number of OH groups per molecule) / OH#

[0120] Preparation of PU hot melt The mixture of each component was heated to 80°C using a paddle mixer (SHIN KWANG GR-150R) at a rotation speed of 500-1000 rpm for 25 minutes, while stirring for 1-3 minutes. Next, the TPU HMA was discharged. The TPU HMA was then post-heat treated at 100°C for 1-5 hours and then pelletized.

[0121] 2) Polyester hot melt adhesive Hot melt adhesive Dynacoll® 7130: Solid, amorphous saturated copolyester. Chemical structure according to International Publication No. 2009 / 010324. Tg: 30℃ OH value: 35 mg KOH / g

[0122] Example 1 - Measurement of Flow Initiation Temperature (Tfb) The flow initiation temperature (Tfb) of a sample is determined by placing the sample(s) into a hollow cylinder with a die equipped with a channel, flowing the molten sample through this channel, applying a load to the sample under a piston in the hollow cylinder, heating the sample until it melts and leaks out of the channel, and determining the temperature at which the sample begins to flow (= flow initiation temperature (Tfb)).

[0123] The experimental setup is described in JIS K 7311 and JIS K 7210 standards. A general setup of the apparatus used is shown in Figure 1. A heatable concentric hollow cylinder with a piston in this hole is shown in Figure 2. As described in detail in Figure 3, the bottom of the cylinder hole is closed with a die having a channel. This cylinder is placed in a device for determining the Tfb. The device is configured so that the channel in the die can be closed by screwing in a die retainer at the bottom of the cylinder and pressing the die against the bottom of the cylinder. Closing the channel in the die is important for removing air from the sample before starting the experiment. Air removal is performed by compressing the sample in the cylinder hole and pressing the piston toward the die with a specific load without raising the temperature of the cylinder. After air removal, the sample is heated by heating the cylinder with the piston placed on the sample with a specific load and raising the temperature steadily, while the temperature around the sample is plotted in parallel. As soon as the sample reaches the flow onset temperature (Tfb), the pressure of the piston under a specific load causes the molten material to begin leaking out of the channel in the die. 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 flow initiation temperature (Tfb).

[0124] The device used in all experiments was the Shimadzu CFT-500D from Shimadzu Corporation (Tokyo, Japan). Samples were collected and cut into sections with a maximum diameter not exceeding the cylinder diameter, preferably 5 mm or less, most preferably 2 mm or less. The temperature of the cylinder with the piston was adjusted to 30°C ± 2°C well before the measurements.

[0125] A 1.9 g sample section was packed into a hole in a preheated cylinder closed with a die having a 1 mm channel (see Figure 1 for details). The sample was moved to the bottom of the hole using a plunger rod. The hole containing the sample was then closed with a piston. The die used for this measurement has Di=1 mm and Dl=10 mm, as shown in Figure 3.

[0126] Next, the die channel was closed with a channel closure device, and air was removed from the sample by repeatedly pushing the piston towards the sample three times with a 100 kg load. After that, the channel closure device was removed and the channel was opened again.

[0127] Next, the sample under the piston was held at a temperature of 30°C for 240 seconds under a 100 kg load. Subsequently, the sample was heated at a heating rate of 3°C / min under a continuous 100 kg load, and the temperature near the sample was continuously plotted.

[0128] The flow onset temperature (Tfb) is the temperature at which the piston begins to move under load and the molten sample begins to pass through the die's channels. A typical diagram for determining the flow onset temperature (Tfb) can be seen in Figure 4.

[0129] It is not essential to use the Shimadzu CFT-500D from Shimadzu Corporation (Tokyo, Japan) for measuring the flow onset temperature (Tfb). Other devices with a similar cylinder shape will yield the same results for the flow onset temperature (Tfb) within the scope of this invention.

[0130] Example 2 - Experiment using hot melt adhesive solution Preparation of polyurethane hot melt adhesive solution The selected polyurethane hot melt is dissolved in MEK solution, and the amount of PU hot melt is adjusted to achieve a solution viscosity of 50–100 (cps, 25°C). The solution viscosity (TPU hot melt already dissolved in MEK solution) is measured using a Brookfield viscometer with a 61 LV spindle at 30 rpm. The solids content of these solutions is 5–15 w / w%.

[0131] Hot melt coating onto eTPU beads via a solution coating pathway The selected PU hot melt adhesive was dissolved in MEK solution, and the solution viscosity was reduced to less than 100 cps (25°C), which can be achieved by adjusting the solids content. The above solution was mixed with eTPU beads (prepared according to International Publication No. 2013 / 153190, Infinergy 230, BASF SE, based on diisocyanate 4, BDO, and polyol 1) using a mechanical stirrer at room temperature for 30 seconds. The beads were dried at room temperature on a Teflon-coated plate, taking care to separate them from each other. After drying for 5-20 minutes, the coated beads were non-adhesive and had storage stability. The amount of hot melt coating was 7%-12% relative to the beads.

[0132] Hot press molding After the coated eTPU beads were placed in the shoe cavity plate, they were heat-press molded under specified conditions. ·Temperature: 120, 130, 140, 150℃ • Heating time: 10-15 minutes • Cooling time: 5-15 minutes

[0133] eTPU beads coated with hot melt 1 and 2 were hot-pressed according to the procedure described in Experiment 2 (heated at 140°C for 15 minutes and cooled for 15 minutes, mold temperature 140°C). The mechanical properties are reported in the table below. For comparison, the properties of an eTPU plate fabricated by steam chest molding are reported.

[0134] [Table 1]

[0135] Example 3 - Experiments using molten hot melt adhesive and spray coating Using the setup shown in Figure 4, we successfully tested with the commercially available non-reactive hot-melt adhesive Dynacoll® 7130. This setup functions at temperatures up to 200°C and viscosities up to 10 mPas. Thermoplastic particle foam (eTPU foam particles) was tempered to 80°C before the coating process. The following conditions were used: Final product: eTPU coated with Dynacoll® 7130 Bulk density: 0.120 kg / l Product yield: 2000g Coating amount: 113.0g (5.65%) Processing speed: 5g / min Atomized air intake rate: 70% Atomizing air pressure: 3.3 bar T1 gas heater outlet: 165℃ T2 nozzle gas control: 168℃ T3 nozzle forward nozzle gas: 166℃ Hot melt container temperature: 165℃ Hot melt container pressure: 2.5 bar Mixer: Plowshare mixer Mixer rotation speed: 50 rpm

[0136] Coated eTPU beads were obtained.

[0137] The same experiment was repeated with a coating amount of 7%.

[0138] Experiment 4. Coating eTPU beads using a spray gun and a kitchen mixer. Granular hot melt 5 was placed in the cartridge unit (TR 80 LCD cartridge) of a spray gun (Reka Klebetechnik). After melting the hot melt 5 at a temperature of 160°C, it was sprayed using a pressure of 6 bar.

[0139] 100g of eTPU beads (prepared according to International Publication No. 2013 / 153190, Infinergy 230 based on diisocyanate 4, BDO, and polyol 1, BASF SE) were placed in a cooking machine (Cooking Chef XL KCL95) and kept at room temperature while being moved with a paddle mixer. Molten hot melt was sprayed onto the beads and kept under movement for 2 minutes. A coating amount of 10 w / w% was achieved.

[0140] The same procedure was repeated while maintaining the bead temperature at 70°C during the spraying process. This resulted in a better distribution of the hot-melt coating on the eTPU beads.

[0141] The same procedure was repeated using hot melt 6, by maintaining the eTPU beads at 70°C during the spraying process.

[0142] Experiment 5. Realization of a plate using coated eTPU beads 65g of eTPU beads coated with hot melt 6 according to Experiment 4, with dimensions (16.3 x 9.6 x 3.3 cm) 3 The 3D part was placed in a preheated mold (length, width, depth). The filled mold was covered with a mold lid that allowed for 50% compression / consolidation. The time spent in the heated press and the residence time for cooling the 3D part before demolding are summarized in the table below.

[0143] For reference, see International Publication No. 2013 / 153190 for eTPU beads weighing 65g (16.3 × 9.6 × 3.3 cm). 3 The material was placed in a preheated mold (length, width, depth). The filled mold was covered with a mold lid that allowed for 50% compression / consolidation. This resulted in a plate with the following dimensions: 16 × 9.5 × 1.6 cm 3 We report on hot-press molded 3D parts that can be obtained using uncoated eTPU beads.

[0144] Woven strip (150 x 25.4 x 1.6 mm) 3Using eTPU strips instead, the tensile strength and elongation measured in accordance with ASTM D 5035:2011, the rebound elasticity measured in accordance with DIN 53512:2000-4, and the density of the resulting 3D parts measured in accordance with DIN EN ISO 845:2009-10 are also reported below.

[0145] [Table 2]

[0146] Experiment 6. Coating of eTPU beads via a powder coating pathway using PU hot melt powder. The selected PU hot melt adhesive 6 was ground into a fine powder (100-600 μm). The powder was mixed with eTPU beads (prepared according to International Publication No. 2013 / 153190, Infinergy 230, BASF SE, based on diisocyanate 4, BDO, and polyol 1) in specified weight ratios to achieve coating amounts of 5 w / w%, 10 w / w%, and 15 w / w%, respectively. The eTPU beads were preheated to at least 120°C. After uniform mixing, residual powder was removed by filtration. The coated beads were non-adhesive and had storage stability. The hot melt coating amount was 5% to 15% relative to the beads.

[0147] Using eTPU beads coated with Hot Melt 6 (10.8 w / w% coating relative to the beads), plates were created by hot press molding according to the procedure described in Experiment 2. The mold temperature was maintained at 110°C for 15 minutes, and the cooling time was 9 minutes.

[0148] The following mechanical data was obtained: [Table 3]

[0149] Experiment 7. Realization of hot-melt coated beads with different chemical properties from eTPU. Additional coating experiments were conducted following the procedures described in Examples 2, 3, and 4, using different beads than eTPU. The same experimental setup was used for coating: loose ePA beads (prepared according to the procedure described in International Publication No. 2021 / 052881), foamed loose ePP beads (Neopor, BASF), eTPO (Argilix-O, JSP Co., Ltd.), foamed loose ePS beads (Styropor), and loose eTPA beads (prepared according to the procedure described in International Publication No. 2017 / 220671).

[0150] Plates from coated beads were achieved according to Experiment 5, either by using the same bead type or by mixing different chemical beads coated with the same hot melt.

[0151] Experiment 8. Realization of composite materials (plates / textiles) using hot-melt coated eTPU beads. 1 piece (16.3×9.6cm 2 A cotton canvas (0.45 mm thick, standard cotton weave, Rocholl Type 10A) was placed in the mold described in Experiment 5. Next, coated eTPU beads were inserted into the mold preheated to 140°C, and a plate was realized according to the procedure described in Experiment 5. A plate bonded to the cotton canvas fabric was realized.

[0152] Experiment 9. Delamination of eTPU plates made with hot-melt coated beads. Following Experiment 7, the eTPU plate bonded to the cotton canvas fabric was placed in an oven preheated to a temperature of 30 minutes. The plate was kept in the oven for 30 minutes. After being removed from the oven, the cotton canvas fabric was easily peeled off the eTPU plate by hand.

[0153] Alternatively, an eTPU plate bonded to a cotton canvas fabric according to Experiment 7 was placed in a water bath maintained at 80°C under agitation (650 rpm). After 30 minutes, delamination of the plate from the fabric was observed.

[0154] The same procedure was repeated by maintaining the water bath temperature at 90°C. After 30 minutes, not only did the fabric detach from the plate, but the beads on the plate also separated from each other and were recovered.

[0155] When the same procedure was repeated while maintaining the water bath temperature at or below 60°C, no delamination or bead disintegration occurred. This ensures the stability of the assembly throughout its service life, including during washing cycles at temperatures below 60°C.

Claims

1. A method for producing moldable thermoplastic particle foam particles with storage stability, which are at least partially coated with a hot melt adhesive, a １ ) A step of bringing the particles into contact with the hot melt adhesive to obtain coated particles, a ２ ) A step of moving the coated particles until the particles lose their adhesive properties. Methods that include...

2. The method according to claim 1, wherein the moldable thermoplastic particle foam has a glass transition temperature (Tg) of less than 100°C as measured by DSC in accordance with DIN EN ISO 11357-3:2013.

3. The method according to claim 1 or 2, wherein the hot melt adhesive is a non-reactive hot melt adhesive.

4. The method according to any one of claims 1 to 3, wherein the hot melt adhesive is brought into contact in a molten state.

5. The method according to any one of claims 1 to 4, wherein the hot melt adhesive in a molten state has a viscosity in the range of 0.1 mPas to 800,000 mPas when measured at 160°C.

6. The method according to any one of claims 1 to 5, wherein the hot melt adhesive in a molten state has a viscosity in the range of 1 mPas to 600,000 mPas when measured at 160°C.

7. The method according to any one of claims 1 to 6, wherein the hot melt adhesive in a molten state has a viscosity in the range of 10 mPas to 500,000 mPas when measured at 160°C.

8. The method according to claim 1, 2, 3, 5, 6, or 7, wherein the hot melt adhesive is brought into contact in a solid state by powder coating.

9. The hot melt adhesive is brought into contact in solution form, the hot melt adhesive is dissolved in an organic solvent, and then, a ３ ) Process a ２ ) followed by the step of removing the organic solvent and / or drying the particles at a temperature below the softening point of the hot melt adhesive to obtain the coated particles. The method according to claim 1, 2, 3, 5, 6, or 7, which performs the following.

10. The method according to any one of claims 1 to 9, wherein the moldable thermoplastic particle foam is a foamed thermoplastic elastomer.

11. The method according to claim 10, wherein the foamed thermoplastic elastomer is a foamed thermoplastic polyurethane.

12. Process a １ The method according to any one of claims 1 to 11, wherein contact is achieved by mixing or spraying.

13. The method according to any one of claims 1 to 12, wherein the particles, which are at least partially coated, are coated in an amount of 0.1% to 40% by weight based on the total weight of the particles and the coating.

14. Process a １ ) after and step a ２ The method according to any one of claims 1 to 13, wherein the particles are separated from each other before )

15. The method according to any one of claims 1 to 14, wherein the hot melt adhesive is a composition comprising a thermoplastic polymer.

16. The method according to claim 15, wherein the thermoplastic polymer is a thermoplastic polyurethane.

17. The method according to claim 15 or 16, wherein the composition comprising the thermoplastic polymer has a flow onset temperature (Tfb) in the range of 50°C to 160°C.

18. The method according to any one of claims 15 to 17, wherein the composition comprising the thermoplastic polymer has a flow onset temperature (Tfb) in the range of 60°C to 160°C.

19. The method according to any one of claims 15 to 18, wherein the composition comprising the thermoplastic polymer has a flow onset temperature (Tfb) in the range of 70°C to 160°C.

20. The method according to any one of claims 15 to 19, wherein the composition comprising the thermoplastic polymer has a flow onset temperature (Tfb) in the range of 70°C to 150°C.

21. A method for creating a sculptural object, b １ ) A step of coating particles according to the method described in any one of claims 1 to 20, b ２ Step b １ Step of shaping the particles obtained from Methods that include...

22. Process b ２ The method according to claim 21, wherein the molding in the ) is performed by steamless thermopress, steam chest molding, and / or by an electromagnetic field, particularly high frequency.

23. Process b ２ The method according to claim 22, wherein the molding in ) is performed by a steamless thermopress.

24. The method according to claim 22 or 23, wherein the thermopress is performed at a temperature of 60°C to 160°C.

25. The method according to any one of claims 22 or 24, wherein the thermopress is performed at a temperature of 80°C to 160°C.

26. The method according to any one of claims 22 to 25, wherein the thermopress is performed at a temperature of 90°C to 140°C.

27. The method according to any one of claims 22 to 26, wherein the thermopress is performed at a temperature of 100°C to 140°C.

28. The method according to any one of claims 21 to 27, wherein the molded body is a composite material of the particles and other materials such as textiles, leather, thermoplastic films, or metal components, particularly electronic components.

29. At least partially coated storage-stable particles of a moldable thermoplastic particle foam, which are at least partially coated with a hot-melt adhesive, wherein the coated particles are not adhesive.

30. Storage-stable particles at least partially coated with a moldable thermoplastic particle foam according to claim 29, wherein the hot-melt adhesive is a non-reactive hot-melt adhesive.

31. A molded body that can be obtained by the method described in any one of claims 21 to 28, or by molding a particle foam as described in claim 29 or 30.

32. Use of the at least partially coated storage-stable particles according to claim 29 or 30, or the molded body according to claim 31, for industrial, consumer, transportation, and / or construction applications.

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