Encapsulation of TPU granules

Abstract

The present invention is directed to particles comprising composition (A) comprising a thermoplastic polyurethane (PU-A) and composition (CB) comprising a thermoplastic polyurethane (PU-B), wherein composition (A) is at least partially coated with composition (B), a method for preparing said particles, and a method for manufacturing an article using said particles.

Description

[Technical Field]

[0001] The present invention is directed to thermoplastic polyurethane pellets, particularly those comprising an aliphatic diisocyanate-based thermoplastic polyurethane at least partially coated with a second thermoplastic polyurethane. In particular, the present invention is directed to particles comprising a composition (A) comprising a thermoplastic polyurethane (PU-A) and a composition (B) comprising a thermoplastic polyurethane (PU-B), wherein composition (A) is at least partially coated with composition (B), a method for preparing the particles, and a method for manufacturing an article using the particles.

[0002] Thermoplastic polyurethanes are typically shipped in pellet form and are therefore stored and formed into articles for ultimate customer use long after they reach the market.

[0003] During storage, transportation, and the molding process, the pellets are exposed to conditions that can adversely affect them. They can be adversely affected by radiation, air, water, mechanical shock, etc. Depending on the properties of the thermoplastic polyurethane, the pellets may also have a tendency to stick together during storage.

[0004] Therefore, preventing these adverse effects on the pellets has been a long-felt need in the market. Various methods have been adopted to prevent these adverse effects on the pellets. Appropriate packaging is required, which is costly and environmentally harmful. Additives are also used to prevent the adverse effects on the pellets from the environment, but these often affect the properties of the thermoplastic polyurethane and are costly.

[0005] Surprisingly, these problems have been solved by at least partially coating the thermoplastic polyurethane composition with a second polyurethane composition, for example by coating the pellets obtained during the preparation process with the second polyurethane composition.

[0006] Encapsulation of materials is a known method "per se." For example, U.S. Patent Application Publication No. 2018 / 0222087 discloses encapsulating additives during polymer preparation to facilitate easier handling. U.S. Patent Application Publication No. 2015 / 0091202 mentions improving the handling of pressure-sensitive hot melt adhesives. This principle has not been recognized for decades to solve the above-mentioned problems associated with handling thermoplastic polyurethane pellets. Particles, such as pellets containing thermoplastic polyurethane, are typically intermediate products for melting processes, and encapsulation of materials by this melting process results in a mixture of various materials, thus changing the properties of the composition. Therefore, the object of the present invention was to provide particles and methods for preparing particles that avoid these problems.

[0007] According to the present invention, this problem is solved by particles comprising a composition (A) comprising a thermoplastic polyurethane (PU-A) and a composition (B) comprising a thermoplastic polyurethane (PU-B), wherein composition (A) is at least partially coated by composition (B).

[0008] Thermoplastic polyurethanes (PU-A) and (PU-B) are typically based on isocyanates, polyols, and chain extenders, which are also considered as components. In addition, additives or catalysts can be used in the preparation process. The properties of thermoplastic polyurethanes can vary. For example, the properties of thermoplastic polyurethanes can depend on the components used, the additives used, and even the ratio of the components used.

[0009] In a first embodiment, the present invention is directed to particles comprising a composition (A) comprising a thermoplastic polyurethane (PU-A) and a composition (B) comprising a thermoplastic polyurethane (PU-B), wherein composition (A) is at least partially coated by composition (B).

[0010] Polyurethane (PU-A) is typically prepared using a diisocyanate (IA), a diol (DA), and optionally a chain extender (CE-A). Polyurethane (PU-B) is typically prepared using a diisocyanate (IB), a diol (DB), and optionally a chain extender (CE-B).

[0011] The properties of the particles according to the invention have proven to be particularly advantageous when the thermoplastic polyurethanes (PU-A) and (PU-B) are based on similar components, for example, the polyisocyanates (IA) and (IB) may be partially identical or identical, the polyols (DA) and (DB) may be partially identical or identical, and the chain extenders (CE-A) and (CE-B) may be partially identical or identical.

[0012] According to a further embodiment, the present invention also provides a method for producing a medicament for the treatment of a pulmonary arthritis. The thermoplastic polyurethane (PU-A) is a reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A); The thermoplastic polyurethane (PU-B) is a reaction product of the components diisocyanate (IB), diol (DB), and optionally a chain extender (CE-B); and at least one of the components of the thermoplastic polyurethane (PU-A) and at least one of the components of the thermoplastic polyurethane (PU-B) are at least partially identical; More preferably, the diol (DA) and the diol (DB), and the diisocyanate (IA) and the diisocyanate (IB), are at least partially identical, and even more preferably, the diol (DA) and the diol (DB), the diisocyanate (IA) and the diisocyanate (IB), and at least the chain extender (CE-A) and the chain extender (CE-B), are at least partially identical. The above particles are the subject of the present invention.

[0013] According to a further embodiment, the present invention also provides a method for producing a medicament for the treatment of a pulmonary arthritis. The thermoplastic polyurethane (PU-A) is a reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A); The thermoplastic polyurethane (PU-B) is a reaction product of the components diisocyanate (IB), diol (DB), and optionally a chain extender (CE-B); and at least one of the components of the thermoplastic polyurethane (PU-A) and at least one of the components of the thermoplastic polyurethane (PU-B) are at least 50% identical, preferably at least 70% identical, more preferably at least 85% identical; More preferably, the diol (DA) and the diol (DB), and the diisocyanate (IA) and the diisocyanate (IB) are at least 50% identical, preferably 70% identical, more preferably 85% identical, and even more preferably, the diol (DA) and the diol (DB), the diisocyanate (IA) and the diisocyanate (IB), and at least the chain extender (CE-A) and the chain extender (CE-B) are at least 50% identical, preferably at least 70% identical, more preferably at least 85% identical. The above particles are the subject of the present invention.

[0014] In the context of the present invention, at least partially identical or the same means that the components used to prepare the thermoplastic polyurethane contain, at least to a certain extent, the same chemical structure.

[0015] To adjust the hardness of the thermoplastic polyurethane, the amounts of the synthetic components used can be varied within a relatively wide molar ratio, and the hardness usually increases as the amount of chain extender increases. The mixing ratio of the components used is preferably adjusted to obtain a thermoplastic polyurethane having a Shore hardness measured according to DIN 53505 in the range of 60A to 60D, for example, in the range of 70A to 100A, preferably in the range of 70A to 98A, more preferably in the range of 70A to 90A.

[0016] Thus, according to a further embodiment, the present invention relates to a composition as described above, wherein the thermoplastic polyurethane has a Shore hardness, measured according to DIN 53505, in the range of 60A to 100A.

[0017] To produce the thermoplastic polyurethanes of the present invention, the isocyanate composition and the polyol composition (PZ) are reacted in the presence of a catalyst and, optionally, coagents and / or adjuvants, in amounts such that the equivalent ratio of NCO groups in the isocyanate to the sum of hydroxyl groups in the polyol used is 0.9 to 1.1:1, preferably 0.98 to 1.02:1, more particularly about 0.99 to 1.01:1.

[0018] The particles are preferably part of a granulation containing these particles. The particles may be rounded or plate-like. In a preferred embodiment, the particles have a maximum dimension of less than 30 mm, more preferably less than 20 mm, more preferably less than 10 mm. At the same time, the lower limit of the maximum diameter of the particles is preferably 0.5 mm, preferably at least 1 mm, more preferably at least 2 mm.

[0019] The term composition indicates that the composition does not only comprise the respective thermoplastic polyurethane, but may comprise several thermoplastic polyurethanes, additives and / or auxiliaries.

[0020] According to the present invention, composition (A) may contain thermoplastic polyurethane (PU-A) in an amount of 50 to 100% by weight, particularly 60 to 98% by weight, and more preferably 70 to 90% by weight, based on the weight of the composition. Composition (B) may contain thermoplastic polyurethane (PU-B) in an amount of 50 to 100% by weight, particularly 60 to 98% by weight, and more preferably 70 to 90% by weight, based on the weight of the composition.

[0021] According to the present invention, composition (A) is at least partially coated with composition (B). In particular, the surface of particles containing or consisting of composition (A) is at least partially coated with composition (B). According to the present invention, the coverage depends on the properties of compositions (A) and (B). For example, when composition (B) is used to shield composition (A) from radiation, the coverage may be in the range of 50% to 100%, particularly 60% to 100%, or 70% to 98%, 80% to 95%, or 85% to 90% of the surface. For example, when composition (B) is used to prevent particles prepared from composition (A) from sticking together, the coverage may be in the range of 40% or 50% to 100%, particularly 60% to 100%, or 70% to 98%, 80% to 95%, or 85% to 90% of the surface.

[0022] According to the present invention, the surface of the particles comprising or consisting of composition (A), in particular composition (A), can also be completely coated with composition (B).

[0023] According to a further embodiment, the present invention is also directed to particles as described above, in which composition (A) is completely coated by composition (B).

[0024] Composition (B) can be applied in the form of a thin layer, for example as a film.

[0025] According to a further embodiment, the present invention also relates to the above particles, wherein composition (A) is coated with a film of composition (B), the film of composition (B) preferably having a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0026] It is particularly advantageous to apply composition (B) to the process of preparation of particles comprising composition (A).

[0027] Preferably, the thermoplastic polyurethane has two functional groups reactive with an organic isocyanate, preferably a diisocyanate, and a polyol, preferably an isocyanate, and preferably has a functionality of 0.5×10 3 g / mol ~ 100 × 10 3 polyols, also called polyol diols, having a number average molecular weight of 0.05×10 g / mol, and, if desired, 3 g / mol ~ 0.499 × 10 3 g / mol) with a chain extender, preferably in the presence of a catalyst, an auxiliary, an additive or a mixture thereof.

[0028] The organic isocyanate, preferably diisocyanate, polymeric diol, and chain extender components, individually or together, are also referred to as components. Components including catalysts and / or auxiliaries and / or additives are also referred to as input materials.

[0029] To adjust the hardness and melt index of the thermoplastic polyurethane (TPU), the molar ratio of the amount of component (b) and the amount of chain extender (c), and optionally the amount of water, can be changed, whereby the hardness and melt viscosity increase as the isocyanate content increases, or as the isocyanate and chain extender (c) content increases, while the melt flow index decreases.

[0030] To produce polyisocyanate polyaddition products, preferably thermoplastic polyurethanes, isocyanates, isocyanate-reactive compounds, and in preferred embodiments, chain extenders, are reacted in the presence of, in preferred embodiments, a catalyst, and optionally, auxiliaries and / or additives, in an equivalent ratio of the NCO groups of the isocyanate, preferably a diisocyanate, to the sum of the hydroxyl groups of the isocyanate-reactive components and the chain extender of 0.95 to 1.10:1, preferably 0.98 to 1.08:1, and in particular about 1.0 to 1.05:1. In a highly preferred embodiment, the equivalent ratio is 1.0.

[0031] The polyisocyanate polyaddition product, preferably a thermoplastic polyurethane, preferably has a viscosity of at least 0.1 x 10 6 g / mol, preferably at least 0.4 × 10 6 g / mol, and in particular at least 0.6 × 10 6 The upper limit of the weight average molecular weight of a TPU is generally determined by processability and the desired range of properties. The weight average molecular weight is 0.8 x 10 6 It is preferred that it does not exceed 10 ...

[0032] Preferably, the isocyanate is an organic isocyanate, more preferably a diisocyanate. Further preferred isocyanates are selected from the group consisting of aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates, or mixtures thereof. More preferably, the isocyanate is an aliphatic isocyanate, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 4,4'-, 2,4'-, and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, or mixtures thereof.

[0033] Aliphatic isocyanates are preferred as they exhibit better stability to electromagnetic radiation, e.g., light. A further advantage of aliphatic isocyanates is that they can be produced on a bio-based basis.

[0034] More preferably, the aliphatic isocyanate is selected from the group consisting of 1,5-pentamethylene diisocyanate, 4,4'-, 2,4'-, and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), or a mixture thereof. The use of 1,5-pentamethylene diisocyanate has the additional advantage that it can be produced biobased.

[0035] Highly preferred aliphatic isocyanates are 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), and especially preferred are 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate.

[0036] According to a further embodiment, the present invention also provides that the diisocyanate (IA) is an aliphatic diisocyanate, preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5 diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and / or 1,3-bis(isocyanatomethyl)cyclohexane. The present invention relates to the above particles, which are selected from the group consisting of hexane (HXDI), 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, or mixtures thereof, and more preferably 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), or H12MDI.

[0037] In a preferred embodiment, prepolymers that are the reaction product of a polymeric diol and an isocyanate are used, and these prepolymers preferably contain free isocyanate groups. The NCO content of these prepolymers is preferably 10% to 25%. Prepolymers offer the advantage that the pre-reaction during prepolymer preparation shortens the reaction time required to prepare the thermoplastic polyurethane itself.

[0038] According to the invention, the properties of composition (A) and composition (B) are adapted depending on the use of the particles and the ratio of composition (A) to composition (B) present in the resulting particles.

[0039] In a preferred embodiment, the Shore A hardness of composition (A) is less than 80, preferably less than 70, more preferably less than 65, more preferably less than 60, more preferably less than 55, and more preferably less than 50.

[0040] In a further embodiment, the hardness of composition (B) is preferably greater than 85 Shore A, preferably greater than 90 Shore A, more preferably greater than 30 Shore D, more preferably greater than 40 Shore D, most preferably greater than 55 Shore D, and at the same time less than 180 Shore D, more preferably less than 150 Shore D.

[0041] According to a further embodiment, the present invention is also directed to the above particles, wherein the Shore A hardness of composition (A), measured according to DIN ISO 7619-1 (2016), is less than 80, preferably less than 70, more preferably less than 65, more preferably less than 60, more preferably less than 55, and more preferably less than 50.

[0042] According to a further embodiment, the present invention also relates to particles as described above, wherein the Shore D hardness of composition (B), measured according to DIN ISO 7619-1 (2016), is greater than 30, preferably greater than 40, preferably greater than 55.

[0043] In a preferred embodiment, the Shore hardness of composition (A) and composition (B) in the particles is measured by the nanoindenter method. To obtain the cross-sectional area, the particles are preferably cut perpendicular to the surface. The cutting step is preferably performed after the particles have been cooled. The particles are cooled below the glass transition temperatures of both composition (A) and composition (B), and the cooling is preferably performed below -8 x 10°C. The cooling is preferably performed in liquid nitrogen, more preferably in nitrogen at a temperature below -8 x 10°C. Cutting at a low temperature prevents the formation of grooves that would interfere with subsequent hardness measurements.

[0044] For preparation, the encapsulated particles are cut to obtain cross-sections. This cutting process is carried out below the glass transition temperature by cryosectioning using a microtome, e.g., a Leica EM UC7 Ultramicrotome, to prevent grooves that would later interfere with the actual measurement. For cooling, the particles are immersed in liquid nitrogen. Afterwards, the particles are fixed via a specimen holder and subsequently trimmed with a diamond knife to prepare an ultra-flat block face. During the subsequent warm-up of the specimen at room temperature, the particles are covered under a nitrogen atmosphere to avoid intensive ice / water condensation.

[0045] The actual indenter measurements are in accordance with DIN EN ISO 14577-1. A Berkovich tip (α=65.27°) can be used as the indenter, and the test is usually performed by the load-controlled method using an XP indentation head. The load is set to 1 mN for Shore D materials and 0.3 mN for Shore A materials. Multiple nanoindenter measurements, preferably 10, are performed in the core (component A) and shell (component B) regions, and an average value is obtained.

[0046] The correlation between the measurement values ​​obtained by the nanoindenter method and the Shore hardness is shown in Figures 3 and 4.

[0047] The Shore hardness of composition (A) and composition (B) can be adjusted by the ratio of the components and isocyanate to the polyol composition used. The ratio of polyol to chain extender used can also be adjusted to change the Shore hardness of the resulting polyurethane.

[0048] One or more polyols are used to prepare polyurethane (PU-A) and polyurethane (PU-B). Conventional polyols are well known to those skilled in the art. Polyols usable in the context of the present invention are particularly well-known polyhydroxyl compounds. The polyol has a statistical average of at least 1.8 and at most 2.4 Zerevitinov-active hydrogen atoms, which is also considered as the functionality of the polymer diol and indicates the amount of isocyanate-reactive groups per molecule, theoretically calculated from a certain amount of substance to one molecule. The functionality is more preferably 1.9 to 2.2, particularly preferably 2. The compound reactive with isocyanate is preferably 0.5 x 10 3 g / mol~8×10 3 g / mol, preferably 0.7 × 10 3 g / mol ~ 6.0 × 10 3 g / mol, specifically 0.8 × 10 3 g / mol ~ 4.0 × 10 3 It has a molecular weight of g / mol.

[0049] The polyol may be a single compound or a mixture of various such compounds, in which case the mixture meets the above requirements.

[0050] These long-chain compounds are typically used in an amount of 1 mol % equivalent to 80 mol % equivalent based on the isocyanate group content in the polyisocyanate.

[0051] The polyol is preferably selected from the group consisting of polyesterols, polyetherols, or polycarbonate diols, more preferably selected from the group consisting of polyether polyols and polycarbonates. Polyether polyols are particularly preferred. More preferably, the polyol is a polymer diol.

[0052] Preference is given to polyols selected from the group consisting of copolyesters based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1,2-ethanediol and 1,4-butanediol; copolyesters based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and mixtures of 1,4-butanediol and 1,6-hexanediol; polyesters based on adipic acid and 3-methyl-pentanediol-1,5 and / or polytetramethylene glycol (polytetrahydrofuran, PTHF); particularly preferably copolyesters based on adipic acid and mixtures of 1,2-ethanediol and 1,4-butanediol; or polyesters based on adipic acid, succinic acid, pentanedioic acid, sebacic acid or mixtures thereof and polytetramethylene glycol (PTHF) or mixtures thereof.

[0053] Preferred polyether polyols are polyether diols, more preferably polyether polyols based on ethylene oxide, propylene oxide and / or butylene oxide.

[0054] Another preferred polyether is polytetrahydrofuran (PTHF). In a preferred embodiment, the polytetrahydrofuran has a viscosity of 0.6×10 measured according to DIN 55672-1. 3 g / mol ~ 1.7 × 10 3 g / mol, more preferably 0.8×10 3 g / mol ~ 1.4 × 10 3 g / mol, and even more preferably 0.9×10 3 g / mol ~ 1.1 × 10 3g / mol, and most preferably 1.0 × 10 3 It has a number average molecular weight of g / mol.

[0055] The number average molecular weight Mn in the context of the present invention is preferably determined in accordance with DIN 55672-1.

[0056] According to a further embodiment, the present invention also provides that the diol (DA) is a polyether diol, more preferably 0.5×10 3 g / mol ~ 1.5 × 10 3 g / mol, more preferably 0.8 × 10 3 g / mol ~ 1.2 × 10 3 g / mol, most preferably 1.0 × 10 3 The present invention relates to particles as described above, having a molecular weight of 1000 g / mol, and most preferably polytetrahydrofuran.

[0057] Polyether polyols are obtained by known methods such as, but not limited to, the reaction between at least one starter molecule, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, sucrose, or sorbitol, and an alkylene oxide, such as EO, PO, a mixture of EO and PO, or tetrahydrofuran.

[0058] Preferred polyether polyols include polytetramethylene ether glycol (also called PTMEG), polypropylene oxide glycol, and polybutylene oxide glycol. Particularly preferred are PTMEG or α-hydro-ω-hydroxypoly(oxytetramethylene) diols, which have a molecular weight of 500 g / mol to 3.0×10 3 g / mol, preferably 600 g / mol to 2.0 × 10 3 g / mol, more preferably 700 g / mol to 1.8 × 10 3 They preferably have a number average molecular weight Mn of 1000 g / mol. They are commercially available under the trade name PolyTHF®.

[0059] Polyether polyols have the advantage that they are more stable to hydrolysis and are therefore applicable in applications where this is a requirement.

[0060] Suitable polyester polyols may also be selected from the group consisting of reaction products of polyhydric alcohols, polymerization products of lactones, and polymerization products of dicarboxylic acids and polyhydric alcohols. The term "lactone" refers to a cyclic ester of a hydroxycarboxylic acid. Such polyester polyols include hydroxyl-terminated reaction products of polyhydric alcohols, polyester polyols obtained as the polymerization product of lactones, such as caprolactone, in combination with polyols, and polyester polyols obtained by the polymerization of polyhydric alcohols and dicarboxylic acids, such as adipic acid. Preferred polyester polyols include the polymerization products of lactones or polycaprolactones and the polymerization products obtained by the polymerization of dicarboxylic acids and polyhydric alcohols.

[0061] In a preferred embodiment, polyester polyols obtained by polymerization of dicarboxylic acids and polyhydric alcohols are used. Suitable dicarboxylic acids include at least one C4-C12 dicarboxylic acid, while at least one C2-C14 diol is suitable as the polyhydric alcohol. Preferably, the C4-C12 dicarboxylic acid is selected from the group consisting of aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sebacic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. More preferably, the dicarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, suberic acid, phthalic acid, isophthalic acid, and terephthalic acid, and most preferably, adipic acid, suberic acid, and phthalic acid. These dicarboxylic acids can be used alone or in the form of a mixture.

[0062] Preferably, the C2-C14 diol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethylpropane-1,3-diol, 1,3-propanediol, 2-methyl-1,3-propanediol, and dipropylene glycol, and can be used alone or in mixtures. More preferably, the C2-C14 diol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol, or a mixture thereof. Most preferably, the C2-C14 diol is selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol, or a mixture thereof.

[0063] Polyesters have low hydrolytic stability and are preferred in applications where biodegradation is required.

[0064] In another preferred embodiment, the polyol is a polycarbonate diol, preferably an aliphatic polycarbonate diol. Typically, polycarbonate diols have good microwave transparency, low dirt uptake, and better flame retardancy. Preferred polycarbonate diols are, for example, alkanediol-based polycarbonate diols. Preferred polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols. Preferred polycarbonate diols are based on butanediol, pentanediol, or hexanediol, particularly 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol, or a mixture thereof, and particularly preferably based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture thereof. Most preferred in the present invention are polycarbonate diols based on butanediol and hexanediol, polycarbonate diols based on pentanediol and hexanediol, polycarbonate diols based on hexanediol, and mixtures of two or more of these polycarbonate diols.

[0065] Preferably, the polycarbonate diol used has a viscosity of 0.5×10 as measured by GPC. 3 ~4.0×10 3 g / mol range, preferably 0.65 × 10 measured by GPC 3 g / mol ~ 3.5 × 10 3 g / mol, particularly preferably 0.8×10 measured by GPC 3 g / mol ~ 3.0 × 10 3 It has a number average molecular weight Mn in the range of g / mol.

[0066] In another preferred embodiment, the polyol is a polysiloxane diol. Preferably, the oligosiloxane or polysiloxane has the formula (I): [ka] wherein Ak preferably represents C2-C4 alkylene, R represents C1-C4 alkyl, and p, q, and q' are each independently a number selected from the range of 0 to 50. In a more preferred moiety (B) of formula (I), p is in the range of 1 to 50, particularly 2 to 50.

[0067] In a preferred embodiment, A represents the same alkylene unit in each residue (C1), and in yet another preferred embodiment, A represents different alkylene units in the same residue (C1). In a preferred embodiment, A is ethylene or propylene in the same residue (C1).

[0068] One preferred polydimethylsiloxane diol has the formula (II): [ka] (wherein m is in the range of 5 to 80), or formula (III): [ka] It has.

[0069] The molecular weight is preferably 0.500 x 10 3 g / mol ~ 15 × 10 3 g / mol, more preferably 1.0 × 10 3 g / mol ~ 3.0 × 10 3 g / mol.

[0070] In a preferred embodiment, the polyol is a mixture of two or more polyols. In a preferred embodiment, the polyol is a mixture of at least one polyether polyol and at least one polycarbonate diol.

[0071] When a mixture of polyether polyol and polycarbonate diol is used, the polycarbonate diol is used in an amount of less than 50 wt %, preferably less than 35 wt %, more preferably less than 15 wt %, and most preferably less than 5 wt %, based on the total weight of the polyol mixture.

[0072] In a preferred embodiment, chain extenders are used in the synthesis of polyurethanes, preferably thermoplastic polyurethanes. The chain extenders are preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds, and are preferably in the range of 0.05×10 3 g / mol ~ 0.499 × 10 3 The chain extender has a molecular weight of 1000 g / mol and preferably has two groups (also called functional groups) that react with isocyanates. The chain extender can be one type of chain extender or a mixture of at least two types of chain extenders.

[0073] The chain extender is preferably a difunctional compound, and preferred examples include diamines or alkanediols having 2 to 10 carbon atoms in the alkylene group, or mixtures thereof.

[0074] In a preferred embodiment, the chain extender (c) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof.

[0075] In a preferred embodiment, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, preferably the respective oligo- and / or polypropylene glycols, or mixtures thereof.

[0076] Particularly preferred chain extenders are 1,3-propanediol, 1,4-butanediol, or 1,6-hexanediol, or mixtures thereof.

[0077] In a preferred embodiment, the chain extender is 1,3-propanediol, 1,4-butanediol, or a mixture thereof. The most preferred chain extender is a mixture of 1,3-propanediol and 1,4-butanediol. The ratio of 1,4-butanediol to 1,3-propanediol is between 55:45 and 80:20, more preferably between 60:40 and 75:25, and more preferably between 65:35 and 75:25.

[0078] According to a further embodiment, the present invention also relates to the above particles, preferably the chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or deca-alkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof. ) is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, preferably the respective oligo- and / or polypropylene glycols, or a mixture thereof, or more preferably the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol, or 1,4-butanediol, or a mixture thereof, most preferably the chain extender (CE-A) is a mixture of 1,3-propanediol or 1,4-butanediol.

[0079] To adjust the hardness of the thermoplastic polyurethane, the amounts of the synthetic components used can be varied within a relatively wide range of molar ratios, and the hardness usually increases as the amount of chain extender increases. The mixing ratio of the components used is preferably adjusted to obtain a thermoplastic polyurethane having a Shore hardness within the above range.

[0080] Catalysts can be used in the preparation of polyurethanes, particularly to promote the reaction between the NCO groups of the isocyanate and the hydroxyl groups of the polyol and chain extender, such as those selected from the group consisting of tertiary amines and organometallic compounds, or mixtures thereof.

[0081] Preferred tertiary amines are selected from the group consisting of triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethyl-piperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.octane], or mixtures thereof.

[0082] Preferred organometallic compounds are selected from the group consisting of titanate esters, iron compounds, tin compounds, and bismuth salts, or mixtures thereof. A preferred iron compound is iron(III) acetylacetonate. A preferred tin compound is selected from the group consisting of tin diacetate, tin dioctoate, tin dilaurate, and dialkyltin salts of aliphatic carboxylic acids, preferably tin dioctoate, or mixtures thereof. A preferred titanium ester is tetrabutyl orthotitanate. In preferred bismuth salts, bismuth exists in oxidation state 2 or 3, especially oxidation state 3. Carboxylate salts are preferred, preferably carboxylate salts having 6 to 14 carbon atoms, especially 8 to 12 carbon atoms. Highly preferred bismuth salts are bismuth(III) neodecanoate, bismuth 2-ethylhexanoate, or bismuth octanoate, or mixtures thereof.

[0083] The catalyst is preferably a compound reactive with isocyanate, preferably used in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of polyol. It is preferred to use a tin catalyst, particularly tin dioctoate.

[0084] A highly preferred catalyst is SDO (tin(II) 2-ethylhexanoate), preferably used in an amount of 0.35 to 0.4 parts by weight based on the composition.

[0085] Furthermore, auxiliaries or additives can be added to the composition / component, preferred examples of which include surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubrication and demolding aids, dyes and pigments, if necessary and preferably stabilizers against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and / or plasticizers.

[0086] In the context of the present invention, stabilizers are additives that protect plastics or plastic compositions from harmful environmental influences. Preferred examples are primary and secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, quenchers, and flame retardants. Examples of commercially available stabilizers are listed in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pp. 98-S136.

[0087] In a preferred embodiment, the ultraviolet absorber is 0.3×10 3 g / mol, especially 0.39 × 10 3 Further, preferred UV absorbers have a number average molecular weight of greater than 5×10 g / mol. 3 Molecular weight not exceeding 2×10 g / mol, particularly preferably 2×10 3 It has a molecular weight not exceeding g / mol.

[0088] The UV absorber is preferably selected from the group consisting of cinnamates, oxanilides and benzotriazoles, or a mixture thereof, and benzotriazoles are particularly suitable as UV absorbers. Examples of particularly suitable UV absorbers are Tinuvin® 213, Tinuvin® 234, Tinuvin® 312, Tinuvin® 571, Tinuvin® 384 and Eversorb® 82.

[0089] The ultraviolet absorber is preferably added in an amount of 0.01 to 5% by weight, preferably 0.1 to 2.0% by weight, and particularly preferably 0.2 to 0.5% by weight, based on the total weight of the composition.

[0090] In many cases, UV stabilization based on antioxidants and UV absorbers as described above is not sufficient to ensure good stability of the composition against the harmful effects of UV light. In this case, hindered amine light stabilizers (HALS) are added to the composition in addition to the antioxidants and / or UV absorbers, or as the sole stabilizer.

[0091] Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Munich, 2001, pp. 123-136.

[0092] Particularly preferred hindered amine light stabilizers are bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin® 765, Ciba Spezialitaetenchemie AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid (Tinuvin® 622). In particular, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid (Tinuvin® 622) is preferred when the titanium content of the final product is less than 150 ppm, preferably less than 50 ppm, and especially less than 10 ppm, based on the components used.

[0093] The HALS compound is preferably used in a concentration of 0.01% to 5% by weight, particularly preferably 0.1% to 1% by weight, in particular 0.15% to 0.3% by weight, based on the total weight of the composition.

[0094] A particularly preferred UV stabilizer contains a mixture of a phenolic stabilizer, a benzotriazole, and a HALS compound in the preferred amounts described above.

[0095] Further information on the abovementioned auxiliaries and additives can be found in the technical literature, for example in Plastics Additives Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001.

[0096] According to the present invention, the amounts of additives used in compositions (A) and (B) may differ, for example, composition (A) may contain little or no additives, and composition (B) may contain additives, such as stabilizers.

[0097] According to a further aspect, the present invention is also directed to a granulate containing particles according to the present invention.

[0098] Another aspect of the present invention is the production of particles according to the present invention.

[0099] The compositions comprising thermoplastic polyurethane (PU-A) or (PU-B) can be produced discontinuously or continuously. Preferred methods for preparing composition (A) and / or composition (B) are, for example, the reactive extruder method, the belt-line method, or the "one-shot" method, preferably the "one-shot" method or the reactive extruder method, and most preferably the reactive extruder method.

[0100] These methods are used either by directly mixing the components or by applying a prepolymer method.

[0101] The polyisocyanate prepolymer can be obtained by reacting the above polyisocyanate in excess with a compound reactive with isocyanate, preferably a polyol, at a temperature of 30°C to 100°C, preferably 8 x 10°C.

[0102] In the "one-shot" method, the components of a diisocyanate, an isocyanate-reactive compound, preferably a polyol, more preferably a polyol diol, and in a more preferred embodiment, a chain extender, are mixed together. This can be done sequentially or simultaneously, in a preferred embodiment, in the presence of a catalyst. In the extruder method, the components of a diisocyanate, an isocyanate-reactive compound, preferably a polyol, more preferably a diol, and in a preferred embodiment, a chain extender, and in a more preferred embodiment, a catalyst are mixed together. The mixing in the reactive extrusion method is preferably carried out at a temperature of 100°C to 280°C, preferably 140°C to 250°C. The resulting thermoplastic polyurethane is preferably in the form of a granule or powder. Auxiliaries and additives can be added during the synthesis of the thermoplastic polyurethane or to the thermoplastic polyurethane. The latter is preferred. This is particularly true when the additives or auxiliaries are not inert to the isocyanate, the chain extender, the isocyanate-reactive compound, or the catalyst.

[0103] The co-agent may be added during the synthesis of the thermoplastic polyurethane. In another preferred embodiment, the co-agent is added to the thermoplastic polyurethane after its synthesis.

[0104] In a preferred embodiment, the synthesis of the thermoplastic polyurethane is carried out in an extruder, more preferably a twin-screw extruder, which, due to its pumping capability, allows for more precise setting of the extruder temperature and output.

[0105] According to the present invention, it is also possible to prepare composition (A) and composition (B) using different methods.

[0106] The input materials for composition (A) and composition (B) are preferably the input materials outlined above. Typically, thermoplastic polyurethane (PU-A) is a reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A), and thermoplastic polyurethane (PU-B) is a reaction product of the components diisocyanate (IB), diol (DB), and optionally a chain extender (CE-B), and at least one of the components of thermoplastic polyurethane (PU-A) and at least one of the components of thermoplastic polyurethane (PU-B) contains at least one similar component, more preferably a similar diol and a similar diisocyanate, even more preferably a similar diol, a similar isocyanate, and a similar chain extender. In this context, "similar" means that when at least one of the components is a mixture of at least two substances, at least one of the at least two substances is chemically identical between thermoplastic polyurethane (PU-A) and thermoplastic polyurethane (PU-B).

[0107] The components and their ratios are preferably selected so as to adjust the Shore hardness of compositions (A) and (B) to the above ranges: the Shore hardness of composition (A) is preferably in the range of 30A to 95A, and the Shore hardness of composition (B) is preferably in the range of 95A to 80D.

[0108] It is more preferred that all of the components of the thermoplastic polyurethane (PU-A) and the thermoplastic polyurethane (PU-B) are similar, and most preferred that all of the components are identical.

[0109] In a preferred embodiment, the diol (DA) or the diol (DB) comprises polytetrahydrofuran, more preferably, the diol (DA) and the diol (DB) comprise polytetrahydrofuran, and the diisocyanate (IA) and the diisocyanate (IB) comprise 4,4'-, 2,4'-, and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), more preferably, the diol (DA) and the diol (DB) comprise polytetrahydrofuran, and the diisocyanate (IA) and the diisocyanate (IB) comprise 4,4'-, 2,4'-, and 2,2'-dicyclohexylmethane diisocyanate (H12MDI). The isocyanate (IA) and diisocyanate (IB) include 4,4'-, 2,4'-, and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), and the chain extender includes butanediol and propanediol, more preferably the ratio of 1,4-butanediol to 1,3-propanediol in the chain extender is between 55:45 and 80:20, more preferably between 60:40 and 75:25, more preferably between 65:35 and 75:25.

[0110] Typically, the Vicat softening temperature of composition (B) is from 150° C. to 300° C., more preferably from 175° C. to 230° C. The Vicat softening temperature is preferably measured according to DIN EN ISO 306 “10 N and 120° C. / h (VST A 120)”.

[0111] Suitable methods for coating compositions or particles are known in principle from the prior art. Preferably, composition (A) is coated with composition (B) during the preparation of the particles.

[0112] According to a further aspect, the present invention also provides a method for producing particles according to the invention, comprising the steps of: (i) extruding strands (SA) of composition (A); (ii) coating the strands (SA) with composition (B) to form strands (S-AB); and (iii) forming particles from the strands (S-AB); The present invention is directed to a method, including:

[0113] Suitable methods may include, for example, co-extrusion of composition (A) and composition (B).

[0114] According to a further embodiment, the present invention is also directed to a method for producing the above particles, in which strands (SA) are co-extruded with tubular strands (SB) of composition (B) to form strands (S-AB).

[0115] Thus, co-extrusion forms a tube filled with a core of composition (A) surrounded by a tube of composition (B). Particles are then formed from the strands, for example by crimping or cutting.

[0116] According to a further embodiment, the present invention is also directed to a method for producing the above particles, in which the strands (S-AB) are crimped to form pellets.

[0117] According to the invention, it is also possible to prepare particles by a process comprising producing layers or strands of composition (A), coating the produced layers or strands with composition (B) to form an intermediate product, and in a second step forming particles from the intermediate product, which forming step is preferably carried out by crimping, cutting, bending, twisting, or a combination thereof.

[0118] According to the invention, it is also possible to prepare particles of composition (A) and subsequently coat the prepared particles with composition (B), i.e., to form pellets from composition (A) and coat the formed pellets with composition (B) in a second step.

[0119] The at least partial coating of composition (A) with composition (B) is preferably carried out by a process selected from spray coating, spray coating in a fluidized bed, coextrusion, dip coating, brushing, pan coating.

[0120] It has been found that the preparation of a coextruded intermediate product having a coaxial structure of composition (A) and composition (B) is particularly advantageous, the core strand of which usually comprises composition (A) and the outer strands comprise composition (B).

[0121] In a further embodiment of the present invention, the particles are obtained from an intermediate product having a sandwich layer structure. A layer of composition (A) is preferably coated with two layers of composition (B), forming a sandwich layer structure with the top and bottom layers of composition (B) and the layer of composition (A) between these two layers. The sandwich intermediate product is preferably coextruded.

[0122] Co-extruding the sandwich intermediate product preferably means that composition (B) and composition (A) are melted. The melting preferably occurs in an extruder. The molten composition (A) and the molten composition (B) are preferably directed to a flat-sheet co-extrusion die. The die forms a sandwich sheet comprising composition (A) as a middle portion and top and bottom layers comprising composition (B). The co-extruded intermediate product is preferably cooled, flattened through a calender unit, or both.

[0123] The temperature in the co-extrusion step is preferably 180°C to 220°C.

[0124] The intermediate product can be formed into particles, preferably by cutting or crimping.

[0125] Crimping is preferred because it allows the composition (A) and the composition (B) to be more completely encapsulated into particles.

[0126] The crimping temperature is an important parameter and depends greatly on the speed of the crimping process, the composition formulation, the cooling temperature, the layer thickness, and the material and design of the crimping equipment. On the one hand, the melt must be cooled and the resulting sheet must have sufficient elongation stability to maintain the web tension for further processing, and on the other hand, the plastic deformability of compositions (A) and (B) must be set within a specific range so that the subsequent crimping and cutting equipment can provide a fully encapsulated article.

[0127] The thickness of the core and shell is adjusted by varying the feed ratio between composition (A) and composition (B) and the take-up speed of the strand towards the sealing device. The resulting pellets are then cooled either by a water bath or by a nozzle, preferably by spraying water onto the particles.

[0128] In a preferred embodiment, the particles are UV curable.

[0129] According to a further aspect, the present invention is also directed to the use of the particles or the granulate described above for the manufacture of an article.

[0130] Therefore, another aspect of the present invention is expanded beads or particles made from particles according to the present invention.

[0131] The expanded beads and moldings made from the expanded beads can be used in a variety of applications, which are incorporated herein by reference (see, e.g., WO 94 / 20568, WO 2007 / 082838, WO 2017 / 030835, WO 2013 / 153190, WO 2010 / 010010).

[0132] Another aspect of the present invention is the use of particles according to the present invention for manufacturing an article.

[0133] The manufacture of these articles is preferably carried out by injection molding, calendaring, film production, powder sintering or extrusion.

[0134] The particles in preferred embodiments are subjected to, for example, injection molding, calendaring, powder sintering, or extrusion to form an article.

[0135] Yet another aspect of the present invention is an article produced using particles according to the present invention or obtained by a method according to the present invention.

[0136] Preferably, the article is selected from the group consisting of cables, cases, mobile phones, sheathing, covers, braking elements, bellows, foils, fibers, film moldings, roofing or flooring materials for buildings or vehicles, nonwovens, gaskets, packaging materials, rolls, shoe soles, shoe midsoles, hoses, cables, cable connectors, cable coverings, pillows, laminates, telephones, profiles, straps, saddles, foams, and preparations which, upon further foaming, can be used to make plug connections, televisions, trailing cables, photovoltaic modules, automotive linings, wiper blades, load-bearing members for elevators, roping arrangements, drive belts for machines, preferably passenger conveyors, handrails for passenger conveyors, and modifiers (meaning substances which affect the properties of other materials) for thermoplastic materials. Each of these articles is itself a preferred embodiment and is also referred to as an application.

[0137] More preferably, the product is selected from a cover, packaging material, case, telephone, mobile phone, television, or cable, more preferably a cable for an electronic device. [Brief explanation of the drawings]

[0138] [Figure 1]1 shows a coextrusion apparatus. Composition (A) is fed to a coextrusion die (3) via melt channel (1). Composition (B) is fed to the coextrusion die (3) via melt channel (2). Melt channels (1) and (2) are combined so that an intermediate product (5) leaves the coextrusion die (3) having a core of composition (A) coated with composition (B). Cooling (4) may be applied. The intermediate product (5) is crimped by a sealing device (6) to form particles (7). [Figure 2] 1 shows a calendering device with a coextrusion die (3) for sandwich sheets. Composition (A) is fed to the coextrusion die (3) via melt channel (1). Composition (B) is fed to the coextrusion die (3) via melt channel (2). Melt channels (1) and (2) are combined so that intermediate product (5) leaves the coextrusion die (3), which is a sandwich sheet having a core sheet of composition (A) coated with two sheets of composition (B). Intermediate product (5) is crimped by a sealing device (6) to form particles (7). [Figure 3] 1 is a graph showing the correlation between Shore A hardness (x-axis) and hardness (unit: MPa) measured by nanoindentation (y-axis). [Figure 4] 1 is a graph showing the correlation between Shore D hardness (x-axis) and hardness (unit: MPa) measured by nanoindentation (y-axis).

[0139] Further embodiments of the invention can be found in the claims and the examples. It will be understood that the features of the subject matter / method / use according to the invention mentioned above and described below can be used not only in the combination specified in each case but also in other combinations without departing from the scope of the invention. Thus, for example, combinations of preferred features with particularly preferred features, or particularly preferred features with features not further characterized, etc. are implicitly encompassed even if this combination is not explicitly mentioned.

[0140] The following are illustrative embodiments of the present invention, but are not intended to limit the present invention. In particular, the present invention also encompasses embodiments that result from the dependency references and hence combinations specified below.

[0141] 1. Particles comprising a composition (A) containing a thermoplastic polyurethane (PU-A) and a composition (B) containing a thermoplastic polyurethane (PU-B), wherein composition (A) is at least partially coated with composition (B).

[0142] 2. Particles (P) comprising a particle comprising a composition (A) comprising a thermoplastic polyurethane (PU-A) and a composition (B) comprising a thermoplastic polyurethane (PU-B), wherein the particle comprising composition (A) is at least partially coated with composition (B).

[0143] 3. Thermoplastic polyurethane (PU-A) is the reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A); Thermoplastic polyurethane (PU-B) is the reaction product of the components diisocyanate (IB), diol (DB), and optionally a chain extender (CE-B), and at least one of the components of the thermoplastic polyurethane (PU-A) and at least one of the components of the thermoplastic polyurethane (PU-B) are at least partially identical; More preferably, the diol (DA) and the diol (DB) and the diisocyanate (IA) and the diisocyanate (IB) are at least partially identical, and even more preferably, the diol (DA) and the diol (DB), the diisocyanate (IA) and the diisocyanate (IB), and at least the chain extender (CE-A) and the chain extender (CE-B) are at least partially identical. 3. The particle of embodiment 1 or 2.

[0144] 4. Particles according to any one of embodiments 1 to 3, wherein at least 50% of the surface of composition (A) is covered by composition (B), preferably at least 60% of the surface, more preferably at least 70% of the surface, in particular at least 80% of the surface, and most preferably at least 90% of the surface.

[0145] 5. The particle of any one of embodiments 1 to 4, wherein composition (A) is completely coated by composition (B).

[0146] 6. Particles according to any one of embodiments 1 to 5, wherein composition (A) is coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0147] 7. A particle according to any one of embodiments 1 to 6, wherein the particle comprising composition (A) is coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0148] 8. Diisocyanate (IA) is an aliphatic diisocyanate, preferably tri-, tetra-, penta-, hexa-, hepta-, and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 4,4 8. The particle of any one of embodiments 1 to 7, wherein the diisocyanate is selected from the group consisting of 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, or a mixture thereof, more preferably 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), or H12MDI.

[0149] 9. The particles of any one of embodiments 1 to 8, wherein the Shore A hardness of composition (A), measured according to DIN ISO 7619-1 (2016), is less than 80, preferably less than 70, more preferably less than 65, more preferably less than 60, more preferably less than 55, more preferably less than 50.

[0150] 10. The diol (DA) is a polyether diol, more preferably 0.5×10 3 g / mol ~ 1.5 × 10 3 g / mol, more preferably 0.8 × 10 3 g / mol ~ 1.2 × 10 3 g / mol, most preferably 1.0 × 10 310. The particles of any one of embodiments 1 to 9, having a molecular weight of 1000 g / mol, and most preferably polytetrahydrofuran.

[0151] 11. The chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof; preferably, the chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof; 11. The particle according to any one of embodiments 1 to 10, wherein the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, preferably the respective oligo- and / or polypropylene glycols, or mixtures thereof; more preferably the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol or 1,4-butanediol, or mixtures thereof; most preferably the chain extender (CE-A) is a mixture of 1,3-propanediol or 1,4-butanediol.

[0152] 12. Particles according to any one of embodiments 1 to 11, wherein the Shore D hardness of composition (B), measured according to DIN ISO 7619-1 (2016), is greater than 30, preferably greater than 40, preferably greater than 55.

[0153] 13. A granulation comprising particles according to any one of embodiments 1 to 12.

[0154] 14. A granule comprising particles containing composition (A) comprising a thermoplastic polyurethane (PU-A) and composition (B) comprising a thermoplastic polyurethane (PU-B), wherein composition (A) is at least partially coated with composition (B).

[0155] 15. A granulated product comprising particles (P) containing particles comprising composition (A) containing thermoplastic polyurethane (PU-A) and composition (B) containing thermoplastic polyurethane (PU-B), wherein the particles comprising composition (A) are at least partially coated with composition (B).

[0156] 16. Thermoplastic polyurethane (PU-A) is the reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A); Thermoplastic polyurethane (PU-B) is the reaction product of the components diisocyanate (IB), diol (DB), and optionally a chain extender (CE-B), and at least one of the components of the thermoplastic polyurethane (PU-A) and at least one of the components of the thermoplastic polyurethane (PU-B) are at least partially identical; More preferably, the diol (DA) and the diol (DB) and the diisocyanate (IA) and the diisocyanate (IB) are at least partially identical, and even more preferably, the diol (DA) and the diol (DB), the diisocyanate (IA) and the diisocyanate (IB), and at least the chain extender (CE-A) and the chain extender (CE-B) are at least partially identical. 16. A granulation according to any one of embodiments 13 to 15.

[0157] 17. A granule according to any one of embodiments 13 to 16, wherein at least 50% of the surface of composition (A) is covered by composition (B), preferably at least 60% of the surface, more preferably at least 70% of the surface, in particular at least 80% of the surface, and most preferably at least 90% of the surface.

[0158] 18. A granulation according to embodiment 13 or 17, wherein composition (A) is completely coated with composition (B).

[0159] 19. A granule according to any one of embodiments 13 to 18, wherein composition (A) is coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0160] 20. A granule according to any one of embodiments 13 to 19, wherein the particles comprising composition (A) are coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0161] 21. Diisocyanate (IA) is an aliphatic diisocyanate, preferably tri-, tetra-, penta-, hexa-, hepta-, and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 4,4' 21. The granulate according to any one of embodiments 13 to 20, wherein the isocyanate is selected from the group consisting of 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, or a mixture thereof, more preferably 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), or H12MDI.

[0162] 22. The granule according to any one of embodiments 13 to 21, wherein the Shore A hardness of composition (A), measured according to DIN ISO 7619-1 (2016), is less than 80, preferably less than 70, more preferably less than 65, more preferably less than 60, more preferably less than 55, more preferably less than 50.

[0163] 23. The diol (DA) is a polyether diol, more preferably 0.5×10 3 g / mol ~ 1.5 × 10 3 g / mol, more preferably 0.8 × 10 3 g / mol ~ 1.2 × 10 3 g / mol, most preferably 1.0 × 10 323. The granulate according to any one of embodiments 13 to 22, wherein the granulate has a molecular weight of 10 ...

[0164] 24. The chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof; preferably, the chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof; 24. The granulate according to any one of embodiments 13 to 23, wherein the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, preferably the respective oligo- and / or polypropylene glycols, or a mixture thereof, more preferably the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol or 1,4-butanediol, or a mixture thereof, and most preferably the chain extender (CE-A) is a mixture of 1,3-propanediol or 1,4-butanediol.

[0165] 25. A granulation according to any one of embodiments 13 to 24, wherein the Shore D hardness of composition (B), measured according to DIN ISO 7619-1 (2016), is greater than 30, preferably greater than 40, preferably greater than 55.

[0166] 26. A method for producing particles according to any one of embodiments 1 to 12, comprising: (i) extruding strands (SA) of composition (A); (ii) coating the strands (SA) with composition (B) to form strands (S-AB); and (iii) forming particles from the strands (S-AB); A method comprising:

[0167] 27. The method of embodiment 26, wherein strand (SA) is co-extruded with tubular strand (SB) of composition (B) to form strand (S-AB).

[0168] 28. The method of embodiment 26 or 27, wherein the strands (S-AB) are crimped to form a pellet.

[0169] 29. Thermoplastic polyurethane (PU-A) is the reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A); Thermoplastic polyurethane (PU-B) is the reaction product of the components diisocyanate (IB), diol (DB), and optionally a chain extender (CE-B), and at least one of the components of the thermoplastic polyurethane (PU-A) and at least one of the components of the thermoplastic polyurethane (PU-B) are at least partially identical; More preferably, the diol (DA) and the diol (DB) and the diisocyanate (IA) and the diisocyanate (IB) are at least partially identical, and even more preferably, the diol (DA) and the diol (DB), the diisocyanate (IA) and the diisocyanate (IB), and at least the chain extender (CE-A) and the chain extender (CE-B) are at least partially identical. 29. The method of any one of embodiments 26 to 28.

[0170] 30. The method of any one of embodiments 26 to 29, wherein composition (A) is coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0171] 31. The method of any one of embodiments 26 to 30, wherein the particles comprising composition (A) are coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

[0172] 32. Diisocyanate (IA) is an aliphatic diisocyanate, preferably tri-, tetra-, penta-, hexa-, hepta-, and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 4,4 32. The method of any one of embodiments 26 to 31, wherein the diisocyanate is selected from the group consisting of 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, or mixtures thereof, more preferably 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), or H12MDI.

[0173] 33. The method of any one of embodiments 26 to 32, wherein the Shore A hardness of composition (A), measured according to DIN ISO 7619-1 (2016), is less than 80, preferably less than 70, more preferably less than 65, more preferably less than 60, more preferably less than 55, more preferably less than 50.

[0174] 34. The diol (DA) is a polyether diol, more preferably 0.5×10 3 g / mol ~ 1.5 × 10 3 g / mol, more preferably 0.8 × 10 3 g / mol ~ 1.2 × 10 3 g / mol, most preferably 1.0 × 10 3 34. The method of any one of embodiments 26 to 33, wherein the polytetrahydrofuran has a molecular weight of 1000 g / mol and is most preferably polytetrahydrofuran.

[0175] 35. The chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof; preferably, the chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof; 35. The method of any one of embodiments 26 to 34, wherein the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, preferably the respective oligo- and / or polypropylene glycols, or mixtures thereof, more preferably the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol, or 1,4-butanediol, or mixtures thereof, and most preferably the chain extender (CE-A) is a mixture of 1,3-propanediol or 1,4-butanediol.

[0176] 36. The method of any one of embodiments 26 to 35, wherein the Shore D hardness of composition (B), measured according to DIN ISO 7619-1 (2016), is greater than 30, preferably greater than 40, preferably greater than 55.

[0177] 37. A method for producing an article, using a particle according to any one of embodiments 1 to 12 or a granulation according to any one of embodiments 13 to 25.

[0178] The present invention will now be further illustrated by the examples, which relate to practical, and in some cases preferred, embodiments of the invention without limiting the scope thereof. [Example]

[0179] 1. Example 1 1.1 Equipment used Extruder 1 (Composition A) Coperion ZSK32 Extruder: Co-rotating twin-screw extruder (reaction extrusion) Diameter: d=32mm, length 56d Mixing zone temperature: 210℃~225℃ Melting zone 18 temperature: 182°C Pressure before die: 70 bar

[0180] Extruder 2 (Composition B) - Non-reactive extrusion, plasticization only Single Screw Extruder Diameter d=20mm, length 25D Three temperature bands: T = 145°C, 180°C, 200°C (all) Flexible hose connected extruder 3 with die: T=220℃ Pressure before die: 100 bar Gear pump: EXTRU 4,7-1; WITTE PUMPS

[0181] Co-extrusion die (coaxial): 2M-Tech; T = 200°C, die diameter: 2.6 mm

[0182] 1.2 Raw materials Composition (A): Starting materials used H12MDI (40% by weight) Polytetrahydrofuran 1000 (51% by weight) 1,4-butanediol (5% by weight) 1,3-propanediol (2% by weight) Composition (B): Thermoplastic polyurethane based on H12MDI (48% by weight), polytetrahydrofuran 1000 (40% by weight) and 1,4-butanediol (pellets)

[0183] 1.3 Preparation A melt of the core material, composition (A), was produced in a Coperion ZSK32 with a diameter of 32 mm and a length 56 times the diameter.

[0184] The index (ratio of isocyanate groups to hydroxyl groups of the diol and chain extender) was adjusted to 980-1000. The chain extender was added in the fifth zone of the reaction extruder. The screw speed was adjusted to 200 rpm. The temperature profile was set between 180°C and 220°C. After a residence time of at least 60 seconds, the melt was conveyed by a gear pump to the entrance of the coextrusion die.

[0185] The melt of the shell material, composition (B), was obtained by plasticizing pellets of composition (B) in a Labtech single-screw extruder. The extruder had a diameter of 20 mm and a length 25 times the diameter. The pellets consisted of composition (B) that had already been synthesized in a first separate process step. To reduce the moisture content of the pellets, the raw materials were dried with dry air at 40°C for 12 hours. The temperature profile of the three heating zones was set between 145°C and 200°C. The Labtech extruder and the die were connected via an electrically heated flexible hose from Winkler.

[0186] In the coextrusion die, the melt stream of composition (A) was formed into a cylindrical strand with a diameter of 2.3 mm, which was then covered with a tubular melt stream of composition (B). The formed core-shell structure was guided into a water bath (room temperature) for cooling and fed into a pelletizer, resulting in cylindrical granules with an open cross-sectional area that was not completely covered with composition (A). The granules showed clear improvement in terms of agglomeration / blocking.

[0187] Example 2 2.1 Equipment used Extruder 1: Mekuma; Model ZK45 / 30 Extruder 2 and Extruder 3: Mekuma; Model ZK30 / 30 Flat film die: FD600-3K; EMO Extrusion Machinery, die width 600mm

[0188] 2.2 Raw materials used Composition (A): Thermoplastic polyurethane based on H12MDI (40% by weight), polytetrahydrofuran 1000 (51% by weight) and a mixture of 1,4-butanediol / 1,3-propanediol Composition (B) H12 Thermoplastic polyurethane based on MDI (48% by weight), polytetrahydrofuran 1000 (40% by weight) and 1,4-butanediol Granules of the core materials, Compositions (A) and (B), were produced by reactive extrusion in a Berstorff ZE 40 twin-screw extruder equipped with a perforated plate and a Gala underwater micropelletizer. The index was adjusted to a range of 950-1050. The chain extender was added in the fifth zone of the reactive extruder. After a residence time of at least 60 seconds, the melt was conveyed by a gear pump to the entrance of the coextrusion die. The die temperature was between 180°C and 220°C.

[0189] 2.3 Particle preparation Three different melt streams were merged in a flat-sheet coextrusion die to obtain a TPU sheet consisting of two outer layers of composition (B) and one inner layer of composition (A), thus forming a sandwich structure. The two polymer melt streams for the outer layer of composition (B) were produced in two identical single-screw extruders (Mekuma, model type ZK30 / 30, diameter 19 mm and length 58 cm). Pellets of composition (B) were metered into the feed stream. Five temperature zones were set between 190°C and 200°C. For the inner layer of composition (A), a Mekuma extruder, model ZK45 / 30, was used for plasticization. The extruder zone temperatures were set between 180°C and 200°C. The width of the multi-manifold sheet die was 600 mm. The die temperature was set between 185°C and 200°C. The screw speed of the ZK30 / 30 extruder was adjusted between 5 and 15 revolutions per minute to obtain an outer layer thickness of 50 to 110 μm. The screw speed of the ZK45 / 30 extruder was set between 50 and 90 revolutions per minute. A horizontally positioned calender unit with three tempering rollers was used to cool the molten sheet. The take-up speed was set between 0.5 and 1 m / min. The temperature of all cooling rollers was set at 15°C. The sheet was then introduced into a granulator and cut into rectangular parallelepipeds measuring 3 mm in length, 3 mm in width, and 2 mm in thickness. The cut edges of the rectangular parallelepipeds were not completely coated with composition (B).

[0190] 3. Methods Used 3.1 Nanoindentation Type: Nanoindenter G200, manufactured by KLA Head: XP indentation head Indenter: Berkovich tip (α=65.27°) Measurement according to ISO 14577-1 Method: Load control (load: 1 mN for composition (A) and composition (B), 0.3 mN for the coextrusion product)

[0191] References: US Patent Application Publication No. 2018 / 0222087 US Patent Application Publication No. 2015 / 0091202 Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), p.98-S136 International Publication No. 94 / 20568 International Publication No. 2007 / 082838 International Publication No. 2017 / 030835 International Publication No. 2013 / 153190 International Publication No. 2010 / 010010

Claims

1. Particles comprising a composition (A) containing a thermoplastic polyurethane (PU-A) and a composition (B) containing a thermoplastic polyurethane (PU-B), wherein the composition (A) is at least partially coated with the composition (B).

2. The thermoplastic polyurethane (PU-A) is a reaction product of the components diisocyanate (IA), diol (DA), and optionally a chain extender (CE-A), The thermoplastic polyurethane (PU-B) is a reaction product of the components diisocyanate (IB), diol (DB), and optionally chain extender (CE-B), and at least one of the components of the thermoplastic polyurethane (PU-A) and at least one of the components of the thermoplastic polyurethane (PU-B) are at least partially identical; More preferably, the diol (D-A) and the diol (D-B), and the diisocyanate (I-A) and the diisocyanate (I-B), are at least partially identical, and even more preferably, the diol (D-A) and the diol (D-B), the diisocyanate (I-A) and the diisocyanate (I-B), and at least the chain extender (CE-A) and the chain extender (CE-B), are at least partially identical. The particles according to claim 1 .

3. 3. The particle according to claim 1, wherein the composition (A) is completely coated with the composition (B).

4. 4. Particles according to any one of claims 1 to 3, wherein composition (A) is coated with a film of composition (B), and the film of composition (B) preferably has a thickness of less than 1 mm, more preferably less than 0.5 mm, more preferably less than 0.1 mm.

5. The diisocyanate (IA) is an aliphatic diisocyanate, preferably tri-, tetra-, penta-, hexa-, hepta-, and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane, and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 4, 5. The particles according to claim 1, wherein the diisocyanate is selected from the group consisting of 4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, or a mixture thereof, more preferably 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), or H12MDI.

6. 6. Particles according to any one of claims 1 to 5, wherein the Shore A hardness of composition (A), measured according to DIN ISO 7619-1 (2016), is less than 80, preferably less than 70, more preferably less than 65, more preferably less than 60, more preferably less than 55, more preferably less than 50.

7. The diol (DA) is a polyether diol, and more preferably 0.5×10 ３ g / mol~1.5×10 ３ g / mol, more preferably 0.8×10 ３ g / mol~1.2×10 ３ g / mol, most preferably 1.0×10 ３ 7. Particles according to any one of claims 1 to 6, having a molecular weight of 1000 g / mol, most preferably polytetrahydrofuran.

8. The chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof, and preferably the chain extender (CE-A) is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and / or decaalkylene glycols, dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanolcyclohexane, neopentyl glycol, and hydroquinone-bis(β-hydroxyethyl)ether (HQEE), or a mixture thereof.

8. Particles according to any one of claims 1 to 7, wherein the chain extender (CE-A) is selected from the group consisting of glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycol, preferably the respective oligo- and / or polypropylene glycol, or a mixture thereof, more preferably the chain extender (CE-A) is selected from the group consisting of 1,3-propanediol or 1,4-butanediol, or a mixture thereof, most preferably the chain extender (CE-A) is a mixture of 1,3-propanediol or 1,4-butanediol.

9. Particles according to any one of claims 1 to 8, wherein the Shore D hardness of composition (B), measured according to DIN ISO 7619-1 (2016), is greater than 30, preferably greater than 40, preferably greater than 55.

10. A granulated product comprising particles according to any one of claims 1 to 9.

11. A method for producing particles according to any one of claims 1 to 9, comprising: (i) extruding strands (SA) of the composition (A); (ii) coating the strands (SA) with the composition (B) to form strands (S-AB); and (iii) forming particles from the strands (S-AB); A method comprising:

12. 12. The method of claim 11, wherein the strand (SA) is co-extruded with a tubular strand (SB) of composition (B) to form a strand (S-AB).

13. 13. The method according to claim 11 or 12, wherein the strands (S-AB) are crimped to form pellets.

14. A method for producing an article, comprising using the particles according to any one of claims 1 to 9 or the granulated product according to claim 10.

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