Soft particle foam made of thermoplastic polyurethane

Abstract

The present invention relates to an expandable pellet-shaped material comprising a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15 A to 43 A, and to a method for producing such an expandable pellet-shaped material. The present invention further includes the use of the expandable pellet-shaped material of the present invention for producing molded articles.

Description

[Technical field]

[0001] The present invention relates to an expandable pellet-shaped material comprising a composition (Z1) containing a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15 A to 43 A, and also to a method for producing such an expandable pellet-shaped material. The present invention further includes the use of the expandable pellet-shaped material of the present invention for producing a molded article. [Background technology]

[0002] Expanded pellet-like materials (based on thermoplastic polyurethanes or other elastomers), also called bead foams (or particle foams), and moulded articles produced therefrom are known (e.g. WO 94 / 20568, WO 2007 / 082838 A1, WO 2017 / 030835, WO 2013 / 153190 A1, WO 2010 / 010010) and can be used in a variety of applications.

[0003] For the purposes of the present invention, "foamed pellet material" or other "bead foam" or "particle foam" refers to foam in the form of beads, the average diameter of the beads being between 0.2 and 20 mm, preferably between 0.5 and 15 mm, in particular between 1 and 12 mm. In the case of non-spherical shapes (e.g. elongated or cylindrical beads), the diameter refers to the longest dimension.

[0004] There is a fundamental need for expanded pellet-like materials or bead foams that can be processed at the lowest possible temperatures to produce the corresponding molded articles while maintaining favorable mechanical properties. This is particularly important in the currently widely used fusion processes (where the energy input for fusing the foam pellets is introduced by an auxiliary medium (e.g. steam)) since it is possible to improve the bonding while reducing damage to the material and foam structure and at the same time obtaining sufficient bonding / fusion.

[0005] To obtain favorable mechanical properties of the molded article produced from the foamed pelletized material, sufficient bonding / fusion of the foam pellets is essential. If the foam beads are not bonded / fused well, their properties will not be fully realized, which will have a general negative effect on the mechanical properties of the resulting molded article. The same applies if the strength of the molded article is reduced. In this case, the mechanical properties of the weakened areas will be poor, resulting in the same results as above. Therefore, the properties of the polymers used must be easily adjustable.

[0006] Polymers based on thermoplastic elastomers (TPEs) are already being used in a wide variety of fields. Depending on the application, it is possible to modify the properties of the polymer. Thermoplastic polyurethanes in particular are used in a wide variety of applications.

[0007] Thermoplastic polyurethanes usually have a hardness of 80 Shore A to 74 Shore D. However, in many applications a softer material is advantageous. For this reason, the state of the art is the addition of plasticizers to thermoplastics that can reduce the Shore hardness. When choosing a plasticizer, it is particularly important to ensure that it is compatible with the thermoplastic polyurethane. It is also necessary to ensure that the mechanical properties of the thermoplastic polyurethane (e.g. abrasion resistance and elastomeric properties) are not compromised.

[0008] For example, WO2011 / 141408A2 discloses a thermoplastic polyurethane containing a glycerol-based plasticizer. A foam based on such a thermoplastic polyurethane is also disclosed. However, the foam described in W2011 / 141408A2 is a block foam, and its property profile is not suitable for many applications.

[0009] In the context of the present invention, "advantageous mechanical properties" is understood to refer to the intended application: the main application of the subject matter of the present invention is in the footwear sector, where the foam-type pellets can be used in the molding of footwear components (e.g. midsoles and insoles) where damping and / or cushioning are relevant. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] WO94 / 20568 [Patent Document 2] WO2007 / 082838A1 [Patent Document 3] WO2017 / 030835 [Patent Document 4] WO2013 / 153190A1 [Patent Document 5] WO2010 / 010010 [Patent Document 6] WO2011 / 141408A2 [Patent Document 7] EP1979401B1 [Patent Document 8] US2015 / 0337102 [Patent Document 9] EP2872309B [Patent Document 10] EP3053732A [Patent Document 11] WO2016 / 146537 [Non-patent literature]

[0011] [Non-Patent Document 1] “Kunststoffhandbuch” [Plastics handbook], volume 7, “Polyurethane” [Polyurethanes], Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1. [Non-Patent Document 2] Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pages 98-136 [Non-Patent Document 3] Saechtling (ed.), Kunststoff-Taschenbuch [Plastics handbook], 27th edition, Hanser-Verlag, Munich, 1998, chapters 3.2.1 and 3.2.4 [Non-Patent Document 4] “Kunststoffhandbuch” [Plastics handbook], volume 7, “Polyurethane” [Polyurethanes], Carl Hanser Verlag, 3rd edition, 1993, chapter 3 [Non-Patent Document 5] Piechota and Roehr in “Integralschaumstoff” [Integral foam], Carl-Hanser-Verlag, Munich, Vienna, 1975 [Non-Patent Document 6] “Kunststoff-Handbuch” [Plastics handbook], volume 7, “Polyurethane” [Polyurethanes], 3rd edition, 1993, chapter 7 [Summary of the Invention] [Problem to be solved by the invention]

[0012] It was therefore an object of the present invention to provide foam-type pellets based on thermoplastic polyurethanes having good mechanical properties and good damping and rebound properties. It was a further object of the present invention to provide a method for the production of corresponding foam-type pellets. [Means for solving the problem]

[0013] This object is achieved according to the invention by an expandable pellet-shaped material comprising a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), said composition (Z1) having a Shore hardness in the range from 15A to 43A. Effect of the Invention

[0014] Surprisingly, it has been found that this type of thermoplastic polyurethane can be easily processed into foamed pellet-like materials, which can then be easily further processed into molded articles having a particularly low elastic modulus and good resilience. Surprisingly, it has been found that foamed pellets based on compositions having a Shore hardness in the range of 15A to 43A result in pellet-like materials with good mechanical properties, which can be easily processed into molded articles. Such molded articles show surprisingly good resilience compared to their low stiffness.

[0015] In the context of the present invention, it has been found that the inventive expanded pellets exhibit a good combination of damping and rebound properties (in particular very soft wear properties) and nevertheless do not disintegrate under high mechanical stress.

[0016] Another advantage of the foamed pellets of the present invention is that they have a low fusion temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Composition (Z1) according to the invention has a Shore hardness in the range from 15A to 43A, measured according to DIN 53505. The Shore hardness is preferably in the range from 20A to 43A, more preferably in the range from 25A to 43A, in each case measured according to DIN ISO 4649A.

[0018] In a further embodiment, the present invention also relates to the expandable pellet-shaped material as described above, wherein composition (Z1) has a Shore hardness in the range of 20A to 43A.

[0019] Surprisingly, it has been found that the melting range and melt flow rate of composition (Z1) also have a positive effect on the properties of the foamed pellet-shaped material.In a further embodiment, the present invention also relates to the foamed pellet-shaped material described above, namely, that the melting range of composition (Z1) starts below 100°C in DSC measurement (heating rate of 20K / min), and that composition (Z1) has a maximum melt flow rate (MFR) of 250g / 10min by composition (Z1) at 180°C and a pressurized mass (according to DIN EN ISO1133) of 21.6 kg.

[0020] Composition (Z1) according to the invention comprises a thermoplastic polyurethane (TPU-1) and a plasticizer (W). In the context of the present invention, composition (Z1) may also comprise further components, for example further thermoplastic polyurethanes or further plasticizers.

[0021] In principle, according to the present invention, all plasticizers that are sufficiently compatible with thermoplastic polyurethane (TPU-1) are suitable. In particular, citric acid derivatives, glycerol derivatives and mixtures of these compounds have been found to be suitable as plasticizers. In the context of the present invention, it is preferred to use, as plasticizer (W), glycerol derivatives, more preferably derivatives of glycerol, in which at least one glycerol hydroxyl group is esterified with a monocarboxylic acid (ii) having 1, 2, 3, 4, 5 or 6 carbon atoms, preferably 2, 3 or 4 carbon atoms, more preferably 2 carbon atoms. This group of substances is referred to below as glycerol carboxylates. Glycerol tricarboxylates are more preferred, and glycerol triacetate is particularly preferred.

[0022] In a further embodiment, the present invention also relates to the expandable pellet-shaped material as described above, wherein the plasticizer (W) is selected from derivatives of citric acid and derivatives of glycerol, or a mixture of two or more thereof, and at least one glycerol hydroxyl group is esterified with a monocarboxylic acid having 1, 2, 3, 4, 5 or 6 carbon atoms.

[0023] In addition to the excellent mechanical stability of the plastics plasticized with the plasticizers of the present invention, these plasticizers have a low tendency to bloom and are non-toxic or less toxic than other plasticizers, and they also exhibit high stability to the temperatures encountered during processing of the TPU, while at the same time the mechanical properties of the TPU are not adversely affected during processing.

[0024] The raw materials required for their manufacture are desirably derived from renewable resources. Their compatibility with other polar plasticizers (especially esters of tricarboxylic acids) allows them to be combined as a means of improving the material or achieving specific properties (e.g., particularly low Shore hardness).

[0025] A further advantage of the plasticizers of the present invention is that they have good miscibility with polar polyurethanes, which means that significantly higher proportions of plasticizer can be incorporated, resulting in lower Shore A hardnesses.

[0026] Compounds commonly used as plasticizers having urethane bonds (e.g., low molecular weight polyurethanes) are also suitable as plasticizers, as are diphenylcresyl phosphate (DPK) and phthalates.

[0027] In a preferred embodiment, in addition to the plasticizer (W) of the invention, at least one further plasticizer (W2), preferably an ester of a tricarboxylic acid, is used.

[0028] In a further embodiment, the present invention also relates to an expandable pellet-shaped material as described above, wherein composition (Z1) comprises an ester of a tricarboxylic acid as plasticizer (W2).

[0029] The tricarboxylic acid preferably has an aliphatic structure, which is branched and has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, particularly preferably 5 to 10 carbon atoms, and most preferably 6 carbon atoms. The carbons of the branched aliphatic structure are directly bonded to each other via single or double bonds. The aliphatic structure preferably has only single bonds between the carbons. In a further preferred embodiment, the tricarboxylic acid comprises at least one hydroxyl group. At least one hydroxyl group is directly bonded to a carbon atom of said aliphatic structure of the tricarboxylic acid, such that in addition to being bonded to three acid groups, at least one hydroxyl group is bonded to the aliphatic structure. In particular, it is preferred that there is only one hydroxyl group on the aliphatic structure of the tricarboxylic acid. A particularly preferred tricarboxylic acid is citric acid.

[0030] In a preferred embodiment, all three acid groups of the tricarboxylic acid are esterified with an alcohol. The alcohol may have an aromatic structure and / or an aliphatic structure. More preferably, the alcohol has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. It is preferable to use an alcohol having an aliphatic structure, more preferably an alcohol having a linear aliphatic structure, and particularly preferably an aliphatic structure having no double bond.

[0031] In further preferred embodiments, the carbon atoms of the alcohol are a multiple of 2 (i.e., 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 carbon atoms). The alcohol is more preferably linear aliphatic.

[0032] In a very particularly preferred embodiment, the alcohol is ethanol. In a second very particularly preferred embodiment, the alcohol is butanol. In an alternative embodiment, the alcohol is propanol. More preferably, all three acid groups of the tricarboxylic acid are esterified with the same alcohol.

[0033] In a further preferred embodiment, at least one hydroxyl group of the tricarboxylic acid is additionally esterified with a carboxylic acid. The carboxylic acid is selected from aromatic or aliphatic carboxylic acids having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 2 to 22 carbon atoms, which are more preferably arranged in a linear chain and in a further preferred embodiment the number of carbon atoms is a multiple of 2. The hydroxyl group is very particularly preferably esterified with acetic acid.

[0034] In a further preferred embodiment, at least one hydroxyl group of the tricarboxylic acid is etherified with the radical ROH. The ROH radical comprises 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 2 to 22 carbon atoms, in a particularly preferred embodiment the number of carbon atoms is a multiple of two, more preferably the alcohol has a linear aliphatic structure. In a further preferred embodiment it is polyethylene glycol or polypropylene glycol. Polyethylene glycol is further preferred. In the above-mentioned embodiment, apart from the oxygen atoms of the three carboxyl groups of the tricarboxylic acid and the oxygen atoms of its hydroxyl groups, preferably no other heteroatoms are present in the ester. In an alternative embodiment, the tricarboxylic acid comprises at least one amine group. In a preferred embodiment, the carboxylic acid forms an acid amide with this amine group. The carboxylic acid is selected from aromatic or aliphatic carboxylic acids having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 22 carbon atoms, in a particularly preferred embodiment the number of carbon atoms in the carboxylic acid is a multiple of two.

[0035] In a further preferred embodiment, at least one amine group of the tricarboxylic acid forms a secondary amine with at least one radical R' or a tertiary amine with a second radical R". The radicals R' and R" each independently have 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 2 to 22 carbon atoms, and in a particularly preferred embodiment the number of carbon atoms of the carboxylic acid is a multiple of 2. In a further preferred embodiment the radical is a polyethylene glycol or polypropylene glycol, preferably polyethylene glycol.

[0036] In a very particularly preferred embodiment, the ester of a tricarboxylic acid used as the second plasticizer is tributyl 2-acetoxy-1,2,3-tricarboxylate.

[0037] For use as polyurethane plasticizers, glycerol carboxylic esters (preferably glycerol tricarboxylic esters) with the lowest possible acid value are advantageous, since free acid groups can contribute to the degradation of any polyester-polyurethanes used and thus adversely affect their stability. In a preferred embodiment, one, two or three hydroxyl groups of glycerol are esterified with monocarboxylic acids, preferably two or three hydroxyl groups are esterified with at least one carboxylic acid, particularly preferably all three hydroxyl groups of glycerol are esterified with monocarboxylic acids.

[0038] In some preferred embodiments, different monocarboxylic acids are present in the glycerol ester. In other preferred embodiments, the esterified hydroxyl groups of glycerol are esterified with the same monocarboxylic acid. The plasticizer of the present invention preferably has a haze value of less than 100, more preferably less than 50, especially less than 30, as an inherent color.

[0039] The plasticizer (W) preferably has an alkali content of less than 40 ppm, more preferably less than 15 ppm, in particular less than 5 ppm.

[0040] The plasticizer (W) of the present invention usually has a water content of 0.2 mass % or less, preferably 0.05 mass % or less, and more preferably 0.02 mass % or less.

[0041] The plasticizer (W) of the present invention is present in composition (Z1) in an amount of, for example, 1% by weight to 80% by weight, preferably 1% by weight to 60% by weight, more preferably 5% by weight to 50% by weight and in particular 10% by weight to 40% by weight, in each case based on the total weight of composition (Z1).

[0042] In a further embodiment, the present invention also relates to the expandable pellet-shaped material as described above, wherein the plasticizer (W) is present in composition (Z1) in an amount ranging from 1% by weight to 60% by weight, based on the total composition (Z1).

[0043] When a plasticizer (W2) is further used, the ratio of the plasticizers may be changed within a wide range. For example, the plasticizer (W2) and the plasticizer (W) can be used in a mass ratio of 2:1 to 1:10, more preferably 1:1 to 1:5, and most preferably 1:1.5 to 1:3.

[0044] According to the invention, the composition (Z1) comprises a thermoplastic polyurethane (TPU-1).

[0045] The preparation of thermoplastic polyurethanes is known in principle. For their preparation, isocyanates and compounds which are reactive towards isocyanates, in particular polyols, and optionally chain extenders are usually used.

[0046] Suitable polyols are known in principle to the skilled artisan and are described, for example, in “Kunststoffhandbuch” [Plastics handbook], volume 7, “Polyurethane” [Polyurethanes], Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. As polyol (P1), it is particularly preferred to use polyesterols or polyetherols as polyols. It is also possible to use polycarbonates. In the context of the present invention, copolymers can also be used. Polyetherpolyols are particularly preferred. The number-average molecular weight of the polyols used in the present invention is preferably in the range of 500 to 5000 g / mol, for example in the range of 550 g / mol to 2000 g / mol, preferably in the range of 600 g / mol to 1500 g / mol, in particular in the range of 650 g / mol to 1000 g / mol.

[0047] According to the invention, polyetherols are suitable, as well as polyesterols, block copolymers, and hybrid polyols (e.g., poly(ester / amide)).Preferred polyetherols according to the invention are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonates, polycarbonate diols, and polycaprolactone.

[0048] Thus, in a further embodiment, the present invention relates to the expandable pellet-form material as described above, wherein the polyol composition comprises a polyol selected from the group consisting of polyetherols, polyesterols, polycaprolactone polyols, and polycarbonate polyols.

[0049] Suitable polyols are, for example, polyols with ether and ester blocks (e.g. polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or other polyethers with polycaprolactone end blocks). According to the invention, preferred polyetherols are polyethylene glycols and polypropylene glycols. Furthermore, polycaprolactone is preferred.

[0050] It is also possible in the present invention to use mixtures of different polyols. The polyols / polyol compositions used preferably have an average functionality of 1.8 to 2.3, preferably 1.9 to 2.2, in particular 2. The polyols used in the present invention preferably have only primary hydroxyl groups.

[0051] In one embodiment of the present invention, a polyol composition (PZ) containing at least polytetrahydrofuran is used. Also, according to the present invention, the polyol composition may contain further polyols in addition to polytetrahydrofuran.

[0052] Further polyols suitable for the present invention are, for example, polyethers, but also polyesters, block copolymers and hybrid polyols (e.g. poly(ester / amide)). Suitable block copolymers are, for example, block copolymers having ether and ester blocks (e.g. polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or other polyethers with polycaprolactone end blocks). Preferred polyethers according to the present invention are polyethylene glycols and polypropylene glycols. As further polyol, polycaprolactone is further preferred.

[0053] In a particularly preferred embodiment, the polytetrahydrofuran has a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol, more preferably in the range of 550 to 2500 g / mol, and particularly preferably in the range of 650 to 2000 g / mol.

[0054] The composition of the polyol composition (PZ) may vary within wide limits in the context of the present invention and may also comprise a mixture of different polyols.

[0055] According to the invention, the polyol composition may comprise a solvent. Suitable solvents are known per se to those skilled in the art.

[0056] When polytetrahydrofuran is used, the number average molecular weight Mn of polytetrahydrofuran is preferably within the range of 500 to 5000 g / mol, and more preferably within the range of 500 to 2000 g / mol.

[0057] In a further embodiment, the present invention also relates to the expandable pellet-shaped material as described above, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofurans having a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol.

[0058] Therefore, in a further embodiment, the present invention relates to the expandable pellet-shaped material as described above, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofurans having a number average molecular weight Mn in the range of 500 g / mol to 2000 g / mol.

[0059] In accordance with the present invention, mixtures of various polytetrahydrofurans (ie, mixtures of polytetrahydrofurans having different molecular weights) may also be used.

[0060] Preferred polyetherols according to the invention are polyethylene glycols, polypropylene glycols and polytetrahydrofurans, as well as mixtures of these polyetherols. Also according to the invention, mixtures of different polytetrahydrofurans, for example with different molecular weights, can be used.

[0061] Polyesterols may also be used, for example polyester polyols based on adipic acid, ethylene glycol and butanediol are suitable.

[0062] In a further embodiment, the present invention also relates to the foamed pellet-like material described above, wherein the thermoplastic polyurethane (TPU-1) is produced using a polyol (P1) selected from the group consisting of polyetherols, polyesterols, polycarbonate alcohols, and hybrid polyols.

[0063] Usually, at least one chain extender (KV) is additionally used. Suitable chain extenders are known per se to the person skilled in the art. Chain extenders are, for example, compounds having two groups reactive towards isocyanate groups, in particular compounds having a molecular weight of less than 500 g / mol. Suitable chain extenders are, for example, diamines or diols. According to the invention, diols are further preferred. It is also possible to use mixtures of two or more chain extenders according to the invention.

[0064] Suitable diols are known in principle to the skilled person. The diols according to the invention preferably have a molecular weight of less than 500 g / mol. Here, according to the invention, it is possible to use, for example, aliphatic, araliphatic, aromatic and / or cycloaliphatic diols as chain extenders having a molecular weight of 50 g / mol to 220 g / mol. Preference is given to alkanediols having 2 to 10 carbon atoms in the alkylene radical (in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols). Particular preference is given according to the invention to 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol.

[0065] In the context of the present invention, suitable chain extenders (KV1) are also branched compounds, such as cyclohexane-1,4-dimethanol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, pinacol, 2-ethylhexane-1,3-diol or cyclohexane-1,4-diol.

[0066] Therefore, in a further embodiment, the present invention relates to the expandable pellet-shaped material as described above, wherein the chain extender (KV1) is selected from the group consisting of 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, and HQEE.

[0067] In a further embodiment, the present invention also relates to the foamed pellet-shaped material as described above, wherein the thermoplastic polyurethane (TPU-1) is produced using a chain extender (KV) selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.

[0068] Suitable isocyanates in the context of the present invention are in particular diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.

[0069] Furthermore, in the context of the present invention, it is possible to use as isocyanate components pre-reacted products (part of the OH components has been reacted with isocyanates in a preceding reaction step) which are reacted with the remaining OH components in a subsequent step, the actual polymer reaction, to form thermoplastic polyurethanes.

[0070] The aliphatic diisocyanates used are customary aliphatic and / or cycloaliphatic diisocyanates, such as, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene 1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, 1 -isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and / or 2,6-diisocyanate, methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI).

[0071] Suitable aromatic diisocyanates are in particular naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanatobiphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane 4,4'-diisocyanate (EDI), methylene diphenyl diisocyanate (MDI), where MDI is understood to mean diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate, dimethyldiphenyl 3,3'-diisocyanate, diphenylethane 1,2-diisocyanate and / or phenylene diisocyanate, or else H12MDI (methylenedicyclohexyl 4,4'-diisocyanate).

[0072] In principle, mixtures can also be used. Examples of mixtures include mixtures that contain at least one further methylene diphenyl diisocyanate in addition to methylene diphenyl 4,4'-diisocyanate. Here, the term "methylene diphenyl diisocyanate" means diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate, or a mixture of two or three isomers. It is therefore also possible to use, for example, diphenylmethane 2,2'- or 2,4'-diisocyanate, or a mixture of two or three isomers as further isocyanates. In this embodiment, the polyisocyanate composition may contain other of the above-mentioned polyisocyanates.

[0073] Preferred examples of high-performance isocyanates include triisocyanates, such as triphenylmethane 4,4',4''-triisocyanate, cyanurates of the above diisocyanates, and oligomers obtained by partial reaction of diisocyanates with water. Examples include biurets of the above diisocyanates and oligomers obtained by controlled reaction of semi-blocked diisocyanates with polyols having an average of two or more, preferably three or more, hydroxyl groups.

[0074] The organic isocyanates used may be aliphatic, cycloaliphatic, aromatic and / or aromatic isocyanates.

[0075] Furthermore, as crosslinking agents, for example the aforementioned high-functionality polyisocyanates and polyols or other high-functionality molecules with multiple isocyanate-reactive functional groups can be used. In the context of the present invention, it is likewise possible to achieve crosslinking of the product by using an excess of isocyanate groups relative to the hydroxyl groups. Examples of higher functional isocyanates are triisocyanates (for example triphenylmethane 4,4',4''-triisocyanate and isocyanurates), as well as the cyanurates of the aforementioned diisocyanates and oligomers obtained by partial reaction of diisocyanates with water (for example biurets of the aforementioned diisocyanates), and also oligomers obtained by controlled reaction of semiblocked diisocyanates with polyols having an average of at least 2, preferably at least 3, hydroxyl groups.

[0076] In the context of the present invention, the amount of crosslinker (i.e. the amount of high-performance isocyanate and high-performance polyol / high-performance chain extender) is here less than or equal to 3% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, based on the total mixture of components.

[0077] Furthermore, the polyisocyanate composition may contain one or more solvents. Suitable solvents are known to those skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone, and hydrocarbons.

[0078] In a further embodiment, the present invention also relates to the foamed pellet-shaped material as described above, wherein the thermoplastic polyurethane (TPU-1) is produced using a diisocyanate selected from the group consisting of diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), methylene dicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI), hexamethylene diisocyanate (HDI), and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

[0079] The relative amounts of the components used may vary widely, for example, the isocyanate and polyol are used in a weight ratio within the range of 1:7 to 1:1.5, preferably 1:5 to 1:3.

[0080] The reaction can be carried out at conventional indices, preferably indices between 60 and 130, more preferably indices between 80 and 110. The index is defined by the ratio of the total isocyanate groups used in the reaction to the groups reactive to isocyanates (i.e., active hydrogen, polyol components, and chain extenders used). An index of 100 corresponds to one active hydrogen atom (i.e., one isocyanate-reactive functional group) per isocyanate group. At indices above 100, there are more isocyanate groups than OH groups.

[0081] In the preparation of the thermoplastic polyurethanes, catalysts and / or customary auxiliaries may be added.

[0082] Catalysts which particularly promote the reaction between the NCO groups of diisocyanates and the hydroxyl groups of isocyanate-reactive compounds and chain extenders are, in a preferred embodiment, tertiary amines, in particular triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane; in another preferred embodiment, the catalysts are organometallic compounds (for example titanates, iron compounds, preferably iron(III) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctate, tin dilaurate, or dialkyltin salts of aliphatic carboxylic acids, preferably dibutyltin diacetate, dibutyltin dilaurate).

[0083] The catalyst is preferably used in an amount of 0.0001 to 0.1 parts by weight based on 100 parts by weight of the compound reactive towards isocyanates. Tin catalysts, in particular tin dioctate, are preferably used. In addition to the catalyst and to the plasticizer (W) of the invention, customary auxiliaries can also be added to the structural components. For example, surface active agents, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and demolding auxiliaries, dyes and pigments, optionally in addition to the stabilizers of the invention, further stabilizers, for example against hydrolysis, light, heat or discolouration, inorganic and / or organic fillers, reinforcing agents and plasticizers. The hydrolysis inhibitors used are preferably oligomeric and / or polymeric aliphatic or aromatic carbodiimides. To stabilize the TPU of the invention against ageing, preferably a stabilizer can be added to the TPU. Stabilizers are additives which, for the purposes of the invention, protect plastics or plastic mixtures against harmful environmental influences. Examples include primary and secondary antioxidants, hindered amine light stabilizers, UV absorbers, hydrolysis stabilizers, quenchers, flame retardants, etc. Examples of commercially available stabilizers are described in the Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pages 98-136. More detailed information on the abovementioned auxiliaries and additives can be found in the technical literature, for example in the Plastics Additive Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001, pages 98-136.

[0084] The TPUs may be produced continuously by known processes (eg, using a reactive extruder or belt process, the "one-shot" process, or the prepolymer process) or discontinuously by known prepolymer processes.

[0085] In these processes, the components to be reacted may be mixed, either sequentially or simultaneously, and the reaction may commence immediately. In the extruder process, the structural components are introduced individually or as a mixture into an extruder and reacted at temperatures preferably between 100°C and 280°C, more preferably between 140°C and 250°C, and the resulting TPU is extruded, cooled and pelletized.

[0086] In a preferred embodiment, at least the plasticizer (W) for the preparation of thermoplastic polyurethane, preferably also at least one second plasticizer (W2) is added during and / or after the preparation of the thermoplastic material. In a preferred embodiment, the plasticizer is metered into at least one of the starting materials in the preparation of the TPU, and in another preferred embodiment, it is mixed with the already prepared TPU, preferably in an extruder. The thermoplastic polyurethane can be subjected to further thermoplastic processing without losing the effect of the plasticizer of the present invention.

[0087] Furthermore, when producing TPU, it is more preferable to add it in parallel with the components to be used.

[0088] In a further aspect, the present invention also relates to a method for producing an expanded pellet-like material, comprising the steps of: (i) providing a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15A to 43A; (ii) impregnating composition (Z1) with a blowing agent under pressure; (iii) expanding composition (Z1) by reducing pressure; Regarding the process.

[0089] In the context of the present invention, composition (Z1) may be used in the form of a melt or in the form of a pelletized material.

[0090] The present invention therefore relates in a further embodiment to a method for producing an expanded pellet-like material, said method comprising the steps of: (i') extruding a composition (Z1) containing a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15A to 43A, to obtain a pellet-shaped material having an average diameter in the range of 0.2 to 10 mm; (ii') impregnating the pellet-shaped material under pressure with 0.1% by mass to 40% by mass of a blowing agent, based on the total mass of the pellet-shaped material; (iii') The pressure is reduced to obtain a foamed pellet-like material.

[0091] Regarding preferred embodiments of the process, suitable starting materials or mixing ratios, reference is made to the corresponding above descriptions.

[0092] The processes for producing expanded pellets starting from thermoplastic polyurethanes are known per se. In the context of the present invention, it has proven advantageous to use butane, propane, pentane, carbon dioxide and nitrogen as blowing agents.

[0093] In a further embodiment, the present invention also relates to the expandable pellet-shaped material as described above, wherein the expanding agent is selected from the group consisting of butane, propane, pentane, carbon dioxide, and nitrogen.

[0094] The method of the invention may include further steps, such as adjusting the temperature.

[0095] The unexpanded polymer mixtures of composition (Z1) required for the production of the foamed pellet-like material are prepared in known manner from the individual components and optionally further components (e.g. processing aids, stabilizers, compatibilizers or pigments). Examples of suitable processes are conventional mixing processes using kneaders in continuous or batch mode or using extruders (e.g. co-rotating twin screw extruders).

[0096] In the case of compatibilizers or auxiliaries (e.g. stabilizers), these may already be incorporated during the manufacture of the components. The individual components are usually combined before the mixing process or metered into the device that performs the mixing. In the case of an extruder, the components are all metered and fed together into the extruder or the individual components are added via a side feed. The processing is carried out at a temperature at which the components are in the plastic state. This temperature depends on the softening / melting range of each component, but must be below the decomposition temperature of each component. Additives (e.g. pigments, fillers or other conventional auxiliaries mentioned above) are not melted at the same time but are incorporated in the solid state.

[0097] Further embodiments according to standard methods are possible here, whereby the processes used for the production of the starting materials can be integrated directly into the production.

[0098] A portion of the conventional auxiliaries mentioned above may be added to the mixture in this step.

[0099] The bead foams of the invention generally have a bulk density of 50 g / l to 200 g / l, preferably 60 g / l to 180 g / l, more preferably 80 g / l to 150 g / l. The bulk density is measured in a manner similar to DIN ISO 697, but unlike the standard, the above values ​​are determined using a container with a volume of 10 l instead of a container with a volume of 0.5 l. This is because measurements using only a volume of 0.5 l would be too inaccurate, especially for foam beads with low density and high mass.

[0100] As mentioned above, the diameter of the individual beads of the expanded pellet-like material is 0.5 to 30 mm, preferably 1 to 15 mm, in particular 3 to 12 mm. In the case of non-spherical (e.g. elongated or cylindrical) expanded pellets, the diameter refers to the longest dimension.

[0101] The foam pellet-type materials are as follows: (i) providing a composition (Z) of the present invention; (ii) impregnating the composition with a blowing agent under pressure; (iii) expanding the composition by reducing pressure; It can be prepared by standard methods known in the prior art.

[0102] The amount of the foaming agent used is preferably 0.1 to 40 parts by mass, particularly preferably 0.5 to 35 parts by mass, and further preferably 1 to 30 parts by mass, based on 100 parts by mass of the composition (Z).

[0103] One embodiment of the above process comprises the steps of: (i) providing the composition (Z) of the present invention in the form of pellets; (ii) pressurizing the pellets with a foaming agent; (iii) expanding the pelletized material by reducing pressure; Includes.

[0104] A further embodiment of the above process comprises the following further steps: (i) providing the composition (Z) of the present invention in the form of pellets; (ii) impregnating the pelletized material with a blowing agent under pressure; (iii-a) reducing the pressure to standard pressure, possibly with prior reduction in temperature, without foaming the pelletized material; (iii-b) Expanding the pelletized material by increasing the temperature; Includes.

[0105] The unexpanded pelletized material herein preferably has an average minimum diameter of 0.2 to 10 mm (as determined by 3D evaluation of the pelletized material (e.g., dynamic image analysis using a Microtrac PartAn 3D optical measurement device)).

[0106] The individual pellets generally have an average mass in the range of 0.1 to 50 mg, preferably in the range of 4 to 40 mg, more preferably in the range of 7 to 32 mg. The average pellet mass (particle mass) is determined as the arithmetic mean by weighing three batches of 10 pellet particles each.

[0107] One embodiment of the above process involves impregnating the pellets with a blowing agent under pressure and then expanding the pellets in steps (I) and (II): (I) impregnating the pellets in the presence of a blowing agent under elevated temperature and pressure using a suitable closed reaction vessel (e.g., an autoclave); (II) Rapidly reducing the pressure without cooling.

[0108] The impregnation in step (I) can be carried out in the absence of water, in the presence of water and optionally a suspending aid, or in the presence of only a blowing agent.

[0109] Suitable suspension aids are, for example, water-insoluble inorganic stabilizers (e.g., tricalcium phosphate, magnesium pyrophosphate, metal carbonates); also polyvinyl alcohol and surfactants (e.g., sodium dodecylarylsulfonate). These are usually used in an amount of 0.05% by mass to 10% by mass based on the composition of the present invention.

[0110] Depending on the pressure selected, the impregnation temperature is in the range of 100° C. to 200° C., the pressure in the reaction vessel is in the range of 2 to 150 bar, preferably in the range of 5 to 100 bar, more preferably in the range of 20 to 60 bar, and the impregnation time is generally in the range of 0.5 to 10 hours.

[0111] The performance of processes in suspension is known to the person skilled in the art and is described extensively in, for example, WO2007 / 082838.

[0112] When the process is carried out in the absence of a blowing agent, care must be taken to avoid agglomeration of the polymer pellet-like material.

[0113] Suitable blowing agents for the process in a suitable closed reaction vessel are, for example, organic liquids or gases which become gaseous at the process conditions (e.g., hydrocarbons or inorganic gases, or mixtures of organic liquids or gases with inorganic gases), which can also be used in combination.

[0114] Examples of suitable hydrocarbons are halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.

[0115] Preferred organic blowing agents are saturated aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms, such as butane and pentane.

[0116] Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide, or a mixture of the abovementioned gases.

[0117] In a further embodiment, the impregnation of the pelletized material with a blowing agent under pressure comprises the process and subsequent expansion of the pelletized material in steps (α) and (β): (α) impregnating the pelletized material under pressure at elevated temperature in the presence of a blowing agent using an extruder; (β) The composition exiting the extruder is pelletized under conditions which prevent uncontrolled foaming.

[0118] Suitable blowing agents for this process variant are volatile organic compounds with a boiling point at standard pressure of 1013 mbar between -25°C and 150°C, in particular between -10°C and 125°C. Hydrocarbons, preferably halogen-free, are suitable, in particular C4-C10 alkanes, such as butane, pentane, hexane, heptane, octane isomers, particularly preferably isopentane. Other, more sterically demanding compounds, such as alcohols, ketones, esters, ethers, organic carbonates, are also possible blowing agents.

[0119] The composition is now mixed in the extruder under pressure while melted with the blowing agent fed to the extruder in step (ii). The mixture including the blowing agent is extruded under pressure, preferably pelletized (e.g., underwater pelletization) with back pressure controlled at a moderate level. This involves the expansion of the molten strands, which in turn results in the expansion of the beads by pelletization.

[0120] The performance of processes via extrusion is known to the person skilled in the art and is described extensively in, for example, WO2007 / 082838 and further in WO2013 / 153190 A1.

[0121] Extruders that can be used are conventional screw machines, in particular single- and twin-screw extruders (such as ZSK type from Werner & Pfleiderer), Co-kneaders, Kombiplast machines, MPC kneading mixers, FCM mixers, KEX kneading screw extruders, and shear roll machines. They are described, for example, in Saechtling (ed.), Kunststoff-Taschenbuch [Plastics handbook], 27th edition, Hanser-Verlag, Munich 1998, chapters 3.2.1 and 3.2.4. The extruder is usually operated at a temperature at which the composition (Z1) is present as a melt, for example 120°C to 250°C, in particular 150 to 210°C, and at a pressure of 40 to 200 bar, preferably 60 to 150 bar, more preferably 80 to 120 bar, after the addition of the blowing agent, to ensure homogenization of the blowing agent and the melt.

[0122] The process can be carried out in an extruder or an arrangement of one or more extruders. For example, the first extruder melts and mixes the components and injects the blowing agent. In the second extruder, the impregnated melt is homogenized and the temperature and / or pressure are adjusted. In the case of a combination of, for example, three extruders, the mixing of the components and the injection of the blowing agent can likewise be separated into two different process sections. If only one extruder is preferably used, all process steps (melting, mixing, injection of the blowing agent, homogenization, and temperature and pressure adjustment) are carried out in one extruder.

[0123] Alternatively, the corresponding foamed pellet-shaped material can be saturated with a supercritical liquid and removed from the supercritical liquid, according to the methods described in WO2014 / 150122 or WO2014 / 150124A1, and then (i') Immersing the article in a heated fluid; or (ii') By ​​irradiating an article with high-energy radiation (e.g., infrared or microwave radiation); Corresponding foamed pellet-shaped materials, which may already be colored, can also be produced directly from the pellet-shaped materials.

[0124] Examples of suitable supercritical liquids are those described in WO2014150122 or for example carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.

[0125] In addition, the supercritical liquid has a Hildebrand solubility parameter of 9 MPa. -1 / 2 It may contain polar liquids such as those listed above.

[0126] The supercritical fluid or heated fluid here may contain a dye, resulting in a colored foamed article.

[0127] The present invention further provides molded articles made from the expandable pellets of the present invention.

[0128] The corresponding mouldings can be produced by methods known to those skilled in the art.

[0129] A preferred method for producing a foamed molded article herein comprises the following steps: (A) introducing the foam pellets of the present invention into a suitable mold; (B) Fusing the foamable pellets of the present invention from step (i).

[0130] The fusing in step (B) is preferably carried out in a closed mould, the fusing being effected by steam, hot air (for example as described in EP 1979401 B1) or high energy radiation (microwave or radio wave).

[0131] The temperature during fusion of the foam pellet-shaped material is preferably below or close to the melting temperature of the polymer from which the foam pellet-shaped material is produced. For standard polymers, the temperature for fusion of the foam pellet-shaped material is accordingly between 100°C and 180°C, preferably between 120°C and 150°C.

[0132] The temperature profile / residence time can be determined individually here, similarly to the processes described, for example, in US 2015 / 0337102 or EP 2872309 B1.

[0133] Fusion by high energy radiation is generally carried out in the microwave or radio wave frequency range, optionally in the presence of water or other polar liquids, such as microwave absorbing hydrocarbons bearing polar groups (e.g. esters of carboxylic acids, esters of diols or triols, or glycols and liquid polyethylene glycols), and can be carried out in a manner similar to the processes described in EP 3053732 A or WO 2016 / 146537.

[0134] As mentioned above, the expandable pelletized material may include a dye, where the dye can be added in a variety of ways.

[0135] In one embodiment, the produced foam pellets may be colored after production by contacting the corresponding foam pellets with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity suitable for the sorption of the carrier liquid onto the foam pellet-like material. This can be carried out in a manner similar to that described in the EP patent application filed under application number 17198591.4.

[0136] Examples of suitable dyes are inorganic or organic pigments. Examples of suitable natural or synthetic inorganic pigments are carbon black, graphite, titanium oxide, iron oxide, zirconium oxide, cobalt oxide compounds, chromium oxide compounds, copper oxide compounds. Organic pigments include azo pigments, polycyclic pigments, etc.

[0137] In a further embodiment, the color may be added during the production of the expandable pelletized material, for example, dye may be added to an extruder during the production of the expandable pelletized material via extrusion.

[0138] Alternatively, already colored material can be used as the starting material for the production of foamed pellet-like material, which is extruded or expanded in a closed container by the process described above.

[0139] Additionally, in the process described in WO2014150122, the supercritical liquid or heated liquid may contain a dye.

[0140] As mentioned above, the moulded articles according to the invention have advantageous properties for the above mentioned applications in the requirements of the footwear and sports footwear sector.

[0141] The tensile and compressive properties of the moulded articles produced from the foamed pellets are characterised by a tensile strength of more than 600 kPa (DIN EN ISO 1798, April 2008) and an elongation at break of more than 100% (DIN EN ISO 1798, April 2008).

[0142] The elasticity of mouldings made from the foamed pellets is greater than 55% (method similar to DIN 53512, April 2000; the deviation from the standard is the height of the test specimen, which should be 12 mm, but the test is carried out at 20 mm to avoid sample collapse and measurement of the substrate).

[0143] As mentioned above, there is a relationship between the density and the compression properties of the molded article produced. The density of the molded article produced is advantageously between 75 and 375 kg / m 3 , preferably 100 to 300 kg / m 3 , more preferably 150 to 200 kg / m 3 (DIN EN ISO 845, October 2009).

[0144] The ratio of the density of the molded article of the present invention to the bulk density of the expandable pellets is generally 1.5 to 2.5, preferably 1.8 to 2.0.

[0145] The invention further provides for the use of the foamed pelletized material of the invention in the manufacture of moldings for shoe midsoles, shoe insoles, shoe combination soles, bicycle saddles, bicycle tires, damping elements, cushions, pads, backrests, arm pads, pads, mattresses, underlays, handles, protective films, in parts for the interior and exterior fields of automobiles, in balls and sports equipment or as flooring, in particular for sports surfaces, track and field surfaces, sports halls, children's play areas, walkways.

[0146] The foamed pellet-shaped material according to the invention is preferably used for the production of moldings for shoe midsoles, shoe insoles, shoe combination soles or shoe cushioning elements. The shoes here are preferably outdoor shoes, sports shoes, sandals, boots, safety shoes, more preferably sports shoes.

[0147] The invention therefore also provides a moulded article, which is a sole of a shoe combination for a shoe, preferably an outdoor shoe, a sports shoe, a sandal, a boot or a safety shoe, more preferably a sports shoe.

[0148] The present invention therefore also provides a moulded article, characterised in that it is an intermediate sole for a shoe, preferably an outdoor shoe, a sports shoe, a sandal, a boot or a safety shoe, more preferably a sports shoe.

[0149] Therefore, the present invention also provides a molded article, which is an insole for shoes, preferably an insole for outdoor shoes, sports shoes, sandals, boots or safety shoes, more preferably an insole for sports shoes.

[0150] The invention therefore also provides a moulded article, which is a cushioning element for a shoe, preferably an outdoor shoe, a sports shoe, a sandal, a boot or a safety shoe, more preferably a sports shoe.

[0151] This cushioning element may be used, for example, in the heel or forefoot.

[0152] The present invention therefore further provides a shoe in which the molded article of the present invention is used as a midsole, intermediate sole or cushion, for example in the heel region or forefoot region, which shoe is preferably an outdoor shoe, a sports shoe, a sandal, a boot or a safety shoe, particularly preferably a sports shoe.

[0153] In a further aspect, the present invention also relates to an expanded pellet-like material obtained or obtainable by the process of the present invention.

[0154] Due to their good mechanical properties and good temperature behavior, the expandable pellets of the invention are particularly suitable for the production of moulded articles, which can be produced, for example, from the expandable pellets of the invention by fusion or bonding.

[0155] In a further aspect, the present invention also relates to the use of the inventive expandable pellet-shaped material or the expandable pellet-shaped material obtained or obtainable by the inventive process for the manufacture of a molded article. In a further aspect, the present invention accordingly also relates to the use of the inventive expandable pellet-shaped material or the expandable pellet-shaped material obtained or obtainable by the inventive process for the manufacture of a molded article, wherein the molded article is manufactured by fusing or bonding the beads to one another.

[0156] The moulded articles obtained according to the invention are suitable for the manufacture, for example, of footwear soles, parts of footwear soles, bicycle saddles, cushions, mattresses, underlays, grips, protective films, parts for the interior and exterior of automobiles, in balls and parts of sports equipment or as flooring and wall panels (in particular sports surfaces, athletics surfaces, sports halls, children's play areas, walkways).

[0157] In a further embodiment, the present invention also relates to the use of the foamed pellet-shaped material of the present invention or the foamed pellet-shaped material obtained or obtainable by the process of the present invention, for the manufacture of molded articles, the molded articles being shoe soles, parts of shoe soles, bicycle saddles, cushions, mattresses, underlays, grips, protective films, parts for the interior and exterior of automobiles.

[0158] In further aspects, the present invention also relates to the use of the expandable pellets or foam beads of the present invention in balls and sports equipment, flooring and wall panels, in particular sports surfaces, athletics surfaces, sports halls, children's play areas and walkways.

[0159] In a further aspect, the present invention also relates to a hybrid material comprising a matrix made of a polymer (PM) and an expanded pellet-like material according to the invention. A material comprising an expanded pellet-like material and a matrix material is called a hybrid material in the context of the present invention. The matrix material here may be made of a compact material as well as a foam.

[0160] Polymers (PM) suitable as matrix materials are known per se to the person skilled in the art. Suitable in the context of the present invention are, for example, ethylene-vinyl acetate copolymers, epoxy-based binders or other polyurethanes. Polyurethane foams or other compact polyurethanes, such as elastic polyurethanes, are suitable here according to the present invention.

[0161] In the present invention, a polymer (PM) was selected that provides sufficient adhesion between the expanded pellets and the matrix so that a mechanically stable hybrid type material was obtained.

[0162] The matrix here may completely or partially surround the expanded pellet-like material. According to the invention, the hybrid material may also contain further components, such as further fillers or other pellets. According to the invention, the hybrid material may also contain a mixture of different polymers (PM). According to the invention, the hybrid material may also contain a mixture of expanded pellets.

[0163] The foam pellets which can be used in addition to the foam pellet-shaped material according to the invention are known per se to the person skilled in the art. Foam pellets made of thermoplastic polyurethane are particularly suitable in the context of the present invention.

[0164] Therefore, in one embodiment, the present invention also relates to a hybrid material comprising a matrix made of a polymer (PM), an expanded pellet-shaped material according to the invention, and a further expanded pellet-shaped material made of a thermoplastic polyurethane.

[0165] The matrix, in the context of the present invention, is composed of a polymer (PM). Examples of suitable matrix materials in the context of the present invention are elastomers or foams, in particular foams based on polyurethanes, such as elastomers such as ethylene-vinyl acetate copolymers, or other thermoplastic polyurethanes.

[0166] The present invention therefore also relates to a hybrid material as described above, in which the polymer (PM) is an elastomer.The present invention further relates to a hybrid material as described above, in which the polymer (PM) is selected from the group consisting of ethylene-vinyl acetate copolymers and thermoplastic or elastic polyurethanes.

[0167] In one embodiment, the present invention also relates to a hybrid material comprising a matrix composed of ethylene-vinyl acetate copolymer and an expanded pellet-shaped material according to the present invention.

[0168] In a further embodiment, the present invention relates to a hybrid material comprising a matrix of ethylene-vinyl acetate copolymer, an expandable pellet-shaped material according to the invention and a further expandable pellet-shaped material, for example made of thermoplastic polyurethane.

[0169] In one embodiment, the present invention relates to a hybrid material comprising a matrix composed of resilient polyurethane and an expanded pellet-like material according to the present invention.

[0170] In a further embodiment, the present invention relates to a hybrid material comprising a matrix composed of a thermoplastic polyurethane or a resilient polyurethane, an expandable pellet-shaped material according to the present invention, and a further expandable pellet-shaped material, for example composed of a thermoplastic polyurethane.

[0171] Suitable thermoplastic and elastic polyurethanes are known per se to those skilled in the art. Suitable polyurethanes are described, for example, in "Kunststoffhandbuch" [Plastics handbook], Volume 7, "Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.

[0172] The polymer (PM) is preferably a polyurethane in the context of the present invention. For the purposes of the present invention, "polyurethane" includes all known resilient polyisocyanate polyaddition products. These include, in particular, solid polyisocyanate polyaddition products, such as viscoelastic gels and thermoplastic polyurethanes, as well as resilient foams based on polyisocyanate polyaddition products, such as flexible foams, semi-rigid foams and monolithic foams. For the purposes of the present invention, "polyurethane" is also understood to mean resilient polymer blends comprising polyurethane and further polymers, as well as foams composed of these polymer blends. The matrix is ​​preferably a cured compact polyurethane binder, a resilient polyurethane foam or a viscoelastic gel.

[0173] "Polyurethane binder" is understood in the context of the present invention to mean a mixture composed to an extent of at least 50% by weight, preferably at least 80% by weight, in particular at least 95% by weight, of prepolymers containing isocyanate groups, hereinafter referred to as isocyanate prepolymers. The viscosity of the polyurethane binders according to the present invention, measured at 25°C according to DIN 53 018, is preferably in the range from 500 to 4000 mPa.s, more preferably from 1000 to 3000 mPa.s.

[0174] In the context of the present invention, "polyurethane foam" is understood to mean foam according to DIN 7726.

[0175] The density of the matrix material is preferably 1.2 to 0.01 g / cm 3 The matrix material is particularly preferably in the range of 0.8 to 0.1 g / cm 3 , especially 0.6 to 0.3 g / cm 3 The foam may be a resilient or monolithic foam or a compact material (eg, a cured polyurethane binder) having a density in the range of 0.1 to 0.5 mm.

[0176] Foams are particularly suitable as matrix materials, and hybrid materials comprising a matrix material made of polyurethane foam preferably have good adhesion between the matrix material and the expanded pellet-like material.

[0177] In one embodiment, the present invention also relates to a hybrid material comprising a matrix made of polyurethane foam and an expanded pellet-like material according to the present invention.

[0178] In a further embodiment, the present invention relates to a hybrid material comprising a matrix made of polyurethane foam, an expanded pellet-shaped material according to the invention and a further expanded pellet-shaped material, for example made of thermoplastic polyurethane.

[0179] In one embodiment, the present invention relates to a hybrid material comprising a matrix made of polyurethane integral foam and an expanded pellet-like material according to the present invention.

[0180] In a further embodiment, the present invention relates to a hybrid material comprising a matrix made of polyurethane integral foam, an expanded pellet-shaped material according to the invention and a further expanded pellet-shaped material, for example made of thermoplastic polyurethane.

[0181] The hybrid material of the present invention comprising a polymer (PM) as a matrix and an expandable pellet-shaped material of the present invention can be produced, for example, by mixing the components used to produce the polymer (PM), the expandable pellet-shaped material and optionally further components and reacting them to obtain the hybrid material, the reaction being preferably carried out under conditions in which the expandable pellet-shaped material is essentially stable.

[0182] Suitable processes and reaction conditions for producing polymers (PM), in particular ethylene-vinyl acetate copolymers or polyurethanes, are known per se to those skilled in the art.

[0183] In a preferred embodiment, the hybrid material of the invention is an integral foam, in particular an integral foam based on polyurethane. Suitable processes for producing integral foams are known per se to the person skilled in the art. The integral foams are preferably produced by a one-shot process using low-pressure or high-pressure techniques in closed, advantageously temperature-controlled moulds. The moulds are usually made of metals such as aluminium or steel. These procedures are described, for example, in Piechota and Roehr in “lntegralschaumstoff” [Integral foam], Carl-Hanser-Verlag, Munich, Vienna, 1975, or in “Kunststoff-Handbuch” [Plastics handbook], volume 7, “Polyurethane” [Polyurethanes], 3rd edition, 1993, chapter 7.

[0184] When the hybrid material of the present invention contains an integral foam, the amount of the reaction mixture introduced into the mold is such that the molded article composed of the resulting integral foam has a density of 0.08 to 0.70 g / cm. 3 , especially 0.12 to 0.60 g / cm 3 The densification level for producing a molded article having compressed edge zones and a cellular core is in the range of 1.1 to 8.5, preferably 2.1 to 7.0.

[0185] It is therefore possible to produce hybrid materials with homogeneous distribution of foam beads, incorporating the foamed pellet-shaped material of the invention in a matrix composed of polymer (PM). The foamed pellet-shaped material of the invention can be easily used in methods for producing hybrid materials, since the individual beads flow freely due to their small size and do not make special demands on processing. Here, it is possible to use techniques that homogeneously distribute the foamed pellet-shaped material (for example slow rotation of the mold).

[0186] Further auxiliaries and / or additives can be optionally added to the reaction mixture for producing the hybrid material of the invention, such as, for example, surfactants, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis stabilizers, odor absorbing substances, bactericidal and bacteriostatic substances, etc.

[0187] Surfactants that can be used are, for example, compounds that are used to promote the homogenization of the starting materials and are also suitable for adjusting the cell structure. For example, emulsifiers, such as castor oil sulfates and sodium salts of fatty acids, as well as salts of fatty acids and amines, such as diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, such as alkali metal or ammonium salts of dodecylbenzene or dinaphthylmethane disulfonic acid, ricinoleic acid; organopolysiloxanes, such as siloxane-oxyalkylene copolymers; foam stabilizers, such as ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oil, castor oil esters or ricinoleic acid esters, Turkish red oil, peanut oil, cell regulators, such as paraffins, fatty alcohols, dimethylpolysiloxanes, etc. Oligomeric acrylates with polyoxyalkylene radicals or fluoroalkane radicals as pendant groups are also suitable for improving the emulsification, cell structure and / or stabilization of the foam.

[0188] Examples of suitable release agents are reaction products of fatty acid esters and polyisocyanates, salts of amino group-containing polysiloxanes and fatty acids, salts of saturated or unsaturated (cyclo)aliphatic carboxylic acids having at least 8 carbon atoms and tertiary amines, and in particular internal release agents (mixtures of montanic acid and at least one aliphatic carboxylic acid having at least 10 carbon atoms with at least difunctional alkanolamines, polyols and / or polyamines having molecular weights of 60 to 400, mixtures of organic amines and stearic acid and metal salts of organic mono- and / or dicarboxylic acids or their anhydrides, or carboxylic acid esters and / or carboxylic acid amides prepared by esterification or amidation of mixtures of imino compounds and metal salts of carboxylic acids and, optionally, carboxylic acids).

[0189] Fillers (especially reinforcing fillers) are understood to mean common organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion resistance of paints and coating compositions (which are known), etc. Specific examples include inorganic fillers such as silicon-based minerals, for example phyllosilicates such as antigorite, bentonite, serpentine, hornblende, amphiboles, chrysotile, talc, etc.; metal oxides such as kaolin, aluminum oxide, titanium oxide, zinc oxide, iron oxide, etc.; metal salts such as chalk, barite, etc.; inorganic pigments such as cadmium sulfide, zinc sulfide, etc., and also glass, etc. It is preferable to use natural and synthetic fibrous minerals such as kaolin (china clay), aluminum silicate, coprecipitates of barium sulfate and aluminum silicate, as well as wollastonite, metal fibers, especially glass fibers of different lengths, which may be arbitrarily sized. Examples of useful organic fillers include carbon black, melamine, rosin, cyclopentadienyl resins, graft polymers, as well as cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters, and especially carbon fibers.

[0190] The inorganic and organic fillers may be used alone or in combination.

[0191] In the hybrid materials of the invention, the proportion by volume of the foamed pellet-like material is in each case preferably at least 20% by volume, particularly preferably at least 50% by volume, more preferably at least 80% by volume and in particular at least 90% by volume, based on the volume of the hybrid system of the invention.

[0192] The hybrid material of the present invention, in particular the hybrid material having a matrix made of cellular polyurethane, is characterized by a very good adhesion between the matrix material and the foamed pellet-like material of the present invention. As a result, the hybrid material of the present invention preferably does not break at the interface between the matrix material and the foamed pellet-like material. This allows the production of a hybrid material with improved mechanical properties (e.g. tear resistance and elasticity) compared to conventional polymer materials of the same density (in particular conventional polyurethane materials).

[0193] The elasticity of the hybrid material of the invention in the form of a monolithic foam is preferably greater than 40%, more preferably greater than 50%, according to DIN 53512.

[0194] Furthermore, the hybrid material of the present invention, especially the material based on the one-piece foam, has low density and high elasticity. Therefore, the one-piece foam based on the hybrid material of the present invention is particularly suitable as a material for shoe soles. The sole is light, comfortable and durable. Such a material is particularly suitable as a midsole for sports shoes.

[0195] The hybrid material of the present invention having a cellular matrix is ​​suitable as a cushioning material for furniture, mattresses, etc.

[0196] Hybrid materials with a matrix consisting of a viscoelastic gel are characterized by enhanced viscoelasticity and improved elastic properties, and are therefore also suitable as cushioning for seats, in particular saddles, such as bicycle saddles or motorcycle saddles.

[0197] Hybrid materials with a compact matrix are suitable, for example, as flooring, in particular as coverings for playing fields, athletics surfaces, sports fields and sports halls.

[0198] The properties of the hybrid material of the present invention can be varied over a wide range depending on the polymer (PM) used, in particular by varying the size, shape and properties of the expanded pelletized material or by adding further additives, for example by further adding non-expanded pellets such as plastic pellets, e.g. rubber pellets.

[0199] The hybrid material of the present invention has high durability and toughness, as evidenced in particular by high tensile strength and elongation at break, and further has low density.

[0200] Further embodiments of the present invention are described in the claims and in the examples. It is understood that the features of the object / process / use according to the invention described above and described below can be used not only in the combinations specified in each case, but also in other combinations, without departing from the scope of the present invention. Thus, for example, a combination of a preferred feature with a particularly preferred feature, or a combination of no feature with a particularly preferred feature, etc., is implicitly included, even if this combination is not explicitly mentioned.

[0201] Exemplary embodiments of the invention are described below, but are not intended to limit the invention. In particular, the invention also encompasses those embodiments resulting from the description of the dependencies specified below and the resulting combinations.

[0202] 1. An expandable pellet-shaped material comprising a composition (Z1) containing a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), wherein the composition (Z1) has a Shore hardness in the range of 15A to 43A.

[0203] 2. The expandable pellet-shaped material according to claim 1, wherein the composition (Z1) has a Shore hardness in the range of 15A to 43A.

[0204] 3. The composition (Z1) has a melting range starting from below 100°C in a DSC measurement at a heating rate of 20 K / min, and the composition (Z1) has a maximum melt flow rate (MFR) of 250 g / 10 min with the composition (Z1) at 180°C and a pressurized mass (according to DIN EN ISO1133) of 21.6 kg. The expandable pellet-shaped material according to claim 1 or 2.

[0205] 4. The expandable pellet-shaped material according to any one of claims 1 to 3, wherein the plasticizer (W) is selected from derivatives of citric acid and derivatives of glycerol, or a mixture of two or more of these, and at least one glycerol hydroxyl group is esterified with a monocarboxylic acid having 1, 2, 3, 4, 5 or 6 carbon atoms.

[0206] 5. The expandable pellet-shaped material according to any one of claims 1 to 4, wherein the plasticizer (W) is present in the composition (Z1) in an amount ranging from 1% by mass to 60% by mass, based on the total of the composition (Z1).

[0207] 6. The expandable pellet-shaped material according to any one of claims 1 to 5, wherein the composition (Z1) comprises an ester of a tricarboxylic acid as plasticizer (W2).

[0208] 7. The foamed pellet-shaped material according to any one of claims 1 to 6, wherein the thermoplastic polyurethane (TPU-1) is produced using a polyol (P1) selected from the group consisting of polyetherol, polyesterol, polycarbonate alcohol, and hybrid polyol.

[0209] 8. The expandable pellet-shaped material according to any one of claims 1 to 7, wherein the thermoplastic polyurethane (TPU-1) is produced using a chain extender (KV) selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.

[0210] 9. The expandable pellet-shaped material according to any one of claims 1 to 8, wherein the thermoplastic polyurethane (TPU-1) is produced using a diisocyanate selected from the group consisting of diphenylmethane 2,2'-, 2,4'-, and / or 4,4'-diisocyanate (MDI); tolylene 2,4- and / or 2,6-diisocyanate (TDI); methylene dicyclohexyl 4,4'-, 2,4'-, and / or 2,2'-diisocyanate (H12MDI); hexamethylene diisocyanate (HDI); and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

[0211] 10. A method for producing a foamed pellet-shaped material, comprising the steps of: (i) providing a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15A to 43A; (ii) impregnating the composition (Z1) with a blowing agent under pressure; (iii) expanding said composition (Z1) by reducing pressure; A manufacturing method comprising: 11. A method for producing a foamed pellet-shaped material, comprising the steps of: (i') extruding a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15A to 43A, thereby obtaining a pellet-shaped material having an average diameter in the range of 0.2 to 10 mm; (ii') impregnating the pellet-shaped material under pressure with 0.1% to 40% by weight of a blowing agent based on the total weight of the pellet-shaped material; and (iii') obtaining a foamed pellet-like material by reducing pressure; A manufacturing method comprising:

[0212] 12. The process according to claim 10 or 11, wherein the blowing agent is selected from the group consisting of butane, propane, pentane, carbon dioxide, and nitrogen.

[0213] 13. The method according to any one of embodiments 10 to 12, wherein the composition (Z1) has a Shore hardness in the range of 15A to 43A.

[0214] 14. The method according to any one of embodiments 10 to 13, wherein the melting range of the composition (Z1) starts from less than 100°C in a DSC measurement at a heating rate of 20K / min, and the composition (Z1) has a maximum melt flow rate (MFR) of 250g / 10min when the composition (Z1) is subjected to a pressurized mass (according to DIN EN ISO1133) of 21.6 kg at 180°C.

[0215] 15. The process according to any one of embodiments 10 to 14, wherein the plasticizer (W) is selected from derivatives of citric acid and derivatives of glycerol, or a mixture of two or more thereof, and at least one glycerol hydroxyl group is esterified with a monocarboxylic acid having 1, 2, 3, 4, 5 or 6 carbon atoms.

[0216] 16. The method according to any one of embodiments 10 to 15, wherein the plasticizer (W) is present in the composition (Z1) in an amount ranging from 1% by weight to 60% by weight, based on the total of the composition (Z1).

[0217] 17. The process according to any one of embodiments 10 to 16, wherein the composition (Z1) comprises an ester of a tricarboxylic acid as plasticizer (W2).

[0218] 18. The method according to any one of embodiments 10 to 17, wherein the thermoplastic polyurethane (TPU-1) is produced using a polyol (P1) selected from the group consisting of polyetherols, polyesterols, polycarbonate alcohols, and hybrid polyols.

[0219] 19. The method of any one of embodiments 10 to 18, wherein the thermoplastic polyurethane (TPU-1) is produced using a chain extender (KV) selected from the group consisting of 1,2-ethylene glycol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol.

[0220] 20. The method according to any one of embodiments 10 to 19, wherein the thermoplastic polyurethane (TPU-1) is produced using a diisocyanate selected from the group consisting of diphenylmethane 2,2'-, 2,4'-, and / or 4,4'-diisocyanate (MDI); tolylene 2,4- and / or 2,6-diisocyanate (TDI); methylene dicyclohexyl 4,4'-, 2,4'-, and / or 2,2'-diisocyanate (H12MDI); hexamethylene diisocyanate (HDI); and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

[0221] 21. Expanded pellet-shaped material obtained or obtainable by the process according to any one of embodiments 10 to 20.

[0222] 22. Use of the expandable pellet-shaped material according to any one of embodiments 1 to 9 or 21 for the manufacture of a molded article.

[0223] 23. The method of use according to embodiment 22, wherein the molded article is produced by fusing or bonding beads of the expanded pellet-like material together.

[0224] 24. The method of use according to embodiment 22 or 23, wherein the molded article is a shoe sole, part of a shoe sole, a bicycle saddle, a cushion, a mattress, padding, a backrest, an arm pad, a pad, an underlay, a handle, a protective film, or an interior or exterior part of an automobile.

[0225] 25. Use of the foamed pellet-like material according to any one of embodiments 1 to 9 or 21 in balls and sports equipment, or as flooring and wall panels, in particular sports surfaces, athletics surfaces, sports halls, children's play areas and walkways.

[0226] 26. A hybrid material comprising a matrix of a polymer (PM) and an expandable pellet material according to any one of embodiments 1 to 9 or 21 or an expandable pellet material obtained or obtainable by the manufacturing method according to any one of embodiments 10 to 20.

[0227] 27. The hybrid material according to embodiment 26, wherein the polymer (PM) is EVA.

[0228] 28. The hybrid material according to embodiment 26, wherein the polymer (PM) is a thermoplastic polyurethane.

[0229] 29. The hybrid material of embodiment 26, wherein the polymer (PM) is a resilient polyurethane.

[0230] 30. The hybrid material according to embodiment 26, wherein the polymer (PM) is a polyurethane foam.

[0231] 31. The hybrid material according to embodiment 26, wherein the polymer (PM) is a polyurethane integral foam. EXAMPLES

[0232] The following examples serve to illustrate the invention but are in no way limiting with respect to its subject matter.

[0233] The following raw materials were used: 4,4'-Diphenylmethane diisocyanate; Polytetrahydrofuran with a number average molar mass of 1 kg / mol; polybutyl adipate prepared from butane-1,4-diol and adipic acid and having a number average molar mass of 2400 g / mol; Polymeric diol made from adipic acid, ethane-1,2-diol, butane-1,4-diol; Butane-1,4-diol; Ethane-1,2-diol; Phenolic antioxidants; Dioctyl adipate; Stannous dioctanoate; Hydrolytic stabilizer (oligomeric carbodiimide produced from TMDXI (= tetramethylxylyl diisocyanate); Acetyl tributyl citrate.

[0234] 2. Manufacturing of TPU pellets 2.1 Example 1 (Comparative Example) 420 parts of 4,4'-diphenylmethane diisocyanate, 88.8 parts of butane-1,4-diol chain extender and 700 parts of polytetrahydrofuran with a number average molar mass of 1 kg / mol are synthesized into TPU in a reactive extruder, the extruder zone temperature being 140°C to 210°C. In addition, 15.3 parts of a phenolic antioxidant and 25 ppm of a 25% aqueous solution of tin dioctyl adipate are added as reaction catalysts. The pelletized TPU thus produced is used to produce extruded strands for which the test values ​​are determined.

[0235] 2.2 Example 2 (Comparative Example) 312 parts of 4,4'-diphenylmethane diisocyanate, 82.1 parts of butane-1,4-diol chain extender, and 800 parts of polybutyl adipate with a number average molar mass of 2400 g / mol, prepared from butane-1,4-diol and adipic acid, are synthesized into TPU by hand casting. In addition, 6.4 parts of a hydrolysis stabilizer (oligomeric carbodiimide prepared from TMDXI (=tetramethylxylyl diisocyanate)) as reaction catalyst and 50 ppm of a 25% solution of tin dioctate are added. The resulting slab is heated at 80°C in an oven with air circulation for 15 hours and then crushed. The pelletized TPU thus prepared is used to produce extruded strands, in which the test values ​​are determined.

[0236] 2.3 Example 3 (present invention) 393 parts of 4,4'-diphenylmethane diisocyanate, 35.5 parts of ethane-1,2-diol chain extender, 1000 parts of polytetrahydrofuran with a number-average molar mass of 1 kg / mol, and 410 parts of acetyl tributyl citrate are synthesized into TPU in a reactive extruder, the extruder zone temperature being 140°C to 210°C. In addition, 15.3 parts of a phenolic antioxidant and 25 ppm of a 25% dioctyl adipate solution of tin dioctate are added as reaction catalysts. The pelletized TPU thus produced is used to produce extruded strands, in which test values ​​are determined.

[0237] 2.4 Example 4 (present invention) 260 parts of 4,4'-MDI, 32.2 parts of ethane-1,2-diol chain extender, 1000 parts of a polymer diol made from adipic acid, ethane-1,2-diol and butane-1,4-diol (the latter in a mass ratio of 1:1 with a number-average molar mass of 2000 g / mol), and 231.2 parts of acetyl tributyl citrate are synthesized into TPU in a reactive extruder, the extruder zone temperature being 140°C to 210°C. In addition, 10 parts of a hydrolysis stabilizer (oligomeric carbodiimide made from TMDXI (= tetramethylxylyl diisocyanate)), 3.08 parts of a phenolic antioxidant and 4.62 parts of a lubricant (partially hydrolyzed Montan acid ester) are added during the reaction. The pelletized TPU thus produced is used for the production of extruded strands, in which the test values ​​are determined.

[0238] 2.5 Example 5 (Invention) 260 parts of 4,4'-MDI, 31.6 parts of ethane-1,2-diol chain extender, 1000 parts of a polymer diol made from adipic acid, ethane-1,2-diol and butane-1,4-diol (the latter in a mass ratio of 1:1 with a number-average molar mass of 2000 g / mol), and 260 parts of acetyl tributyl citrate are synthesized into TPU in a reactive extruder, the extruder zone temperature being 140 ° C to 210 ° C. In addition, 10 parts of a hydrolysis stabilizer (oligomeric carbodiimide made from TMDXI (= tetramethylxylyl diisocyanate)), 3.08 parts of a phenolic antioxidant and 4.62 parts of a lubricant (partially hydrolyzed Montan acid ester) are added during the reaction. The pelletized TPU thus produced is used for the production of extruded strands, in which the test values ​​are determined.

[0239] 2.6 Example 6 (Invention) 260 parts of 4,4'-MDI, 32.2 parts of ethane-1,2-diol chain extender, 1000 parts of a polymer diol made from adipic acid, ethane-1,2-diol and butane-1,4-diol (the latter in a mass ratio of 1:1 with a number-average molar mass of 2000 g / mol), and 231.2 parts of acetyl tributyl citrate are synthesized into TPU in a reactive extruder, the extruder zone temperature being 140°C to 210°C. In addition, 10 parts of a hydrolysis stabilizer (oligomeric carbodiimide made from TMDXI (= tetramethylxylyl diisocyanate)), 3.08 parts of a phenolic antioxidant and 4.62 parts of a lubricant (partially hydrolyzed Montan acid ester) are added during the reaction. The pelletized TPU thus produced is used for the production of extruded strands, in which the test values ​​are determined. The product obtained is heated to 85 °C in a heatable mixer (DiOsa type) and mixed with 25% by weight of glycerol triacetate. After a mixing process of 90 minutes, the product is cooled to room temperature under stirring. The plasticizer is homogeneously absorbed into the TPU. The pelletized TPU thus produced is used to produce extruded strands for which the test values ​​are determined.

[0240] 2.7 Example 7 (Invention) 260 parts of 4,4'-MDI, 32.2 parts of ethane-1,2-diol chain extender, 1000 parts of a polymer diol made from adipic acid, ethane-1,2-diol and butane-1,4-diol (the latter in a mass ratio of 1:1 with a number-average molar mass of 2000 g / mol), and 231.2 parts of acetyl tributyl citrate are synthesized into TPU in a reactive extruder, the extruder zone temperature being 140°C to 210°C. In addition, 10 parts of a hydrolysis stabilizer (oligomeric carbodiimide made from TMDXI (= tetramethylxylyl diisocyanate)), 3.08 parts of a phenolic antioxidant and 4.62 parts of a lubricant (partially hydrolyzed Montan acid ester) are added during the reaction. The pelletized TPU thus produced is used for the production of extruded strands, in which the test values ​​are determined. The product is heated to 85°C in a heatable mixer (DiOsa type) and mixed with 45% by weight of glycerol triacetate. After a mixing process of 180 minutes, the product is cooled to room temperature while stirring. The plasticizer is homogeneously absorbed into the TPU. The pelletized TPU thus produced is used to produce extruded strands on which the test values ​​are determined.

[0241] 3. Characteristics of the product obtained The test is carried out in accordance with DIN 53505 (Shore).

[0242] [Table 1]

[0243] 4. Beads foam manufacturing The pelletized TPU samples (Examples 1 to 7) were pressurized with supercritical CO2 in a high-pressure autoclave according to Table 2 to permeate the TPU with CO2. 。 The beads were then subjected to a pressure change, during which the previously high-pressure CO2 expanded to normal pressure, foaming the partially softened TPU in the process. This gas expansion caused the TPU to cool rapidly, solidifying it into a stable bead foam.

[0244] [Table 2]

[0245] [Table 3]

[0246] 5.Measurement method Measurement methods that can be used to characterize materials include; DSC, DMA, TMA, NMR, FT-IR, GPC Mechanical properties (eTPU) Foam density DIN EN ISO 845:2009-10 Tear resistance DIN EN ISO 8067:2009-06 Dimensional stability test ISO 2796:1986-08 Tensile Test ASTM D5035:2011 Elasticity DIN 53512:2000-4

Claims

1. A foamed pellet-like material comprising a composition (Z1) containing a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15A to 43A.

2. 2. The expanded pellet-like material according to claim 1, wherein said composition (Z1) has a Shore hardness in the range of 20A to 43A.

3. 3. The expanded pellet-like material according to claim 1 or 2, wherein the melting range of the composition (Z1) starts below 100 ° C. in a DSC measurement at a heating rate of 20 K / min, and the composition (Z1) has a maximum melt flow rate (MFR) of 250 g / 10 min at 180 ° C. and a pressurized mass of 21.6 kg according to DIN EN ISO 1133.

4. The expanded pellet-like material according to any one of claims 1 to 3, wherein the plasticizer (W) is selected from derivatives of citric acid and derivatives of glycerol, or a mixture of two or more thereof, and at least one glycerol hydroxyl group is esterified with a monocarboxylic acid having 1, 2, 3, 4, 5 or 6 carbon atoms.

5. The expanded pellet-like material according to any one of claims 1 to 4, wherein the plasticizer (W) is present in the composition (Z1) in an amount ranging from 1% by weight to 60% by weight, based on the total of the composition (Z1).

6. The expanded pellet-like material according to any one of claims 1 to 5, wherein the composition (Z1) comprises an ester of a tricarboxylic acid as plasticizer (W2).

7. The expanded pellet-like material according to any one of claims 1 to 6, wherein the thermoplastic polyurethane (TPU-1) is produced using a polyol (P1) selected from the group consisting of polyetherols, polyesterols, polycarbonate alcohols, and hybrid polyols.

8. The expanded pellet-like material according to any one of claims 1 to 7, wherein the thermoplastic polyurethane (TPU-1) is produced using a chain extender (KV) selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.

9. 9. The expanded pellet-like material of any one of claims 1 to 8, wherein the thermoplastic polyurethane (TPU-1) is produced using a diisocyanate selected from the group consisting of diphenylmethane 2,2'-, 2,4'-, and / or 4,4'-diisocyanate (MDI); tolylene 2,4- and / or 2,6-diisocyanate (TDI); methylene dicyclohexyl 4,4'-, 2,4'-, and / or 2,2'-diisocyanate (H12MDI); hexamethylene diisocyanate (HDI); and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

10. The thermoplastic polyurethane (TPU-1) is produced using a polyol (P1) selected from the group consisting of polyetherol, polyesterol, polycarbonate alcohol, and hybrid polyol, and a diisocyanate selected from the group consisting of diphenylmethane 2,2'-, 2,4'-, and / or 4,4'-diisocyanate (MDI); tolylene 2,4- and / or 2,6-diisocyanate (TDI); methylene dicyclohexyl 4,4'-, 2,4'-, and / or 2,2'-diisocyanate (H12MDI); hexamethylene diisocyanate (HDI); and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), and 10. The expanded pellet-like material according to any one of claims 1 to 9, wherein the plasticizer (W) is selected from derivatives of citric acid and derivatives of glycerol, or a mixture of two or more thereof, and at least one glycerol hydroxyl group is esterified with a monocarboxylic acid having 1, 2, 3, 4, 5 or 6 carbon atoms.

11. 1. A method for producing an expanded pellet-like material, comprising the steps of: (i) providing a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), said composition (Z1) having a Shore hardness in the range of 15A to 43A; (ii) impregnating the composition (Z1) with a foaming agent under pressure; (iii) expanding the composition (Z1) by reducing pressure; A manufacturing method comprising:

12. 1. A method for producing an expanded pellet-like material, comprising the steps of: (i') extruding a composition (Z1) comprising a thermoplastic polyurethane (TPU-1) and at least one plasticizer (W), the composition (Z1) having a Shore hardness in the range of 15A to 43A, thereby obtaining a pellet-shaped material having an average diameter in the range of 0.2 to 10 mm; (ii') impregnating the pelletized material under pressure with 0.1% to 40% by weight of a blowing agent, based on the total weight of the pelletized material; and (iii') obtaining a foamed pellet-like material by reducing pressure; A manufacturing method comprising:

13. 13. The process of claim 11 or 12, wherein the blowing agent is selected from the group consisting of butane, propane, pentane, carbon dioxide, and nitrogen.

14. Use of the expanded pellet-like material according to any one of claims 1 to 10 for the production of moulded articles.

15. 15. The method of claim 14, wherein the molded article is produced by fusing or bonding beads of the expanded pellet-like material together.

16. 16. The method according to claim 14 or 15, wherein the molded article is a shoe sole, a part of a shoe sole, a bicycle saddle, a cushion, a mattress, padding, a backrest, an arm pad, a pad, an underlay, a handle, a protective film, or an interior or exterior part of an automobile.

17. Use of the expanded pellet-like material according to any one of claims 1 to 10 in balls or sports equipment or as flooring or wall panels.

18. A hybrid type material comprising a matrix composed of a polymer (PM) and the expanded pellet-shaped material according to any one of claims 1 to 10.

Images