WO2022162048A1

WO2022162048A1 - Particle foam made of tpe with a shore hardness between 20d and 90d

Info

Publication number: WO2022162048A1
Application number: PCT/EP2022/051856
Authority: WO
Inventors: Frank Prissok; Elmar Poeselt; Peter Gutmann
Original assignee: Basf Se
Priority date: 2021-01-28
Filing date: 2022-01-27
Publication date: 2022-08-04
Also published as: TW202239842A

Abstract

The present invention relates to a foamed granular material consisting of a composition (Z1), the composition containing at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range of 20 to 90 and a second thermoplastic elastomer (TPE-2), to a method for preparing a foamed granular particle foam of this kind, and to a method for preparing a shaped article from the foamed granular material, and to the use of the foamed granular material according to the invention to produce shoe soles, bicycle saddles, bicycle tyres, damping elements, cushioning, mattresses, padding, grips, protective films, in components for automotive interiors and exteriors, in balls and sports equipment or as a floor covering, in particular for sports surfaces, athletics tracks, sports halls, children's play areas and pavements.

Description

Particle foam made of TPE with a shore hardness between 20D and 90D

The present invention relates to a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2); Process for the production of such a foamed granulate, as well as a process for the production of a molding from the foamed granulate and the use of the foamed granulate according to the invention for the production of shoe soles, bicycle saddles, bicycle tires, damping elements, padding, mattresses, underlays, handles, protective films, in components in the automobile interior - and outdoors, in balls and sports equipment or as a floor covering, in particular for sports areas, athletics tracks, sports halls, children's playgrounds and sidewalks.

Foams, in particular also particle foams, have been known for a long time and are widely described in the literature, e.g. in Ullmann's "Encyclopedia of Industrial Chemistry", 4th edition, volume 20, page 416 ff.

Highly elastic, predominantly closed-cell foams, such as particle foams made from thermoplastic polyurethane, which are produced in autoclaves or using the extruder process, have good mechanical properties and, in some cases, good resilience as well. Hybrid foams made from particles of thermoplastic elastomers and system foam or binders are also known. Depending on the foam density, the manufacturing method and the matrix material, a relatively broad level of stiffness can be achieved. The properties of the foam can also be influenced by post-treatment of the foam, such as tempering.

Particle foams or foam particles or else foamed granules based on thermoplastic polyurethane, also referred to as TPU in this document, are disclosed in WO 94/20568 A1. A disadvantage of the TPU foams described in WO 94/20568 A1 is the high energy consumption during production and processing. A water vapor pressure of 4.5 bar to 7 bar at temperatures of 145°C to 165°C is used. Furthermore, WO 94/20568 A1 describes expanded, i.e. foamed, TPU particles which can be processed into molded parts. These TPU foam particles are produced at temperatures of 150° C. and higher and, according to the examples, have a bulk density of between 55 and 180 g/l, which is a disadvantage when these particles are transported and stored because of the increased space requirement.

JP2019157107 and CN 110294860 describe a composition comprising a thermoplastic polyamide elastomer and a thermoplastic polyurethane elastomer and the use of such compositions for the production of shoe soles.

CN110355970 describes a manufacturing process for colored TPU foam particles and moldings made from them. CN 109867946 and CN 107151373 disclose thermoplastic polyurethane foam particles, a further polymer being used in addition to a thermoplastic polyurethane elastomer.

JP2016190989 discloses particle foams based on polyamides.

WO 2018/232968 A1 describes processes for producing foams based on thermoplastic polyester elastomers

CN 108239386 discloses an extruded and foamed thermoplastic polyurethane elastomer particle and a manufacturing method thereof. CN 105968767 describes a polymethylethylene carbonate foam material and manufacturing processes thereof.

WO 2007/082838 A1 discloses an expandable, preferably particulate, thermoplastic polyurethane containing blowing agent, the thermoplastic polyurethane having a Shore hardness of between A 44 and A 84. The Shore hardness of the TPU is measured on the compact, i.e. non-expanded TPU. WO 2007/082838 A1 also discloses processes for producing expandable, preferably particulate, thermoplastic polyurethane containing blowing agent and processes for producing expanded thermoplastic polyurethane and processes for producing foam based on thermoplastic polyurethane and foams or expanded thermoplastic polyurethanes obtainable in this way.

However, the mechanical properties, in particular the elongation at break, of the moldings obtainable from the foamed granules are not sufficient for many applications. Furthermore, the rebound resilience of the foams known in the prior art is not sufficient for many applications. Furthermore, it is difficult to process harder materials into shaped bodies, since the corresponding foamed granules are difficult to weld.

One of the objects on which the present invention is based was therefore to find foamed granules or moldings produced from foamed granules with very high rebound in combination with good mechanical properties. In addition, it was an object on which the present invention is based to provide foamed granules which can be easily processed to form molded articles.

According to the invention, this object is achieved by a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2 ). It has been found that the rebound resilience of the foamed granules or of moldings that are produced from the foamed granules depends to a large extent on the matrix polymer used. The hardness of the polymer used is also crucial. Further advantages result from a defined, as complete as possible closed cell structure of the foam and a sufficient wall thickness of the individual foam cells. Surprisingly, it was found that foamed granules or moldings can be produced from the compositions used according to the invention, which have a rebound resilience of more than 65%.

Adding a softer material reduces the temperature required for foaming. In addition, the softer material makes it easier to weld because it melts at lower temperatures. Blends can also be used to combine and set different glass temperatures in one material.

The foamed granules according to the invention consist of the composition (Z1). The composition (Z1) contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2). According to the invention, the composition (Z1) can also contain other components, in particular other thermoplastic elastomers. According to the invention, the thermoplastic elastomer (TPE-1) has a Shore D hardness in the range from 20 to 90. The properties of the thermoplastic elastomer (TPE-2) can vary widely.

Suitable thermoplastic elastomers are known per se to those skilled in the art. For example, the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester or a thermoplastic styrene-butadiene block copolymer, provided it has a Shore D hardness in the range from 20 to 90.

Accordingly, the present invention also relates to a further embodiment of a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene-butadiene block copolymers.

According to a further embodiment, also a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides or thermoplastic copolyester elastomers.

Suitable thermoplastic polyether esters and polyester esters can be prepared by all standard processes known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms or their esters with suitable aliphatic and aromatic diols and polyols (cf. “Polymer Chemistry ", Interscience Publ., New York, 1961, pp. 111-127; Kunststoff Handbuch, Volume VIII, C. Hanser Verlag, Munich 1973 and Journal of Polymer Science, Part A1, 4, pages 1851-1859 (1966)). Suitable aromatic dicarboxylic acids include, for example, phthalic acid, iso- and terephthalic acid and their esters. Suitable aliphatic dicarboxylic acids include, for example, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebaconic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids, and maleic acid, fumaric acid, aconitic acid, itoconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids.

Examples of suitable diol components are diols of the general formula HO-(CH2)n-OH, where n=2 to 20, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol ) Polyether oils of the general formula HO-(CH2)n-O-(CH2)m-OH, where n is the same or different from m and n or m=2 to 20, unsaturated diols and polyether oils such as, for example, butene-1,4-diol; diols and polyethers containing aromatic units; as well as polyester.

In addition to the carboxylic acids mentioned or their esters and the alcohols mentioned, all other common representatives of these classes of compounds can be used to provide the polyether esters and polyester esters used according to the invention.

The thermoplastic polyetheramides can be obtained by any standard process known from the literature by reacting amines and carboxylic acids or their esters. Amines and/or carboxylic acids also contain ether units of the type R-O-R, where R = organic radical (aliphatic and/or aromatic). In general, monomers of the following compound classes are used: HOOC-R'-NH2, where R' can be aromatic and aliphatic, preferably containing ether units of the type R-O-R, where R = organic radical (aliphatic and/or aromatic); aromatic dicarboxylic acids, including, for example, phthalic acid, iso- and terephthalic acid or their esters, and aromatic dicarboxylic acids containing ether units of the R-O-R type, where R=organic radical (aliphatic and/or aromatic); aliphatic dicarboxylic acids, including e.g. cyclohexane-1,4-dicarboxylic acid, adipic acid, sebaconic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and maleic acid, fumaric acid, aconitic acid, itoconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated and aliphatic dicarboxylic acids containing ether units of the R-O-R type, can be, where R = organic residue (aliphatic and/or aromatic); Diamines of the general formula H2N-R"-NH2, where R" can be aromatic and aliphatic, preferably containing ether units of the type R-O-R, where R=organic radical (aliphatic and/or aromatic); Lactams, such as E-caprolactam, pyrrolidone or laurolactam; as well as amino acids.

In addition to the carboxylic acids mentioned or their esters and the amines, lactams and amino acids mentioned, all other common representatives of these classes of compounds can be used to provide the polyetheramine used according to the invention. The thermoplastic elastomers with a block copolymer structure used according to the invention preferably contain vinylaromatic, butadiene and isoprene and also polyolefin and vinylic units, for example ethylene, propylene and vinyl acetate units. Styrene-butadiene copolymers are preferred.

The thermoplastic elastomers used according to the invention with a block copolymer structure, polyetheramides, polyetheresters and polyesteresters are preferably chosen so that their melting points are <300°C, preferably <250°C, in particular <220°C.

The thermoplastic elastomers used according to the invention with a block copolymer structure, polyetheramides, polyetheresters and polyesteresters are preferably selected such that their melting points are >95°C, preferably >110°C, in particular >140°C.

The thermoplastic elastomers used according to the invention with a block copolymer structure, polyetheramides, polyetheresters and polyesteresters can be partially crystalline or amorphous.

In the context of the present invention, the thermoplastic elastomer (TPE-1) contained in the composition (Z1) is particularly advantageous, a thermoplastic polyurethane with a Shore D hardness in the range from 20 to 90.

Accordingly, according to a further embodiment, the present invention also relates to a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.

The thermoplastic elastomer (TPE-2) according to the invention can also be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester or a thermoplastic styrene-butadiene block copolymer. Accordingly, the present invention also relates to a further embodiment of a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyether esters, polyester esters or thermoplastic styrene butadiene block copolymers.

The foamed granules consisting of the composition (Z1) have particularly advantageous property profiles when the thermoplastic elastomer (TPE-2) has a particularly low hard segment content, for example a hard segment content of less than 25%. Within the scope of the present invention, the hard segment content or hard segment proportion is determined according to the formula disclosed in WO 2007/118827 A1.

Accordingly, the present invention also relates to a further embodiment of a foamed granulate as described above, wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25%, for example less than 23% or less than 20%. According to the invention, the composition (Z1) contains at least the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2). The composition can also contain other components. In the context of the present invention, however, the composition (Z1) preferably contains no further elastomers in addition to the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2).

The ratio of the thermoplastic elastomers used (TPE-1) and (TPE-2) can vary within wide ranges. The composition (Z1) preferably contains the thermoplastic elastomer (TPE-2) in an amount in the range from 1 to 60% by weight, based on the total composition (Z1), more preferably in an amount in the range from 5 to 50% by weight. %, particularly preferably in an amount in the range from 10 to 30% by weight, based in each case on the total composition (Z1).

For example, within the scope of the present invention, the thermoplastic elastomer (TPE-1) can be a thermoplastic polyetheramide and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic polyetherester and the thermoplastic elastomer ( TPE-2) a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic styrene-butadiene block copolymer and the thermoplastic elastomer (TPE-2) can be a thermoplastic polyurethane or the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane and the thermoplastic elastomer (TPE-2) can be a thermoplastic styrene-butadiene block copolymer.

A thermoplastic polyurethane is preferably used as the thermoplastic elastomer (TPE-1) and (TPE-2). According to the invention, the composition (Z1) accordingly preferably contains a first thermoplastic elastomer (TPE-1) and a second thermoplastic elastomer (TPE-2), both the (TPE-1) being a thermoplastic polyurethane (TPU-1) and also the ( TPE-2) is a thermoplastic polyurethane (TPU-2).

Thermoplastic polyurethanes are known from the prior art. They are usually obtained by reacting a polyisocyanate composition with a polyol composition, the polyol composition usually comprising a polyol and a chain extender.

In the context of the present invention, use is usually made of thermoplastic polyurethanes which are obtained or obtainable by reacting a polyisocyanate composition with a polyol composition. The polyol composition usually contains at least one polyol. Polyols are known in principle to those skilled in the art and are described, for example, in "Plastics Manual, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Polyester oils or polyether oils are particularly preferably used as polyols. Likewise, polycarbonates can be used. Copolymers can also be used within the scope of the present invention. The number-average molecular weight of the polyols used according to the invention is preferably between 0.5×10 ³ g/mol and 8×10 ³ g/mol, preferably between 0.6×10 ³ g/mol and 5×10 ³ g/mol, in particular between 0.8×10 ³ g/mol and 3 x 10 ³ g/mol.

According to the invention, polyether oils are suitable, but also polyester oils, block copolymers and hybrid polyols such as poly(ester/amide). According to the invention, preferred polyether oils are polyethylene glycols, polypropylene glycols, polyadipates, polycarbonate(diol)s and polycaprolactone.

The polyol composition preferably contains a polyol selected from the group consisting of polyether oils, polyester oils, polycaprolactones and polycarbonates.

Suitable block copolymers are, for example, those which have ether and ester blocks, such as polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks. According to the invention, preferred polyether oils are polyethylene glycols and polypropylene glycols. Polycaprolactone is also preferred.

The polyol used advantageously has a molecular weight Mn in the range from 500 g/mol to 4000 g/mol, preferably in the range from 800 g/mol to 3000 g/mol.

Mixtures of different polyols can also be used according to the invention. The polyols used or the polyol composition preferably have an average functionality of between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2. The polyols used according to the invention preferably have only primary hydroxyl groups.

At least one polyol composition containing at least polytetrahydrofuran is preferably used. According to the invention, the polyol composition can also contain other polyols in addition to polytetrahydrofuran.

According to the invention, for example, polyethers are suitable as further polyols, but also polyesters, block copolymers and hybrid polyols such as poly(ester/amide). Suitable block copolymers are, for example, those which have ether and ester blocks, such as polycaprolactone with polyethylene oxide or polypropylene oxide end blocks or polyethers with polycaprolactone end blocks. According to the invention, preferred polyether oils are polyethylene glycols and polypropylene glycols. Another preferred polyol is polycaprolactone. Examples of suitable polyols are polyether oils such as polytrimethylene oxide or polytetramethylene oxide.

It has proven advantageous that the polyol composition contains at least one polytetrahydrofuran and at least one other polyol selected from the group consisting of another polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and polycaprolactone.

The polytetrahydrofuran preferably has a number-average molecular weight Mn in the range from 500 g/mol to 5000 g/mol, more preferably in the range from 550 to 2500 g/mol, particularly preferably in the range from 650 to 2000 g/mol.

Within the scope of the present invention, the composition of the polyol composition can vary within wide limits. For example, the content of the first polyol, preferably polytetrahydrofuran, can be in the range from 15% to 85%, preferably in the range from 20% to 80%, more preferably in the range from 25% to 75%.

According to the invention, the polyol composition can also contain a solvent. Suitable solvents are known per se to those skilled in the art.

If polytetrahydrofuran is used, the number-average molecular weight Mn of the polytetrahydrofuran is, for example, in the range from 500 g/mol to 5000 g/mol, preferably in the range from 500 to 3000 g/mol. More preferably, the number-average molecular weight Mn of the polytetrahydrofuran is in the range from 500 to 1400 g/mol.

According to the invention, mixtures of different polytetrahydrofurans can also be used, i.e. mixtures of polytetrahydrofurans with different molecular weights.

Suitable chain extenders are, for example, compounds which have at least two functional groups which are reactive toward isocyanates, for example hydroxyl groups, amino groups or thiol groups.

Examples of suitable chain extenders are compounds selected from the group consisting of aliphatic and aromatic diols with a molecular weight of <500 g/mol, preferably <350 g/mol.

According to the invention, diols are preferably used as chain extenders. Aliphatic, araliphatic, aromatic and/or cycloaliphatic diols with a molecular weight of 50 g/mol to 220 g/mol can preferably be used here. Alkanediols having 2 to 10 carbon atoms in the alkylene radical are preferred, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or deca-alkylene glycols. For the present invention, particular preference is given to 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. Also branched compounds such as 1,4-cyclohexyldimethanol, 2-butyl-2-ethylpopanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, pinacol, 2-ethyl-1,3-hexanediol, 1,4- Cyclohexanediol or N-phenyldiethanolamine are suitable as chain extenders in the context of the present invention. Mixed compounds such as 4-aminobutanol are also suitable.

According to the invention, other chain extenders can also be used. According to the invention, compounds with amino groups can also be used, for example diamines. Mixtures of diols and diamines can also be used.

In the context of the present invention, the amount of chain extender used and of the polyols used can vary within wide ranges.

In a preferred embodiment, the chain extender mixture is chosen such that the softer of the thermoplastic elastomers used, for example the TPU, has a softening point of less than 190° C., preferably less than 160° C. and very preferably less than 150° C.

Unless otherwise stated, the softening point is, in the context of the present invention, using DMA (measured on a 2 mm injection molded sheet tempered for 20 h at 100° C. based on DIN EN ISO 6721-1:2011, with a frequency of 1 Hz and a Heating rate of 20 K/min measured from - 80 °C to 200 °C.

According to the invention, a polyisocyanate composition containing at least one polyisocyanate is used to produce the thermoplastic polyurethane.

In the context of the present invention, preferred polyisocyanates are diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates. Suitable isocyanates are known per se to those skilled in the art.

According to the invention it is also possible for the isocyanate composition to contain 4,4'-methylenediphenyl diisocyanate and at least one further methylenediphenyl diisocyanate. According to the invention, the term methylenediphenyl diisocyanate is understood as meaning 2,2'-, 2,4'- and/or 4,4'-diphenylmethane diisocyanate or a mixture of two or three isomers. Thus, according to the invention, 2,2'- or 2,4'-diphenylmethane diisocyanate or a mixture of two or three isomers can be used as a further isocyanate. According to the invention, the polyisocyanate composition can also contain other polyisocyanates.

Furthermore, pre-reacted products can be used as isocyanate components in which part of the OH components in an upstream reaction step with a Isocyanate are reacted. In a subsequent step, the actual polymer reaction, the products obtained are reacted with the remaining OH components and then form the thermoplastic polyurethane.

Customary aliphatic and/or cycloaliphatic diisocyanates are used as aliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethyltetramethylene-1,4 - diisocyanate, hexamethylene-1,6-diisocyanate (HDI), pentamethylene-1,5-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), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and/or 1-Methyl-2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and/or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI).

Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-, 2,4'- and/or 2,2- '- methylenedicyclohexyl diisocyanate (H12MDI); 4,4'-, 2,4'- and/or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane or mixtures thereof are particularly preferred.

Suitable aromatic diisocyanates are, in particular, 1,5-naphthylene diisocyanate (NDI), 2,4- and/or 2,6-tolylene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-Phenylene diisocyanate (PDI), diphenylethane-4,4'-diisocyanate (EDI), diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylene diisocyanate.

For example, polyisocyanate compositions containing 4,4'-MDI and 2,4-MDI, polyisocyanate compositions containing 4,4'-MDI and 3,3'-dimethyl-4,4'-diisocyanato-diphenyl ( TODI) or polyisocyanate compositions containing 4,4'-MDI and 1,5-naphthylene diisocyanate (NDI).

According to the invention, three or more isocyanates can also be used. The polyisocyanate composition usually contains 4,4'-MDI in an amount of 2 to 50%, based on the total polyisocyanate composition, and the further isocyanate in an amount of 3 to 20%, based on the total polyisocyanate composition.

Preferred examples of higher functional isocyanates are triisocyanates, e.g. B. triphenylmethane-4,4',4"-triisocyanate, furthermore the cyanurates of the aforementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, e.g of semi-blocked diisocyanates with polyols having on average more than two and preferably three or more hydroxy groups. According to the invention, the polyisocyanate composition can also contain one or more solvents. Suitable solvents are known to those skilled in the art. For example, non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons are suitable.

Crosslinking agents can also be used within the scope of the present invention, for example the abovementioned higher-functionality polyisocyanates or polyols or else other higher-functionality molecules having a plurality of functional groups which are reactive toward isocyanates. It is also possible within the scope of the present invention to achieve crosslinking of the products by using an excess of isocyanate groups in relation to the hydroxyl groups.

According to the invention, the components are used in a ratio such that the molar ratio of the sum of the functionalities of the polyol composition used to the sum of the functionalities of the isocyanate composition used is in the range from 1:0.8 to 1:1.3. The ratio is preferably in the range from 1:0.9 to 1:1.2, more preferably in the range from 1:0.965 to 1:1.11, more preferably in the range from 1:0.97 to 1:1.11 , more preferably in the range from 1:0.97 to 1:1.05, particularly preferably in the range from 1:0.98 to 1:1.03.

Another variable that is taken into account when converting the components is the isocyanate index. The index is defined here by the ratio of the total isocyanate groups used in the reaction to the isocyanate-reactive groups, ie in particular the reactive groups of the polyol component. If the index is 1000, there is one active hydrogen atom for one isocyanate group. At indexes above 1000, there are more isocyanate groups than isocyanate-reactive groups. The index in the reaction of the components is preferably in the range from 965 to 1110, for example in the range from 970 to 1110, more preferably in the range from 970 to 1050, particularly preferably in the range from 980 to 1030.

According to the invention, further additives can be added during the production of the thermoplastic polyurethane, for example catalysts or auxiliaries and additives. Additives and auxiliaries are known per se to those skilled in the art. According to the invention, combinations of several additives can also be used. Suitable auxiliaries and additives can be found, for example, in the Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl Hanser Verlag, Munich 1966 (S103-113).

Suitable catalysts are also known in principle from the prior art. Suitable catalysts are, for example, organic metal compounds selected from the group consisting of tin, titanium, zirconium, hafnium, bismuth, zinc, aluminum and iron organyls, such as tin organyl compounds, preferably tin dialkyls such as dimethyltin or diethyltin, or organotin compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds such as bismuth alkyl compounds or the like, or iron compounds, preferably iron(MI) acetylacetonate or the metal salts of carboxylic acids such as tin(II) isooctoate, tin dioctoate , titanic acid ester or bismuth (III) neodecanoate.

The proportion of hard segments in the thermoplastic polyurethanes (TPU-1) used according to the invention is usually in the range from 5 to 70%, in particular in the range from 10 to 50%, preferably in the range from 15 to 45%. Within the scope of the present invention, the hard segment content or hard segment proportion is determined according to the formula disclosed in WO 2007/118827 A1.

Surprisingly, it has been shown that the composition (Z1) is well suited for the production of foamed materials. The composition (Z1) can be processed in a manner known per se to give foamed materials. If appropriate, additives such as blowing agents, cell regulators, surface-active substances, nucleating agents, fillers, hollow microspheres and/or release agents are used. Suitable processes and additives are disclosed, for example, in WO2014/198779 A1, in WO 2007/082838 A1 or WO 94/20568 A1.

According to the invention, the composition (Z1) is produced in a manner known per se from the individual thermoplastic elastomers (TPE-1) and (TPE-2) and optionally further components. Suitable methods are, for example, customary mixing methods in a kneader or an extruder.

According to a further aspect, the present invention also relates to a method for producing a foamed granulate.

According to a further aspect, the present invention also relates to a method for producing a foamed granulate comprising the steps

(i) providing a composition (Z1) in the form of granules, the composition containing at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);

(ii) producing a foamed granulate from the granulate provided according to step (i).

Suitable processes for producing a foamed granulate according to step (ii) from the granulate provided according to step (i) are, for example, the suspension process or the extrusion process.

The present invention relates to a method for producing a foamed granulate comprising the steps (i) providing a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);

(ii) impregnation of the composition (Z1) with a propellant under pressure;

(iii) expanding the composition (Z1) by means of pressure drop.

In the context of the present invention, the composition (Z1) can be used in the form of a melt or in the form of granules.

With regard to preferred embodiments of the process, suitable starting materials or mixing ratios, reference is made to the above statements, which apply accordingly.

The method according to the invention can include further steps, for example temperature adjustments.

The non-expanded polymer mixture of the composition (Z1) required for the production of the foamed granules is produced in a known manner from the individual components and optionally further components such as, for example, processing aids, stabilizers, compatibilizers or pigments. Suitable methods are, for example, conventional mixing methods using a kneader, continuously or batchwise, or an extruder such as a co-rotating twin-screw extruder.

In the case of compatibilizers or auxiliaries, such as stabilizers, these can also be incorporated into the components during their manufacture. The individual components are usually combined before the mixing process or metered into the apparatus that takes over the mixing. In the case of an extruder, the components are all metered into the intake and conveyed together into the extruder, or individual components are added via a side metering.

Processing takes place at a temperature at which the components are in a plasticized state. The temperature depends on the softening or melting ranges of the components, but must be below the decomposition temperature of each component. Additives such as pigments or fillers or other of the usual auxiliaries mentioned above are not melted, but incorporated in the solid state.

In this case, further embodiments are possible according to common methods, in which case the processes used in the production of the starting materials can be directly included in the production.

In this step, some of the usual adjuvants mentioned above can be added to the mixture. The foamed granules or particle foams according to the invention generally have a bulk density of 50 g/l to 200 g/l, preferably 60 g/l to 180 g/l, particularly preferably 80 g/l to 150 g/l. The bulk density is measured analogously to DIN ISO 697:1984, in which, in contrast to the standard, a vessel with a volume of 10 l is used instead of a vessel with a volume of 0.5 l when determining the above values, since especially with the foam particles with low density and large mass, a measurement with a volume of only 0.5 l is too imprecise.

As stated above, the diameter of the individual particles of the foamed granules is between 0.5 and 30; preferably 1 to 15 and in particular between 3 to 12 mm. In the case of non-spherical, e.g. oblong or cylindrical foamed granules, diameter means the longest dimension.

The production of the foamed granules can be carried out by the usual methods known in the prior art

(i) providing a composition (Z) according to the invention;

(ii) impregnating the composition with a blowing agent under pressure;

(iii) expanding the composition by means of pressure drop.

According to the invention, the composition (Z) comprises the composition (Z1). The composition (Z) can contain further components. The composition (Z) preferably consists of the composition (Z1).

The amount of blowing agent is preferably from 0.1 to 40, in particular from 0.5 to 35 and particularly preferably from 1 to 30 parts by weight, based on 100 parts by weight of the amount of composition (Z) used.

An embodiment of the above method comprises

(i) providing a composition (Z) according to the invention in the form of granules;

(ii) impregnating the granules with a blowing agent under pressure;

(iii) Expanding the granules by means of pressure drop.

Another embodiment of the above method includes a further step:

(ii) impregnating the granules with a blowing agent under pressure;

(iii-a) Reducing the pressure to atmospheric pressure without foaming the granules, possibly by reducing the temperature beforehand

(iii-b) foaming of the granules by increasing the temperature.

The unexpanded granules preferably have an average minimum diameter of 0.2-10 mm (determined via 3D evaluation of the granules, eg via dynamic image analysis using an optical measuring apparatus called PartAn 3D from Microtrac). The individual granules generally have an average mass in the range from 0.1 to 50 mg, preferably in the range from 4 to 40 mg and particularly preferably in the range from 7 to 32 mg. This mean mass of the granules (particle weight) is determined as the arithmetic mean by weighing 10 granulate particles each time 3 times.

One embodiment of the above method comprises impregnating the granules with a blowing agent under pressure and then expanding the granules in steps (I) and (II):

(I) Impregnation of the granules in the presence of a blowing agent under pressure at elevated temperatures in a suitable, closed reaction vessel (e.g. autoclave)

(II) Sudden relaxation without cooling

Here, the impregnation in step (I) can be carried out in the presence of water and optionally suspension auxiliaries or only in the presence of the blowing agent and the absence of water.

Suitable suspension aids are, for example, water-insoluble inorganic stabilizers such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates; also polyvinyl alcohol and surfactants such as sodium dodecylarylsulfonate. They are usually used in amounts of 0.05 to 10% by weight, based on the composition according to the invention.

Depending on the selected pressure, the impregnation temperatures are in the range of 100°C-200°C, the pressure in the reaction vessel being between 2-150 bar, preferably between 5 and 100 bar, particularly preferably between 20 and 60 bar, the impregnation time is generally 0.3 to 10 hours.

Carrying out the process in suspension is known to the person skilled in the art and is described in detail, for example, in WO2007/082838.

When carrying out the process in the absence of water, care must be taken to avoid aggregation of the polymer granules.

Suitable blowing agents for carrying out the process in a suitable closed reaction vessel are, for example, organic liquids and gases which are in a gaseous state under the processing conditions, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, these also being combined can become.

Examples of suitable hydrocarbons are halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons. Preferred organic blowing agents are saturated, aliphatic hydrocarbons, especially those having 3 to 8 carbon atoms, such as butane or pentane.

Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the gases mentioned above.

In a further embodiment, the impregnation of the granules with a blowing agent under pressure comprises processes and subsequent expansion of the granules in steps (a) and (ß):

(a) Impregnation of the granules in the presence of a blowing agent under pressure at elevated temperatures in an extruder

(ß) Granulation of the mass emerging from the extruder under conditions which prevent uncontrolled foaming.

Suitable blowing agents in this variant of the process are volatile organic compounds with a boiling point of -25°C to 150°C, in particular -10°C to 125°C, at standard pressure 1013 mbar. Hydrocarbons (preferably halogen-free) are highly suitable, in particular C4-10 alkanes, for example the isomers of butane, pentane, hexane, heptane and octane, particularly preferably isopentane. Other possible blowing agents are sterically demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates. Carbon dioxide or nitrogen or mixtures of carbon dioxide and nitrogen are also suitable as blowing agents in the context of the present invention.

In this case, the composition in step (ii) is mixed under pressure in an extruder, with melting, with the blowing agent which is fed to the extruder. The mixture containing blowing agent is pressed out under pressure, preferably with moderately controlled counter pressure (e.g. underwater granulation) and granulated. Here, the strand of melt foams and the particle foams are obtained by granulation.

Carrying out the process via extrusion is known to the person skilled in the art and is described in detail, for example, in WO2007/082838 and WO 2013/153190 A1.

Suitable extruders are all the usual screw machines, in particular single-screw and twin-screw extruders (eg type ZSK from Werner & Pfleiderer), co-kneaders, Kombiplast machines, M PC kneading mixers, FCM mixers, KEX kneading screw extruders and shear roller extruders, such as they eg in Saechtling (ed.), Kunststoff-Taschenbuch, 27th edition, Hanser-Verlag Munich 1998, chap. 3.2.1 and 3.2.4. The extruder is usually operated at a temperature at which the composition (Z1) is in the form of a melt, for example at 120° C. to 250° C., in particular 150 to 210° C., and a pressure of 40 to 200 bar after addition of the blowing agent , preferably from 60 to 150 bar, particularly preferably from 80 to 120 bar, in order to ensure homogenization of the blowing agent with the melt. This can be carried out in an extruder or in an arrangement of one or more extruders. For example, the components can be melted and blended in a first extruder and a blowing agent can be injected. In the second extruder, the impregnated melt is homogenized and the temperature and/or pressure is adjusted. If, for example, three extruders are combined, the mixing of the components and the injection of the blowing agent can also be divided into two different parts of the process. If, as is preferred, only one extruder is used, then all the process steps, melting, mixing, injection of the blowing agent, homogenization and setting the temperature and/or the pressure are carried out in one extruder.

Alternatively, according to the methods described in WO 2014/150122 or WO 2014/150124 A1, the corresponding foamed granules, which may even have already been colored, can be produced directly from the granules by impregnating the corresponding granules with a supercritical fluid from which the supercritical fluid is produced removed is followed by

(i') immersing the article in a heated fluid or

(ii') irradiating the item with energetic radiation (e.g. infrared or microwave radiation).

Suitable supercritical fluids are, for example, those described in WO2014150122 or , for example carbon dioxide, nitrogen dioxide, ethane, ethylene, oxygen or nitrogen, preferably carbon dioxide or nitrogen.

The supercritical fluid can also contain a polar liquid with a Hildebrand solubility parameter equal to or greater than 9 MPa ^1/2 .

Here, the supercritical fluid or the heated fluid may also contain a colorant, thereby obtaining a colored foamed article.

The particles can be provided with an antiblocking agent before and/or after foaming. Suitable antiblocking agents are, for example, talc, metal compounds such as tricalcium phosphate, calcium carbonate, silicic acids, in particular pyrogenic silicic acids such as Aerosil(R) from Degussa, salts of long-chain (eg C 10-22) carboxylic acids, for example stearic acid salts such as calcium stearate, esters of long-chain carboxylic acids, for example glycerol esters such as the glycerol stearates, and silicone oils. The antiblocking agent is generally applied to the particles by mixing, spraying, tumbling or other customary methods. It is usually used in amounts of from 0.01 to 20, preferably from 0.1 to 10, particularly preferably from 0.5 to 6 parts by weight, based on 100 parts by weight of the amount of composition (Z1) used. According to the invention, for example, the amount of blowing agent, impregnation time, cooling time, cooling rate, type and amount of additives, type of blowing agent, foaming process, or process parameters such as residence time, temperature or shear can be varied in order to influence the properties of the foam particles obtained.

Accordingly, according to a further embodiment, the present invention also relates to a foamed granulate as described above, the closed-cell content of the foam being greater than 60%, determined according to DIN ISO 4590:2016.

The expanded particles are generally at least approximately spherical and usually have an average diameter at the narrowest point of 1 mm to 20 mm, preferably 2 mm to 12 mm and in particular 3 mm to 10 mm.

Accordingly, according to a further embodiment, the present invention also relates to a foamed granulate, as described above, wherein the particles have an average diameter in the range of 1 mm to 20 mm, determined at the narrowest point, measured using a scale microscope.

Another object of the present invention is a shaped body produced from the foamed granules according to the invention.

The corresponding moldings can be produced by methods known to those skilled in the art. Shaped bodies can be produced from the foamed granules according to the invention, for example by welding them together in a closed mold under the action of heat. For this purpose, for example, the particles are filled into the mold and, after the mold is closed, steam or hot air is introduced, as a result of which the particles expand further and fuse together to form a foam, preferably with a density in the range from 8 to 600 g/l. The foams can be semi-finished products, for example panels, profiles or webs, or finished molded parts with a simple or complicated geometry. Accordingly, the term includes foam, foam semi-finished products and foam moldings.

According to a further aspect, the present invention also relates to a method for producing a shaped body, comprising the steps

(a) providing a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);

(b) Production of a shaped body from the foamed granulate provided according to step (a). According to step (b), the molding can be produced from the foamed granules according to the invention in a manner known per se. A suitable method is, for example, welding using steam, hot air or high-energy radiation.

A preferred method for producing a foam molding comprises the following steps:

(A) introducing the foamed granules according to the invention in an appropriate form,

(B) Fusion of the foamed granules according to the invention from step (i).

The fusing in step (B) preferably takes place in a closed form, it being possible for the fusing to take place using steam, hot air (as described, for example, in EP1979401 B1) or energetic radiation (microwaves or radio waves).

Accordingly, according to a further embodiment, the present invention also relates to a method for producing a shaped body as described above, wherein the shaped body is produced in step (b) by welding the particles provided in step (a) using steam, hot air or high-energy radiation.

The temperature when fusing the foamed granules is preferably below or close to the melting point of the polymer from which the foamed granules were produced. Accordingly, for common polymers, the temperature for fusing the foamed granules is between 100.degree. C. and 180.degree. C., preferably between 120 and 150.degree.

Temperature profiles / residence times can be determined individually, e.g. in analogy to the methods described in US20150337102 or EP2872309B1.

Welding using energetic radiation generally takes place in the frequency range of microwaves or radio waves, if necessary in the presence of water or other polar liquids, such as, for example, microwave-absorbing hydrocarbons containing polar groups (such as, for example, esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols) and can be carried out analogously to the methods described in EP3053732A or WO1 6146537.

As stated above, the foamed granules can also contain coloring agents. Here, the addition of dyes can be done in different ways.

In one embodiment, the foamed granules produced can be colored after production. Here, the corresponding foamed granules are brought into contact with a carrier liquid containing a dye, the carrier liquid (TF) having a polarity which is suitable for sorption of the carrier liquid into the foamed granules. It can be carried out analogously to the methods described in the EP application with the application number 17198591.4. Suitable dyes are, for example, inorganic or organic pigments. Examples of suitable natural or synthetic inorganic pigments are carbon black, graphite, titanium oxides, iron oxides, zirconium oxides, cobalt oxide compounds, chromium oxide compounds, copper oxide compounds. Suitable organic pigments are, for example, azo pigments and polycyclic pigments.

In a further embodiment, the color can be added during the production of the foamed granules. For example, the colorant can be added during manufacture of the foamed granules via extrusion into the extruder.

Alternatively, already colored material can be used as the starting material for the production of the foamed granulate, which is extruded or expanded in a closed vessel according to the abovementioned processes. Furthermore, in the method described in WO2014150122, the supercritical fluid or the heated fluid can contain a dye.

The moldings according to the invention have advantageous properties for the above-mentioned applications in the shoe or sports shoe sector.

Here, the tensile and compression properties of the moldings produced from the foamed granules are characterized in that the tensile strength is above 600 kPa (DIN EN ISO 1798, April 2008) and the elongation at break is above 100% (DIN EN ISO 1798, April 2008) .

The rebound resilience of the moldings made from the foamed granules is above 55% (analogous to DIN 53512, April 2000; the deviation from the standard is the test body height, which should be 12 mm, but this test is carried out with 20 mm to avoid "punching through". of the sample and to avoid measuring the background).

The density of the moldings produced is advantageously between 75 and 375 kg/m ³ , preferably between 100 and 300 kg/m ³ , particularly preferably between 150 and 200 kg/m ³ (DIN EN ISO 845, October 2009).

The ratio of the density of the molding to the bulk density of the foamed granules according to the invention is generally between 1.5 and 2.5, preferably 1.8 to 2.0.

The subject matter of the invention is also the use of a foamed granulate according to the invention for the production of a molded body for shoe soles, parts of a shoe sole, for example shoe midsoles, shoe insoles, shoe combination soles, Bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, components in automobile interiors and exteriors, in balls and sports equipment or as floor coverings and wall coverings, especially for sports areas, athletic tracks, sports halls, children's playgrounds and sidewalks.

The subject matter of the invention is also the use of the expanded particles for the production of foams, and also foams obtainable from the expanded particles.

According to a further aspect, the present invention also relates to shaped bodies obtainable or obtained by the process according to the invention for producing a shaped body as described above.

In addition to good mechanical properties, the moldings according to the invention have a high elongation at break. Accordingly, according to a further embodiment, the present invention also relates to a shaped body as described above, wherein the shaped body has an elongation at break of greater than 100%, determined according to DIN EN ISO 1798.

According to the invention, by using the composition (Z1) or the combination of the thermoplastic elastomers (TPE-1) and (TPE-2), it is also possible to produce moldings by means of steam welding using harder materials and thus, for example, to obtain moldings with a lower density , which are advantageous for applications, for example in the shoe sector.

It is also possible according to the invention to use the combination of the thermoplastic elastomers (TPE-1) and (TPE-2) to set the material properties such as viscoelastic properties or stiffness in certain temperature ranges or the surface properties such as haptics and paintability in a targeted manner.

The blend components added according to the invention make it possible to obtain foam particles and particle foams based on thermoplastic elastomers, in particular thermoplastic polyurethanes (TPU), which cannot be obtained or produced in this way from one-component systems.

Surprisingly, advantageous products are obtained in particular by combining low-melting, soft elastomers with compatible higher-melting, hard elastomers.

The combination of predominantly high-melting elastomer with a lower proportion of low-melting elastomer shows particular advantages in processing and weldability with steam and the production of molded parts. The combination of predominantly low-melting elastomer with a lower proportion of high-melting elastomer shows special advantages in the low bulk density that can be achieved, which means a weight saving in a component and thus a cost and benefit advantage.

Due to the elastomeric properties, the particle foams according to the invention are particularly suitable for applications in the sports, shoe and comfort sectors.

According to a further aspect, the present invention also relates to the use of the foamed granules according to the invention or a foamed granules obtainable or obtained according to a method according to the invention for the production of shoe soles, bicycle saddles, bicycle tires, damping elements, padding, mattresses, underlays, handles, protective films, in components in the Automotive interiors and exteriors, in balls and sports equipment or as a floor covering, in particular for sports surfaces, athletics tracks, sports halls, children's playgrounds and sidewalks.

It is also advantageous that the foams according to the invention can be thermoplastically recycled without any problems. For this purpose, for example, the foamed materials are extruded using an extruder with a degassing device, where the extrusion can optionally be preceded by mechanical comminution. They can then be processed back into foams in the manner described above.

Preference is given to using a foamed granulate according to the invention for the production of a molding for shoe soles, parts of a shoe sole, for example shoe midsoles, shoe insoles, shoe combination soles, bicycle saddles, bicycle tires, damping elements, padding, mattresses, underlays, handles, protective films, or components in automobile interiors and outdoor area.

In this case, the shoe is preferably a street shoe, sports shoe, sandals, boots or safety shoe, particularly preferably a sports shoe.

A further object of the present invention is therefore also a shaped body, the shaped body being a combined shoe sole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.

A further object of the present invention is therefore also a shaped body, the shaped body being a midsole for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.

A further object of the present invention is therefore also a shaped body, the shaped body being an insert for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes. A further object of the present invention is therefore also a shaped body, the shaped body being a cushioning element for shoes, preferably for street shoes, sports shoes, sandals, boots or safety shoes, particularly preferably sports shoes.

The padding element can be used in the heel area or forefoot area, for example.

Another subject of the present invention is therefore also a shoe in which the molded body according to the invention is used as a midsole, midsole or padding in the heel area, forefoot area, for example, the shoe preferably being a street shoe, sports shoe, sandal, boot or safety shoe, particularly preferably a sports shoe is.

According to a further aspect, the present invention also relates to a hybrid material containing a matrix made of a polymer (PM) and a foamed granulate according to the present invention. Materials which comprise a foamed granulate and a matrix material are referred to as hybrid materials in the context of this invention. The matrix material can consist of a compact material or also of a foam.

Polymers (PM) suitable as matrix material are known per se to those skilled in the art. For example, ethylene-vinyl acetate copolymers, epoxy-based binders or also polyurethanes are suitable within the scope of the present invention. Polyurethane foams or also compact polyurethanes such as thermoplastic polyurethanes are suitable according to the invention.

According to the invention, the polymer (PM) is selected in such a way that there is sufficient adhesion between the foamed granules and the matrix in order to obtain a mechanically stable hybrid material.

The matrix can completely or partially surround the foamed granules. According to the invention, the hybrid material can contain other components, for example other fillers or granules. According to the invention, the hybrid material can also contain mixtures of different polymers (PM). The hybrid material can also contain mixtures of foamed granules.

Foamed granules which can be used in addition to the foamed granules according to the present invention are known per se to those skilled in the art. In particular, foamed granules of thermoplastic polyurethanes are suitable for the purposes of the present invention. According to one embodiment, the present invention accordingly also relates to a hybrid material containing a matrix made from a polymer (PM), a foamed granulate according to the present invention and a further foamed granulate made from a thermoplastic polyurethane.

In the context of the present invention, the matrix consists of a polymer (PM). Suitable matrix materials in the context of the present invention are, for example, elastomers or foams, in particular foams based on polyurethanes, for example elastomers such as ethylene-vinyl acetate copolymers or also thermoplastic polyurethanes.

Accordingly, the present invention also relates to a hybrid material as described above, in which the polymer (PM) is an elastomer. Furthermore, the present invention relates to a hybrid material as described above, wherein the polymer (PM) is selected from the group consisting of ethylene-vinyl acetate copolymers and thermoplastic polyurethanes.

According to one embodiment, the present invention also relates to a hybrid material containing a matrix of an ethylene-vinyl acetate copolymer and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made from an ethylene-vinyl acetate copolymer, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.

According to one embodiment, the present invention relates to a hybrid material containing a matrix made of a thermoplastic polyurethane and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made from a thermoplastic polyurethane, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.

Suitable thermoplastic polyurethanes are known per se to those skilled in the art. Suitable thermoplastic polyurethanes are described, for example, in "Plastics Manual, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.

In the context of the present invention, the polymer (PM) is preferably a polyurethane. For the purposes of the invention, polyurethane includes all known elastic polyisocyanate polyaddition products. These include, in particular, solid polyisocyanate polyadducts, such as viscoelastic gels or thermoplastic polyurethanes, and elastic foams based on polyisocyanate polyadducts, such as flexible foams, semirigid foams or integral skin foams. Next are below Polyurethanes in the context of the invention mean elastic polymer blends containing polyurethanes and other polymers, and foams made from these polymer blends. Preferably, the matrix is a cured compact polyurethane binder, a resilient polyurethane foam, or a viscoelastic gel.

In the context of the present invention, a polyurethane binder is understood to mean a mixture which consists of at least 50% by weight, preferably at least 80% by weight and in particular at least 95% by weight of a prepolymer containing isocyanate groups, hereinafter referred to as isocyanate prepolymer referred to, exists. The viscosity of the polyurethane binder according to the invention is preferably in a range from 500 to 4000 mPa.s, particularly preferably from 1000 to 3000 mPa.s, measured at 25° C. according to DIN 53 018.

In the context of the invention, polyurethane foams are foams according to DIN 7726.

The density of the matrix material is preferably in the range from 1.2 to 0.01 g/cm ³ . The matrix material is particularly preferably an elastic foam or an integral foam with a density in the range from 0.8 to 0.1 g/cm ³ , in particular from 0.6 to 0.3 g/cm ³ , or a compact material, for example a cured polyurethane binder.

Foams in particular are suitable as matrix material. Hybrid materials that contain a matrix material made from a polyurethane foam preferably exhibit good adhesion between the matrix material and the foamed granules.

According to one embodiment, the present invention also relates to a hybrid material containing a matrix of a polyurethane foam and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made from a polyurethane foam, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane.

According to one embodiment, the present invention relates to a hybrid material containing a matrix made of a polyurethane integral foam and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material containing a matrix made from a polyurethane integral foam, a foamed granulate according to the present invention and another foamed granulate, for example made from a thermoplastic polyurethane. A hybrid material according to the invention, containing a polymer (PM) as a matrix and foamed granules according to the invention, can be produced, for example, by mixing the components used to produce the polymer (PM) and the foamed granules, if appropriate with other components, and reacting them to form the hybrid material, the Reaction preferably takes place under conditions under which the foamed granules are essentially stable.

Suitable processes and reaction conditions for preparing the polymer (PM), in particular an ethylene-vinyl acetate copolymer or a polyurethane, are known per se to those skilled in the art.

In a preferred embodiment, the hybrid materials according to the invention are integral skin foams, in particular integral skin foams based on polyurethanes. Suitable methods for producing integral skin foams are known per se to those skilled in the art. The integral skin foams are preferably produced by the one-shot process using low-pressure or high-pressure technology in closed, suitably temperature-controlled molds. The molds are usually made of metal, such as aluminum or steel. These procedures are described, for example, by Piechota and Röhr in "Integral foam, Carl-Hanser-Verlag, Munich, Vienna, 1975, or in Kunststoff-Handbuch, Volume 7, Polyurethane, 3rd edition, 1993, Chapter 7.

If the hybrid material according to the invention comprises an integral foam, the amount of reaction mixture introduced into the mold is such that the moldings obtained from integral foams have a density of 0.08 to 0.70 g/cm ³ , in particular 0.12 to 0.60 g/ ^cm3 . The degrees of compaction for producing the shaped bodies with a compacted edge zone and a cellular core are in the range from 1.1 to 8.5, preferably from 2.1 to 7.0.

It is thus possible to produce hybrid materials with a matrix of a polymer (PM) and the foamed granules according to the invention contained therein, in which there is a homogeneous distribution of the foamed particles. The foamed granules according to the invention can easily be used in a process for producing a hybrid material, since the individual particles are free-flowing due to their small size and do not place any special demands on processing. Techniques for homogeneous distribution of the foamed granules, such as slow rotation of the mold, can be used.

If appropriate, auxiliaries and/or additives can also be added to the reaction mixture for the production of the hybrid materials according to the invention. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis inhibitors, odor-absorbing substances and fungistatic and bacteriostatic substances. Suitable surface-active substances are, for example, compounds which serve to support the homogenization of the starting materials and may also be suitable for regulating the cell structure. Mention may be made, for example, of emulsifiers, such as the sodium salts of castor oil sulfates or fatty acids, and salts of fatty acids with amines, for example diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene or dinaphthylmethanedisulfonic acid and ricinoleic acid; Foam stabilizers, such as siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or. ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. Oligomeric acrylates with polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying effect, the cell structure and/or stabilizing the foam.

Examples of suitable release agents are: reaction products of fatty acid esters with polyisocyanates, salts of amino-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 such as carboxylic acid esters and/or -amides, prepared by esterification or amidation of a mixture 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 with molecular weights of 60 to 400 g/mol, mixtures of organic amines, metal salts of Stearic acid and organic mono and/or dicarboxylic acids or their anhydrides or mixtures of an imino compound, the metal salt of a carboxylic acid and optionally a carboxylic acid.

Fillers, in particular fillers with a reinforcing effect, are to be understood as meaning the customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc. which are known per se. Specific examples which may be mentioned are: inorganic fillers such as silicate minerals, for example phyllosilicates such as antigorite, bentonite, serpentine, hornblende, amphibole, chrisotile, talc; Metal oxides such as kaolin, aluminum oxide, titanium oxide, zinc oxide and iron oxide, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide and glass, etc. Preferably used are kaolin (china clay), aluminum silicate and co-precipitates of barium sulfate and aluminum silicate as well as natural and synthetic fibrous Minerals such as wollastonite, metal and in particular glass fibers of various lengths, which may or may not be sized. Suitable organic fillers are, for example: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers and cellulose fibers, polyamide, polyacrylonitrile, polyurethane and polyester fibers based on aromatic and/or aliphatic dicarboxylic acid esters and in particular carbon fibers. The inorganic and organic fillers can be used individually or as mixtures.

In a hybrid material according to the invention, the volume fraction of the foamed granules is preferably 20 percent by volume and more, particularly preferably 50 percent by volume and more preferably 80 percent by volume and more and in particular 90 percent by volume and more, based in each case on the volume of the hybrid system according to the invention.

The hybrid materials according to the invention, in particular hybrid materials with a matrix of cellular polyurethane, are characterized by very good adhesion of the matrix material to the foamed granulate according to the invention. A hybrid material according to the invention preferably does not tear at the interface between matrix material and foamed granules. This makes it possible to produce hybrid materials which, with the same density, have improved mechanical properties, such as tear propagation resistance and elasticity, compared to conventional polymer materials, in particular conventional polyurethane materials.

The elasticity of hybrid materials according to the invention in the form of integral foams is preferably greater than 40% and particularly preferably greater than 50% according to DIN 53512.

Furthermore, the hybrid materials according to the invention, in particular those based on integral foams, show high rebound resilience at low density. In particular, integral skin foams based on hybrid materials according to the invention are therefore outstandingly suitable as materials for shoe soles. As a result, light and comfortable soles with good durability properties are obtained. Such materials are particularly suitable as midsoles for sports shoes.

The hybrid materials according to the invention with a cellular matrix are suitable, for example, for padding, for example of furniture, and mattresses.

Hybrid materials with a matrix of viscoelastic gel are characterized by increased viscoelasticity and improved elastic properties. These materials are therefore also suitable as upholstery materials, for example for seats, especially saddles such as bicycle saddles or motorcycle saddles.

Hybrid materials with a compact matrix are suitable, for example, as floor coverings, in particular as coverings for playgrounds, athletic tracks, sports fields and sports halls. The properties of the hybrid materials according to the invention can vary widely depending on the polymer (PM) used and can be achieved in particular by varying the size, shape and nature of the expanded granules, or by adding other additives, for example other non-foamed granules such as plastic granules, for example rubber granules, can be varied within wide limits.

The hybrid materials according to the invention have a high level of durability and resilience, which is particularly evident in the high tensile strength and elongation at break. In addition, hybrid materials according to the invention have a low density.

Further embodiments of the present invention can be found in the claims and the examples. It goes without saying that the features of the object/method/uses according to the invention mentioned above and explained below can be used not only in the combination specified in each case, but also in other combinations, without departing from the scope of the invention. So e.g. B. also implicitly includes the combination of a preferred feature with a particularly preferred feature, or an uncharacterized feature with a particularly preferred feature, etc., even if this combination is not expressly mentioned.

The following are exemplary embodiments of the present invention, which do not limit the present invention. In particular, the present invention also includes those embodiments that result from the back-references given below and combinations thereof. In particular, it is noted that where a range of embodiments is mentioned, for example in connection with the phrase “according to any one of embodiments (1) to (4)”, each of the embodiments in that range is intended to be explicitly disclosed. The wording is considered to be synonymous for the person skilled in the art with the expression “according to one of the embodiments (1), (2), (3) and (4)”. It is explicitly stated that the following embodiments do not constitute the patent claims, but rather a structured part of the description concerning general and preferred aspects of the present invention.

An embodiment (1) of the present invention relates to a foamed granulate consisting of a composition (Z1), wherein the composition contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer ( TPE-2).

A further preferred embodiment (2), which specifies embodiment (1), relates to the foamed granules from a composition (Z1) according to embodiment (1), wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.

Another preferred embodiment (3), which substantiates embodiment (1) or (2), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) or (2), wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, or thermoplastic copolyester elastomers.

Another preferred embodiment (4), which substantiates embodiments (1) to (3), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (3), wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.

Another preferred embodiment (5), which substantiates embodiments (1) to (4), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (4), wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.

Another preferred embodiment (6), which substantiates embodiments (1) to (5), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (5), wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25%.

A further preferred embodiment (7), which substantiates embodiments (1) to (6), relates to the foamed granules from a composition (Z1) according to one of embodiments (1) to (6), the closed-cell content of the foam being greater than 60% is determined according to DIN ISO 4590:2016.

Another preferred embodiment (8), which substantiates embodiments (1) to (7), relates to the foamed granules of a composition (Z1) according to one of embodiments (1) to (7), the particles being determined at the narrowest point have an average diameter in the range from 1 mm to 20 mm, measured using a graduated microscope.

A further preferred embodiment (9) of the invention relates to a method for producing a foamed granulate, preferably according to one of the embodiments (1) to (8), comprising the steps

(i) providing a composition (Z1) in the form of granules, the composition containing at least one thermoplastic elastomer (TPE-1). a Shore D hardness in the range of 20 to 90 and a second thermoplastic elastomer (TPE-2);

Another preferred embodiment (10), which specifies embodiment (9), relates to the method according to embodiment (9), wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyether esters , polyester esters or thermoplastic styrene butadiene block copolymers.

Another preferred embodiment (11), which specifies embodiment (9) or (10), relates to the method according to embodiment (9) or (10), where the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes , thermoplastic polyetheramides, or thermoplastic copolyester elastomers.

Another preferred embodiment (12), which specifies embodiments (9) to (11), relates to the method according to one of embodiments (9) to (11), where the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.

Another preferred embodiment (13), which specifies embodiments (9) to (12), relates to the method according to one of embodiments (9) to (12), wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.

Another preferred embodiment (14), which substantiates embodiments (9) to (13), relates to the method according to one of embodiments (9) to (13), wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25% having.

Another preferred embodiment (15), which substantiates embodiments (9) to (14), relates to the method according to one of embodiments (9) to (14), wherein the closed cell content of the foam is greater than 60%, determined according to DIN ISO 4590 :2016.

Another preferred embodiment (16), which specifies embodiments (9) to (15), relates to the method according to one of embodiments (9) to (15), the particles having an average diameter in the range of 1 mm at the narrowest point up to 20 mm, measured using a scale microscope.

A further preferred embodiment (17) of the invention relates to a method for producing a shaped body comprising the steps (a) Providing foamed granules, preferably foamed granules according to one of embodiments (1) to (8), consisting of a composition (Z1), wherein the composition comprises at least one thermoplastic elastomer (TPE-1) with a Shore D hardness of im range of 20 to 90 and a second thermoplastic elastomer (TPE-2);

(b) Production of a shaped body from the foamed granulate provided according to step (a).

Another preferred embodiment (18), which specifies embodiment (17), relates to the method according to embodiment (17), wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyether esters , polyester esters or thermoplastic styrene butadiene block copolymers.

Another preferred embodiment (19), which specifies embodiments (17) to (18), relates to the method according to one of embodiments (17) to (18), wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, or thermoplastic copolyester elastomers.

Another preferred embodiment (20), which specifies embodiments (17) to (19), relates to the method according to one of embodiments (17) to (19), where the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.

Another preferred embodiment (21), which specifies embodiments (17) to (20), relates to the method according to one of embodiments (17) to (20), wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene butadiene block copolymers.

Another preferred embodiment (22), which substantiates embodiments (17) to (21), relates to the method according to one of embodiments (17) to (21), wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25% having.

Another preferred embodiment (23), which substantiates embodiments (17) to (22), relates to the method according to one of embodiments (17) to (22), wherein the closed cell content of the foam is greater than 60%, determined according to DIN ISO 4590 :2016.

Another preferred embodiment (24), which specifies embodiments (17) to (23), relates to the method according to one of embodiments (17) to (23), the particles having an average diameter in the range of 1 mm at the narrowest point up to 20 mm, measured using a scale microscope. A further preferred embodiment (25), which specifies embodiments (17) to (24), relates to the method according to one of the embodiments (17) to (24), wherein the production of the shaped body according to step (b) by means of welding the according to step ( a) provided particles by means of steam, hot air or high-energy radiation.

A further preferred embodiment (26) of the invention relates to a shaped body obtainable or obtained by a process according to embodiment (9) or (17).

A further preferred embodiment (27) of the invention relates to a shaped body obtainable or obtained by a method comprising the steps

(a) Providing foamed granules, preferably foamed granules according to one of embodiments (1) to (8), consisting of a composition (Z1), wherein the composition comprises at least one thermoplastic elastomer (TPE-1) with a Shore D hardness of im range of 20 to 90 and a second thermoplastic elastomer (TPE-2);

Another preferred embodiment (28), which specifies one of the embodiments (26) or (27), relates to a shaped body according to one of the embodiments (26) or (27), wherein the shaped body has an elongation at break of greater than 100%, determined according to DIN EN ISO 1798.

Another preferred embodiment (29), which specifies one of the embodiments (26) to (28), relates to a shaped body according to one of the embodiments (26) to (28), wherein the shaped body is a shoe sole, bicycle saddle, bicycle tire, damping element, padding, Mattress, underlay, handle, protective film, a component in the automotive interior and exterior, a ball and sports equipment or a floor covering, in particular for sports areas, athletics tracks, sports halls, children's playgrounds and sidewalks.

Another preferred embodiment (30) of the invention relates to the use of foamed granules according to one of embodiments (1) to (8) or foamed granules obtainable or obtained by a process according to one of embodiments (9) to (16) for the production of Shoe soles, bicycle saddles, bicycle tires, damping elements, upholstery, mattresses, underlays, handles, protective films, in components for automotive interiors and exteriors, in balls and sports equipment or as floor coverings, especially for sports surfaces, athletic tracks, sports halls, children's playgrounds and sidewalks.

The following examples serve to illustrate the invention but are in no way limiting of the subject matter of the present invention. EXAMPLES

1. Raw materials used

TPU1 TPU based on MDI, butanediol, polytetrahydrofuran Mn=1000g/mol with a shore hardness of 70A

TPU2 TPU based on MDI, butanediol, polytetrahydrofuran Mn=1000g/mol with a shore hardness of 80A

TPU3 TPU based on MDI, butanediol, polytetrahydrofuran Mn=1000g/mol with a shore hardness of 90A

TPA polyetheramide based on a flexible polytetrahydrofuran and crystalline polyamide units from Arkema, Shore 82A (Pebax 3533)

2. Manufacture of the eTPU

Dried granulate mixture of thermoplastic elastomers (Table 1) are mixed and melted in a twin-screw extruder with a screw diameter of 44 mm and a length-to-diameter ratio of 42.

Table 1: Composition of the blends and reference materials

After melting, a mixture of CO2 (2 parts by weight) and N2 (0.2 parts by weight) was added as blowing agent. When passing through the remaining extruder section, the blowing agent and the polymer melt were mixed with one another so that a homogeneous mixture was formed. The total throughput of the extruder, which includes the polymers and the blowing agents, was 40 kg/h.

The melt mixture was then pressed into a perforated plate (LP) by means of a gear pump (ZRP) via a starter valve with screen changer (AV) and in the cutting chamber of the underwater granulation (UWG) to form granules (25 mg). cut and carried away with the tempered and pressurized water, thereby expanding. After the expanded granules have been separated from the water by means of a centrifugal dryer, the expanded granules are dried at 60° C. for 3 hours.

The temperatures used for the plant components are listed in Table 2 for the blends.

Table 2: Temperature data of the plant components for the blends and reference materials

The bulk densities of the expanded granules resulting for the individual blends are listed in Table 3. The bulk density is measured analogously to DIN ISO 697, whereby when determining the above values, in contrast to the standard, a vessel with a volume of 10 l is used instead of a vessel with a volume of 0.5 l, since this is especially the case with the foam particles with a low density and large mass a measurement with only 0.5 l volume is too imprecise.

Table 3: Data on the blends and reference materials

According to Tables 1 to 3, it is clear that the blend systems 2 and 3 according to the invention compared to the analogous reference materials (Ref 2 and 3) advantages in the production of the foamed particles in terms of lower Plant temperatures (Table 2) and achieved lower bulk densities (Table 3).

3. Production of the moldings

The expanded granules were then welded on a molding machine from Kurtz ersa GmbH (Boost Foamer) to form square sheets with a side length of 200 mm and a thickness of 10 mm or 20 mm by exposure to steam. With the plate thickness, the welding parameters differ only with regard to the cooling. The welding parameters of the different materials were chosen in such a way that the plate side of the final molded part, which faced the moving side (mil) of the tool, had the lowest possible number of collapsed ETPU particles. If necessary, the gap vaporization also took place through the movable side of the tool. It was not always possible to obtain a satisfactory surface finish in the comparative examples. Irrespective of the experiment, a cooling time of 120 s for a plate thickness of 20 mm and 100 s for a 10 mm thick plate was always set at the end of the fixed (M1) and the moving side of the tool.

The respective steaming conditions are listed in Table 4 as steam pressures. This results in a lower maximum steam pressure required for welding the polyurethane particles of the examples compared to those of the comparative examples.

Table 4: Vapor overpressures and times for welding the materials

These advantages over the respective reference materials (reference 1 to 3) also show when the foam particles according to the invention (blends 1 to 3) are welded together; they can be welded in a shorter time at lower vapor pressures.

4. Properties of the moldings

All of the following tests were carried out on panels with a thickness of 10 mm. For the rebound test, two 10 mm thick plates were placed on top of each other to reach a height of 20 mm. Table 5 shows that the blend systems compared to the respective reference materials show advantages in the form of higher values in at least one of the two properties examined.

Table 5: Results of the measurement of the properties of the welded panels from the blend systems and the associated reference materials

Furthermore, a high degree of closed cells could be achieved with all blend systems, as Table 6 shows.

Table 6: Results of the measurement of closed cells according to DIN EN ISO 4590

5 measurement methods / DIN standards

Density E-TPU DIN EN ISO 845

closed cell determination

(uncorrected) DIN EN ISO 4590

Shore hardness DIN ISO 7619-1 (3s)

Resilience/rebound DIN 53512

Elongation at break DIN EN ISO 1798

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Claims

patent claims

1 . Foamed granulate consisting of a composition (Z1), wherein the composition (Z1) contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2).

2. Foamed granules according to claim 1, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, thermoplastic copolyester elastomers, polyether esters or polyester esters.

3. Foamed granules according to one of claims 1 or 2, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes and thermoplastic polyetheramides.

4. Foamed granules according to any one of claims 1 to 3, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.

5. Foamed granules according to any one of claims 1 to 4, wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyester esters and thermoplastic styrene butadiene block copolymers.

6. Foamed granules according to any one of claims 1 to 5, wherein the thermoplastic elastomer (TPE-2) has a hard segment content of less than 25%.

7. Foamed granules according to any one of claims 1 to 6, wherein the closed cell content of the foam is greater than 60%, determined according to DIN ISO 4590:2016.

8. Foamed granules according to any one of claims 1 to 7, wherein the particles have an average diameter in the range from 1 mm to 20 mm, determined at the narrowest point, measured using a scale microscope.

9. A method for producing a foamed granulate, preferably according to any one of claims 1 to 8, comprising the steps

(i) providing a composition (Z1) in the form of granules, wherein the composition (Z1) contains at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2 ); (ii) producing a foamed granulate from the granulate provided according to step (i).

10. A method for producing a shaped body comprising the steps

(a) providing a foamed granulate, preferably a foamed granulate according to any one of claims 1 to 8, consisting of a composition (Z1), wherein the composition (Z1) at least one thermoplastic elastomer (TPE-1) with a Shore D hardness in the range from 20 to 90 and a second thermoplastic elastomer (TPE-2);

11. The method according to claim 10, wherein the production of the shaped body according to step (b) takes place by means of welding the particles provided according to step (a) by means of steam, hot air or high-energy radiation.

12. Moldings obtainable or obtained by a process according to claim 9 or 11.

13. Shaped body according to claim 12, wherein the shaped body has an elongation at break of greater than 100%, determined according to DIN EN ISO 1798.

14. Use of a foamed granulate according to any one of claims 1 to 8 or a foamed granulate obtainable or obtained according to a method according to claim 9 for the production of shoe soles, bicycle saddles, bicycle tires, damping elements, padding, mattresses, underlays, handles, protective films, in components in Automotive interiors and exteriors, in balls and sports equipment or as a floor covering, especially for sports areas, athletics tracks, sports halls, children's playgrounds and sidewalks.