Comfort eTPU

Abstract

The present invention relates to a molded article containing a foam made of a thermoplastic elastomer (TPE-1), which has a storage modulus (G modulus) at 25°C and 1 Hz in the range of 0.01 to 0.5 MPa and a molding density of 20 to 400 kg / m 3 and a comfort factor greater than 4. The invention further relates to a method for producing such a molded article and to the use of the molded article of the invention for the production of floors, mattresses, seating furniture, bicycle saddles, car seats, motorcycle seats, shoe components as shoe insoles, packaging, shock absorbers, protectors, fall protection mats, elastic insulation or seals.

Description

[Technical field]

[0001] The present invention relates to a molded article containing a foam made of a thermoplastic elastomer (TPE-1), and the foam has a storage modulus (G modulus) in the range of 0.01 to 0.5 MPa at 25°C and 1 Hz, and a molded density of 20 to 400 kg / m 3 and a comfort factor, i.e. the compression hardness ratio (StH65% / StH25%), determined according to Reference Example 3, of greater than 4. The invention further relates to a process for producing such a moulded article and to the use of the moulded article according to the invention for the production of floors, mattresses, seating furniture, bicycle saddles, car seats, motorcycle seats, shoe parts such as shoe insoles, packaging, shock absorbers, protectors, fall protection mats, elastic insulation or sealing materials. [Background technology]

[0002] Foams, including in particular bead foams, have been known for a long time and have been described many times in the literature, for example in Ullmann "Encyklopaedie der technischen Chemie" [Encyclopedia of Industrial Chemistry], 4th edition, volume 20, pp. 416ff.

[0003] Highly elastic, mainly closed-cell foams, such as bead foams made of thermoplastic elastomers, produced for example in autoclaves or extruders, exhibit special dynamic properties and in some cases also good elasticity. Hybrid foams made of thermoplastic elastomer beads and system foams or binders are also known. Depending on the foam density, the production method and the matrix material, it is possible to produce a relatively wide range of overall stiffness levels. Post-treatment of the foam, such as heat treatment, can also affect the foam properties.

[0004] Foamed pellet materials, also called bead foams (or particle foams), and moulded articles produced therefrom based on thermoplastic polyurethanes or other elastomers are known (e.g. WO 94 / 20568, WO 2007 / 082838 A1, WO 2017 / 030835, WO 2013 / 153190 A1, WO 2010 / 010010) and have a wide variety of possible applications.

[0005] In the context of the present invention, "foamed pellet material", otherwise "bead foam" or "particle foam", refers to foam in the form of beads, the average diameter of the beads being between 0.2 and 20 mm, preferably between 0.5 and 15 mm, in particular between 1 and 12 mm. In the case of non-spherical, e.g. elongated or cylindrical, beads, the diameter refers to the longest dimension.

[0006] Polymers based on thermoplastic polyurethanes (TPUs) are already used in many different fields. The properties of the polymers can be modified depending on the application. Thermoplastic polyurethanes in particular are used in many different ways.

[0007] For upholstery applications, good damping properties are necessary to ensure a high level of seating comfort. However, when sitting on a soft seat material, very strong compression is often experienced by the material, and above a relatively high level of compression the material, which is usually an open-cell PU foam, suddenly becomes hard, resulting in the material becoming uncomfortably hard for the user. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] WO94 / 20568 [Patent Document 2] WO2007 / 082838A1 [Patent Document 3] WO2017 / 030835 [Patent Document 4] WO2013 / 153190A1 [Patent Document 5] WO2010 / 010010 [Non-patent literature]

[0009] [Non-Patent Document 1] Ullmann, "Encyklopaedie der technischen Chemie" [Encyclopedia of Industrial Chemistry], 4th ed., Vol. 20, pp. 416ff. Summary of the Invention [Problem to be solved by the invention]

[0010] It is therefore an object of the present invention to provide a moulded article based on a thermoplastic elastomer, which has good damping properties and adjustable rebound properties, while at the same time providing a high level of seating comfort. Particularly suitable materials are those whose stiffness increases slowly with increasing compression, in order to increase stability when seated. It is a further object of the present invention to provide a method for producing the corresponding moulded article. [Means for solving the problem]

[0011] The object of the present invention is to provide a molded article comprising a foamed material made of a thermoplastic elastomer (TPE-1), the foamed material having a storage modulus (G modulus) at 25° C. and 1 Hz determined in accordance with Reference Example 1 (molded TPE product) in the range of 0.01 to 0.5 MPa and a molded density determined in accordance with Reference Example 2 in the range of 20 to 400 kg / m 3 This is achieved by a molded article in which the foam is a foam pellet material. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 compares stress-strain curves for examples according to the invention and comparative examples, where force (y-axis) is plotted against distance (%, x-axis). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention also relates to a molded article comprising a foam made of a thermoplastic elastomer (TPE-1), the foam having a storage modulus (G modulus) at 25°C and 1 Hz in the range of 0.01 to 0.5 MPa as determined in accordance with Reference Example 1 (molded TPE article) and a molded density in the range of 20 to 400 kg / m as determined in accordance with Reference Example 2. 3 wherein the foam has a comfort factor of greater than 4, determined according to Reference Example 3.

[0014] When the foam is present in the molded article in the form of discontinuous beads, the molded density determined according to Reference Example 2 corresponds to or is greater than the bulk density determined according to Reference Example 4 in the context of the present invention.

[0015] Surprisingly, mainly closed-cell foams based on thermoplastic elastomers, especially those with low storage modulus and molded densities of 20 to 400 kg / m 3 It was found that by using foam pellets in the range of 0.01 to 0.5 MPa at 25°C and 1 Hz, a low-rigidity foam can be realized that does not compress suddenly when seated on, but steadily hardens gradually according to the degree of compression. The specified properties, i.e., a storage modulus (G modulus) in the range of 0.01 to 0.5 MPa at 25°C and 1 Hz determined according to Reference Example 1 (TPE molded body), and a stiffness of 20 to 400 kg / m2 determined according to Reference Example 2, are achieved. 3Through the use according to the invention of foam pellet materials having a molding density in the range of 0.1 to 0.5, it is possible to obtain moldings with a combination of properties that are particularly advantageous for seating furniture, for example. It has thus been found that a comfort factor of more than 4, determined according to Example 3, has a significant effect on the comfort when sitting. Through the combination according to the invention of the properties of the foams used, it is possible to obtain moldings with a comfort factor of more than 4, determined according to Example 3. The compression behavior of the moldings resembles initially the compression behavior of open-cell soft foams and later the compression behavior of closed-cell bead foams. That is to say, the hardening does not suddenly take effect, as in the case of open-cell soft foams. Instead, the back pressure increases continuously, slowing down the user.

[0016] Surprisingly, it is not only the G modulus of the thermoplastic elastomer that is important for the initial stiffness, but also the G modulus of the foam and the density of the foam. Also, a regular foam structure is even more advantageous, since it is compressed and therefore appears softer from the start.

[0017] Thus, for example, in the diagram shown in FIG. 1 which compares the stress-strain curves of the embodiment according to the present invention and the comparative example, it can be seen that the initial stage is flat from the beginning and then gradually increases.

[0018] The present invention also relates to a molded article comprising a foam made of a thermoplastic elastomer (TPE-1), the foam having a storage modulus (G modulus) at 25°C and 1 Hz in the range of 0.01 to 0.5 MPa as determined in accordance with Reference Example 1 (molded TPE article) and a molded density in the range of 20 to 400 kg / m as determined in accordance with Reference Example 2. 3and the foam has a comfort factor of more than 4, determined according to Reference Example 3. According to the invention, in the context of the present invention, the foam may be a slabstock foam or else it may consist of or contain a foam pellet material. According to the invention, it is possible here for the molded article to contain beads of foam pellet material in the form of individual beads or in fused form, for example in the form of fused or adhesively bonded beads of foam pellet material. According to the invention, it is also possible for the beads of foam pellet material to be surrounded by a matrix, i.e. to be embedded, for example, in a certain foam or compact polymer. A foam that is a foam pellet material is understood in the context of the present invention to mean an embodiment in which the foam consists of or contains a foam pellet material. According to the present invention, the foam that is a foam pellet material can also be a foam pellet material surrounded by a matrix.

[0019] According to the invention, the foam preferably has a comfort factor, determined according to Reference Example 3, greater than 4, preferably in the range of 4 to 12, for example in the range of 5 to 11, otherwise in the range of 5 to 10 (in each case determined according to Reference Example 3).

[0020] The process of producing foamed pellets from thermoplastic elastomers is known per se to those skilled in the art. When using a foamed pellet material made of thermoplastic elastomer (TPE-1) according to the present invention, the bulk density of the foamed pellet material is, for example, within the range of 20 g / l to 250 g / l, preferably 50 g / l to 180 g / l, more preferably 60 g / l to 150 g / l.

[0021] For example, the diameter of the foamed pellets is between 0.2 and 20 mm, preferably between 1 and 15 mm, in particular between 3 and 12 mm. In the case of non-spherical, e.g. elongated or cylindrical, foamed pellets, the diameter refers to the longest dimension.

[0022] In one embodiment, the present invention also relates to the above molded article, wherein the foam is a foam pellet material.

[0023] Suitable thermoplastic elastomers for producing the foams or molded articles of the present invention are known per se to the person skilled in the art. Suitable thermoplastic elastomers are described, for example, in the "Handbook of Thermoplastic Elastomers", 2nd edition, June 2014. For example, the thermoplastic elastomer (TPE-1) can be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester, a thermoplastic olefin-based elastomer, a crosslinked thermoplastic olefin-based elastomer, or a thermoplastic vulcanizate or a thermoplastic styrene-butadiene block copolymer. According to the present invention, the thermoplastic elastomer (TPE-1) can preferably be a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester, or a thermoplastic styrene-butadiene block copolymer.

[0024] The thermoplastic elastomer (TPE-1) in the context of the present invention is more preferably a thermoplastic polyurethane, a thermoplastic polyetheramide or a polyester ester or a polyether ester.

[0025] In a further embodiment, the present invention therefore also relates to a molded article as described above, in which the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters, thermoplastic olefin-based elastomers, crosslinked thermoplastic olefin-based elastomers, thermoplastic vulcanizates or thermoplastic styrene-butadiene block copolymers, in particular selected from thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters or thermoplastic styrene-butadiene block copolymers.

[0026] Suitable thermoplastic elastomers are in particular those which, in the compact state, have a G modulus in the range of 0.8 to 8.5 MPa, determined according to Reference Example 6. Accordingly, in a further embodiment, the present invention also relates to a molded article as described herein, in which the thermoplastic elastomer (TPE-1) in the compact state has a G modulus in the range of 0.8 to 8.5 MPa, determined according to Reference Example 6.

[0027] Suitable processes for producing these thermoplastic elastomers or foams or foam pellets composed of the aforementioned thermoplastic elastomers are likewise known per se to those skilled in the art.

[0028] Suitable thermoplastic polyetheresters and polyesteresters can be prepared according to any standard method known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids or their esters having 4 to 20 carbon atoms with suitable aliphatic and aromatic di- and polyols (see "Polymer Chemistry", Interscience Publ., New York, 1961, pp. 111-127; Kunststoffhandbuch [Plastics Handbook], Vol. VIII, C. Hanser Verlag, Munich 1973 and Journal of Polymer Science, Part A1, 4, pp. 1851-1859 (1966)).

[0029] Specific examples of suitable aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and their esters.Specific examples of suitable aliphatic dicarboxylic acids include saturated dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, and decane dicarboxylic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid, and tetrahydroterephthalic acid.

[0030] Specific examples of suitable diol components include those having the general formula HO-(CH2)n -OH (wherein n=2 to 20), such as ethylene glycol, propane-1,3-diol, butane-1,4-diol or hexane-1,6-diol, with the general formula HO-(CH2) n -O-(CH2) m Mention may be made of polyetherols of the formula -OH, where n is equal to or unequal to m, n, m=2 to 20; unsaturated diols and polyetherols, such as butene-1,4-diol; diols and polyethers containing aromatic units; and polyesterols.

[0031] As well as the listed carboxylic acids and their esters and the listed alcohols, it is also possible to use any other standard representatives of these classes of compounds to provide the polyetheresters and polyesteresters for use in accordance with the present invention.

[0032] Thermoplastic polyetheramides can be obtained according to any standard method known from the literature, by reaction of amines with carboxylic acids or their esters, where the amines and / or carboxylic acids further comprise ether units of the ROR type, where R=organic radical (aliphatic and / or aromatic). In general, monomers from the following classes of compounds are used: HOOC-R'-NH2, where R' can be aromatic and aliphatic, and preferably comprise ether units of the ROR type, where R=organic radical (aliphatic and / or aromatic); aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid or their esters, and aromatic dicarboxylic acids with ether units of the ROR type, where R=organic radical (aliphatic and / or aromatic); aliphatic dicarboxylic acids, such as cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, azelanic acid and decanedicarboxylic acid, as saturated dicarboxylic acids. Carboxylic acids and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid, and aliphatic dicarboxylic acids with ether units of the ROR type, where R=organic radical (aliphatic and / or aromatic); diamines of the general formula H2N-R″-NH2, where R″ can be aromatic and aliphatic, preferably with ether units of the ROR type, where R=organic radical (aliphatic and / or aromatic); lactams, such as ε-caprolactam, pyrrolidone or laurolactam; and amino acids.

[0033] As well as the listed carboxylic acids and their esters and the listed amines, lactams and amino acids, any other standard representatives of these classes can also be used to provide polyetheramines for use in accordance with the present invention.

[0034] The thermoplastic elastomers having a block copolymer structure used according to the invention preferably comprise vinyl aromatic units, butadiene units and isoprene units, but also polyolefin units and vinyl units, such as ethylene, propylene, vinyl acetate units. Preference is given to styrene-butadiene copolymers.

[0035] The thermoplastic elastomers having a block copolymer structure, polyetheramides, polyetheresters and polyesters used according to the invention are preferably selected so that their melting points are below 300°C, preferably below 250°C and in particular below 220°C.

[0036] The thermoplastic elastomers having a block copolymer structure, polyetheramides, polyetheresters and polyetheresters used according to the invention may be semi-crystalline or amorphous.

[0037] A suitable thermoplastic olefin elastomer (TPO) has a hard segment and a soft segment, the hard segment being a polyolefin such as polypropylene or polyethylene, and the soft segment being a rubber component such as ethylene-propylene rubber. A blend of a polyolefin and a rubber component, a dynamic crosslinking type, or a polymerization type is suitable.

[0038] Suitable structures include, for example, ethylene-propylene rubber (EPM) dispersed in polypropylene, crosslinked or partially crosslinked ethylene-propylene-diene rubber (EPDM) dispersed in polypropylene, random copolymers of ethylene with α-olefins such as propylene and butene, or block copolymers of polyethylene blocks with ethylene / α-olefin copolymer blocks. Examples of suitable α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-n-decene, 3-methyl-1-butene, and 4-methyl-1-pentene, or mixtures of these olefins.

[0039] Suitable semi-crystalline polyolefins are, for example, homopolymers of ethylene or propylene, or copolymers having monomer units of ethylene and / or propylene, such as copolymers of ethylene and propylene or α-olefins having 4 to 12 carbon atoms, copolymers of propylene and α-olefins having 4 to 12 carbon atoms, etc. The concentration of ethylene or propylene in these copolymers is preferably high enough here so that the copolymers are semi-crystalline.

[0040] In the case of random copolymers, the ethylene or propylene content is suitably, for example, about 70 mole percent or more.

[0041] Suitable polypropylenes are propylene homopolymers or polypropylene block copolymers, such as random copolymers of propylene and up to about 6 mole percent ethylene.

[0042] Suitable thermoplastic styrene block copolymers usually include a polystyrene block and an elastomeric block. Suitable styrene blocks are selected from, for example, polystyrene, substituted polystyrene, poly(α-methylstyrene), ring-halogenated styrene, and ring-alkylated styrene. Suitable elastomeric blocks are, for example, polydiene blocks such as polybutadiene and polyisoprene, poly(ethylene / butylene) copolymers and poly(ethylene / propylene) copolymers, polyisobutylene, or other polypropylene sulfides or polydiethylsiloxane.

[0043] In the context of the present invention, it is particularly advantageous that the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane.

[0044] Thermoplastic polyurethanes are known from the prior art. They are typically obtained by reacting a polyisocyanate composition with a polyol composition, which typically comprises a polyol and a chain extender.

[0045] According to the invention, the thermoplastic elastomers used may contain other additives, such as surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and demolding aids, dyes and pigments, and optionally customary auxiliaries, such as stabilizers against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers. Suitable auxiliary and additive substances can be found, for example, in Kunststoffhandbuch [Plastics Handbook], Volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (pages 103-113).

[0046] In the present invention, it has been found that in addition to the storage modulus (G modulus) and density of the foam, the comfort coefficient in particular has a large effect on the sitting comfort.

[0047] According to the invention, it has proven to be advantageous if the compression hardness of the foam at 10% compression is equal to or less than 22 kPa, more preferably less than 20 kPa or less than 15 kPa, after the 4th cycle, as measured according to Reference Example 5. In the context of the present invention, "after the 4th cycle" is understood to mean that the corresponding value may already have been reached in a previous measurement cycle, i.e. the measured value falls within the range of the invention by the time of the 4th measurement or after the 4th cycle.

[0048] The foam preferably has a compression hardness at 25% compression, determined according to Reference Example 5, of 65 kPa or less after the fourth cycle.

[0049] In a further embodiment, the present invention accordingly relates to a molded article as described herein, wherein the foam has a compression hardness of 22 kPa or less at 10% compression, determined according to Reference Example 5, after the fourth cycle.

[0050] In a further embodiment, the invention accordingly relates to a molded article as described herein, wherein the foam has a compression hardness of 65 kPa or less at 25% compression, determined according to Reference Example 5, after the fourth cycle.

[0051] In one embodiment, the present invention also relates to a molded article as described herein, wherein the foam has a compression hardness at 65% compression, determined after the fourth cycle according to Reference Example 5, in the range of 300-700 kPa.

[0052] In one embodiment, the present invention also relates to a molded article as described herein, wherein the foam has a compression hardness at 10% compression, determined after the fourth cycle according to Reference Example 5, in the range of 1 to 20 kPa.

[0053] In accordance with the present invention, it has been found that the compression hardness of the molded product can be influenced by a combination of the G modulus of the foam of the thermoplastic elastomer (TPE-1) used and the adjustment of the density of the foam within the range of the present invention, which can be varied in accordance with the present invention, for example, by appropriate conditions during foam production.

[0054] It is also possible in the present invention to use foam pellet materials that are fused or fused by adding appropriate means, in which case the foam or molded article can be adjusted to an appropriate density during fusion.

[0055] According to the invention, the molded article can comprise beads of foamed pellet material in a loose, free form, in which case the molded article can also comprise, for example, a suitable shell, which will essentially determine the shape of the molded article.

[0056] In one embodiment, the invention relates to a molded article as described herein, further comprising a shell and beads of expanded pellet material.

[0057] The shell material and shape can be varied within wide limits within the scope of the present invention, provided the shell is capable of closing and is suitable for forming a molded article with loose, discrete beads of foamed pellet material.

[0058] In accordance with the present invention, beads of foamed pellet material can be, for example, welded together to form a foam of suitable density. It is also within the scope of the present invention to subject the foamed pellet material to, for example, heat treatment, radiation, or solvent treatment prior to welding or bonding.

[0059] In one embodiment, the invention also relates to a molded article as described herein, wherein the foam comprises fused beads.

[0060] According to the present invention, it is also possible to embed the foam pellet material in a matrix and make the foam a hybrid foam.

[0061] In one embodiment, the present invention also relates to a molded article as described herein, wherein the foam is a hybrid foam including a foamed pellet material comprised of a thermoplastic elastomer (TPE-1).

[0062] A material comprising a foamed pellet material and a matrix material is called a hybrid material in the context of the present invention. The matrix material here can consist of a dense material as well as a foam.

[0063] Polymers (PM) suitable as matrix materials are known per se to the skilled person. Suitable in the context of the present invention are, for example, ethylene-vinyl acetate copolymers, epoxy-based binders or polyurethanes. Polyurethane foams or other compact polyurethanes, for example elastic polyurethanes, are suitable here according to the present invention. According to the present invention, the thermoplastic elastomers used as matrix materials can contain other additives, for example surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and demolding aids, dyes and pigments, optionally customary auxiliaries, such as stabilizers against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers. Suitable auxiliary and additive substances can be found, for example, in Kunststoffhandbuch [Handbook of Plastics], Volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (pages 103-113).

[0064] According to the invention, the polymer (PM) is selected to ensure sufficient adhesion between the foamed pellet material and the matrix, so as to obtain a hybrid material that is mechanically stable at least on the surface.

[0065] The matrix can completely or partially surround the foamed pellet material. According to the invention, the hybrid material can contain further components, for example further fillers or pellets. According to the invention, the hybrid material can also contain a mixture of different polymers (PM). The hybrid material can also contain a mixture of foamed pellets.

[0066] Other foam pellets that can be used besides the foam pellet material according to the invention are known per se to those skilled in the art. Foam pellets made of thermoplastic elastomers, in particular thermoplastic polyurethanes, are particularly suitable in the context of the present invention.

[0067] Thus, hybrid materials comprising a matrix composed of a polymer (PM), a foamed pellet material composed of a thermoplastic elastomer (TPE-1) and a further foamed pellet material composed of a thermoplastic polyurethane are also suitable in the context of the present invention.

[0068] The matrix may, within the scope of the present invention, consist, for example, of a polymer (PM).Specific examples of suitable matrix materials in the context of the present invention are elastomers or foams, in particular foams based on polyurethanes, such as elastomers such as ethylene-vinyl acetate copolymers or other thermoplastic or elastomeric polyurethanes.

[0069] Suitable matrix materials are known per se to the person skilled in the art. For example, adhesive systems based on epoxy or polyurethane, which are known per se, can be used.

[0070] Suitable thermoplastic and elastomeric polyurethanes are known per se to those skilled in the art. Suitable polyurethanes are described, for example, in "Kunststoffhandbuch" [Plastics Handbook], Volume 7, "Polyurethane" [Polyurethane], Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.

[0071] As polymer (PM), in the context of the present invention, it is preferably polyurethane. For the present invention, the term "polyurethane" includes all known polyisocyanate polyaddition products. These products include, in particular, solid polyisocyanate polyaddition products, such as viscoelastic gels or thermoplastic polyurethanes, and resilient foams based on polyisocyanate polyaddition products, such as flexible foams, semi-rigid foams or monolithic foams. For the purposes of the present invention, "polyurethane" is further understood to mean resilient polymer blends comprising polyurethane and further polymers, and foams composed of these polymer blends. As matrix, it is preferred to use a hardened dense polyurethane binder, a resilient polyurethane foam or a gel.

[0072] "Polyurethane binder" is understood in the context of the present invention to mean a mixture consisting of at least 50% by weight, preferably at least 80% by weight, in particular at least 95% by weight, of prepolymers containing isocyanate groups (hereinafter referred to as isocyanate prepolymers). The viscosity of the polyurethane binder according to the present invention is preferably in the range of 500 to 4000 mPa·s, more preferably 1000 to 3000 mPa·s, measured at 25°C according to DIN 53019-1:2008-09.

[0073] Polyurethane foams suitable in the context of the present invention are known per se to those skilled in the art.

[0074] The density of the matrix material is 2~0.001g / cm 3 The matrix material preferably has a density of 0.8 to 0.1 g / cm 3 , especially 0.6 to 0.1 g / cm 3 Particularly preferred are resilient or monolithic foams having densities in the range of 0.1 to 0.5, or dense materials such as cured polyurethane binders.

[0075] Foams are particularly suitable as the matrix material. Hybrid materials containing a matrix material made of polyurethane foam preferably have good adhesion between the matrix material and the foam pellet material.

[0076] A suitable hybrid material according to the invention, comprising a polymer (PM) as a matrix and a foamed pellet material, can be produced, for example, by mixing the components used to produce the polymer (PM) and the foamed pellet material, optionally with further components, and reacting them to produce the hybrid material, the reaction being preferably carried out under conditions in which the foamed pellet material is essentially stable.

[0077] Suitable processes and reaction conditions for producing polymers (PM), in particular ethylene-vinyl acetate copolymers or polyurethanes, are known per se to those skilled in the art.

[0078] In a preferred embodiment, the hybrid material suitable for the present invention is an integral foam, in particular an integral foam based on polyurethane. Suitable processes for producing integral foams are known per se to the person skilled in the art. The integral foams are preferably produced by a one-shot process using low-pressure or high-pressure techniques in a closed, advantageously temperature-controlled mould. The mould is usually made of metal, for example aluminium or steel. These procedures are described, for example, by Piechota and Roehr in “Integralschaumstoff” [Integral Foams], Carl-Hanser-Verlag, Munich, Vienna, 1975, or in “Kunststoffhandbuch” [Plastics Handbook], Vol. 7, “Polyurethane” [Polyurethane], 3rd edition 1993, chapter 7.

[0079] It is thus possible to produce a hybrid material having a matrix composed of a polymer (PM) in which the foamed pellet material of the present invention is present, which can be easily used in the process of producing the hybrid material, for example by compression molding.

[0080] The volume fraction of the foamed pellet material in the hybrid material suitable according to the invention is preferably 20% by volume or more, more preferably 50% by volume or more, preferably 80% by volume or more, in particular 90% by volume or more, based on the volume of the hybrid system.

[0081] Hybrid materials suitable as foams in the context of the present invention, in particular those with a matrix made of cellular polyurethane, are characterized by a very good adhesion of the matrix material to the foamed pellet material of the present invention. As a result, it is preferable that no tears occur in the hybrid material of the present invention at the interface between the matrix material and the foamed pellet material. This makes it possible to produce hybrid materials with improved mechanical properties, such as tear propagation resistance and elasticity, compared to conventional polymeric materials of the same density, in particular conventional polyurethane materials.

[0082] The resilience of the hybrid material of the invention in the form of an integral foam is preferably greater than 30%, more preferably greater than 50%, according to DIN 53512:2000-04.

[0083] The properties of the hybrid material can be varied within wide limits depending on the polymer (PM) used. It is possible to adjust the properties of the hybrid material within wide limits by changing the size, shape and properties of the expanded pellet material or by otherwise adding further additives, for example by adding further non-expanded pellet materials such as plastic pellets, for example rubber pellets.

[0084] In a further aspect, the present invention relates to a method for producing a pharmaceutical composition comprising the steps of: (i) A thermoplastic elastomer (TPE-1) is used, and the storage modulus (G modulus) at 25°C and 1 Hz determined in accordance with Reference Example 1 (TPE molded body) is in the range of 0.01 to 0.5 MPa, and the molded density determined in accordance with Reference Example 2 is in the range of 20 to 400 kg / m 3 providing a foam having a comfort factor greater than 4, as determined in accordance with Example 3; (ii) processing the foam into a molded article. The present invention also relates to a method for producing a molded article, comprising:

[0085] Regarding the preferred embodiment, please refer to the above description.

[0086] In the context of the present invention, the method of the present invention comprises steps (i) and (ii). The foam made of thermoplastic elastomer (TPE-1) prepared according to step (i) can be a slabstock foam or else it can be a foamed pellet material. According to the present invention, it is also possible to process the foam before preparing it in step (i). In the context of the present invention, the foam can be, for example, a welded or bonded foamed pellet material or else it can be a foamed pellet material embedded in a matrix foam or in a matrix polymer. Thus, for example, it is also possible within the scope of the present invention to start with a foam made of thermoplastic elastomer (TPE-1) whose density and / or G modulus and / or comfort factor are outside the scope of the present invention, and further adjust its density, G modulus and comfort factor by suitable processing.

[0087] In one embodiment, the present invention also relates to a method of making a molded article as described herein, wherein the foam is a foamed pellet material.

[0088] The present invention comprises the following steps: (i) A thermoplastic elastomer (TPE-1) is used, and the storage modulus (G modulus) at 25°C and 1 Hz determined in accordance with Reference Example 1 (TPE molded body) is in the range of 0.01 to 0.5 MPa, and the molded density determined in accordance with Reference Example 2 is in the range of 20 to 400 kg / m 3 providing a foam in the range of (ii) processing the foam into a molded article. The present invention also relates to a method for producing a molded article, comprising:

[0089] Suitable processes for producing moulded articles from foamed pellet material are known per se to those skilled in the art.

[0090] If the moulded article comprises a shell and beads of foamed pellet material in loose bulk form, then it is possible to, for example, fill or pack the shell according to step (ii) to form the moulded article. Suitable means for filling the shell with the foamed pellet material are known per se to the person skilled in the art. For example, the shell can be filled by injection, stacking, pushing, pressing, robotic positioning, spinning, suction, etc.

[0091] Within the scope of the present invention, it is also possible to carry out steps (i) and (ii) of the method simultaneously, i.e., for example, to first provide a foamed pellet material according to step (i) and then process it into a molded article by welding, joining or foam molding according to step (ii).

[0092] In one embodiment, the present invention also relates to a method as described herein, wherein the treating according to step (ii) is carried out by means of welding, expanding or bonding beads of the expanded pellet material.

[0093] According to the present invention, for example, a mold is first prepared and foam pellet raw material is poured into the mold to produce a molded product. The amount of foam pellet raw material poured into the mold is adjusted according to the size of the mold and the desired density of the molded product. Within the scope of the present invention, the method can also include further steps, such as temperature adjustment. Also within the scope of the present invention, the molded product can include further components. It is therefore also possible to produce a molded product using a molded body or foam beads composed of further materials.

[0094] The treatment in step (ii) is preferably carried out in a closed mould and fusing can be achieved by steam, hot air (eg as described in EP1979401B1), variable temperature welding or high energy radiation (eg microwave or radio wave).

[0095] The temperature at which the foam pellet material is fused is preferably less than or close to the melting temperature of the polymer from which the foam pellet material is produced.

[0096] Welding by high-energy radiation, generally in the microwave or radio frequency range, optionally in the presence of water or other polar liquids, such as microwave absorbing hydrocarbons with polar groups (e.g. esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycols), can be carried out in a manner similar to the processes described in EP 3053732A or WO 16146537.

[0097] For example, a molded product is produced by welding at a temperature within a range of 100° C. to 170° C. The temperature during welding of the expanded beads is preferably between 100° C. and 140° C.

[0098] The welding can be carried out, for example, by welding the components to one another in a closed mold under the action of heat, optionally under pressure. For this purpose, the components, i.e. at least the foamed pellet material, are poured into a mold, the mold is closed, and steam or hot air is introduced to further expand the beads of the foamed pellet material and fuse them to one another to form a foam. According to the invention, depending on the thickness of the components, it is also possible to heat the mold from the outside with a heat medium such as water or oil in order to fuse the beads to one another.

[0099] The method according to the invention may include further steps, such as a temperature adjustment step.

[0100] Further embodiments according to standard methods are possible here: The processes used for producing the starting materials can also be directly integrated into the manufacturing production.

[0101] The present invention further relates to a shaped article obtained or obtainable by the process described herein.

[0102] The molded article of the present invention is particularly suitable as a cushioning member, and is also suitable as a shoe sole, a part of a shoe sole, a bicycle saddle, a cushioning material, a mattress, a padding, a backrest, an arm pad, a pad, an underlay, a handle, a protective film, a protector, a damping element, or a part of the interior or exterior area of ​​a car.

[0103] In a further embodiment, the present invention accordingly relates to a molded article as described herein, which is a shoe sole, a part of a shoe sole, a bicycle saddle, a cushioning material, a mattress, padding, a backrest, an arm pad, a pad, an underlay, a handle, a protective film, a protector, a damping member, or a part of an interior or exterior area of ​​a motor vehicle.

[0104] In a further aspect, the present invention further relates to the use of the molded articles of the present invention in the manufacture of floors, mattresses, seating furniture, bicycle saddles, car seats, motorcycle seats, shoe components such as shoe insoles, packaging, shock absorbing materials.

[0105] Further embodiments of the invention can be found in the claims and the examples. It is to be understood that the features of the subject matter / method / use of the invention described above and the features of the subject matter / method / use of the invention described and clarified hereinafter can be used not only in the combinations specified in each case, but also in other combinations without departing from the scope of the invention. Thus, for example, combinations of preferred features with particularly preferred features, or even less preferred features with particularly preferred features, etc., are implicitly encompassed even if this combination is not explicitly described.

[0106] In the following, exemplary embodiments of the present invention are described without limiting the present invention, and in particular, the present invention also encompasses those embodiments resulting from reference to and combination of the dependencies defined below.

[0107] 1. A molded article comprising a foam made of a thermoplastic elastomer (TPE-1), wherein the foam has a storage modulus (G modulus) at 25°C and 1 Hz in the range of 0.01 to 0.5 MPa as determined in accordance with Reference Example 1 (TPE molded article), and a molded density in the range of 20 to 400 kg / m as determined in accordance with Reference Example 2. 3 wherein the foam has a comfort factor of greater than 4, determined according to Reference Example 3.

[0108] 2. The molded article according to embodiment 1, wherein the compression hardness of the foam measured in accordance with Reference Example 5 at 10% compression after the fourth cycle is 22 kPa or less.

[0109] 3. The molded article according to any one of embodiments 1 or 2, wherein the foam has a compression hardness of 65 kPa or less at 25% compression determined after the fourth cycle according to Reference Example 5.

[0110] 4. The molded article of any one of embodiments 1 to 3, wherein the foam is a foamed pellet material.

[0111] 5. The molded article according to any one of embodiments 1 to 4, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters, thermoplastic olefin-based elastomers, crosslinked thermoplastic olefin-based elastomers, thermoplastic vulcanizates, or thermoplastic styrene-butadiene block copolymers.

[0112] 6. The molded article according to any one of the preceding claims, 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.

[0113] 7. The molded article according to any one of embodiments 1 to 6, wherein the thermoplastic elastomer (TPE-1) in a dense state has a G elastic modulus, determined in accordance with Reference Example 6, in the range of 0.8 to 8.5 MPa.

[0114] 8. The molded article of any one of the preceding embodiments, wherein the molded article comprises a shell and a bead of foamed pellet material.

[0115] 9. The molded article of any one of the preceding embodiments, wherein the foam is a welded bead of foam pellet material.

[0116] 10. The molded article of any one of the preceding embodiments, wherein the foam is a hybrid foam comprising a foam pellet material composed of a thermoplastic elastomer (TPE-1).

[0117] 11. The following process (i) preparing a foam made of a thermoplastic elastomer (TPE-1), wherein the foam has a storage modulus (G modulus) at 25°C and 1 Hz in the range of 0.01 to 0.5 MPa as determined in accordance with Reference Example 1 (molded TPE product) and a molded density in the range of 20 to 400 kg / m as determined in accordance with Reference Example 2; 3 wherein the foam has a comfort factor of greater than 4, as determined in accordance with Reference Example 3; and (ii) processing the foam into a molded article. A method for producing a molded article, comprising:

[0118] 12. The method of embodiment 11, wherein the foam is a foam pellet material.

[0119] 13. The method of embodiment 12, wherein the processing according to step (ii) is carried out by welding, expanding or bonding beads of the foamed pellet material.

[0120] 14. The method of any one of embodiments 11 to 13, wherein the foam has a compression hardness at 10% compression, determined after the fourth cycle as measured according to Reference Example 5, of 22 kPa or less.

[0121] 15. The method of any one of embodiments 11 to 14, wherein the foam has a compression hardness of 65 kPa or less at 25% compression, determined after 4 cycles according to Reference Example 5.

[0122] 16. The method according to any one of embodiments 11 to 15, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters, thermoplastic olefin-based elastomers, crosslinked thermoplastic olefin-based elastomers, thermoplastic vulcanizates or thermoplastic styrene-butadiene block copolymers.

[0123] 17. The method of any one of embodiments 11 to 16, 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.

[0124] 18. The method according to any one of embodiments 11 to 17, wherein the thermoplastic elastomer (TPE-1) in a dense state has a G modulus, determined according to Reference Example 6, in the range of 0.8 to 8.5 MPa.

[0125] 19. A molded article obtained or obtainable by the method according to any one of embodiments 11 to 18.

[0126] 20. The article of embodiment 17, wherein the article is a shoe sole, part of a shoe sole, a bicycle saddle, cushioning, a mattress, padding, a backrest, an arm pad, a pad, an underlay, a handle, a protective film, a protector, a damping element, a fall protection mat, an elastic insulation material, a sealant, or a part of an interior or exterior area of ​​an automobile.

[0127] 21. A method of using the molded article according to any one of embodiments 1 to 10, 19 or 20 for producing a floor, a mattress, a seating furniture, a bicycle saddle, a car seat, a motorcycle seat, a shoe part such as an insole, a packaging, a shock absorber, a protector, a fall protection mat, an elastic insulation material or a sealing material.

[0128] 22. A molded article comprising a foam made of a thermoplastic elastomer (TPE-1), wherein the foam has a storage modulus (G modulus) at 25°C and 1 Hz determined in accordance with Reference Example 1 (TPE molded article) in the range of 0.01 to 0.5 MPa, and a molded density determined in accordance with Reference Example 2 in the range of 20 to 400 kg / m 3 wherein the foam is a foam pellet material.

[0129] 23. The molded article according to claim 22, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters, thermoplastic olefin-based elastomers, crosslinked thermoplastic olefin-based elastomers, thermoplastic vulcanizates or thermoplastic styrene-butadiene block copolymers.

[0130] 24. The molded article of any of embodiments 22 or 23, 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.

[0131] 25. The molded article according to any one of embodiments 22 to 24, wherein the thermoplastic elastomer (TPE-1) in a dense state has a G elastic modulus determined in accordance with Reference Example 6 in the range of 0.8 to 8.5 MPa.

[0132] 26. The molded article of any one of embodiments 22-25, wherein the molded article comprises a shell and a bead of foamed pellet material.

[0133] 27. The molded article of any one of embodiments 22-25, wherein the foam comprises a welded bead of foam pellet material.

[0134] 28. The molded article of any one of embodiments 22-25, wherein the foam is a hybrid foam including a foam pellet material composed of a thermoplastic elastomer (TPE-1).

[0135] 29. The following process (i) preparing a foam made of a thermoplastic elastomer (TPE-1), wherein the foam has a storage modulus (G modulus) at 25° C. and 1 Hz in the range of 0.01 to 0.5 MPa, as determined in accordance with Reference Example 1 (molded TPE product), and a molded density in the range of 20 to 400 kg / m, as determined in accordance with Reference Example 2; 3 wherein the foam is a foam pellet material; and (ii) processing the foam into a molded article. A method for producing a molded article, comprising:

[0136] 30. The method of embodiment 29, wherein the treating according to step (ii) is carried out by means of welding, foaming or bonding beads of the foamed pellet material.

[0137] 31. The method of any one of embodiments 29 to 31, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters, thermoplastic olefin-based elastomers, crosslinked thermoplastic olefin-based elastomers, thermoplastic vulcanizates, or thermoplastic styrene-butadiene block copolymers.

[0138] 32. The method of any one of embodiments 29 to 31, 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.

[0139] 33. The method according to any one of embodiments 29 to 32, wherein the thermoplastic elastomer (TPE-1) in a dense state has a G modulus, determined according to Reference Example 6, in the range of 0.8 to 8.5 MPa.

[0140] 34. A molded article obtained or obtainable by the method according to any one of embodiments 29 to 33.

[0141] 35. The article of embodiment 34, wherein the article is a shoe sole, part of a shoe sole, a bicycle saddle, cushioning, a mattress, padding, a backrest, an arm pad, a pad, an underlay, a handle, a protective film, a protector, a damping element, a fall protection mat, an elastic insulation material, a sealant, or a part of an interior or exterior area of ​​an automobile.

[0142] 36. Use of the molded article according to any one of embodiments 22 to 28 or 34 or 35 for the manufacture of floors, mattresses, seating furniture, bicycle saddles, car seats, motorcycle seats, shoe parts such as shoe insoles, packaging, shock absorbers, protectors, fall protection mats, elastic insulation materials or sealing materials.

[0143] The following examples are intended to illustrate the invention and are not intended to limit the subject matter in any way. EXAMPLES

[0144] I. Manufacturing example 1. Preparation of Example Materials and Comparative Materials The production of the example materials TPU1-4 identified below was carried out on a Coperion ZSK58MC twin screw extruder having a processing length of 48D (12 barrels).

[0145] The melt was discharged from the extruder using a gear pump. After filtering the melt, the polymer melt was processed into pellets in an underwater pelletizer and these pellets were continuously dried in a heated fluidized bed at 40-90°C.

[0146] Polyol, chain extender, diisocyanate, and optionally catalyst were metered into the first zone. Further additives were added in zone 8.

[0147] The barrel temperature is in the range of 150-230°C. The melt is poured into an underwater pelletizer with a melt temperature of 180-210°C. The screw speed is 180-240 min -1 The throughput is in the range of 180 to 220 kg / h.

[0148] The amounts of raw materials used in the preparation of the example materials are summarized in Table 1.

[0149] [Table 1]

[0150] This formulation and synthesis results in a thermoplastic polyurethane with the properties listed in Table 2. The storage modulus (G modulus) was determined according to Reference Example 1 (dense pellet material), and the melt flow rate (MFR) of the pellets was measured according to DIN EN ISO1133-2:2012. The conditions used are shown in Table 2.

[0151] [Table 2]

[0152] 2. General manufacturing method by extrusion process in examples and comparative examples After the raw material was produced, it was further processed into expanded thermoplastic polyurethane pellets as follows. For this, the dried TPU was mixed in a twin-screw extruder (ZSK40, Coperion) with further additives, 0.2% talc (particle size 5.6 μm-D50, volume distribution) as nucleating agent, optionally TPU mixed with 4,4'-diphenylmethane diisocyanate (additive 1) with an average functionality of 2.05 in a separate extrusion step, optionally triacetin (additive 2) as plasticizer, and optionally polystyrene (melt flow rate, 200 ° C / 5 kg: 3 g / 10 min) (additive 3) and melted in the temperature range of 130-220 ° C. CO2 and N2 as blowing agents were injected into the melt in the extruder to compound the thermoplastic polyurethane and other additives to form a homogeneous melt. The compositions of the individual examples and comparative examples are shown in Table 3. The material is then forced by a gear pump (approximately 130-200 °C depending on material composition) into a die plate (approximately 130-200 °C depending on material composition), cut into pellets in the cutting chamber of an underwater pelletizer (UWP), transported with temperature-controlled pressurized water, and expanded in the process. The expanded pellets are separated from the water in a centrifugal dryer, after which the expanded pellets are dried at 50-60 °C for 2 hours. The water temperature and water pressure, amounts of CO2 and N2 used in the individual examples and comparative examples, as well as the mass of beads measured according to Reference Example 4 and the resulting bulk density are shown in Table 3.

[0153] The foam pellet material is processed by an autoclave process, which is a standard process known in the prior art. (i) providing a TPU composition of the present invention; (ii) impregnating the composition with a blowing agent under pressure; and (iii) Expanding the composition using a pressure reduction Manufactured by.

[0154] The amount of the foaming agent used is preferably 0.1 to 40 parts by mass, particularly preferably 0.5 to 35 parts by mass, and particularly preferably 1 to 30 parts by mass, based on 100 parts by mass of the composition (Z) used.

[0155] The impregnation in step (ii) may be carried out in the presence of water and, optionally, a suspending aid, or in the presence of a blowing agent only, in the absence of water.

[0156] The performance of this process in suspension is known to those skilled in the art and is extensively described, for example, in WO2007 / 082838.

[0157] 3. General manufacturing method of the examples and comparative examples using the autoclave process (tank process) 100.0 parts by weight of pellet material (corresponding to 27.5% by weight of the total suspension without blowing agent), 257 parts by weight of water (corresponding to 70.6% by weight of the total suspension without blowing agent), 6.7 parts by weight of calcium carbonate (suspending agent) (corresponding to 1.8% by weight of the total suspension without blowing agent), 0.13 parts by weight of a surface active substance (Lutensol AT25, suspending aid) (corresponding to 0.04% by weight of the total suspension without blowing agent), and an appropriate amount of butane as a blowing agent (based on the amount of pellet material used) were heated with stirring.

[0158] Nitrogen is then further injected into the liquid phase at 50°C to adjust the internal pressure to a given pressure (800 kPa). Expansion by the expansion device then occurs when the impregnation temperature (IMT) is reached and, optionally, after a holding time (HZ), the final impregnation pressure (IMP) is established. Here, the gas space is adjusted to a constant discharge pressure (AP) and kept constant during the expansion. The expansion jet downstream of the expansion device can optionally be cooled with water at a defined temperature and with a defined volumetric flow rate (water quenching).

[0159] The retention time refers to the time during which the temperature of the liquid phase is in the range from 5°C lower than the impregnation temperature to 2°C higher than the impregnation temperature.

[0160] The suspending agent / suspending aid system (dispersant / surfactant) is removed, and after drying, the bulk density (SD) of the resulting foamed beads is measured according to Reference Example 4.

[0161] The exact manufacturing parameters and the bulk densities of the resulting batches are given in Table 4.

[0162] [Table 3]

[0163] [Table 4]

[0164] The foamed pellets produced by the extrusion and tank processes were then contacted with steam and fused to square slabs with a side length of 200 mm and a thickness of 20 mm in a molding machine from Kurtz ersa GmbH (Energy Foamer K68). The fusion parameters for the individual examples and comparative examples are selected so as to obtain as few as possible collapsed eTPU beads on the surface of the final molded part. In each experiment, a cooling time of 120 seconds was always provided at the fixed and moving ends of the mold. The respective steaming conditions are given in Table 5 in the form of steam pressure and steaming time. The obtained slabs were heated at 70 ° C for 4 hours.

[0165] [Table 5]

[0166] The G elastic modulus of the welded molded article was measured in accordance with Reference Example 1 (TPE molded article). The results are summarized in Table 6.

[0167] The G modulus of each of the loose individual expanded beads (Examples 1 to 8) was measured in accordance with Reference Example 1 (expanded pellet material) and is summarized in Table 6.

[0168] [Table 6]

[0169] The comfort of seating furniture and mattresses is generally evaluated by the SAG factor (determined according to DIN EN ISO2439:2009-05). The SAG factor is calculated from the ratio of the indentation hardness at 65% to the indentation hardness at 25% using a punch with an area smaller than the test specimen. As an amendment to the standard, the various examples and comparative examples were evaluated using the compression hardness judgment and the comfort factor was determined according to Reference Example 3.

[0170] The density of the molded body was measured in the same manner as in Reference Example 2.

[0171] The compression hardness was measured in accordance with Reference Example 5.

[0172] The results of the compression hardness tests of the examples and comparative examples are summarized in Tables 7 and 8. Table 7 shows the compression hardness for the first cycle, and Table 8 shows the values ​​for different cycles. The indication of the cycles is important in that the eTPU changes as a result of the first compression. As a result, the compression hardness measured in the next cycle is significantly lower. From the fourth cycle onwards, at the latest, the changes are less pronounced, as shown by an example in Table 8. The measurements for the four cycles were carried out on a part made from the eTPU of Comparative Example 1.

[0173] [Table 7]

[0174] [Table 8]

[0175] The G modulus of the redensified TPU composed of expanded TPU was determined according to Reference Example 6 (production of injection-molded slabs) and Reference Example 1 (determination of the G modulus (densified material)).

[0176] 4. Examples of manufacturing hybrid materials from slabstock foam (binder) and eTPU (Examples 17 to 22) The beads prepared above were used to produce moldings with a PU foam system as binder. For this, the liquid formulation components were first mixed according to the recipe for component A (Table 10) and then mixed with component B (Table 11) in a mixing ratio of 100:104 for 10 seconds using a laboratory stirrer (model EWTHV-05 from Vollrath GmbH). The reacted PU system was then immediately weighed onto the beads in a ratio of 20% by weight PU system:80% by weight beads and intensively mixed for 30 seconds with a laboratory stirrer in a polyethylene plastic container before being pumped into the mold. The mold used was a wooden open frame with internal dimensions of 20x20x1.4 cm, treated with a release agent. After smoothing the surface with a Teflon film, the system was left in the mold for at least 30 minutes to harden. Before testing the test slabs, they were stored at room temperature for at least 2 days to ensure that the PU system had fully reacted. The compression hardness of the obtained test slabs is shown in Table 12. The compression hardness and density were measured in the same manner as for the eTPU slabs.

[0177] 5. Comparative Examples of Producing Hybrid Materials from Slabstock Foam (Binder) and eTPU (Comparative Examples 8 to 10) 5.1. Comparative Example 8 Molded bodies were produced using the PU foam system from Example 7. For this, the liquid formulation components were first mixed according to the recipe (Table 10) and then mixed with component B (Table 11) in a mixing ratio of 100:104 using a laboratory stirrer (model EWTHV-05 from Vollrath GmbH) for 10 seconds. The residual NCO content of component B was 18%. The residual NCO content is determined by potentiometric titration with chlorobenzene-amine solution.

[0178] The reacted PU system was then immediately weighed onto the beads in a ratio of 61.5% PU system:38.5% beads by weight and mixed intensively for 30 seconds with a laboratory stirrer in a polyethylene plastic container before being poured into a mould. The mould used was a wooden mould with inner dimensions of 20x20x2cm covered with a Teflon film. After filling, the mould was tightly closed with a lid. The mouldings were left in the mould for 120 minutes to ensure that the PU foam system was fully cured. Before testing the test slabs were stored at room temperature for at least 2 days to ensure that the PU system was fully reacted.

[0179] 5.2. Comparative Example 9 Using the PU system from Example 6, a molded article was produced in the same manner as in Comparative Example 9.

[0180] 5.3. Comparative Example 10 Using the PU system from Comparative Example 1, a molded body was produced in the same manner as in Comparative Example 9.

[0181] [Table 9]

[0182] [Table 10]

[0183] [Table 11]

[0184] [Table 12]

[0185] II. Measurement method 1. Reference Example 1: Determination of G Modulus (Storage Modulus) 1.1.Dense materials The G modulus of dense thermoplastic elastomers is determined by dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1-7:2018-03 on test specimens, more specifically on injection-molded slabs. The test specimens are previously heated at 100°C for 20 h and then measured in the same manner with a stepwise heating program of 5°C from -80 to 120°C at a continuous heating rate of 2°C / min, under torsion, 1 Hz, from which the storage modulus at 25°C (G modulus) is determined.

[0186] 1.2.Foam pellet material To measure the G modulus of individual loose, liberated foamed beads, the beads are first poured into a cylinder and repeatedly compressed to the highest possible packing density, after which the compression modulus is determined under quasi-static compression from which the storage modulus (G modulus) is calculated.

[0187] 1.3. eTPE Molded Body The G modulus of the welding examples and comparative welding examples is determined on the eTPE moulded parts by dynamic mechanical analysis (DMA) according to DIN EN ISO6721-1-7:2018-03. The eTPE moulded parts are previously heated at 70 ° C for 4 h and then measured in the same way with a stepwise heating program of 5 ° C from -80 to 120 ° C at a continuous heating rate of 2 ° C / min, under torsion, 1 Hz, from which the G modulus at 25 ° C is determined. To prepare the 50 × 12 × 5 mm test specimens used for this purpose, first an eTPU slab (200 × 200 × 10 mm or 20 mm) is cut in half lengthwise. The top and bottom skins are then peeled off with a splitter to obtain a sheet with a thickness of 5 mm. Care is taken to cut the sheet from the middle of the slab. Test specimens are then punched out of this sheet.

[0188] 2. Reference Example 2: Determination of molding density Before the actual test, the length and width of the specimen are measured using calipers (accuracy: ±0.01mm, both measured at one point in the center of the part) and the mass of the specimen is measured using a precision balance (accuracy: ±0.001g). The thickness of the specimen is measured on a compression hardness tester using a "crosshead" displacement measuring system (accuracy: ±0.25mm). Its volume and density can then be calculated from the measured values.

[0189] 3. Reference Example 3: Determination of comfort coefficient Similar to the SAG factor, the comfort factor is considered as the ratio of the compression hardness (StH) at 65% compression to the compression hardness at 25% compression. Comparative measurements of eTPU slabs and soft foam slabs have shown that the two measurement methods (SAG value measurement and compression hardness test) show the same tendency, even when comparing different materials. For eTPU, the absolute values ​​of the determined ratios may differ from each other. This is because, unlike the compression hardness measurement, the measured values ​​for the SAG factor determination are influenced by the presence and condition of a skin on the test specimen. However, the compression hardness can also be used to compare different materials, since the influence of the skin on the properties can also vary greatly depending on the application of the component in question.

[0190] 4. Reference Example 4: Determination of bulk density The bulk density of the bead foam is determined gravimetrically via the volume and mass of the bed layer of particles in a container (10 L). This is done by filling a funnel with about 11-12 L of beads, with the bottom outlet closed. When filling, the 10 L container is placed directly under and in the center of the funnel. The closure of the funnel is then opened so that the beads flow evenly into the container of the specified volume (10 L). The surface of the container is smoothed with a flat edge blade at an angle of 45°. Then, using a balance, its mass is measured gravimetrically. For this, it is necessary to measure the mass of the empty container beforehand, or to subtract the mass of the empty container later to obtain the mass of the bed layer. The value obtained by dividing the mass by the volume corresponds to the bulk density of the bead foam. It is necessary to take care not to subject the container to vibrations or shocks, both when filling the sample container with beads and when carrying the container to the balance.

[0191] 5. Reference Example 5: Determination of Compressive Hardness The test specimens used for the measurements (50 mm x 50 mm x original thickness of the test slab (usually 20 mm, thickness may vary slightly due to shrinkage, skin not removed)) are cut with a band saw from the test slabs (200 x 200 x 20 mm, dimensions may vary slightly due to shrinkage). The slabs are preconditioned for 16 hours under standard climatic conditions (23 ± 2°C, humidity 50 ± 5%). The compression hardness tests are also carried out under these climatic conditions.

[0192] Before the actual test, the length and width of the test piece are measured using a vernier caliper (accuracy: ±0.01 mm, both measured at one point in the center of the part), and the mass of the test piece is measured using a precision balance (accuracy: ±0.001 g).

[0193] The compressive hardness was measured using a 50 kN force transducer (class 1 according to DIN EN ISO7500-1:2018-06), a crosshead displacement transducer (class 1 according to DIN EN ISO9513:2013), two parallel non-perforated pressure plates (diameter 200 mm, maximum permissible force 250 kN, maximum permissible surface pressure 300 N / mm 2) for the determination of the density of the specimen. The length, width and mass are incorporated in the ZwickRoell test method. The thickness of the specimen is determined on a universal testing machine using a "crosshead" displacement measuring system (accuracy: ±0.25 mm). The measurement itself is carried out at a test speed of 50 mm / min and an initial force of 1 N. The stress values ​​at compression rates of 10, 25, 50, 65 and 75% are recorded respectively. The evaluation is based on the values ​​for the first and fourth compressions. The compressive hardness is calculated according to formula (4). The compressive hardness σ here is the compressive stress (kPa) determined for a deformation during the loading process (e.g. 50%). σ = (F x / A0)×1000 (4) F x = Force at x% deformation [N] A0 = initial cross-sectional area of ​​the test piece [mm 2 ]

[0194] 6. Reference Example 6: Determination of the G modulus of densified foam Test pieces for determining the G modulus from the eTPU material are produced by injection molding. To do this, the eTPU material is removed from the component and then ground in a grinder (Dreher S26 / 26GFX-Spez-L 8 mm sieve pass). The eTPU pieces obtained are then dried for 3 hours at 110 ° C and processed into 2 mm thick test pieces in an injection molding machine under conditions of maximum cylinder temperature 210-215 ° C, die temperature 210-220 ° C, mold temperature 35 ° C (cycle time 75 seconds). The test pieces thus obtained are immediately heated at 100 ° C for 20 hours. The storage modulus (G modulus) was then determined according to Reference Example 1 (dense material).

[0195] References Ullmann's "Encyklopaedie der technischen Chemie" [Encyclopedia of Industrial Chemistry], 4th edition, vol. 20, pp. 416ff. WO94 / 20568 WO2007 / 082838A1 WO2017 / 030835 WO2013 / 153190A1 WO2010 / 010010 “Handbook of Thermoplastic Elastomers”, 2nd edition, June 2014 “Polymer Chemistry”, Interscience Publ., New York, 1961, pp. 111-127. “Kunststoffhandbuch” [Plastics Handbook], Volume VIII, C. Hanser Verlag, Munich 1973 Journal of Polymer Science, Part A1, 4, pp. 1851-1859 (1966) “Kunststoffhandbuch” [Plastics Handbook], Volume VII, Carl Hanser Verlag, Munich 1966 (pp. 103-113) “Kunststoffhandbuch” [Handbook of Plastics], Volume 7, [Polyurethanes], Carl Hanser Verlag, 3rd edition 1993, Chapter 3 “Integralschaumstoff” [Integral Form], Carl-Hanser-Verlag, Munich and Vienna, 1975 “Kunststoffhandbuch” [Plastics Handbook, Volume 7, [Polyurethanes], 3rd edition 1993, Chapter 7 EP1979401B1 EP3053732A1 WO2016 / 146537A1

Claims

1. A molded article comprising a foam made of a thermoplastic elastomer (TPE-1), wherein the storage modulus (G modulus) of the foam at 25° C. and 1 Hz determined in accordance with Reference Example 1 (TPE molded article) is in the range of 0.01 to 0.5 MPa, and the molded density of the foam determined in accordance with Reference Example 2 is 20 to 400 kg / m ３ is in the range of The foam is a foam pellet material; The molded article, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethane, thermoplastic polyetheramide, polyetherester, polyesterester, thermoplastic olefin-based elastomer, crosslinked thermoplastic olefin-based elastomer, or thermoplastic styrene-butadiene block copolymer.

2. 2. The molded article according to claim 1, wherein the thermoplastic elastomer (TPE-1) in a dense state has a G modulus, determined according to Reference Example 6, in the range of 0.8 to 8.5 MPa.

3. 3. The molded article of claim 1 or 2, wherein the molded article comprises a shell and beads of foamed pellet material.

4. 3. The molded article of claim 1 or 2, wherein the molded article comprises fused beads of foamed pellet material.

5. The molded article according to any one of claims 1 to 4, wherein the molded article comprises a hybrid material comprising a foamed pellet material composed of a thermoplastic elastomer (TPE-1) and a matrix material.

6. (i) A process for providing a foamed product made of a thermoplastic elastomer (TPE-1), wherein the storage modulus (G modulus) of the foamed product at 25° C. and 1 Hz determined in accordance with Reference Example 1 (molded TPE product) is in the range of 0.01 to 0.5 MPa, and the molded density of the foamed product determined in accordance with Reference Example 2 is in the range of 20 to 400 kg / m ３ is in the range The foam is a foam pellet material; the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyetheramides, polyetheresters, polyesteresters, thermoplastic olefin-based elastomers, crosslinked thermoplastic olefin-based elastomers, or thermoplastic styrene-butadiene block copolymers; and (ii) processing the foam into a molded article. A method for producing a molded article, comprising:

7. 7. The method of claim 6, wherein the processing according to step (ii) is carried out by welding, foaming or bonding beads of the foamed pellet material.

8. Use of the molded article according to any one of claims 1 to 5 for the manufacture of floors, mattresses, seating furniture, bicycle saddles, car seats, motorcycle seats, shoe parts such as shoe insoles, packaging, shock absorbers, protectors, fall protection mats, elastic insulation or sealing materials.

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