Comfort eTPU

Abstract

Molded articles contain a foam composed of a thermoplastic elastotner (TPE-1). The foam has a storage modulus (G modulus) at 25° C. and 1 Hz within the range from 0.01 to 0.5 MPa, a molding density within the range from 20 to 400 kg/m.sup.3, and a comfort factor of greater than 4. A process produces molded articles of this kind, and the molded article can be used for producing floors, mattresses, seating furniture, bicycle saddles, car seats, motorcycle seats, components of a shoe, shoe inserts, packaging, shock absorbers, protectors, fall protection mats, elastic insulating material, or sealing material.

Claims

1-11. (canceled)

12. A molded article, comprising: a foam composed of a thermoplastic elastomer (TPE-1), wherein the foam has a storage modulus (G modulus) at 25° C. and 1 Hz within a range from 0.01 to 0.5 MPa, determined by a dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1-7:2018-03, and a molding density within a range from 20 to 400 kg/m.sup.3, wherein the foam is a foamed pellet material, and wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester, a thermoplastic olefin-based elastomer, a crosslinked thermoplastic olefin-based elastomer, a thermoplastic vulcanizate, and a thermoplastic styrene-butadiene block copolymer.

13. The molded article according to claim 12, wherein the thermoplastic elastomer (TPE-1) in a compact state has a G modulus at 25° C. and 1 Hz within a range from 0.8 to 8.5 MPa, determined by the dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1-7:2018-03.

14. The molded article according to claim 12, wherein the molded article comprises a shell and beads of the foamed pellet material.

15. The molded article according to claim 12, wherein the foam consists of welded beads of the foamed pellet material.

16. The molded article according to claim 12, wherein the foam is a hybrid foam comprising the foamed pellet material composed of the thermoplastic elastomer (TPE-1).

17. A process for producing a molded article, comprising: (i) providing a foam composed of a thermoplastic elastomer (TPE-1), wherein the foam has a storage modulus (G modulus) at 25° C. and 1 Hz within the range from 0.01 to 0.5 MPa, determined by a dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1-7:2018-03, and a molding density within the range from 20 to 400 kg/m.sup.3, wherein the foam is a foamed pellet material, wherein the thermoplastic elastomer (TPE-1) is selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester, a thermoplastic olefin-based elastomer, a crosslinked thermoplastic olefin-based elastomer, a thermoplastic vulcanizate, and a thermoplastic styrene-butadiene block copolymer; and (ii) processing the foam into a molded article.

18. The process according to claim 17, wherein the processing in (ii) takes place by welding, foaming, or bonding beads of the foamed pellet material.

19. A molded article, obtained or obtainable by the process according to claim 17.

20. The molded article according to claim 19, wherein the molded article is a shoe sole, a part of a shoe sole, a bicycle saddle, a cushioning, a mattress, a 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 insulating material, a sealing material or a component in an automotive interior and exterior sector.

21. A method, comprising: producing an article with the molded article according to claim 12, wherein the article is a floor, a mattress, a seating furniture, a bicycle saddle, a car seat, a motorcycle seat, a component of a shoe, a shoe insert, a packaging, a shock absorber, a protector, a fail protection mat, an elastic insulating material, or a sealing material.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0148] FIG. 1 shows a diagram comparing the stress-strain curves of an example according to the invention with that of a comparative example. The force (y-axis) is here plotted against the distance (%, x-axis).

[0149] The examples that follow serve to illustrate the invention but are in no way limiting with regard to the subject matter of the present invention.

EXAMPLES

[0150] I. Production Examples

1. Preparation of the Example Materials and Comparative Materials

[0151] The production of the example materials TPU 1 to 4 specified hereinbelow was carried out in a ZSK58 MC twin-screw extruder from Coperion, having a processing length of 48D (12 barrels).

[0152] The melt was discharged from the extruder by means of a gear pump. After filtration of the melt. the polymer melt was processed by means of an underwater pelletization system into pellets that were dried continuously at 40-90° C. in a heated fluidized bed.

[0153] The polyol, the chain extender and the diisocyanate and optionally a catalyst were metered into the first zone. The supply of further additives took place in zone 8.

[0154] The barrel temperatures are in the range of 150-230° C. The melt is discharged into the underwater pelletization system with melt temperatures of 180-210° C. The screw speed is between 180 and 240 min'. The throughput is in the range of 180-220 kg/h.

[0155] The amounts of the feedstocks used for the production of the example materials are summarized in Table 1.

TABLE-US-00001 TABLE 1 Composition of the materials used Feedstocks TPU 1 TPU 2 TPU 3 TPU 4 TPU 5 Polyether polyol having an OH value of 1000 1000 1000 1000 112.2 and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) [parts by weight] Polyester polyol having an OH value of 56 1000 and exclusively primary OH groups (based on ethane-1,2-diol and butane-1,4-diol in a ratio of 1:1 and adipic acid, functionality: 2) [parts by weight] Aromatic isocyanate (methylene diphenyl 455.5 260 500 630 503 4,4′-diisocyanate) [parts by weight] Butane-1,4-diol [parts by weight] 89.9 136.74 91.1 Monoethylene glycol [parts by weight] 51.03 32.23 Acetyl tributyl citrate [parts by weight] 382.86 231.17 Sterically hindered amine as light stabilizer 3.83 3.28 3.28 (HALS) [parts by weight] Phenol-based primary antioxidant 9.57 13.08 16.1 17.85 16.4 [parts by weight] Wax based on distearylethylenediamide 5.74 4.62 0.4 0.89 1.64 [parts by weight] Oxalanilide-based UV absorber 5.74 4.93 4.93 [parts by weight] Carbodiimide-based hydrolysis inhibitor 10 [parts by weight] Tin(II) isooctoate (50% in dioctyl adipate) 50 ppm 50 ppm 50 ppm 50 ppm 50 ppm [parts by weight]

[0156] This blending and synthesis produces thermoplastic polyurethanes having the properties listed in Table 2. The storage modulus (G modulus) was determined in accordance with Reference Example 1 (compact pellet material). The melt flow rate (MFR) was measured on the pellets in accordance with DIN EN ISO 1133-2:2012. The conditions employed are listed in Table 2.

TABLE-US-00002 TABLE 2 Properties of the produced compact example materials MFR (190° C., 3.8 kg) MFR (190° C., 21.6 kg) G modulus DIN EN ISO DIN EN ISO at 25° C. 1133-2: 2012 1133-2: 2012 TPU 1 1.9 MPa 28 TPU 2 1.3 MPa 145 TPU 3 7.3 MPa 31 TPU 4 9.5 MPa 76 TPU 5 8.3 MPa 38

2. General Method of Production for the Examples and Comparative Examples According to the Extrusion Process

[0157] After the feedstocks had been produced, they were further processed into expanded thermoplastic polyurethane pellets as follows. For this, the dried TPUs were mixed in a twin-screw extruder (ZSK 40, Coperion) with further additives 0.2% talc (particle size 5.6 μm—D50, volume distribution) as nucleating agent, optionally a TPU that in a separate extrusion process had been admixed with 4,4′-diphenylmethane diisocyanate having an average functionality of 2.05 (additive 1), and optionally with triacetin as plasticizer (additive 2) and optionally with a polystyrene (melt flow rate, 200° C./5 kg: 3 g/10 min) (additive 3) and melted within a temperature range from 130 to 220° C. As the blowing agent, CO.sub.2 and N.sub.2 were injected into the melt in the extruder and blended with the thermoplastic polyurethane and the other additives to form a homogeneous melt. The composition of the individual examples and comparative examples is listed in Table 3. The material was then pressed using a gear pump (approx. 130-200° C. depending on the material composition) into a die plate (130-200° C. depending on the material composition), cut into pellets in the cutting chamber of the underwater pelletization system (UWP), and transported away with the temperature-controlled and pressurized water, undergoing expansion in the process. After separating the expanded pellets from the water by means of a centrifugal dryer, the expanded pellets are dried at 50-60° C. for 2 h. The water temperature and the water pressure used for the individual examples and comparative examples, the amount of CO.sub.2 and N.sub.2, and the bead mass and the resulting bulk density in accordance with Reference Example 4 are listed in Table 3.

[0158] The foamed pellet material was produced by the autoclave process, a standard process known in the prior art, through [0159] (i) providing a TPU composition of the invention; [0160] (ii) impregnating the composition with a blowing agent under pressure; [0161] (iii) expanding the composition by means of a pressure drop.

[0162] The amount of blowing agent is preferably 0.1 to 40, especially 0.5 to 35, and particularly preferably 1 to 30, parts by weight based on 1.00 parts by weight of the amount of composition (7) used.

[0163] The impregnation in step (ii) may take place in the presence of water and optionally suspension auxiliaries or solely in the presence of the blowing agent and in the absence of water.

[0164] The performance of the process in suspension is known to those skilled in the art and has been described extensively, for example in WO2007/082838.

3. General Method of Production for the Examples and Comparative Examples According to the Autoclave Process (Tank Process)

[0165] 100.0 parts by weight (corresponding to 27.5% by weight based on the overall suspension without blowing agent) of the pellet material, 257 parts by weight (corresponding, to 70.6% by weight based on the overall suspension without blowing agent) of water, 6.7 parts by weight (corresponding to 1.8% by weight based on the overall suspension without blowing agent) of calcium carbonate (suspending agent), 0.13 parts by weight (corresponding to 0.04% by weight based on the overall suspension without blowing agent) of a surface-active substance (Lutensol AT 25, suspension auxiliary), and the appropriate amount of butane as blowing agent (based on the amount of pellet material used) were heated while stirring.

[0166] Nitrogen was then additionally injected into the liquid phase at 50° C. and the internal pressure was adjusted to a predefined pressure (800 kPa). This is followed, on reaching the impregnation temperature (IMT) and optionally after observing a hold time (HZ), and at the impregnation pressure (IMP) established at the end, by expansion via an expansion device. The gas space is here adjusted to a fixed expulsion pressure (AP) and kept constant during the expansion. The expansion jet downstream of the expansion device may optionally be cooled with a defined volume flow rate of water at a defined temperature (water quench).

[0167] The hold time defines the time at which the temperature of the liquid phase is within a temperature range from 5° C. below the impregnation temperature to 2° C. above the impregnation temperature.

[0168] After removal of the suspending, agent/suspension auxiliary system (dispersant/surfactant) and drying, the bulk density (SD) of the resulting foam beads is measured in accordance with Reference Example 4.

[0169] The exact production parameters and the bulk density of the resulting batches are listed in Table 4.

[0170] Tables 3a and 3b: Data for the examples and comparative examples (extrusion process)

TABLE-US-00003 Proportion Proportion Proportion Proportion of of of Bead eTPU TPU of ex. m. additive 1 additive 2 additive 3 mass beads used (% by wt.) (% by wt.) (% by wt.) (% by wt.) (mg) Ex. 1 TPU 1 98.8 1.0 — — 23 Ex. 2 TPU 1 99.3 0.5 — — 23 Ex. 3 TPU 1 98.3 1.5 — — 24 Ex. 4 TPU 1 98.8 1.0 — — 23 Ex. 5 TPU 1 93.8 1.0 5.0 — 23 Ex. 6 TPU 2 95.8 4.0 — — 23 Comp. TPU 3 99.4 0.6 — — 32 Ex. 1 Comp. TPU 4 88.6 0.6 — 10 32 Ex. 2

TABLE-US-00004 Water Water Bulk density CO.sub.2 N.sub.2 pressure temperature eTPU after 10 days (% by (% by in the UWP in the UWP beads (g/l) wt.) wt.) (bar) (° C.) Ex. 1 168 1.4 0.21 9.4 37 Ex. 2 175 1.4 0.21 9.4 38 Ex. 3 169 1.4 0.21 9.4 37 Ex. 4 160 1.4 0.21 9.4 40 Ex. 5 160 1.4 0.21 9.4 36 Ex. 6 117 1.0 0.21 9.4 36 Comp. 161 1.5 0.1 7.1 40 Ex. 1 Comp. 196 1.5 0.15 7.1 43 Ex. 2

TABLE-US-00005 TABLE 4 Data for the examples and comparative examples (autoclave process) Bulk Impreg- density Applied N.sub.2 nation Impreg- Particle after Butane pressure Hold temper- nation Expulsion TPU mass 10 days (% by at 50° C. time ature pressure pressure Water eTPU used (mg) (g/l) wt.) (bar) (min) (° C.) (bar) (bar) quench Ex. 7 TPU 3 16 82 24 8 3 114 23.2 34 yes Ex. 8 TPU 5 35 70 24 8 10 123 27 34 no Comp. TPU 5 32 112 24 8 3 126 29.4 34 yes Ex. 3

[0171] The expanded pellets, produced by the extrusion process as well as by the tank process, were then welded in a molding machine from Kurtz ersa GmbH (Energy Foamer K68) into square slabs having a side length of 200 mm and a thickness of 20 mm by contacting with steam. The welding parameters for the various examples and comparative examples are chosen such that the surfaces of the final molding exhibit the lowest possible number of collapsed eTPU beads. In each experiment, a cooling time of 120 s was always set at the end for the fixed and the moving side of the mold. The respective steam-treatment conditions are listed in Table 5 in the form of the steam pressures and the respective steam-treatment time. The slabs obtained were heated at 70° C. for 4 h.

[0172] Tables 5a and 5b: Steam overpressures and times for the welding of the materials of the examples and comparative examples

TABLE-US-00006 Gap Gap Gap Gap steaming on steaming on steaming on steaming on eTPU Gap fixed side fixed side moving side moving side Component used (mm) (bar) (s) (bar) (s) Ex. 9 Ex. 1 22 — — 0.4 18 Ex. 10 Ex. 2 22 — — 0.5 15 Ex. 11 Ex. 3 22 — —  0.75 18 Ex. 12 Ex. 4 22 — — 0.5 15 Ex. 13 Ex. 5 22 — — 0.2 18 Ex. 14 Ex. 6 22 0.8 20 0.8 20 Ex. 15 Ex. 7 10 — — — — Ex. 16 Ex. 8 22 — — — — Comp. Comp. 22 — — 0.9 18 Ex. 4 Ex. 1 Comp. Ex. 7 24 — — — — Ex. 5 Comp. Comp. 22 — — — — Ex. 6 Ex. 3 Comp. Comp. 22 — — — — Ex. 7 Ex. 2

TABLE-US-00007 Cross-steam Cross-steam Cross-steam Cross-steam on fixed on fixed on moving on moving Autoclave side/back- side/back- side/back- side/back- steam fixed/ pressure pressure pressure pressure moving side Autoclave Component (bar) (s) (bar) (s) (bar) steam (s) Ex. 9 0.4 10 — — 0.5/0.5 10 Ex. 10 0.5 15 — — 0.5/0.5 10 Ex. 11 0.8 15 — — 0.8/0.8 10 Ex. 12 0.4 10 — — 0.4/0.4 10 Ex. 13 — — — — 0.4/0.4 10 Ex. 14 0.9 20 — — 0.9/0.9 10 Ex. 15 0.8/0.8 30/20 — — 0.5/0.5 15 Ex. 16 1.3/1.2 30/25 1.3/1.2 30/25 1.8/1.8 40 Comp. 1.3 30 1.3 30 1.3/0.8 10 Ex. 4 Comp. .sup. 1/0.8 30/20 — — 0.6/0.6 15 Ex. 5 Comp. .sup. 1/0.9 40/30 0.7/0.6 40/30 1.8/1.8 40 Ex. 6 Comp. 0.8/0.7 20/25 0.8/0.7 20/25 1.95/1.05 60 Ex. 7

[0173] The G modulus of the welded moldings is determined in accordance with Reference Example 1 (TPE molding). The results are summarized in Table 6.

[0174] The G modulus of individual, loose foam beads (Examples 1 to 8) was determined in accordance with Reference Example 1 (foamed pellet material) and is summarized in Table 6.

TABLE-US-00008 TABLE 6 G modulus (storage modulus) measured at 25° C. and 1 Hz G modulus at 25° C. Examples [MPa] Ex. 1 to 8 <0.5 Ex. 9 0.21 Ex. 10 0.19 Ex. 11 0.22 Ex. 12 0.20 Ex. 13 0.17 Ex. 14 0.11 Ex. 16 0.45 Comp. Ex. 4 0.52 Comp. Ex. 5 0.60 Comp. Ex. 6 0.72 Comp. Ex. 7 1.67

[0175] The comfort of seating furniture and mattresses is commonly evaluated by means of the SAG factor (determined in accordance with DIN EN ISO 2439:2009-05). The SAG factor is calculated from the ratio of the indentation hardness at an indentation depth of 65% to the indentation hardness at an indentation depth of 25% using a punch that is smaller in area than the test specimen. As a modification of the standard, the various examples and comparative examples were evaluated using a determination of compression hardness to determine a comfort factor in accordance with Reference Example 3.

[0176] The density of the molding was determined in accordance with Reference Example 2.

[0177] The compression hardness was determined in accordance with Reference Example 5.

[0178] The results of the compression hardness test for the examples and comparative examples are summarized in Tables 7 and 8. Table 7 shows the compression hardnesses from the 1st cycle and Table 8 shows the values from different cycles. The specification of the cycle is important in that the eTPU changes as a result of the first compression, As a result, the compression hardnesses measured in the next cycle are significantly lower. From no later than the 4th cycle onwards, the change is much less pronounced, which is illustrated by way of example by an example in Table 8. The measurements for the 4 cycles were performed on components produced from eTPU from Comparative Example 1.

TABLE-US-00009 TABLE 7 Results of the compression hardness test (1st cycle) of the welded slabs of the examples and comparative examples Density of the test Compression Compression Compression Compression Compression StH 65%/ specimen hardness 10% hardness 25% hardness 50% hardness 65% hardness 75% StH 25% Name (kg/m.sup.3) (kPa) (kPa) (kPa) (kPa) (kPa) (kPa/kPa) Ex. 9 336 14 55 220 587 2018 10.7 Ex. 10 332 17 59 214 573 1967 9.7 Ex. 11 341 17 61 234 649 2423 10.6 Ex. 12 323 15 55 207 540 1785 9.8 Ex. 13 301 12 45 171 437 1306 9.7 Ex. 14 281 7 31 122 307 790 9.9 Ex. 15 182 28 72 180 363 809 5.0 Ex. 16 143 26 67 160 305 591 4.5 Comp. 274 30 90 302 781 2438 8.7 Ex. 4 Comp. 238 53 127 292 619 1610 4.9 Ex. 5 Comp. 236 77 156 330 652 1473 4.2 Ex. 6 Comp. 369 167 415 1241 4134 19230 10.0 Ex. 7

TABLE-US-00010 TABLE 8 Results of the compression hardness test (for different cycles) of the welded slabs of the examples and comparative examples Test specimen Compression Compression Compression Compression Compression StH 65%/ density Cycle hardness 10% hardness 25% hardness 50% hardness 65% hardness 75% StH 25% Name (kg/m.sup.3) (—) (kPa) (kPa) (kPa) (kPa) (kPa) (kPa/kPa) Ex. 15 182 4 17 56 152 325 772 5.8 Comp. 238 1 54 127 292 619 1608 4.9 Ex. 5 2 37 103 256 563 1542 5.4 3 34 100 250 550 1528 5.5 4 33 98 247 544 1517 5.6 Comp. 236 4 42 114 274 572 1410 5.0 Ex. 6

[0179] The G modulus of recompacted TPU composed of expanded TPU was determined in accordance with Reference Example 6 (production of the injection molded slabs) and Reference Example 1 (determination of the G modulus (compact material)).

4. Examples for the Production of Hybrid Materials from Slabstock Foam (Binder) and eTPU (Examples 17 to 22)

[0180] The beads produced above were used to produce moldings using a PU foam system as binder. For this, the liquid formulation components were first compounded according to the formulation of component A (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. This reacting PU system was then immediately weighed out onto the beads in a ratio of 20% by weight of PU system:80% by weight of beads and mixed intensively with the aid of a laboratory stirrer in a plastic vessel made of polyethylene for 30 sec prior to being discharged into the mold. The molds used were open wooden frames treated with release agent and having internal dimensions of 20×20×1.4 cm. After smoothing the surface with Teflon film, the system was left in the mold to harden for at least 30 min. Before the test slabs were tested, they were stored at room temperature for at least 2 days in order to ensure that the PU system had reacted completely. The compression hardnesses of the test slabs obtained are listed in Table 12. The compression hardnesses and the density are determined in the same way as for the eTPU slabs.

5. Comparative Examples for the Production of Hybrid Materials from Slabstock Foam (Binder) and eTPU (Comparative Examples 8 to 10)

5.1 Comparative Example 8

[0181] Moldings were produced from Example 7 using a PU foam system. For this, the liquid formulation components were first compounded according to the formulation (Table 1.0) 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 sec. Component B had a residual NCO content of 18%. The residual NCO content is determined by potentiometric titration using, a chlorobenzene-amine solution.

[0182] This reacting PU system was then immediately weighed out onto the beads in a ratio of 61.5% by weight of PU system:38.5% by weight of beads and mixed intensively with the aid of a laboratory stirrer in a plastic vessel made of polyethylene for 30 sec prior to being poured into the mold. The mold used a wooden mold coated with Teflon film and having internal dimensions of 20×20×2. cm. After being filled, the mold was tightly closed with a lid. To ensure the PU foam system had hardened sufficiently, the moldings were left in the mold for 120 minutes. Before the test slabs were tested, they were stored at room temperature for at least 2 days in order to ensure that the PU system had reacted completely.

5.2 Comparative Example 9

[0183] Moldings were produced from Example 6 using a PU system in an analogous manner to Comparative Example 9.

5.3 Comparative example 10

[0184] Moldings were produced from Comparative Example 1 using a PU system in an analogous manner to Comparative Example 9.

TABLE-US-00011 TABLE 9 Composition of component A OH/NH H2O Name % by wt. value [%] Polyether polyol having an OH value 67.0 56.0 0.015 of 56 and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) [parts by weight] Castor oil 21.0 160.5 0.030 Monoethylene glycol 4.6 1810.0 0.200 Hydroxyphenylbenzotriazole-based UV 3.0 180.0 0.040 stabilizer Silicone-based surfactant 2.0 115.0 0.200 50% water and 50% fatty acid sulfonate 2.0 0.0 50.000 1-Methylimidazole 0.4 4.0 0.500

TABLE-US-00012 TABLE 10 Composition of component B having a residual NCO of 18% Name % by wt. Aromatic isocyanate (4,4′-methylenediphenyl diisocyanate) 61.4 [parts by weight] Carbodiimide-modified MDI 2 (4,4′MMDI[76]/CARBODIIMIDMOD. 4,4′MMDI[24]) Phenol-based primary antioxidant 0.09 Diglycol bis(chloroformate) 0.01 Polyol blend of 89.05% polypropylene glycol having a 36.5 number-average molecular weight (Mn) of 2000 g/mol (functionality = 2) and 10.95% tripropylene glycol

TABLE-US-00013 TABLE 11 Results of the compression hardness test (1st cycle) of the hybrid materials composed of binder and eTPU for the examples and comparative examples (slab thickness 20 mm). Component Compression Compression Compression Compression Compression StH 65%/ eTPU density hardness 10% hardness 25% hardness 50% hardness 65% hardness 75% StH 25% used (kg/m.sup.3) (kPa) (kPa) (kPa) (kPa) (kPa) (kPa/kPa) Ex. 17 Ex. 2 235 16 39 129 350 1004 9.0 Ex. 18 Ex. 1 238 18 42 134 364 1050 8.7 Ex. 19 Ex. 3 240 20 48 150 419 1211 8.7 Ex. 20 Ex. 4 215 13 34 116 320 878 9.4 Ex. 21 Ex. 5 198 7 20 79 233 679 11.7 Ex. 22 Ex. 6 180 8 21 80 213 509 10.1 Comp. Ex. 7 351 114 208 517 1263 3939 6.1 Ex. 8 Comp. Ex. 6 253 101 192 445 986 2616 5.1 Ex. 9 Comp. Comp. 321 172 286 625 1460 4319 5.1 Ex. 10 Ex. 1

TABLE-US-00014 TABLE 12 Results of the compression hardness test (4th cycle) of the hybrid materials composed of binder and eTPU for the examples and comparative examples (slab thickness 20 mm) Component Compression Compression Compression Compression Compression StH 65%/ eTPU density hardness 10% hardness 25% hardness 50% hardness 65% hardness 75% StH 25% used (kg/m.sup.3) (kPa) (kPa) (kPa) (kPa) (kPa) (kPa/kPa) Comp. Ex. 7 351 46 125 353 913 3436 7.3 Ex. 8 Comp. Ex. 6 253 48 129 337 776 2311 6.0 Ex. 9 Comp. Comp. 321 60 156 398 1005 3707 6.4 Ex. 10 Ex. 1

[0185] II. Measurement Methods

1. Reference Example 1: Determination of the G Modulus (Storage Modulus)

[0186] 1.1 Compact Material

[0187] The G modulus of a compact thermoplastic elastomer is determined by means of a dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1-7:2018-03 on test specimens, more particularly on injection molded slabs, which have previously been heated at 100° C. for 20 h, but measured from −80 to 120° C. with a 5° C. stepped heating program in a comparable manner at a continuous heating rate of 2° C./min, under torsion, at 1 Hz, and the storage modulus (G modulus) at 25° C. is determined therefrom.

[0188] 1.2 Foamed Pellet Material

[0189] To determine the G modulus of individual, loose foam beads, these are first poured into a cylinder and compacted by repeated compression so that the highest possible packing density is achieved. Subsequently, the compression modulus, from which the storage modulus (G modulus) is calculated, is then determined under quasi-static compression.

[0190] 1.3 eTPE Moldings

[0191] The G modulus of the welded examples and welded comparative examples is determined by means of a dynamic mechanical analysis (DMA) in accordance with DIN EN ISO 6721-1-7:2018-03 on the eTPE molded articles, which have previously been heated at 70° C. for 4 h, but measured from −80 to 120° C. with a C stepped heating program in a comparable manner at a continuous heating rate of 2° C./min, under torsion, at 1 Hz, and the G modulus at 25° C. determined therefrom. For the production of the test specimens employed for this purpose and having dimensions of 50×1.2×5 mm, an eTPU slab (200×200×1.0 or 2.0 mm) is first cut in half lengthways. The skin is then removed at the top and bottom with a splitting machine so as to obtain a sheet with a thickness of 5 mom. Care is taken to ensure that the sheet is cut out of the slab in the middle. The test specimen is then punched out of this sheet.

2. Reference Example 2: Determination of the Molding Density

[0192] Before the actual test, the length and width of the test specimen are determined using calipers (accuracy: ±0.01. mm, measurement in each case is made at one point in the center of the component) and the weight of the test specimen is determined using a precision balance (accuracy: ±0.001 g). The thickness of the test specimen is determined by the compression hardness testing machine using the “crosshead” displacement measurement system (accuracy: ±0.25 mm). The measured values can then be used to calculate the volume and the density.

Reference Example 3: Determination of the Comfort Factor

[0193] By analogy with the SAG factor, the comfort factor is deemed to be the ratio of the compression hardness (StH) at a compression of 65% to the compression hardness at a compression of 25%. Comparative measurements with eTPU slabs and flexible foam slabs show that the two measurement methods (SAG value determination and compression hardness test) display the same trends when comparing different materials. The absolute values of the ratios determined may differ from one another for eTPU, this being attributable to the fact that—unlike in the compression hardness determination—the measurement in the SAG factor determination is influenced by the presence or the condition of the skin on the test specimen. Since the influence of the skin on the properties can however also vary greatly depending on what the component is being used for, the compression hardness can also be used to compare different materials.

4. Reference Example 4: Determination of the Bulk Density

[0194] The bulk density of the bead foams is determined gravimetrically via the volume and the mass of a particle bed in a vessel (10 L). This is done by filling a funnel, which is closed at the lower outlet, with about 11 to 12 L of beads. For filling, the 10 L vessel is positioned centrally beneath the funnel. The closure of the funnel is then opened so that the heads flow evenly into the container with a defined volume (10 L). The surface of the container is leveled with a flat edge at a 45° angle. The mass is then determined gravimetrically using a balance. This must either be tared beforehand on the empty weight of the container, or the empty weight must be subtracted afterwards in order to obtain the weight of the bed. The weight divided by the volume then corresponds to the bulk density of the bead foam. Both when filling the sample vessel with beads and when transporting it to the balance, care must be taken to ensure that the vessel is not exposed to any vibration or impacts.

5. Reference Example 5: Determination of Compression Hardness

[0195] The test specimens used for the measurement (50 mm×50 mm×original thickness of the test slab (usually 20 mm, thickness can vary slightly depending on shrinkage, the outer skin is not removed)) are cut from a test slab (200×200×20 mm, dimensions may vary slightly depending on shrinkage) using a handsaw. The slab is conditioned beforehand under standard climatic conditions (23±2° C. and 50±5% humidity) for 16 h. The compression hardness test likewise takes place under these climatic conditions.

[0196] Before the actual test, the length and width of the test specimen are determined using calipers (accuracy: ±0.01. mm, measurement in each case is made at one point in the center of the component) and the weight of the test specimen is determined using a precision balance (accuracy: ±0.001 g).

[0197] The compression hardness is determined using a testing machine equipped with a 50 kN force transducer (class 1 according to DIN EN ISO 7500-1:2018-06), a crosshead displacement transducer (class 1 according to DIN EN ISO 9513:2013), and two parallel unperforated pressure plates (diameter 200 mm, max. permitted force 250 kN, max. permitted surface pressure 300 N/mm.sup.2). For the determination of the density of the test specimens, the length, width, and weight are loaded into the Zwick test method. The thickness of the test specimen is determined by the universal testing machine using the “crosshead” displacement measurement system (accuracy: ±0.25 mm). The measurement itself is carried out at a testing speed of 50 mm/min and an initial force of 1 N. The stress values for compressions of 10, 25, 50, 65, and 75% are each recorded. The evaluation is based on the values for the 1st compression and also the 4th compression. The compression hardness is calculated according to equation (4). The compression hardness σ is here the compressive stress in kPa determined for a deformation (e.g. 50%) during the loading process.

σ=(F.sub.x/A.sub.0)×1000   (4) [0198] F.sub.x=Force at x % deformation [N] [0199] A.sub.0=Initial cross-section of the test specimen [mm.sup.2]

6. Reference Example 6: Determination of the G Modulus of a Compacted Foam

[0200] The test specimens for determination of the G modulus from eTPU materials are produced by injection molding. To do this, the eTPU material is removed from the component and then ground in a mill (8 mm sieve path on a Dreher S26/26 GFX-Spez-L). The eTPU pieces obtained were then dried at 110° C. for 3 h and processed into 2 mm thick test specimens in an injection molding machine at a maximum cylinder temperature of 210-215° C., die temperature of 210-220° C., and a mold temperature of 35° C. (cycle time 75 s). The test specimens thus obtained were immediately heated at 100° C. for 20 h. The storage modulus (G modulus) was then determined in accordance with Reference Example 1 (compact material).

CITED LITERATURE

[0201] Ullmann's “Encyklopädie der technischen Chemie” [Encyclopedia of industrial Chemistry], 4th edition, volume 20, pp. 416 ff.

[0202] WO 94/20568

[0203] WO 2007/082838 A1

[0204] WO2017/030835

[0205] WO 2013/153190 A1

[0206] WO2010/010010

[0207] “Handbook of Thermoplastic Elastomers”, 2nd edition, June 2014.

[0208] “Polymer Chemistry”, Interscience Publ., New York, 1961, pp. 111-127

[0209] “Kunststoffhandbuch” [Plastics handbook], volume VIII, C. Hanser Verlag, Munich 1973 Journal of Polymer Science, Part A1, 4, pages 1851-1859 (1966)

[0210] “Kunststoffhandbuch” [Plastics Handbook], volume VII, Carl Hanser Verlag, Munich 1966 (pp. 103-113)

[0211] “Kunststoffhandbuch” [Plastics Handbook], volume 7, “Polyurethane” [Polyurethanes], Carl Hanser Verlag, 3rd edition 1993, chapter 3

[0212] “Integralschaumstoff” [Integral foam], Carl-Hanser-Verlag, Munich, Vienna, 1975

[0213] “Kunststoff-Handbuch” [Plastics handbook], volume 7, “Polyurethane” [Polyurethanes], 3rd edition, 1993, chapter 7

[0214] EP 1979401 B1

[0215] EP 3053732 A1

[0216] WO 2016/146537 A1