Nucleating agent for compact thermoplastic polyurethanes

Abstract

The present invention relates to a process for producing a composition (I) at least comprising a compact thermoplastic polyurethane (P1), comprising the providing of at least one compact thermoplastic polyurethane (P1) or a reaction mixture for production of a compact thermoplastic polyurethane (R-P1), the adding of at least one compound (N) that has a conjugated, nitrogen-containing aromatic structure as nucleating agent to the at least one thermoplastic polyurethane (P1) or to the reaction mixture for production of a compact thermoplastic polyurethane (R-P1), wherein the compound (N) is a solid; and the mixing of the nucleating agent and the thermoplastic polyurethane (P1) or the reaction mixture (R-P1) to obtain a composition (I). The nucleating agent is used here in an amount in the range from 0.01% by weight to 2.0% by weight, based on the thermoplastic polyurethane (P1) or the reaction mixture (R-P1). Further relates the present composition comprising at least one compact thermoplastic polyurethane and at least one compound (N) that has a conjugated, nitrogen-containing aromatic structure as nucleating agent, wherein the compound (N) is a solid, and the use of the compounds mentioned as nucleating agents for a compact thermoplastic polyurethane.

Claims

1. A process for producing a composition (I) comprising a compact polyurethane (P1), the process comprising: (i) adding at least one compound (N) that has a conjugated, nitrogen-containing aromatic structure as a nucleating agent to a polyurethane (P1) or to a reaction mixture for production of a compact polyurethane (R-P1), wherein the compound (N) is a solid; and (ii) mixing the nucleating agent and the polyurethane (P1) or the reaction mixture (R-P1) to obtain a composition (I), wherein a total amount of nucleating agents used is in a range from 0.01% by weight to 2.0% by weight, based on the polyurethane (P1) or the reaction mixture (R-P1), wherein the nucleating agent is at least one compound selected from the group consisting of a quinacridone, a monoazo compound, a perylene, a diketopyrrolopyrrole, an isoindoline, a phthalocyanine, and a derivative of one of these compounds.

2. The process according to claim 1, wherein the compact polyurethane is a compact thermoplastic polyurethane.

3. The process according to claim 1, further comprising (iii) and (iv): (iii) heating the composition (I) to a temperature in a region of a melting range of a thermoplastic polyurethane (P1) with at least partial melting of the thermoplastic polyurethane (P1); and (iv) cooling the composition.

4. The process according to claim 3, wherein the composition (I) in (iii) is heated to a temperature in the region of the melting temperature of a hard phase or above the melting temperature of the hard phase of the thermoplastic polyurethane (P1).

5. The process according to claim 1, wherein the total amount of the nucleating agents used is in a range from 0.04% by weight to 0.3% by weight, based on the polyurethane (P1) or the reaction mixture (R-P1).

6. The process according to claim 1, wherein the nucleating agent is at least one compound selected from the group consisting of a quinacridone, a diketopyrrolopyrrole, a phthalocyanine, and a derivative of one of these compounds.

7. The process according to claim 1, wherein the nucleating agent has been subjected to: a treatment comprising grinding; a treatment with a solvent, acid, alkali, bleach, crystallization or extraction; a finishing operation to reduce or prevent flocculation or lump formation; a finishing operation to control particle size; or a finishing operation to regulate viscosity.

8. The process according to claim 1, wherein the nucleating agent is used in solid form with a specific surface area in a range from 10 m.sup.2/g to 150 m.sup.2/g.

9. The process according to claim 1, wherein the nucleating agent is used in combination with a further additive.

10. The process according to claim 9, wherein the further additive is at least one selected from the group consisting of carbon black and a wax-based demolding agent.

Description

EXAMPLES

1. TPU Production Example

(1) 1.1 Feedstocks:

(2) Polyol 1: polyether polyol having an OH number of 112.2 and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) Polyol 2: polyester polyol having an OH number of 56 and exclusively primary OH groups (based on hexanediol, butanediol, adipic acid, functionality: 2) Polyol 4: polyester polyol having an OH number of 46 and exclusively primary OH groups (based on adipic acid and butanediol, functionality: 2) Polyol 5: polyester polyol having an OH number of 112 and exclusively primary OH groups (based on adipic acid and butanediol, functionality: 2) Polyol 6: polyester polyol having an OH number of 56 and exclusively primary OH groups (based on -caprolactone and neopentyl glycol) Polyol 7: polyether polyol having an OH number of 56 and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) (PTHF 2000) Polyol 8: polyester polyol having an OH number of 55 and exclusively primary OH groups (based on adipic acid and butanediol, functionality: 2) Polyol 9: polyether polyol having an OH number of 248 and exclusively secondary OH groups (based on propylene glycol, functionality: 2) Polyol 10: polyether polyol having an OH number of 55 and exclusively secondary OH groups (based on propylene glycol, functionality: 2) Isocyanate 1: aromatic isocyanate (methylene diphenyl 4,4-diisocyanate) Isocyanate 2: aliphatic isocyanate (hexamethylene 4,4-diisocyanate) Isocyanate 3: aliphatic isocyanate (hexamethylene 1,6-diisocyanate) Isocyanate 4: aromatic isocyanate (naphthylene 1,5-diisocyanate) Isocyanate 5 prepolymer based on 86.9% methylene diphenyl 4,4-diisocyanate, 8.2% dipropylene glycol and 4.9% polypropylene glycol (Mn=450 g/mol, OH functionality of 2, polyol 9) having a residual NCO content of 22.9% Isocyanate 6 prepolymer based on 37.8% methylene diphenyl 4,4-diisocyanate and 62.2% polytetrahydrofuran (Mn=2000 g/mol, OH functionality of 2) and a residual NCO content of 10% Chain extender 1 (CE 1): propane-1,3-diol Chain extender 2 (CE 2): butane-1,4-diol Chain extender 3 (CE 3): hexane-1,6-diol Chain extender 4 (CE 4): hydroquinone bis(2-hydroxyethyl) ether (HQEE) Chain extender 5 (CE 5): ethane-1,2-diol Catalyst 1: tin(II) isooctoate (50% in dioctyl adipate) Catalyst 2: 1,4-diazabicydo[2.2.2]octane 33% in dipropylene glycol Catalyst 3: 2% of a 19% solution of zinc neodecanoate and 0.5% of a 16% bismuth neodecanoate solution in polyol 10 Catalyst 4: 5% Polycat SA 1/10 consisting of DBU and phenol (1:1 molar) in polyol 10 Catalyst 5: 33% solution of triethylenediamine dissolved in dipropylene glycol Stabilizer 1: sterically hindered phenol Stabilizer 2: polymeric carbodiimide Additive 1: ester wax Additive 2: silicone-containing antifoam Additive 3: fatty acid-based oil as demolding aid Additive 4: KCaNa zeolite A in castor oil Demolding aid 1: a masterbatch consisting of amide wax, diatomaceous earth and silica and a TPU with Shore 80 A and an MFR of 20-50 g/10 min (determined at 190 C. and 21.6 kg) Nucleating agent 1: 2,9-dimethylquinacridone Nucleating agent 2: quinacridonequinone Nucleating agent 3: 2,9-dichloroquinacridone Nucleating agent 4: beta-quinacridone, C.I. Pigment Violet 19 Nucleating agent 5: gamma-quinacridone, phthalimide treatment, C.I. Pigment Violet 19 Nucleating agent 6: gamma-quinacridone, ground acid extraction, C.I. Pigment Violet 19 Nucleating agent 7: gamma-quinacridone, ground bleached phthalimide treatment, C.I. Pigment Violet 19 Nucleating agent 8: solid solution of gamma-quinacridone and 2,9-dichloroquinacridone (ratio 1:9), acid extraction, plus acid treatment and dimethylimidazole treatment Nucleating agent 9: solid solution of gamma-quinacridone and 2,9-dichloroquinacridone (ratio 1:3), acid extraction, neutralized Nucleating agent 10: solid solution of gamma-quinacridone and 2,9-dichloroquinacridone (ratio 1:3), acid extraction, plus acid treatment, C.I. Pigment Red 202 Nucleating agent 11: solid solution of gamma-quinacridone and 2,9-dichloroquinacridone (ratio 1:9), acid extraction plus acid treatment, C.I. Pigment Red 202 Nucleating agent 12: 2,9-dichloroquinacridone, ground, acid extraction, C.I. Pigment Red 202 Nucleating agent 13: solid solution of gamma-quinacridone and 2,9-dimethylquinacridone (ratio 1:3), acid treatment, C.I. Pigment Violet 42 Nucleating agent 14: solid solution of gamma-quinacridone and 2,9-dimethylquinacridone (ratio 1:3), C.I. Pigment Red 122 Nucleating agent 15: solid solution of quinacridonequinone and gamma-quinacridone, C.I. Pigment Orange 48 Nucleating agent 25: diketopyrrolopyrrole derivative, C.I. Pigment rot 264 Nucleating agent 26: diketopyrrolopyrrole derivative, C.I. Pigment orange 71 Nucleating agent 27: dichlorodiketopyrrolopyrrole derivative, with fine particle size Nucleating agent 28: nucleating agent 27, but with coarser particle size distribution Nucleating agent 29: dichlorodiketopyrrolopyrrole derivative, with very fine particle size Nucleating agent 30: diketopyrrolopyrrole derivative, C.I. Pigment orange 73 Nucleating agent 31: pyrrolopyrrole derivative, C.I. Pigment red 272 Nucleating agent 32: monoazo salt, C.I. Pigment Yellow 168 Nucleating agent 33: perylene, C.I. Pigment Red 149 Nucleating agent 34: perylene, C.I. Pigment Violet 29 Nucleating agent 35: Cu phthalocyanine pigment, C.I. Pigment Blue 15:4 Nucleating agent 36: isoindoline, C.I. Pigment Yellow 139 Nucleating agent 37: perylene, C.I. Pigment Red 178 Nucleating agent 38: perylene, C.I. Pigment Red 179 Nucleating agent 39: isoindolinone, C.I. Pigment Yellow 110 Nucleating agent 40: benzimidazolone, C.I. Pigment Yellow 151 Nucleating agent 41: hydrogenated form of 2,9-dichloroquinacridone Structure:

(3) ##STR00008## Nucleating agent 42: hydrogenated form of gamma-quinacridone Structure:

(4) ##STR00009## C.I. means Colour Index
1.2 General Production Example for Batchwise Synthesis

(5) A thermoplastic polyurethane (TPU) was synthesized from isocyanate, chain extender, stabilizer, catalyst and polyol while stirring in a reaction vessel. The polyol, the chain extender, stabilizer and catalyst were initially charged in a vessel at 80 C. and mixed with the isocyanate that had been preheated to 48 C. with vigorous stirring. On attainment of a reaction temperature of 110 C., the solution was poured out onto a hotplate heated to 125 C., and the TPU slab obtained, after heat treatment (15 hours at 80 C.), was pelletized and processed by injection molding.

(6) The synthesis and properties of thermoplastic polyurethanes that were produced by batchwise synthesis are summarized in tables 1 to 3.

(7) TABLE-US-00002 TABLE 1 Synthesis examples Feedstock Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polyol 1 [g] 1000 1000 Polyol 6 [g] 1000 1000 1000 1000 1000 Isocyanate 1 [g] 658 523.24 611.15 697.12 630 647.4 Isocyanate 2 [g] 824.4 CE 1 [g] 119.5 CE 2 [g] 188.06 236.71 135.2 CE 3 [g] 225.97 CE 4 [g] 306.9 CE 5 [g] 146.7 Stabilizer 2 [g] 15 15 15 15 8 Cat 1 [ppm] 400 Index 1000 1000 1000 1000 1000 1000 1000

(8) TABLE-US-00003 TABLE 2 Synthesis examples Feedstock Example 8 Example 9 Example 12 Example 13 Example 14 Example 15 Example 16 Polyol 1 [g] 1000 1000 1000 1000 Polyol 5 [g] 1000 Polyol 2 [g] 1000 Polyol 4 [g] 1000 Isocyanate 1 [g] 630 670 700 600 920 Isocyanate 3 [g] 1197 Isocyanate 2 [g] 1203 CE 1 [g] 204 CE 2 [g] 136.74 149.73 205.26 177.66 323 CE 3 [g] 723 Catalyst 1 45 150 Stabilizer 1 [g] 17.85 8 10 8 21.5 14.7 12.9 Additive 1 [g] 1 5

(9) In the case of example 18, the diisocyanate that had been preheated to 48 C. was added to the remaining components that had been preheated to 60 C. On attainment of a reaction temperature of 80 C., the solution was poured out onto a hotplate heated to 80 C., and the TPU slab obtained was processed further as described above.

(10) TABLE-US-00004 TABLE 3 Synthesis examples Feedstock Example 17 Example 18 Example 19 Example 29 Example 30 Example 31 Polyol 1 [g] 750 573.6 500 600 Polyol 2 [g] 750 Polyol 4 [g] 1000 Polyol 7 [g] 500 Isocyanate 1 [g] 690 344.2 585 393.77 372 717.71 CE 2 [g] 180.1 72.2 175.76 102.85 66.42 204.40 Catalyst 1 [ppm] 20 Stabilizer 1 [g] 10 14.53 7.65 Stabilizer 2 [g] 8 Index 1000 990 1000 1000 1000
1.3 General Example for Continuous Synthesis

(11) A mixture of isocyanate, chain extender, a stabilizer and polyol having an average molar mass of 1 kg/mol was heated to 80 C. and mixed vigorously in a mixing head. The reaction mixture obtained was applied to a circulating PTFE belt at a temperature of 112 C. The reaction mixture that had solidified to form a solid strip material (slab) at the end of the belt was fed continuously at about 80 C. via intake rolls directly to a comminution and homogenization apparatus. It was comminuted therein at temperatures of about 105 C. and conveyed to a single-shaft extruder connected thereto by a tangential flange. The housing temperatures were about 170 C. to 190 C. in the intake region, and 210 to 230 C. in the middle zone. The melt that exited at the die plate was processed by means of underwater pelletization to give homogeneous lenticular pellets and then dried.

(12) The synthesis and properties of thermoplastic polyurethanes that were produced by continuous synthesis are summarized in table 4 and table 5.

(13) TABLE-US-00005 TABLE 4 Synthesis examples: Exam- Exam- Exam- Exam- Exam- ple 8 ple 9 ple 10 ple 11 ple 12 Polyol 1 [g] 1000 1000 Polyol 2 [g] 1000 Polyol 4 [g] 1000 Polyol 5 [g] 1000 Isocyanate 1 [g] 630 670 556.96 1100 700 CE 2 [g] 136.74 149.73 159.7 306 205.6 Stabilizer 1 [g] 17.85 12 Stabilizer 2 [g] 8 8 10

(14) TABLE-US-00006 TABLE 5 Examples of properties of the TPUs without nucleating agent (2 mm injection-molded plaques that had been heat-treated at 100 C. for 20 h beforehand): Exam- Exam- Exam- Exam- Exam- ple 8 ple 9 ple 10 ple 11 ple 12 Shore A 87 96 91 96 Shore D 36 47 53 47 Tensile strength 45 55 55 50 55 [MPa] Elongation at break 600 550 550 450 550 [%] Tear propagation 70 120 90 150 120 resistance [kN/m] Compression set 25 30 25 40 30 (72 h/23 C./30 min) [%] Compression set 45 45 40 50 45 (24 h/70 C./30 min) [%] Abrasion [mm.sup.3] 25 30 30 30 30
1.4 Addition of the Nucleating Agents

(15) The nucleating agent was added either as a masterbatch based on the TPU formulation corresponding to the TPU to which it was ultimately to be added or as a masterbatch based on a TPU with Shore 80 A and an MFR of 20-50 g/10 min (190 C./21.6 kg). A further option is direct addition of the nucleating agent during the extrusion or injection molding or in a separate compounding step. Alternatively, the nucleating agent is added at an early stage during the TPU synthesis.

(16) 1.4.1 Addition by Compounding

(17) (a) Laboratory Scale:

(18) The TPU pellets are first predried at 80 C. under reduced pressure for 16 hours, then admixed with the additives according to the tables below. The unit % here represents percent by weight in relation to the polymer specified. The TPU is compounded in the presence of the nucleating agent in the molten state under a nitrogen atmosphere and under high shear. The screw speed was 100 revolutions per minute and the mean residence time was about 3 minutes. One type of apparatus used for this purpose was a laboratory twin-screw extruder having co-rotating screws, such as the micro-compounder (15 cm.sup.3) from Xplore Instruments B.V. The force that arises during the compounding was detected constantly. The compounding force at the end of the compounding method (i.e. after 3 minutes) was recorded and serves for estimation of the rheological quality of the melt, or retention of the molecular weight, since there is a correlation between the molecular weight and the compounding force.

(19) Molded articles were subsequently produced by receiving the polymer melt obtained in the micro-compounder in a heated transfer vessel. Then the melt was transferred directly into a 10 cm.sup.3 micro-injector (Xplore Instruments B.V.), where the polymer melt was injected into a smooth mold at a pressure of 5 bar and with a mold temperature of 40 C. The injection moldings are round plaques having a diameter of 40 mm and a thickness of 1 mm.

(20) (b) Pilot Scale:

(21) The TPU polymer was predried at 80 C. under reduced pressure for 16 hours and then premixed with the additives. The mixture was added in a twin-screw extruder (Collin GmbH, screw diameter 25 mm, L/D ratio=32, with co-rotating screws) and processed at 210 C. (die temperature), at a screw speed of 120 revolutions per minute. The extruded compound obtained was cooled underwater and pelletized continuously.

(22) Subsequently, the compounded pellets were predried again at 80 C. under reduced pressure for 16 hours, then injection-molded with an Arburg 370S injection-molding machine (closing force 880 kN) at 220 C., and with a mold temperature of 30 C. The injection moldings are plaques of 100 mm100 mm2 mm (or 100 mm100 mm4 mm as in the examples of table 17).

(23) (c) Characterization

(24) Differential Scanning Calorimetry (DSC):

(25) The DSC instrument was used for analysis of the crystallization characteristics of the various compounds and the reference materials. All measurements were effected under nitrogen atmosphere. The specimens (about 5-10 mg) were tested with the following program: isothermal for 10 minutes at 100 C., then heating to 230 C. at 20 C./min, holding of the temperature of 230 C. (all examples in tables 6, 7, 8, 9 and 10, except for compounding numbers 28, 29 and 30) or 250 C. (compounding numbers 28, 29 and 30) for 3 minutes, then cooling to 30 C. at 20 C./min, then holding for 3 minutes, then heating again to 230 C. at 20 C./min, holding the temperature of 230 C. (all examples except 28, 29 and 30) or 250 C. (examples 28, 29 and 30) for 3 minutes, then cooling to 30 C. at 20 C./min. In tables 12, 13, 15 and 16, testing was effected with the following program: isothermal for 10 minutes at 100 C., then heating to 190 C. at 20 C./min, holding the temperature of 190 C. for 3 minutes, then cooling to 30 C. at 20 C./min, then holding for 3 minutes, then heating again to 230 C. (except in the case of compounds based on example 19 in table 16, where a temperature of 240 C. was taken) at 20 C./min, holding the temperature of 230 C. (except in the case of compounds based on example 19 in table 16, where a temperature of 240 C. was taken) for 3 minutes, then cooling to 30 C. at 20 C./min. The data listed in the further tables are the crystallization temperatures Tc [ C.] that correspond to the peak temperatures of the DSC spectra during the second cooling phase.

(26) Determination of Molecular Weight:

(27) The molecular weight was analyzed by GPC. The total molecular weight including the allophanates was listed as solution 10 (soln. 10) and the molecular weight of the TPU without allophanate as solution 7 (soln. 7).

(28) Test methods that can be used for the material characterization include the following: DSC, DMA, TMA, NMR, FT-IR, GPC

(29) TABLE-US-00007 Shore A & D hardness DIN 7619-1, Tensile strength DIN 53 504, Elongation at break DIN 53 504, Tear propagation resistance DIN 53 515, Abrasion DIN 4649 Vicat DIN EN ISO 306 Compression set (CS) DIN ISO 815 Resilience DIN standard 53512
1.4.2 Addition of the Quinacridone-Based Nucleating Agents

(30) Tables 6 to 10 list the crystallization temperatures that were obtained from the TPU after compounding and heat treatment.

(31) TABLE-US-00008 TABLE 6a Compound list (pilot scale production) Compound number Feedstocks 1 2 3 4 5 6 7 8 Processing lab & lab lab lab lab pilot pilot pilot method pilot Example 8 100 99.95 99.95 98 99.95 Example 9 100 99.95 99.95 Nucleating agent 1 0.05 Nucleating agent 2 0.05 Nucleating agent 12 0.05 0.2 Nucleating agent 15 0.05 0.05 Tc1 [ C.] 79.2 102.0 83.4 126.7 115.3 129.4 136.7 127.3 Tc2 [ C.] 79.0 99.6 82.4 126.7 113.3 127.0 135.7 125.7 Compounding force 1370 1370 1260 1260 1260 [N] Molecular weight of 91 90 95 93 soln. 10 [kg/mol] Molecular weight of 82 83 86 84 soln. 7 [kg/mol] Shore A hardness 89 89 89 89 [] Shore D hardness 40 41 40 40 [] Yield stress 42 43 44 42 [MPa] - MD Yield stress 42 45 45 43 [MPa] - CD Elongation at break 600 590 620 600 [%] - MD Elongation at break 650 620 630 630 [%] - CD Tear propagation 74 72 73 71 resistance [kN/m] MD = machine direction, CD = cross direction

(32) TABLE-US-00009 TABLE 6b Compound list (pilot scale production) Compound number Feedstocks 9 10 11 12 13 14 15 Processing pilot lab lab lab lab lab lab method Example 8 98 99.995 99.99 99.975 99.9 99.5 99.0 Example 9 Nucleating agent 1 2 Nucleating agent 2 0.005 0.01 0.025 0.1 0.5 1.0 Nucleating agent 12 Nucleating agent 15 Tc1 [ C.] 129.7 80.6 79.7 78.9 107.0 111.7 115.4 Tc2 [ C.] 128.7 80.0 79.3 79.3 107.6 109.0 113.4 Compounding force 1800 1870 1780 1795 1835 1875 [N] Molecular weight of 92 soln. 10 [kg/mol] Molecular weight of 85 soln. 7 [kg/mol] Shore A hardness 89 [] Shore D hardness 37 [] Yield stress 45 [MPa] - MD Yield stress 46 [MPa] - CD Elongation at break 610 [%] - MD Elongation at break 630 [%] - CD Tear propagation 71 resistance [kN/m] MD = machine direction, CD = cross direction

(33) TABLE-US-00010 TABLE 7a Compound list (laboratory scale production) Compound number Feedstocks 16 17 18 19 20 21 22 Processing lab & lab lab lab lab pilot pilot method pilot Example 8 99.95 99.8 99.95 99.95 99.8 99.8 99.95 Example 12 Nucleating agent 2 Nucleating agent 3 0.05 0.2 Nucleating agent 4 0.05 Nucleating agent 5 0.05 Nucleating agent 6 0.2 Nucleating agent 7 0.2 Nucleating agent 8 0.05 Nucleating agent 9 Nucleating agent 10 Nucleating agent 11 Nucleating agent 13 Nucleating agent 14 Nucleating agent 15 Additive 1 Tc1 [ C.] 116.6 109.5 117.0 108.3 103.0 104.0 119.3 Tc2 [ C.] 132.7 130.1 115.0 108.0 103.0 100.3 116.7 Molecular weight of soln. 10 [kg/mol] Molecular weight of soln. 7 [kg/mol]

(34) TABLE-US-00011 TABLE 7b Compound list (laboratory scale production) Compound number Feedstocks 23 24 25 26 27 28 29 30 Processing pilot pilot lab lab lab lab lab lab method Example 8 99.95 99.95 99.995 99.99 99.975 Example 12 100 99.95 99.95 Nucleating agent 2 0.05 Nucleating agent 3 Nucleating agent 4 Nucleating agent 5 Nucleating agent 6 Nucleating agent 7 Nucleating agent 8 Nucleating agent 9 0.05 Nucleating agent 10 0.05 Nucleating agent 11 0.05 Nucleating agent 13 0.05 Nucleating agent 14 0.05 Nucleating agent 15 0.05 Additive 1 Tc1 [ C.] 119.3 120.0 126.3 102.3 117.9 105 157 160 Tc2 [ C.] 117.3 119.3 126.0 77.3 114.3 Molecular weight of 95 96 96 soln. 10 [kg/mol] Molecular weight of 91 90 89 soln. 7 [kg/mol]

(35) TABLE-US-00012 TABLE 8 Compound list (laboratory scale production) Compound number Feedstocks 32 33 34 40 Processing method lab lab lab lab Example 8 99.95 99.95 99.95 99.8 Nucleating agent 16 0.05 Nucleating agent 17 0.05 Nucleating agent 18 0.05 Nucleating agent 21 0.2 Tc1 [ C.] 119.0 117.9 104.3 103.3 Tc2 [ C.] 116.0 114.3 101.3 105.0

(36) TABLE-US-00013 TABLE 9 Compound list (laboratory scale production) Compound number Feedstocks 47 48 49 50 51 Processing method lab lab lab lab lab Example 13 100 99.95 99.8 99.95 99.8 Nucleating agent 2 0.05 0.2 Nucleating agent 11 0.05 0.2 Tc1 [ C.] 109.8 160.5 165.0 171.5 176.2 Tc2 [ C.] 106.8 156.1 162.6 168.1 175.2

(37) TABLE-US-00014 TABLE 10 Compound list (laboratory scale production) Compound number Feedstocks 47 48 49 50 51 52 53 54 55 56 Processing lab lab lab lab lab lab lab lab lab lab method Example 14 100 99.95 99.8 99.95 99.8 Example 15 100 99.95 99.8 99.95 99.8 Nucleating agent 2 0.05 0.2 0.05 0.2 Nucleating agent 11 0.05 0.2 0.05 0.2 Tc1 [ C.] 151.9 161.5 161.9 153.1 156.5 129.1 130.1 129.7 132.0 132.5 Tc2 [ C.] 155.2 160.8 161.9 156.1 157.5 129.1 129.8 129.9 131.7 132.1

(38) The mechanical properties of 2 mm TPU injection-molded plaques of TPUs with and without nucleating agents are listed in table 11 (after storage at room temperature after injection molding for 24 hours, pilot scale production).

(39) TABLE-US-00015 TABLE 11 Examples of properties of the TPUs with nucleating agents: TPU Example 8 Example 9 Masterbatch 10% of a masterbatch 10% of a masterbatch based on example 6 with based on example 7 with or without the respective or without the respective nucleating agent nucleating agent Nucleating agent Nuc. Nuc. Nuc. Nuc. agent 2 agent 11 agent 2 agent 11 Final concentration of 0.3% 0.3% 0.3% 0.3% the nucleating agent Density [g/cm.sup.3] 1.12 1.12 1.121 1.214 1.215 1.216 Shore A 88 89 89 Shore D 38 39 39 47 47 47 Tensile strength [MPa] 30 31 33 40 42 43 Elongation at break [%] 640 640 620 550 550 540 Tensile stress at 100% 5.8 5.7 6 7.9 7.9 7.7 elongation [MPa] Tear propagation 58 58 63 83 89 89 resistance [kN/m] CS (24 h/70 C./30 min) 71 69 56 73 56 48 [%] CS (24 h/100 C./30 min) 89 90 85 95 89 77 [%] Vicat temperature [ C.] 86.7 90.4 96.7 103.8 108.2 115.5 Abrasion [mm.sup.3] 73 63 60 74 60 76
1.4.3 Addition of the Diketopyrrolopyrrole-Based Nucleating Agents

(40) Tables 12 and 13 list the crystallization temperatures that were obtained from the TPU after compounding and heat treatment.

(41) TABLE-US-00016 TABLE 12 Compound list (laboratory scale production) DSC 10 min-100 C., 30 C.-190 C.-30 C., then 30 C.-230 C.-30 C. First run Second run Fcomp Mw Mw Tm Hm Tc Tm Hm Tc 3 solu. 7 solu. 10 Formulation ( C.) (J/g) ( C.) ( C.) (J/g) ( C.) N kDa kDa 100% example 8 173.1 11.9 122.9 180.5 11.7 78.9 3785 82 88 99.95% example 8 + 165.0 13.6 121.3 179.7 11.8 116.7 3698 0.05% nucleating agent 26 99.8% example 8 + 163.4 13.1 121.0 180.4 10.3 108.6 3695 0.2% nucleating agent 26 99.95% example 8 + 169.0 13.9 122.3 179.3 11.2 119.3 3688 0.05% nucleating agent 25 99.8% example 8 + 164.0 13.7 126.0 179.3 11.7 127.6 3535 82 87 0.2% nucleating agent 25 99.95% example 8 + 163.3 15.0 131.0 179.0 13.1 79.9 0.05% nucleating agent 27 99.8% example 8 + 165.6 15.3 135.0 177.6 15.1 118.7 0.2% nucleating agent 27 99.95% example 8 + 164.3 12.7 124.4 179.2 12.1 79.7 0.05% nucleating agent 28 99.8% example 8 + 163.0 11.4 129.6 176.3 13.5 117.7 0.2% nucleating agent 28 99.95% example 8 + 168.2 15.7 134.7 181.5 12.6 118.4 3380 0.05% nucleating agent 29 99.8% example 8 + 165.8 14.9 127.1 183.5 9.9 114.1 3303 0.2% nucleating agent 29 99.8% example 8 + 167.6 13.7 119.7 164.6 11.5 80.0 3443 0.2% nucleating agent 30 99.95% example 8 + 174.9 13.9 127.4 183.2 10.5 83.0 2990 0.025% nucleating agent 29 + 0.025% nucleating agent 30 99.8% example 8 + 164.9 14.4 128.0 182.0 11.0 125.7 3088 0.1% nucleating agent 29 + 0.1% nucleating agent 30 99.95% example 8 + 175.2 15.8 132.4 183.5 10.4 83.4 2818 0.05% nucleating agent 31 99.8% example 8 + 171.5 14.8 132.1 183.5 9.6 106.0 3028 0.2% nucleating agent 31

(42) TABLE-US-00017 TABLE 13 Compound list (laboratory scale production) DSC 10 min-100 C., 30 C.-190 C.-30 C., then 30 C.-230 C.-30 C., except for example 27: 240 C. rather than 230 C. 1st run 2nd run Fcomp Mw Mw Tm Hm Tc Tm Hm Tc 3 solu. 7 solu. 10 Formulation ( C.) (J/g) ( C.) ( C.) (J/g) ( C.) N kDa kDa 100% example 6 174.3 1.0 198.9 2.3 107.8 4140 64 70 99.95% example 6 + 170.8 2.0 198.1 2.5 168.0 3555 58 61 0.05% nucleating agent 25 99.8% example 6 + 176.5 1.8 198.1 2.0 166.9 3063 63 68 0.2% nucleating agent 25 100% example 26 161.9 11.2 133.7 181.9 7.6 80.3 3283 63 66 99.95% example 26 + 163.6 10.5 141.0 180.3 8.3 147.4 3078 58 60 0.05% nucleating agent 25 99.8% example 26 + 167.3 12.5 141.3 180.9 10.2 149.4 2690 59 61 0.2% nucleating agent 25 100% example 27 120.3 1.0 203.1 12.2 169.0 1935 69 74 99.95% example 27 + 120.0 1.0 202.7 17.2 172.3 2170 0.05% nucleating agent 25 99.8% example 27 + 119.0 1.1 202.4 15.9 177.3 1558 62 68 0.2% nucleating agent 25

(43) The mechanical properties of 2 mm TPU injection-molded plaques of TPUs with and without nucleating agents (after storage at room temperature after injection molding for 24 hours, pilot scale production) are listed in table 14.

(44) TABLE-US-00018 TABLE 14 Examples of properties of the TPUs with nucleating agents: TPU Example 8 Example 9 Masterbatch 10% of a masterbatch 10% of a masterbatch based on example 8 based on example 9 with or without the with or without the respective nucleating respective nucleating agent agent Nucleating agent Nucleating Nucleating agent 25 agent 25 Final concentration of the 0.3% 0.3% nucleating agent Density [g/cm.sup.3] 1.12 1.12 1.214 1.215 Shore A 88 89 Shore D 38 39 47 47 Tensile strength [MPa] 30 31 40 41 Elongation at break [%] 640 650 550 530 Tensile stress at 100% 5.8 5.8 7.9 7.8 elongation [MPa] Tear propagation 58 60 83 86 resistance [kN/m] CS (24 h/70 C./30 71 69 73 55 min) [%] CS (24 h/100 C./30 89 87 95 84 min) [%] Vicat temperature [ C.] 86.7 90.9 103.8 110.8 Abrasion [mm.sup.3] 73 76 74 72
1.4.4 Addition of the Nucleating Agents from the Monoazo, Perylene, Phthalocyanine, Isoindoline Classes

(45) The mechanical properties of 1 mm TPU injection-molded plaques of TPUs with and without nucleating agents (thickness 1 mm, laboratory scale production) are listed in table 15a.

(46) TABLE-US-00019 TABLE 15 Compound list: mini-extruder, injection molding of plaques DSC: 10 min-100 C., 30 C.-190 C.-30 C., then 30 C.-230 C.-30 C., 1st cycle 2nd cycle Fcomp Mw Mw Tm Hm Tc Tm Hm Tc 3 solu. 7 solu. 10 ( C.) (J/g) ( C.) ( C.) (J/g) ( C.) N kDa kDa 100% example 8 173.1 11.9 122.9 180.5 11.7 78.9 3785 82 88 Comparison 1 99% example 8 + 166.9 15.7 135.1 181.2 13.0 81.3 1% talc, fine type, suitable for crystallization, D50 = 2.0 micron Comparison 2 98% example 8 + 169.2 14.6 132.4 179.5 12.3 81.0 2% talc, fine type, suitable for crystallization, D50 = 2.0 micron Comparison 3 95% example 8 + 165.3 13.2 131.7 179.3 12.3 100.3 5% talc, fine type, suitable for crystallization, D50 = 2.0 micron Comparison 4 98% example 8 + 163.6 15.0 122.4 179.6 11.6 80.6 2% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 5 95% example 8 + 169.9 16.2 125.7 179.5 12.6 101.4 5% talc, fine type, suitable for crystallization, D50 = 2.2 micron 99.95% example 8 + 169.7 12.4 124.3 178.0 12.6 93.9 3205 0.05% nucleating agent 32 99.8% example 8 + 162.4 12.8 123.0 179.0 7.0 114.3 3728 83 87 0.2% nucleating agent 32 99.95% example 8 + 164.4 13.0 124.3 180.1 11.1 114.3 2853 83 88 0.05% nucleating agent 33 99.8% example 8 + 172.3 14.4 126.6 180.0 11.7 122.7 3670 82 87 0.2% nucleating agent 33 99.95% example 8 + 159.7 15.5 121.0 178.7 12.0 126.0 3685 0.05% nucleating agent 34 99.8% example 8 + 169.4 13.9 120.9 179.7 11.1 121.9 3755 86 93 0.2% nucleating agent 34 99.95% example 8 + 170.3 14.3 127.3 178.0 13.0 117.7 3258 79 83 0.05% nucleating agent 35 99.8% example 8 + 174.0 14.3 122.6 180.7 11.3 106.6 3665 82 88 0.2% nucleating agent 35 99.95% example 8 + 165.7 15.2 128.7 177.7 14.4 95.9 0.05% nucleating agent 36 99.8% example 8 + 164.6 13.3 127.4 177.6 13.2 107.4 0.2% nucleating agent 36 99.95% example 8 + 163.9 14.4 130.7 179.9 12.5 104.7 0.05% nucleating agent 37 99.8% example 8 + 169.4 14.4 130.9 180.4 11.5 116.6 0.2% nucleating agent 37 99.95% example 8 + 165.0 14.8 125.0 179.3 12.4 78.9 0.05% nucleating agent 38 99.8% example 8 + 165.2 14.0 119.7 164.9 11.8 115.3 0.2% nucleating agent 38
1.4.5 Addition of the Nucleating Agents from the Diketopyrrolopyrrole, Phthalocyanine, Isoindolinone, Monoazo and Perylene Classes in Further TPU Types

(47) The mechanical properties of 1 mm TPU injection-molded plaques of TPUs with and without nucleating agents (thickness 1 mm, laboratory scale production) are listed in table 15b and 16.

(48) TABLE-US-00020 TABLE 15b Compound list: mini-extruder 99.95% example 8 + 118.1 1.3 130.6 183.7 10.6 82.6 0.05% nucleating agent 41 99.8% example 8 + 117.7 1.2 136.7 181.9 10.2 129.7 0.2% nucleating agent 41 99.95% example 8 + 119.7 1.0 138.7 182.6 13.4 88.0 0.05% nucleating agent 42 99.8% example 8 + 117.4 1.2 139.0 182.6 12.2 85.6 0.2% nucleating agent 42 100% example 9 149.3 186.6 11.3 87.0 99.95% example 9 + 149.4 187.5 11.0 87.1 0.05% nucleating agent 39 99.9% example 9 + 151.7 185.6 13.2 100.6 0.1% nucleating agent 39 99.8% example 9 + 150.8 184.5 12.3 109.4 0.2% nucleating agent 39 99.95% example 9 + 143.1 184.8 10.4 134.4 0.05% nucleating agent 2 99.9% example 9 + 142.1 184.5 9.9 135.8 0.1% nucleating agent 2 99.8% example 9 + 142.7 183.9 10.2 138.4 0.2% nucleating agent 2 99.95% example 9 + 141.8 184.5 9.9 140.1 0.05% nucleating agent 15 99.9% example 9 + 139.4 185.6 10.0 140.1 0.1% nucleating agent 15 99.8% example 9 + 142.1 185.2 10.5 143.8 0.2% nucleating agent 15 99.95% example 9 + 142.7 184.3 11.1 140.0 0.05% nucleating agent 1 99.9% example 9 + 140.0 185.3 10.0 141.7 0.1% nucleating agent 1 99.8% example 9 + 144.0 186.6 9.0 138.0 0.2% nucleating agent 1 99.95% example 9 + 142.2 184.0 8.9 141.6 0.05% nucleating agent 3 99.9% example 9 + 143.4 186.6 9.2 135.0 0.1% nucleating agent 3 99.8% example 9 + 144.1 187.2 11.1 136.7 0.2% nucleating agent 3 99.95% example 9 + 142.7 186.9 10.9 148.1 0.05% nucleating agent 12 99.9% example 9 + 146.7 187.3 10.3 148.7 0.1% nucleating agent 12 99.8% example 9 + 148.0 187.6 11.3 149.1 0.2% nucleating agent 12 99.95% example 9 + 146.0 185.3 11.6 150.4 0.05% nucleating agent 11 99.9% example 9 + 148.0 187.3 11.1 147.7 0.1% nucleating agent 11 99.8% example 9 + 147.7 187.9 11.0 150.0 0.2% nucleating agent 11 99.95% example 9 + 141.7 185.6 10.6 118.0 0.05% nucleating agent 5 99.9% example 9 + 142.7 186.6 10.2 122.0 0.1% nucleating agent 5 99.8% example 9 + 143.4 184.2 9.5 133.4 0.2% nucleating agent 5 99.95% example 9 + 145.3 187.3 9.3 142.7 0.05% nucleating agent 25 99.9% example 9 + 146.0 185.3 9.4 151.1 0.1% nucleating agent 25 99.8% example 9 + 148.6 185.4 11.8 152.3 0.2% nucleating agent 25 99.95% example 9 + 148.0 185.3 11.5 119.7 0.05% nucleating agent 35 99.9% example 9 + 148.1 185.9 9.8 120.7 0.1% nucleating agent 35 99.8% example 9 + 148.7 187.3 11.0 119.7 0.2% nucleating agent 35 99.95% example 9 + 139.7 186.6 7.3 133.4 0.05% nucleating agent 34 99.9% example 9 + 140.0 186.0 8.3 134.7 0.1% nucleating agent 34 99.8% example 9 + 145.4 186.9 8.9 136.8 0.2% nucleating x agent 34

(49) TABLE-US-00021 TABLE 16 Compound list: mini-extruder, injection molding of plaques (thickness 1 mm, laboratory scale production) DSC: 10 min-100 C., 30 C.-190 C.-30 C., then 30 C.-230 C.-30 C., in the case of compounds with example 19: Tmax 240 C. rather than 230 C. 1st cycle 2nd cycle Fcomp Tm Hm Tc Tm Hm Tc 3 ( C.) (J/g) ( C.) ( C.) (J/g) ( C.) N 100% example 17 174.3 1.0 198.9 2.3 107.8 4140 Comparison 6 99% example 28 + 178.5 1.8 200.5 3.0 120.5 4175 1% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 7 98% example 28 + 176.2 1.4 199.2 2.5 127.2 4315 2% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 8 95% example 28 + 173.5 2.8 198.5 1.8 143.6 3965 5% talc, fine type, suitable for crystallization, D50 = 2.2 micron 99.95% example 28 + 175.2 1.5 199.1 2.5 140.0 3828 0.05% nucleating agent 32 99.8% example 28 + 175.0 1.8 199.2 2.4 142.2 3548 0.2% nucleating agent 32 99.95% example 28 + 174.8 1.1 198.8 2.4 137.9 3250 0.05% nucleating agent 35 99.8% example 28 + 172.9 0.7 198.2 2.0 142.2 3065 0.2% nucleating agent 35 100% example 18 161.9 11.2 133.7 181.9 7.6 80.3 3283 Comparison 9 99% example 26 + 171.2 3.3 141.0 161.6 5.5 85.0 2870 1% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 98% example 26 + 169.3 8.3 140.3 163.3 3.6 103.3 2888 10 2% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 95% example 26 + 164.2 9.9 141.7 188.5 1.0 111.4 2963 11 5% talc, fine type, suitable for crystallization, D50 = 2.2 micron 99.95% example 26 + 171.5 11.6 139.0 186.2 2.1 131.8 2315 0.05% nucleating agent 32 99.8% example 26 + 167.6 12.6 141.7 185.9 7.0 124.7 2720 0.2% nucleating agent 32 99.95% example 26 + 168.5 7.5 144.1 183.5 8.0 110.4 fehlt 0.05% nucleating agent 35 99.8% example 26 + 172.2 12.7 140.7 188.2 1.7 117.4 2533 0.2% nucleating agent 35 100% example 19 120.3 1.0 203.1 12.2 169.0 1935 Comparison 99% example 27 + 120.0 1.0 202.7 12.6 168.7 2210 12 1% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 98% example 27 + 188.1 0.9 201.5 12.1 173.9 2160 13 2% talc, fine type, suitable for crystallization, D50 = 2.2 micron Comparison 95% example 27 + 119.0 1.0 201.7 14.2 171.6 2000 14 5% talc, fine type, suitable for crystallization, D50 = 2.2 micron 99.95% example 27 + 119.7 1.1 202.1 15.9 169.2 1850 0.05% nucleating agent 32 99.8% example 27 + 118.3 0.9 202.0 15.1 171.6 1950 0.2% nucleating agent 32 99.95% example 27 + 119.7 1.1 202.7 15.9 172.0 1943 0.05% nucleating agent 35 99.8% example 27 + 118.0 1.0 203.4 16.1 172.3 1805 0.2% nucleating agent 35

(50) Table 17 shows further results. Compounding was conducted in a 25 mm L/D 32 twin-screw extruder. Injection molding was effected in an Arburg 370S (closure force 880 kN). The plaque thickness was 4 mm, pilot scale production.

(51) TABLE-US-00022 TABLE 17 Compound list: DSC: 10 min-100 C., 30 C.-190 C.-30 C., then 30 C.-230 C.-30 C., Injection molding 1st cycle 2nd cycle temperature Tm Hm Tc Tm Hm Tc [ C.] ( C.) (J/g) ( C.) ( C.) (J/g) ( C.) 190 100% example 8 170.5 5.4 124.0 167.8 10.7 82.6 225 100% example 8 167.3 12.4 128.3 166.3 13.3 84.0 190 99.95% example 8 + 168.0 11.7 125.9 166.4 13.0 117.3 0.05% nucleating agent 33 225 99.95% example 8 + 168.3 10.9 127.6 183.0 13.2 118.6 0.05% nucleating agent 33 190 99.8% example 8 + 179.0 11.9 127.0 183.3 13.3 121.6 0.2% nucleating agent 33 225 99.8% example 8 + 170.6 12.7 129.0 184.0 13.3 122.0 0.2% nucleating agent 33 190 99.95% example 8 + 172.0 11.1 123.6 166.4 11.4 121.3 0.05% nucleating agent 34 225 99.95% example 8 + 165.7 9.9 128.6 184.0 12.5 124.6 0.05% nucleating agent 34 190 99.8% example 8 + 172.8 9.3 123.3 166.8 8.4 125.3 0.2% nucleating agent 34 225 99.8% example 8 + 168.0 11.4 126.0 167.6 12.9 127.0 0.2% nucleating agent 34
1.5 Determination of the Cycle Times

(52) The comparison of the total cycle times is conducted in a DEMAG ergotech 200/500-610 injection molding machine with a 40 mm three-zone screw. As injection molding 1, a cylinder (outside 80 mm, depth 40 mm) with a wall thickness of 8 mm is produced in a split mold. Injection is effected here via an open hot-runner die into an 8-fold cold-runner star distributor. As injection molding 2, a disk ( 125 mm, thickness 27 mm) is produced in a split mold. Injection is effected here via a central cold-runner sprue gate. Demolding is effected by means of a ring ejector, which strips the shell off from the core present in the cavity for demolding. A force sensor present in the ejector system transmits the force required to strip off the shell.

(53) The pellets are dried at 90 C. for 3 h. The processing temperatures of the various screw zones are between 195 C. and 230 C. The nucleating agent is added as a masterbatch. The final concentration of the nucleating agent in the TPU is 0.3%.

(54) The masterbatch was obtained by incorporating the nucleating agent by compounding to give a TPU having Shore 80 A and an MFR of 20-50 g/10 min (190 C./21.6 kg) in a twin-screw extruder (co-rotating screws) with screw diameter 16 mm and a length/diameter ratio of 44.

(55) TABLE-US-00023 TABLE 18 Injection molding parameters Mold temperature Cooling [ C.] Demolding Injection Nucleating Cycle time time Injection Closure force TPU molding agent [s] [s] side side [N] Example 8 1 200 130 75 70 1900 Example 8 1 0.3% 155 85 75 70 1500 nucleating agent 2 Example 8 1 0.3% 150 75 75 70 300 nucleating agent 2 + 0.2% demolding aid 1 Example 8 1 0.3% 170 100 75 70 3700 nucleating agent 25 Example 1 119 75 75 70 300 10 Example 1 0.3% 89 45 75 70 300 10 nucleating agent 2 Example 1 194 140 75 70 5000 11 Example 1 0.3% 158 105 75 70 3000 11 nucleating agent 2 Example 1 197 150 24 40 29 Example 1 1% 127 80 24 40 29 demolding aid 2 Example 1 1% 87 40 24 40 29 demolding aid 2 + 0.3% nucleating agent 12 Example 1 315 260 24 40 30 Example 1 1% 265 200 24 40 30 demolding aid 2 Example 1 1% 205 150 24 40 30 demolding aid 2 + 0.3% nucleating agent 12 Example 2 314 230 35 35 31 Example 2 0.5% 304 220 35 35 31 demolding aid 1 + 0.5% demolding aid 2 Example 2 0.3% 294 210 35 35 31 nucleating agent 12 Example 2 0.5% 274 190 35 35 31 demolding aid 1, 0.5% demolding aid 2, 0.3% nucleating agent 12

(56) The mechanical properties of 2 mm TPU injection-molded plaques of TPUs with and without nucleating agents are listed in table 19a. Table 19a shows the positive interaction of the claimed nucleating agents with co-additives such as carbon black and demolding agents.

(57) TABLE-US-00024 TABLE 19a Examples of properties of the TPUs with nucleating agents (after storage at room temperature for 24 hours after injection molding): TPU Example 8 Example 9 Masterbatch 10% of a masterbatch 10% of a masterbatch based on example 8 based on example 9 with or without the with or without the respective nucleating respective nucleating agent agent Nucleating agent Nucleating Nucleating agent 25 agent 25 Final concentration of the 0.3% 0.3% nucleating agent Density [g/cm.sup.3] 1.12 1.12 1.214 1.215 Shore A 88 89 Shore D 38 39 47 47 Tensile strength [MPa] 30 31 40 41 Elongation at break [%] 640 650 550 530 Tensile stress at 100% 5.8 5.8 7.9 7.8 elongation [MPa] Tear propagation 58 60 83 86 resistance [kN/m] CS (24 h/70 C./30 71 69 73 55 min) [%] CS (24 h/100 C./30 89 87 95 84 min) [%] Vicat temperature [ C.] 86.7 90.9 103.8 110.8 Abrasion [mm.sup.3] 73 76 74 72

(58) In addition, experiments were conducted by the same production method as described above, but with further co-additives, in masterbatch form according to these formulations:

(59) Feedstocks:

(60) Carbon black with iodine number 88-96 mg/g and residue on 325 mesh screen (mesh size 0.044 mm, according to ASTM D 1514)<30 ppm Co-additive 1 15% carbon black+10% demolding agent 2 in TPU Ca stearate with CaO content 8-11%, bulk density 170-220 g/L.

(61) TABLE-US-00025 TABLE 19b Mold temperature Cycle Cooling [ C.] Demolding Injection time time Injection Closure force TPU molding Additives [s] [s] side side [N] Example 2 214 140 29 Example 2 1% demolding aid 146 70 29 2, 10% co-additive 1 Example 2 0.2% demolding 111 35 29 agent 2, 0.3% carbon black, 0.3% nucleating agent 12 Example 2 324 270 30 Example 2 1% demolding aid 2 284 200 30 Example 2 1% demolding aid 236 150 30 2, 10% co-additive 1 Example 2 0.2% demolding 217 130 30 agent 2, 0.3% carbon black, 0.3% nucleating agent 12 Example 2 0.2% demolding 212 125 30 agent 2, 0.3% carbon black, 0.3% nucleating agent 12, 0.03% Ca stearate

2. Cast Elastomer Production Examples

(62) All components including the catalyst and nucleating agent (A component) apart from the isocyanate were combined and homogenized by mixing at 1200 rpm with a Speedmixer for 2 min and then heated to 50 C. Thereafter, the isocyanate (B component) which had first been heated to 50 C., and to 80 C. in the case of isocyanate 6, was added to the A component. The reaction mixture was then stirred at 1700-1950 rpm with a Speedmixer for 30 s and then transferred rapidly and evenly into a mold at 90-100 C. and flattened with the aid of a wooden splint. The mold had different thicknesses: 2, 6 and 10 mm.

(63) After curing, the test specimens were promptly subjected to heat treatment on a Teflon film in a heating cabinet at 90 C. for 24 h.

(64) TABLE-US-00026 TABLE 20 Synthesis examples: Example Example Example Example Example Example Example 20 21 22 23 24 25 26 Polyol 1 [g] 25.93 25.74 25.97 25.84 Polyol 7 [g] 49.38 25.92 25.73 25.96 25.83 Polyol 8 [g] 55.9 55.62 Isocyanate 4 39.98 [g] Isocyanate 5 38.65 38.65 36.26 36.26 39.22 39.03 [g] CE 2 [g] 10.65 5.7 5.66 6.06 6.03 5.71 5.68 Catalyst 3 0.05 0.05 0.07 0.07 [g] Additive 3 0.61 0.61 [g] Additive 4 2.45 2.43 1.73 2.46 2.44 [g] Catalyst 4 0.07 0.07 [g] Additive 2 0.61 0.61 0.61 0.61 [g] Nucleating 0.05 0.5 agent 15 Nucleating 0.5 0.5 agent 25 Index 1000 1010 1010 1020 1020 1020 1020

(65) TABLE-US-00027 TABLE 21 Mechanical properties of the examples Example Example Example Example Example Example Example 20 21 22 23 24 25 26 Resilience [%] 32 39 43 28 35 27 39 Shore A 83 83 84 81 86 83 81 hardness Tensile strength 33 37 39 56 52 45 44 [MPa] Elongation at 400 430 440 540 540 430 430 break [%] Tear 26 22 29 35 43 21 21 propagation resistance [kN/m] CS 15 18 16 13 19 14 17 72 h/23 C./30 min [%] CS 31 27 25 19 24 21 22 24 h/70 C./30 min [%] CS 32 27 27 22 27 22 20 24 h/80 C./30 min [%]

3. Methods of Measurement

(66) Test methods that can be used for the material characterization include the following: DSC, DMA, TMA, NMR, FT-IR, GPC

(67) TABLE-US-00028 Shore A & D hardness DIN 7619-1, Tensile strength DIN 53 504, Elongation at break DIN 53 504, Tear propagation resistance DIN 53 515, Abrasion DIN 4649 Vicat DIN EN ISO 306 Compression set (CS) DIN ISO 815

4. Tests in a Specific Cast Elastomer

(68) 100 g of a prepolymer that had been preheated to 80 C., obtained from 37.42% isocyanate 1, 41.67% polyol 7 and 20.91% polyol 1, were introduced together with 7.62 g of a mixture, preheated to 40 C., of nucleating agent 25 (0.25% or 0.5%), chain extender 2 and 0.6 g of catalyst 5 into a casting mold at 120 C. The material was demolded after 30 minutes and heat-treated at 110 C. for 16 hours.

(69) The flat test specimens thus obtained were then diecut and tested in accordance with ASTM D790 (bending test) and ASTM D412 (tensile test).

(70) TABLE-US-00029 TABLE 22 0.25% 0.5% nucleating nucleating Blank agent 25 agent 25 Flexural modulus [MPa] 59.0 135.4 157.7 Flexural strength [MPa] 4.1 9.2 10.4 Tensile strength at 10% elongation 3.1 6.4 6.6 [MPa] Tensile strength at 100% elongation 8.1 9.4 9.6 [MPa] Tensile strength at 300% elongation 14.2 13.7 14.3 [MPa] Elongation at break [%] 3.6 3.5 3.3

5. Comparative Experiments

(71) (a) Comparative Examples in Polybutylene Succinate

(72) Data for polybutylene succinate utilized:

(73) Density: 1.25 g/cm.sup.3

(74) Melting temperature: 114 C.+/3 C.

(75) Determination of Tc1 and Tc2:

(76) DSC program: two cycles 30 C.200 C. (3 min at 200 C.)30 C., heating and cooling rates 10 K/min, under nitrogen. Tc1 is the temperature peak in the first cooling and Tc2 in the second cooling.

(77) Compounds were produced with polybutylene succinate. The results of the experiments are summarized in tables 23a and 23b.

(78) TABLE-US-00030 TABLE 23a Compound number PBS- PBS- PBS- Feedstocks PBS PBS1 PBS2 PBS3 PBS4 PBS5 PBS6 PBS7 PBS8 PBS9 10 11 12 Processing lab lab lab lab lab lab lab lab lab lab lab lab lab method Polybutylene 100 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 succinate Nucleating 0.05 0.2 agent 39 Nucleating 0.05 0.2 agent 40 Nucleating 0.05 0.2 agent 2 Nucleating 0.05 0.2 agent 1 Nucleating 0.05 0.2 agent 3 Nucleating 0.05 0.2 agent 19 Nucleating agent 25 Tc1 [ C.] 87.4 86.1 88.9 87.2 87.0 84.8 85.5 86.9 87.1 87.0 86.1 85.8 86.6 Tc2 [ C.] 85.0 84.2 88.6 84.7 84.6 81.7 79.4 85.5 85.6 85.5 83.5 83.4 80.6

(79) TABLE-US-00031 TABLE 23b Compound number PBS- PBS- PBS- PBS- PBS- PBS- PBS- PBS- PBS- PBS- Feedstocks 13 14 15 16 17 18 19 20 21 22 Processing lab lab lab lab lab lab lab lab lab lab method Polybutylene 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 succinate Nucleating 0.05 0.2 agent 25 Nucleating 0.05 0.2 agent 31 Nucleating 0.05 0.2 agent 29 Nucleating 0.05 0.2 agent 35 Nucleating 0.05 0.2 agent 34 Tc1 [ C.] 85.6 86.4 87.9 86.1 87.6 85.8 87.5 87.9 87.1 86.6 Tc2 [ C.] 83.7 84.5 85.5 84.1 85.9 83.3 85.7 85.7 83.9 84.8 n.c. = no crystallization peak apparent in the DSC spectrum

(80) These results show that none of the compounds claimed at all are effective in polybutylene succinate. Therefore, the person skilled in the art was in no way able to conclude from such data that these compounds could be active in TPU.

(81) (b) Comparative Examples in Polylactic Acid

(82) Data for polylactic acid utilized:

(83) Density: 1.24 g/cm.sup.3

(84) Melting temperature: 170 C.+/1 C.

(85) Melt flow index (190 C., 2.16 kg): 35 dg/min

(86) Suitable for injection molding applications

(87) PDLA content: about 1.5%

(88) Determination of Tc1 and Tc2:

(89) DSC program: two cycles 30 C.230 C. (3 min at 230 C.)30 C., heating and cooling rates 10 K/min, under nitrogen. Tc1 is the temperature peak in the first cooling and Tc2 in the second cooling.

(90) Compounds were produced with polylactic acid. The results of the experiments are summarized in tables 24a and 24b.

(91) TABLE-US-00032 TABLE 24a Compound number PL- PL- Feedstocks PL PL1 PL2 PL3 PL4 P5L PL6 PL7 PL8 PL9 10 11 Processing lab lab lab lab lab lab lab lab lab lab lab lab method Polylactic acid 100 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 Nucleating 0.05 0.2 agent 39 Nucleating 0.05 0.2 agent 40 Nucleating 0.05 0.2 agent 2 Nucleating 0.05 0.2 agent 1 Nucleating 0.05 0.2 agent 3 Nucleating 0.05 agent 19 Tc1 [ C.] n.c. 135.9 138.6 116.3 97.3 108.6 110.6 101.9 98.3 95.1 92.9 90.9 Tc2 [ C.] n.c. 135.7 138.6 115.6 95.6 110.2 110.3 102.1 101.1 95.1 93.1 91.6

(92) TABLE-US-00033 TABLE 24b Compound number PL- PL- PL- PL- PL- PL- PL- PL- PL- PL- PL- Feedstocks 12 13 14 15 16 17 18 19 20 21 22 Processing lab lab lab lab lab lab lab lab lab lab lab method Polylactic acid 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 99.95 99.8 Nucleating 0.2 agent 19 Nucleating 0.05 0.2 agent 25 Nucleating 0.05 0.2 agent 31 Nucleating 0.05 0.2 agent 29 Nucleating 0.05 0.2 agent 35 Nucleating 0.05 0.2 agent 34 Tc1 [ C.] 94.7 95.0 99.7 119.8 121.2 132.6 134.2 135.1 137.9 n.c. n.c. Tc2 [ C.] 96.8 99.0 100.0 121.4 121.2 132.8 134.5 135.3 138.7 n.c. n.c. n.c. = no crystallization peak apparent in the DSC spectrum

(93) These results show that some but not all compounds claimed are also effective in polylactic acid. Therefore, the person skilled in the art was not able to conclude from such data that these compounds would also be active in TPU.

(94) (c) Comparative Examples in Nylon-6

(95) Figures for nylon-6 utilized:

(96) Density: 1.13 g/cm.sup.3

(97) Melting temperature: 170 C.+/1 C.

(98) Melt flow index (175 C., 5 kg): 130 dg/min (on dried specimen)

(99) Determination of Tc1 and Tc2:

(100) DSC program: two cycles 30 C.280 C. (3 min at 280 C.)30 C., heating and cooling rates 20 K/min, under nitrogen. Tc1 is the temperature peak in the first cooling and Tc2 in the second cooling.

(101) Compounds were produced with nylon-6. The results of the experiments are summarized in table 25.

(102) TABLE-US-00034 TABLE 25 Compound number Feedstocks PA PA1 PA2 PA3 PA4 PA5 Processing lab lab lab lab lab lab method Nylon-6 100 99.95 99.8 99.95 99.8 99.8 Nucleating 0.05 0.2 agent 39 Nucleating 0.05 0.2 agent 40 Talc 0.2 Tc1 [ C.] 181.8 180.8 180.0 188.3 188.0 188.1 Tc2 [ C.] 181.1 180.1 179.0 187.3 187.3 187.8

(103) These results show that the tested compounds are slightly effective in polyamide, but no more than talc. Therefore, the person skilled in the art was not able to conclude from these data that these compounds would also be particularly active in TPU.

(104) (d) Comparative Examples of Commercial Nucleating Agents in Example 8

(105) Compounds were produced analogously to example 8, using commercial nucleating agents. The results of the experiments are summarized in table 26.

(106) Tc1 was not measured, just Tc2 (after Tmax=230 C.).

(107) TABLE-US-00035 TABLE 26 Compound number Feedstocks T-1 T-2 T-3 T-4 T-5 T-6 T-7 T-8 Processing lab lab lab lab lab lab lab lab lab method Example 8 100 99.9 99.8 99.5 98 95 99.5 99.5 99.5 Talc, fine type, 0.1 0.2 0.5 2 5 suitable for crystallization, with D50 = 2.2 micron Reaction mixture of 0.5 sodium salt of montanic acids and montan wax and montanic acids (Licomont NAV 101) 1,3:2,4-bis(3,4- 0.5 dimethylbenzylidene)- sorbitol (Millad 3988) Mixture with 2,2- 0.5 methylenebis(2,4-di- tert-butylphenyl) phosphate lithium salt as main constituent (ADK-Stab NA-71) Tc2 [ C.] 79.7 78.3 78.6 78.9 80.6 101.4 n.c. 76.3 n.c. n.c. = no crystallization peak apparent in the DSC spectrum
(e) Comparative Examples of Commercial Nucleating Agents in Example 11

(108) Compounds were produced analogously to example 11, using commercial nucleating agents. The results of the experiments are summarized in table 27. The additives were incorporated in a laboratory extruder.

(109) DSC: 20 K/min in heating and cooling run, Tmax 250 C., time at Tmax=2 min

(110) TABLE-US-00036 TABLE 27 Compound number Feedstocks T-9 T-10 T-11 T-12 T-13 T-14 Processing method lab lab lab lab lab lab lab Example 11 100 99.7 99.7 99.7 99.5 99.5 99.5 2,2-Methylenebis(4,6-di-t- 0.3 butylphenyl) phosphate, sodium salt (Irgastab NA11) Zinc glycerolate (Irgastab 0.3 NA287) 1,3,5-tris[2,2-dimethyl- 0.3 propionylamino]benzene (Irgaclear XT386) Ultrafine, surface-treated 0.5 calcium carbonate (Socal 312) Acrylonitrile-butadiene- 0.5 styrene copolymer with high butadiene content (Elix 152 I) Hydrophobic silica-kaolinite 0.5 mixture modified with an alkylsilane (Aktisil PF777) Tc [ C.] 84 88 106 95 93 78 88
(f) Comparative Examples of Commercial Nucleating Agents in Example 12

(111) Compounds were produced analogously to example 12, using commercial nucleating agents. The results of the experiments are summarized in table 28. The additives were incorporated in a laboratory extruder.

(112) DSC: 20 K/min in heating and cooling run. Tmax 250 C., time at Tmax=2 min

(113) TABLE-US-00037 TABLE 28 Compound number Feedstocks T-15 T-16 T-17 T-18 T-19 T-20 Processing method lab lab lab lab lab lab lab Example 12 100 99.7 99.7 99.7 99.5 99.5 99.5 2,2-Methylenebis(4,6-di-t- 0.3 butylphenyl) phosphate, sodium salt (Irgastab NA11) Zinc glycerolate (Irgastab 0.3 NA287) 1,3,5-tris[2,2-dimethyl- 0.3 propionylamino]benzene (Irgaclear XT386) Ultrafine, surface-treated 0.5 calcium carbonate (Socal 312) Acrylonitrile-butadiene-styrene 0.5 copolymer with high butadiene content (Elix 152 I) Hydrophobic silica-kaolinite 0.5 mixture modified with an alkylsilane (Aktisil PF777) Tc [ C.] 106 104 100 104 103 105 107

(114) These results show that the typical commercial nucleating agents are not active at all in TPU example 8, or even have an adverse interaction on the morphology and on the crystallization kinetics of TPU from example 8. Therefore, the person skilled in the art was not able to conclude from these data that these compounds would also be particularly active in TPU.

(115) It is even more astonishing that the compounds claimed in this invention are known effective nucleating agents in polypropylene, as reported, for example, in Journ. Of Pol. Sci. Part B: Pol. Phys., 40, 2002, 2504-2515 for quinacridones, or Journ. Appl. Polym. Sci., 90, 2003, 3957-3964, for phthalocyanines, or patent U.S. Pat. No. 6,995,202 (filing date Jul. 11, 2003) for the warpage characteristics of diketopyrrolopyrrole (indeed, warpage is a side-effect of crystallization), or patent U.S. Pat. No. 9,029,446 (filing date Jul. 12, 2009) with regard to phthalocyanines, quinacridones, perylenes, dioxazines, isoindolinones, isoindolines and diketopyrrolopyrrole (admittedly together with trisamide in this patent).

(116) It is therefore very astonishing that compounds that are very active in a nonpolar polymer such as polypropylene are then entirely inactive in a polar polymer such as polybutylene succinate, and those that are only partly active in other polar polymers such as polylactic acid or polyamide show such a high crystallizing effect in a polar polymer such as TPU.