SKI BOOTS WITH TEMPERATURE-INDEPENDENT MODULUS OF ELASTICITY

Abstract

The present invention relates to a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) comprising MDI with a polyol composition (PZ), wherein the polyol composition (PZ) comprises at least one polyol (P1) and a chain extender (KV1), wherein the polyol (P1) is selected from polytetrahydrofurans having an average molecular weight Mn in the range from 1200 to 2000 g/mol and the chain extender (KV1) is selected from the group consisting of 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol and also to a process for producing a ski shoe or a part of a ski shoe from the thermoplastic polyurethane according to the invention and to the ski shoe or part of a ski shoe per se.

Claims

1-9. (canceled)

10. A process for producing a ski shoe or a part of a ski shoe, the process comprising: producing a ski shoe or a part of a ski shoe from a thermoplastic polyurethane (TPU-1) obtained by reaction of an isocyanate composition (IZ) comprising MDI with a polyol composition (PZ), comprising a polyol (P1) and a chain extender (KV1), wherein the polyol (P1) comprises a polytetrahydrofuran having an average molecular weight Mn in a range of from 1200 to 2000 g/mol, and wherein the chain extender (KV1) comprises 1,3-propanediol, 1,4-butanediol, or 1,6-hexanediol.

11. The process of claim 10, wherein the thermoplastic polyurethane (TPU-1) is processed by injection molding in the producing.

12. The process of claim 10, wherein the polyol (P1) comprises a polytetrahydrofuran having an average molecular weight Mn in a range of from 1300 to 1700 g/mol.

13. The process of claim 10, wherein the chain extender (KV1) is 1,4-butanediol.

14. The process of claim 10, wherein the thermoplastic polyurethane has a hard phase fraction greater than 0.40, and wherein the hard phase fraction is defined by a formula (I) $\begin{array}{cc}\mathrm{Hard}\mathrm{phase}\mathrm{fraction}=\left\{\underset{x=1}{\overset{x}{.Math.}}\left[\left(m_{\mathrm{KVx}}/M_{\mathrm{KVx}}\right)*M_{\mathrm{Iso}}+m_{\mathrm{KVx}}\right]\right\}/m_{\mathrm{ges}},& \left(I\right)\end{array}$ wherein M.sub.KVx is molar mass of the chain extender x in g/mol, m.sub.KVx is mass of the chain extender x in g, M.sub.Iso is molar mass of the isocyanate in g/mol, m.sub.ges is total mass of all starting materials in g, and x is a number of chain extenders.

15. The process of claim 10, wherein the thermoplastic polyurethane of the ski shoe or the part has a Charpy notched impact strength at −30° C. according to DIN EN ISO 179-1/1 eA of greater than 10 kJ/m.sup.2.

16. A ski shoe or part of a ski shoe, obtained by the process of claim 10.

17. The ski shoe or part of a ski shoe of claim 16, wherein the thermoplastic polyurethane has a Charpy notched impact strength at −30° C. according to DIN EN ISO 179-1/1 eA of greater than 10 kJ/m.sup.2.

18. A thermoplastic polyurethane (TPU-1), obtained by reacting an isocyanate composition (IZ) comprising MDI with a polyol composition (PZ) comprising a polyol (P1) and a chain extender (KV1), wherein the polyol (P1) comprises a polytetrahydrofuran having an average molecular weight Mn in a range of from 1200 to 2000 g/mol, wherein the chain extender (KV1) comprises 1,3-propanediol, 1,4-butanediol, or 1,6-hexanediol, wherein the thermoplastic polyurethane has a hard phase fraction greater than 0.40, and wherein the hard phase fraction is defined by a formula (I) $\begin{array}{cc}\mathrm{Hard}\mathrm{phase}\mathrm{fraction}=\left\{\underset{x=1}{\overset{x}{.Math.}}\left[\left(m_{\mathrm{KVx}}/M_{\mathrm{KVx}}\right)*M_{\mathrm{Iso}}+m_{\mathrm{KVx}}\right]\right\}/m_{\mathrm{ges}},& \left(I\right)\end{array}$ wherein M.sub.KVx is molar mass of the chain extender x in g/mol, m.sub.KVx is mass of the chain extender x in g, M.sub.Iso is molar mass of the isocyanate in g/mol, m.sub.ges is total mass of all starting materials in g, and x is a number of chain extenders.

19. The polyurethane of claim 18, wherein the chain extender (KV1) is 1,4-butanediol.

Description

EXAMPLES

1. Example 1—Raw Materials

[0098] Poly PTHF® 1000: Polytetrahydrofuran 1000, CAS number: 25190-06-1, BASF SE, 67056 Ludwigshafen, GERMANY, intermediates division.

[0099] Poly PTHF® 2000: Polytetrahydrofuran 2000, CAS number: 25190-06-1, BASF SE, 67056 Ludwigshafen, GERMANY, intermediates division.

[0100] 1,4-butanediol: butane-1,4-diol, CAS number: 110-63-4, BASF SE, 67056 Ludwigshafen, GERMANY, intermediates division.

[0101] Lupranat MET: 4,4′-methylenediphenyl diisocyanate, CAS number: 101-68-8, BASF SE, 67056 Ludwigshafen, GERMANY

[0102] Color masterbatch 1: Elastollan Konz 315 F (red), BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde

[0103] Color masterbatch 2: Elastollan Konz 530/1 (blue), BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde

2. Example 2—Production of Materials

[0104] Materials A-N were produced using a ZSK 58 twin-screw extruder from Werner and Pfleiderer Stuttgart with a 48 D screw divided into 12 barrels. Pelletization was carried out using customary underwater pelletization apparatus from Gala (UWG). The formulations for the individual materials are summarized in table 1.

[0105] TPU materials having average molar weights of the polyol component greater than 2000 Dalton were not producible.

3. Determination of Properties

[0106] Mechanical properties were determined on injection molded bodies. Determination of density was performed according to DIN EN ISO 1183-1 (A), hardness according to DIN 53505, tensile strength, breaking elongation and elastic moduli according to DIN EN ISO 527, tear propagation resistance according to DIN ISO 34-1, B (b), notched impact strengths according to DIN EN ISO 179-1/1eA and abrasion according to DIN 53516.

[0107] The properties for the individual materials are summarized in table 1.

4. Notched Impact Strengths at Low Temperatures

[0108] The inventive examples (EB) in table 1 illustrate that the use of a PTHF having average molar weights in the range of 1400-1700 affords materials having a high impact strength at low temperatures. Materials having approximately identical stiffness at 20° C. were to be compared.

[0109] Thus for example for the inventive material J a notched impact strength of 117 kJ/m.sup.2 was measured at −30° C. while for the noninventive material K a notched impact strength of 8 kJ/m.sup.2 was determined at −30° C.

[0110] Similarly, the inventive materials A and E may be compared to the noninventive material D for example. For material A a notched impact strength of 120 kJ/m.sup.2 was measured at −30° C. while for the noninventive material D a notched impact strength of 9 kJ/m.sup.2 was determined at −30° C. For material A a notched impact strength of 110 kJ/m.sup.2 was measured at −20° C. while for the noninventive material D a notched impact strength of 15 kJ/m.sup.2 was determined at −20° C.

[0111] Furthermore, the examples D to I, all having a hard phase fraction of 53%, show that the notched impact strength at −30° C. for the inventive materials (E-I) having average molar weights for the PTHF in the range of 1400-1700 are always above 20 kJ/m.sup.2. Despite the much lower elastic modulus at 20° C. the noninventive example D is markedly below 20 kJ/m.sup.2 for notched impact strengths at −30° C.

5. Stiffening at Low Temperatures

[0112] The inventive examples (EB) in table 1 illustrate that the use of a PTHF having average molar weights in the range of 1400-1700 affords materials whose stiffness (elastic modulus) increases only moderately at low temperatures. Materials having approximately identical stiffness at 20° C. were to be compared.

[0113] Thus for example for the inventive material J an increase in the elastic modulus to 180% is registered from 20° C. to −30° C. while for the noninventive material K an increase to 340% is determined.

[0114] Similarly, the inventive material A may be compared to the noninventive material D for example. For the inventive material A an increase in the elastic modulus of 260% is registered from 20° C. to −30° C. while for the noninventive material D an increase in the elastic modulus to 660% is determined.

TABLE-US-00001 TABLE 1a Formulations and properties of materials A-G Material A B C D E F G EB inv. Example/VB comp. EB EB EB VB EB EB EB example HP fraction [%] 47 49 51 53 53 53 53 Average molar weight of PTHF 1700 1700 1700 1000 1200 1400 1500 [Dalton] Poly THF 2000 OHN: 56.1 [g] 37.64 36.16 34.76 0 12.83 22.52 26.54 Poly THF 1000 OHN: 112.2 [g] 8.06 7.74 7.44 37.09 25.58 16.85 13.24 Lupranat MET [g] 40.9 42.15 43.34 47.94 46.62 45.64 45.23 Butanediol, 1,4- [g] 12.31 12.85 13.37 13.87 13.87 13.89 13.89 Density [g/cm.sup.3] 1.14 1.14 1.15 1.17 1.16 1.16 1.16 Hardness [Shore D] 53 54 57 59 59 60 60 Tensile strength [MPa] 37 42 43 57 42 49 41 Elongation at break [%] 370 370 380 430 360 370 330 Tear propagation resistance 96 107 114 171 176 171 168 [kN/m] Abrasion [mm.sup.3] 40 40 43 32 51 58 50 Elastic modulus at 20° C. [MPa] 281 382 435 205 353 528 591 Elastic modulus at 0° C. [MPa] 395 514 587 438 556 870 807 Elastic modulus at −10° C. [MPa] 477 586 680 608 758 954 902 Elastic modulus at −20° C. [MPa] 571 712 809 922 1169 1191 1134 Elastic modulus at −30° C. [MPa] 736 885 1064 1345 1301 1334 1260 Percentage increase in elastic 262 231 244 656 368 253 213 modulus from room temperature to −30° C. Charpy notched impact strength 107 104 102 175 139 117 114 at −10° C. [kJ/m.sup.2] Charpy notched impact strength 110 112 114 15 122 118 116 at −20° C. [kJ/m.sup.2] Charpy notched impact strength 120 120 124 9 25 113 121 at −30° C. [kJ/m.sup.2] Colorability with 2% color 3 3 3 1 1 1 2 masterbatch 1 (*) Colorability with 2% color 3 3 3 1 1 1 2 masterbatch 2 (*) n.d.—not determined

TABLE-US-00002 TABLE 1b Formulations and properties of materials H-N Material H I J K L M N EB inv. Example/VB comp. EB EB EB VB EB EB EB example HP fraction [%] 53 53 57 60.5 62.5 72 60.5 Average molar weight of PTHF 1600 1700 1700 1000 1700 1700 1400 [Dalton] Poly THF 2000 OHN: 56.1 [g] 30.13 33.34 30.54 0 26.63 19.83 18.93 Poly THF 1000 OHN: 112.2 [g] 10.05 7.14 6.54 31.38 5.7 4.24 14.2 Lupranat MET [g] 44.84 44.53 46.9 52.25 50.2 55.95 49.92 Butanediol, 1,4- [g] 13.88 13.89 14.92 15.99 16.37 18.88 15.85 Density [g/cm.sup.3] 1.15 1.15 1.16 1.20 1.18 1.20 n.d. Hardness [Shore D] 58 57 62 75 66 74 n.d. Tensile strength [MPa] 42 43 43 65 44 51 n.d. Elongation at break [%] 330 360 310 380 260 180 n.d. Tear propagation resistance 168 126 155 220 183 238 n.d. [kN/m] Abrasion [mm.sup.3] 48 47 52 22 75 113 n.d. Elastic modulus at 20° C. [MPa] 550 561 803 774 1101 1597 n.d. Elastic modulus at 0° C. [MPa] 731 700 943 1370 1354 2000 n.d. Elastic modulus at −10° C. [MPa] 783 816 1043 1841 1431 2256 n.d. Elastic modulus at −20° C. [MPa] 940 927 1170 2171 1606 2525 n.d. Elastic modulus at −30° C. [MPa] 1137 1286 1439 2642 1980 2835 n.d. Percentage increase in elastic 206 229 179 341 179 178 n.d. modulus from room temperature to −30° C. Charpy notched impact strength 105 105 114 9 91 n.d. n.d. at −10° C. [kJ/m.sup.2] Charpy notched impact strength 107 118 122 9 82 n.d. n.d. at −20° C. [kJ/m.sup.2] Charpy notched impact strength 119 123 117 8 31 n.d. n.d. at −30° C. [kJ/m.sup.2] Colorability with 2% color 3 3 5 1 5 5 1 masterbatch 1 Colorability with 2% color 3 3 5 1 5 5 1 masterbatch 2 n.d.—not determined (*) Assessment of colorability: 1—very good 2—good 3—satisfactory 4—adequate 5—inadequate

CITED LITERATURE

[0115] WO2007/118827A1

[0116] Kunststoffhandbuch, volume VII, edited by Vieweg and Höchtlen, Carl Hanser Verlag, Munich 1966 (p. 103-113)

[0117] EP 0 922 552 A1

[0118] DE 101 03 424 A1

[0119] WO 2006/072461 A1