TPU with low self-nucleation

Abstract

The present invention relate to a thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein (TPU-1) is characterized by a specific crystallization behavior measured using dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013. The present invention furthermore is directed to a process for preparing an article from said thermoplastic polyurethane as well as the use of a thermoplastic polyurethane according to the present invention for the preparation of a shaped article, preferably a film.

Description

[0001] 240448W001

[0002] TPU with low self-nucleation

[0003] The present invention relates to a thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein (TPU-1) is characterized by a specific crystallization behavior measured using dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013. The present invention furthermore is directed to a process for preparing an article from said thermoplastic polyurethane as well as the use of a thermoplastic polyurethane according to the present invention for the preparation of a shaped article, preferably a film.

[0004] Thermoplastic polyurethanes have various uses in the industrial area, sports and leisure, construction and automobility, and consumer goods. Thermoplastic polyurethanes have the additional advantage that they can easily be recycled. Processes for the preparation of compact and also foamed thermoplastic polyurethanes are in principle known from the state of the art.

[0005] It is known that additives can be used to adjust the properties of the thermoplastic polyurethane depending on the respective application. However, the use of additives often has a negative effect on the mechanical properties of the material.

[0006] In particular for extrusion applications such as blown film production, thermoplastic polyurethanes are required that do not crystallize too quickly even in phases without significant shearing and tempering, but at the same time must have good mechanical properties in the application.

[0007] According to the present invention, this object has been achieved by a thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-1 is characterized in that a sample (S1 ) of (TPU-1)

[0008] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0009] (II) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g wherein sample (S1) is

[0010] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0011] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO

[0012] 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;

[0013] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s. 240448W001

[0014] - 2 -

[0015] The present invention is further directed to a thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-T is characterized in that a sample (ST) of (TPU-T)

[0016] (I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is

[0017] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;

[0018] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C.

[0019] It has surprisingly been found that thermoplastic polyurethanes with advantageous properties can be prepared by adjusting the composition of the thermoplastic polyurethane used for the preparation. It has been found that the composition can be adjusted in a way that the thermoplastic polyurethane does not have hard blocks that crystallize less well due to their symmetry, This specific adjustment allows to prepare thermoplastic polyurethanes which do not crystallize too quickly, but at the same time must have good mechanical properties.

[0020] Self-nucleation of TPUs can lead to an increase in crystallization temperature of the material which in turn has an influence on the processing conditions of the material. In particular in processes to prepare blown films, the material is processed without significant shearing for a certain time. Early crystallization could lead to defects in the film formation.

[0021] Thermoplastic polyurethane (TPU-1 ) is obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC). (TPU-1) is characterized by a very specific crystallization behavior. A sample (S1 ) of (TPU-1)

[0022] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0023] (II) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g.

[0024] According to the present invention, the sample (S1 ) is

[0025] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0026] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO

[0027] 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C; and subsequently

[0028] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s. 240448W001

[0029] - 3 -

[0030] The respective properties are determined using dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013.

[0031] Preferably, (T3) is in the range of from 100 to 250°C. According to a further embodiment, the present invention also relates to a thermoplastic polyurethane as disclosed above, wherein (T3) is in the range of from 100 to 250°C.

[0032] The present invention is further directed to a thermoplastic polyurethane (TPU-T) which is obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC). (TPU-T) is characterized in that a sample (ST) of (TPU-T)

[0033] (i') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content.

[0034] Sample (ST) is

[0035] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement; and

[0036] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C.

[0037] Preferably, (T3') is in the range of from 100 to 250°C. According to a further embodiment, the present invention also relates to a thermoplastic polyurethane as disclosed above, wherein (T3') is in the range of from 100 to 250°C.

[0038] Thermoplastic polyurethane (TPU-1) and (TPU-T) can be prepared from a polyol composition (PC) and an isocyanate composition (IC). By choosing the respective polyol composition, isocyanate composition and ratio of the components used, the properties of the thermoplastic polyurethane obtained can be adjusted.

[0039] One feature of the thermoplastic polyurethane which can be adjusted to influence the crystallization behavior of the thermoplastic polyurethane is the hard segment content.

[0040] The quantitative ratios of the components used for the preparation of (TPU-1) and (TPU-T) respectively are preferably selected such that a hard segment content in the range from 15% to 43% is obtained, preferably in the range of from 20% to 40%, in particular in the range of from 20% to 35%. The hard segment content calculated according to the formula (I) unless otherwise noted: 240448W001

[0041] - 4 -

[0042] According to a further embodiment, the present invention also relates to a thermoplastic polyurethane as disclosed above, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43%, preferably in the range of from 20 to 35 % calculated according to the formula

[0043] Suitable polyols and isocyanates for the preparation of thermoplastic polyurethanes are in principle known to the person skilled in the art.

[0044] According to the invention, the polyol composition (PC) comprises at least one polyol (P1 ). Suitable polyols are known in principle to those skilled in the art and described for example in "Kunststoffhandbuch [Plastics Handbook], volume 7, Polyurethane [Polyurethanes]”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. Particular preference is given to using, as polyol (P1 ), polyesterols or polyetherols as polyols. It is likewise possible to use polycarbonates. Copolymers may also be used in the context of the present invention. Polyether polyols are particularly preferred. The number-average molecular weight of the polyols used according to the invention is preferably in the range from 500 to 5000 g / mol, by way of example in the range from 550 g / mol to 2000 g / mol, preferably in the range from 600 g / mol to 1500 g / mol, especially between 650 g / mol and 1000 g / mol. According to the present invention, the polyols used can be fossil based or non-fossil based.

[0045] Polyol (P1) may for example be selected from unoolar polyols such as for example polycaprolactones or polyethers such as polytrimethyleneoxides, polytetramethyleneoxides , or polypropyleneglycols. Polyol (P1) may be selected from the group consisting of polypropylene glycols, polytetrahydrofuranes, polyadipates, polycarbonates, polycarbonate diols and polycaprolactones.

[0046] Polyetherols, but also polyesterols, block copolymers and hybrid polyols such as for example poly(ester / amide), are suitable according to the invention. According to the invention, preferred polyetherols are polyethylene glycols, polypropylene glycols, polytetramethylene oxides, polytrimethylene oxides. Suitable polyols may also be selected from polyadipates, polycarbonates, polycarbonate diols and polycaprolactone.

[0047] Suitable polyols are also those having ether and ester blocks, for example polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, or else polyethers having pol-ycaprolactone end blocks. According to the invention, preferred polyetherols are polyethylene glycols and polypropylene glycols. Suitable polyols are for example polytetramethylene gylcole or polytrimenthylene glycole. Polycaprolactone is also preferred. According to the present invention, also polyesterols may be used, in particular non fossil based polyesterols. Suitable polyesterols are for example based on succinic acid or adipic acid. Polyols based on castor oil or lignin based polyols may also be used. 240448W001

[0048] - 5 -

[0049] It is also possible in accordance with the invention to use mixtures of different polyols. The polyols / the polyol composition used preferably have / has an average functionality of between 1.8 and 2.3, preferably between 1.9 and 2.2, in particular 2.

[0050] In an embodiment of the present invention, a polyol composition (PC) is used which comprises at least polytetrahydrofuran. According to the invention, the polyol composition may also comprise further polyols in addition to polytetrahydrofuran.

[0051] In a particularly preferred embodiment, the polytetrahydrofuran has a number-average molecular weight Mn in the range from 500 g / mol to 5000 g / mol, preferably in the range of from 500 g / mol to 2000 g / mol, further preferably in the range from 500 to 2000 g / mol, particularly preferably in the range from 500 to 1500 g / mol. Mixtures of various polytetrahydrofurans can also be used in accordance with the invention, that is to say mixtures of polytetrahydrofurans having different molecular weights. Unless otherwise noted, in the context of the invention the molecular weight of the polyols is determined according to DIN 55672-1 :2016-03 using tetrahydrofuran as a solvent.

[0052] Within the context of the present invention, the composition of the polyol composition (PC) can vary within wide ranges. The polyol composition can also comprise mixtures of various polyols.

[0053] According to the invention, the polyol composition may also comprise a solvent. Suitable solvents are known per se to those skilled in the art.

[0054] According to a further embodiment, the present invention also relates to a thermoplastic polyurethane as disclosed above, wherein polyol composition (PC) comprises a polyol selected from the group consisting of polytetrahydrofu- ranes and polyesters based on adipic acid.

[0055] According to the invention, at least one chain extender (CE1) may be present in the polyol composition (PC). Suitable chain extenders are known per se to those skilled in the art. By way of example, chain extenders are compounds having two groups which are reactive towards isocyanate groups, in particular those having a molecular weight of less than 500 g / mol. Suitable chain extenders are for example diamines or diols. Diols are more preferred according to the invention. Within the scope of the pre-sent invention, mixtures of two or more chain extenders may also be used.

[0056] Suitable diols are known in principle to those skilled in the art. According to the invention, the diol preferably has a molecular weight of < 500 g / mol. According to the invention, aliphatic, araliphatic, aromatic and / or cycloaliphatic diols having a molecular weight of 50 g / mol to 220 g / mol can be used here as chain extenders, for example. Preference is given to alkanediols having 2 to 10 carbon atoms in the alkylene radical, especially di-, tri-, tetra-, penta-, hexa-, 240448W001

[0057] - 6 - hepta-, octa-, nona- and / or decaalkylene glycols. For the present invention, particular preference is given to 1,2-eth- ylene glycol, propane-1, 3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1 ,6-diol, preferably propane-1, 3-diol, ethane-1,2-diol, butane-1,4-diol, pentane-1 ,5-diol, hexane-1, 6-diol and HQEE.

[0058] According to a further embodiment, the present invention also relates to a thermoplastic polyurethane as disclosed above, wherein the polyol composition (PC) comprises at least one linear chain extender and preferably is free of branched chain extenders.

[0059] For the preparation of (TPU-1) and (TPU-T), at least one polyisocyanate is used. According to the invention, the polyisocyanate composition may also comprise two or more polyisocyanates. Isocyanates used with preference are aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1 ,5-diisocyanate, 2-ethylbutylene 1 ,4-diisocyanate, pentamethylene 1 ,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclo- hexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and / or 1 ,3-bis(isocyanatomethyl)cy- clohexane (HXDI), paraphenylene 2,4-diisocyanate (PPDI), tetramethylenexylene 2,4-diisocyanate (TMXDI), dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate (H12 MDI), hexamethylene 1,6-diisocyanate (HDI), cyclohexane 1,4- diisocyanate, 1 -methylcyclohexane 2,4- and / or 2,6-diisocyanate, diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocya- nate (MDI), naphthylene 1 ,5-diisocyanate (NDI), tolylene 2,4- and / or 2,6-diisocyanate (TDI), diphenylmethane diisocyanate, 3,3,‘-dimethyl-4,4‘-diisocyanato-diphenyl (TODI), dimethyldiphenyl 3,3'-diisocyanate, diphenylethane 1,2- diisocyanate and / or phenylene diisocyanate or prepolymers of these isocyanates and polyols or isocyanates and iso- cyanate-reactive components.

[0060] Particular preference is given to diphenylmethane 4,4'-diisocyanate (MDI), paraphenylene 2,4-diisocyanate (PPDI), naphthylene 1 ,5-diisocyanate (NDI), 3,3,‘-dimethyl-4,4‘-diisocyanato-diphenyl (TODI) , and linear aliphatic diisocyanates such as for example pentamethylene-1,5-diisocyanate, hexamethylene 1,6-diisocyanate.

[0061] (TPU-1) and (TPU-T) may also comprise further components, such as for example customary auxiliaries. Examples include surface-active substances, fillers, further flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release assistants, dyes and pigments, optionally stabilizers, to counter hydrolysis, light, heat or discoloration, for example; organic and / or inorganic fillers, reinforcing agents, flame retardants, antistatic additives and plasticizers. Suitable auxiliaries and adjuvants may be found in, for example, Kunststoffhandbuch, volume VII, edited by Vieweg and Hdchtlen, Carl Hanser Verlag, Munich 1966 (pp. 103-113).

[0062] It has surprisingly been found that the thermoplastic polyurethane (TPU-1) or (TPU-T) is particularly suitable for extrusion processes, in particular for the preparation of films.

[0063] According to a further aspect, the present invention is also directed to a process for preparing an article comprising 240448W001

[0064] - 7 -

[0065] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) or (TPU-T) according to the present invention,

[0066] (II) preparing the article from composition (C1) by extrusion.

[0067] Composition (C1) may comprise the thermoplastic polyurethane (TPU-1) or (TPU-T) and further components, such as for example further thermoplastic polyurethanes. According to the invention, it is also possible that composition (C1) consist of (TPU-1) or (TPU-T).

[0068] According to a further aspect, the present invention is also directed to an article obtained or obtainable according to the process as disclosed above.

[0069] According to a further aspect, the present invention is also directed to the use of a thermoplastic polyurethane as disclosed above for the preparation of a shaped article, preferably a film. The invention further provides for the use of a thermoplastic polyurethane of the invention as described above for preparing a foam, for example a foam for consumer articles, preferably selected from the group consisting of footwear, in parts for automotive, sport and leisure, or furniture. It has been found that the composition according to the present invention can be advantageously used to prepare foams with low density.

[0070] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The process of any one of embodiments 1 to 3", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1, 2 and 3". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

[0071] 1. Thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-1 is characterized in that a sample (S1) of (TPU-1)

[0072] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0073] (ii) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g wherein sample (S1) is

[0074] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0075] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO

[0076] 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C; 240448W001

[0077] - 8 -

[0078] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s.

[0079] 2. Thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-T is characterized in that a sample (ST) of (TPU-T)

[0080] (I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is

[0081] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;

[0082] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C.

[0083] 3. The thermoplastic polyurethane according to embodiment 1 or embodiment 2, wherein (T3) is in the range of from 100 to 250°C.

[0084] 4. The thermoplastic polyurethane according to any one of embodiments 1 to 3, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43%, preferably in the range of from 20 to 35 %.

[0085] 5. The thermoplastic polyurethane according to any one of embodiments 1 to 4, wherein polyol composition (PC) comprises a polyol selected from the group consisting of polytetrahydrofuranes and polyesters based on adipic acid.

[0086] 6. The thermoplastic polyurethane according to any one of embodiments 1 to 5, wherein the polyol composition (PC) comprises at least one linear chain extender and preferably is free of branched chain extenders.

[0087] 7. Process for preparing an article comprising

[0088] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) or (TPU-T) according to any one of embodiments 1 to 6,

[0089] (II) preparing the article from composition (C1) by extrusion.

[0090] 8. Process for preparing an article comprising 240448W001

[0091] - 9 -

[0092] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-1 is characterized in that a sample (S1) of (TPU-1)

[0093] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0094] (ii) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g wherein sample (S1) is

[0095] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0096] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;

[0097] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s,

[0098] (II) preparing the article from composition (C1) by extrusion.

[0099] 9. Process for preparing an article comprising

[0100] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-T is characterized in that a sample (ST) of (TPU-T)

[0101] (I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is

[0102] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;

[0103] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C,

[0104] (II) preparing the article from composition (C1) by extrusion.

[0105] 10. The process according to embodiment 8 or embodiment 9, wherein (T3) is in the range of from 100 to 250°C. 240448W001

[0106] - 10 -

[0107] 11 . The process according to any one of embodiments 8 to 10, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43%, preferably in the range of from 20 to 35 %.

[0108] 12. The process according to any one of embodiments 8 to 11, wherein polyol composition (PC) comprises a polyol selected from the group consisting of polytetrahydrofuranes and polyesters based on adipic acid.

[0109] 13. The process according to any one of embodiments 8 to 12, wherein the polyol composition (PC) comprises at least one linear chain extender and preferably is free of branched chain extenders.

[0110] 14. Article, obtained or obtainable according to the process according to any one of embodiments 7 to 13.

[0111] 15. Use of a thermoplastic polyurethane according to any one of embodiments 1 to 6 for the preparation of a shaped article, preferably a film.

[0112] 16. Process for preparing an article comprising

[0113] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein (TPU-1) is characterized in that a sample (S1) of (TPU-1)

[0114] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0115] (ii) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g wherein sample (S1) is

[0116] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0117] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;

[0118] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s;

[0119] (II) preparing the article from composition (C1) by extrusion.

[0120] 17. Process for preparing an article comprising

[0121] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein the hard segment content 240448W001

[0122] - 11 - of the thermoplastic polyurethane is in the range of from 15 to 43% and wherein (TPU-1) is characterized in that a sample (S1) of (TPU-1)

[0123] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0124] (ii) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g wherein sample (S1) is

[0125] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0126] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;

[0127] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s;

[0128] (II) preparing the article from composition (C1) by extrusion.

[0129] 18. Process for preparing an article comprising

[0130] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IO), wherein TPU-T is characterized in that a sample (ST) of (TPU-T)

[0131] (I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is

[0132] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;

[0133] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C;

[0134] (II) preparing the article from composition (C1) by extrusion.

[0135] 19. Thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IO), wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43% and wherein (TPU-1) is characterized in that a sample (S1) of (TPU-1)

[0136] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or 240448W001

[0137] - 12 -

[0138] (ii) shows no crystallization peak with a crystallization enthalpy (Ecryst) in a range of > 0.5 J / g wherein sample (S1) is

[0139] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0140] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO

[0141] 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;

[0142] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s.

[0143] 20. Thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-T is characterized in that a sample (ST) of (TPU-T)

[0144] (I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is

[0145] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;

[0146] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C.

[0147] 21 . The thermoplastic polyurethane according to embodiment 20, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43%.

[0148] 22. The thermoplastic polyurethane according to any one of embodiments 19 to 21, wherein (T3) is in the range of from 100 to 250°C.

[0149] 23. The thermoplastic polyurethane according to any one of embodiments 19 to 22, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 20 to 35 %.

[0150] 24. The thermoplastic polyurethane according to any one of embodiments 19 to 23, wherein polyol composition (PC) comprises a polyol selected from the group consisting of polytetrahydrofuranes and polyesters based on adipic acid.

[0151] 25. The thermoplastic polyurethane according to any one of embodiments 19 to 24, wherein the polyol composition (PC) comprises at least one linear chain extender and preferably is free of branched chain extenders. 240448W001

[0152] - 13 -

[0153] 26. Process for preparing an article comprising

[0154] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) or (TPU-1 ') according to any one of embodiments 19 to 25,

[0155] (II) preparing the article from composition (C1) by extrusion.

[0156] 27. Article, obtained or obtainable according to the process according to embodiment 26.

[0157] 28. Use of a thermoplastic polyurethane according to any one of embodiments 19 to 25 for the preparation of a shaped article, preferably a film.

[0158] 29. Thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43% and wherein (TPU-1) is characterized in that a sample (S1) of (TPU-1)

[0159] (I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or

[0160] (ii) shows no crystallization peak with a crystallization enthalpy (ECryst) in a range of > 0.5 J / g wherein sample (S1) is

[0161] (a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;

[0162] (b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO

[0163] 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;

[0164] (c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s.

[0165] 30. Thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43% and wherein TPU-T is characterized in that a sample (ST) of (TPU-T)

[0166] (I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is

[0167] (a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;

[0168] (b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C. 240448W001

[0169] - 14 -

[0170] 31 . The thermoplastic polyurethane according to embodiment 30, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 20 to 40%.

[0171] 32. The thermoplastic polyurethane according to any one of embodiments 29 to 31 , wherein (T3) is in the range of from 100 to 250°C.

[0172] 33. The thermoplastic polyurethane according to any one of embodiments 29 to 32, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 20 to 35 %.

[0173] 34. The thermoplastic polyurethane according to any one of embodiments 29 to 33, wherein polyol composition (PC) comprises a polyol selected from the group consisting of polytetrahydrofuranes and polyesters based on adipic acid.

[0174] 35. The thermoplastic polyurethane according to any one of embodiments 29 to 34, wherein the polyol composition (PC) comprises at least one linear chain extender and preferably is free of branched chain extenders.

[0175] 36. Process for preparing an article comprising

[0176] (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) or (TPU-T) according to any one of embodiments 29 to 35,

[0177] (II) preparing the article from composition (C1) by extrusion.

[0178] 37. Article, obtained or obtainable according to the process according to embodiment 36.

[0179] 38. Use of a thermoplastic polyurethane according to any one of embodiments 29 to 35 for the preparation of a shaped article, preferably a film.

[0180] The present invention is further illustrated by the following examples.

[0181] EXAMPLES

[0182] 1 . Used raw materials:

[0183] Polyol 1 : Polyetherpolyol with an OH-number of 112.3 functionalized with primary OH-groups (based on tetramethylene oxide, functionality of 2)

[0184] Polyol 2: Polyetherpolyol with an OH-number of 56.0 functionalized with primary OH-groups (based on tetramethylene oxide, functionality of 2) 240448W001

[0185] - 15 -

[0186] Polyol 3: Polyesterpolyol with an OH-number of 56.0 functionalized with primary OH-groups (based on adipic acid and 1,6-hexane diol 1 1,4-butane diol (ratio 1 :2), functionality of 2)

[0187] Polyol 4: Polyesterpolyol with an OH-number of 45.5 functionalized with primary OH-groups (based on adipic acid and 1,4-butane diol, functionality of 2)

[0188] Polyol 5: Polyesterpolyol with an OH-number of 112.0 functionalized with primary OH-groups (based on adipic acid and 1,4-butane diol, functionality of 2)

[0189] Polyol 6: Polyesterpolyol with an OH-number of 140.0 functionalized with primary OH-groups (based on adipic acid and 1,4-butane diol, functionality of 2)

[0190] Polyol 7: Polyesterpolyol with an OH-number of 187.0 functionalized with primary OH-groups (based on adipic acid and 1,4-butane diol, functionality of 2)

[0191] Polyol 8: Polyesterpolyol with an OH-number of 56.0 functionalized with primary OH-groups (based on 1,2-ethane diol and 1,4-butane diol (1 :1), functionality of 2)

[0192] Polyol 9: Polyesterpolyol with an OH-number of 38.0 functionalized with primary OH-groups (based on 1,2-ethane diol and 1,4-butane diol (1 :1), functionality of 2)

[0193] Chain extender 1 : 1,4-butane diol

[0194] Isocyanate 1 : aromatic isocyanate (4,4‘-methylenediphenyl diisocyanate)

[0195] Additive 1 : Antioxidant based on sterically hindered phenol

[0196] Additive 2: Wax based on Ethylene bis(stearamide)

[0197] Additive 3: Stabilizer against hydrolysis based on polycarbodiimide

[0198] Additive 4: Montan ester wax

[0199] Additive 5: light stabilizer

[0200] Plasticizer 1 : Tributyl O-Acetylcitrate

[0201] 2. TPU Synthesis

[0202] All formulations are listed in Table 1.

[0203] All TPUs apart of TPU 4, TPU 10, TPU 18 and TPU 19 were obtained respectively by the addition of isocyanate (pre-heated to 50 °C) to a mixture in a reaction vessel stirred at 80 °C containing chain extender, additives, and the respective polyol composition according to Table 1. After reaching a temperature of 110 °C the melt was poured out on a 125 °C warm heating plate. After 10 minutes the obtained slab was put in a heating oven for 15 hours at 80 °C. Finally, the TPU slab was granulated and test plates by injection molding were produced, which were annealed for 20 hours at 100 °C. 240448W001

[0204] - 16 -

[0205] The TPUs TPU 4, TPU 10, TPU 18, and TPU 19 were obtained respectively by the addition of isocyanate (pre-heated to 50 °C) to a mixture in a reaction vessel stirred at 60 °C containing chain extender, additives, and the respective polyol composition according to Table 1.

[0206] 5 After reaching a temperature of 80 °C the melt was poured out on an 80 °C warm heating plate. After 10 minutes the obtained slab was put in a heating oven for 15 hours at 80 °C. Finally, the TPU slab was granulated and test plates by injection molding were produced, which were annealed for 20 hours at 100 °C. 0 Table 1 a: TPU formulations

[0207] 240448W001

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[0209] Table 1 b: TPU formulations

[0210] Table 1c: TPU formulations 240448W001

[0211] - 18 -

[0212] The TPUs were characterized by DSC according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min and a pre-drying step of 10 min at 100 °C. The hold time at the maximal temperature (Tmax = 250 °C) after the first heating run was 2 minutes. Subsequently the cooling run was performed with a cooling rate of 20 °C / min. The crystallization peak minimum (Tcryst) during this cooling run was evaluated.

[0213] By using a new TPU sample another DSC measurement was carried out with a maximal temperature 10 °C higher than the end of the melting endotherm taken from the first heating run of the first DSC investigation. After a hold time of 30 seconds at the maximal temperature of the first heating run the cooling run was carried out with a cooling rate of 20 °C / min.

[0214] Table 2: DSC results 240448W001

[0215] - 19 -

[0216] Examples of the materials were processed on a blown film extruder (30er Brabender equipped with a three zone screw with a mixing element) to obtain 30 m to 150 pm thick films. The screw speed was 15 rpm. The results are summarized in tables 3 to 5.

[0217] Table 3: Temperature profile Table 4: 240448W001

[0218] - 20 -

[0219] Table 5:

[0220] 3dLz[%]= remaining elongation after test

[0221] Creep test based on DIN EN ISO 899-1 :2018: A test specimen is subjected to a constant load which is ob- tained by elongating the sample by 5%. After a holding time of 2 h at room temperature the resulting deformation is measured as a function of time (retardation).

[0222] Literature cited Kunststoffhandbuch [Plastics Handbook], volume 7, Polyurethane [Polyurethanes]”, Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.

Claims

240448W001- 21 -Claims1. Thermoplastic polyurethane (TPU-1) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43% and wherein (TPU-1) is characterized in that a sample (S1) of (TPU-1)(I) shows the highest exothermic maximum (EM) in a temperature range below 100°C or(ii) shows no crystallization peak with a crystallization enthalpy (Ecryst) in a range of > 0.5 J / g wherein sample (S1) is(a) subjected to a pre-treatment including an annealing step for 20 h at a temperature (T1) of 100°C and a separate drying step at a temperature (T2) of 100 °C for 10 min immediately before the measurement;(b) subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3) of 15°C above the end of the first endothermal peak (EP1) which starts in the temperature range of 100 to 110 °C;(c) subjected to a cooling run with a temperature rate of 20°C / min after 30 s.

2. Thermoplastic polyurethane (TPU-T) obtained or obtainable from a polyol composition (PC) and an isocyanate composition (IC), wherein TPU-T is characterized in that a sample (ST) of (TPU-T)(I') shows a separate endothermal peak (EP2') with an enthalpy of greater than 1 J / g with an endothermal maximum in the temperature range of 205 to 240 °C independent of the hard segment content, wherein sample (ST) is(a') subjected to a pre-treatment including an annealing step for 20 h at a temperature (TT) of 100°C and a separate drying step at a temperature (T2') of 100 °C for 10 min immediately before the measurement;(b') subjected to a first heating run of a dynamic scanning calorimetry (DSC) according to DIN EN ISO 11357-3:2013 with a heating rate of 20 °C / min up to a temperature (T3') of up to 250°C.

3. The thermoplastic polyurethane according to claim 2, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 15 to 43%.

4. The thermoplastic polyurethane according to any one of claims 1 to 3, wherein (T3) is in the range of from 100 to 250°C.

5. The thermoplastic polyurethane according to any one of claims 1 to 4, wherein the hard segment content of the thermoplastic polyurethane is in the range of from 20 to 35 %.240448W001- 22 -6. The thermoplastic polyurethane according to any one of claims 1 to 5, wherein polyol composition (PC) comprises a polyol selected from the group consisting of polytetrahydrofuranes and polyesters based on adipic acid.

7. The thermoplastic polyurethane according to any one of claims 1 to 6, wherein the polyol composition (PC) comprises at least one linear chain extender and preferably is free of branched chain extenders.

8. Process for preparing an article comprising (I) providing a composition (C1) comprising a thermoplastic polyurethane (TPU-1) or (TPU-T) according to any one of claims 1 to 7,(II) preparing the article from composition (C1) by extrusion.

9. Article, obtained or obtainable according to the process according to claim 8.

10. Use of a thermoplastic polyurethane according to any one of claims 1 to 7 for the preparation of a shaped article, preferably a film.

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