Ultra-lightweight ski boots

Abstract

The present invention relates to a composition comprising hollow glass microspheres and a thermoplastic polyurethane (TPU-1) obtained or obtainable by reacting an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), the polyol composition (PZ) comprising at least one polyol (P1) selected from polytetrahydrofurans having an average molecular weight Mn in the range of 900 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. The present invention also relates to a ski boot, preferably a ski boot, particularly preferably an outer shell of a ski boot, based on such a thermoplastic polyurethane, and to a method for producing the ski boot.

Description

[Technical field]

[0001] The present invention relates to a composition comprising a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ) comprising at least one polyol (P1) selected from polytetrahydrofurans having an average molecular weight Mn in the range of 900 to 2000 g / mol and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. The present invention further relates to a ski boot, preferably a ski boot, particularly preferably an outer shell of a ski boot, based on such a thermoplastic polyurethane, and to a method for producing the ski boot. [Background technology]

[0002] The production of ski boots, for example ski boots, in particular the outer hard shell of a ski boot, from thermoplastics by injection molding is known.

[0003] Thus, WO 2007 / 118827 A1 discloses a ski boot based on thermoplastic polyurethanes obtainable by conversion of isocyanates with isocyanate-reactive compounds having a molecular weight (Mw) of 500 to 10 000 g / mol and chain extenders having a molecular weight of 50 to 499 g / mol, wherein the chain extenders used are mixtures comprising a main chain extender and one or more co-chain extenders.

[0004] PCT / EP2019 / 064694 relates to a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), the polyol composition (PZ) comprising at least one polyol (P1) and a chain extender (KV1), the polyol (P1) being selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol and the chain extender (KV1) being selected from the group consisting of 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, and its use for the manufacture of ski shoes, in particular ski boots.

[0005] US2018 / 0352894 reports a sports boot comprising a material including a polymer, such as thermoplastic polyurethane, and hollow microball fillers.

[0006] In the development of ski boots there is a particular need to reduce the total mass of the ski boot, so the wall thickness of the outer shell of the ski boot is often reduced.

[0007] The profile of requirements for thermoplastic polyurethanes suitable for producing such ski boots, and in particular their outer shells, is complex. The low temperature properties must be very good, i.e. the material must show sufficient flexibility at the application temperature and not break or peel off. The material must also have a very high stiffness so that a sufficient stiffness of the ski boot can be achieved even with a thin wall thickness, preferably in combination with a low density of the material. It is also advantageous that the change in stiffness in the temperature range from -30 to 20°C is as small as possible, since this makes the handling properties of the ski boot temperature independent. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] WO2007 / 118827A1 [Patent Document 2] PCT / EP2019 / 064694 [Patent Document 3] US2018 / 0352894 Summary of the Invention [Problem to be solved by the invention]

[0009] The materials known from the prior art provide an insufficient fulfillment of these requirements.The object of the present invention is therefore to develop a thermoplastic polyurethane for the manufacture of ski boots which combines very high stiffness with good low temperature properties and low density. [Means for solving the problem]

[0010] This object is achieved according to the present invention by (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 900 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres This is achieved by a composition comprising:

[0011] The invention further relates to a method for producing a ski boot or a part of a ski boot, or a protective suit or a part of a protective suit, comprising the following steps: (A) (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing ski boots or parts of ski boots or protective clothing or parts of protective clothing from the composition provided by step (A); This is achieved by a method comprising:

[0012] Surprisingly, it has been found that the use of a thermoplastic polyurethane (TPU-1) obtained or obtainable using specific isocyanate and polyol components, in combination with the use of hollow glass microspheres, results in a composition having a profile of properties particularly suitable for the manufacture of ski boots. The composition according to the invention has a low density and a modulus of elasticity typically exceeding 150 MPa.

[0013] The composition according to the present invention comprises a thermoplastic polyurethane (TPU-1) and hollow glass microspheres. The thermoplastic polyurethane (TPU-1) is obtained or can be obtained by reacting an isocyanate composition (IZ) containing MDI with a polyol composition (PZ). The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofurans having an average molecular weight Mn in the range of 900 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] According to the present invention, an isocyanate composition (IZ) containing MDI is reacted with a polyol composition (PZ) containing at least one polyol (P1) and a chain extender (KV1). In the context of the present invention, the polyol composition (PZ) may also contain further polyols or further chain extenders. The isocyanate component (IZ) may also contain further isocyanates in addition to MDI.

[0015] Thermoplastic polyurethanes are known in principle. They are typically prepared by reacting isocyanates, isocyanate-reactive compounds and, optionally, chain extenders, optionally in the presence of at least one catalyst and / or customary auxiliaries and / or additives. The isocyanates, isocyanate-reactive compounds and chain extenders are individually or collectively referred to as building block components.

[0016] According to the present invention, the polyol component comprises at least a polyol (P1) as an isocyanate-reactive compound. In the context of the present invention, the polyol (P1) is selected from polytetrahydrofurans having an average molecular weight Mn in the range of 1200 to 2000 g / mol, preferably from polytetrahydrofurans having an average molecular weight Mn in the range of 1300 to 1900 g / mol, more preferably from polytetrahydrofurans having an average molecular weight Mn in the range of 1400 to 1800 g / mol, for example from 1500 to 1700 g / mol.

[0017] Surprisingly, it has been found that the compositions according to the invention exhibit sufficient hardness to be used, in particular for producing ski boots, and are easily pigmentable, despite the molecular weight of the polyol used.

[0018] Thus, in a further embodiment, the present invention provides a thermoplastic polyurethane as described hereinbefore, wherein the polyol (P1) is selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1300 to 1900 g / mol.

[0019] However, in the context of the present invention, the polyol component may also comprise further isocyanate-reactive compounds.

[0020] Further isocyanate-reactive compounds which may in principle be used include any suitable compounds known to the person skilled in the art. In the context of the present invention, it is thus possible to use any suitable diol, for example further polyether diols.

[0021] In the context of the present invention, the chain extender (KV1) is selected from the group consisting of 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol. According to the present invention, it is also possible to use two or more chain extenders, for example a mixture of 1,4-butanediol with a further chain extender. In the context of the present invention, it is preferred to use only one chain extender (KV1).

[0022] In the context of the present invention, it is preferred to use 1,4-butanediol as chain extender. Thus, in a further embodiment, the present invention relates to a thermoplastic polyurethane as described hereinabove, wherein the chain extender (KV1) is 1,4-butanediol.

[0023] In the context of the present invention, the isocyanate composition (IZ) containing MDI is used in the preparation of a thermoplastic polyurethane (TPU-1).

[0024] According to the invention, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) can be used. It is particularly preferred to use only 4,4'-MDI.

[0025] Thus, in a further embodiment, the present invention relates to a composition as described hereinbefore, wherein the thermoplastic polyurethane is based on 4,4'-diphenylmethane diisocyanate (MDI).

[0026] The thermoplastic polyurethane of the boot according to the invention preferably has a hard phase fraction of more than 0.4, particularly preferably more than 0.5. In a further embodiment, the invention thus provides a thermoplastic polyurethane as described hereinabove, in which the thermoplastic polyurethane has a hard phase fraction of more than 0.40, said hard phase fraction being defined by the following formula:

[0027]

number

[0028] The formula has the following definition: M KVx : Molar mass of chain extender x (g / mol) m KVx : Mass of chain extender x (g) M Iso : Molar mass of the isocyanate used (g / mol) m ges : Total mass of all starting materials (g) x: number of chain extenders

[0029] The thermoplastic polyurethane according to the present invention preferably has an elastic modulus in the range of 150 to 1100 MPa, more preferably in the range of 400 to 1000 MPa to 500-900 MPa.

[0030] The thermoplastic polyurethanes according to the invention have good low temperature properties, which are characterized, for example, by the Charpy notched impact strength at -20°C.

[0031] In another embodiment, the present invention provides a Charpy notched impact strength of 5 kJ / m at -20°C according to DIN EN ISO179-1 / 1eA. 2 More than 10 kJ / m 2 For example, in the context of the present invention, a thermoplastic polyurethane may have a modulus of elasticity of about 500 MPa.

[0032] To adjust the hardness of the TPU, the constituent unit components may be varied within a relatively wide molar ratio range. An advantageous molar ratio of polyol to the total chain extender used is, for example, 1:1 to 1:15, preferably 1:4 to 1:12, in particular 1:5 to 1:10, more preferably 1:5 to 1:8, where the hardness of the TPU increases with increasing chain extender content.

[0033] The reaction may be carried out with the customary index, preferably with an index between 950 and 1050, particularly preferably between 970 and 1010, in particular between 980 and 1000, more preferably with an index in the range of 992 to 998. The index is defined as the ratio of all isocyanate groups used for the reaction to isocyanate-reactive groups, i.e. active hydrogen. An index of 1000 corresponds to one active hydrogen atom, i.e. one isocyanate-reactive functional group, per isocyanate group. At an index of more than 1000, there are more isocyanate groups than OH groups. The TPU may be produced continuously by known methods, for example by the "one-shot" method or the prepolymer method using a reactive extruder or belt method, or discontinuously by known prepolymer methods. In these methods, the components to be reacted may be mixed with one another continuously or simultaneously, with immediate initiation of the reaction. In the extruder process, the building block components and any catalyst and / or further auxiliary and additive substances, either individually or as a mixture, are introduced into an extruder at a temperature of, for example, 100° C. to 280° C., preferably 140° C. to 250° C., and the resulting TPU is extruded, cooled and pelletized.

[0034] The catalysts and auxiliary or additive substances used for the preparation of thermoplastic polyurethanes are known per se to the person skilled in the art.

[0035] In a preferred embodiment, the catalysts, which in particular accelerate the reaction between the NCO groups of the diisocyanates, the hydroxyl groups of the isocyanate-reactive compounds and the chain extenders, are tertiary amines, in particular triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane; in another preferred embodiment, they are organometallic compounds, such as titanate esters, iron compounds, preferably iron(III) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctoate, tin dilaurate or dialkyltin salts of aliphatic carboxylic acids, preferably dibutyltin diacetate, dibutyltin dilaurate or bismuth salts, in which the bismuth is preferably in the oxidation state 2 or 3, in particular 3. Salts of carboxylic acids are preferred. The carboxylic acids used are preferably carboxylic acids having from 6 to 14 carbon atoms, particularly preferably having from 8 to 12 carbon atoms. Examples of suitable bismuth salts are bismuth(III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate.

[0036] The catalyst is preferably used in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of the isocyanate-reactive compound. It is preferable to use a tin catalyst, in particular tin dioctoate.

[0037] In addition to the catalyst, it is also possible to use conventional auxiliaries.Examples include surface-active substances, fillers, additional flame retardants, nucleating agents, oxidation stabilizers, lubrication and release aids, dyes and pigments, any stabilizers, such as those against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.Suitable auxiliaries and / or additives are described, for example, in Kunststoffhandbuch, Vol. 7, Carl Hanser Verlag, Munich, 1966 (pp. 103-113), edited by Vieweg and Hoechtlen.

[0038] Methods for producing thermoplastic polyurethanes are disclosed, for example, in EP0922552A1, DE10103424A1 or WO2006 / 072461A1. The production is typically carried out in a belt apparatus or reactive extruder, but can also be carried out on a laboratory scale, for example by manual casting. Depending on the physical properties of the components, these components are all mixed directly with each other, or the individual components are premixed and / or prereacted, for example to give a prepolymer, and only then undergo polyaddition. In a further embodiment, a thermoplastic polyurethane is first produced from the building block components, optionally with a catalyst, optionally with the incorporation of auxiliaries. The homogeneous distribution is preferably carried out in an extruder, preferably a twin-screw extruder.

[0039] To produce the thermoplastic polyurethanes according to the present invention, the constituent unit components are reacted, preferably in the presence of a catalyst and any auxiliary and / or additives, typically in amounts such that the equivalent ratio of the NCO groups of the diisocyanate to the total amount of hydroxyl groups of the components used is 0.95 to 1.05:1, preferably 0.98 to 1.00:1, more preferably 0.992 to 0.998:1.

[0040] Preferably, the thermoplastic polyurethanes produced according to the invention have an average molecular weight (M) in the range of 50,000 to 200,000 Daltons, preferably in the range of 80,000 to 120,000 Daltons. w The thermoplastic polyurethane has an average molecular weight (M w The upper limit of ) is generally determined by processability as well as the spectrum of desired properties.

[0041] The composition according to the invention further comprises hollow glass microspheres. Hollow glass microspheres are known in principle to those skilled in the art. Suitable are, for example, hollow glass microspheres prepared using borosilicate glass, for example soda-lime borosilicate glass.

[0042] Thus, according to a further embodiment, the present invention relates to the composition as disclosed above, wherein the glass is a soda lime borosilicate glass.

[0043] The diameter of the hollow glass microspheres can vary within a wide range: suitable are, for example, microspheres with an average diameter in the range of 5 to 100 μm, preferably in the range of 10 to 75 μm, more preferably in the range of 20 to 50 μm, for example in the range of 20 to 40 μm.

[0044] Thus, according to a further embodiment, the present invention relates to a composition as disclosed above, wherein the microspheres have an average diameter in the range of 5 to 100 μm.

[0045] It has proven particularly advantageous to use hollow glass microspheres in an amount of 1 to 25% by weight, based on the sum of components (i) and (ii).More preferably, the amount of hollow glass microspheres in the composition is in the range of 2 to 15% by weight, based on the sum of components (i) and (ii), in particular in the range of 5 to 10% by weight, based on the sum of components (i) and (ii).

[0046] Thus, according to a further embodiment, the present invention relates to a composition as disclosed above, wherein the composition comprises microspheres in an amount of 1 to 25% by weight based on the sum of components (i) and (ii).

[0047] The composition according to the invention typically has a viscosity of 1.1 g / cm 3 and typically has a modulus of elasticity greater than 150 MPa. Furthermore, the impact strength and notched impact strength at -20°C are typically greater than 5 kJ / m 2 Exceeds.

[0048] The invention therefore relates in a further aspect to a method for producing a boot or a part of a boot, comprising the following steps: (A) (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing a ski boot or a part of a ski boot from the composition provided in step (A); The present invention relates to a method comprising the steps of:

[0049] The methods for preparing the compositions according to the invention are in principle known to those skilled in the art. It has been found to be advantageous to apply only low shear forces when preparing the compositions according to the invention.

[0050] The preparation of step (B) may be carried out using methods that are conventional per se, preferably by injection molding. Thus, in yet another embodiment, the present invention also relates to a method as described hereinabove, in which the composition according to step (B) is processed by injection molding.

[0051] Furthermore, the present invention relates to the use of the compositions disclosed above for the manufacture of ski boots or parts of ski boots or for the manufacture of protective equipment, in particular helmets.

[0052] The above description of the components preferably used in connection with the preferred embodiments is incorporated herein by reference.

[0053] The present invention further relates to a ski boot, preferably a ski boot, particularly preferably an outer shell for a ski boot, based on the above-mentioned composition.The present invention further relates to a method for producing a ski boot, preferably a ski boot, particularly preferably an outer shell for a ski boot, in which a composition according to the invention is processed by injection moulding to obtain an outer shell for a ski boot, preferably a ski boot, particularly preferably a ski boot.

[0054] The present invention further relates to a protective suit, preferably a helmet, based on the above composition.The present invention further relates to a method for producing a protective suit, preferably a helmet, in which the composition according to the invention is processed by injection molding to obtain a protective suit, preferably a helmet.

[0055] The compositions according to the invention are used for the manufacture of ski boots, preferably ski boots, in particular outer shells for ski boots, heels for ski boots, cuffs for the shafts of ski boots, protective clothing, in particular helmets, and decorative elements. It is known to manufacture these products using conventional injection molding methods.

[0056] The present invention therefore also relates in a further aspect to a boot or part of a boot obtained or obtainable by the method described herein above. With regard to preferred embodiments, the above description is incorporated herein by reference.

[0057] Further embodiments of the invention are evident from the claims and the examples. It will be understood that the features of the subject matter / method according to the invention or the use according to the invention listed above and elucidated below can be used not only in the combinations specified in each case, but also in other combinations without departing from the scope of the invention. Thus, for example, combinations of preferred features with particularly preferred features, or combinations of features not further characterized with particularly preferred features, etc., are thus implicitly encompassed, even if this combination is not explicitly mentioned.

[0058] Exemplary embodiments of the invention are described below, but are not intended to limit the invention. In particular, the invention encompasses the embodiments resulting from the dependent references and therefore also the combinations specified below.

[0059] 1. (i) A thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 900 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres A composition comprising:

[0060] 2. The composition according to embodiment 1, wherein the polyol (P1) is chosen from polytetrahydrofurans having an average molecular weight Mn ranging from 1300 to 1900 g / mol.

[0061] 3. The composition of embodiment 1 or 2, wherein the chain extender (KV1) is 1,4-butanediol.

[0062] 4. The thermoplastic polyurethane has a hard phase fraction greater than 0.40, the hard phase fraction being defined by the following formula:

[0063]

number

[0064] The formula has the following definition: M KVx : Molar mass of chain extender x (g / mol) m KVx : Mass of chain extender x (g) MIso : Molar mass of the isocyanate used (g / mol) m ges : Total mass of all starting materials (g) x: number of chain extenders 3. The composition of embodiment 1 or 2.

[0065] 5. The composition of any one of embodiments 1 to 4, wherein the glass is a soda lime borosilicate glass.

[0066] 6. A composition described in any one of embodiments 1 to 5, wherein the microspheres have an average diameter in the range of 5 to 100 μm.

[0067] 7. The composition of any one of the preceding embodiments, wherein the composition comprises microspheres in an amount of 1 to 25% by weight based on the sum of components (i) and (ii).

[0068] 8. A method for producing a ski boot or a part of a ski boot, comprising the following steps: (A) (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing a ski boot or a part of a ski boot from the composition provided by step (A); The method includes:

[0069] 9. The method according to embodiment 8, wherein the polyol (P1) is selected from polytetrahydrofurans having an average molecular weight Mn in the range of 1300 to 1900 g / mol.

[0070] 10. The method of embodiment 8 or 9, wherein the chain extender (KV1) is 1,4-butanediol.

[0071] 11. The thermoplastic polyurethane has a hard phase fraction greater than 0.40, the hard phase fraction being defined by the following formula:

[0072]

number

[0073] The formula has the following definition: M KVx : Molar mass of chain extender x (g / mol) m KVx : Mass of chain extender x (g) M Iso : Molar mass of the isocyanate used (g / mol) m ges : Total mass of all starting materials (g) x: number of chain extenders The method according to any one of embodiments 8 to 10.

[0074] 12. The method of any one of claims 8 to 11, wherein the glass is a soda lime borosilicate glass.

[0075] 13. The method of any one of embodiments 8 to 12, wherein the microspheres have an average diameter in the range of 5 to 100 μm.

[0076] 14. The method of any one of embodiments 8 to 13, wherein the composition comprises microspheres in an amount of 1 to 25% by weight based on the sum of components (i) and (ii).

[0077] 15. The method of any one of embodiments 8 to 14, wherein the composition according to step (B) is processed by injection molding.

[0078] 16. A ski boot or part of a ski boot obtained or obtainable by the method according to any one of embodiments 8 to 15.

[0079] 17. The following steps: (A) (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing a ski boot or a part of a ski boot from the composition provided by step (A); 2. A ski boot or part of a ski boot obtained or obtainable by a process comprising the steps of:

[0080] 18. Use of a composition according to any one of embodiments 1 to 7 for the manufacture of ski boots or parts of ski boots or protective clothing.

[0081] 19. A method for manufacturing protective clothing or a part of protective clothing, comprising the steps of: (A) (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing a protective garment or a part of a protective garment from the composition provided by step (A); The method includes:

[0082] 20. The method according to embodiment 19, wherein the polyol (P1) is selected from polytetrahydrofurans having an average molecular weight Mn in the range of 1300 to 1900 g / mol.

[0083] 21. The method of embodiment 19 or 20, wherein the chain extender (KV1) is 1,4-butanediol.

[0084] 22. The thermoplastic polyurethane has a hard phase fraction greater than 0.40, the hard phase fraction being defined by the following formula:

[0085]

number

[0086] The formula has the following definition: M KVx : Molar mass of chain extender x (g / mol) m KVx : Mass of chain extender x (g) M Iso : Molar mass of the isocyanate used (g / mol) m ges : Total mass of all starting materials (g) x: number of chain extenders 22. The method according to any one of embodiments 19 to 21.

[0087] 23. The method of any one of embodiments 19 to 22, wherein the glass is a soda lime borosilicate glass.

[0088] 24. The method of any one of embodiments 19 to 23, wherein the microspheres have an average diameter in the range of 5 to 100 μm.

[0089] 25. The method of any one of embodiments 19 to 24, wherein the composition comprises microspheres in an amount of 1 to 25% by weight based on the sum of components (i) and (ii).

[0090] 26. The method of any one of embodiments 19 to 25, wherein the composition according to step (B) is processed by injection molding.

[0091] 27. A protective suit or part of a protective suit obtained or obtainable by the method according to any one of embodiments 19 to 26.

[0092] 28. The following steps: (A) (i) a thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol; Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing a protective garment or a part of a protective garment from the composition provided by step (A); Protective clothing or part of protective clothing obtained or obtainable by a process comprising the steps of:

[0093] The following examples are intended to illustrate the invention but are not intended to limit the subject matter in any way. EXAMPLES

[0094] 1. Materials used 3M Specialty Materials' iMK16 Glass Bubbles: GLASS BUBBLES IM16K, target crush strength (90% remaining): 16000psi, true density 0.46g / cm 3 , particle size distribution (10%) 3M QCM 193.2:12 volume μm, particle size distribution (50%) 3M QCM 193.2:20 volume μm, particle size distribution (90%) 3M QCM 193.2:30 volume μm, effective top size, 3M QCM 193.2:40 volume μm, alkalinity <0.5meq / g.

[0095] TPU1: Elastollan 1157D13U from BASF Polyurethanes GmbH Lemfoerde: TPU, based on PTHF with a Shore hardness of 57D and an average molecular weight (Mn) of 1700 Daltons, 1,4-butanediol, MDI

[0096] 2. Example 2 - Preparation of Materials The materials according to Examples 1-4 were produced using a Berstorff ZE40A twin screw extruder with a 35D screw split into 10 barrels. The formulations of the individual materials are summarized in Table 1.

[0097] [Table 1]

[0098] 3. Characterization The mechanical properties of the injection molded bodies were determined and the properties of the individual materials are summarized in Tables 2, 3 and 4.

[0099] [Table 2]

[0100] [Table 3]

[0101] [Table 4]

[0102] The examples show that the addition of glass bubbles significantly reduces the density of the resulting material. The increase in the modulus of elasticity (%) with decreasing temperature is surprisingly low. At the same time, the material has good mechanical properties, in particular good impact strength at low temperatures. The material according to the invention allows, for example, the production of lighter ski boots.

[0103] 4. Method Resin flow rate ratio (MFR) DIN EN ISO1133 Density DIN EN ISO1183-1, A Hardness [Shore D] DIN ISO7619-1 Tensile strength DIN EN ISO527 Elongation at break DIN EN ISO527 Tear propagation resistance DIN ISO34-1, B(b) Elasticity DIN EN ISO527 Charpy impact strength at 23°C DIN EN ISO179-1 / 1eU Charpy impact strength at -20℃ DIN EN ISO179-1 / 1eU Charpy notched impact strength at 23°C DIN EN ISO179-1 / 1eU Charpy notch impact strength at -20°C DIN EN ISO179-1 / 1eU

[0104] References WO2007 / 118827A1 PCT / EP2019 / 064694 US2018 / 0352894 In Kunststoffhandbuch, edited by Vieweg and Hoechtlen, Volume 7, Carl Hanser Verlag, Munich 1966 (pp. 103-113) EP0922552A1 DE10103424A1 WO2006 / 072461A1

Claims

1. A method for producing a ski boot or a part of a ski boot, comprising the following steps: (A) (i) A thermoplastic polyurethane (TPU-1) obtained or obtainable by reaction of an isocyanate composition (IZ) containing MDI with a polyol composition (PZ), The polyol composition (PZ) comprises at least one polyol (P1) selected from polytetrahydrofuran having an average molecular weight Mn in the range of 1200 to 2000 g / mol, and a chain extender (KV1) selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, Thermoplastic polyurethane (TPU-1), and (ii) Hollow glass microspheres providing a composition comprising (B) producing a ski boot or a part of a ski boot from the composition provided by step (A); The method includes:

2. 2. The process according to claim 1, wherein the polyol (P1) is chosen from polytetrahydrofurans having an average molecular weight Mn ranging from 1300 to 1900 g / mol.

3. The method according to claim 1 or 2, wherein the chain extender (KV1) is 1,4-butanediol.

4. The thermoplastic polyurethane has a hard phase fraction greater than 0.40, the hard phase fraction being defined by the following formula: [0010] The formula has the following definition: M ＫＶｘ : Molar mass of chain extender x (g / mol) m ＫＶｘ : mass of chain extender x (g) M Ｉｓｏ : molar mass of the isocyanate used (g / mol) m ｇｅｓ : total mass of all starting materials (g) x: number of chain extenders 4. The method according to any one of claims 1 to 3.

5. 5. The method of claim 1, wherein the glass is a soda lime borosilicate glass.

6. The method according to any one of claims 1 to 5, wherein the microspheres have an average diameter in the range of 5 to 100 µm.

7. The method of any one of claims 1 to 6, wherein the composition comprises the microspheres in an amount of 1 to 25% by weight based on the total of components (i) and (ii).

8. 8. The method according to claim 1, wherein the composition according to step (B) is processed by injection molding.

9. A ski boot or part of a ski boot obtained or obtainable by a method according to any one of claims 1 to 8.

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