Thermoplastic polyurethane (TPU) composition having improved properties

Abstract

The present invention relates to a thermoplastic polyurethane composition containing polystyrene and a phosphorus-containing flame retardant.

Description

Technical Field

[0001] The present invention relates to a thermoplastic polyurethane composition having improved mechanical, optical and sensory properties.

[0002] Description of Related Art Thermoplastic polyurethanes are well known and are applied in many fields due to their good mechanical properties (see, for example, EP 00617079, EP 1167429, WO 2015 / 128213, WO 2020 / 002200, WO 2022 / 058514, EP 2021 / 087062, WO 2020 / 221786).

[0003] Currently, in many fields, not only good mechanical properties are required, but also tactile, visual, and sensory properties are increasingly becoming the focus of customers.

[0004] Summary of the Invention Problems Therefore, the problem of the present invention was to develop a new thermoplastic polyurethane that has good mechanical properties and at the same time meets the tactile, visual, and sensory requirements of customers.

[0005] Solutions Surprisingly, it has been found that the thermoplastic polyurethane according to claim 1 meets these requirements.

[0006] Detailed Description of the Invention In a first aspect and Embodiment 1, the present invention relates to a thermoplastic polyurethane composition, wherein the thermoplastic polyurethane is finally a reaction product of at least the following components, a diisocyanate, a polymeric diol, and a chain extender, in the presence of a catalyst, and the composition further comprises polystyrene, a phosphorus-containing flame retardant, and finally additives and / or adjuvants, and the polystyrene is preferably contained in an amount of 0.5 wt% to 15 wt% based on the total amount of the composition. The total amount of the composition is 100 wt%.

[0007] The term "composition" indicates that the composition may contain several polymers, additives and / or adjuvants, rather than only thermoplastic polyurethane.

[0008] Preferably, the thermoplastic polyurethane is prepared by reacting an organic isocyanate, preferably an organic diisocyanate, with an isocyanate-reactive compound, preferably in a preferred embodiment, a polyol having two isocyanate-reactive functional groups (also called a polymer diol).

[0009] The isocyanate-reactive compound preferably has a number average molecular weight of 0.5×10 3 g / mol to 100×10 3 g / mol and, if desired, preferably in the presence of a catalyst, adjuvant, additive, or a mixture thereof, preferably has a chain extender having a molecular weight of 0.05×10 3 g / mol to 0.499×10 3 g / mol.

[0010] The components, the organic isocyanate, preferably the diisocyanate, the isocyanate-reactive compound, preferably in a preferred embodiment, the polymer diol, and the chain extender, are also treated individually or together as constituents. When applicable, the constituents containing a catalyst and / or adjuvant and / or additive are also called the input materials.

[0011] To adjust the hardness and melt flow index of the thermoplastic polyurethane (TPU), the molar ratio of the amounts of the constituents and the chain extender can be varied, whereby the hardness and melt viscosity increase with an increase in the isocyanate content or an increase in the contents of the isocyanate and the chain extender, while the melt flow index decreases.

[0012] To prepare the thermoplastic polyurethane, the constituent components, namely isocyanate, polyol, and chain extender, in a preferred embodiment, in the presence of a catalyst, as well as optionally auxiliaries and / or additives, are reacted in such amounts that the equivalent ratio of the NCO groups of the isocyanate, preferably diisocyanate, to the total of the hydroxyl groups of the isocyanate-reactive components is 0.95:1 to 1.10:1, preferably 0.98:1 to 1.08:1, particularly 1.0:1 to 1.05:1.

[0013] The thermoplastic polyurethane preferably has a weight average molecular weight of at least 0.04×10 6 g / mol, more preferably at least 0.06×10 6 g / mol, more preferably at least 0.07×10 6 g / mol, more preferably at least 0.08×10 6 g / mol. The upper limit of the weight average molecular weight of the TPU is generally determined by the processability and the desired property range. Preferably, the weight average molecular weight does not exceed 0.5×10 6 g / mol, more preferably does not exceed 0.4×10 6 g / mol, more preferably does not exceed 0.25×10 6 g / mol, more preferably does not exceed 0.2×10 6 g / mol. The weight average molecular weight outlined herein is preferably determined by gel permeation chromatography using dimethylformamide (DMF) as the solvent, more preferably in accordance with DIN55672-1.

[0014] Isocyanate In a preferred embodiment 2 according to embodiment 1 or one of its preferred embodiments, the isocyanate comprises an organic isocyanate, more preferably a diisocyanate. Even more preferably, this isocyanate is selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates, or a mixture thereof.

[0015] In preferred embodiment 3 according to one or a preferred one of the preceding embodiments, the isocyanate is selected from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-phenylene diisocyanate (PPDI), 2,4-tetramethylene xylylene diisocyanate (TMXDI), 4,4’-, 2,4’- and 2,2’-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2,6-cyclohexane diisocyanate, 2,2’-diphenylmethane diisocyanate, 2,4’-diphenylmethane diisocyanate, 4,4’-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate (TDI), 3,3’-dimethyl-diphenyl diisocyanate, 1,2-diphenylethane diisocyanate, phenylene diisocyanate, or a mixture thereof.

[0016] When stability against electromagnetic waves, such as light, is important, aliphatic isocyanates are preferred, but when high mechanical strength of polyurethanes, especially thermoplastic polyurethanes, is required, aromatic polyisocyanates are preferred. A further advantage of aliphatic isocyanates is that they may be produced from bio-based sources.

[0017] A highly preferred aliphatic isocyanate is 1,5-pentamethylene diisocyanate. This has the additional advantage that it can be produced from a bio-based source.

[0018] In a preferred embodiment 4 according to one of the preceding embodiments or one of their preferred embodiments, the isocyanate comprises 2,2’-, 2,4’- or 4,4’-diphenylmethane diisocyanate (MDI), or a mixture thereof, and a particularly preferred isocyanate comprises 4,4’-diphenylmethane diisocyanate.

[0019] Polyol In a preferred embodiment 5 according to one of the preceding embodiments or one of their preferred embodiments, the polyol has on average statistically at least 1.8 and at most 3.0 Zerewitinoff active hydrogen atoms. This number is also called the functionality of the isocyanate-reactive compound and indicates the amount of isocyanate-reactive groups of the molecules calculated theoretically from the amount of substance up to 1 molecule. The functionality is preferably from 1.8 to 2.6, more preferably from 1.9 to 2.2, and particularly preferably 2. The compound reactive with isocyanate preferably has a number average molecular weight of 0.5×10 3 g / mol to 8×10 3 g / mol, more preferably 0.7×10 3 g / mol to 6.0×10 3 g / mol, even more preferably 0.8×10 3 g / mol to 4.0×10 3 g / mol.

[0020] Preferably, the polyol is linear and is either a single polyol or a mixture of different polyols, in which case the mixture meets the above requirements.

[0021] The polyol is preferably selected from the group consisting of polyesterols, polyetherols or polycarbonate diols, or a mixture thereof. More preferably, the polyol is selected from the group consisting of polyether diols and polycarbonate diols. Particularly preferably, the polyol is a polyether diol.

[0022] Polyether polyol In a preferred embodiment 6 according to one of the preceding embodiments or one of their preferred embodiments, the polyol comprises a polyether polyol, preferably a polyether diol, and more preferably, the polyether diol is based on ethylene oxide, propylene oxide and / or butylene oxide units, or a mixture thereof.

[0023] More preferably, the polyether polyol comprises polytetramethylene ether glycol (also called PTMEG or PTHF), poly-1,3-propanediol, or poly-1,4-butanediol, or a mixture thereof. Particularly preferably, it is PTHF.

[0024] In a preferred embodiment 7 according to one of the preceding embodiments or one of their preferred embodiments, the polyether polyol has a number average molecular weight of 0.6×10 3 g / mol to 2.0×10 3 g / mol, preferably 0.8×10 3 g / mol to 1.9×10 3 g / mol, more preferably 0.8×10 3 g / mol to 1.2×10 3 g / mol, or 1.3×10 3 g / mol to 1.9×10 3 g / mol, most preferably 1.0×10 3 g / mol or 1.4×10 3 g / mol.

[0025] The number average molecular weight Mn in the context of the present invention is preferably determined in accordance with DIN 55672-1.

[0026] A very preferred polyether polyol is polytetrahydrofuran (PTHF), preferably having the molecular weight shown above for the polyether polyol.

[0027] The polyether polyol is obtained by known methods such as the reaction between at least one starting molecule such as ethylene glycol, propylene glycol, etc. and an alkylene oxide such as ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide, or a reaction derived from tetrahydrofuran.

[0028] In another preferred embodiment 8 according to one of the preceding embodiments or one of their preferred embodiments, 1,3-propanediol, poly-1,4-butanediol diol, or a mixture thereof is 1.2×10 3 g / mol to 1.8×10 3 g / mol, more preferably 1.3×10 3 g / mol to 1.5×10 3 g / mol, most preferably 1.4×10 3 g / mol. In a preferred embodiment, the polyol is a mixture of poly-butane-1,4-diol having a molecular weight of 1.0×10 3 g / mol and 2.0×10 3 g / mol.

[0029] The polyether polyol has the advantage of being more stable to hydrolysis and is thus applicable to uses where this is a requirement.

[0030] Polyester polyol In Preferred Embodiment 9 according to one or a preferred one of the preceding embodiments, the polyol includes a polyester polyol. Preferably, the polyester is selected from the group consisting of a reaction product of a polyhydric alcohol, a polymerization product of a lactone, and a polymerization product of a dicarboxylic acid and a polyhydric alcohol. The term "lactone" refers to a cyclic ester of a hydroxycarboxylic acid. Such polyester polyols include polyester polyols obtained as a hydroxyl-terminated reaction product of a polyhydric alcohol, a polymerization product of a lactone such as caprolactone and a polyol, and a polyester polyol obtained by polymerization of a dicarboxylic acid such as adipic acid and a polyhydric alcohol. Preferred polyester polyols include a polymerization product of a lactone or polycaprolactone and a polymerization product obtained by polymerization of a dicarboxylic acid and a polyhydric alcohol.

[0031] Preferably, the polyester polyol is obtained by polymerizing a dicarboxylic acid and a polyhydric alcohol. Preferred dicarboxylic acids are at least one of C4-C12 dicarboxylic acids, while at least one of C2-C14 diols is suitable as the polyhydric alcohol. Preferably, the C4-C12 dicarboxylic acid is selected from the group consisting of aliphatic dicarboxylic acids preferably selected from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, or a mixture thereof, and the aromatic dicarboxylic acid is preferably selected from phthalic acid, isophthalic acid and terephthalic acid, or a mixture thereof. More preferably, the dicarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, suberic acid, phthalic acid, isophthalic acid and terephthalic acid, or a mixture thereof. Most preferably, the dicarboxylic acid is selected from the group consisting of adipic acid, suberic acid and phthalic acid, or a mixture thereof.

[0032] Preferably, the C2-C14 diol used to obtain the polyester polyol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-propan-1,3-diol, 1,3-propanediol, 2-methyl-1,3-propanediol and dipropylene glycol, or a mixture thereof. More preferably, the diol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol or a mixture thereof. Most preferably, it is selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol or a mixture thereof.

[0033] The polyester polyol has low stability against hydrolysis and is preferred in applications where biodegradability is required.

[0034] Polycarbonate diol In Preferred Embodiment 10 according to one of the preceding embodiments or one of their preferred embodiments, the polyol included a polycarbonate diol, preferably an aliphatic polycarbonate diol. Preferred polycarbonate diols are polycarbonate diols based on alkanediols. The production of polycarbonate diols can be carried out by polycondensation of phosgene and diol or ring-opening polymerization of cyclic carbonates. As a preferred alternative to phosgene synthesis, transesterification with a carbonic acid diester is applied.

[0035] Preferred polycarbonate diols are strictly OH-bifunctional polycarbonate diols, preferably strictly OH-bifunctional aliphatic polycarbonate diols. Preferred polycarbonate diols are based on butanediol, pentanediol or hexanediol. In particular, the polycarbonate diol is based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol, or a mixture thereof. More preferred polycarbonate diols are based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture thereof. Even more preferred are polycarbonate diols based on butanediol and hexanediol, polycarbonate diols based on pentanediol and hexanediol, polycarbonate diols based on hexanediol, or mixtures thereof.

[0036] Preferably, the polycarbonate diol has a number average molecular weight Mn in the range of 0.5×10 3 ~4.0×10 3 g / mol, preferably in the range of 0.65×10 3 g / mol to 3.0×10 3 g / mol, preferably in the range of 0.8×10 3 g / mol to 2.5×10 3 g / mol, and more preferably, the number average molecular weight is in the range of 1.8×10 3 g / mol to 2.2×10 3 g / mol or 0.8×10 3 g / mol to 1.2×10 3 g / mol.

[0037] The polycarbonate diol has better permeability to microwaves, less uptake of dirt, and exhibits better flame retardancy.

[0038] Mixture of polyols In one preferred embodiment, the polyol is a single polyol, and in another preferred embodiment, the polyol is a mixture of two or more of the above preferred polyols.

[0039] In a preferred embodiment 11 according to one of the preceding embodiments or one of their preferred embodiments, the polyol is a mixture of at least one polyether polyol and at least one polycarbonate diol.

[0040] In the mixture of polyether polyol and polycarbonate diol, the polycarbonate diol is preferably used in an amount of less than 50% by weight, preferably less than 30% by weight, based on the total weight of the polyol.

[0041] Chain extender Furthermore, a chain extender is used in the synthesis of the thermoplastic polyurethane. In a preferred embodiment 12 according to one of the preceding embodiments or one of their preferred embodiments, the chain extender comprises aliphatic, araliphatic, aromatic and / or alicyclic compounds. Preferably, the chain extender has a number average molecular weight of 0.05×10 3 g / mol to 0.499×10 3 g / mol. The chain extender preferably has two isocyanate-reactive groups. These groups are also called functional groups. The chain extender can be either a single chain extender or a mixture of at least two chain extenders.

[0042] In a preferred embodiment 13 according to one of the preceding embodiments or one of their preferred embodiments, the chain extender is a difunctional compound, and preferred examples are preferably diamines or alkanediols having 2 to 10 carbon atoms in the alkylene group, or mixtures thereof.

[0043] In a preferred embodiment 14 according to one or a preferred one of the preceding embodiments, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycol dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanol cyclohexane, neopentyl glycol and hydroquinone bis(β-hydroxyethyl) ether (HQEE), or a mixture thereof.

[0044] More preferably, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycol, preferably the respective oligo- and / or polyalkylene glycol, or a mixture thereof.

[0045] In a preferred embodiment 15 according to one or a preferred one of the preceding embodiments, the chain extender comprises 1,2-ethylene diol, 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol, or a mixture thereof, and most preferably, the chain extender comprises 1,4-butanediol.

[0046] Catalyst In a preferred embodiment 16 according to any one of the preceding embodiments or a preferred one of them, the composition further comprises a catalyst. The catalyst is a single catalyst or a mixture of several catalysts.

[0047] The catalyst preferably promotes the reaction between the NCO groups of the isocyanate and the hydroxyl groups of the polyol and the chain extender. In a preferred embodiment, the catalyst is selected from the group consisting of tertiary amines and organometallic compounds, or a mixture thereof.

[0048] Preferred organometallic compounds are selected from the group consisting of titanium esters, iron compounds, tin compounds, and bismuth salts, or a mixture thereof. A preferred iron compound is iron(III) acetylacetonate. Preferred tin compounds are selected from the group consisting of tin diacetate, tin dioctanoate, tin dilaurate, tin(II) neodecanoate, and dialkyltin salts of aliphatic carboxylic acids, or a mixture thereof. Preferably, the catalyst is tin dioctanoate, tin(II) neodecanoate, or a mixture thereof. A preferred titanium ester is tetrabutyl orthotitanate. In a preferred bismuth salt, bismuth is present in an oxidation state of 2 or 3, particularly 3, and salts of carboxylic acids, preferably carboxylic acids having 6 to 14 carbon atoms, particularly preferably 8 to 12 carbon atoms, are preferred. Highly preferred bismuth salts are bismuth(III) neodecanoate, bismuth 2-ethylhexanoate, or bismuth octanoate, or a mixture thereof.

[0049] The catalyst is preferably used in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of the polyol. It is preferred to use a tin catalyst, particularly tin dioctanoate.

[0050] In preferred embodiment 17 according to any of the preceding embodiments or one of their preferred embodiments, the composition contains SDO (tin(II) 2-ethylhexanoate), tin(II) neodecanoate, or a mixture thereof, and is preferably used in an amount of 0.35 to 0.4 parts by weight based on the total composition.

[0051] The catalyst is either a single substance or a mixture of at least two substances.

[0052] Auxiliary agent In preferred embodiment 18 according to one of the preceding embodiments or one of its preferred embodiments, an auxiliary agent or an additive is included in the composition. The additive or auxiliary agent is either a single substance or a mixture of at least two substances. Preferred examples include surfactants, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubrication aids, mold release aids, dyes, pigments, inorganic or organic fillers, reinforcing agents, plasticizers, antistatic agents, stabilizers, preferably stabilizers against hydrolysis, light, heat or discoloration.

[0053] A stabilizer in the meaning of the present invention is an additive that protects plastics or plastic compositions from the effects of a harmful environment. Preferred examples are primary or secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, phosphites, hydrolysis inhibitors, quenchers, and flame retardants. Examples of commercially available stabilizers are shown in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pp. 98 - S136.

[0054] Preferably, the UV absorber has a number average molecular weight greater than 0.3×10 3 g / Mol, particularly greater than 0.39×10 3 g / Mol. Further, a preferred UV absorber has a molecular weight not exceeding 5×10 3 g / Mol.

[0055] The UV absorber is preferably selected from the group consisting of cinnamates, oxanilides, benzophenones and benzotriazoles, or a mixture thereof, and benzotriazole is particularly suitable as a UV absorber. Examples of particularly suitable UV absorbers are Tinuvin® 213, Tinuvin® 234, Tinuvin® 312, Tinuvin® 571, Tinuvin® 384 and Eversorb® 82.

[0056] Preferably, the UV absorber is added in an amount of 0.01 wt% to 5 wt%, preferably 0.1 wt% to 2.0 wt%, particularly 0.2 wt% to 0.5 wt% based on the total weight of the composition.

[0057] In many cases, UV stabilization based on antioxidants and UV absorbers as described above is not sufficient to guarantee good stability of the composition against the harmful effects of ultraviolet light. In this case, in addition to the antioxidant and / or UV absorber, or as a single stabilizer, a hindered amine light stabilizer (HALS) is added to the composition.

[0058] Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Munich, 2001, pp. 123 - 136.

[0059] Particularly preferred hindered amine light stabilizers are bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin® 765, Ciba Spezialitatenchemie AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622). In particular, when the titanium content of the final product is less than 150 ppm, preferably less than 50 ppm, particularly less than 10 ppm, based on the components used, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622) is preferred.

[0060] The HALS compound is preferably used at a concentration of 0.01 wt% to 5 wt%, particularly preferably 0.1 wt% to 1 wt%, particularly 0.15 wt% to 0.3 wt% based on the total weight of the composition.

[0061] Particularly preferred UV stabilizers contain a mixture of phenolic stabilizers, benzotriazoles and HALS compounds in the above preferred amounts.

[0062] Further information on the above auxiliaries and additives can be found in technical literature, for example, Plastics Additives Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001.

[0063] Polystyrene Surprisingly, when polystyrene is added to a composition containing thermoplastic polyurethane, the surface of the composition discolors, whereby scratches and the like are less prominent, which has been found to be a great advantage for customers.

[0064] In a preferred embodiment 19 according to one of the preceding embodiments or one of their preferred embodiments, polystyrene is included in an amount of 0.5 wt% to 15 wt%, more preferably 0.5 wt% to 7 wt%, based on the total amount of the composition. The total amount of the composition is 100 wt%.

[0065] Preferred polystyrene is an impact polystyrene copolymer based on the monomers styrene and butadiene.

[0066] In a preferred embodiment, polystyrene satisfies at least one of the following properties, most preferably all of the following properties.

[0067] Preferably, the impact polystyrene copolymer preferably has a modulus of elasticity of 1500 to 3300 N / mm, preferably 1700 to 2500 N / mm, measured according to DIN53 457. The tensile strength of the polystyrene copolymer is preferably 18 to 35, preferably 20 to 26 N / mm, measured according to DIN53 455. 2 Preferably 1700 to 2500 N / mm 2 The tensile strength of the polystyrene copolymer is preferably 18 to 35, preferably 20 to 26 N / mm, measured according to DIN53 455. 2 is.

[0068] The tear elongation of polystyrene is preferably 30% to 55%, more preferably 40% to 50%, measured according to DIN53 455.

[0069] The impact strength (Charpy) of polystyrene at -40 °C is preferably measured according to DIN 53 453 and is 50 kJ / m 2 ~100 kJ / m 2 and preferably 60 kJ / m 2 ~70 kJ / m 2 The Vicat softening temperature of polystyrene is preferably measured according to DIN 53 460 VTS / A / 50 and is 75 °C to 97 °C, preferably 80 to 90 [°C].

[0070] In a preferred embodiment 20 according to one of the preceding embodiments or one of their preferred embodiments, the composition comprises cresol, phenol, piperazine, resorcinol, derivatives of bisphenol A, or mixtures thereof.

[0071] Flame retardant The composition according to any of the preceding embodiments or one of their preferred embodiments further comprises a phosphorus-containing flame retardant.

[0072] The flame retardant is used in the form of a single substance or a mixture of several substances of the same type or different types of flame retardants in the composition. In a preferred embodiment, the flame retardant is a liquid, preferably a liquid at a temperature of 21 °C. In a preferred embodiment, the liquid has a viscosity at 25 °C of 1 mPas to 1×10 3 mPas, preferably 1 mPas to 3×10 3 mPas, more preferably 5 mPas to 1×10 3 mPas, more preferably 3×10 mPas to 0.8×10 3 mPas, more preferably 3.5×10 2 mPas to 8×10 2 mPas. The viscosity is preferably the kinematic viscosity.

[0073] In the preferred embodiment 21 according to one of the preceding embodiments or one of their preferred embodiments, the phosphorus-containing flame retardant is a derivative of phosphorous acid, phosphonic acid, or phosphinic acid, or a mixture thereof.

[0074] In the preferred embodiment 22 according to one of the preceding embodiments or one of their preferred embodiments, the phosphorus-containing flame retardant is contained in the composition in an amount of 5% to 40% by weight, more preferably 10% to 30% by weight. Further, when no non-phosphorus-containing flame retardant is present in the composition, the amount of the phosphorus-containing flame retardant in the composition is preferably 15% to 30% by weight.

[0075] Preferably, the flame retardant has an average particle size D50 in the range of 0.1 μm to 100 μm, preferably 0.5 μm to 60 μm, particularly preferably 3 μm to 50 μm. The particles preferably have an average particle size D99 of less than 100 μm, more preferably less than 90 μm. In the context of the present invention, the flame retardant preferably has an average particle size D50 in the range of 0.1 μm to 100 μm and an average particle size D99 of less than 100 μm. In the context of the present invention, the particle size distribution may be unimodal or multimodal, more preferably bimodal.

[0076] Phosphate ester The phosphate ester is preferably a triester, more preferably a trialkyl phosphate. Another preferred phosphate ester is a triaryl phosphate, more preferably triphenyl phosphate.

[0077] In the preferred embodiment 23 according to one of the preceding embodiments or one of their preferred embodiments, the phosphate ester has the general formula (I)

Chemical formula

[0078] When R in the general formula (I) is an alkyl moiety, the preferably used alkyl moieties are those having 1 to 8 carbon atoms. Cyclohexyl is a preferred example of a cycloalkyl group. In other preferred embodiments, R represents phenyl or alkyl-substituted phenyl.

[0079] Preferably, n is 1 or an integer from 3 to 6.

[0080] In preferred embodiment 24 according to one of the preceding embodiments or one of their preferred embodiments, the phosphate ester is selected from the group consisting of resorcinol bis-diphenyl phosphate (RDP), bisphenol-A bis-(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK), or is the corresponding oligomer, or is a mixture thereof. The oligomer preferably has an average degree of oligomerization of n = 3 to 6.

[0081] Most preferably, the flame retardant comprises resorcinol bis-diphenyl phosphate (RDP), more preferably in the form of an oligomer having an average degree of oligomerization of n = 3 to 6. The phosphate derivative is preferably included in an amount of 1 wt% to 25 wt%, preferably 2 wt% to 12 wt%, most preferably 2 wt% to 6 wt% based on the total composition.

[0082] These flame retardants are liquid at room temperature, are thus more readily processable, and furthermore exhibit a plasticizer effect in the composition which is particularly preferred when the composition is flexible, and are thus particularly advantageous.

[0083] Phosphinate In preferred embodiment 25 of the composition according to one of the preceding embodiments or one of their preferred embodiments, the flame retardant comprises a derivative of phosphinic acid.

[0084] Preferably, the derivative of phosphinic acid is selected from salts of phosphinic acid containing organic or inorganic cations or organic esters, or is a mixture thereof.

[0085] Phosphoric acid esters have the general formula R1R2(P=O)OR3, where the three organic groups R1, R2, and R3 may all be the same or different. The groups R1, R2, and R3 are either aliphatic or aromatic, preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms. Preferably, at least one of the groups is aliphatic, preferably all the groups are aliphatic, and most preferably R1 and R2 are ethyl groups. It is more preferable that R3 is also aliphatic, and it is more preferably an ethyl group or a methyl group. In a preferred embodiment, R1, R2, and R3 are simultaneously ethyl groups or methyl groups.

[0086] Another preferred derivative of phosphoric acid is phosphinate, i.e., the general formula: R1R2(P=O)O - Me + which is a salt of phosphoric acid having. The R1 and R2 groups are either aliphatic or aromatic. More preferably, R1 and R2 independently have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms. Preferably, at least one of the R1 or R2 groups is aliphatic, and preferably both groups are aliphatic. Me + is preferably an alkali metal or alkaline earth metal, or a mixture thereof, and more preferably Me + is aluminum, calcium, or zinc, or a mixture thereof, and more preferably Me + is aluminum or zinc, or a mixture thereof, and most preferably Me + is aluminum.

[0087] Another preferred derivative of phosphoric acid is the metal hypophosphite having the general formula: H2(P=O)O - Me + and preferably Me + is an alkali metal or alkaline earth metal, or a mixture thereof, and preferably Me +It is aluminum, titanium, or zinc, or a mixture thereof. Particularly preferred salts are aluminum hypophosphite or calcium hypophosphite, or a mixture thereof, and most preferably aluminum hypophosphite.

[0088] In a preferred embodiment 26 of the composition according to one of the preceding embodiments or one of their preferred embodiments, the flame retardant comprises diethylaluminum phosphinate and the above-mentioned preferred derivatives of phosphoric acid. More preferably, the derivative of phosphoric acid is selected from the group consisting of resorcinol bis-diphenyl phosphate (RDP), bisphenol-A bis-(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK), or is the corresponding oligomer, or a mixture thereof. The oligomer preferably has an average degree of oligomerization of n = 3 to 6.

[0089] In a preferred embodiment 27 according to one of the preceding embodiments or one of their preferred embodiments, the flame retardant comprises diethylaluminum phosphinate and resorcinol bis(diphenyl phosphate) (RDP), more preferably RDP in the form of an oligomer having an average degree of oligomerization of n = 3 to 6.

[0090] In a preferred embodiment, the content of the derivative of phosphinic acid in the composition ranges from 5 to 45% by weight, particularly 7 to 30% by weight, more preferably 8 to 18% by weight, and even more preferably 10 to 15% by weight based on the total weight of the composition.

[0091] In a preferred embodiment, aluminum diethylphosphinate has an average particle size D50 in the range of 20 μm to 80 μm, preferably 20 μm to 40 μm.

[0092] Melamine polyphosphate In preferred embodiment 28, the composition according to one of the preceding embodiments or one of their preferred embodiments contains melamine polyphosphate.

[0093] Preferably, the melamine polyphosphate has a phosphorus content in the range of 7 to 20% by weight, preferably in the range of 10 to 17% by weight, more preferably in the range of 12 to 14% by weight, based on the total weight of the melamine polyphosphate.

[0094] The melamine polyphosphate preferably consists of particles having an average particle size D50 in the range of 0.1 μm to 100 μm, preferably 0.5 μm to 60 μm, particularly preferably 1 μm to 10 μm.

[0095] In preferred embodiment 29 according to preceding embodiment 28 or one of their preferred embodiments, the melamine polyphosphate is present in the composition in an amount of 2 to 35% by weight, particularly 3 to 15% by weight, more preferably 4 to 8% by weight, based on the whole composition.

[0096] In preferred embodiment 30, the composition according to any of the preceding embodiments or one of their preferred embodiments does not contain melamine cyanurate. "Does not contain melamine cyanurate" preferably means that the composition contains less than 5% by weight of melamine cyanurate, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.01% by weight, more preferably less than 50 ppm, preferably less than 20 ppm. In a highly preferred embodiment, the composition contains 0 ppm of melamine cyanurate.

[0097] In preferred embodiment 31 according to any of the preceding embodiments or one of their preferred embodiments, the flame retardant contains phosphinates, preferably diethylaluminum phosphinate, and the above-mentioned preferred derivatives of phosphoric acid, most preferably resorcinol bis(diphenyl phosphate) (RDP), more preferably in the form of an oligomer having an average degree of oligomerization of n = 3 to 6, and the above-mentioned preferred melamine polyphosphate.

[0098] Piperazine pyrophosphate and poly(piperazine pyrophosphate) In a preferred embodiment 32 according to one of the preceding embodiments, preferably embodiments 1 to 27, or one of their preferred embodiments, the flame retardant comprises piperazine pyrophosphate or poly(piperazine pyrophosphate), or a mixture thereof.

[0099] In the context of the present invention, the (poly)piperazine pyrophosphate used herein means piperazine pyrophosphate represented by the following formula (I) or (II), or a mixture of piperazine pyrophosphate represented by formula (I) and poly(piperazine pyrophosphate) represented by formula (II). [Chemical formula] [Chemical formula] (n in formula (II) is an integer from 2 to 100.)

[0100] Preferably, it is piperazine pyrophosphate.

[0101] Preferably, piperazine pyrophosphate or poly(piperazine pyrophosphate) consists of particles, preferably particles having an average particle size D98 in the range of 5 μm to 100 μm, more preferably 10 μm to 90 μm, still more preferably 20 μm to 80 μm, and most preferably 30 to 70 μm.

[0102] Preferably, piperazine pyrophosphate is present in the composition in an amount of 2 to 35% by weight, particularly 3 to 15% by weight, more preferably 4 to 8% by weight, based on the total composition.

[0103] Ammonium polyphosphate In a preferred embodiment 32 according to one of the preceding embodiments, preferably one of embodiments 1 to 27, or one of their preferred embodiments, the flame retardant comprises ammonium polyphosphate.

[0104] Preferred ammonium polyphosphates are preferably, but not exclusively, those found in J. Am. Chem. Soc. 91, 62 (1969), preferably those having crystal structure phase 1, or those having crystal structure phase 2, or mixtures thereof.

[0105] Preferably, the ammonium polyphosphate has a number average molecular weight greater than 20×10 3 and preferably greater than 80×10 3 and more preferably greater than 1×10 5 . The average number average molecular weight of the ammonium polyphosphate is preferably from 20×10 3 to 1.5×10 5 .

[0106] In a preferred embodiment 33 according to a preceding embodiment 32 or one of their preferred embodiments, the phosphate component is coated. The coating is at least in part.

[0107] The coating of the phosphate results in a composition with a low tendency to bloom.

[0108] Preferred coated ammonium polyphosphates are described in U.S. Patent No. 4,347,334, U.S. Patent No. 4,467,056, U.S. Patent No. 4,514,328, and U.S. Patent No. 4,639,331, which are hereby incorporated by reference. Such encapsulated ammonium polyphosphates preferably comprise a cured water-insoluble resin that encapsulates the individual ammonium polyphosphate particles. The resin is preferably based on urea resin, epoxy resin, or silane.

[0109] Preferred coatings are based on organofunctional silanes or mixtures thereof, or on oligomeric organosiloxanes or mixtures thereof. Preferred organofunctional silanes are alkoxysilanes having aminoalkyl functionality, epoxyalkyl-, acryloxyalkyl-, methacryloxyalkyl-, mercaptoalkyl-, alkenyl-, or alkyl functionality, or mixtures thereof, and the alkoxy groups are preferably methoxy, ethoxy or propoxy groups, or mixtures thereof.

[0110] Particularly preferred organofunctional alkoxysilanes are 3-aminopropyltrialkoxysilane, 3-aminopropylmethyldialkoxysilane, 3-glycidyloxypropyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyldialkoxysilane, vinyltrialkoxysilane, vinyltris(2-methoxyethoxy)silane, propyltrialkoxysilane, butyltrialkoxysilane, pentyltrialkoxysilane, hexyltrialkoxysilane, heptyltrialkoxysilane, octyltrialkoxysilane, propylmethyldialkoxysilane and butylmethyldialkoxysilane, or mixtures thereof, and the alkoxy groups are preferably methoxy, ethoxy or propoxy groups, or mixtures thereof.

[0111] The coating is preferably applied in an amount of 0.05 wt% to 10 wt%, particularly preferably 0.1 wt% to 3 wt%, very particularly preferably 0.5 wt% to 1.5 wt% of the silicon-containing coating agent, based on the amount of the flame retardant.

[0112] Preferably, ammonium polyphosphate has a solubility in water of less than 1.0 g / l, in particular less than 0.1 g / l. The solubility in water is preferably determined by shaking 50 g of each flame with 200 g of water at 20 °C for 1 hour, filtering through a 0.2 μm filter, drying the filter together with the filtrate at 70 °C for 12 hours, and quantifying the filtrate.

[0113] Ammonium polyphosphate preferably consists of particles having an average particle size D50 of 0.1 μm to 100 μm, preferably 0.5 μm to 60 μm, particularly preferably 1 μm to 30 μm, and very particularly preferably 5 μm to 25 μm. Preferably, ammonium polyphosphate is a dry powder, more preferably a free-flowing powder.

[0114] In another preferred embodiment, the particles preferably have an average particle size D99 of less than 100 μm, more preferably less than 90 μm. In the context of the present invention, the particles preferably have an average particle size D50 in the range of 0.1 μm to 100 μm and an average particle size D99 of less than 100 μm. Preferably, the particle size distribution is unimodal, multimodal, for example bimodal, or a mixture thereof.

[0115] Preferably, ammonium polyphosphate is present in the composition in an amount of 2 to 35% by weight, in particular 3 to 15% by weight, more preferably 4 to 8% by weight, based on the total composition.

[0116] Preferred combinations of flame retardants In a preferred embodiment 34 of the composition according to one of the preceding embodiments, preferably one of embodiments 1 to 27, or one of their preferred embodiments, the phosphorus-containing flame retardant comprises the above-mentioned preferred derivative of phosphoric acid as the first flame retardant F1, the above-mentioned preferred derivative of phosphinic acid as the second flame retardant F2, and a third flame retardant F3 selected from melamine polyphosphate, piperazine pyrophosphate, polypiperazine pyrophosphate, ammonium polyphosphate, or a mixture thereof. A very preferred third flame retardant F3 is melamine polyphosphate. The reason is that it has low water solubility.

[0117] In a preferred embodiment 35 of a composition according to one of the preceding embodiments, preferably one of embodiments 1 to 27, or one of their preferred embodiments, the phosphorus-containing flame retardant comprises, as flame retardant F1, a derivative of a phosphoric acid ester, preferably resorcinol bis(diphenyl phosphate) (RDP), diphenyl cresyl phosphate (DPK), or bisphenol A bis-(diphenyl phosphate) (BDP), or a mixture thereof, as flame retardant F2, a derivative of phosphinic acid, preferably a phosphinate having the formula: R1R2(P=O)O-Me (wherein R1 and R2 are ethyl groups and Me is aluminum or zinc), and a third flame retardant F3, the third flame retardant F2 being selected from melamine polyphosphate, piperazine pyrophosphate, polypiperazine pyrophosphate, ammonium phosphate, ammonium polyphosphate, or a mixture thereof. The preferred third flame retardant F3 is melamine polyphosphate.

[0118] In a preferred embodiment 36 of a composition according to one of the preceding embodiments, preferably one of embodiments 1 to 27, or one of their preferred embodiments, the phosphorus-containing flame retardant comprises, as flame retardant F1, resorcinol bis(diphenyl phosphate) (RDP), as flame retardant F2, aluminum diethyl phosphinate or aluminum hypophosphite, or a mixture thereof, preferably aluminum diethyl phosphinate, and as flame retardant F3, melamine polyphosphate.

[0119] In a preferred embodiment 37 of a composition according to one of the preceding embodiments, preferably one of embodiments 1 to 27, or one of their preferred embodiments, the phosphorus-containing flame retardant includes, as flame retardant F1, resorcinol bis(diphenyl phosphate) (RDP), as flame retardant F2, aluminium diethylphosphinate or aluminium hypophosphite, or a mixture thereof, preferably aluminium diethylphosphinate, and as flame retardant F3, ammonium polyphosphate which is preferred in embodiments 32 to 33.

[0120] The composition in the preferred embodiment includes an additional flame retardant. The preferred non-phosphorus-containing flame retardant is preferably selected from melamine cyanurate, metal hydroxides, or a mixture thereof. When the non-phosphorus-containing flame retardant is included in the composition, the amount of the phosphorus-containing flame retardant is preferably 5 wt% to 15 wt% based on the whole composition.

[0121] In a preferred embodiment 38 according to any of the preceding embodiments or one of their preferred embodiments, the total amount of all flame retardants is 15 wt% to 50 wt%, more preferably 15 wt% to 35 wt%.

[0122] Preferably, the flame retardant has a water content of less than 1 wt%, more preferably less than 0.5 wt%, particularly less than 0.25 wt%.

[0123] In a preferred embodiment 39 according to any of the preceding embodiments or one of their preferred embodiments, the composition preferably has a Shore hardness of 75 Shore A to 100 Shore A, more preferably 80 Shore A to 95 Shore A, as measured according to DIN ISO 7619-1:2016.

[0124] In a preferred embodiment 40 according to any of the preceding embodiments or one of their preferred embodiments, the composition further comprises an aroma. Sometimes, the odor of a composition containing a thermoplastic polyurethane, especially one further containing additives or adjuvants, can be unpleasant or intolerable. This often applies when the thermoplastic polyurethane contains substances such as polystyrene, resorcinol bis(diphenyl phosphate) (RDP), diphenyl cresyl phosphate (DPK), bisphenol A bis-(diphenyl phosphate) (BDP), or other derivatives of cresol, phenol, resorcinol, or bisphenol A.

[0125] Preferably, the aroma is a fragrance diluted to the concentration used in the composition in ethanol, preferably the fragrance of 0.01% by weight of aroma in ethanol, which is considered preferable by more than 50% of at least 5 odd-numbered groups of people. It is a substance or a mixture of substances.

[0126] In a preferred embodiment 41 according to the preceding embodiment 40, the aroma is liquid at 20 °C. In a preferred embodiment, the aroma has a vapor pressure at 20 °C of 10 Pa to 180 Pa, or a vapor pressure at 50 °C of 50 Pa to 1×10³ Pa. The vapor pressure is preferably measured in accordance with DIN EN13016-1:2018DE.

[0127] Surprisingly, it has been found that the preferred aromas herein can compensate for the unpleasant or intolerable odor of each composition of the articles produced from these compositions, even in very small amounts, despite the enormous heat applied in the manufacturing process of thermoplastic polyurethanes.

[0128] In a preferred embodiment 42 according to the preceding embodiments 40 to 41, the aroma is 1×10 -5 % by weight to 1% by weight, more preferably 5×10 -4 % by weight to 2×10 -3It is included in an amount of % by weight. The whole composition is 100% by weight. Preferably, the fragrance is mixed with a polymer, preferably a thermoplastic polyurethane. This mixture, also called an aromatic masterbatch, is used to impart the fragrance to the composition. This premixing has the advantage that a small amount of the fragrance can be better distributed in the composition.

[0129] In a preferred embodiment 43 according to one of the preceding embodiments 40 to 42 or one of their preferred embodiments, the fragrance is selected from pineapple, anemone, anise, banana, flower, lavandina, sugarcane, strawberry, pine, cocoa, coffee, peanut, coconut, pineapple, green apple, pomegranate, mango, blueberry, apple, orange, lemon, lime, grapefruit, grape, vanilla sugarwatermelon, tomato, potato chips, talc, avocado, or a mixture thereof.

[0130] In a preferred embodiment 44 according to the preceding embodiments 40 to 43, the fragrance is selected from flower, lavandina, strawberry, green apple, pomegranate, vanilla sugar, talc, or a mixture thereof. Most preferably, the fragrance contains pomegranate.

[0131] In a preferred embodiment, the aromatic lavandina contains at least one of the following aromatic substances: 2,6-dimethyloct-7-en-2-ol, terpineol, acetate, geraniol, 4-tert-butylcyclohexyl acetate, coumarin, linalyl acetate, linalool, bornean-2-one, 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethan-1-one, octan-2-one, cineole, piperonal, P-mentha-1,4(8)-diene, 5-cyclohexadecene-1-one, caryophyllene, d-limonene, pin-2(3)-ene, (-)-pin-2(10)-ene, neryl acetate, or a mixture thereof. More preferably, the mixture contains 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19 of these aromatic substances.

[0132] In a preferred embodiment, the aromatic strawberry contains at least one of the following aromatic substances: 2,2,4,6,6-pentamethylheptane, benzyl alcohol, ethyl 2,3-epoxy-3-phenylbutyrate, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylinden[5,6-c]pyran, 2-phenylethanol, d-limonene, phenethyl acetate, tricyclodecane dimethanol, isopentyl acetate, ethyl butyrate, allyl heptanoate, linalool, hexyl salicylate, (E)-anethole, 2,4-dimethylcyclohex-3-ene-1-carbaldehyde, damascenone, toluene, or a mixture thereof. More preferably, the mixture contains 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17 of these aromatic substances.

[0133] In a preferred embodiment, the aromatic green apple contains at least one of the following aromatic substances: 2,2,4,6,6-pentamethylheptane, cis-2-tert-butylcyclohexyl acetate, 2,6-dimethyloct-7-en-2-ol, undecan-4-one, ethyl hexanoate, isopentyl acetate, a reaction mass of allyl (2-methylbutoxy)acetate and allyl (3-methylbutoxy)acetate, ethyl butyrate, hexanal, ethyl 2-naphthyl ether, methyl cinnamate, 2,4-dimethylcyclohex-3-ene-1-carbaldehyde, 2,4-dimethylcyclohex-3-ene-1-carbaldehyde, trans-hex-2-enal, 3,5-dimethylcyclohex-3-ene-1-carbaldehyde, or a mixture thereof. More preferably, the mixture contains 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 of these aromatic substances.

[0134] In a preferred embodiment, the aromatic pomelo includes at least one of the following aromatic substances: 2,2,4,6,6-pentamethylheptane, 3-methoxy-3-methylbutan-1-ol, diethyl malonate, tetrahydro-2-isobutyl-4-methylpyran-4-ol, mixed isomers (cis and trans), benzyl acetate, cis-2-tert-butylcyclohexyl acetate, 2,6-dimethyloct-7-en-2-ol, d-limonene, (E)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one, linalool, linalyl acetate, a-methyl-1,3-benzodioxole-5-propionaldehyde, a,a-dimethylphenethyl butyrate, ethyl octanoate, undecan-4-olide, ethyl 2,3-epoxy-3-phenylbutyrate, Ethyl 2-naphthyl ether, diphenyl ether, a reaction mass of cis-4-(isopropyl)cyclohexanemethanol and trans-4-(isopropyl)cyclohexanemethanol, 1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one, 3-(p-cumenyl)-2-methylpropionaldehyde, toluene, or a mixture thereof. More preferably, the mixture includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 of these aromatic substances.

[0135] In a preferred embodiment, the aromatic vanilla is at least one of the following aroma substances: 2,2,4,6,6-pentamethylheptane, 2,2,4,6,6-pentamethylheptane, 3-ethoxy-4-hydroxybenzaldehyde, vanillin, resin acids and rosin acids, hydrogenated, Me esters, linalool, 3-(2,2-dimethyl-3-hydroxypropyl)toluene, 3-(p-cumenyl)propionaldehyde, a reaction mass of cis-4-(isopropyl)cyclohexanemethanol and trans-4-(isopropyl)cyclohexanemethanol, 3-p-cumenyl-2-methylpropionaldehyde, or a mixture thereof. More preferably, the mixture contains 1, 2, 3, 4, 5, 6, 7, 8 or 9 of these aroma substances.

[0136] In a preferred embodiment, the aromatic talc is at least one of the following aroma substances: 2,2,4,6,6-pentamethylheptane, benzyl benzoate, coumarin, citronellyl acetate, 3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, cinnamyl alcohol, (E)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one, benzyl acetate, terpineol, acetate, (E)-oxacyclohexadec-12-en-2-one, octane-4-olide, veratraldehyde, neryl acetate, hexyl salicylate, linalool, a reaction mass of 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylinden[5,6-c]pyran, a reaction mass of 2-methylbutyl salicylate and pentyl salicylate, 4-methylanisole, P-mentha-1,4(8)-diene, isoeugenol, toluene, or a mixture thereof. More preferably, the mixture contains 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or 21 of these aroma substances.

[0137] In a preferred embodiment, the fragrant talc contains at least one of the following fragrances: linalyl acetate, 2,6-dimethyloct-7-en-2-ol, 3,7-dimethyloctan-3-ol, cis-2-tert-butylcyclohexyl acetate, 2-acetoxy-2,3,8,8-tetramethyloctahydronaphthalene, [1aS-(1aα,4aβ,8aR*)]-1,1a,4,4a,5,6,7,8-octahydro-2,4a,8,8-tetramethylcyclopropa[d]naphthalene, cedryl methyl ketone, tetrahydro-2-isobutyl-4-methylpyran-4-ol, mixed isomers (cis and trans), cineole, 2,6-di-tert-butyl-p-cresol, 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethan-1-one, nerolidol, d-limonene, α-cedrene, [3R-(3α,3aβ,7β,8aα)]-octahydro-3,8,8-trimethyl-6-methylene-1H-3a,7-methanoazulene, geraniol, the reaction mass of allyl (2-methylbutoxy)acetate and allyl (3-methylbutoxy)acetate, p-mentha-1,4-diene, the reaction mass of (2E)-tridec-2-enenitrile and (2Z)-tridec-2-enenitrile and (3E)-tridec-3-enenitrile and (3Z)-tridec-3-enenitrile, [1s-(1α,3aβ,4α,8aβ)]-decahydro-4,8,8-trimethyl-9-methylene-1,4-methanoazulene, or a mixture thereof. More preferably, the mixture contains 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 of these fragrances.

[0138] Manufacturing process Another aspect and embodiment 45 of the present invention is a manufacturing process of a composition containing a thermoplastic polyurethane according to any one of the preceding embodiments 1 to 44 or one of their preferred embodiments.

[0139] Preferably, the manufacturing process is discontinuous or continuous. Preferred manufacturing processes are reaction extruder processes, belt line processes, or "one-shot" processes, preferably "one-shot" processes or reaction extruder processes, most preferably reaction extruder processes.

[0140] These processes are used either by directly mixing the components or alternatively by applying a prepolymer process.

[0141] The polyisocyanate prepolymer can be obtained by reacting an excess of the preferred polyisocyanate in Embodiments 2-4 with a polyol at a temperature of 30°C to 100°C, preferably 80°C.

[0142] In the "one-shot" process, the components diisocyanate, polyol, and chain extender are mixed with each other. This is done in the presence of a catalyst, preferably continuously or simultaneously in a preferred embodiment. In the extruder process, the components diisocyanate, polyol, and chain extender, and in a more preferred embodiment also a catalyst, are mixed. The mixing in the reaction extrusion process is preferably carried out at a temperature of 100°C to 280°C, more preferably 140°C to 250°C. The resulting thermoplastic polyurethane is preferably in the form of granules or powder. Auxiliaries and additives may be added during the synthesis of the thermoplastic polyurethane or added to the thermoplastic polyurethane. The latter is preferred. This is especially true when the additive or auxiliary is not inert to isocyanates, chain extenders, compounds reactive with isocyanates, or catalysts. Polystyrene is mixed with the thermoplastic polyurethane and finally further contains a catalyst, auxiliary, or additive, or a mixture thereof, to form a composition.

[0143] In a preferred embodiment, the synthesis of the thermoplastic polyurethane is carried out in an extruder, more preferably a twin-screw extruder is used. Since the twin-screw extruder operates in positive conveyance, more accurate setting of the temperature and output of the extruder is possible.

[0144] In a preferred embodiment, the composition is produced by processing a thermoplastic polyurethane, a polystyrene, and a flame retardant in one step. In another preferred embodiment, the thermoplastic polyurethane is produced by a first step using a reactive extruder, a belt assembly, or other suitable apparatus for producing the thermoplastic polyurethane, preferably as granules, into which a polystyrene and a phosphorus-containing flame retardant, and, if applicable, further additives or adjuvants are then introduced in at least one further step or, alternatively, in a plurality of steps until the composition is reached.

[0145] The mixing of the thermoplastic polyurethane with the other components is preferably carried out in a mixing unit, preferably a kneader or an extruder, more preferably a twin-screw extruder. In a preferred embodiment, the flame retardant introduced into the mixing unit in at least one further step is a liquid, preferably a liquid at a temperature of 21 °C. In another preferred embodiment, the flame retardant is a liquid at a temperature that spreads downstream of the filling point in the flow direction of the material in the extruder. Pellet / Powder

[0146] In a preferred embodiment 46, a thermoplastic polyurethane composition according to one of embodiments 1 to 44 or a preferred embodiment thereof, a composition derived by a process according to one of embodiments 45 or a preferred embodiment thereof is in the form of pellets or powder. The pellets or powder in the preferred embodiment are compact materials. In another preferred embodiment, the pellets are expanded materials also referred to as expanded beads or expanded powder. The beads, each expanded bead, refer to particles having a maximum expansion of 1 mm to 5 cm in the preferred embodiment. The powder in the preferred embodiment refers to particles having a maximum size of 1 mm. Preferably, the size of the powder is 1×10 -6 -m to 1 mm.

[0147] Accordingly, another aspect and embodiment 47 of the present invention is a foamed bead or foamed particle made from a composition obtained according to one of embodiments 1 to 44 or one of their preferred embodiments, or according to embodiment 45 or one of their preferred embodiments.

[0148] The foamed beads and the molded articles produced therefrom may be used in various applications incorporated herein by reference (see, for example, WO 94 / 20568, WO 2007 / 082838, WO 2017 / 030835, WO 2013 / 153190, WO 2010 / 010010).

[0149] Compositions achieved according to one of the embodiments of the preferred embodiments, pellets, powders or foamed beads respectively, are formed, injection molded, calendered, powder sintered, or extrusion molded to form articles.

[0150] Article Another aspect and embodiment 48 of the present invention is an article produced using a composition according to one of embodiments 1 to 44 or its preferred embodiment, derived from pellets or powders according to embodiment 46 or 47 or one of their preferred embodiments respectively, or obtained by a process according to embodiment 45 or one of its preferred embodiments.

[0151] Preferably, the article is selected from the group consisting of a cable, a case, a mobile phone, a coating, a cover, a damping element, a bellows, a foil, a fiber, a film, a molded body, a roof or floor for a building or vehicle, a non-woven fabric, a gasket, a packaging material, a roll, a shoe sole, an insole of a shoe, a hose, a cable, a cable connector, a cable sheath, a pillow, a laminate, a telephone, a profile, a strap, a saddle, a foam, a plug connection by additional foaming of a preparation, a TV, a trailing cable, a solar module, a lining of an automobile, a wiper blade, an elevator load support member, a rope configuration, a drive belt for a machine, preferably a passenger conveyor, a handrail for a passenger conveyor, a modifier for a thermoplastic material, which means a substance that affects the properties of another material. Each of these articles is in itself a preferred embodiment and is also referred to as an application.

[0152] More preferably, the product is selected from a cover, a packaging material, a case, a telephone, a mobile phone, a TV, or a cable, and more preferably for electronic devices.

[0153] A preferred embodiment 49 according to embodiment 48 is a cable comprising a composition according to any one of the preceding embodiments 1 to 44 or one of their preferred embodiments.

[0154] In a preferred embodiment 50 according to the preceding embodiment 49, the cable is a charging cable for a means of transport, more preferably for a vehicle.

[0155] Use for manufacturing an article Another aspect and embodiment 51 of the present invention is the use of a composition according to one of embodiments 1 to 44 or a preferred embodiment thereof, or according to embodiment 45 or a preferred embodiment thereof, for manufacturing an article.

[0156] The present invention is further illustrated by the set of embodiments below and combinations of embodiments resulting from the dependencies and cross-references as shown. It should be explicitly noted that the set of embodiments below does not represent a set of claims determining the scope of protection, but rather a properly structured part of the description of the general and preferred aspects of the present invention.

Example

[0157] 1. Example - Raw Materials Elastollan A: A TPU with a Shore hardness of 85A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on polytetrahydrofuran polyol (PTHF) having a molar weight Mn of 1000 g / mol, 1,4 - butanediol, and diphenylmethane - 4,4’ - diisocyanat.

[0158] Elastollan B: A mixture of polytetrahydrofuran polyol (PTHF) having a molar weight Mn of 1000 g / mol (425 parts by weight) and polytetrahydrofuran polyol (PTHF) having a molar weight Mn of 2000 g / mol (575 parts by weight), 1,4 - butanediol, and a TPU with a Shore hardness of 85A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemforde, based on diphenylmethane - 4,4’ - diisocyanat.

[0159] Styrolution PS 485N, CAS number: 9003 - 55 - 8, polymer (C8H8C4H6) x 、styrene - butadiene copolymer, HIPS, from INEOS Styrolution Group GmbH, Mainzer Landstrase 50, DE - 60325 Frankfurt, melt volume rate, 200 °C / 5 kg (ISO1133): 4 cm 3 / 10 min.

[0160] Melapur 200 / 70: Melamine polyphosphate (nitrogen content 42 - 44 wt%, phosphorus content 12 - 14 wt%), CAS No.: 218768-84-4, BASF SE, 67056 Ludwigshafen, Germany, particle size D99% <= 70 μm, median particle diameter D50% <= 10 μm, water content % (w / w) < 0.3.

[0161] Fyrolflex RDP: Resorcinol bis(diphenyl phosphate), CAS No.: 125997-21-9, Supresta Netherlands B.V., Office Park De Hoef, Hoefseweg 1, 3821 AE Amersfoort, Netherlands, viscosity at 25°C = 700 mPas, acid value < 0.1 mg KOH / g, water content % (w / w) < 0.1.

[0162] Melapur MC 15 ED: Melamine cyanurate (1,3,5-triazine-2,4,6(1H,3H,5H)-trione, salt with 1,3,5-triazine-2,4,6-triamine (1:1)), CAS No.: 37640-57-6, BASF SE, 67056 Ludwigshafen, Germany, particle size D99% <= 50 μm, D50% <= 4.5 μm, water content % (w / w) < 0.2.

[0163] Exolit OP 1230: Aluminium diethylphosphinate, CAS No.: 225789-38-8, Clariant Produkte (Deutschland) GmbH, Chemiepark Knapsack, 50351 Hurth, water content % (w / w) < 0.2, particle size D99% <= 90 μm, average particle diameter D50 = 20 - 40 μm.

[0164] PR26234: Perfume, Light Blue Lavandina 2516 Mod.I, Industrie Chimiche Muller&Koster S.p.A., Via Papa Giovanni XXIII 12, 20050 Lissone - Milano - Italy.

[0165] PR27785: Perfume, Strawberry 844 / 3958 Plast, Industrie Chimiche Muller&Koster S.p.A., Via Papa Giovanni XXIII 12, 20050 Lissone - Milano - Italy.

[0166] PR27867: Perfume, Green Apple R 5077 SSA - Plast, Industrie Chimiche Muller&Koster S.p.A., Via Papa Giovanni XXIII 12, 20050 Lissone - Milano - Italy.

[0167] PR30367: Perfume, Pomegranate R 5240 Plast, Industrie Chimiche Muller&Koster S.p.A., Via Papa Giovanni XXIII 12, 20050 Lissone - Milano - Italy.

[0168] PR31753: Perfume, Vanilla Sugar R 5098 Plast, Industrie Chimiche Muller&Koster S.p.A., Via Papa Giovanni XXIII 12, 20050 Lissone - Milano - Italy.

[0169] PR37816: Perfume, Flowers V 6509, Industrie Chimiche Muller&Koster S.p.A., Via Papa Giovanni XXIII 12, 20050 Lissone - Milano - Italy.

[0170] 2. Examples - Manufacture of Compositions Tables 1a and 1b list the compositions in which the individual components are shown in parts by weight (pbw). The compositions in each case were produced using a Berstorff ZE 40 A twin-screw extruder equipped with a 35D screw divided into 10 barrels. Pellets were obtained using Gala's underwater pelletizing unit.

[0171] All thermoplastic polyurethanes used have an average molecular weight exceeding 150,000 Da. [Table 1-1]

[0172] For all tables: IE = Invention Example, CE = Comparative Example [Table 1-2]

[0173] 3. Examples - Measurement of Flame Retardancy and Surface Properties To evaluate the flame retardancy, test specimens with a thickness of 5 mm from each composition were tested horizontally in a cone calorimeter according to ISO 5660 Part 1 and Part 2 (2002-12) with a radiation intensity of 35 kW / m 2 . Test specimens for cone measurement with dimensions of 100×100×5 mm were injection-molded using an Arburg 520S with a screw diameter of 30 mm. The important parameters for cone measurement of different materials are shown in Tables 2a and 2b. The Invention Examples (IE) show similar total heat release (THE) and peak heat release (PHRR) compared to the Comparative Examples (CE). [Table 2-1] [Table 2-2]

[0174] To further evaluate the flame retardancy, cables were manufactured using a conventional extrusion line for cable sheathing (smooth tube extruder, 45 mm diameter), and a conventional three-zone screw with a compression ratio of 2.5:1 was used.

[0175] After drying the composition at 120 °C for 5 hours, it was extrusion molded. The following temperature profile was used: Zone 1 - Zone 6: 195 / 200 / 205 / 210 / 215 / 215 °C.

[0176] 2.5 mm 2 Three insulated cores with a copper cross-sectional area of and one insulated core with a copper cross-sectional area of were twisted together, and a sheath (sheath thickness 1.5 - 3.1 mm, outer diameter 10 mm) was applied by extrusion using the pressure extrusion method. 2 Three insulated cores with a copper cross-sectional area of 2.5 mm² and one insulated core with a copper cross-sectional area of 0.5 mm² were twisted together, and a sheath (sheath thickness 1.5 - 3.1 mm, outer diameter 10 mm) was applied by extrusion using the pressure extrusion method.

[0177] The cable surfaces of Comparative Example (CE) 1 and Invention Examples (IE) 3 - 11 appear matte. The cable surface of Comparative Example 2 appears shiny. The matte surface is more desirable - it has scratch resistance and is visually appealing.

[0178] The IEC60332 flame test was conducted on these cables. The test was performed on three cables each. The results are summarized in Table 3.

Table 3

[0179] The results show that all examples have very good flame retardancy characteristics.

[0180] 4. Examples - Conductivity of Smoke Gas The conductivity determined using DIN EN60754-2 (2015) was found to be lower in the invention examples compared to Comparative Example 1 containing melamine cyanurate. The mixture of the present invention appears to be much less corrosive compared to Composition 1 of the comparative examples. The results are shown in Table 4a and Table 4b.

Table 4-1

Table 4-2

[0181] 5. Examples - Mechanical Properties and Surface Finish The composition was extruded using an Arenz single-screw extruder having a three-zone screw with a mixing section (screw ratio 1:3) to obtain a film having a thickness of 1.6 mm.

[0182] After drying the composition at 120 °C for 5 hours, it was extruded. The following temperature profile was used: Zone 1 - Zone 6: 195 / 200 / 205 / 210 / 215 / 215 °C.

[0183] The density, Shore hardness, tensile strength, tear propagation resistance, abrasion, and elongation at break of the corresponding test specimens were measured. All compositions have good mechanical properties. The results are listed in Table 5a and Table 5b.

[0184] The film surfaces of Comparative Example 1 and Examples 3 - 11 of the present invention appear matte. The cable surface of Comparative Example 2 appears shiny. A matte surface is desirable - it has scratch resistance and is visually appealing.

Table 5-1

Table 5-2

[0185] 6. Examples - Low Temperature Properties To evaluate the low temperature properties, dynamic mechanical analysis was performed (DMA, ISO6721-2, frequency 1 Hz). The glass transition temperatures (Max G”) of different materials are shown in Table 6. Example 5 of the present invention has a significantly lower glass transition temperature than the other materials.

Table 6

[0186] 7. Example - Odor Using VW PV 3900 (2019 - 04), the odors of different materials were evaluated. The material (25 g) was placed in a 1 l test container and stored at 80 °C for 2 hours. Then, odor evaluation was conducted. For this, the following grades were used. The average of the grades by 5 testers is shown in Table 7a and Table 7b. 1 - Imperceptible 2 - Perceptible, not unpleasant 3 - Clearly perceptible, not unpleasant 4 - Unpleasant 5 - Strongly unpleasant 6 - Intolerable

Table 7 - 1

Table 7 - 2

[0187] 8. Example - Methods: Density: DIN EN ISO1183 - 1, A Shore hardness A: DIN ISO7619 - 1, Shore A (3 s) Tensile strength: DIN EN ISO527 Elongation at break: DIN EN ISO527 Tear strength: DIN ISO34 - 1, B(b Wear: DIN53516 Cone calorimeter test: ISO5660 Part 1 and Part 2 (2002 - 12) Odor: VW PV 3900 (2019 - 04)

[0188] 9. Summary Table 8 shows the different characteristics of different examples. All examples have very good flame retardancy, but only Examples 3 - 11 of the present invention combine a matte finish and a low conductivity of smoke and gas. Examples 4 - 11 of the present invention have a much better odor compared to Example 3 of the present invention. Examples 5 - 11 of the present invention have better low - temperature flexibility compared to Examples 3 - 4 of the present invention. Examples 6 - 11 of the present invention have a better odor than Examples 3 - 5 of the present invention.

Table 8

Claims

1. A thermoplastic polyurethane composition wherein the thermoplastic polyurethane comprises at least the following components a) Isocyanates b) Polyols c) Chain extenders It is a reaction product of, The composition further comprises polystyrene and a phosphorus-containing flame retardant, wherein the polystyrene is present in an amount of 0.5% to 15% by weight based on the total amount of the composition.

2. The composition according to claim 1, wherein the phosphorus-containing flame retardant comprises a derivative of phosphorous acid, phosphonic acid, or phosphinic acid, or a mixture thereof.

3. The composition according to claim 1 or 2, comprising cresol, phenol, resorcinol, or a derivative of bisphenol A, or a mixture thereof.

4. The composition according to claim 1 or 2, wherein the phosphorus-containing flame retardant comprises a phosphate ester.

5. The composition according to claim 1 or 2, wherein the phosphorus-containing flame retardant is present in an amount of 10% to 30% by weight.

6. The composition according to claim 1 or 2, wherein polystyrene is contained in an amount of 0.5% to 7% by weight based on the total amount of the composition.

7. The composition according to claim 1 or 2, wherein the polyol comprises a polyether polyol, more preferably a polyether polyol selected from the group consisting of polypropanediol, polybutanediol, polypentanediol, and polyhexanediol, or a mixture thereof.

8. The aforementioned polyol is 0.6 × 10 ３ ~2.0 x 10 ３ The composition according to claim 1 or 2, having a number-average molecular weight in g / mol according to DIN 55672-1:2016-03.

9. The composition according to claim 1 or 2, wherein the composition has a Shore hardness of 75A to 100A, more preferably 80A to 95A.

10. The composition according to claim 1 or 2, comprising an aromatic component.

11. The composition according to claim 10, wherein the aromatic component is liquid at 20°C.

12. The aromatic components are preferably 1 × 10 based on the entire composition. －４ % by weight to 1% by weight, more preferably 5 × 10 －３ Weight%~2×10 －３ The composition according to claim 10, which is contained in an amount of weight percent.

13. A cable comprising the composition according to claim 1 or 2.

14. The cable according to claim 13, wherein the cable is a means of transport, more preferably a charging cable for a vehicle.