Thermoplastic polyurethane (TPU) compositions with improved properties

Abstract

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

Description

Background Art

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

[0002] Related technical notes

[0003] Thermoplastic polyurethanes are well known for their good mechanical properties and are used in many fields, see, for example, EP 00617079 A1, EP 1167429 A1, WO 2015 / 128213, WO 2020 / 002200, WO 2022 / 058514, PCT / EP2021 / 087062, and WO 2020 / 221786.

[0004] In many areas, consumers now demand not only good mechanical properties but are also paying increasing attention to tactile, visual and sensory properties. Summary of the invention

[0005] question

[0006] The challenge of the present invention is therefore to develop a new thermoplastic polyurethane having good mechanical properties while satisfying the tactile, visual and sensory requirements of consumers.

[0007] Solution

[0008] Surprisingly, it has been found that the thermoplastic polyurethane according to claim 1 meets these requirements. DETAILED DESCRIPTION

[0009] In the first aspect and embodiment 1, the present invention relates to a thermoplastic polyurethane composition, wherein the thermoplastic polyurethane is the reaction product of at least the following synergistic components: diisocyanate, polymer diol, chain extender, finally in the presence of a catalyst, and the composition further comprises polystyrene, phosphorus-containing flame retardant, and final additives and / or auxiliary agents, wherein the content of polystyrene is preferably between 0.5% and 15% by weight with reference to the total amount of the composition (the total amount of the composition is referred to as 100% by weight).

[0010] The term "composition" means that the composition comprises not only the thermoplastic polyurethane but may also comprise several polymers, additives and / or auxiliaries.

[0011] Preferably, the thermoplastic polyurethane is prepared by reacting an organic isocyanate (preferably an organic diisocyanate) with an isocyanate-reactive compound (in a preferred embodiment a polyol, preferably having two isocyanate-reactive functional groups, also referred to as a polymer diol). The isocyanate-reactive compound preferably has a molecular weight of 0.5×10 3 g / mol to 100×10 3 g / mol, and the chain extender (if necessary) preferably has a molecular weight of 0.05×10 3 g / mol to 0.499×10 3 The molecular weight of g / mol is preferably determined in the presence of a catalyst, an auxiliary agent, an additive or a mixture thereof.

[0012] The components organic isocyanate (preferably diisocyanate), isocyanate-reactive compound (in a preferred embodiment, polymer diol) and chain extender can also be used alone or together as synergistic components. The synergistic components including catalysts and / or auxiliaries and / or additives (if applicable) are also referred to as input materials.

[0013] In order to adjust the hardness and melt flow index of thermoplastic polyurethane (TPU), the molar ratio of the amount of synergistic component and chain extender can be changed, whereby the hardness and melt viscosity increase with increasing isocyanate content or with increasing isocyanate and chain extender content, while the melt flow index decreases.

[0014] To prepare thermoplastic polyurethanes, the synergistic components isocyanate, polyol and chain extender are reacted in a preferred embodiment in the presence of catalysts and optional auxiliaries and / or additives in amounts such that the equivalent ratio of the NCO groups of the isocyanate (preferably diisocyanate) to the sum of the hydroxyl groups of the components reactive toward isocyanate is from 0.95:1 to 1.10:1, preferably from 0.98:1 to 1.08:1 and in particular from 1.0:1 to 1.05:1.

[0015] Thermoplastic polyurethane preferably has a viscosity 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, and more preferably at least 0.08×10 6 The upper limit of the weight average molecular weight of TPU is usually determined by processability and the desired range of properties. Preferably, the weight average molecular weight does not exceed 0.5×10 6 g / mol, more preferably 0.4×10 6 g / mol, more preferably 0.25×10 6g / mol, and more preferably 0.2×10 6 g / mol. The weight average molecular weight as outlined herein is preferably determined by gel permeation chromatography, more preferably according to DIN 55672-1, wherein dimethylformamide (DMF) is used as solvent.

[0016] Isocyanate

[0017] In a preferred embodiment 2 according to embodiment 1 or a preferred embodiment thereof, the isocyanate comprises an organic isocyanate, more preferably a diisocyanate. Further preferred isocyanates are selected from the group consisting of aliphatic, alicyclic, araliphatic and aromatic isocyanates, or mixtures thereof.

[0018] In a preferred embodiment 3 according to one of the preceding embodiments or a preferred embodiment thereof, the isocyanate is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate 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-p-phenylene diisocyanate (PPDI) , 2,4-tetramethylene xylene diisocyanate (TMXDI), 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and / or 1-methyl-2,6-cyclohexane diisocyanate Acid ester, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene 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.

[0019] When stability to electromagnetic waves, such as light, is important, aliphatic isocyanates are preferred, whereas when high mechanical strength of the polyurethane, especially thermoplastic polyurethane, is required, aromatic polyisocyanates are preferred.Another advantage of aliphatic isocyanates is that they can be produced on a bio-based basis.

[0020] A very preferred aliphatic isocyanate is 1,5-pentamethylene diisocyanate. This has the additional advantage that it can be produced on a biological basis.

[0021] In preferred embodiment 4 of one embodiment of the aforementioned embodiment or a preferred embodiment thereof, the isocyanate comprises 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate or 4,4'-diphenylmethane diisocyanate (MDI) or a mixture thereof, and a particularly preferred isocyanate comprises 4,4'-diphenylmethane diisocyanate.

[0022] Polyols

[0023] In a preferred embodiment 5 of one of the preceding embodiments or a preferred embodiment thereof, the polyol has, on average, at least 1.8 and at most 3.0 Zerewitinoff active hydrogen atoms. This value is also referred to as the functionality of the isocyanate-reactive compound and represents the amount of isocyanate-reactive groups in one molecule calculated theoretically from a certain amount of substance. The functionality is preferably between 1.8 and 2.6, further preferably between 1.9 and 2.2, and particularly preferably 2. The number average molecular weight of the isocyanate-reactive compound is preferably between 0.5×10 3 g / mol and 8×10 3 g / mol, more preferably between 0.7×10 3 g / mol and 6.0×10 3 g / mol, more preferably between 0.8×10 3 g / mol and 4.0×10 3 Between g / mol.

[0024] Preferably, the polyol is linear and is a single polyol or a mixture of different polyols, in which case the mixture meets the above requirements.

[0025] 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 polycarbonates. Particularly preferred polyols are polyether diols.

[0026] Polyether polyols

[0027] In a preferred embodiment 6 according to one of the preceding embodiments or a preferred embodiment thereof, the polyol comprises a polyether polyol, preferably a polyether diol, further preferably a polyether diol based on ethylene oxide, propylene oxide, and / or butylene oxide monomers, or a mixture thereof.

[0028] More preferred polyether polyols include polytetramethylene ether glycol (also known as PTMEG or PTHF), polypropylene glycol or polybutylene glycol, or a mixture thereof. Particularly preferred is PTHF.

[0029] In a preferred embodiment 7 according to one embodiment of the preceding embodiment or a preferred embodiment of a preferred embodiment thereof, the number average molecular weight of the polyether polyol is between 0.6×10 3 g / mol and 2.0×10 3 g / mol, preferably between 0.8×10 3 g / mol and 1.9×10 3 g / mol, and more preferably the number average molecular weight is between 0.8×10 3 g / mol and 1.2×10 3 g / mol, or between 1.3×10 3 g / mol and 1.9×10 3 g / mol, and the most preferred is 1.0×10 3 g / mol or 1.4×10 3 g / mol.

[0030] The number-average molecular weight Mn in the context of the present invention is preferably determined in accordance with DIN 55672-1.

[0031] A very preferred polyether polyol is polytetrahydrofuran (PTHF), preferably having the molecular weight of the polyether polyol indicated above.

[0032] Polyether polyols are obtained by known methods such as, but not limited to, the reaction between at least one starter molecule (such as ethylene glycol, propylene glycol) and an alkylene oxide (such as ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide), or derived from tetrahydrofuran.

[0033] In another preferred embodiment 8 according to one of the preceding embodiments or one of its preferred embodiments, the number average molecular weight of 1,3-propylene glycol, poly 1,4-butylene glycol or a mixture thereof is between 1.2×10 3 g / mol and 1.8×10 3g / mol, more preferably between 1.3×10 3 g / mol and 1.5×10 3 g / mol, the most preferred is 1.4×10 3 In a preferred embodiment, the polyol has a molecular weight of 1.0×10 3 g / mol to 2.0×10 3 A mixture of polybutane-1,4-diols with a concentration of 1.5 g / mol.

[0034] Polyether polyols have the advantage that they are more stable to hydrolysis and will therefore be used in applications requiring this.

[0035] Polyester polyols

[0036] In a preferred embodiment 9 according to an embodiment in the foregoing embodiment or a preferred embodiment in its preferred embodiment, the polyol includes a polyester polyol. Preferably, the polyester is selected from the group consisting of the reaction product of a polyol, the polymerization product of a lactone, and the polymerization product of a dicarboxylic acid and a polyol. The term "lactone" refers to the cyclic ester of a hydroxycarboxylic acid. Such polyester polyols include the hydroxy-terminated reaction product of a polyol, the polyester polyol obtained as the polymerization product of a lactone (e.g., caprolactone) and a polyol, and the polyester polyol obtained by the polymerization of a dicarboxylic acid (e.g., adipic acid) and a polyol. Preferred polyester polyols include the polymerization product of a lactone or polycaprolactone and the polymerization product obtained by the polymerization of a dicarboxylic acid and a polyol.

[0037] Preferably, polyester polyol is obtained by polymerization of dicarboxylic acid and polyol.Preferred dicarboxylic acid is at least one of C4 dicarboxylic acid to C12 dicarboxylic acid, and at least one of C2 glycol to C14 glycol is suitable as polyol.Preferably, C4 dicarboxylic acid to C12 dicarboxylic acid is selected from the group consisting of the following items: aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the aliphatic dicarboxylic acid is preferably selected from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, or is their mixture, the aromatic dicarboxylic acid is preferably selected from phthalic acid, isophthalic acid and terephthalic acid, or is their mixture.More preferably, dicarboxylic acid is selected from the group consisting of the following items: succinic acid, glutaric acid, adipic acid, suberic acid, phthalic acid, isophthalic acid and terephthalic acid, or is their mixture.Most preferably, dicarboxylic acid is selected from the group consisting of the following items: adipic acid, suberic acid and phthalic acid, or is their mixture.

[0038] Preferably, the C2 diol to C14 diol for obtaining 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-propane-1,3-diol, 1,3-propylene glycol, 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.

[0039] Polyester polyols have poor hydrolytic stability and are preferred in applications where biodegradability is required.

[0040] Polycarbonate diol

[0041] In a preferred embodiment 10 according to an embodiment in the foregoing embodiment or a preferred embodiment thereof, the polyol comprises a polycarbonate diol, preferably an aliphatic polycarbonate diol. Preferred polycarbonate diols are polycarbonate diols based on alkane diols. The preparation of polycarbonate diols can be carried out by the polycondensation reaction of phosgene and diols or by the ring-opening polymerization reaction of cyclic carbonates. As a preferred alternative to phosgene synthesis, carbonic acid diesters can be used to carry out transesterification.

[0042] Preferred polycarbonate diols are completely hydroxy difunctional polycarbonate diols, preferably completely hydroxy difunctional aliphatic polycarbonate diols. Preferred polycarbonate diols are based on butanediol, pentanediol or hexanediol. Polycarbonate diols are especially based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol or mixtures thereof. More preferred polycarbonate diols are based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures thereof. 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.

[0043] Preferably, the number average molecular weight Mn of the polycarbonate diol is 0.5×10 3 g / mol to 4.0×10 3 g / mol, preferably 0.65×10 3 g / mol to 3.0×10 3 g / mol, preferably 0.8×10 3 g / mol to 2.5×103 g / mol, and the more preferred number average molecular weight is between 1.8×10 3 g / mol and 2.2×10 3 g / mol or between 0.8×10 3 g / mol and 1.2×10 3 Between g / mol.

[0044] Polycarbonate diols have better microwave permeability, less dirt absorption and better flame retardancy.

[0045] Polyol mixture

[0046] In one preferred embodiment, the polyol is a single polyol, and in another preferred embodiment, the polyol is a mixture of two or more polyols as described above as preferred.

[0047] In a preferred embodiment 11 according to one of the preceding embodiments or a preferred embodiment thereof, the polyol is a mixture of at least one polyether polyol and at least one polycarbonate diol.

[0048] 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.

[0049] Chain Extender

[0050] In addition, a chain extender is used in the synthesis of the thermoplastic polyurethane. In a preferred embodiment 12 of one of the preceding embodiments or a preferred embodiment thereof, the chain extender comprises an aliphatic, araliphatic, aromatic and / or alicyclic compound. Preferably, the number average molecular weight of the chain extender is 0.05×10 3 g / mol to 0.499×10 3 g / mol. The chain extender preferably has two groups reactive toward isocyanate. These groups are also referred to as functional groups. The chain extender is a single chain extender or a mixture of at least two chain extenders.

[0051] In a preferred embodiment 13 according to one of the preceding embodiments or a preferred embodiment thereof, the chain extender is a difunctional compound, preferably exemplified by a diamine or an alkanediol, preferably having 2 to 10 carbon atoms in the alkylene radical, or a mixture thereof.

[0052] In a preferred embodiment 14 according to one of the preceding embodiments or one of its preferred embodiments, the chain extender is selected from the group consisting of 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol of dialkylene glycol, dipropylene glycol of trialkylene glycol, dipropylene glycol of tetraalkylene glycol, dipropylene glycol of pentaalkylene glycol, dipropylene glycol of hexaalkylene glycol, dipropylene glycol of heptaalkylene glycol, dipropylene glycol of octaalkylene glycol, dipropylene glycol of nonaalkylene glycol and / or dipropylene glycol of decanediol, 1,4-cyclohexanediol, 1,4-dimethanol cyclohexane, neopentyl glycol and hydroquinone bis(β-hydroxyethyl) ether (HQEE), or a mixture thereof.

[0053] More preferably, the chain extender is selected from the group consisting of 1,2-ethanediol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol, dialkylene glycol, trialkylene glycol, tetraalkylene glycol, pentaalkylene glycol, hexaalkylene glycol, heptaalkylene glycol, octaalkylene glycol, nonaalkylene glycol and / or decanediol, preferably the corresponding oligoalkylene glycols and / or polyalkylene glycols, or mixtures thereof.

[0054] In a preferred embodiment 15 according to one of the preceding embodiments or a preferred embodiment thereof, the chain extender comprises 1,2-ethanediol, 1,3-propylene glycol, 1,4-butanediol or 1,6-hexanediol, or a mixture thereof, most preferably the chain extender comprises 1,4-butanediol.

[0055] catalyst

[0056] In a preferred embodiment 16 according to any one of the preceding embodiments or one of its preferred embodiments, the composition further comprises a catalyst. The catalyst is a single catalyst or a mixture of several catalysts.

[0057] The catalyst preferably accelerates 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.

[0058] Preferred organometallic compounds are selected from the group consisting of titanates, iron compounds, tin compounds and bismuth salts, or mixtures thereof. Preferred iron compounds are iron (III) acetylacetonate. Preferred tin compounds are selected from the group consisting of tin diacetate, tin dioctoate, tin dilaurate, tin (II) neodecanoate and dialkyltin salts of aliphatic carboxylic acids, or mixtures thereof. Preferably, the catalyst is tin dioctoate, tin (II) neodecanoate, or mixtures thereof. Preferred titanates are tetrabutyl orthotitanate. In preferred bismuth salts, bismuth exists in oxidation state 2 or 3, particularly 3, preferably salts of carboxylic acids, preferably having 6 to 14 carbon atoms, particularly preferably carboxylic acids having 8 to 12 carbon atoms. Very preferred bismuth salts are bismuth (III) neodecanoate, bismuth 2-ethylhexanoate or bismuth octoate, or mixtures thereof.

[0059] The catalyst is preferably used in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of polyol. It is preferred to use a tin catalyst, especially tin dioctoate.

[0060] In a preferred embodiment 17 according to any one of the preceding embodiments or a preferred embodiment thereof, the composition comprises SDO (tin (II) 2-ethylhexanoate), tin (II) neodecanoate or a mixture thereof, preferably used at 0.35 parts to 0.4 parts per weight with reference to the entire composition.

[0061] The catalyst is a single substance or a mixture of at least two substances.

[0062] Additives

[0063] In a preferred embodiment 18 of one of the preceding embodiments or a preferred embodiment thereof, the composition contains an auxiliary agent or additive. 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, lubricating aids, demoulding aids, dyes, pigments, inorganic fillers or organic fillers, reinforcing agents, plasticizers, antistatic agents, stabilizers, preferably stabilizers against hydrolysis, light, heat or discoloration.

[0064] Stabilizers in the sense of the present invention are additives which protect plastics or plastic compositions from harmful environmental influences. Preferred examples are primary or secondary antioxidants, hindered phenols, hindered amine light stabilizers, UV absorbers, phosphites, hydrolysis inhibitors, quenchers and flame retardants. Examples of commercially available stabilizers are given in Plastics Additives Handbook, 5th edition, ed. H. Zweifel, Hanser Publishers, Munich, 2001 ([1]), pp. 98-S136.

[0065] Preferably, the number average molecular weight of the ultraviolet absorber is greater than 0.3×10 3 g / Mol, especially greater than 0.39×10 3 g / Mol. In addition, the preferred ultraviolet absorber has a 3 Molecular weight in g / Mol.

[0066] The UV absorber is preferably selected from the group consisting of cinnamate, oxanilide, benzophenone and benzotriazole, or a mixture thereof, and particularly suitable as the UV absorber is benzotriazole. Examples of particularly suitable UV absorbers are 213. 234. 312, 571, 384 and 82.

[0067] Preferably, the ultraviolet absorber is added in an amount of 0.01 to 5 wt %, preferably 0.1 to 2.0 wt %, particularly 0.2 to 0.5 wt %, based on the total weight of the composition.

[0068] Usually, the UV stabilization based on antioxidants and UV absorbers as described above is not sufficient to ensure good stability of the composition against the harmful effects of UV rays. In this case, in addition to the antioxidants and / or UV absorbers, or as a single stabilizer, a hindered amine light stabilizer (HALS) is added to the composition.

[0069] Examples of commercially available HALS stabilizers may be found in Zaastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Munich, 2001, pages 123-136.

[0070] A particularly preferred hindered amine light stabilizer is bis-(1,2,2,6,6-pentamethylpiperidinyl) sebacate ( 765, Ciba AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid ( 622). In particular, if the titanium content of the end product is less than 150 ppm, preferably less than 50 ppm, in particular 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 ( 622).

[0071] The HALS compounds are preferably used in a concentration of 0.01 to 5% by weight, particularly preferably 0.1 to 1% by weight, in particular 0.15 to 0.3% by weight, based on the total weight of the composition.

[0072] Particularly preferred UV stabilizers contain a mixture of a phenolic stabilizer, a benzotriazole, and a HALS compound in the preferred amounts described above.

[0073] Further information on the abovementioned auxiliaries and additives can be found in the technical literature, for example in Plastics Additives Handbook, 5th edition, ed. H. Zweifel, Hanser Publishers, Munich, 2001.

[0074] Polystyrene

[0075] Surprisingly it has been found that the addition of polystyrene to a composition comprising thermoplastic polyurethane causes the surface of the composition to lose its gloss and therefore scratches etc. are less noticeable, which is a huge advantage for the consumer.

[0076] In preferred embodiment 19 of one embodiment according to the preceding embodiment or a preferred embodiment thereof, the content of polystyrene is between 0.5 wt% and 15 wt%, more preferably between 0.5 wt% and 7 wt%, with reference to the total amount of the composition (the total amount of the composition is 100 wt%).

[0077] The preferred polystyrene is an impact polystyrene copolymer based on styrene monomers and butadiene monomers.

[0078] In a preferred embodiment, the polystyrene satisfies at least one of the following characteristics, and most preferably satisfies all of the following characteristics.

[0079] Preferably, the elastic modulus of the impact polystyrene copolymer is 1500 N / mm 2 Up to 3300N / mm 2 , preferably measured according to DIN 53 457, preferably between 1700 N / mm2 and 2500N / mm 2 The tensile strength of the polystyrene copolymer is preferably between 18 N / mm 2 and 35N / mm 2 Between, preferably 20N / mm 2 Up to 26N / mm 2 , preferably measured according to DIN 53 455.

[0080] The elongation at tear of the polystyrene is preferably between 30% and 55%, preferably measured according to DIN 53 455, more preferably between 40% and 50%.

[0081] The impact strength (Charpy) of polystyrene at -40°C is preferably between 50 kJ / m 2 and 100 kJ / m 2 between 20 and 30 kJ / m, preferably measured according to DIN 53 453, preferably 60 kJ / m 2 Up to 70kJ / m 2 The Vicat softening temperature of the polystyrene is preferably between 75° C. and 97° C., preferably measured in accordance with DIN 53460 VTS / A / 50, preferably from 80 [° C.] to 90 [° C.].

[0082] In a preferred embodiment 20 according to one of the preceding embodiments or a preferred embodiment thereof, the composition comprises cresol, phenol, piperazine, resorcinol, a derivative of bisphenol A, or a mixture thereof.

[0083] Flame retardants

[0084] The composition according to any one of the preceding embodiments or a preferred embodiment thereof, further comprising a phosphorus-containing flame retardant.

[0085] The flame retardant is used in the composition as a single substance or as a mixture of several substances of the same type of flame retardant or different types of flame retardants. In a preferred embodiment, the flame retardant is a liquid, preferably a liquid at a temperature of 21° C. In a preferred embodiment, the viscosity of the liquid at 25° C. is between 1 mPas and 1×10 3 mPas, preferably between 1 mPas and 3×10 3 mPas, more preferably between 5mPas and 1×10 3 mPas, more preferably between 3×10 mPas and 0.8×10 3 mPas, more preferably between 3,5×10 2 mPas and 8×102 The viscosity is preferably a dynamic viscosity.

[0086] In a preferred embodiment 21 according to one of the preceding embodiments or a preferred embodiment thereof, the phosphorus-containing flame retardant is a derivative of phosphoric acid, a derivative of phosphonic acid or a derivative of phosphinic acid, or a mixture thereof.

[0087] In a preferred embodiment 22 of an embodiment according to one of the preceding embodiments or a preferred embodiment thereof, the amount of the phosphorus-containing flame retardant is between 5% and 40% by weight of the composition, more preferably between 10% and 30% by weight. If no additional non-phosphorus-containing flame retardant is present in the composition, the amount of the phosphorus-containing flame retardant in the composition is preferably between 15% and 30% by weight.

[0088] Preferably, the flame retardant has an average particle size D50 in the range between 0.1 μm and 100 μm, preferably between 0.5 μm and 60 μm, particularly preferably between 3 μm and 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 can be unimodal or multimodal, more preferably bimodal.

[0089] Phosphate

[0090] The phosphate ester is preferably a triester, more preferably a trialkyl phosphate. Other preferred phosphate esters are triaryl phosphates, more preferably triphenyl phosphate.

[0091] In a preferred embodiment 23 according to one of the preceding embodiments or a preferred embodiment thereof, the phosphate ester has the general formula (I).

[0092]

[0093] wherein R represents a substituted alkyl, cycloalkyl or phenyl group, and n is an integer in the range of 1 to 15.

[0094] If R in the general formula (I) is an alkyl moiety, the alkyl moieties preferably used are those having 1 to 8 carbon atoms. Cyclohexyl is a preferred example of a cycloalkyl group. In other preferred embodiments, R represents a phenyl group or an alkyl-substituted phenyl group.

[0095] Preferably, n is 1, or an integer from 3 to 6.

[0096] In a preferred embodiment 24 according to one of the preceding embodiments or a preferred embodiment thereof, the phosphate ester is selected from the group consisting of resorcinol bis(diphenyl phosphate) (RDP), bisphenol-A bis-(diphenyl phosphate) (BDP) and diphenylcresyl phosphate (DPK), or a corresponding oligomer, or a mixture thereof. The oligomer preferably has an average degree of oligomerization of n=3 to 6.

[0097] The most preferred flame retardant comprises resorcinol bis(diphenyl phosphate) (RDP), more preferably in the form of oligomers with an average degree of oligomerization n = 3 to 6. The content of phosphoric acid derivatives is preferably between 1% and 25% by weight, preferably between 2% and 12% by weight, most preferably between 2% and 6% by weight, with reference to the entire composition.

[0098] These flame retardants are particularly advantageous since they are liquid at room temperature and therefore have better processability and furthermore exhibit a plasticizer effect in the composition, which is particularly preferred when the composition is to have flexibility.

[0099] Phosphinates

[0100] In a preferred embodiment 25 according to one of the preceding embodiments or a preferred embodiment thereof, the flame retardant comprises a derivative of phosphinic acid.

[0101] Preferably, the derivative of phosphinic acid is selected from phosphinic acid salts containing organic or inorganic cations or from organic esters, or a mixture thereof.

[0102] The phosphinate has the general formula R1R2(P=O)OR3, wherein all three organic radicals R1, R2 and R3 may be identical or different. The free radicals R1, R2 and R3 are aliphatic or aromatic and preferably have 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 3. Preferably at least one of the free radicals is aliphatic, preferably all of the free radicals are aliphatic, very particularly preferably R1 and R2 are ethyl radicals. More preferably R3 is also aliphatic, and more preferably an ethyl radical or a methyl radical. In a preferred embodiment R1, R2 and R3 are simultaneously ethyl radicals or methyl radicals.

[0103] Other preferred derivatives of phosphinic acid are phosphinates, i.e. salts of the general formula R1R2(P=O)O - Me +The R1 radical and the R2 radical are aliphatic or aromatic. Further preferably, R1 and R2 independently have 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 3. Preferably, at least one of the R1 radical or the R2 radical is aliphatic, preferably both radicals are aliphatic, Me + Preferably, it is an alkali metal or an alkaline earth metal, or a mixture thereof, more preferably Me + is aluminum, calcium or zinc, or a mixture thereof, more preferably Me + Aluminum or zinc, or a mixture thereof, most preferably Me + For aluminum.

[0104] Other preferred derivatives of phosphinic acid are metal hypophosphites having the following general formula: H2(P=O)O - Me + , preferably Me + is an alkali metal or alkaline earth metal, or a mixture thereof, 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, most preferably aluminum hypophosphite.

[0105] In a preferred embodiment 26 of a composition according to one of the preceding embodiments or a preferred embodiment thereof, the flame retardant comprises aluminum diethylphosphinate and a preferred phosphoric acid derivative as described above, more preferably a phosphoric acid derivative selected from the group consisting of resorcinol bis(diphenyl phosphate) (RDP), bisphenol-A bis-(diphenyl phosphate) (BDP) and diphenylcresyl phosphate (DPK), or a corresponding oligomer, or a mixture thereof. The oligomer preferably has an average degree of oligomerization of n=3 to 6.

[0106] In a preferred embodiment 27 according to one of the preceding embodiments or a preferred embodiment thereof, the flame retardant comprises aluminum diethylphosphinate and resorcinol bis(diphenyl phosphate) (RDP), more preferably RDP is in the form of oligomers with an average degree of oligomerization n=3 to 6.

[0107] In a preferred embodiment, the content of the derivative of phosphinic acid in the composition is in the range of 5 wt % to 45 wt %, based on the total composition, in particular in the range of 7 wt % to 30 wt %, more preferably in the range of 8 wt % to 18 wt %, more preferably in the range of 10 wt % to 15 wt %, based on the weight of the entire composition.

[0108] In a preferred embodiment, aluminum diethylphosphinate has an average particle size D50 in the range between 20 μm and 80 μm, preferably between 20 μm and 40 μm.

[0109] Melamine polyphosphate

[0110] In a preferred embodiment 28 of a composition according to one of the preceding embodiments or a preferred embodiment thereof, the composition comprises melamine polyphosphate.

[0111] Preferably, the phosphorus content of the melamine polyphosphate is in the range of 7 to 20 wt %, preferably in the range of 10 to 17 wt %, more preferably in the range of 12 to 14 wt %, with reference to the total weight of the melamine polyphosphate.

[0112] Melamine polyphosphate preferably consists of particles having an average particle size D50 generally in the range of 0.1 μm to 100 μm, preferably 0.5 μm to 60 μm, particularly preferably 1 μm to 10 μm.

[0113] In a preferred embodiment 29 according to a preferred embodiment of the preceding embodiment 28 or a preferred embodiment thereof, the content of melamine polyphosphate present in the composition is between 2% and 35% by weight, in particular between 3% and 15% by weight, more preferably between 4% and 8% by weight, based on the total composition.

[0114] In a preferred embodiment 30 of a composition according to any of the preceding embodiments or one of its preferred embodiments, the composition is free of melamine cyanurate. "Free of 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 very preferred embodiment, the composition contains 0 ppm of melamine cyanurate.

[0115] In a preferred embodiment 31 according to any one of the preceding embodiments or a preferred embodiment thereof, the flame retardant comprises a phosphinate, preferably aluminum diethylphosphinate, and a derivative of phosphoric acid as preferably described above, most preferably resorcinol bis(diphenyl phosphate) (RDP), more preferably in the form of oligomers with an average degree of oligomerization n=3 to 6, and a polyphosphate melamine as preferably described above.

[0116] Piperazine pyrophosphate and polypiperazine pyrophosphate

[0117] In a preferred embodiment 32 of a preferred embodiment according to one of the preceding embodiments (preferably according to embodiments 1 to 27) or one of its preferred embodiments, the flame retardant comprises piperazine pyrophosphate or polypiperazine pyrophosphate, or a mixture thereof.

[0118] In the context of the present invention, the (poly)piperazine pyrophosphate used herein refers to the piperazine pyrophosphate represented by the following formula (I) or (II), or a mixture of the piperazine pyrophosphate represented by formula (I) and the poly (piperazine pyrophosphate) represented by formula (II).

[0119]

[0120] wherein n in formula (II) is an integer from 2 to 100.

[0121] Piperazine pyrophosphate is preferred.

[0122] Preferably, the piperazine pyrophosphate or piperazine phosphate focused consists of particles preferably having an average particle size D98 in the range of 5 to 100 μm, more preferably 10 to 90 μm, more preferably 20 to 80 μm, most preferably 30 to 70 μm.

[0123] Preferably, piperazine pyrophosphate is present in the composition in an amount of between 2% and 35% by weight, in particular between 3% and 15% by weight, more preferably between 4% and 8% by weight, based on the total composition.

[0124] Ammonium Polyphosphate

[0125] In a preferred embodiment 32 of a preferred embodiment according to one of the preceding embodiments (preferably according to embodiments 1 to 27) or one of its preferred embodiments, the flame retardant comprises ammonium polyphosphate.

[0126] Preferred ammonium polyphosphates are preferably, but not exclusively, those found in J. Am. Chem. Soc. 91, 62 (1969), preferably those having a crystal structure phase 1, or those having a crystal structure phase 2, or mixtures thereof.

[0127] Preferably, the ammonium polyphosphate has a value exceeding 20×10 3 , preferably more than 80×10 3 , more preferably more than 1×10 5 The average molecular weight of ammonium polyphosphate is preferably between 20×10 3 and 1.5×10 5 between.

[0128] In a preferred embodiment 33 of one of the preceding embodiments 32 or a preferred embodiment thereof, the phosphate component is coated at least partially.

[0129] The coating of phosphates results in compositions having a lower blooming tendency.

[0130] Preferred coated ammonium polyphosphates are described in US 4,347,334, US 4,467,056, US 4,514,328 and US 4,639,331, which are incorporated herein by reference. Such encapsulated ammonium polyphosphates preferably comprise a hardened water-insoluble resin encapsulating individual ammonium polyphosphate particles. The resin is preferably based on urea resins, epoxy resins or silanes.

[0131] Preferred coatings are based on organofunctional silanes or mixtures thereof, or on oligomeric organosiloxanes, or mixtures thereof. Preferred organofunctional silanes are alkoxysilanes with aminoalkyl-functional groups, epoxyalkyl-functional groups, acryloxyalkyl-functional groups, methacryloxyalkyl-functional groups, mercaptoalkyl-functional groups, alkenyl-functional groups or alkyl functional groups, or mixtures thereof, wherein the alkoxy groups are preferably methoxy, ethoxy or propoxy groups, or mixtures thereof.

[0132] Particularly preferred organofunctional alkoxysilanes are: 3-aminopropyltrialkoxysilane, 3-aminopropylmethyldialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-acryloxypropyltrialkoxysilane, 3-methacryloxypropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyldialkoxysilane, vinyltrialkoxysilane, vinyltri(2-methoxyethoxy)silane, propyltrialkoxysilane, butyltrialkoxysilane, pentyltrialkoxysilane, hexyltrialkoxysilane, heptyltrialkoxysilane, octyltrialkoxysilane, propylmethyldialkoxysilane and butylmethyldialkoxysilane, or mixtures thereof, wherein the alkoxy groups are preferably methoxy, ethoxy or propoxy groups, or mixtures thereof.

[0133] The coating is preferably applied in an amount of 0.05 to 10% by weight, particularly preferably 0.1 to 3% by weight, very particularly preferably 0.5 to 1.5% by weight, based on the amount of flame retardant, of the silicon-containing coating agent.

[0134] Preferably, the solubility of the ammonium polyphosphate in water is less than 1.0 g / l, in particular less than 0.1 g / l. The solubility in water is preferably determined as follows: 50 g of the corresponding sample is shaken with 200 g of water at 20° C. for 1 hour, filtered through a 0.2 μm filter, the filter is dried with the filtrate at 70° C. for 12 hours and the filtrate is determined.

[0135] The ammonium polyphosphate preferably consists of particles having an average particle size D50 between 0.1 μm and 100 μm, preferably between 0.5 μm and 60 μm, particularly preferably between 1 μm and 30 μm, very particularly preferably between 5 μm and 25 μm. Preferably, the ammonium polyphosphate is a dry powder, more preferably a free-flowing powder.

[0136] 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 or multimodal (e.g. bimodal), or a mixture thereof.

[0137] The ammonium polyphosphate is present in the composition in an amount of between 2% and 35% by weight, in particular between 3% and 15% by weight, more preferably between 4% and 8% by weight, based on the total composition.

[0138] Preferred combination of flame retardants

[0139] In a preferred embodiment 34 of a composition according to one of the preceding embodiments (preferably according to embodiments 1 to 27) or a preferred embodiment thereof, the phosphorus-containing flame retardant comprises a phosphoric acid derivative as preferred as the first flame retardant F1 as described above, a derivative of phosphinic acid as preferred as the second flame retardant F2 as described above, and a third flame retardant F3 selected from polymelamine phosphate, piperazine pyrophosphate, polypiperazine pyrophosphate, ammonium polyphosphate, or a mixture thereof. A very preferred third flame retardant F3 is melamine polyphosphate. This is because it has a low solubility in water.

[0140] In a preferred embodiment 35 of a composition according to one of the preceding embodiments (preferably according to embodiments 1 to 27) or one of its preferred embodiments, the phosphorus-containing flame retardant comprises a derivative of a phosphate ester as flame retardant F1, preferably resorcinol bis(diphenyl phosphate) (RDP), diphenylcresyl phosphate (DPK), or bisphenol A bis-(diphenyl phosphate) (BDP), or a mixture thereof; a derivative of a phosphinic acid as flame retardant F2, preferably a phosphinic acid salt having the formula: R1R2(P=O)O-Me, wherein R1 and R2 are ethyl radicals, and Me is aluminum or zinc; and a third flame retardant F3, wherein the third flame retardant F2 is selected from polyphosphate melamine, pyrophosphate piperazine, pyrophosphate polypiperazine, ammonium phosphate, ammonium polyphosphate, or a mixture thereof. The preferred third flame retardant F3 is polyphosphate melamine.

[0141] In a preferred embodiment 36 of a composition according to one of the preceding embodiments (preferably according to embodiments 1 to 27) or one of its preferred embodiments, the phosphorus-containing flame retardant comprises resorcinol bis(diphenyl phosphate) (RDP) as flame retardant F1, aluminum diethylphosphinate or aluminum phosphinate or a mixture thereof, preferably aluminum diethylphosphinate, as flame retardant F2, and melamine polyphosphate as flame retardant F3.

[0142] In a preferred embodiment 37 of a composition according to one of the preceding embodiments (preferably according to embodiments 1 to 27) or a preferred embodiment thereof, the phosphorus-containing flame retardant comprises resorcinol bis(diphenyl phosphate) (RDP) as flame retardant F1, diethylaluminum phosphite or aluminum phosphite or a mixture thereof, preferably diethylaluminum phosphite, as flame retardant F2, and polyphosphoamine as flame retardant F3, as preferred in embodiments 32 to 33.

[0143] The composition in a preferred embodiment also includes a flame retardant. Preferred non-phosphorus-containing flame retardants are preferably selected from melamine cyanurate, metal hydroxides or mixtures thereof. If a non-phosphorus-containing flame retardant is included in the composition, the content of the phosphorus-containing flame retardant is preferably between 5% and 15% by weight with reference to the entire composition.

[0144] In preferred embodiment 38 according to any one of the preceding embodiments or one of its preferred embodiments, the total amount of all flame retardants is between 15 wt% and 50 wt%, more preferably between 15 wt% and 35 wt%.

[0145] Preferably, the flame retardant has a water content of less than 1% by weight, more preferably less than 0.5% by weight, in particular less than 0.25% by weight.

[0146] In a preferred embodiment 39 of a preferred embodiment according to any of the preceding embodiments or a preferred embodiment thereof, the Shore hardness of the composition is between 75 Shore A and 100 Shore A, more preferably between 80 Shore A and 95 Shore A, preferably measured according to DIN ISO 7619-1:2016.

[0147] In a preferred embodiment 40 according to any one of the preceding embodiments or a preferred embodiment thereof, the composition further comprises a fragrance. Sometimes it is found that the smell of thermoplastic polyurethanes, especially the smell of compositions that also comprise additives or auxiliaries, is annoying or even unbearable. This is often the case when the thermoplastic polyurethane comprises, for example, polystyrene, resorcinol bis(diphenyl phosphate) (RDP), diphenylcresyl phosphate (DPK), bisphenol A bis-(diphenyl phosphate) (BDP) or other derivatives of cresol, phenol, resorcinol or bisphenol A.

[0148] Preferably, the fragrance is a substance or mixture of substances which is diluted in ethanol to a concentration for use in the composition, preferably 0.01 wt% fragrance in ethanol, and is considered pleasant to more than 50% of a group of an odd number of at least 5 people.

[0149] In a preferred embodiment 41 according to the previous embodiment 40, the fragrance is liquid at 20° C. In a preferred embodiment, the fragrance has a vapor pressure of between 10 Pa and 180 Pa at 20° C., or a vapor pressure of between 50 Pa and 1×10*3*Pa at 50° C. The vapor pressure is preferably determined according to DIN EN 13016-1:2018DE.

[0150] Surprisingly, it has been found that the preferred fragrances herein can compensate for the annoying or even intolerable odor of composition articles made from these compositions, respectively, even in very small amounts and despite the high amounts of heat applied by the thermoplastic polyurethane production process.

[0151] In a preferred embodiment 42 according to the aforementioned embodiments 40 to 41, the content of the fragrance is between 1×10 -5 % and 1% by weight, more preferably between 5×10 -4 wt% and 2×10 -3The whole composition is 100 wt%. Preferably, the fragrance is mixed with a polymer (preferably a thermoplastic polyurethane). This mixture is also referred to as a fragrance masterbatch, which is used to bring the fragrance into the composition. The advantage of this premixing is that a low amount of fragrance can be better distributed in the composition.

[0152] In a preferred embodiment 43 according to one of the preceding embodiments 40 to 42 or a preferred embodiment thereof, the fragrance is selected from pineapple, anemone, fennel, banana, flower, lavender, sugar cane, strawberry, pine, cocoa, coffee beans, peanuts, coconut, pineapple, green apple, pomegranate, mango, blueberry, apple, orange, lemon, lime, grapefruit, grape, vanilla candy watermelon, tomato, potato chips, talcum powder, avocado, or a mixture thereof.

[0153] In a preferred embodiment 44 according to the aforementioned embodiments 40 to 43, the fragrance is selected from flowers, lavender, strawberry, green apple, pomegranate, vanilla sugar, talcum powder, or a mixture thereof. The most preferred fragrance includes pomegranate.

[0154] In a preferred embodiment, the aromatic lavender includes at least one of the following aromatic substances: 2,6-dimethyl-7-octen-2-ol, terpineol, acetate, geraniol, 4-tert-butylcyclohexyl acetate, coumarin, linalool acetate, linalool, bornyl-2-one, 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethan-1-one, 2-octanone, eucalyptol, piperonal, P-menth-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 comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19 of these aroma substances.

[0155] In a preferred embodiment, the aroma strawberry includes at least one of the following aroma 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-hexamethylindeno[5,6-c]pyran, 2-phenylethanol, d-limonene, phenethyl acetate, tricyclodecane dimethanol, isoamyl acetate, ethyl butyrate, allyl heptanoate, linalool, hexyl salicylate, (E)-anethole, 2,4-dimethylcyclohex-3-ene-1-carboxaldehyde, damascenone, 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 or 17 of these aroma substances.

[0156] In a preferred embodiment, the aromatic green apple comprises at least one of the following aromatic substances: 2,2,4,6,6-pentamethylheptane, cis-2-tert-butylcyclohexyl acetate, 2,6-dimethyl-7-octen-2-ol, undecane-4-lactone, ethyl hexanoate, isoamyl acetate, reaction mass of (2-methylbutoxy) allyl acetate and (3-methylbutoxy) allyl acetate, ethyl butyrate, hexanal, 2-naphthylethyl ester, methyl cinnamate, 2,4-dimethylcyclohex-3-ene-1-carboxaldehyde, 2,4-dimethylcyclohex-3-ene-1-carboxaldehyde, trans-2-hexenal, 3,5-dimethylcyclohex-3-ene-1-carboxaldehyde, or a mixture thereof. More preferably, the mixture comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 of these aromatic substances.

[0157] In a preferred embodiment, the aromatic pomegranate includes at least one of the following aromatic substances: 2,2,4,6,6-pentamethylheptane, 3-methoxy-3-methyl-1-butanol, diethyl malonate, tetrahydro-2-isobutyl-4-methylpyran-4-ol, mixed isomers (cis and trans), benzyl acetate, cis-2-tert-butylcyclohexyl acetate, 2,6-dimethyl-7-octen-2-ol, d-limonene, (E)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-butene-2-one, limonene, The present invention relates to a mixture of 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21 or 22 kinds of aromatic substances.

[0158] In a preferred embodiment, the aromatic vanilla comprises at least one of the following aromatic substances: 2,2,4,6,6-pentamethylheptane, 2,2,4,6,6-pentamethylheptane, 3-ethoxy-4-hydroxybenzaldehyde, vanillin, resin acid and rosin acid, hydrogenated Me ester, linalool, 3-(2,2-dimethyl-3-hydroxypropyl)toluene, 3-(p-cumyl)propanal, cis-4-(isopropyl)cyclohexanemethanol and trans-4-(isopropyl)cyclohexanemethanol reaction material, 3-p-cumyl-2-methylpropanal, or a mixture thereof. More preferably, the mixture comprises 1, 2, 3, 4, 5, 6, 7, 8 or 9 of these aromatic substances.

[0159] In a preferred embodiment, the fragrance talc comprises at least one of the following fragrance substances: 2,2,4,6,6-pentamethylheptane, benzyl benzoate, coumarin, citronellyl acetate, 3-methyl-4-(2,6,6-trimethyl-2-cyclohexene-1-yl)-3-butene-2-one, cinnamyl alcohol, (E)-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-3-butene-2-one reaction mass, benzyl acetate, terpineol The aromatic compound of the present invention is selected from the group consisting of alcohol, acetate, (E)-oxacyclohexane-12-ene-2-one, octan-4-lactone, veratraldehyde, neryl acetate, hexyl salicylate, linalool, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylindeno[5,6-c]pyran, the reaction mass of 2-methylbutyl salicylate and amyl salicylate, 4-methylanisole, p-menthane-1,4(8)-diene, isoeugenol, toluene, or a mixture thereof. More preferably, the mixture comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21 of these aromatic substances.

[0160] In a preferred embodiment, the fragrance talc comprises at least one of the following fragrance substances: linalool acetate, 2,6-dimethyl-7-octen-2-ol, 3,7-dimethyl-3-octanol, 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-tetramethylcyclopropane and [d] naphthalene, cedryl methyl ketone, tetrahydro-2-isobutyl-4-methylpyran-4-ol, mixed isomers (cis and trans), eucalyptol, 2,6-di-tert-butyl-p-cresol, 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexahydro- methyl-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-methyleneazulene, geraniol, the reaction material of (2-methylbutoxy)acetate and (3-methylbutoxy)acetate, p-menthane-1,4-diene, (2E)-tridec-2-enenitrile and (2Z)-tridec-2-enenitrile and the reaction material of (3E)-tridec-3-enenitrile and (3Z)-tridec-3-enenitrile, [1s-(1α,3aβ,4α,8aβ)]-decahydro-4,8,8-trimethyl-9-methylene-1,4-methyleneazulene, or a mixture thereof. More preferably, the mixture comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 of these aroma substances.

[0161] Production method

[0162] Another aspect of the present invention and embodiment 45 is a method for producing a composition comprising a thermoplastic polyurethane according to any one of the aforementioned embodiments 1 to 44 or a preferred embodiment thereof.

[0163] Preferably, the production process is discontinuous or continuous.Preferred production processes are reactive extruder processes, endless line processes, or "one-step" processes, preferably "one-step" processes or reactive extruder processes, most preferably reactive extruder processes.

[0164] These methods are used either by direct admixture of the synergistic components or alternatively by employing a prepolymer method.

[0165] The polyisocyanate prepolymers are obtainable by reacting an excess of the preferred polyisocyanates of embodiments 2 to 4 with polyols at a temperature of 30°C to 100°C, preferably at 8×10°C.

[0166] In the "one-step" method, the synergistic components diisocyanate, polyol and chain extender are mixed with each other. In a preferred embodiment in the presence of a catalyst, this can be carried out continuously or simultaneously. In the extruder method, the synergistic components diisocyanate, polyol and chain extender, and in another preferred embodiment, the catalyst are mixed. The mixing in the reactive extrusion method is preferably carried out at a temperature between 100°C and 280°C, more preferably between 140°C and 250°C. The obtained thermoplastic polyurethane is preferably in granular or powder form. Auxiliary agents and additives can be added during the synthesis of the thermoplastic polyurethane, or added to the thermoplastic polyurethane. The latter is preferred. This is especially the case if the additive or auxiliary agent is not inert to isocyanate, chain extender, isocyanate-reactive compound or catalyst. The polystyrene is mixed with the thermoplastic polyurethane, and finally the catalyst, auxiliary agent, or additive, or a mixture thereof, is added to form a composition.

[0167] In a preferred embodiment, the synthesis of the thermoplastic polyurethane is carried out in an extruder, more preferably using a twin-screw extruder. A twin-screw extruder operates in forward conveying mode, and therefore the temperature and output of the extruder can be set more accurately.

[0168] In a preferred embodiment, the thermoplastic polyurethane, polystyrene and flame retardant are processed in one step to prepare the composition. In another preferred embodiment, the thermoplastic polyurethane is produced by using a reaction extruder, a belt assembly or other suitable equipment to produce the thermoplastic polyurethane, preferably as granules, and then in at least one other step or in multiple steps, polystyrene and phosphorus-containing flame retardant and (if applicable) other additives or auxiliary agents and aromatics are introduced therein to obtain the composition.

[0169] The mixing of the thermoplastic polyurethane with the other components is preferably carried out in a mixing device, preferably a kneader or an extruder, more preferably a twin-screw extruder. In a preferred embodiment, the flame retardant introduced into the mixing device in at least one further step is liquid, preferably liquid at a temperature of 21° C. In another preferred embodiment, the flame retardant is liquid at a temperature prevailing downstream of the filling point in the flow direction of the material in the extruder.

[0170] Granules / Powder

[0171] In a preferred embodiment 46 of a thermoplastic polyurethane composition according to one of embodiments 1 to 44 or its preferred embodiments, the composition obtained by the method according to embodiment 45 or its preferred embodiments is in the form of pellets or powder. In a preferred embodiment, the pellets or powder are dense materials. In another preferred embodiment, the pellets are expanded materials, also called foamed beads or foamed powders. In a preferred embodiment, beads (respectively expanded beads) refer to particles with a maximum extension between 1 mm and 5 cm. In a preferred embodiment, powder refers to particles with a maximum size of 1 mm. Preferably, the size of the powder is between 1×10 -6 Between m and 1mm.

[0172] Therefore, another aspect of the present invention and embodiment 47 are foamed beads or foamed particles made from a composition obtained according to one embodiment of embodiments 1 to 44 or one of its preferred embodiments, or according to embodiment 45 or one of its preferred embodiments.

[0173] The foamed beads and also the molded bodies produced therefrom can be used in various applications (see, for example, WO 94 / 20568, WO 2007 / 082838 A1, WO 2017030835, WO 2013 / 153190 A1, WO 2010010010), which are incorporated herein by reference.

[0174] The composition obtained according to one of the embodiments in a preferred embodiment (pellets, powder or foamed beads, respectively) is molded, injection molded, calendered, powder sintered or extruded to form an article.

[0175] Products

[0176] Another aspect of the present invention and embodiment 48 is an article produced with a composition according to one of embodiments 1 to 44 or a preferred embodiment thereof, which is respectively obtained from granules or powders according to embodiment 46 or 47 or a preferred embodiment thereof, or by a method according to embodiment 45 or a preferred embodiment thereof.

[0177] Preferably, the article is selected from the group consisting of: cables, boxes, mobile phones, coatings, coverings, damping elements, bellows, foils, fibers, films, molded bodies, roofs or floors of buildings or vehicles, nonwoven fabrics, gaskets, packaging materials, rollers, soles, midsoles of shoes, hoses, cables, cable connectors, cable jackets, pillows, laminates, telephones, profiles, strips, saddles, foams, additional foaming by preparations, plug connections, televisions, trailing cables, solar modules, automotive linings, wiper blades, elevator load-bearing components, rope arrangements, drive belts for machines, preferably passenger conveyors, handrails for passenger conveyors, thermoplastic material modifiers, meaning substances that influence the properties of another material. Each of these articles is itself a preferred embodiment, also referred to as application.

[0178] More preferably, the product is selected from a cover, a packaging material, a casing, a phone, a mobile phone, a television or a cable, more preferably for an electronic device.

[0179] 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 a preferred embodiment thereof.

[0180] In a preferred embodiment 50 according to the previous embodiment 49, the cable is a charging cable for a vessel, more preferably for a vehicle.

[0181] Used in the production of products

[0182] Another aspect of the present invention and embodiment 51 is the use of a composition for producing an article according to one of embodiments 1 to 44 or a preferred embodiment thereof, or according to embodiment 45 or a preferred embodiment thereof.

[0183] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the shown dependencies and backward references, and it is expressly noted that the following set of embodiments is not a set of claims determining the scope of protection, but rather a suitably structured part of the description of the general and preferred aspects of the present invention.

[0184] Example

[0185] 1. Example - Raw materials

[0186] Elastollan A : TPU with a Shore hardness of 85A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Based on polytetrahydrofuran polyol (PTHF) with a molar mass Mn of 1000 g / mol, 1,4 - butanediol, diphenylmethane - 4,4'-diisocyanate.

[0187] Elastollan B : TPU with a Shore hardness of 85A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 A mixture based on polytetrahydrofuran polyol (PTHF) with a molar mass Mn of 1000 g / mol (425 parts by weight) and polytetrahydrofuran polyol (PTHF) with a molar mass Mn of 2000 g / mol (575 parts by weight), 1,4 - butanediol, diphenylmethane - 4,4'-diisocyanate.

[0188] Styrolution PS 485N, CAS number: 9003 - 55 - 8, polymer (C8H8C4H6) x , styrene - butadiene copolymer, HIPS, INEOS Styrolution Group GmbH, Mainzer Land - straße 50, DE - 60325 Frankfurt, melt volume rate, 200 °C / 5 kg (ISO 1133): 4 cm 3 / 10 min.

[0189] Melapur200 / 70 : Melamine polyphosphate (nitrogen content 42 wt% - 44 wt%, phosphorus content 12 wt% - 14 wt%), CAS number: 218768 - 84 - 4, BASF SE, 67056 Ludwigshafen, Germany, particle size D99% <= 70 μm, average particle size D50% <= 10 μm, water content% (w / w) < 0.3.

[0190] FyrolflexRDP: Resorcinol bis(diphenyl phosphate), CAS No.: 125997-21-9, Supresta Netherlands B.V., Office Park De Hoef, Hoefseweg 1, 3821AE Amersfoort, Netherlands, viscosity at 25°C = 700 mPas, acid value < 0.1 mg KOH / g, water content % (w / w) < 0.1.

[0191] MelapurMC15ED : Melamine cyanurate (compound of 1,3,5-triazine-2,4,6(1H,3H,5H)-trione 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.

[0192] Exolit OP 1230 : Aluminium diethylphosphinate, CAS No.: 225789-38-8, Clariant Produkte (Deutschland) GmbH, Chemiepark Knapsack, 50351 Hürth, water content % (w / w) < 0.2, particle size D99% <= 90 μm, average particle size (D50) 20 μm - 40 μm.

[0193] PR26234: Aromatic agent, light blue lavender 2516 Mod.I, Industrie Chimche Muller and Koster S.p.A., Via Papa GIOVANNI XXIII 12, 20050 Liscate - Milan - Italy.

[0194] PR27785: Aromatic agent, strawberry 844 / 3958 Plast, Industrie Chimche Muller and Koster S.p.A., Via Papa GIOVANNI XXIII 12, 20050 Liscate - Milan - Italy.

[0195] PR27867: Aromatic agent, green apple R 5077 SSA - Plast, Industrie Chimche Muller and Koster S.p.A., Via Papa GIOVANNI XXIII 12, 20050 Liscate - Milan - Italy.

[0196] PR30367: Fragrances, Pomegranate R 5240 Plast, Industrie Chimche Muller and Koster S.pA, Via Papa GIOVANNI XXIII 12, 20050 Liscate - Milan - Italy.

[0197] PR31753: Fragrance, Vanilla Sugar R 5098 Plast, Industrie Chimche Muller and Koster S.pA, Via Papa GIOVANNI XXIII 12, 20050 Liscate - Milan - Italy.

[0198] PR37816: Fragrances, Flowers V 6509, Industrie Chimche Muller and Koster SpA, Via Papa GIOVANNI XXIII 12, 20050 Liscate - Milan - Italy.

[0199] 2. Example—Preparation of Compositions

[0200] Tables 1a and 1b list the compositions, wherein the ingredients are expressed in parts by weight (pbw). The compositions in each case were produced with a Berstorff ZE 40A twin-screw extruder with a 35D screw, divided into 10 barrels. The granules were obtained using an underwater granulation unit from Gala.

[0201] All thermoplastic polyurethanes employed had an average molecular weight of more than 150.000 Da.

[0202] Table 1a

[0203] 1(CE) 2(CE) 3(IE) 4(IE) 5(IE) Elastollan A 64 75.5 65 70.5 Elastollan B 70.5 Styrolution PS 485N 10 6.5 6.5 Exolit OP 1230 15 10 12.5 12.5 Fyrolflex RDP 6 2 10 4 4 Melapur 200 / 70 7.5 5 6.5 6.5 <![CDATA[ Melapur MC 15 ED ]]> 30

[0204] For all tables: IE = Inventive Examples, CE = Comparative Examples

[0205] Table 1b

[0206] 6(IE) 7(IE) 8(IE) 9(IE) 10(IE) 11(IE) Elastollan B 70.49 70.49 70.49 70.49 70.49 70.49 Styrolution PS 485N 6.5 6.5 6.5 6.5 6.5 6.5 Exolit OP 1230 12.5 12.5 12.5 12.5 12.5 12.5 Fyrolflex RDP 4 4 4 4 4 4 Melapur 200 / 70 6.5 6.5 6.5 6.5 6.5 6.5 Light blue lavender 2516Mod.I 0.01 Strawberry 844 / 3958Plast 0.01 Green Apple R 5077SSA-Plast 0.01 Pomegranate R 5240Plast 0.01 Vanilla Sugar R 5098Plast 0.01 Flower V 6509 0.01

[0207] 3. Example—Measurement of flame retardancy and surface properties

[0208] To evaluate the flame retardancy, according to ISO 5660 Parts 1 and 2 (2002-12), a test with an intensity of 35 kW / m 2The radiation of the samples with a thickness of 5 mm from the corresponding compositions were tested horizontally in a cone calorimeter. Cone measurement samples with dimensions of 100×100×5 mm were injection molded using an Arburg 520S with a screw diameter of 30 mm. The key parameters of the cone measurement of different materials are given in Tables 2a and 2b. Compared with the comparative example (CE), the inventive example (IE) shows similar total heat release (THE) and peak heat release (PHRR).

[0209] Table 2a

[0210] 1(CE) 2(CE) 3(IE) 4(IE) 5(IE) Total heat release (THR) <![CDATA[[MJ / m 2 ]]]> 140 138 130 134 135 Peak exothermicity (PHRR) <![CDATA[[kW / m 2 ]]]> 400 366 320 340 335

[0211] Table 2b

[0212]

[0213] To further evaluate flame retardancy, cables were produced using a conventional extrusion line for cable jacketing (smooth tube extruder, 45 mm diameter) with a conventional three-zone screw with a compression ratio of 2.5:1.

[0214] The composition was dried at 120°C for 5 h before extrusion. The following temperature profile was used: Zone 1 to Zone 6: 195 / 200 / 205 / 210 / 215 / 215°C.

[0215] The stranding has 2.5mm 2 The copper cross section has three insulating cores and has a 0.5mm 2 An insulating core of copper cross section and a sheath is applied by extrusion by a pressure extrusion method (sheath thickness 1.5-3.1 mm, outer diameter 10 mm).

[0216] The cable of Comparative Example (CE) 1 and Inventive Examples (IE) 3 to 11 had a matte surface. The cable of Comparative Example 2 had a glossy surface. Matte surfaces are more desirable - they exhibit graffiti resistance and are visually appealing.

[0217] The cables were subjected to the IEC 60332 flame test. Three cables were tested in each case. The results are summarized in Table 3.

[0218] Table 3

[0219]

[0220]

[0221] *Number of tests performed / Number of tests passed.

[0222] The results show that all examples have very good flame retardant properties.

[0223] 4. Example - Conductivity of Flue Gas

[0224] Compared to comparative example 1 containing melamine cyanurate, the conductivity of the inventive example determined using DIN EN 60754-2 (2015) is lower. Compared to comparative example composition 1, the inventive mixture is less corrosive. The results are given in Table 4a and Table 4b.

[0225] Table 4a

[0226]

[0227] Table 4b

[0228]

[0229] 5. Example—Mechanical Properties and Surface Finish

[0230] The composition was extruded using an Arenz single screw extruder (screw ratio 1:3) with a three-zone screw and a mixing zone to give a film 1.6 mm thick.

[0231] The composition was dried at 120°C for 5 h before extrusion. The following temperature profile was used: Zone 1 to Zone 6: 195 / 200 / 205 / 210 / 215 / 215°C.

[0232] The density, Shore hardness, tensile strength, tear propagation resistance, abrasion and elongation at break of the corresponding samples were measured. All compositions have good mechanical properties. The results are given in Table 5a and Table 5b.

[0233] The films of Comparative Example 1 and Inventive Examples 3-11 had matte surfaces. The cable of Comparative Example 2 had glossy surfaces. Matt surfaces are desirable - they exhibit visual appeal that resists graffiti.

[0234] Table 5a

[0235]

[0236] Table 5b

[0237]

[0238] 6. Example—Low Temperature Characteristics

[0239] In order to evaluate the low temperature properties, a dynamic mechanical analysis (DMA, ISO 6721-2, frequency 1 Hz) was performed. The glass transition temperatures of the different materials (Max G") are listed in Table 6. The glass transition temperature of Example 5 according to the invention is significantly lower than that of the other materials.

[0240] Table 6

[0241] 1(CE) 2(CE) 3(IE) 4(IE) 5(IE) G" from DMA [℃] -40 -40 -40 -40 -55

[0242] 7. Example - Smell

[0243] The odor of the different materials was evaluated using VW PV 3900 (2019-04). The material (25 g) was placed in a 1 L test container and stored at 80 ° C for 2 h. The odor evaluation was then performed. The following ratings were used here. Tables 7a and 7b list the average values ​​of the ratings given by 5 testers.

[0244] 1—Cannot feel

[0245] 2—Perceptible, no interference

[0246] 3—Clearly perceptible, no interference

[0247] 4—Interference

[0248] 5—Strong interference

[0249] 6—Unbearable

[0250] Table 7a

[0251] 1(CE) 2(IE) 3(IE) 4(IE) 5(IE) grade VW PV 3900 (2019-04) 3.3 2.8 5.2 3.8 3.6

[0252] Table 7b

[0253]

[0254] 8. Embodiment - Method :

[0255] Density: DIN EN ISO 1183-1, A

[0256] Shore hardness A: DIN ISO 7619-1, Shore A (3s)

[0257] Tensile strength: DIN EN ISO 527

[0258] Elongation at break: DIN EN ISO 527

[0259] Tear strength: DIN ISO 34-1, B(b

[0260] Abrasion: DIN 53516

[0261] Cone calorimeter test: ISO 5660 Part 1 and Part 2 (2002-12)

[0262] Smell: VW PV 3900 (2019-04) 9. Summary of the invention

[0264] Table 8 shows the different properties of the different examples. All examples have very good flame retardancy, but only inventive examples 3-11 combine a matte finish and low conductivity of smoke. Inventive examples 4-11 have better odor than inventive example 3. Inventive examples 5-11 have better cold flexibility than inventive examples 3-4. Inventive examples 6-11 have better odor than inventive examples 3-5.

[0265] Table 8

[0266]

[0267] *)DIN EN 60754-2 2015

Claims

1. A thermoplastic polyurethane composition, wherein the thermoplastic polyurethane is the reaction product of at least the following synergistic components a) Isocyanate b) Polyols c) chain extenders, The composition further comprises polystyrene and a phosphorus-containing flame retardant, and the content of the polystyrene is between 0.5 wt % and 15 wt % with reference to the total amount of the composition.

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

3. The composition according to any one of the preceding claims, comprising a derivative of cresol, a derivative of phenol, a derivative of resorcinol, a derivative of bisphenol A, or a mixture thereof.

4. The composition of any one of the preceding claims, wherein the phosphorus-containing flame retardant comprises a phosphate ester.

5. The composition of any one of the preceding claims, wherein the phosphorus-containing flame retardant is between 10% and 30% by weight.

6. The composition according to any one of the preceding claims, wherein the content of polystyrene is between 0.5% and 7% by weight with reference to the total amount of the composition.

7. A composition according to any one of the preceding claims, wherein the polyol comprises a polyether polyol, more preferably selected from the group consisting of polypropylene glycol, polybutylene glycol, polypentylene glycol and polyhexylene glycol, or mixtures thereof.

8. The composition according to any one of the preceding claims, wherein the number average molecular weight of the polyol is between 0.6×10 3 g / mol and 2.0×10 3 Between g / mol.

9. A composition according to any one of the preceding claims, wherein the composition has a Shore hardness of between 75A and 100A, more preferably between 80A and 95A.

10. A composition according to any preceding claim comprising a fragrance.

11. A composition according to any preceding claim, wherein the fragrance is a liquid at 20°C.

12. A composition according to any one of the preceding claims, wherein the content of fragrance is preferably between 1×10 -4 wt% and 1 wt%, more preferably between 5×10 -3 wt% and 2×10 -3 weight%.

13. Cable comprising a composition according to any one of the preceding claims.

14. Cable according to the preceding claim, wherein the cable is a charging cable for a vessel, more preferably for a vehicle.

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