Flame-retardant polyamide molding material

Abstract

Provide a flame-retardant polyamide molding material especially for railway applications. 【Solution means】Preferably, a flame-retardant polyamide molding material comprising the following: A) 34 to 88% by weight of a semi-crystalline aliphatic polyamide having a C / N ratio of at least 8; B) 6 to 21% by weight of a flame retardant comprising the following B1 and B2, B1) 50 to 100% by weight of at least one metal phosphinate; B2) 0 to 50% by weight of at least one flame-retardant synergist and / or at least one nitrogen- and phosphorus-containing flame retardant; where the total of components B1 and B2 is 100% by weight of component B; C) 1 to 10% by weight of graphite; D) 0 to 25% by weight of a polyamide elastomer; E) 0 to 10% by weight of a plasticizer; F) 0 to 10% by weight of a polyolefin; G) 0 to 5% by weight of an additive different from A to F;

Description

[Technical Field]

[0001] The present invention relates to a halogen-free, flame-retardant polyamide molding material based on a long-chain aliphatic polyamide, which has a high LOI value and good processing characteristics in the extrusion process. The present invention further relates to a method for producing the polyamide molding material and its use. Prior Art

[0002] Flame-retardant polyamide molding materials are known in themselves from the prior art.

[0003] A polyamide molding material having a matrix of polyamide 12 and further containing a flame retardant and a plasticizer is known from EP-A-3 127 937. The molding material may also contain additional additives and polyolefins. In addition to polyamide 12, a polyamide elastomer based on polyamide 12 may be included in the matrix. The molding material has been proposed for flexible parts, particularly for flame retardant applications in the railway sector. The examples do not include graphite, nor is it disclosed that the use of graphite with a low concentration of flame retardant in the molding material may increase the LOI.

[0004] EP-A-3502186 describes a plasticized flame-retardant thermoplastic polyamide molding material having particularly good processing properties, good flame retardancy and good flexibility, as well as, for example, washout resistance to fuel, and the use of such polyamide molding materials. The material is suitable, for example, as a material for fuel lines (fuel piping) in the automotive sector, or for generally flexible molded articles, including lines particularly for the railway sector. This polyamide is based on long-chain aliphatic dicarboxylic acids. Again, there is no mention of graphite.

[0005] EP-A-2 410 020 discloses a non-reinforced halogen-free flame-retardant polyamide molding material and its use for manufacturing electrical and / or electronic components, with particular emphasis on compatibility with the soldering process. Only partially aromatic polyamides based on terephthalic acid are considered as the polyamide base. SUMMARY OF THE INVENTION

[0006] Therefore, an object of the present invention is to provide a novel, preferably non-reinforced polyamide molding material having sufficient flexibility, which is flame-retardant and halogen-free, has a high LOI value (limiting oxygen index), has sufficient notch impact strength at low temperatures, and particularly has good processing characteristics in an extrusion process or an extrusion blow molding process. The molding material according to the present invention should have an LOI value determined by DIN EN ISO 4589-2:2017 greater than 32%, preferably at least 34%, particularly preferably at least 36%.

[0007] This object is solved by the molding material defined in the claims, the method for manufacturing the molding material defined in the claims, and a component (component) made of such a molding material, as well as the use of the molding material shown in the claims.

[0008] Therefore, the present invention proposes a halogen-free flame-retardant polyamide molding material based on a semi-crystalline aliphatic polyamide, which is particularly suitable for railway applications.

[0009] It has been surprisingly found that a halogen-free flame retardant based on metal phosphinate can be advantageously used in combination with graphite for flexible polyamide molding materials containing at least one of the following components: plasticizer, impact modifier, and polyamide elastomer. The proposed molding material has, in particular, an LOI greater than 32%, preferably at least 34%, and especially preferably at least 36%, as determined according to DIN EN ISO 4589-2:2017; a tensile modulus in the range of 500 to 1500 MPa as determined according to ISO 527:2012; an elongation at break greater than 100%, as determined according to ISO 527:2012; and a notched impact strength at -45°C, as determined according to ISO 179 / 1(2023) or ISO 179 / 2(2020), preferably at least 4 kJ / m 2 It is characterized by being such.

[0010] Specifically, the present invention relates to a polyamide molding material comprising, preferably, the following: A semicrystalline aliphatic polyamide with a C / N ratio of at least 8, comprising 34-88% by weight; Flame retardant in a quantity of 6-21% by weight, comprising the following B1 and B2: B1 50-100% by weight of at least one metal phosphinate; B2 0-50% by weight of at least one flame retardant synergistic agent and / or at least one nitrogen and phosphorus-containing flame retardant; Here, the sum of components B1 and B2 equals 100% by weight of component B; C 1-10% by weight, graphite; D: 0-25% by weight of polyamide elastomer; E 0-10% by weight, plasticizer; F 0-10% by weight of polyolefin; G: An additive in a weight of 0-5%; different from additives A-F. Here, the total weight ratio of components D to F is 5 to 30% by weight with respect to the total weight percentage of components A to G, and the total weight ratio of components A to G is 100% by weight.

[0011] The polyamide molding material according to the present invention preferably does not contain reinforcing fibers, and thus particularly does not contain glass fibers or carbon fibers. Furthermore, it is preferable that the polyamide molding material does not contain aromatic and / or semi-aromatic polyamides.

[0012] In the context of the present invention, the term "polyamide" (abbreviation PA) is understood as a general term encompassing homopolyamides and copolyamides, regardless of their molar mass or viscosity. The notation rules and abbreviations selected for polyamides and their monomers correspond to those defined in ISO 16396-1 (2015(D)).

[0013] Regarding the polyamide (A) according to the present invention, the dicarboxylic acid component and diamine component used, or monomers such as aminocarboxylic acids or lactams, and optionally the monofunctional regulator used, form repeating units or end groups in the form of amides by condensation, and these are derived from the respective monomers. In principle, these constitute at least 95 mol%, particularly at least 99 mol%, of all the repeating units and end groups present in the polyamide (A). Furthermore, the polyamide (A) may have a small amount of other repeating units that can result from the decomposition or side reactions of monomers, such as diamines.

[0014] Regarding the amounts, the secondary components (B1) and (B2) are not related to the amounts with respect to the total weight percentage of the entire polyamide molding material or components (A) to (G), and it is emphasized that the amounts shown are related to 100% of component (B) in each case, that is, the total amount of components (B1) and (B2) is 100% of (B). [[ID=二十]]

[0015] [[ID=二十一]] As long as amounts are indicated for components (A) to (G) below, the indicated ranges are understood to be relative to the total weight percentage of components (A) to (G), respectively. Further, the total weight ratio of components (A) to (G) does not exceed 100% by weight, and it is applicable that the total weight ratio of sub-components (B1) and (B2) does not exceed 100% by weight of component (B).

[0016] The terms "comprising" and "including" in the claims and the specification of this patent mean that further components are not excluded. In the context of the present invention, the term "consisting only of" should be understood as a preferred embodiment of the term "comprising" or "including". When a group is defined as "comprising" or "including" a number of components, this should preferably be understood as meaning that a group "consisting only of" these components is disclosed. The term "consisting only of" means that further components are excluded, and thus, it means that no further components are included in the molding material beyond the specifically listed components.

[0017] The present invention is characterized in that, in particular, in addition to components (A), (B) and (C), at least one of components (D), (E) and (F) must be present in the molding material, where the total of components (D), (E) and (F) is 5 to 30% by weight, preferably 7 to 26% by weight, particularly preferably 8 to 24% by weight or 10 to 24% by weight, in each case relative to the total weight percentage of components (A) to (G). Here, at least one of components (D), (E) and (F) means that one component, i.e., (D) or (E) or (F), or a combination of two of these components, or a combination of the three components (D), (E) and (F) is present in the molding material.

[0018] Ingredient (A) The polyamide of component (A) is a semi-crystalline aliphatic polyamide, preferably a long-chain aliphatic polyamide, and its C / N ratio is at least 8, particularly preferably at least 10, and even more particularly preferably 10 to 13.

[0019] The C / N ratio of individual polyamides is obtained from the ratio of the total carbon atoms (C) of the monomers that form polyamide units, i.e., dicarboxylic acids, diamines, lactams, and aminocarboxylic acids, which can react to form amide bonds in the polyamide, to the total nitrogen atoms (N) in these monomers. If a polyamide contains several polyamide units (abbreviated as PA units), such as PA 11 / 913 (30:70 mol%) containing PA units "11" and "913", the C / N ratio of individual PA units is weighted according to their mole fraction in the polyamide. For example, for PA11 / 913 (30:70 mol%), this results in a C / N ratio of (0.3 × 11) + 0.7 × (9 + 13) / 2 = 11.

[0020] In the sense of the present invention, a semi-crystalline polyamide is a polyamide that has a melting point and preferably has a heat of fusion of at least 20 J / g, and particularly preferably 20 to 80 J / g, as measured by dynamic differential scanning calorimetry (DSC) at a heating rate of 20 K / min according to ISO 11357-3 (2013).

[0021] In the context of the present invention, the term "aliphatic polyamide" means that the repeating units and monomers from which the polyamide is derived are based exclusively on acyclic (open-chain) and cyclic saturated or unsaturated carbon compounds that do not contain aromatic structural units.

[0022] The polyamide (A) is preferably selected from the group consisting of PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, PA12, or mixtures thereof. Among the polyamides A, those with a C / N ratio of at least 10 are preferred. Therefore, polyamides PA1010, PA1012, PA11, PA12, or mixtures thereof are particularly preferred, and polyamides PA11 and PA12 are particularly preferred.

[0023] Component (A) preferably has a solution viscosity determined according to DIN EN ISO 307 (2007) of η rel = 1.5 to 2.8, preferably η rel = 1.6 to 2.3 (in both cases measured at 20 °C in a solution of 0.5 g of polymer dissolved in 100 ml of m-cresol). η rel = 1.5 to 2.8, preferably η rel = 1.6 to 2.3, and polyamide types PA1010, PA1012, PA11 and / or PA12 having a solution viscosity in this range are particularly preferred as component (A).

[0024] The average solution viscosity is η rel = 1.8 to 2.1, or preferably η rel = 1.9 to 2.0, and polyamide types PA1010, PA1012, PA11 and / or PA12 are particularly preferred as component (A) because these types are advantageous in terms of processability, especially in the extrusion process. Advantageously, mixtures of these polyamide types having different solution viscosities are also used, provided that in this case all mixing components have a solution viscosity within the indicated range.

[0025] Advantageously, from the perspective of particularly good processability, the molding material according to the invention has a melt volume flow rate (MVR) measured according to ISO1133 (2011) at 275 °C and a load of 5 kg in the range of 3 to 120 cm 3 / 10 min, particularly in the range of 5 to 100 cm 3 / 10 min, more preferably in the range of 10 to 60 cm 3 / 10 min.

[0026] According to one preferred embodiment, the polyamide molding material is characterized in that the proportion of component (A) is in the range of 48 to 84% by weight, preferably in the range of 53 to 78.9% by weight, based on the total weight percentage of components (A) to (G).

[0027] Therefore, in the context of the present invention, the polyamide molding material is preferably characterized by the following: the polyamide (A) is selected as a polyamide having a C / N ratio of at least 10, preferably 10 to 13, or selected from the group consisting of PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, PA12 or mixtures thereof, or selected from the group consisting of PA1010, PA1012, PA11, PA12 and mixtures thereof, and / or, according to DIN EN ISO 307:2007, the solution viscosity measured at 20°C in a solution of 0.5 g of polymer dissolved in 100 ml of m-cresol is η rel = in the range of 1.5 to 2.8, preferably η rel It falls within the range of 1.6 to 2.3.

[0028] Ingredient (B) The flame retardant component (B) is present in the polyamide molding material in a proportion of 6 to 21% by weight relative to the sum of the weight percentages of components (A) through (G). This may be a flame retardant consisting solely of a metal phosphinate (B1) (or a mixture of systems of this type), or it may be mixed with at least one flame retardant (B2) different from component (B1), containing at least one flame retardant synergist and / or nitrogen and phosphorus, up to 50% by weight. The percentage values ​​in each case are relative to 100% by weight of component (B). That is, the sum of (B1) and (B2) is always 100% by weight of component (B).

[0029] According to one preferred embodiment, the polyamide molding material is characterized in that the proportion of component (B) is in the range of 7 to 16% by weight, preferably 8 to 14% by weight, relative to the sum of the weight percentages of components (A) to (G) in each case.

[0030] With respect to the composition of component (B), it is more preferable that component (B) consists of 55-100% by weight of (B1) and 0-45% by weight of (B2), preferably 60-100% by weight of (B1) and 0-40% by weight of (B2), and particularly preferably 75-98% by weight of (B1) and 2-25% by weight of (B2), where the sum of the weight percentages of (B1) and (B2) is 100% by weight of component (B) in each case. In another preferred embodiment, component (B) consists only of component (B1), and therefore component (B2) is not contained in the molding material.

[0031] Preferably, at least one metal phosphinate of component (B1) is selected as a phosphinate and / or diphosphinate, where it is preferably a phosphinate of general formula (I) and / or a phosphinate of formula (II) and / or a polymer thereof. [ka] During the ceremony, R1 and R2 are either the same or different, and are preferably C1-C8 alkyl, linear or branched, and / or aryl; R3 is a C1-C10 alkylene, linear or branched, a C6-C10 arylene, an alkylarylene, or an arylalkylene; M is a metal ion from the second or third main group or subgroup of the periodic table; m is either 2 or 3; n is either 1 or 3; x is either 1 or 2. Preferably, Al, Ca, and Zn are used as the metal ion M.

[0032] Component (B2) is preferably melamine or a condensation product of melamine, such as melem, melam, melon, or a reaction product of melamine and polyphosphate, or a reaction product of a condensation product of melamine and polyphosphate, or a mixture thereof.

[0033] Suitable components (B2) include, for example, stanates, particularly calcium stanate, zinc stanate, or zinc hydroxystanate; borates, such as calcium borate or zinc borate; metallocene compounds, particularly dicyclopentadienyl iron compounds, such as ferrocene; aluminum or zinc salts of phosphate; and flame retardant synergistic agents such as polyethyleneimine.

[0034] Preferably, component (B2) is melamine polyphosphate, zinc stannate, zinc borate, aluminum phosphite (aluminum salt of phosphate), ferrocene, or polyethyleneimine.

[0035] Metallocenes are coordination compounds, i.e., complexes, also known as sandwich complexes. Typical examples include unsubstituted or substituted bis(η) 5 -cyclopentadienyl) iron. Bis(η 5 -Cyclopentadienyl iron is also called ferrocene.

[0036] In the context of this invention, the polyethyleneimine of component (B2) is understood to be a polymer in which an NH group or an N group is present in its main chain, each separated from one another by two methylene groups, which are described, for example, in "Encycl. Polym. Sci. Eng. 1, 680-739". Homopolymers, copolymers, and their derivatives are also included in the context of this invention. Preferably, branched polyethyleneimine homopolymers are used.

[0037] Homopolymers (homopolymers) are generally obtained by polymerizing ethyleneimine (aziridine) in aqueous or organic solutions in the presence of an acid-releasing compound, an acid, or a Lewis acid. These types of homopolymers are branched polymers and generally contain primary, secondary, and tertiary amino groups in a ratio of approximately 30%, 40%, and 30%. 13The distribution of amino groups determined by 13C-NMR spectroscopy is preferably in the range of 1:0.7:0.5 to 1:1.5:1 for the ratio of primary:secondary:tertiary amino groups, and particularly in the range of 1:0.8:0.6 to 1:1.2:0.8.

[0038] As comonomers, compounds having at least two amino functions are preferably used. Preferred comonomers are called alkylenediamines, for example, having 2 to 10 carbon atoms in the alkylene group, with ethylenediamine and propylenediamine being preferred. Additional preferred comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, trippropylenetriamine, dihexamethylenetriamine, aminopropylethylenediamine, and bis-aminopropylethylenediamine. Preferred polyethyleneimines have a weight-average molecular weight (weight average) Mw of 800 to 50,000 g / mol, particularly preferably 1,100 to 25,000 g / mol. The weight-average molecular weight Mw is determined by light scattering according to ASTM D4001.

[0039] The polyethyleneimine of component (B2) is preferably a branched polyethyleneimine homopolymer having a primary amino-terminal group concentration in the range of 7,000 to 12,000 μeq / g (mmol / kg).

[0040] As component (B2), polyphosphate melamine is particularly preferred. These types of flame retardants are known from the prior art. Herein reference is DE 103 46 3261, and in this regard, the disclosures of that document are expressly incorporated herein.

[0041] With regard to flame retardants, it is particularly preferable that component (B2), and by extension the entire polyamide molding material, does not contain polyphosphate melamine and / or melamine cyanurate.

[0042] Ingredients (C) According to one preferred embodiment, the polyamide molding material is characterized in that the proportion of component (C) is in the range of 2 to 8% by weight, preferably 3 to 7% by weight, relative to the sum of the weight percentages of components (A) to (G). Component (C) is graphite.

[0043] Graphite is a naturally occurring allotrope of carbon. Its atoms are arranged in a hexagonal crystal pattern with a hexagonal shape characteristic of carbon, thus forming a hexagonal stacked lattice. The characteristic gray color of graphite comes from its opaque gray to black crystal structure. Each carbon atom in each layer is bonded to three other carbon atoms. This results in a two-dimensional hexagonal network. Strong bonds are dominant within each layer, but the bonds between different layers are extremely weak. Therefore, layers can easily slide relative to each other and can even separate. For this reason, graphite is very soft and is therefore also used as a lubricant. Graphite has electrical and thermal conductivity and good chemical resistance.

[0044] According to the present invention, natural or synthetic graphite can be used. According to the present invention, the graphite may be made into a powder by grinding. The particle size is preferably in the range of 5 μm to 300 mm, and particularly preferably in the range of 5 μm to 25 mm. After grinding, the median diameter D50 (D50 median) of the graphite used according to the present invention is in the range of 3 to 30 μm, and particularly preferably in the range of 5 to 20 μm. Furthermore, it is preferable that the median diameter D90 (D90 median) is in the range of 10 to 25 μm. The specific surface area (BET) of the graphite used according to the present invention, as determined according to ASTM D-3037-93, is 5 to 50 m². 2 / g, particularly preferably 10-30mg 2The value is / g. The graphite used in this invention is preferably not expandable graphite. That is, the molding material preferably does not contain expandable graphite. This is because expandable graphite has a rather small effect on improving the LOI value and at the same time has a stronger adverse effect on the mechanical properties of the molding material. Expandable graphite is produced by treating natural graphite with an acid (sulfuric acid or nitric acid) and an oxidizing agent (hydrogen peroxide, potassium permanganate, and chromic acid). This causes the acid to be inserted between the graphite layers. During heating, expandable graphite expands to several times its original volume.

[0045] The polyamide elastomer of component (D) is preferably, Hard segments based on polyamides PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, PA12, preferably hard segments of polyamides PA1010, PA1012, PA11, PA12, particularly preferably hard segments of PA12, Preferably, the soft segments are based exclusively on polyetherdiols, dimer diols (based on dimerized fatty acids having 20 to 44 carbon atoms), and / or polyetherdiamines. It is a polyamide elastomer composed of the following:

[0046] The polyetherdiol of this soft segment is preferably composed solely of at least one C2-C5, preferably C2-C4, polyoxyalkylene structural unit, and is particularly preferably selected from the following group: ethylene oxide, propylene oxide, tetrahydrofuran, or a mixture thereof.

[0047] The dimerol according to the present invention (having 20 to 44 carbon atoms, preferably 24 to 36 carbon atoms) is preferably an aliphatic or alicyclic diol produced by the dimerization and subsequent hydrogenation of an unsaturated fatty acid. C36 dimerol (CAS number 147853-32-5) and C44 dimerol are particularly preferred.

[0048] Alternatively or additionally, the polyetherdiamine soft segment may preferably be composed solely of at least one C2-C5, preferably C2-C4, polyoxyalkylene structural unit, particularly preferably selected from the following group: ethylene oxide, propylene oxide, tetrahydrofuran, or a mixture thereof.

[0049] According to one preferred embodiment, the polyamide hard segment has a number-average molar mass in the range of 500 to 10000 g / mol, preferably in the range of 700 to 5000 g / mol, and particularly preferably in the range of 750 to 3000 g / mol.

[0050] On the other hand, the soft segment has a number-average molar mass preferably in the range of 200 to 4000 g / mol, particularly preferably in the range of 200 to 3000 g / mol, and more preferably in the range of 300 to 2500 g / mol.

[0051] According to one preferred embodiment, the proportion of the polyamide hard segment is in the range of 45 to 95% by weight, preferably 50 to 80% by weight, and the proportion of the soft segment is in the range of 5 to 55% by weight, preferably 20 to 50% by weight, in either case relative to 100% by weight of component (D).

[0052] One particularly preferred embodiment of component (D) is characterized by not containing an ester bond.

[0053] According to another embodiment, the polyamide elastomer has at least one amorphous phase, which preferably originates from an ether moiety, which is a soft segment unit. The glass transition temperature (glass transition point) of this amorphous phase is, according to one preferred embodiment, up to 20°C. This amorphous phase of the polyetheramide preferably has a glass transition point below 0°C, more preferably below -20°C. The glass transition point of the soft segment is preferably in the range of -70°C to 0°C, particularly preferably in the range of -60°C to -20°C, in either case determined by DSC measurement according to ISO 11357-2.

[0054] The production of polyamide elastomers is preferably carried out by a one-step or two-step polycondensation process. In the one-step method, the polyamide-forming components are mixed with dimerol and / or polyether components (so that the end groups of the individual components are equimolar as much as possible) and polycondensed at a temperature in the range of 180–300°C until the desired viscosity is achieved. When block unit structures are desired, the two-step method is advantageously used. In this case, in the first step, polyamide units having carboxyl or amino-terminated groups are formed at a temperature of 180–320°C and a pressure of 0–20 bar, and these are then polycondensed with soft segment units at a temperature in the range of 180–280°C under atmospheric pressure or reduced pressure (vacuum) to form a high molecular weight copolymer. When soft segment units having hydroxyl-terminated groups are used, an esterification catalyst, such as an organic titanate or zirconate, is advantageously used to accelerate the reaction.

[0055] The polyamide elastomer according to the present invention preferably has a tensile modulus of up to 1000 MPa, particularly preferably up to 700 MPa, and more preferably up to 600 MPa. Therefore, the polyamide elastomer has a rigidity in the range of a tensile modulus of up to 50 to 700 MPa, particularly preferably in the range of 80 to 600 MPa.

[0056] According to one preferred embodiment, the polyamide molding material is characterized in that the proportion of component (D) is in the range of 0 to 20% by weight, preferably 6 to 18% by weight or 8 to 18% by weight, relative to the sum of the weight percentages of components (A) to (G).

[0057] Ingredient (E) In the polyamide molding material, there is a plasticizer in a proportion of 0 to 10% by weight relative to the sum of the weight percentages of components (A) to (G). Unlike the other components of the polyamide molding material, the plasticizer is not of the type of system according to (A), (B), (C), (D), (F), and / or (G). Therefore, component (E) is explicitly different from components (A), (B), (C), (D), (F), and / or (G). According to one preferred embodiment of the molding material, the proportion of the plasticizer of component (E) is in the range of 0 to 7% by weight, preferably 1 to 6% by weight, relative to the sum of the weight percentages of components (A) to (G). More preferably, the proportion of component (E) is in the range of 1 to 5% by weight, relative to the sum of the weight percentages of components (A) to (G).

[0058] Preferably, the plasticizer of component (E) is based on an aryl sulfonic acid amide having 2 to 12 carbon atoms, an ester of p-hydroxybenzoic acid having 2 to 20 carbon atoms in the alcohol component, a phosphonate, or a phosphate. Preferably, silicone oil can also be used as component (E).

[0059] The plasticizer of component (E) is preferably selected from the following group: aryl sulfonamide having 2 to 12 carbon atoms, p-hydroxybenzoic acid ester having 2 to 20 carbon atoms in the alcohol component, organic phosphonate, organic phosphate, and silicone oil.

[0060] Preferred phosphorus-containing plasticizers include, in particular, diphenylcresyl phosphate, tris(2-ethylhexyl) phosphate, diphenyl-2-ethylhexyl phosphate, tricresyl phosphate, alkyl or aryl phosphonates, diethyl phosphonates, or cyclic phosphonates, such as Aflammit PLF 710.

[0061] Preferred esters of 4-hydroxybenzoic acid are octyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, i-hexadecyl p-hydroxybenzoate, and 2-hexyldecyl p-hydroxybenzoate.

[0062] Preferred representative examples of arylsulfonic acid amides are benzenesulfonic acid amide, benzenesulfonic acid-N-alkylamide (where the alkyl group has a total of 1 to 20 carbon atoms), preferably benzenesulfonic acid-N-butylamide, benzenesulfonic acid-N-octylamide, benzenesulfonic acid-N-ethylhexylamide, benzenesulfonic acid-N-cyclohexylamide, toluenesulfonic acid amide, toluenesulfonic acid-N-alkylamide (where the alkyl group contains 1 to 20 carbon atoms), preferably toluenesulfonic acid-N-ethylamide and toluenesulfonic acid-N-butylamide.

[0063] Furthermore, the plasticizer of component (E) is preferably a silicone oil having a siloxane-based chain molecule as its basic structure. These are characterized by the periodic alternating arrangement of silicon atoms and oxygen atoms within the polymer chain. In a narrower sense, silicone oil is a general molecular formula [R 1 R 2 It is understood to be a polymerized siloxane (diorganopolysiloxane) with an organic side chain, represented by SiO]n. A typical example is polydimethylsiloxane, in which the organic group R in the above formula is present. 1 and R 2The group is a methyl group. A silicone oil with an average molecular weight of 162 to 150,000 g / mol, preferably 500 to 20,000 g / mol, is preferred. The kinematic viscosity according to DIN 53019 is preferably 0.65 to 100,000 mm². 2 A range of / s(mPas), particularly preferably 10 to 1,000 mm 2 It is within the range of / s(mPas).

[0064] Component (E) preferably contains at least one of the following plasticizers, and preferably consists of at least one of the following plasticizers: polydimethylsiloxane, octyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, i-hexadecyl p-hydroxybenzoate, 2-hexyldecyl p-hydroxybenzoate, benzenesulfonic acid amide, benzenesulfonic acid-N-alkylamide (where the alkyl group has a total of 1 to 20 carbon atoms), preferably benzenesulfonic acid-N-butylamide, benzenesulfonic acid-N- Octylamide, benzenesulfonic acid-N-ethylhexylamide, benzenesulfonic acid-N-(2-hydroxypropyl)amide, benzenesulfonic acid-N-cyclohexylamide, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, o- or p-toluenesulfonic acid-N-alkylamide (where the alkyl group contains 1 to 20 carbon atoms), preferably o-toluenesulfonic acid-N-ethylamide, p-toluenesulfonic acid-N-ethylamide, o-toluenesulfonic acid-N-butylamide, and p-toluenesulfonic acid-N-butylamide. The listed systems can be used individually or in mixtures. A mixture of benzenesulfonic acid-N-alkylamide and p-toluenesulfonic acid amide is particularly preferred.

[0065] In particular, it is preferable to use only N-butylbenzenesulfonamide as component (E).

[0066] The plasticizer is preferably an aryl sulfonamide. That is, component (E) contains only aryl sulfonamides as plasticizers, and is particularly preferably N-butylbenzenesulfonamide.

[0067] In another preferred embodiment, the plasticizer (E) consists solely of a silicone oil, particularly preferably a polydimethylsiloxane-based silicone oil. With respect to the improvement of the LOI value, the silicone oil is thought to produce a synergistic effect through its interaction with graphite.

[0068] Ingredients (F) Polyolefins may optionally be present in the polyamide molding material up to a maximum of 10% by weight (i.e., in a proportion of 0 to 10% by weight) relative to the total weight percentage of components (A) to (G). The proportion of component (F) in the molding material is preferably in the range of 0 to 7% by weight, and more preferably in the range of 1 to 6% by weight, relative to the total weight percentage of components (A) to (G). Particularly preferably, the proportion of component (F) is in the range of 1 to 5% by weight, relative to the total weight percentage of components (A) to (G).

[0069] According to one preferred embodiment, this polyolefin of component (F) is configured, preferably as a copolymer, and particularly preferably as a terpolymer, from at least one or a combination of the following constituent units: ethylene, propylene, butylene, acrylate, methacrylate, acrylic acid, methacrylic acid, maleic anhydride, glycidyl methacrylate, diene, particularly butadiene, and / or isoprene. Particularly preferred are ethylene-propylene copolymers and ethylene-butylene copolymers grafted with maleic anhydride. and / or ethylene-methacrylic acid-acrylate terpolymers neutralized with metal ions, particularly preferably zinc ions.

[0070] According to another preferred embodiment, at least one polyolefin of component (F) is selected from the following group: ethylene propylene rubber (EPM, EPR), ethylene propylene diene rubber (EPDM), styrene-containing elastomers, particularly SEBS, SBS, SEPS, acrylate rubber, nitrile rubber (NBR, H-NBR), and silicone rubber.

[0071] According to another preferred embodiment relating to component (F), at least one polyolefin is functionalized, preferably with maleic anhydride, acrylic acid, and / or glycidyl methacrylate. In this case, the degree of grafting is preferably in the range of 0.05 to 10% by weight.

[0072] More preferably, component (F) is a polyolefin ionomer, preferably a polyolefin ionomer in which the present carboxyl groups are partially or completely neutralized by a metal base, and the carboxylate groups have metal ions, preferably zinc ions. The polyolefin ionomer of component (F) is particularly preferably a fully or partially neutralized copolymer consisting of ethylene and (meth)acrylic acid and containing zinc ions.

[0073] With respect to components (D), (E), and (F), at least one of these components must be present in the molding material, and the sum of components (D), (E), and (F) is 5 to 30% by weight, preferably 7 to 26% by weight, and particularly preferably 8 to 24% by weight or 10 to 24% by weight, relative to the sum of the weight percentages of components (A) to (G).

[0074] Ingredients (G) As described above, the polyamide molding material may contain, as component (G), an additive up to a maximum of 5% by weight relative to the total weight percentage of components (A) to (G). Here again, it is emphasized that the additive in component (G) is different from the other components (A) to (F). The proportion of component (G) in the molding material is preferably in the range of 0 to 2.0% by weight, and particularly preferably in the range of 0.1 to 2.0% by weight, relative to the total weight percentage of components (A) to (G). According to one preferred embodiment, additives to component (G) are selected from the following group: stabilizers, anti-aging agents, antioxidants, anti-ozone agents, processing stabilizers, processing aids, viscosity modifiers, light stabilizers, UV stabilizers, UV absorbers, in particular copper halide and alkali halide-based inorganic heat stabilizers, organic heat stabilizers, fluorescent whitening agents, crystallization accelerators, crystallization retarders (crystal growth inhibitors), flow aids, lubricants, lubricants (flow accelerators), mold release agents, colorants, in particular dyes, inorganic pigments, organic pigments, carbon black, and mixtures thereof.

[0075] One particularly preferred embodiment of the proposed polyamide molding material is characterized by being configured as follows: Polyamide molding material consisting of the following: (A) 34 to 88% by weight of polyamides selected from the group consisting of PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, PA12, or mixtures thereof; (B) 6-21% by weight of a flame retardant consisting of the following (B1) and (B2): (B1) 50-100% by weight of at least one metal phosphinate; (B2) 0 to 50% by weight of at least one flame retardant synergistic agent and / or at least one nitrogen and phosphorus-containing flame retardant; Here, the sum of components (B1) and (B2) equals 100% by weight of component (B); (C) 1-10% by weight of graphite; (D) A polyamide elastomer consisting of 0-25% by weight of polyamide hard segments and soft segments; Here, the polyamide hard segments are PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, or PA12. The soft segment is preferably based solely on a polyetherdiol composed of at least one constituent unit selected from the following group: ethylene oxide, propylene oxide, tetrahydrofuran; Here, the polyamide elastomer preferably does not contain ester bonds; (E) A plasticizer in an amount of 0-10% by weight, selected from the group consisting of aryl sulfonamides having 2-12 carbon atoms, p-hydroxybenzoic acid esters having 2-20 carbon atoms in the alcohol component, organic phosphonates, organic phosphates, and silicone oils; (F) A polyolefin selected as a copolymer comprising 0-10% by weight of the following constituent units: ethylene, propylene, butylene, acrylate, methacrylate, acrylic acid, methacrylic acid (preferably functionalized with maleic anhydride), and / or a polyolefin selected as a polyolefin ionomer; (G) 0-5% by weight of additives different from components (A) through (F); Here, the sum of the weight percentages of components (D) to (F) is between 5 and 30% by weight relative to the sum of the weight percentages of components (A) to (G), and the sum of the weight percentages of components (A) to (G) is 100% by weight.

[0076] Another particularly preferred embodiment of the proposed polyamide molding material is characterized by being configured as follows: Polyamide molding material consisting of the following: (A) Polyamide selected from the group consisting of PA1010, PA1012, PA11, PA12 or mixtures thereof in an amount of 48-84% by weight; (B) 7-16% by weight of a flame retardant consisting of the following (B1) and (B2): (B1) 50-100% by weight of at least one metal phosphinate selected from phosphinates and / or diphosphinates; (B2) 0 to 50% by weight of at least one flame retardant synergistic agent and / or at least one nitrogen and phosphorus-containing flame retardant, selected from melamine polyphosphate, zinc stannate, zinc borate, ferrocene, or polyethyleneimine; Here, the sum of components (B1) and (B2) equals 100% by weight of component (B); (C) 2-8% by weight of graphite; (D) A polyamide elastomer comprising 0-20% by weight of PA1010, PA1012, PA11, or PA12 polyamide hard segments and soft segments; where the soft segments are preferably based solely on a polyetherdiol composed of at least one constituent unit selected from the following group: ethylene oxide, propylene oxide, tetrahydrofuran; Here, the polyamide elastomer preferably does not contain ester bonds; (E) 0-7% by weight of a plasticizer selected as N-butylbenzenesulfonamide and / or silicone oil; (F) A polyolefin selected as a copolymer comprising 0-7% by weight of the following constituent units: ethylene, propylene, butylene, acrylate, methacrylate, acrylic acid, methacrylic acid (preferably functionalized with maleic anhydride), and / or a polyolefin selected as a polyolefin ionomer; (G) Additives in an amount of 0-2.0% by weight, different from components (A) to (F); Here, the sum of the weight percentages of components (D) to (F) is between 7 and 26% by weight of the sum of the weight percentages of components (A) to (G), and the sum of the weight percentages of components (A) to (G) is 100% by weight.

[0077] A polyamide molding material having the following characteristics is preferred: • The elongation at break, as determined according to ISO 527:2012, is at least 100%, and particularly preferably at least 120%; • and / or, the tensile modulus determined according to ISO 527:2012 is in the range of 500 to 1500 MPa; • and / or, the notched impact strength at -45°C, as determined according to ISO 179-1 (2023) or ISO 179-2 (2020), is at least 4 kJ / m 2 is; • and / or the Limiting Oxygen Index (LOI), as determined in accordance with DIN EN ISO 4589-2:2017, is greater than 32%, particularly preferably at least 34%, and more preferably at least 36%.

[0078] Furthermore, the present invention relates to a method for producing the polyamide molding material described above, wherein components (A), (C), (D), (F), and (G) are preferably pre-mixed separately from component (B) and fed separately into the compounder's feeder. Alternatively, (B) may be metered and added to the molten mixture of (A), (D), and (F) via a side feeder. If necessary, component (E) may also be pre-mixed separately or injected in liquid form into the molten mixture of the remaining components. Components (F) and (G) may be selectively mixed with (A) or (B), but (A) is preferred. To obtain more compact granules, the molten mixture is preferably degassed under atmospheric pressure or vacuum.

[0079] Furthermore, the present invention relates to granules, powders, or components made from the polyamide molding material described above.

[0080] In particular, the present invention relates to flexible components, especially components for fire protection (flame retardant) applications in the railway sector, and preferably coatings, covers, films, profiles, tubes, corrugated tubes, hollow bodies, seals, panels, brackets, housings, sheaths (covering materials), electrical and electronic components, for example, preferably plugs and fans (ventilation materials), and preferably approved in accordance with DIN EN 45545.

[0081] The component preferably has a tensile modulus in the range of 500 to 1500 MPa, and / or elongation at break greater than 100%, and / or 4 kJ / m at a temperature of -45°C. 2 It has the above impact strength with notches.

[0082] The present invention further relates to a method for manufacturing such articles. The method is preferably characterized by molding the polyamide molding material described above into an article by extrusion molding or extrusion blow molding, injection molding, or overmolding (back injection molding).

[0083] Finally, the present invention relates to the use of the above-described polyamide molding material for manufacturing such parts.

[0084] Further embodiments of the present invention are provided in the dependent claims.

[0085] [Detailed description of preferred embodiments] Preferred embodiments of the present invention will be described below by reference to examples, but these are for illustrative purposes only and should not be interpreted as limiting.

[0086] Manufacturing of polyamide molding materials Component (A) was compounded with additives (D), (B), (C), (F), and (G) in the proportions shown in the table below, according to the following method: The raw materials for components (A), (C), (D), (F), and (G) were pre-mixed and weighed into the feeder of a twin-screw extruder (Werner & Pfleiderer, ZSK 25 model) via a belt scale. Component (B) was weighed and fed into the feeder separately via a screw conveyor. Alternatively, component (B) may also be pre-mixed with components (A), (C), (D), (F), and (G), or similarly weighed and fed into the feeder separately via a screw conveyor. The plasticizer (E) was weighed and supplied via a pump upstream of the nozzle's 5th zone. Alternatively, the plasticizer may be pre-mixed with component (A) in the extruder. The pump throughput was calibrated in advance. High-viscosity plasticizers can be processed more easily at high temperatures using a heat-retaining pump. The molten material was degassed under atmospheric pressure upstream of the nozzle's 2nd zone (open degassing zone). The process was carried out at a cylinder temperature of 270-290°C, a screw rotation speed of 200 rpm, and a throughput of 15 kg / h. The compound was discharged from the nozzle, the strand was cooled, and then granulated. After that, it was dried under vacuum at 80°C for 24 hours.

[0087] Manufacturing of molded products The molded parts were manufactured using an injection molding machine (Arburg Allrounder 320-210-750) with a cylinder heating profile of 240-260°C and an injection pressure of 1200-1800 bar. The mold temperature was 40°C. The shape of the molded parts conformed to the specifications of the relevant test standards. The composition of the molding material and the characteristics of the molded parts produced therefrom are summarized in Table 1.

[0088] The following materials were used: PA12: Polyamide PA12, solution viscosity η rel = 1.9, melting point 178℃, EMS-CHEMIE AG Graphite: Timrex KS15, synthetic graphite, particle size: 8 μm (D50), 17 μm (D90), specific surface area (BET): 20 m² 2 / g, Imerys Graphite & Carbon Ltd. PA Elastomer: Grillflex ELG 3630, a polyetheramide with PA12 hard segments and tetrahydrofuran-based soft segments, solution viscosity η rel =1.7, melting point Tm=155℃, EMS-CHEMIE AG BBSA: N-butylbenzenesulfonamide AK100: Silicone oil, viscosity 100 mm 2 / s polydimethylsiloxane, Wacker AK5000: Silicone oil, viscosity 5000 mmHg 2 / s polydimethylsiloxane, Wacker FR: Exolit OP1230, flame retardant, organophosphate, aluminum phosphinate, Clariant Int. AG Polyolefin: Surlyn 9320, ethylene-methacrylic acid-acrylate terpolymer, partially neutralized with zinc ions, DuPont Stabilizer: A mixture of copper iodide and potassium iodide (weight ratio 1:5) Carbon Black: Euthylen black 00-6005C4, 40% carbon black by weight PE masterbatch, BASF Lupasol: Lupasol G20 WFR, polyethyleneimine, BASF Plutocen: Plutocen FC, Ferrocene, Innospec

[0089] Table 1: Examples B1-B5 of the present invention [Table 1]

[0090] Compared to comparative examples VB1 and VB2, Examples B1 to B5 of the present invention exhibit a remarkably high LOI of at least 40%. The addition of graphite causes a significant increase in the LOI value. The molding material of Example B1 has an LOI of 40%, while the molding material of VB1 has an LOI of only 30%. Despite the use of graphite, the notched impact strength at low temperatures, fracture stress, and elongation at fracture can be maintained at levels comparable to the comparative examples.

[0091] As the comparison between Examples B1 and B2 shows, replacing the plasticizer N-butylbenzenesulfonamide with polydimethylsiloxane (silicone oil) again significantly increases the LOI. The increase in LOI is even greater when graphite is present in the molding material. The comparison between VB1 and VB2 shows that using silicone oil instead of N-butylbenzenesulfonamide only increases the LOI by 2%. In contrast, when the molding material contains graphite, as in B1 and B2, the LOI increases by 5%.

[0092] Table 2: Examples B6-B8 and Comparative Examples VB1 and VB2 according to the present invention TIFF2026075617000003.tif201169

[0093] Unless otherwise specified, measurements were performed using the following dry test specimens according to the specifications below. Specifically, after injection molding, the test specimens were stored on silica gel in a dry environment at room temperature for at least 48 hours before being subjected to testing.

[0094] Thermal behavior (melting point (TM), enthalpy of fusion (ΔHm), glass transition temperature (Tg)) The temperature was measured using granules in accordance with ISO standard 11357:2013 (11357-2 for glass transition temperature, and 11357-3 for melting temperature and enthalpy of fusion). Differential scanning calorimetry (DSC) was performed at a heating rate of 20°C / min.

[0095] Relative viscosity (η) rel )The measurement was performed at a temperature of 20°C on a solution prepared by dissolving 0.5 g of polymer in 100 ml of m-cresol, in accordance with DIN EN ISO 307:2007. Granules were used as the sample.

[0096] Tensile modulus, breaking strength, and elongation at break: Tensile modulus, breaking strength, and elongation at break were measured according to ISO 527 (2012) at a temperature of 23°C using ISO tensile test specimens (standard ISO / CD 3167, type AI, 170 × 20 / 10 × 4 mm) at a tensile speed of 1 mm / min (tensile modulus) or 50 mm / min (breaking strength, elongation at break).

[0097] Charpy impact strength and notched impact strength The values ​​were measured in accordance with ISO 179 / 1(2023) or ISO 179 / 2(2020) at temperatures of 23°C and -45°C using ISO test specimens (standard ISO / CD 3167, type B1, 80 × 10 × 4 mm).

[0098] Oxygen Index (LOI = Limiting Oxygen Index) LOI is the minimum oxygen concentration in the oxygen-nitrogen mixture at which combustion of a vertically positioned test specimen (ISO test specimen, standard ISO / CD 3167, type B1, 80 × 10 × 4 mm) is sustained under the test conditions, and is expressed as a volume percentage. LOI is measured according to DIN EN ISO 4589-1 and 4589-2 (2017). Prior to LOI measurement, the test specimens were conditioned at a temperature of 23°C and a relative humidity of 50% for 7 days.

[0099] MVR The melt volume flow rate is measured using a capillary rheometer in accordance with ISO 1133 (2012). The material (granules) was melted in a cylinder heated to 275°C and extruded through a specified nozzle (capillary) under pressure from a 5 kg load. The volume of the flowing polymer molten material was measured as a function of time.

Claims

1. A polyamide molding material containing, preferably comprising, the following: A. Semicrystalline aliphatic polyamides containing 34–88% by weight, with a C / N ratio of at least 8; B A flame retardant consisting of B1 and B2 in an amount of 6 to 21% by weight, B1 50 to 100% by weight of at least one metal phosphinate; B2 0 to 50% by weight of at least one flame retardant synergistic agent and / or at least one nitrogen and phosphorus-containing flame retardant; Here, the sum of components B1 and B2 is 100% by weight of component B; C 1-10% by weight of graphite; D 0-25% by weight of polyamide elastomer; E 0-10% by weight of plasticizer; F 0-10% by weight of polyolefin; G: 0-5% by weight of additives different from A-F; Here, the sum of the weight percentages of components D to F is 5 to 30% by weight relative to the sum of the weight percentages of components A to G, and the sum of the weight percentages of components A to G is 100% by weight.

2. Polyamide A is Selected from semicrystalline aliphatic polyamides having a C / N ratio of at least 10, preferably 10 to 13; or selected from the group consisting of PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, PA12, or mixtures thereof; Alternatively, a selection will be made from the group consisting of PA1010, PA1012, PA11, PA12 and mixtures thereof; and / or, when measured in a solution prepared by dissolving 0.5 g of polymer in 100 ml of m-cresol at 20°C in accordance with DIN EN ISO 307:2007, η rel = in the range of 1.5 to 2.8, preferably η rel It is characterized by having a solution viscosity in the range of 1.6 to 2.

3. The polyamide molding material according to claim 1.

3. The proportion of component B is in the range of 7 to 16% by weight, preferably 8 to 14% by weight, relative to components A to G; and / or, component B consists of 55 to 100% by weight of B1 and 0 to 45% by weight of B2, preferably 60 to 100% by weight of B1 and 0 to 40% by weight of B2, particularly preferably 75 to 98% by weight of B1 and 2 to 25% by weight of B2, and even more preferably 100% by weight of B1 and 0% by weight of B2, where the sum of the weight percentages of B1 and B2 is 100% by weight of component B. A polyamide molding material according to any one of the prior claims, characterized in that

4. At least one metal phosphinate of component B1 is selected as a phosphinate and / or diphosphinate, preferably a phosphinate of general formula (I) and / or general formula (II) and / or a polymer thereof. 【Chemistry 1】 (In the formula, R1 and R2 are the same or different, preferably C1-C8-alkyl (linear or branched) and / or aryl; R3 is a C1-C10-alkylene (linear or branched), C6-C10-arylene, -alkylarylene, or arylalkylene; M is a metal ion belonging to the second or third main or subgroup of the periodic table; m is either 2 or 3; n is either 1 or 3; x is either 1 or 2; (Preferably Al, Ca, and Zn are used as the metal ion M.) A polyamide molding material according to any one of the preceding claims, characterized in that

5. The polyamide molding material according to any one of the preceding claims, characterized in that the proportion of component C is in the range of 2 to 8% by weight, preferably 3 to 7% by weight, relative to the sum of the weight percentages of components A to G.

6. The polyamide elastomer of component D has a hard segment based on polyamide PA610, PA612, PA614, PA616, PA1010, PA1012, PA1014, PA1016, PA11, PA12 and a soft segment based on the following (preferably only the following): Polyetherdiols based on (preferably based on only) at least one constituent unit selected from the group consisting of ethylene oxide, propylene oxide, tetrahydrofuran, or mixtures thereof, and / or polyetherdiamines based on dimerized fatty acids having 20 to 44 carbon atoms, and / or at least one constituent unit selected from the group consisting of ethylene oxide, propylene oxide, tetrahydrofuran, or mixtures thereof (preferably based on only these); Here, preferably, the polyamide hard segment has a number-average molar mass in the range of 500 to 10,000 g / mol, preferably 700 to 5,000 g / mol, and particularly preferably 750 to 3,000 g / mol; and / or, the soft segment has a number-average molar mass in the range of 200 to 4000 g / mol, preferably 200 to 3000 g / mol, and particularly preferably 300 to 2500 g / mol; and / or, therein, the proportion of polyamide hard segments is 45 to 95% by weight, preferably 50 to 80% by weight, and the proportion of soft segments is 5 to 55% by weight, preferably 20 to 50% by weight, relative to 100% by weight of component D; and / or, component D preferably does not contain an ester bond; and / or, the proportion of component D is in the range of 0 to 20% by weight, preferably 6 to 18% by weight or 8 to 18% by weight, relative to the sum of the weight percentages of components A to G. A polyamide molding material according to any one of the prior claims, characterized in that

7. The proportion of plasticizer in component E is in the range of 0 to 7% by weight, preferably 1 to 6% by weight or 1 to 5% by weight, relative to the sum of the weight percentages of components A to G; and / or, the plasticizer of component E is selected from the group consisting of aryl sulfonamides having 2 to 12 carbon atoms, p-hydroxybenzoic acid esters having 2 to 20 carbon atoms in the alcohol component, organic phosphonates or phosphates, and silicone oils. A polyamide molding material according to any one of the prior claims, characterized by the above.

8. A polyamide molding material according to any one of the preceding claims, characterized in that component E is silicone oil.

9. The proportion of component F is in the range of 0 to 7% by weight, preferably 1 to 6% by weight or 1 to 5% by weight, relative to the sum of the weight percentages of components A to G; and / or, at least one polyolefin of component F is composed of at least one or a combination of the following constituent units: ethylene, propylene, butylene, acrylate, methacrylate, acrylic acid, methacrylic acid, maleic anhydride, glycidyl methacrylate, diene, particularly butadiene and / or isoprene, preferably as a copolymer, particularly preferably as a terpolymer; and / or, at least one polyolefin of component F is selected from the group consisting of ethylene-propylene rubber, ethylene-propylene-diene rubber, styrene-containing elastomers, particularly SEBS, SBS, SEPS, acrylate rubber, nitrile rubber, and silicone rubber; and / or, at least one polyolefin of component F is functionalized with maleic anhydride, acrylic acid and / or glycidyl methacrylate, and preferably has a grafting degree in the range of 0.05 to 10% by weight; and / or, component F is a polyolefin ionomer, and the carboxyl groups present therein are partially or completely neutralized by a metal base. A polyamide molding material according to any one of the prior claims, characterized by the above.

10. The polyamide molding material according to any one of the preceding claims, characterized in that the proportion of component G is in the range of 0 to 2.0% by weight, preferably 0.1 to 2.0% by weight, relative to the sum of the weight percentages of components A to G.

11. A polyamide molding material according to any one of the preceding claims, characterized by comprising the following: A. Polyamide selected from the group consisting of PA1010, PA1012, PA11, PA12, or mixtures thereof, in an amount of 34 to 88% by weight; B A flame retardant consisting of B1 and B2 in an amount of 6 to 21% by weight, B1 50 to 100% by weight of at least one metal phosphinate; B2 0 to 50% by weight of at least one flame retardant synergistic agent and / or at least one nitrogen and phosphorus-containing flame retardant; Here, the sum of components B1 and B2 is 100% by weight of component B; C 1-10% by weight of graphite; D is a polyamide elastomer in a weight of 0 to 25%. PA1010, PA1012, PA11 or PA12 polyamide hard segments, It consists of a soft segment based on (preferably based solely on) a polyetherdiol composed of at least one structural unit selected from the group consisting of ethylene oxide, propylene oxide, and tetrahydrofuran; Here, the polyamide elastomer preferably does not contain ester bonds; E 0 to 10% by weight of a plasticizer selected as N-butylbenzenesulfonamide and / or silicone oil; F 0 to 10% by weight of polyolefin, selected as a copolymer composed of at least one or a combination of the following constituent units: ethylene, propylene, butylene, acrylate, methacrylate, acrylic acid, methacrylic acid (preferably functionalized with maleic anhydride) and / or selected as a polyolefin ionomer; G: 0-5% by weight of additives different from A through F; Here, the sum of components D to F is 5 to 30% by weight of the sum of the weight percentages of components A to G, and the sum of the weight percentages of components A to G is 100% by weight.

12. A method for producing a polyamide molding material according to any one of the preceding claims, characterized in that component A and components B to G, or preferably components C, D, F and G, are mixed at the same time, wherein the mixing is preferably carried out at a temperature range of 240 to 300°C, particularly 250 to 290°C, the plasticizer E is added to the mixture individually as a liquid or as granules after being pre-mixed with component A, and the flame retardant B is mixed into the remaining mixture, which is already in a molten state, preferably as a separate powder.

13. A component made of a polyamide molded material as described in any one of claims 1 to 11, preferably manufactured by the method described in claim 12, and particularly for fire protection applications in the railway sector, preferably a coating, cover, film, profile, tube, corrugated tube, hollow body, seal, panel, bracket, housing, sheath, electrical and electronic component, preferably a plug and fan (preferably approved under DIN EN 45545), component.

14. A method for manufacturing a part according to claim 13, preferably characterized by molding a polyamide molding material according to any one of claims 1 to 11 into a part by extrusion molding, extrusion blow molding, injection molding, or overmolding.

15. Use of a polyamide molding material according to any one of claims 1 to 11, preferably for manufacturing a part according to claim 13, manufactured by the method of claim 12.

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