Mixed metal oxide compositions as stabilizers for flame retardant polyamides

Abstract

A thermoplastic molding composition comprising a thermoplastic polyamide, red phosphorus and a mixed metal oxide comprising Cu and Cr; a process for producing the thermoplastic molding composition; the use of the thermoplastic molding composition for producing a molded article, a fiber, a film or an extruded article; a molded article, fiber, film or extruded article made from the thermoplastic molding composition; and the use of mixed metal oxides comprising Cu and Cr in the form of their oxides for stabilizing red phosphorus as a flame retardant in polyamide compositions while maintaining the electrical properties of the polyamide compositions.

Description

[0001] Description

[0002] The present invention relates to a thermoplastic molding composition comprising a thermoplastic polyamide, red phosphorus, and a mixed metal oxide comprising Cu and Cr; a process for producing the thermoplastic molding composition; the use of the thermoplastic molding composition for producing molded articles, fibers, films or extruded articles; molded articles, fibers, films or extruded articles made from the thermoplastic molding composition; and the use of a mixed metal oxide comprising Cu and Cr in the form of their oxides for stabilizing red phosphorus as a flame retardant in a polyamide composition while maintaining the electrical properties of the polyamide composition.

[0003] It is known that adding red phosphorus to thermoplastics, especially to reinforced or filled polyamides, results in effective fire protection (DE-A-1931387). However, under adverse conditions, such as elevated temperature or humidity, or in the presence of bases or oxygen, red phosphorus tends to form decomposition products, such as phosphines and acids of monovalent to pentavalent phosphorus. Although the red phosphorus incorporated into the thermoplastic (e.g., into the polyamide) has substantial protection against thermal oxidation due to entrapment in the polymer, decomposition products can still form over an extended period. This is disadvantageous because if the granules are not processed correctly during the injection molding process, the resulting phosphines can cause odor problems and are furthermore toxic. The simultaneously generated phosphoric acid can deposit on the surface of the molded article, with the particular result that the molded article has reduced tracking resistance. Thus, there have been ongoing attempts to improve the stability of red phosphorus used as a plastic flame retardant. For example, a stabilizing effect can be achieved by adding oxides or hydroxides of zinc, magnesium or copper. In DE-A-2625691, in addition to the said stabilization via metal oxides, polymers are also used to coat the phosphorus particles. However, the coating or encapsulation process is very complex, and the stabilizing effect of the system is not always satisfactory.

[0004] US 4187207 A relates to a substance composition comprising a polyamide, an amount of red phosphorus sufficient to render the polyamide flame retardant, and an amount of cadmium oxide sufficient to delay the release of phosphine during heating of the polyamide.

[0005] US2013 / 0072606A1 relates to a thermoplastic molding composition comprising a thermoplastic polyamide, red phosphorus, and a stabilizer mixture consisting of the elements Ag and ZnO.

[0006] WO 2013 / 124128A1 relates to a thermoplastic molding composition comprising a thermoplastic polyamide, red phosphorus, a catalyst comprising a mixture of CuO and ZnO, and a carrier material.

[0007] US 3883475 A relates to a molding composition of a thermoplastic material, which thermoplastic material contains

[0008] red phosphorus and a substance for binding phosphine, and the substance for binding phosphine is selected from the group consisting of: MoS2, HgO, PbO2, AgNO3, HgCI2, FeCI3·6H2O, CuO and activated carbon.

[0009] It is mentioned in US 3883475 A that it is noteworthy that many other compounds with active surfaces (such as alumina, silica or molecular sieves) are not suitable or are only suitable at much higher concentrations for binding phosphine in the molding composition of thermoplastic materials.

[0010] However, for example, in the applications of polyamides in the battery technology and propulsion technology of electric vehicles, not only the fire resistance of polyamides (especially reinforced or filled polyamides) is relevant, but also their electrical properties are relevant.

[0011] Therefore, the present invention is based on the object of providing a thermoplastic molding composition containing red phosphorus, which red phosphorus has effective stability as a flame retardant, that is, exhibits less deposition of phosphoric acid and less formation of phosphine, while maintaining electrical properties such as the tracking index. In addition, the stabilizer is intended to be characterized by good stability during processing and particularly uniform processability in the plastic melt.

[0012] This object is achieved by a thermoplastic molding composition, which thermoplastic molding composition contains

[0013] a) 10% to 99.85% by weight of at least one thermoplastic polyamide as component A),

[0014] b) 0.1% to 60% by weight of red phosphorus as component B),

[0015] c) 0.05% to 20% by weight of at least one mixed metal oxide containing Cu and Cr in their oxide forms as component C),

[0016] d) 0% to 40% by weight of at least one impact modifier as component D),

[0017] e) 0% to 60% by weight of at least one filler as component E),

[0018] h) 0% to 40% by weight of at least one further additive as component F),

[0019] wherein the total of the weight percentages of components A), B), C), optionally D), optionally E) and optionally F) is 100% by weight.

[0020] This object is further achieved by a process for producing the thermoplastic molding composition according to the invention, which process comprises the step of mixing components A), B), C) and optionally D), optionally E) and optionally F).

[0021] This object is further achieved by the use of the thermoplastic molding composition according to the invention for producing molded articles, fibers, films or extruded articles.

[0022] This object is further achieved by a molded article, fiber, film or extruded article made from the thermoplastic molding composition according to the invention.

[0023] This object is further achieved by the use of a mixed metal oxide comprising Cu and Cr in their oxide forms for stabilizing red phosphorus as a flame retardant in a polyamide composition while maintaining the electrical properties (such as the tracking index) of the polyamide composition.

[0024] The inventors have found that by including a mixed metal oxide comprising Cu and Cr in their oxide forms, not only is red phosphorus effectively stabilized in the polyamide composition, but the electrical properties of the polyamide composition, such as the tracking index, are maintained. This is surprising because it is generally known that other metal oxides or metal salts adversely affect the electrical properties.

[0025] In the context of the present invention, "at least one" means exactly one or a mixture of two or more different components.

[0026] Component A)

[0027] As component A), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 10% to 99.85% by weight, preferably from 20% to 98% by weight, more preferably from 30% to 90% by weight of at least one thermoplastic polyamide.

[0028] If component D, E) or F) or a combination thereof is present in the thermoplastic molding composition, the maximum amount of component A) is reduced by the minimum amount of each of component D), E), F) or a combination thereof.

[0029] The polyamide (A) of the molding composition according to the invention generally has a viscosity value of from 90 ml / g to 350 ml / g, preferably from 100 ml / g to 240 ml / g. The viscosity value (VN) of the polyamide and polyamide composition according to the invention is determined in sulfuric acid (96% [m / m] sulfuric acid containing 0.5% [m / v] polyamide at 25 °C) in accordance with EN ISO 307:2019, unless otherwise stated.

[0030] Preferably, a semi-crystalline or amorphous polyamide having a molecular weight (weight average) of at least 5000, such as described by way of example in the following US patents: 2071250, 2071251, 2130523, 2130948, 2241322, 2312966, 2512606 and 3393210.

[0031] Examples of these polymers are polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polyoctanamide and polylaurolactam; and polyamides obtained by the reaction of dicarboxylic acids with diamines.

[0032] The dicarboxylic acids that can be used are alkane dicarboxylic acids and aromatic dicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms. By way of example only, those dicarboxylic acids that may be mentioned here are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic acid and / or isophthalic acid.

[0033] Particularly suitable diamines are alkane diamines having 6 to 12, in particular 6 to 8 carbon atoms, and m-xylenediamine, bis[4-aminophenyl]methane, bis[4-aminocyclohexyl]methane, 2,2-bis[4-aminophenyl]propane, 2,2-bis[4-aminocyclohexyl]propane and 1,5-diamino-2-methylpentane.

[0034] Preferred polyamides are hexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam, and also PA 6 / 66 copolyamides, in particular having a proportion of caprolactam units of 5% to 95% by weight (e.g., C31 from BASF SE).

[0035] Other suitable polyamides can be obtained by direct polymerization of ω-aminoalkyl nitriles, such as aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) in the presence of water, for example as described in DE-A 10313681, EP-A 1198491 and EP 0 922065.

[0036] Also mention may be made, for example, of polyamides (PA 46) that can be obtained by condensation of 1,4-diaminobutane with adipic acid at elevated temperature. The preparation methods of polyamides of this structure are described, for example, in EP-A38094, EP-A 38582 and EP-A39524.

[0037] Other suitable examples are polyamides obtainable by copolymerization of two or more of the above monomers, and mixtures of two or more polyamides in any desired mixing ratio. Particularly preferred are mixtures of PA 66 with other polyamides, in particular blends of PA 6 and PA 66, as well as PA6 / 66 copolyamides and PA 66 / 6 copolyamides.

[0038] Other copolyamides which have proven particularly advantageous are semi-aromatic copolyamides, such as, PA 6 / 6T and PA 66 / 6T, where the triamine content of these is preferably less than 0.5% by weight, preferably less than 0.3% by weight (see EP-A 299444). Other polyamides with high heat resistance are known from EP-A 1994075 (PA 6T / 6I / MXD6).

[0039] The processes described in EP-A 129195 and EP-A 129196 can be used to prepare preferably semi-aromatic copolyamides with a low triamine content.

[0040] The following non-exhaustive list includes the above polyamides A) and other polyamides A) which can be used for the purposes of the present invention, and the monomers contained therein:

[0041] AB polymers:

[0042]

[0043]

[0044] AA / BB polymers:

[0045]

[0046] AA / BB polymers:

[0047]

[0048] Preferred polyamides A) are PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA 6 / 636, PA 6T / 6, PA6T / 6I, PA 6T / 6I / 66, PA 9T, PA 6T / 66 or mixtures thereof.

[0049] Most preferred are PA 6, PA 66, PA 6 / 66 and PA 66 / 6 as well as PA 6 / 636, or mixtures thereof. Most preferred are PA 6, PA 66 or mixtures thereof.

[0050] Suitable copolyamides consist of:

[0051] A1) 20.0 to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine,

[0052] A2) 0 to 50.0% by weight of units derived from ε-caprolactam,

[0053] A3) 0 to 80.0% by weight of units derived from adipic acid and hexamethylenediamine,

[0054] A4) 0 to 40.0% by weight of other polyamide-forming monomers,

[0055] wherein the proportion of component A2) or A3) or A4) or a mixture thereof is at least 10.0% by weight.

[0056] Component A1) comprises 20.0 to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

[0057] In addition to the units derived from terephthalic acid and hexamethylenediamine, the copolyamide optionally comprises units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine and / or units derived from further polyamide-forming monomers.

[0058] The aromatic dicarboxylic acid A4) contains 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic acids and isophthalic acids such as 3-tert-butylisophthalic acid; polycyclic dicarboxylic acids such as 4,4′-diphenyldicarboxylic acid and 3,3′-diphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid and 3,3′-diphenylmethanedicarboxylic acid, 4,4′-sulfonyldiphenylcarboxylic acid and 3,3′-sulfonyldiphenylcarboxylic acid, 1,4-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, and thus isophthalic acid is particularly preferred.

[0059] Furthermore, the polyamide-forming monomer A4) can be derived from a dicarboxylic acid having 4 to 16 carbon atoms and an aliphatic or cycloaliphatic diamine having 4 to 16 carbon atoms, and an aminocarboxylic acid / corresponding lactam having 7 to 12 carbon atoms. Examples of suitable monomers of these types are suberic acid, azelaic acid and sebacic acid as representatives of aliphatic dicarboxylic acids; 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4′-diaminodicyclohexylmethane, 2,2-(4,4′-diaminodicyclohexylpropane) and 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane as representatives of diamines or metaxylylenediamine as a representative of diamines and caprolactam, enantholactam, ω-aminoundecanoic acid and laurolactam as representatives of lactams / aminocarboxylic acids.

[0060] Examples of such copolyamides are described in more detail in DE - A 102009011668.

[0061] As component A), the thermoplastic molding material may comprise at least one copolyamide produced by polymerization of the components

[0062] A′) 15% to 84% by weight of at least one lactam,

[0063] B′) 16% to 85% by weight of a monomer mixture (M) comprising the following components

[0064] B1′) at least one C 32 -C 40 -dimeric acid and

[0065] B2′) at least one C4 - C 12 -diamine,

[0066] wherein the weight percentages of components A′) and B′) are in each case based on the sum of the weight percentages of components A′) and B′).

[0067] In the context of the present invention, the terms "component A′)" and "at least one lactam" are used synonymously and thus have the same meaning.

[0068] This also applies to the terms "component B′)" and "monomer mixture (M)". These terms are also used synonymously in the context of the present invention and thus have the same meaning.

[0069] According to the invention, at least one copolyamide is produced by polymerization of 15% to 84% by weight of component A′) and 16% to 85% by weight of component B′), preferably by polymerization of 40% to 83% by weight of component A′) and 17% to 60% by weight of component B′), and particularly preferably by polymerization of 60% to 80% by weight of component A′) and 20% to 40% by weight of component B′), wherein the weight percentages of components A′) and B′) are each based on the sum of the weight percentages of components A′) and B′).

[0070] The sum of the weight percentages of components A′) and B′) is preferably 100% by weight.

[0071] It should be understood that the weight percentages of components A′) and B′) relate to the weight percentages of components A′) and B′) before polymerization (i.e., when components A′) and B′) have not yet reacted with each other). During the polymerization of components A′) and B′), the weight ratio of components A′) and B′) can optionally change.

[0072] According to the present invention, at least one copolyamide is produced by the polymerization of components A') and B'). The polymerization of components A') and B') is known to those skilled in the art. The polymerization of components A') and B') is generally a condensation reaction. During the condensation reaction, component A') reacts with components B1') and B2') present in component B'), and optionally with component B3') which may also be present in component B') as described below. This results in the formation of amide bonds between the individual components. During the polymerization, component A') is generally at least partially in an open-chain form, i.e., in the amino acid form.

[0073] The polymerization of components A') and B') can be carried out in the presence of a catalyst. Suitable catalysts include all catalysts known to those skilled in the art for catalyzing the polymerization of components A') and B'). Such catalysts are known to those skilled in the art. Preferred catalysts are phosphorus compounds such as sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenyl phosphite.

[0074] The polymerization of components A') and B') forms at least one copolyamide, and thus the copolyamide contains units derived from component A') and units derived from component B'). The units derived from component B') include units derived from components B1') and B2') and optionally units derived from component B3').

[0075] The polymerization of components A') and B') forms a copolyamide as a copolymer. The copolymer can be a random copolymer. It can equally be a block copolymer.

[0076] In the block copolymer, blocks of units derived from component B') and blocks of units derived from component A') are formed. These occur in an alternating sequence. In the random copolymer, the units derived from component A') alternate with the units derived from component B'). This alternation is random. For example, two units derived from component B') can be followed by one unit derived from component A'), then followed by a unit derived from component B'), and then a unit containing three units derived from component A').

[0077] It is preferred when at least one copolyamide is a random copolymer.

[0078] The production of at least one copolyamide preferably comprises the following steps:

[0079] I) Polymerize components A') and B') to obtain at least a first copolyamide,

[0080] II) Granulate at least one first copolyamide obtained in step I) to obtain at least one granulated copolyamide,

[0081] III) Extract at least one of the granulated copolyamides obtained in step II) with water to obtain at least one of the extracted copolyamides.

[0082] IV) Dry at least one of the extracted copolyamides obtained in step III) at a certain temperature (TT) to obtain at least one copolyamide.

[0083] The polymerization in step I) can be carried out in any reactor known to those skilled in the art. A stirred tank reactor is preferred. It is also possible to use auxiliaries known to those skilled in the art, such as antifoaming agents, such as polydimethylsiloxane (PDMS), to improve reaction management.

[0084] In step II), at least one of the first copolyamides obtained in step I) can be granulated by any method known to those skilled in the art, such as strand granulation or underwater granulation.

[0085] The extraction in step III) can be achieved by any method known to those skilled in the art.

[0086] During the extraction in step III), by-products usually formed during the polymerization of components A′) and B′) in step I) are extracted from at least one of the granulated copolyamides.

[0087] In step IV), at least one of the extracted copolyamides obtained in step III) is dried. The drying process is known to those skilled in the art. According to the present invention, at least one of the extracted copolyamides is dried at a certain temperature (TT). The temperature (TT) is preferably higher than the glass transition temperature (T G(C) ) of at least one copolyamide, and lower than the melting temperature (T M(C) ) of at least one copolyamide.

[0088] The drying in step IV) is usually carried out for a period in the range of 1 hour to 100 hours, preferably in the range of 2 hours to 50 hours, and particularly preferably in the range of 3 hours to 40 hours.

[0089] It is considered that the drying in step IV) further increases the molecular weight of at least one copolyamide.

[0090] At least one copolyamide usually has a glass transition temperature (T G(C) ). The glass transition temperature (T G(C) ) is determined according to ISO 11357-2:2014, for example, in the range of 20 °C to 50 °C, preferably in the range of 23 °C to 47 °C, and particularly preferably in the range of 25 °C to 45 °C.

[0091] In the context of the present invention, according to ISO 11357-2:2014, the glass transition temperature (T G(C) ) of at least one copolyamide is based on the glass transition temperature (T G(C) ) of the dry copolyamide.

[0092] In the context of the present invention, "dry" is understood to mean that based on the total weight of at least one copolyamide, at least one copolyamide contains less than 1% by weight, preferably less than 0.5% by weight, and particularly preferably less than 0.1% by weight of water. "Dry" is more preferably understood to mean that at least one copolyamide does not contain water, and most preferably at least one copolyamide does not contain a solvent.

[0093] Furthermore, at least one copolyamide generally has a melting temperature (T M(C) ). The melting temperature (T M(C) ) of at least one copolyamide is determined according to ISO 11357-3:2014, for example, in the range of 150 °C to 210 °C, preferably in the range of 160 °C to 205 °C, and particularly preferably in the range of 160 °C to 200 °C.

[0094] At least one copolyamide generally has a viscosity value (VN (C) ) in the range of 150 ml / g - 300 ml / g determined in a 0.5% by weight solution of at least one copolyamide in a phenol / ortho-dichlorobenzene mixture with a weight ratio of 1:1.

[0095] It is preferred when the viscosity value (VN (C) ) of at least one copolyamide determined in a 0.5% by weight solution of at least one copolyamide in a phenol / ortho-dichlorobenzene mixture with a weight ratio of 1:1 is in the range of 160 mL / g to 290 mL / g, and particularly preferably in the range of 170 mL / g to 280 mL / g.

[0096] Component A′)

[0097] According to the present invention, component A') is at least one lactam.

[0098] In the context of the present invention, "at least one lactam" is understood to precisely mean one lactam or a mixture of 2 or more lactams.

[0099] Lactams are known to those skilled in the art. According to the present invention, lactams preferably having 4 to 12 carbon atoms are preferred.

[0100] In the context of the present invention, "lactam" is understood to mean a cyclic amide preferably having 4 to 12 carbon atoms, particularly preferably 5 to 8 carbon atoms, in the ring.

[0101] Suitable lactams are, for example, selected from the group consisting of: 3-aminopropanol lactam (prop-3-lactam; β-lactam; β-propiolactam), 4-aminobutanol lactam (but-4-lactam; γ-lactam; γ-butyrolactam), aminopentanol lactam (2-piperidone; δ-lactam; δ-valerolactam), 6-aminohexanol lactam (hex-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanol lactam (hept-7-lactam; ζ-lactam; ζ-heptanolactam), 8-aminooctanol lactam (oct-8-lactam; η-lactam; η-octanolactam), 9-aminononanol lactam (non-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanol lactam (decan-10-lactam; ω-decanolactam), 11-aminoundecanol lactam (undecan-11-lactam; ω-undecanolactam) and 12-aminododecanol lactam (dodecan-12-lactam; ω-dodecanolactam).

[0102] Accordingly, the present invention also provides a method in which component A′) is selected from the group consisting of: 3-aminopropiolactam, 4-aminobutyrolactam, 5-aminovalerolactam, 6-aminohexanol lactam, 7-aminoheptanol lactam, 8-aminooctanol lactam, 9-aminononanol lactam, 10-aminodecanol lactam, 11-aminoundecanol lactam and 12-aminododecanol lactam.

[0103] The lactam can be unsubstituted or at least monosubstituted. If at least monosubstituted lactam is used, the nitrogen atom and / or its ring carbon atoms can carry one, two or more substituents independently of each other selected from the group consisting of: C1-alkyl to C 10 -alkyl, C5-cycloalkyl to C6-cycloalkyl and C5-aryl to C 10 -aryl.

[0104] Suitable C1-alkyl to C 10 -alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Suitable C5-cycloalkyl to C6-cycloalkyl substituents are, for example, cyclohexyl. Preferred C5-aryl to C 10 -aryl substituents are phenyl or anthryl.

[0105] Unsubstituted lactams are preferably used, preferably γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam). Particularly preferred are δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam), and ε-caprolactam is particularly preferred.

[0106] Monomer mixture (M)

[0107] According to the present invention, component B′) is a monomer mixture (M). The monomer mixture (M) comprises component B1′), at least one C 32 -C 40 -dimer acid and B2′), at least one C4-C 12 -diamine.

[0108] In the context of the present invention, the monomer mixture (M) is to be understood to mean a mixture of two or more monomers, wherein at least components B1′) and B2′) are present in the monomer mixture (M).

[0109] In the context of the present invention, the terms "component B1′)" and "at least one C 32 -C 40 -dimer acid" are used synonymously and thus have the same meaning. This also applies to the terms "component B2′)" and "at least one C4-C 12 -diamine". These terms are also used synonymously in the context of the present invention and thus have the same meaning.

[0110] The monomer mixture (M) comprises, for example, component B1′) in the range from 45 mol% to 55 mol% and component B2′) in the range from 45 mol% to 55 mol%, in each case based on the sum of the mole percentages of components B1′) and B2′), preferably based on the total amount of substance of the monomer mixture (M).

[0111] Preferably, when component B′) comprises component B1′) in the range from 47 mol% to 53 mol% and component B2′) in the range from 47 mol% to 53 mol%, in each case based on the sum of the mole percentages of components B1′) and B2′), preferably based on the total amount of substance of component B′).

[0112] Particularly preferably, when component B′) comprises component B1′) in the range from 49 mol% to 51 mol% and component B2′) in the range from 49 mol% to 51 mol%, in each case based on the sum of the mole percentages of components B1′) and B2′), preferably based on the total amount of substance of component B′).

[0113] The sum of the mole percentages of components B1′) and B2′) present in component B′) is generally 100 mol%.

[0114] Component B′) may additionally comprise component B3′), at least one C4-C 20 -diacid.

[0115] In the context of the present invention, the terms "component B3′)" and "at least one C4-C20 The term “-dioic acid” is used synonymously and thus has the same meaning.

[0116] When component B′) additionally contains component B3′), preferably when component B′) contains component B1′) in the range of 25 mol% to 54.9 mol%, component B2′) in the range of 45 mol% to 55 mol%, and component B3′) in the range of 0.1 mol% to 25 mol%, in each case based on the total amount of the substances of component B′).

[0117] Particularly preferably, when component B′) then contains component B1′) in the range of 13 mol% to 52.9 mol%, component B2′) in the range of 47 mol% to 53 mol%, and component B3′) in the range of 0.1 mol% to 13 mol%, in each case based on the total amount of the substances of component B′).

[0118] Most preferably, when component B′) then contains component B1′) in the range of 7 mol% to 50.9 mol%, component B2′) in the range of 49 mol% to 51 mol%, and component B3′) in the range of 0.1 mol% to 7 mol%, in each case based on the total amount of the substances of component B′).

[0119] When component B′) additionally contains component B3′), the sum of the mole percentages of components B1′), B2′), and B3′) is usually 100 mol%.

[0120] The monomer mixture (M) can also contain water.

[0121] Components B1′) and B2′) of component B′) and optionally B3′) can react with each other to obtain an amide. This reaction itself is known to those skilled in the art. Thus, component B′) can contain components B1′), B2′), and optionally B3′) in a fully reacted form, in a partially reacted form, or in an unreacted form. It is preferred when component B′) contains components B1′), B2′), and optionally B3′) in an unreacted form.

[0122] Thus, in the context of the present invention, the term “in an unreacted form” should be understood to mean that component B1′) is present as at least one C 32 -C 40 -dimeric acid, and component B2′) is present as at least one C4-C 12 -diamine, and optionally component B3′) is present as at least one C4-C 20 -dioic acid.

[0123] If components B1'), B2') and optionally B3') have reacted at least in part, then components B1'), B2') and optionally B3') are thus at least in part in amide form.

[0124] Component B1′)

[0125] According to the invention, component B1') is at least one C 32 -C 40 -dimer acid.

[0126] In the context of the present invention, "at least one C 32 -C 40 -dimer acid" is to be understood as precisely meaning one C 32 -C 40 -dimer acid or a mixture of two or more C 32 -C 40 -dimer acids.

[0127] Dimer acids are also known as dimer fatty acids. C 32 -C 40 -dimer acids per se are known to those skilled in the art and are generally produced by dimerization of unsaturated fatty acids. For example, this dimerization can be catalyzed by clay.

[0128] Suitable unsaturated fatty acids for producing at least one C 32 -C 40 -dimer acid are known to those skilled in the art and are, for example, unsaturated C 16 -fatty acids, unsaturated C 18 -fatty acids and unsaturated C 20 -fatty acids.

[0129] Thus, it is preferred when component B1') is produced from unsaturated fatty acids selected from the group consisting of: unsaturated C 16 -fatty acids, unsaturated C 18 -fatty acids and unsaturated C 20 -fatty acids, wherein unsaturated C 18 -fatty acids are particularly preferred.

[0130] For example, a suitable unsaturated C 16 -fatty acid is palmitoleic acid ((9Z)-hexadec-9-enoic acid).

[0131] Suitable unsaturated C 18- Fatty acids are selected from the group consisting of: petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), linoleic acid ((9Z,12Z)-octadec-9,12-dienoic acid), α-linolenic acid ((9Z,12Z,15Z)-octadec-9,12,15-trienoic acid), γ-linolenic acid ((6Z,9Z,12Z)-octadec-6,9,12-trienoic acid), calendic acid ((8E,10E,12Z)-octadec-8,10,12-trienoic acid), punicic acid ((9Z,11E,13Z)-octadec-9,11,13-trienoic acid), α-eleostearic acid ((9Z,11E,13E)-octadec-9,11,13-trienoic acid), and β-eleostearic acid ((9E,11E,13E)-octadec-9,11,13-trienoic acid). Particularly preferred are unsaturated C 18 - fatty acids: petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), linoleic acid ((9Z,12Z)-octadec-9,12-dienoic acid).

[0132] Suitable unsaturated C 20 - fatty acids are for example selected from the group consisting of: gadoleic acid ((9Z)-eicosenoic acid), eicosenoic acid ((11Z)-eicosenoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid), and eicosapentaenoic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).

[0133] Component B1′) is particularly preferably at least one C 36 - dimer acid.

[0134] At least one C 36 - dimer acid is preferably produced from unsaturated C 18 - fatty acids. When C 36 - dimer acid is produced from C

[0135] C 18 - fatty acids are selected from the group consisting of: petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), and linoleic acid ((9Z,12Z)-octadec-9,12-dienoic acid).

[0136] Component B1′) produced from unsaturated fatty acids may also form trimeric acids, and residues of unreacted unsaturated fatty acids may also remain.

[0137] The formation of trimeric acids is known to those skilled in the art.

[0138] According to the invention, component B1′) preferably contains not more than 0.5% by weight of unreacted unsaturated fatty acids and not more than 0.5% by weight of trimeric acids, particularly preferably not more than 0.2% by weight of unreacted unsaturated fatty acids and not more than 0.2% by weight of trimeric acids, in each case based on the total weight of component B1′).

[0139] Thus, dimer fatty acids (also referred to as dimerized fatty acids or dimer acids) should be understood in a general sense, particularly in the context of the present invention, as mixtures produced by the oligomerization of unsaturated fatty acids. They are produced, for example, by the catalytic dimerization of plant-derived unsaturated fatty acids, where the starting materials used are in particular unsaturated C 16 -fatty acids to C 20 -fatty acids. The bonding mainly occurs through the Diels-Alder mechanism, and depending on the number and position of the double bonds in the fatty acids used to produce the dimer fatty acids, a mixture of dimer products mainly having alicyclic, linear aliphatic, branched aliphatic and C6-aromatic hydrocarbon groups between the carboxyl groups is produced. Depending on the mechanism and / or any subsequent hydrogenation, the aliphatic groups can be saturated or unsaturated, and the proportion of aromatic groups can also vary. Then, for example, the group between the carboxylic acid groups contains 32 to 40 carbon atoms. Fatty acids having 18 carbon atoms are preferably used for production, so that the dimer product has 36 carbon atoms. The group connecting the carboxyl groups of the dimer fatty acids preferably does not contain unsaturated bonds and aromatic hydrocarbon groups.

[0140] In the context of the present invention, C 18 -fatty acids are preferably used for production. Particularly preferred are linolenic acid, linoleic acid and / or oleic acid.

[0141] Depending on the reaction management, the oligomerization described above provides a mixture mainly containing dimer molecules, trimer molecules, monomer molecules and other by-products. Purification by distillation is conventional. Commercial dimer fatty acids usually contain at least 80% by weight of dimer molecules, at most 19% by weight of trimer molecules, and at most 1% by weight of monomer molecules and other by-products.

[0142] Dimer fatty acids preferably consisting of at least 90% by weight, preferably at least 95% by weight, very particularly preferably at least 98% by weight of dimer fatty acid molecules are used.

[0143] The proportions of monomeric, dimeric, trimeric molecules and other by-products in the dimer acid can be determined, for example, by gas chromatography (GC). Before performing the GC analysis, the dimer acid is converted into the corresponding methyl ester by the boron trifluoride method (see DIN EN ISO 5509) and then analyzed by GC.

[0144] Thus, in the context of the present invention, the essential feature of "dimer acid" is that it gives rise to the oligomerization of unsaturated fatty acids. This oligomerization mainly forms, i.e., preferably at least 80% by weight, particularly preferably at least 90% by weight, very particularly preferably at least 95% by weight, and especially at least 98% by weight, of dimeric products. Thus, the fact that the oligomerization mainly forms dimeric products containing precisely two fatty acid molecules justifies this naming which is common in any case. Thus, an alternative expression for the related term "dimer acid" is "mixture containing dimerized fatty acids".

[0145] The dimer acid to be used is commercially available. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008, Empol 1012, Empol 1061, and Empol 1062 from BASF SE, and Unidyme 10 and Unidyme T1 from Arizona Chemical.

[0146] Component B1') has an acid value, for example, in the range from 190 mg KOH / g to 200 mg KOH / g.

[0147] Component B2′)

[0148] According to the invention, component B2') is at least one C4-C 12 -diamine.

[0149] In the context of the present invention, "at least one C4-C 12 -diamine" is to be understood as precisely meaning one C4-C 12 -diamine or a mixture of two or more C4-C 12 -diamines.

[0150] In the context of the compounds of the present invention, "C4-C12-diamine" is to be understood as an aliphatic and / or aromatic compound having from four to twelve carbon atoms and two amino groups (-NH2 groups). The aliphatic and / or aromatic compound may be unsubstituted or else at least monosubstituted. If the aliphatic and / or aromatic compound is additionally at least monosubstituted, the aliphatic and / or aromatic compound may carry one, two or more substituents which do not participate in the polymerization of components A') and B'). Such substituents are, for example, alkyl or cycloalkyl substituents. These are known per se to the person skilled in the art. At least one C4-C 12 -diamine is preferably unsubstituted.

[0151] Suitable components B2') are selected, for example, from the group consisting of: 1,4-diaminobutane (butane-1,4-diamine; tetramethylenediamine; putrescine), 1,5-diaminopentane (pentamethylenediamine; pentane-1,5-diamine; cadaverine), 1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine), 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane (decamethylenediamine), 1,11-diaminoundecane (undecamethylenediamine) and 1,12-diaminododecane (dodecamethylenediamine).

[0152] It is preferred when component B2') is selected from the group consisting of: tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.

[0153] Component B3′)

[0154] According to the invention, component B3'), which may optionally be present in component B'), is at least one C4-C 20 -dicarboxylic acid.

[0155] In the context of the present invention, "at least one C4-C 20 -dicarboxylic acid" is to be understood as precisely meaning one C4-C 20 -dicarboxylic acid or a mixture of two or more C4-C 20 -dicarboxylic acids.

[0156] In the context of the present invention, "C4-C 20-dioic acid” shall be understood as an aliphatic and / or aromatic compound having from two to eighteen carbon atoms and two carboxyl groups (-COOH groups). The aliphatic and / or aromatic compound may be unsubstituted or alternatively at least monosubstituted. If the aliphatic and / or aromatic compound is alternatively at least monosubstituted, the aliphatic and / or aromatic compound may carry one, two or more substituents that do not participate in the polymerization of components A′) and B′). Such substituents are, for example, alkyl or cycloalkyl substituents. These are known to those skilled in the art. Preferably, at least one C4-C 20 -dioic acid is unsubstituted.

[0157] Suitable components B3′) are, for example, selected from the group consisting of: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.

[0158] It is preferred when component B3′) is selected from the group consisting of: glutaric acid, adipic acid, sebacic acid and dodecanedioic acid.

[0159] Most preferably, component A) is selected from the group consisting of: PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA6 / 6.36, PA610, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T and PA 6T / 66, more preferably PA 6, PA6.6, PA 66 / 6, PA 6 / 6.6 and mixtures thereof, and most preferably PA 6 and PA 66 and mixtures thereof.

[0160] Component B)

[0161] As component B), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains 0.1% to 60% by weight, preferably 0.5% to 40% by weight, more preferably 1% to 15% by weight of red phosphorus.

[0162] Elemental red phosphorus is preferably used as component B).

[0163] Red phosphorus is preferably used in an untreated form, especially in combination with glass fiber-reinforced molding compositions.

[0164] However, phosphorus can be surface-treated, for example, with "desensitizers" such as low molecular weight liquid substances such as silicone oil, paraffin oil or esters of phthalic acid (in particular dioctyl phthalate, see EP 176836) or esters of adipic acid, or with polymeric or oligomeric compounds such as phenolic resins or aminoplastics, or with polyurethanes (see EP-A 384232, DE-A19648503). Based on 100% by weight of B), the content of these "desensitizers" is usually from 0.05% to 5% by weight.

[0165] A concentrate (masterbatch) of red phosphorus is also suitable as a flame retardant, for example, in polyamides or elastomers. Also in said masterbatch, red phosphorus is preferably used in untreated form. Particularly suitable concentrated polymers are polyolefin homopolymers and polyolefin copolymers. However, if polyamide is not used as the thermoplastic material, the proportion of the concentrated polymer should not exceed 35% by weight based on the weight of components A) and B) in the molding composition according to the invention.

[0166] Preferred concentrate compositions comprise

[0167] B1) 30% to 90% by weight, preferably 45% to 70% by weight of polyamide or elastomer, and

[0168] B2) 10% to 70% by weight, in particular 30% to 55% by weight of red phosphorus.

[0169] Suitable elastomers B1) are the elastomers mentioned below as component D), such as polyolefin homopolymers and polyolefin copolymers which can be grafted, for example, with maleic anhydride.

[0170] Suitable polyamides B1) are as described above (see component A)). The polyamide B1) for the concentrate (masterbatch) can be different from component A) or can preferably be the same as component A) so as not to have an adverse effect on the molding composition due to any incompatibility or melting point difference.

[0171] The average particle size (d50) of the phosphorus particles dispersed in the molding composition preferably ranges from 0.0001 mm to 0.5 mm; in particular from 0.001 mm to 0.2 mm, determined by laser diffraction according to ISO 13320:2009.

[0172] Component C)

[0173] As component C), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 0.05% to 20% by weight, preferably from 0.07% to 5% by weight, more preferably from 0.1% to 3% by weight, and most preferably from 0.5% to 2% by weight of at least one mixed metal oxide comprising Cu and Cr in their oxide forms.

[0174] In addition to Cu and Cr, the mixed metal oxides comprising Cu and Cr in their oxide forms according to the invention may further comprise additional metals, usually in their oxide forms, such as Mn, Fe, Al and / or Co.

[0175] Preferably, component C) comprises:

[0176] c1) 15 parts by weight to 25 parts by weight, preferably 17 parts by weight to 22 parts by weight of Cu;

[0177] c2) 20 parts by weight to 40 parts by weight, preferably 25 parts by weight to 38 parts by weight of Cr;

[0178] c3) 0.5 parts by weight to 15 parts by weight, preferably 5 parts by weight to 13 parts by weight of Fe;

[0179] c4) 0 parts by weight to 20 parts by weight of Mn, Al and / or Co;

[0180] wherein components c1), c2), c3) and optionally c4) are present in their oxide forms, and the amounts of components c1), c2), c3) and optionally c4) are calculated based on the respective metals.

[0181] More preferably, component C) is present in the form of a spinel structure, preferably having the general formula CuCr2O4. Most preferably, component C) is copper chromite. Copper chromite may contain additional metals, usually in their oxide forms, such as Mn, Fe, Al and / or Co, as described above.

[0182] According to ISO 9277:2010 under nitrogen (BET method), component C) preferably has a BET surface area of 1 m 2 / g to 200 m 2 / g, preferably 1.5 m 2 / g to 100 m 2 / g, more preferably 10 m 2 / g to 80 m 2 / g.

[0183] Component C) has an average primary particle size of from 0.05 μm to 200 μm, preferably from 0.1 μm to 50 μm, more preferably from 0.5 μm to 25 μm, determined by dynamic light scattering in accordance with ISO 22412:2017.

[0184] Suitable Component C) is commercially available, for example as Pigment Black 28 (C.I. 77428), for example from The Shepherd Color Company.

[0185] Component D)

[0186] As Component D), based on the total amount of Components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 0% to 40% by weight, preferably from 1% to 30% by weight, and more preferably from 2% to 20% by weight of at least one impact modifier.

[0187] An "impact modifier" is also commonly referred to as an elastomeric polymer, elastomer or rubber.

[0188] If Component D) is present, the maximum amount of Component A) is reduced by the minimum amount of Component D) such that the total amount of Components A) to F) remains 100% by weight.

[0189] These are very generally copolymers composed of at least two of the following monomers: ethylene C 3-12 - olefins, carboxylates such as C 1-18 -(meth)acrylate C-alkyl esters, carboxylic acids such as (meth)acrylic acid, carboxylic anhydrides such as maleic anhydride, chloroprene, vinyl acetate, styrene, acrylonitrile, carboxamides, carboximides, compounds containing amino groups, compounds containing hydroxyl groups, compounds containing epoxy groups.

[0190] Such polymers are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Volume 14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pages 392 to 406 and in the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, UK, 1977). Some preferred types of such elastomers are described below.

[0191] Preferred types of such elastomers are those known as ethylene-propylene (EPM) rubbers and ethylene-propylene-diene (EPDM) rubbers.

[0192] EPM rubbers generally do not actually have residual double bonds, while EPDM rubbers can have 1 to 20 double bonds per 100 carbon atoms.

[0193] Examples of diene monomers useful for EPDM rubbers are conjugated dienes such as isoprene and butadiene; non-conjugated dienes having 5 to 25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene; cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene; and vinyl norbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene and 2-isopropenyl-5-norbornene; and tricyclic dienes such as 3-methyltricyclo[5.2.1.02′6]-3,8-decadiene; and mixtures thereof. 1,5-Hexadiene, 5-ethylidene norbornene and dicyclopentadiene are preferred.

[0194] Based on the total weight of the rubber, the diene content of the EPDM rubber is preferably from 0.5% to 50% by weight, in particular from 1% to 8% by weight.

[0195] EPM rubbers and EPDM rubbers may also preferably have been grafted with reactive carboxylic acids or their derivatives. Examples thereof are acrylic acid, methacrylic acid and their derivatives such as glycidyl (meth)acrylate and maleic anhydride.

[0196] Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or with esters of these acids are another group of preferred rubbers. The rubber may also contain dicarboxylic acids such as maleic acid and fumaric acid, or derivatives of these acids such as esters and acid anhydrides, and / or monomers containing epoxy groups. These monomers containing dicarboxylic acid derivatives or containing epoxy groups are preferably incorporated into the rubber by adding monomers containing dicarboxylic acid groups and / or epoxy groups and having the general formula I or II or III or IV to the monomer mixture,

[0197] (I)

[0198] R 1 (COOR 2 )=C(COOR 3 )R 4

[0199]

[0200] wherein R 1 to R 9 are hydrogen or alkyl groups having 1 to 6 carbon atoms, and m is an integer from 0 to 20, g is an integer from 0 to 10, and p is an integer from 0 to 5.

[0201] Group R 1 to R 9 is preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether, and vinyl glycidyl ether.

[0202] Preferred compounds of formulae I, II, and IV are maleic acid, maleic anhydride, and (meth)acrylate esters containing epoxy groups (such as glycidyl acrylate and glycidyl methacrylate), as well as esters with tertiary alcohols (such as tert-butyl acrylate). Although the latter do not have a free carboxyl group, they behave similarly to free acids and are therefore referred to as monomers with latent carboxyl groups.

[0203] The copolymer advantageously consists of 50% to 98% by weight of ethylene, 0.1% to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups, with the balance being (meth)acrylate esters.

[0204] Particularly preferred is the use of a copolymer consisting of:

[0205] 50% to 98% by weight, especially 55% to 95% by weight of ethylene,

[0206] 0.1% to 40% by weight, especially 0.3% to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic acid, and / or maleic anhydride, and

[0207] 1% to 45% by weight, especially 5% to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

[0208] Other preferred (meth)acrylate esters are methyl ester, ethyl ester, propyl ester, isobutyl ester, and tert-butyl ester.

[0209] Comonomers that can be used together with these are vinyl esters and vinyl ethers.

[0210] The above-mentioned ethylene copolymers can be prepared by methods known per se, preferably by random copolymerization under high pressure and high temperature. Suitable methods are well known.

[0211] Other preferred elastomers are emulsion polymers, the preparation of which is described, for example, by Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts that can be used are known per se.

[0212] In principle, elastomers with a homogeneous structure or those with a shell structure can be used. The shell type structure is determined by the order of addition of the individual monomers. The morphology of the polymer is also affected by this order of addition.

[0213] Monomers for the rubber part for preparing elastomers that may be mentioned here only as examples are acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, and mixtures thereof. These monomers can be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ether, and with other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate, or propyl acrylate.

[0214] The soft or rubbery phase (glass transition temperature below 0 °C) of the elastomer can be the core, the outer cladding, or the intermediate shell (in the case where the structure of the elastomer has more than two shells). Elastomers with more than one shell can also have more than one shell consisting of the rubbery phase.

[0215] If one or more hard components (glass transition temperature above 20 °C) are included in the structure of the elastomer in addition to the rubbery phase, these hard components are generally prepared by polymerizing styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, or an acrylate or methacrylate such as methyl acrylate, ethyl acrylate, or methyl methacrylate as the main monomer.

[0216] In addition to these, relatively small proportions of other comonomers can also be used.

[0217] In some cases, it has proven advantageous to use emulsion polymers having reactive groups on their surface. Examples of this type of group are epoxy groups, carboxyl groups, latent carboxyl groups, amino groups, and amide groups, and functional groups that can be introduced by using monomers of the following general formula:

[0218]

[0219] where the substituents can be defined as follows:

[0220] R 10 is hydrogen or C1-C4-alkyl,

[0221] R 11 is hydrogen, C1-C8-alkyl, or aryl, especially phenyl,

[0222] R 12 is hydrogen, C1-C 10 -alkyl, C6-C 12 -aryl, or -OR 13 ,

[0223] R 13 is C1-C8-alkyl or C6-C 12 -aryl, which may optionally be substituted by a group containing O or by a group containing N,

[0224] X is a chemical bond, a (C1-C 10 -alkylene or a C6-C 12 -arylene, or

[0225]

[0226] Y is O-Z or NH-Z, and

[0227] Z is a C1-C 10 -alkylene or a C6-C 12 -arylene.

[0228] The graft monomers described in EP-A 208187 are also suitable for introducing reactive groups at the surface.

[0229] Other examples that may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates, such as (N-tert-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and (N,N-diethylamino)ethyl acrylate.

[0230] The particles of the rubber phase can also be crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dicyclopentadienyl diacrylate, as well as the compounds described in EP-A 50265.

[0231] Monomers called graft-linking monomers can also be used, i.e., monomers having two or more polymerizable double bonds that react at different rates during polymerization. Compounds of this type are preferably used, in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group(s) polymerize(s) significantly more slowly, for example. The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If another phase is then grafted onto this type of rubber, at least some of the double bonds present in the rubber react with the graft monomer to form chemical bonds, i.e., the phase grafted thereon has at least a certain degree of chemical bonding to the graft matrix.

[0232] Examples of this type of graft-linking monomer are monomers containing allyl, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate, as well as the corresponding monoallyl compounds of these dicarboxylic acids. In addition to these, there is a wide variety of other suitable graft-linking monomers. For further details, reference may be made here, for example, to U.S. Patent No. 4,148,846.

[0233] Based on the impact-modified polymer, the proportion of these crosslinking monomers in the impact-modified polymer is usually at most 5% by weight, preferably not exceeding 3% by weight.

[0234] Some preferred emulsion polymers are listed below. First of all, graft polymers having a core and at least one shell and having the following structure can be mentioned here:

[0235]

[0236] Instead of graft polymers having more than one shell in their structure, homogeneous (i.e., single-shell) elastomers composed of 1,3-butadiene, isoprene, and n-butyl acrylate or composed of their copolymers can also be used. These products can also be prepared by concomitantly using crosslinking monomers or monomers having reactive groups.

[0237] Examples of preferred emulsion polymers are n-butyl acrylate-(meth)acrylic acid copolymers, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl methacrylate copolymers, graft polymers having a core composed of n-butyl acrylate or based on butadiene and an outer layer composed of the above copolymers and copolymers of ethylene and comonomers providing reactive groups.

[0238] The elastomers can also be prepared by other conventional methods, for example, by suspension polymerization.

[0239] Also preferred are silicone rubbers as described in DE-A 37 25 576, EP-A235 690, DE-A38 00 603, and EP-A 319 290.

[0240] Particularly preferred impact modifiers D) are ethylene copolymers containing functional monomers as described above.

[0241] Based on 100% by weight of D), the proportion of the functional monomer is 0.1% to 20% by weight, preferably 0.2% to 10% by weight, and particularly 0.3% to 3.5% by weight.

[0242] Particularly preferably, component D) is at least one copolymer composed of:

[0243] i) 80% to 99.9% by weight, preferably 90% to 99.8% by weight, more preferably 96.5% to 99.7% by weight of ethylene as component i), and

[0244] ii) 0.1% to 20% by weight, preferably 0.2% to 10% by weight, more preferably 0.3% to 3.5% by weight of at least one functional monomer different from ethylene as component ii),

[0245] where the sum of components i) and ii) is 100% by weight,

[0246] wherein the copolymer may additionally be grafted with maleic anhydride.

[0247] The functional monomers are preferably selected from the group consisting of: C 3-12 -olefins, carboxylic acid esters such as C 1-18 -(meth)acrylate, carboxylic acids such as (meth)acrylic acid, carboxylic anhydrides such as maleic anhydride, chloroprene, vinyl acetate, styrene, acrylonitrile, carboxamides, carboximides, compounds containing amino groups, compounds containing hydroxyl groups, compounds containing epoxy groups, and mixtures thereof.

[0248] The term “(meth)acrylic” means “methacrylic or acrylic”, for example, “(meth)acrylic acid” means “methacrylic acid or acrylic acid”.

[0249] Particularly preferred monomers consist of ethylenically unsaturated monocarboxylic or dicarboxylic acids or functional derivatives of such acids. In principle, any of the primary, secondary, and tertiary C1-C 18 -(meth)acrylate alkyl esters are suitable, but esters having 1 to 12 carbon atoms, particularly esters having 2 to 10 carbon atoms, are preferred.

[0250] Examples of these are methyl, ethyl, propyl, n-butyl, isobutyl, and tert-butyl (meth)acrylate, 2-ethylhexyl acrylate, octyl acrylate, and decyl acrylate. Among them, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

[0251] Instead of or in addition to these esters, the olefin polymer may also contain acid-functional and / or latent acid-functional monomers of ethylenically unsaturated monocarboxylic or dicarboxylic acids, or monomers containing epoxy groups.

[0252] Other examples of monomers that may be mentioned are (meth)acrylic acid, the tertiary alkyl esters of said acid, particularly tert-butyl acrylate, and dicarboxylic acids such as maleic acid and fumaric acid, and derivatives of said acids, and monoesters of these acids.

[0253] Latent acid-functional monomers are compounds that form free acid groups during the polymerization conditions and during the incorporation of the olefin polymer into the molding composition, respectively. Examples of these that may be mentioned are acid anhydrides of dicarboxylic acids having up to 20 carbon atoms (particularly maleic anhydride) and the tertiary C2-C 12 -(meth)acrylate alkyl esters (particularly tert-butyl acrylate and tert-butyl methacrylate).

[0254] The acid-functional or latent acid-functional monomers and the monomers containing epoxy groups are preferably incorporated into the olefin polymer by adding compounds of general formulas I-IV to the monomer mixture.

[0255] Preferred impact modifiers are ethylene - propylene rubber, ethylene - propylene - diene - rubber, ethylene - butyl acrylate copolymer, copolymers of ethylene and / or propylene with maleic anhydride, ethylene - butyl acrylate - acrylic acid - maleic anhydride copolymer, and mixtures thereof.

[0256] The melt index of the above - mentioned ethylene copolymers typically ranges from 1 g / 10 min to 80 g / 10 min (measured at 190 °C and 2.16 kg load).

[0257] The molar mass of the ethylene copolymer is from 10,000 g / mol to 500,000 g / mol, preferably from 15,000 g / mol to 400,000 g / mol (Mn, determined by calibration with PS in 1,2,4 - trichlorobenzene by GPC).

[0258] In a particular embodiment, an ethylene - α - olefin copolymer produced by means of a so - called "single - site catalyst" is used. Further details can be found in U.S. Patent No. 5,272,236. In this case, for polyolefins, the ethylene - α - olefin copolymer has a narrow molecular weight distribution, less than 4, preferably less than 3.5.

[0259] Also suitable impact modifiers are, for example, polyethylene containing butyl acrylate comonomer, polyolefin elastomers such as ethylene copolymers functionalized with maleic anhydride, ethylene (meth)acrylate copolymers grafted with maleic anhydride, polyolefin elastomers such as ethylene copolymers grafted with maleic anhydride, ethylene (meth)acrylate copolymers, triblock copolymers based on styrene grafted with maleic anhydride and ethylene / butene, and random terpolymers of ethylene, acrylate and maleic anhydride.

[0260] Examples of suitable commercial elastomers that can be used as impact modifiers are available, for example, from Lyondellbasell under the names Lucalen A2540D and Lucalen A2700M. Lucalen A2540D is a low - density polyethylene containing butyl acrylate comonomer. It has a density of 0.923 g / cm 3 and a Vicat softening temperature of 85 °C, and when the proportion of butyl acrylate is 6.5 wt%, the melting temperature is 103 °C. Lucalen A2700M is also a low - density polyethylene containing butyl acrylate comonomer. It has a density of 0.924 g / cm 3 and a Vicat softening temperature of 60 °C and a melting temperature of 95 °C.

[0261] The polymer resin Exxelor from ExxonMobil TMVA 1801 is a semi-crystalline ethylene copolymer functionalized with maleic anhydride by reactive extrusion and has a medium viscosity. The polymer backbone is fully saturated. The density is 0.880 g / cm 3 , and the proportion of maleic anhydride is generally in the range of 0.5 wt% to 1.0 wt%. Other suitable polymer resins are Exxelor from ExxonMobil TM VA 1850 and VA 1803.

[0262] Polymer resins from Dow A560 is a chemically modified ethylene acrylate copolymer, from Dow N493 is a maleic anhydride grafted ethylene copolymer with low Tg, from Dow N416 is a chemically modified ethylene elastomer, and from Dow is an ionomer composed of ethylene-methyl methacrylate copolymer.

[0263] From Polymer resins of Corporation FG 1901 is a linear triblock copolymer based on styrene and ethylene / butene, with a polystyrene content of 30%. From Corporation's FG 1924 is a linear triblock copolymer based on styrene and ethylene / butene, with a polystyrene content of 13 wt%. From Corporation's G1567 is a linear triblock copolymer based on styrene and ethylene / butene, with a polystyrene content of 13 wt%.

[0264] Polymer resins from Arkema 4503, 4700 and 4720 are random terpolymers of ethylene, acrylate and maleic anhydride. From Arkema's Series 3, 5 and 8 are random terpolymers of ethylene, acrylate and maleic anhydride.

[0265] Polymer resins from Mitsui Series M are acid-modified α-olefin copolymer grades grafted with polar groups (MA 8510 and MA 9015, MH 7510, 7010, MD 715 and MH 7020, MH 5010, MH 5020, MH 5040).

[0266] Polymer resins from NINGBO, CHINA is a polyolefin elastomer as a resin grafted with maleic anhydride.

[0267] Polymer resin from Shenyang Ketong Plastic Co., Ltd is a maleic anhydride-grafted polyolefin elastomer.

[0268] Polymer resin from Fine-Blend CMG5805 and CMG5805-L are polyolefin elastomers grafted with maleic anhydride.

[0269] Of course, mixtures of the rubber types listed above can also be used.

[0270] Component E)

[0271] As component E), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains 0 wt% to 60 wt%, preferably 0 wt% to 50 wt% of at least one filler, preferably at least one fibrous and / or particulate filler as component E).

[0272] If component E) is present, the maximum amount of component A) is reduced by the minimum amount of component E) such that the total amount of components A) to F) remains 100 wt%.

[0273] Preferably, based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), component E) is present in an amount of 5 wt% to 60 wt%, more preferably 10 wt% to 50 wt%.

[0274] Mixtures of two or more different fibrous and / or particulate fillers can be used.

[0275] Component E) is preferably selected from the group consisting of: carbon fibers, glass beads such as solid or hollow glass beads, glass fibers, frosted glass, amorphous quartz glass, aluminoborosilicate glass with an alkali content of about 1% (E glass), amorphous silica, quartz powder, alkaline earth metal silicates, especially calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, lithium montmorillonite, pseudoboehmite of the formula AIO(OH), magnesium carbonate, talc, aramid fibers, potassium titanate fibers, barium carbonate, alkaline earth metal oxides, metal fibers, ceramic fibers, titanium dioxide, alumina, gypsum, zirconia, antimony oxide, clay, silica-alumina, sericite, diatomaceous earth, silica, carbon black, glass hollow microspheres ( balloons), red oxides, zinc oxide and mixtures thereof.

[0276] Other fillers that may be mentioned are layered or needle-shaped fillers, and if present, the amount of these fillers is preferably from 0.1% to 10%. Materials preferably used for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite and The layered nano-fillers are organically modified by methods of the prior art to have good compatibility with the organic binder. Adding the layered or needle-shaped fillers to the thermoplastic molding composition of the present invention further improves the mechanical strength.

[0277] For the purposes of the present invention, the needle-shaped mineral filler is a mineral filler with strongly developed needle-shaped characteristics. An example is acicular wollastonite. The mineral preferably has an L / D (length to diameter) ratio of from 8:1 to 35:1, preferably from 8:1 to 11:1. The mineral filler may optionally be pretreated with the above-mentioned silane compounds, but the pretreatment is not necessary.

[0278] The preferred fibrous or particulate filler E) is glass fiber. Glass fibers are usually chopped fibers, also known as short fibers, having a length in the range of 0.1 mm to 1 mm, long fibers having a length in the range of 1 mm to 50 mm, and continuous fibers having a length of >50 mm. Continuous fibers are used in fiber-reinforced plastics in the form of rovings or fabrics.

[0279] Ground glass fibers are also available, and the length of the ground glass fibers after grinding is usually in the range of 70 μm to 200 μm.

[0280] Particularly preferred are glass fibers in the form of rovings or chopped glass as described above.

[0281] More preferred glass fibers used as component E) are chopped long glass fibers, which have an average starting length in the range of 1 mm to 50 mm, more preferably in the range of 1 mm to 10 mm, and most preferably in the range of 2 mm to 7 mm, determined by laser diffraction method - particle size analysis (laser particle size determination / laser diffraction method) according to ISO 13320:2009. The most preferred glass fibers used as component E) have an average fiber diameter in the range of 7 μm to 18 μm, more preferably in the range of 9 μm to 15 μm, determined by the laser diffraction method according to ISO 13320:2009.

[0282] In a preferred embodiment, the preferred glass fibers used as component E) are modified with a suitable sizing system or adhesion promoter / adhesion promoter system. A silane-based sizing system or adhesion promoter is preferably used to improve the compatibility with the thermoplastic.

[0283] Suitable silane compounds have the general formula (II):

[0284] (X-(CH2) n ) k -Si-(O-C m H 2m+1 ) 4-k

[0285] X is -NH2, HO-, carboxyl,

[0286] N is an integer from 2 to 10, preferably from 3 to 4,

[0287] M is an integer from 1 to 5, preferably from 1 to 2, and

[0288] K is an integer from 1 to 3, preferably 1.

[0289] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and the corresponding silanes containing a glycidyl group or a carboxyl group as substituent X.

[0290] For the modification of glass fibers preferably used as component E), the adhesion promoter, preferably a silane compound of formula (II), is preferably used in an amount of 0.01% to 2% by weight, more preferably in an amount of 0.025% to 1.5% by weight, and most preferably in an amount of 0.05% to 1% by weight, in each case based on 100% by weight of component E).

[0291] As a result of processing to obtain the thermoplastic molding composition, the glass fibers preferably used as component E) can be shorter in the composition than the glass fibers initially used. Thus, the arithmetic mean value of the glass fiber length after processing determined by high-resolution X-ray computed tomography is generally only in the range of 150 μm to 300 μm.

[0292] Those skilled in the art distinguish different types of glass fibers, some of which are listed here for example (https: / / polser.com / en / frp / fibreglass-types):

[0293]

[0294] Particularly preferred are glass fibers in the form of E-glass. These can be used as rovings or in the form of commercially available chopped glass, where suitable rovings and chopped glass fibers are as described above. The E-glass fibers are modified with a suitable sizing system or adhesion promoter / adhesion promoter system. Preferred is the use of a silane-based sizing system or adhesion promoter to improve compatibility with the thermoplastic. Suitable silane compounds are as described above.

[0295] It is also possible to use non-fibrous and non-foamed ground glass having a particle size distribution determined according to ISO 13320:2009 by laser diffraction method and having a d in the range from 5 μm to 250 μm, preferably in the range from 10 μm to 150 μm, more preferably in the range from 15 μm to 80 μm, most preferably in the range from 16 μm to 25 μm 90 of the component E). Regarding the d 90 values, the determination of these values and the meaning of these values, reference is made to Chemie Ingenieur Technik (72), pages 273 - 276, 3 / 2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d 90 value is the particle size (volume distribution) below which 90% of the particle amount lies.

[0296] According to the invention, it is preferred when the non-fibrous and non-foamed ground glass has a particulate, non-cylindrical shape and has a length-to-thickness ratio of less than 5, preferably less than 3, more preferably less than 2, determined according to ISO 13320:2009 by laser diffraction method. It should be understood that a zero value is not possible.

[0297] The non-foamed and non-fibrous ground glass is additionally characterized in that the non-foamed and non-fibrous ground glass generally does not have the glass geometry of typical fiberglass, which has a major axis ratio (L / D ratio) greater than 5 determined according to ISO 13320:2009 by laser diffraction method for its cylindrical or elliptical cross-section.

[0298] The non-foamed and non-fibrous ground glass is preferably obtained by grinding glass with a mill, preferably a ball mill, and more preferably subsequently sieving or screening. In one embodiment, the preferred starting material for grinding the non-fibrous and non-foamed ground glass used as component E) also includes glass waste, especially in the production of glass products, which is produced as an unwanted by-product and / or defective primary product (referred to as defective material). These especially include waste glass, recycled glass and broken glass obtained especially in the production of window or bottle glass, and in the production of glass containing fillers and reinforcing agents, especially in the form of so-called melt blocks. The glass can be colored, but preferably colorless glass is used as the starting material for component E).

[0299] As component F), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 0% to 40% by weight, preferably from 0% to 30% by weight, of at least one additional additive as component F).

[0300] If component F) is present, the maximum amount of component A) is reduced by the minimum amount of component F) such that the total amount of components A) to F) remains 100% by weight.

[0301] Component F) is preferably selected from one or more elements of the group consisting of lubricants and release agents as component F1), oxidation inhibitors and heat stabilizers as component F2), colorants as component F3), and conventional processing aids such as agents resistant to ultraviolet decomposition, nucleating agents, and plasticizers as component F4).

[0302] Component F1)

[0303] As component F1), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 0% to 3% by weight, preferably from 0.05% to 1.5% by weight, more preferably from 0.1% to 1% by weight, of at least one lubricant and / or release agent.

[0304] Salts of Al, alkali metals or alkaline earth metals, or esters or amides of fatty acids having from 10 to 44 carbon atoms, preferably having from 12 to 44 carbon atoms, are preferred as lubricants.

[0305] The metal ions are preferably alkaline earth metals and Al or Zn, particularly preferably Ca.

[0306] Preferred metal salts are calcium stearate and calcium montanate, and aluminum distearate.

[0307] Mixtures of various salts in any desired mixing ratio can also be used.

[0308] The carboxylic acid can be mono- or dibasic. Examples that may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid, and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0309] The fatty alcohols can be mono- to tetravalent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preferably glycerol and pentaerythritol.

[0310] The aliphatic amines can be mono- or tri-functional. Examples of these aliphatic amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, bis(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. The preferred esters or amides are accordingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

[0311] Mixtures of various esters or amides can also be used, or combinations of esters and amides in any desired mixing ratio.

[0312] The materials used as release agents are generally long-chain carboxylic acids and their soaps, esters or amides, and other materials used are waxes such as polar or non-polar polyethylene waxes, ester waxes and amide waxes, and release agent combinations based on amide waxes, based on ester waxes and / or based on saponified waxes, combinations based on at least one fatty acid amide ester wax, natural and / or synthetic silica and montan wax, and combinations comprising at least one amide wax, at least one ester wax and / or at least one saponified wax.

[0313] Component F2)

[0314] As component F2), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 0 wt% to 3 wt%, preferably from 0.01 wt% to 2.5 wt%, more preferably from 0.02 wt% to 2 wt%, most preferably from 0.05 wt% to 1 wt% of at least one oxidation inhibitor and / or heat stabilizer.

[0315] The heat stabilizers are preferably selected from copper compounds, amines such as aromatic secondary amines, for example 4-amino-2,2,6,6-tetramethylpiperidine (TAD) and diphenylamine, hindered phenols, phosphites, phosphonites, hydroquinones and mixtures thereof.

[0316] As component F2), from 0.05 wt% to 3 wt%, preferably from 0.1 wt% to 2 wt%, in particular from 0.1 wt% to 1 wt% of at least one hindered phenol antioxidant can be used.

[0317] This component F2) preferably has a molecular weight greater than 500 g / mol, more preferably greater than 1000 g / mol. In addition, component H should preferably exhibit high thermal stability, for example a maximum 5% weight loss, more preferably a maximum 2% weight loss, measured in a TGA (thermogravimetric analysis) experiment at 300 °C in nitrogen (from 40 °C to 120 °C at 10 °C / min, isothermal at the latter temperature for 15 minutes, then from 120 °C to 600 °C at 20 °C / min).

[0318] Component F2) preferably has at least one, more preferably at least two phenolic groups substituted by at least one branched C 3-12 alkyl group as a steric group. The substituted phenolic group is covalently linked to the structure of component F2).

[0319] Suitable sterically hindered phenols F2) are in principle all compounds having a phenolic structure and having at least one bulky group on the phenolic ring. Bulky groups are, for example, branched C 3-12 -alkyl groups, preferably branched C 3-6 -alkyl groups, more preferably isopropyl or tert-butyl groups.

[0320] Compounds of the following formula are preferably used:

[0321]

[0322] wherein:

[0323] R 1 and R 2 are alkyl groups, substituted alkyl groups or substituted triazole groups, and wherein the groups R 1 and R 2 can be the same or different, and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group. The alkyl and alkoxy residues preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The substituents are preferably C 1-12 -alkyl, more preferably C 1-6 -alkyl, most preferably C 1-4 -alkyl. At least one of R 1 to R 3 is preferably a bulky group as defined above.

[0324] Antioxidants of the above type are described, for example, in DE-A 27 02 661 (US-A 4 360 617).

[0325] Another group of preferred sterically hindered phenols is provided by those groups derived from substituted phenylcarboxylic acids, especially those derived from substituted phenylpropionic acids, which preferably have at least one bulky group on the phenyl. The groups contain at least one, preferably two, covalently linked substituted phenylcarboxylic acid units, which preferably have at least one bulky group on the phenyl.

[0326] Preferred phenylcarboxylic acids are phenyl-C 1-12 -carboxylic acid, more preferably phenyl-C 2-6 -carboxylic acid. As described above, the phenyl group is preferably a phenolic group having at least one bulky group on the phenolic ring. Thus, the above-mentioned sterically hindered phenols are preferably reacted with C 1-12 -alkane carboxylic acid, more preferably straight-chain C2-6 - Covalently linked to alkane carboxylic acids.

[0327] Such particularly preferred compounds are compounds of the following formula

[0328]

[0329] wherein R 4 , R 5 , R 7 and R 8 are, independently of one another, C1-C8-alkyl groups which may themselves have substituents (at least one of these groups being a bulky group), and R 6 is a divalent aliphatic group having 1 to 10 carbon atoms and whose main chain may also have C-O bonds. At least one of R 4 to R 8 is a bulky group as defined above.

[0330] Preferred compounds corresponding to these structural formulas are

[0331]

[0332] ( 245, from BASF SE)

[0333]

[0334] ( 259, from BASF SE)

[0335] As examples of sterically hindered phenols, all of the following substances should be mentioned:

[0336] 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010 from BASF SE), 3,5-Di-tert-butyl-4-hydroxybenzylphosphonic acid distearyl ester, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazolylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine.

[0337] Compounds that have proven to be particularly effective and are therefore preferably used are 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( 259), pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and N,N′-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide ( 1098), and the above-mentioned products from BASF SE 245 and 1010, which have particularly good applicability.

[0338] In certain cases, sterically hindered phenols having no more than one steric group relative to the ortho position of the phenolic hydroxyl group have proven to be particularly advantageous; especially when evaluating the color fastness during long-term storage in diffused light.

[0339] Furthermore, it is advantageous to use sterically hindered phenol antioxidants that also have a sufficiently high molecular weight, preferably greater than 500 g / mol, especially higher than 1000 g / mol. In addition, they preferably exhibit high thermal stability measured by TGA (thermogravimetric analysis), with less than 2% degradation up to 300 °C in a nitrogen atmosphere.

[0340] The molding composition of the present invention may contain 0.05% to 3% by weight, preferably 0.1% to 1.5% by weight, and especially 0.1% to 1% by weight of at least one copper stabilizer (preferably a Cu(I) halide, especially a mixture with an alkali metal halide (preferably KI), especially a mixture in a ratio of 1:4) or a sterically hindered phenol, or a mixture thereof, as component E3).

[0341] The monovalent copper salts preferably used are cuprous acetate, cuprous chloride, cuprous bromide, and cuprous iodide. The material contains copper in an amount of 5 ppm to 500 ppm, preferably 10 ppm to 250 ppm, based on the polyamide.

[0342] Particularly advantageous properties are obtained especially if the copper is present in a molecular distribution in the polyamide. If a concentrate containing polyamide, a monovalent copper salt, and an alkali metal halide in the form of a solid, homogeneous solution is added to the molding composition, the above-mentioned advantageous properties can be achieved. For example, a typical concentrate consists of 79% to 95% by weight of polyamide and 21% to 5% by weight of a mixture composed of cuprous iodide or cuprous bromide and potassium iodide. Based on the total weight of the solution, the copper concentration in the solid homogeneous solution is preferably 0.3% to 3% by weight, especially 0.5% to 2% by weight, and the molar ratio of cuprous iodide to potassium iodide is 1 to 11.5, preferably 1 to 5.

[0343] Polyamides suitable for concentrates are homopolyamides and copolyamides, in particular PA6 and PA6.6.

[0344] According to a preferred embodiment of the invention, the molding composition is free of copper, in particular free of copper stabilizers such as Cu / (I) halides, and combinations of Cu(I) halides with alkali metal halides.

[0345] More preferably, the thermoplastic molding composition of the invention is free of metal halides. Systems free of metal halides, so-called electro-friendly systems, are of great interest because in almost all industries, there is a growing trend towards electromobility, electrification and connectivity.

[0346] Therefore, the thermoplastic molding composition is preferably free of metal halides, in particular Cu halides and alkali metal halides.

[0347] Component F3)

[0348] As component F3), based on the total amount of components A), B), C), optionally D), optionally E) and optionally F), the thermoplastic molding composition contains from 0 wt% to 5 wt%, preferably from 0.05 wt% to 3 wt%, more preferably from 0.1 wt% to 2 wt%, most preferably from 0.25 wt% to 1 wt% of at least one colorant.

[0349] A colorant in the meaning of the present invention is a pigment or a dye or a mixture thereof.

[0350] A preferred colorant F3) is aniline black.

[0351] Aniline black is generally a group of black or grey phenazine dyes (azine dyes) related to induline and occurring in various forms (water-soluble, oil-soluble, alcohol-soluble), used for the dyeing and printing of wool, for the black dyeing of silk, and for the coloring of leather, shoe polish, varnish, plastics, baking enamels, inks, etc., and as a microscopic dye.

[0352] Aniline black is industrially obtained by heating nitrobenzene, aniline and aniline hydrochloride with metallic iron and FeCl3 (the name is derived from the Latin niger = black).

[0353] Aniline black can be used in the free base form or in the form of a salt (e.g. hydrochloride).

[0354] Further details on aniline black can be found, for example, in the electronic encyclopedia Rompp Online, 2.8th edition, Thieme-Verlag Stuttgart, 2006, under the keyword "aniline black".

[0355] Other suitable colorants are inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide, and carbon black, as well as organic pigments such as phthalocyanine, quinacridone, perylene, and dyes such as anthraquinone.

[0356] Component F4)

[0357] As component F4), based on the total amount of components A), B), C), optionally D), optionally E), and optionally F), the thermoplastic molding composition contains from 0% to 5% by weight, preferably from 0.05% to 3% by weight, more preferably from 0.1% to 2% by weight, and most preferably from 0.25% to 1% by weight of at least one conventional processing aid.

[0358] Examples of conventional processing aids as component F4) are reagents resistant to ultraviolet decomposition, nucleating agents, plasticizers, etc.

[0359] Reagents resistant to ultraviolet decomposition are UV stabilizers. Suitable UV stabilizers are known in the art and are, for example, various substituted resorcinols, salicylates, benzotriazoles, and benzophenones. Aniline black can also be used.

[0360] Examples of materials that can be used as nucleating agents are sodium phenylphosphinate, alumina, silica, and preferably talc.

[0361] Suitable plasticizers are described in Kunststoff-Handbuch, Band VI Polyamide, Carl Hanser Verlag München 1966, Section 3.4.2.1.b), and suitable plasticizers are described in Tables 7 on pages 238 and 239. They can be divided into aromatic hydroxy compounds, sulfonamides, and other plasticizers such as lactams, lactones, alcohols, etc.

[0362] Suitable plasticizers are, for example, poly(triethylene glycol) (PPD), preferably poly(triethylene glycol) (PPD) with a number average molecular weight of 255, and poly(triethylene glycol) benzoate (PPDB), n-butylbenzenesulfonamide (NBBS), polyethylene glycol dibenzoate (M n = 410), poly(1,2-propanediol) dibenzoate (M n = 400), monomer amides, especially sulfonamides, such as N-alkylarylsulfonamides, p-alkylbenzenesulfonamides, and compounds based on guanidine, mixtures of lactam compounds and polyethylene glycols, aromatic esters of poly(triethylene glycol) with a number average molecular weight of 1000 or less, or compounds of the general formula (1).

[0363] R1-O-(CH2CH2-O-) nR2 (1)

[0364] where n = 1 to 10

[0365] R1 and R2 are independently H, C 1-12 -alkyl, phenyl or tolyl,

[0366] having a boiling point above 250 °C.

[0367] Preferred plasticizers of the general formula (1) are based on triethylene glycol, tetraethylene glycol, pentaethylene glycol or mixtures thereof. Most preferred is tetraethylene glycol. Thus, n most preferably has a value of 3.8 to 4.2, most preferably 4.

[0368] Tetraethylene glycol is non-toxic and has a high plasticizing efficiency. Compared to sulfonamides and lactams, only half the amount of tetraethylene glycol is required to achieve the same plasticizing effect and the same reduction in glass transition temperature. Thus, in a preferred embodiment, in the presence of the plasticizer as component F4), the thermoplastic molding composition comprises a compound of formula (1) as the plasticizer.

[0369] Composition

[0370] The composition according to the invention is characterized by effective fire protection and at the same time good electrical properties, which are obtained by effectively stabilizing red phosphorus in the polyamide with a mixed metal oxide containing Cu and Cr in their oxide form, which does not have a negative impact on the electrical properties.

[0371] The weight ratio between component B) and component C) is preferably 1.5 to 100:1, more preferably 2 to 90:1, and most preferably 4 to 80:1.

[0372] Thus, the thermoplastic molding composition according to the invention comprises

[0373] a) 10% to 99.85% by weight, preferably 20% to 98% by weight, more preferably 30% to 90% by weight of at least one thermoplastic polyamide as component A),

[0374] b) 0.1% to 60% by weight, preferably 0.5% to 40% by weight, more preferably 1% to 15% by weight of red phosphorus as component B),

[0375] c) 0.05% to 20% by weight, preferably 0.07% to 5% by weight and more preferably 0.1% to 2% by weight of at least one mixed metal oxide containing Cu and Cr in their oxide form as component C),

[0376] d) 0% to 40% by weight, preferably 1% to 30% by weight as component D)

[0377] and more preferably from 2% to 20% by weight of at least one impact modifier,

[0378] e) from 0% to 60% by weight, preferably from 0% to 50% by weight, of at least one filler as component E),

[0379] f) from 0% to 40% by weight, preferably from 0% to 30% by weight, of at least one further additive as component F),

[0380] wherein the sum of the weight percentages of components A), B), C), optionally D), optionally E) and optionally F) is 100% by weight,

[0381] wherein component C) preferably comprises:

[0382] c1) 15 to 25 parts by weight of Cu;

[0383] c2) 20 to 40 parts by weight of Cr;

[0384] c3) 0.5 to 15 parts by weight of Fe;

[0385] c4) 0 to 20 parts by weight of Mn, Al and / or Co;

[0386] wherein components c1), c2), c3) and optionally c4) are present in the form of their oxides and the amounts of components c1), c2), c3) and optionally c4) are calculated based on the respective metals, and more preferably component C) is present in the form of a spinel structure.

[0387] Suitable and preferred components A), B), C), D), E) and F) and the amounts of said components in the thermoplastic molding composition according to the invention are as described above.

[0388] The thermoplastic molding composition according to the invention is a filled composition, i.e. it comprises from 5% to 60% by weight, more preferably from 10% to 50% by weight, of at least one filler, preferably at least one fibrous and / or particulate filler as component E), or a non-filled composition, i.e. it comprises 0% by weight of filler as component E).

[0389] In one embodiment, the thermoplastic molding composition according to the invention is a filled composition which comprises

[0390] a) from 10% to 94.85% by weight, preferably from 20% to 88% by weight, more preferably from 30% to 88% by weight, of at least one thermoplastic polyamide as component A),

[0391] b) 0.1% to 60% by weight, preferably 0.5% to 40% by weight, more preferably 1% to 15% by weight of red phosphorus as component B),

[0392] c) 0.05% to 20% by weight, preferably 0.07% to 5% by weight, and more preferably 0.1% to 2% by weight of at least one mixed metal oxide containing Cu and Cr in their oxide forms as component C),

[0393] d) 0% to 40% by weight, preferably 1% to 30% by weight

[0394] and more preferably 2% to 20% by weight of at least one impact modifier as component D),

[0395] e) 5% to 60% by weight, preferably 10% to 50% by weight of at least one filler as component E),

[0396] f) 0% to 40% by weight, preferably 0% to 30% by weight of at least one additional additive as component F),

[0397] wherein the total of the weight percentages of components A), B), C), D), optionally E) and optionally F) is 100% by weight.

[0398] wherein component C) preferably contains:

[0399] c1) 15 parts by weight to 25 parts by weight of Cu;

[0400] c2) 20 parts by weight to 40 parts by weight of Cr;

[0401] c3) 0.5 parts by weight to 15 parts by weight of Fe;

[0402] c4) 0 parts by weight to 20 parts by weight of Mn, Al and / or Co;

[0403] wherein components c1), c2), c3) and optionally c4) are present in their oxide forms, and the amounts of components c1), c2), c3) and optionally c4) are calculated based on the respective metals, and more preferably component C) is present in the form of a spinel structure.

[0404] Suitable and preferred components A), B), C), D), E) and F) and the amounts of said components in the thermoplastic molding composition of the present invention are as described above.

[0405] The thermoplastic molding composition of the present invention is characterized by good flame retardancy, excellent phosphorus stability and at the same time good electrical properties, especially good tracking resistance.

[0406] The flame retardancy of the molding composition is determined according to method UL94-V (Underwriters Laboratories Inc. Standard of Safety, “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, pages 14 to 18, Northbrook 1998). The glow wire resistance is determined according to IEC 60695-2-12 from 2019 with the glow wire flammability index (GWFI). The molding compositions of the invention meet the requirements for heat resistance and glow wire resistance (UL 94 / 1.6 mm V-0 and GWFI 960 °C, 0.8 mm).

[0407] In addition, the molding compositions of the invention have a comparative tracking index (CTI) of at least 450 V, preferably 475 V, more preferably 490 V. The CTI value (comparative tracking index) indicates the tendency of a material to form a creepage path when exposed to contamination and high humidity. The more a material can resist damage due to high field strengths and creepage currents, the more likely it is to be used in electrical applications. The measurement is carried out according to IEC 60112 (Method for determining the proof and comparative tracking indices of solid insulating materials).

[0408] The thermoplastic molding compositions of the invention can be produced by methods known per se by mixing the starting components in conventional mixing devices, such as screw-based extruders, Brabender mixers or Banbury mixers, and then extruding them. The extrudate can be cooled and granulated. It is also possible to premix the individual components and then add the remaining starting materials separately and / or likewise in the form of a mixture. The mixing temperature is generally from 230 °C to 320 °C.

[0409] In another preferred mode of operation, components B) to C) and, if present, D) and E) can be mixed, compounded and granulated with the prepolymer. The resulting granules are then solid-phase condensed continuously or batchwise under an inert gas at a temperature below the melting point of component A) until the desired viscosity is reached.

[0410] The thermoplastic molding compositions of the invention are characterized by good flame retardancy and excellent phosphorus stability and also good electrical properties at the same time. These materials are therefore suitable for the production of any type of fiber, foil and molded article. Some examples are mentioned below: plug connectors, plugs, plug parts, cable harness assemblies, circuit mountings, circuit mounting assemblies, three-dimensional injection molded circuit mountings, electrical connector elements and electromechanical assemblies.

[0411] In the present invention, the molded articles or semi-finished products produced from the thermoplastic molding compositions can be used, for example, in the motor vehicle industry, the electrical industry, the electronics industry, the telecommunications industry, the information technology industry, the entertainment industry or the computer industry, for vehicles and other means of transport, for ships, for spacecraft, for the home, for office equipment, for sports, for medicine and generally for articles and building components that require improved fire protection.

[0412] The polyamide with improved flowability can be used in the kitchen and home sector for the production of components of kitchen equipment (such as stoves, irons, buttons), as well as for applications in the garden and leisure sector. Examples

[0413] The following components were used:

[0414] Component a:

[0415] Nylon-6,6 with an intrinsic viscosity IV of 150 mL / g, measured in a 0.5 wt% solution in 96 wt% sulfuric acid at 25 °C according to ISO 307 (using A27 from BASF SE).

[0416] Component b:

[0417] Red phosphorus with an average particle size (d50) of 10 μm to 30 μm in a 50% concentrate in an olefin polymer with a melt index MFI (190 / 2.16) of 10 g / 10 min made from 59.8 wt% ethylene, 35 wt% n-butyl acrylate, 4.5 wt% acrylic acid and 0.7 wt% maleic anhydride (Component D). The copolymer is produced by copolymerization of the monomers at elevated temperature and elevated pressure.

[0418] The d50 value was determined by laser diffraction according to ISO 13320:2009.

[0419] Component c: Commercially available copper chromite black spinel (CAS: 68186-91-4). Composition: 19.5 wt% Cu, 33.0 wt% Cr, 12.2 wt% Fe and 0.55 wt% Mn. Cu, Cr, Fe and Mn are present in the form of their oxides (total amount of copper chromite black spinel is 100 wt%), and the amounts of Cu, Cr, Fe and Mn are calculated as the respective metals.

[0420] c / 1 = Commercially available Cu-(I)-oxide (CAS: 1317-39-1).

[0421] Component d: Commercially available zinc oxide (for comparison).

[0422] Component e:

[0423] Standard chopped glass fibers for polyamides, length = 4.5 mm, diameter = 10 μm.

[0424] Component f / 1:

[0425] N,N′-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide( 1098)

[0426] Component f / 2: Commercially available calcium stearate

[0427] Component f / 3: 30% concentrate of carbon black in PA6( B27)

[0428] To provide evidence of the improved phosphorus stability and good electrical properties according to the present invention, suitable plastic molding compositions were manufactured by compounding. For this purpose, the individual components were mixed in a ZSK 26 (Berstorff) twin-screw extruder at a throughput of 20 kg / h and a uniform temperature profile of approximately 270 °C, extruded in the form of strands, cooled until granulation was possible, and granulated.

[0429] The test specimens listed in Table 1 for the study were injection molded in an Arburg 420C injection molding machine at a melt temperature of approximately 270 °C and a mold temperature of approximately 80 °C.

[0430] First, the flame retardancy of the molding composition was determined by the UL 94V method (Underwriters Laboratories Inc. Standard of Safety, “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, pages 14 to 18, Northbrook 1998).

[0431] The glow wire resistance GWFI (glow wire flammability index) was tested on a plate according to DIN EN 60695-2-12. The GWFI test is a general applicability test for plastics in contact with components with an electrical potential. The temperature determined is the highest temperature that satisfies one of the following conditions in three consecutive tests: (a) the specimen is not ignited or (b) the afterflame time or glow time within 30 s after exposure to the glow wire, and the support is not ignited.

[0432] The CTI (comparative tracking index) was measured according to IEC 60112 (Method for determining the test number and comparative tracking path index of solid insulating materials).

[0433] Testing of plastic parts for phosphorus deposition:

[0434] Cut the plastic sample (125 mm × 12.5 mm × 1.6 mm) in half and place each half in a 10 ml glass beaker. Place the silver contact material (10 mm × 50 mm × 0.125 mm) in a short test tube. Then place three samples in a 100 ml screw-cap bottle, add 5 ml of water, and place the sealed system in an oven at 70 °C. After 28 days, remove the test tube and fill it with water to the top, and place all the contents in a glass beaker. Add 5 ml of concentrated hydrochloric acid thereto and evaporate the mixture to almost dryness. Then remove the metal sample and rinse it with water; mix 1 ml of sulfuric acid with the residue and evaporate the mixture again to almost dryness. Then dilute with 20 ml of water, add 4 ml of a 5% potassium persulfate solution, and heat the mixture for 30 minutes. Then determine phosphorus by using molybdenum blue photometry, in μg phosphorus / plastic sample.

[0435] The table gives the composition of the molding composition and the measurement results.

[0436] Table 1

[0437]

[0438] * When the amount of Cu-(I)-oxide in Comparative Example 3 increases, the CTI becomes worse and the composition is not usable.

[0439] Based on the data in Table 1, it is evident that the addition of a mixed oxide based on copper and chromium strongly reduces the deposition of phosphorus while maintaining the electrical properties (CTI value) at a high level.

Claims

1. A thermoplastic molding composition, the thermoplastic molding composition comprising a) 10% to 99.85% by weight of at least one thermoplastic polyamide as component A), b) 0.1% to 60% by weight of red phosphorus as component B), c) 0.05% to 20% by weight of at least one mixed metal oxide containing Cu and Cr in their oxide forms as component C), d) 0% to 40% by weight of at least one impact modifier as component D), e) 0% to 60% by weight of at least one filler as component E), h) 0% to 40% by weight of at least one additional additive as component F), wherein the sum of the weight percentages of components A), B), C), optionally D), optionally E) and optionally F) is 100% by weight.

2. The thermoplastic molding composition according to claim 1, wherein component A) is selected from aliphatic polyamides and semi-aromatic polyamides, preferably selected from PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA 6 / 636, PA610, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T and PA 6T / 66 and mixtures thereof, more preferably selected from PA 6, PA 66, PA 66 / 6, PA 6 / 66, PA 6 / 636 and mixtures thereof, and most preferably PA 6 and PA 66 and mixtures thereof.

3. The thermoplastic molding composition according to claim 1 or 2, wherein the amount of component B) is 0.5% to 20% by weight, preferably 1% to 15% by weight.

4. The thermoplastic molding composition according to any one of claims 1 to 3, wherein component C) comprises: c1) 15 parts by weight to 25 parts by weight of Cu; c2) 20 parts by weight to 40 parts by weight of Cr; c3) 0.5 parts by weight to 15 parts by weight of Fe; c4) 0 parts by weight to 20 parts by weight of Mn, Al and / or Co; wherein components c1), c2), c3) and optionally c4) are present in their oxide forms, and the amounts of components c1), c2), c3) and optionally c4) are calculated based on the respective metals, and preferably component C) is present in the form of a spinel structure.

5. The thermoplastic molding composition according to any one of claims 1 to 4, wherein component C) is copper chromite.

6. The thermoplastic molding composition according to any one of claims 1 to 5, wherein component C) has a BET surface area of from 1 m 2 / g to 200 m 2 / g, preferably from 1.5 m 2 / g to 100 m 2 / g, according to ISO 9277:2010 under nitrogen.

7. The thermoplastic molding composition according to any one of claims 1 to 6, wherein component C) has an average primary particle size of 0.05 μm to 200 μm, preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 25 μm as determined by dynamic light scattering according to ISO22412:2017.

8. The thermoplastic molding composition according to any one of claims 1 to 7, wherein component D) is at least one copolymer consisting of: i) 80% to 99.9% by weight of ethylene as component i), and ii) at least one functional monomer different from ethylene, in an amount of 0.1% to 20% by weight of component ii), wherein the copolymer may additionally be grafted with maleic anhydride.

9. The thermoplastic molding composition according to claim 8, wherein component ii) is selected from the group consisting of: C 3-12 - olefins, carboxylic acid esters such as C 1-18 - alkyl esters, carboxylic acids such as (meth)acrylic acid, carboxylic anhydrides such as maleic anhydride, chloroprene, vinyl acetate, styrene, acrylonitrile, carboxamides, carboximides, compounds containing amino groups, compounds containing hydroxyl groups, compounds containing epoxy groups, and mixtures thereof.

10. The thermoplastic molding composition according to any one of claims 1 to 9, wherein component E) is at least one fibrous or particulate filler or a mixture thereof, preferably, component E) is selected from the group consisting of: carbon fiber, glass beads such as solid or hollow glass beads, glass fiber, ground glass, amorphous silica glass, aluminoborosilicate glass having an alkali content of about 1%, amorphous silica, quartz powder, alkaline earth metal silicate, especially calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, cyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, hectorite, pseudoboehmite of the formula AIO(OH), magnesium carbonate, talc, aramid fiber, potassium titanate fiber, barium carbonate, alkaline earth metal oxide, metal fiber, ceramic fiber, titanium dioxide, alumina, gypsum, zirconia, antimony oxide, clay, silica-alumina, sericite, diatomaceous earth, silica, carbon black, glass hollow microsphere, red oxide, zinc oxide and mixtures thereof.

11. The thermoplastic molding composition according to any one of claims 1 to 10, wherein component F) is selected from one or more elements of the group consisting of a lubricant and a mold release agent as component F1), an oxidation inhibitor and a heat stabilizer as component F2), a colorant as component F3), and conventional processing aids such as a reagent resistant to ultraviolet decomposition, a nucleating agent, and a plasticizer as component F4).

12. A method for producing the thermoplastic molding composition according to any one of claims 1 to 11, the method comprising the step of mixing components A), B), C) and optionally D), optionally E) and optionally F).

13. Use of the thermoplastic molding composition according to any one of claims 1 to 11 or the thermoplastic molding composition obtained by the method according to claim 12 for producing a molded article, a fiber, a film or an extruded article.

14. A molded article, a fiber, a film or an extruded article, which is made of the thermoplastic molding composition according to any one of claims 1 to 11 or the thermoplastic molding composition obtained by the method according to claim 12.

15. Use of a mixed metal oxide containing Cu and Cr in their oxide forms for stabilizing red phosphorus as a flame retardant in a polyamide composition while maintaining the electrical properties of the polyamide composition.

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