Thermoplastic molding composition with improved color stability -1

Abstract

A thermoplastic molding composition comprising as component A) at least one thermoplastic polyamide, as component B) at least one of sodium hypophosphite or sodium hypophosphite hydrate, as component C) at least one polyamide 6I / 6T, and as component D) preferably a colorant or a mixture of two or more colorants, more preferably an orange colorant or a mixture of two or more colorants which result in an orange color; a method for producing the thermoplastic molding composition of the invention, comprising the step of mixing components A), B), C) and optionally D); more preferably colored, most preferably orange-colored moldings, fibers, films and the like. the use of the thermoplastic molding composition of the invention for producing molded and extruded articles, preferably molded articles; molded or extruded articles made from the thermoplastic molding composition of the invention; molded or extruded articles of the invention that are high-voltage components; a process for producing molded or extruded articles of the invention by injection molding or extrusion of the thermoplastic molding composition of the invention; and the use of a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate and ii) at least one polyamide 6I / 6T to improve the color stability of a thermoplastic polyamide molding composition comprising at least one polyamide different from polyamide 6I / 6T.

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic molding composition comprising as component A) at least one thermoplastic polyamide, as component B) at least one of sodium hypophosphite or sodium hypophosphite hydrate, as component C) at least one polyamide 6I / 6T, and as component D) preferably a colorant or a mixture of two or more colorants, more preferably an orange colorant or a mixture of two or more colorants which result in an orange color; a process for producing the thermoplastic molding composition of the invention, comprising the step of mixing components A), B), C) and optionally D); more preferably colored, most preferably orange-colored moldings, fibers, films and the use of the thermoplastic molding composition of the invention for producing molded and extruded articles, preferably molded articles; molded or extruded articles made from the thermoplastic molding composition of the invention; molded or extruded articles of the invention that are high-voltage components; a process for producing molded or extruded articles of the invention by injection molding or extrusion of the thermoplastic molding composition of the invention; and the use of a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate and ii) at least one polyamide 6I / 6T to improve the color stability of thermoplastic polyamide molding compositions containing at least one polyamide different from polyamide 6I / 6T.

[0002] Among engineering plastics, polyamides are particularly important in automotive applications due to their excellent mechanical and electrical properties and high chemical resistance. With the transition from internal combustion engines (ICEs) to electric vehicles (at least partially (hybrid vehicles [HEVs, PHEVs, BEV REX]) or completely (electric vehicles [BEVs, FCEVs]), new requirements for materials used in automotive applications are emerging. For example, while a 12V on-board voltage system is typically sufficient for conventional automobiles with an internal combustion engine (ICE) as the sole propulsion means, hybrid and electric vehicles with electric motors as drive units require significantly higher voltages. Engineers must meet strict design parameters for dielectric strength, creep resistance, tracking resistance, and the ability to color-code various electrical systems. The orange color selected for the high-voltage system and main battery charging path helps operators and rescue teams ensure safe handling during maintenance or in the event of an accident. It is important that the orange color is maintained throughout the life of the hybrid or electric vehicle.

[0003] Polyamides are generally prone to thermo-oxidative degradation, which causes yellowing upon heat treatment, which also affects the color of products, such as orange-colored products.

[0004] The art suggests retarding thermo-oxidative degradation by adding known heat stabilizers, including H donors, hydroperoxide decomposers, alkyl radical scavengers, and metal deactivators. An overview of various classes of heat stabilizers can be found in Chapter 1 (pp. 3-19) of Plastic Additives Handbook, edited by Hans Zweifel (5th ed., Carl Hanser Verlag, Munich). A frequently used system is a sterically hindered phenolic antioxidant, optionally combined with an organic triaryl phosphite. Improved color (i.e., reduced yellowness) can be further achieved in polyamides by using certain phosphorus compounds. Phosphorus compounds function as color stabilizers for polyamides by reducing the extent of oxidative and thermal degradation and can be added during polymerization or the compounding step.

[0005] For example, U.S. Pat. No. 5,929,200 relates to the incorporation of certain phosphorus compounds in conjunction with certain polyvalent metal compounds into the polyamide melt or polyamide manufacturing polymerization process, resulting in polyamides with improved color properties.

[0006] US Pat. No. 10,865,288 discloses a low-color polyamide containing 25 to 50 ppm of phosphorus, the phosphorus being present as a phosphorus-containing compound.

[0007] US Patent Application Publication No. 2022 / 0153962 relates to high-voltage components containing polymer compositions based on at least one polyamide and 10,10'-oxybis-12H-phthaloperin-12-one, in particular high-voltage components for electric vehicles, and the use of 10,10'-oxybis-12H-phthaloperin-12-one for marking polyamide-based manufactured articles as high-voltage components.

[0008] However, there remains a need for improved color stability of polyamides at elevated temperatures, particularly for orange colored products.

[0009] It is therefore an object of the present application to provide a thermoplastic molding composition with high color stability, in particular an orange thermoplastic molding composition with high color stability at high temperatures.

[0010] The purpose of this is to a) as component A), 10 to 99.98 wt. % of at least one thermoplastic polyamide different from component C), b) as component B), 0.01 to 0.5 wt. % of at least one sodium hypophosphite or hydrate thereof, preferably sodium hypophosphite monohydrate; c) as component C), 0.01 to 20 wt. % of at least one polyamide 6I / 6T; d) as component D), 0 to 5% by weight of a colorant or a mixture of two or more colorants, preferably an orange colorant or a mixture of two or more colorants which produce an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produce an orange color, having shades corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably having shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system, e) as component E), 0-5 wt. % of at least one laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably at least one pigment system comprising antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof; f) as component F), 0 to 60 wt. % of at least one fibrous and / or particulate filler; g) as component G), 0 to 55 wt. % of at least one flame retardant additive; h) as component H), 0 to 25 wt. % of at least one further additive; Including, The total weight percentage of components A) to H) is 100% by weight. This is achieved by means of a thermoplastic molding composition.

[0011] When sodium hypophosphite monohydrate is used, the amount of component B) calculated as sodium is 0.002 to 0.11% by weight. When sodium hypophosphite is used, the amount of sodium is 0.0026 to 0.13% by weight.

[0012] This object is further achieved by a method for producing the thermoplastic molding composition of the invention, which comprises the step of mixing components A), B), C) and optionally D), optionally E), optionally F), optionally G) and optionally H).

[0013] This object is further achieved by the use of the thermoplastic molding composition according to the invention or obtained by the process according to the invention for producing fibers, films, moldings and extrusions.

[0014] This object is further achieved by fibers, films, moldings or extrusions made from the thermoplastic molding composition according to the invention or from the thermoplastic molding composition obtained by the process according to the invention.

[0015] This object is further achieved by a process for producing the inventive fibers, films, moldings or extrusions by injection molding, extrusion or blow molding of the inventive thermoplastic molding composition or of a thermoplastic molding composition obtained by the inventive process.

[0016] This object is further achieved by the use of a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate and ii) at least one polyamide 6I / 6T to improve the color stability, in particular the color stability at high temperatures, of thermoplastic polyamide molding compositions comprising at least one polyamide different from polyamide 6I / 6T.

[0017] The inventors have found that by using a combination of at least one of sodium hypophosphite and a hydrate of sodium hypophosphite, preferably the monohydrate, with at least one polyamide 6I / 6T, it is possible to obtain a polyamide composition having very high color stability.

[0018] In the sense of this application, improved "color stability" means improved color stability during storage. Color stability is tested by observing the YI (Yellowness Index) value of an uncolored product or the ΔE (Color Difference) value of a colored product at specified time intervals and elevated temperatures. The inventors have found that the color buildup in the thermoplastic molding compositions of the present invention is lower than the color buildup in comparative polyamide compositions that do not contain both at least one metal hypophosphite and at least one polyamide 6I / 6T.

[0019] The thermoplastic molding compositions of the present invention are particularly suitable for providing orange pigmented compositions for high voltage applications, especially in automobiles.

[0020] In the case of the orange-coloured thermoplastic moulding composition of the invention, the colour difference ΔE after 1000 hours at 120°C is preferably less than 20, preferably ΔE<10, more preferably ΔE<5, from the L*a*b coordinates of the colour number starting with "2" on the RAL colour chart.

[0021] The thermoplastic molding compositions of the present invention are particularly suitable for use in / as high voltage components, especially in automotive applications.

[0022] The term "high voltage" according to the present invention is to be understood as an operating voltage of more than 30 V (DC) or more than 20 V (AC), preferably more than 60 V (DC) or more than 30 V (AC). Thus, a "high voltage component" according to the present invention is a component, preferably a component of an electric vehicle, that is subjected to an operating (working) voltage of more than 30 V, preferably more than 60 V (DC) or more than 20 V, preferably more than 30 V (AC).

[0023] According to ISO 6469-3:2021, the outer coverings of cables and harnesses of high-voltage electrical circuits that are not inside an enclosure or behind a barrier shall be marked in orange.

[0024] In the context of the present invention, "at least one" means either exactly one, or a mixture of two or more different components.

[0025] Ingredient A) As component A), the thermoplastic molding composition contains 10 to 99.98% by weight, preferably 20 to 85% by weight, more preferably 30 to 75% by weight, of at least one thermoplastic polyamide different from component C) (listed below), based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0026] If components D, E, F, G or H or combinations thereof are present in the thermoplastic molding composition, the maximum amount of component A) is reduced by the minimum amount of each of components D, E, F, G or H or combinations thereof.

[0027] The polyamide A) of the molding composition according to the invention generally has a viscosity number of 90 to 350 ml / g, preferably 100 to 240 ml / g. The viscosity number (VN) of the polyamides and polyamide compositions according to the invention is determined in sulfuric acid according to EN ISO 307:2019 (0.5% [m / v] polyamide in 96% by weight [m / m] sulfuric acid at 25°C), unless otherwise indicated.

[0028] Semicrystalline or amorphous polyamides having a molecular weight (weight average) of at least 5000 are preferred, as described, for example, in the following U.S. patents: 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210.

[0029] Examples of these are polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycaprylolactam and polylaurolactam, as well as polyamides obtained via the reaction of dicarboxylic acids with diamines.

[0030] Dicarboxylic acids that can be used are alkanedicarboxylic acids having 6 to 12, especially 6 to 10, carbon atoms, and aromatic dicarboxylic acids. Merely by way of example, mention may be made here of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and terephthalic and / or isophthalic acid.

[0031] Particularly suitable diamines are alkanediamines having 6 to 12, especially 6 to 8, carbon atoms, as well as m-xylylenediamine, di[4-aminophenyl]methane, di[4-aminocyclohexyl]methane, 2,2-di[4-aminophenyl]propane, 2,2-di[4-aminocyclohexyl]propane and 1,5-diamino-2-methylpantan.

[0032] Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide, and polycaprolactam, and in particular PA 6 / 66 copolyamide with a proportion of caprolactam units of 5 to 95% by weight (for example Ultramid® C31 from BASF SE).

[0033] Other suitable polyamides can be obtained from ω-aminoalkylnitriles, such as aminocapronitrile (PA 6), and adiponitrile with hexamethylenediamine (PA 66), via what is known as direct polymerization in the presence of water, as described, for example, in DE-A 10313681, EP-A 1198491 and EP-A 0922065.

[0034] Mention may also be made, by way of example, of the polyamide (PA 46) obtainable by condensing 1,4-diaminobutane with adipic acid at elevated temperatures. Methods for preparing polyamides of this structure are described, by way of example, in EP-A-38094, EP-A-38582 and EP-A-39524.

[0035] Other suitable examples are polyamides obtainable by copolymerization of two or more of the above-mentioned 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 with PA 66, as well as PA 6 / 66 copolyamides and PA 66 / 6 copolyamides.

[0036] Other copolyamides that have proven particularly advantageous are semi-aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T, which preferably have a triamine content of less than 0.5% by weight, more preferably less than 0.3% by weight (see EP-A-299444). Another polyamide that is resistant to high temperatures is known from EP-A-1994075 (PA 6T / 6I / MXD6).

[0037] The methods described in EP-A-129195 and EP-A-129196 can be used to prepare the preferred semi-aromatic copolyamides having a low triamine content.

[0038] Although not comprehensive, the following list includes the polyamides A) described above and other polyamides A) useful for the purposes of the present invention, as well as the monomers they contain.

[0039] AB polymer: PA 4 Pyrrolidone PA 6 ε-caprolactam PA 7 Ethanol Lactam PA 8 Caprylolactam PA 9 9-aminopelargonic acid PA 11 11-aminoundecanoic acid PA 12 Laurolactam

[0040] AA / BB polymer: PA 46 Tetramethylenediamine, Adipic Acid PA 66 Hexamethylenediamine, Adipic Acid PA 69 Hexamethylenediamine, Azelaic Acid PA 610 Hexamethylenediamine, Sebacic Acid PA 612 Hexamethylenediamine, Decanedicarboxylic acid PA 613 Hexamethylenediamine, Undecanedicarboxylic Acid PA 1212 1,12-Dodecanediamine, Decanedicarboxylic acid PA 1313 1,13-Diaminotridecane, undecanedicarboxylic acid PA 6T Hexamethylenediamine, Terephthalic Acid PA MXD6 m-xylylenediamine, adipic acid

[0041] AA / BB polymer: PA 6I Hexamethylenediamine, Isophthalic Acid PA 6-3-T Trimethylhexamethylenediamine, Terephthalic Acid PA 6 / 6.36 (see below) PA 6 / 6T (see PA 6 and PA 6T) PA 6 / 66 (see PA 6 and PA 66) PA 6 / 12 (see PA 6 and PA 12) PA 66 / 6 / 610 (see PA 66, PA 6 and PA 610) PA 6I / 6T (see PA 6I and PA 6T) PA PACM 12 Diaminodicyclohexylmethane, Laurolactam PA 6I / 6T / PACM PA 6I / 6T + diaminodicyclohexylmethane PA 12 / MACMI Laurolactam, Dimethyldiaminodicyclohexylmethane, Isophthalic Acid PA 12 / MACMT Laurolactam, Dimethyldiaminodicyclohexylmethane, Terephthalic Acid PA PDA-T Phenylenediamine, Terephthalic Acid

[0042] Preferred polyamides A) are PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA 6 / 636, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T, PA 6T / 66, or mixtures thereof.

[0043] Most preferred are PA 6, PA 66, PA 6 / 66 and PA 66 / 6, and PA 6 / 636, or mixtures thereof. Most preferred are PA 6, PA 66, or mixtures thereof.

[0044] Suitable copolyamides are A1) 20.0 to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine; A2) 0 to 50.0% by weight of units derived from ε-caprolactam; A3) 0 to 80.0% by weight of units derived from adipic acid and hexamethylenediamine; A4) 0 to 40.0 wt. % of further polyamide-forming monomers Constructed from The proportion of component A2) or A3) or A4) or mixtures thereof is at least 10.0% by weight.

[0045] Component A1) contains 20.0 to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

[0046] In addition to units derived from terephthalic acid and hexamethylenediamine, the copolyamide optionally contains units derived from ε-caprolactam, and / or units derived from adipic acid and hexamethylenediamine, and / or units derived from further polyamide-forming monomers.

[0047] The aromatic dicarboxylic acids A4) contain 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic acids and isophthalic acids such as 3t-butylisophthalic acid, polycyclic dicarboxylic acids such as 4,4'- and 3,3'-diphenyldicarboxylic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'-sulfodiphenylcarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, with isophthalic acid being particularly preferred.

[0048] Furthermore, the polyamide-forming monomers A4) may be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms, or from aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of this type 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 or meta-xylylenediamine as representatives of diamines and caprolactams, and enantholactam, γ-aminoundecanoic acid and laurolactam as representatives of lactams / aminocarboxylic acids.

[0049] Examples of such copolyamides are described in more detail in DE 102009011668 A1.

[0050] As component A), the thermoplastic molding material may comprise: A') 15% to 84% by weight of at least one lactam; B') the following components: B1') At least one C 32 ~C 40 dimer acids, and B2') At least one C4-C 12 -diamine 16% to 85% by weight of a monomer mixture (M) containing and at least one copolyamide prepared by polymerization of 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').

[0051] In the context of the present invention, the terms "component A')" and "at least one lactam" are used synonymously and therefore have the same meaning.

[0052] The same applies to the terms "component B')" and "monomer mixture (M)", which are likewise used synonymously in the context of the present invention and therefore have the same meaning.

[0053] According to the invention, at least one copolyamide is prepared by polymerizing 15% to 84% by weight of component A') with 16% to 85% by weight of component B'), preferably by polymerizing 40 to 83% by weight of component A') with 17 to 60% by weight of component B'), particularly preferably by polymerizing 60 to 80% by weight of component A') with 20 to 40% by weight of component B'), the weight percentages of components A') and B') respectively being based on the sum of the weight percentages of components A') and B').

[0054] The sum of the weight percentages of components A') and B') is preferably 100% by weight.

[0055] It will be understood that the weight percentages of components A') and B') refer 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') to B') may optionally vary.

[0056] According to the present invention, at least one copolyamide is produced by 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 typically a condensation reaction. During the condensation reaction, component A') reacts with components B1') and B2') present in component B'), and optionally with component B3'), described below, which may also be present in component B'). This results in the formation of amide bonds between the individual components. During the polymerization, component A') is typically at least partially in open-chain form, i.e., in the form of an amino acid.

[0057] 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 that catalyze 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 triphenylphosphite.

[0058] The polymerization of components A') and B') forms at least one copolyamide, which therefore comprises units derived from component A') and units derived from component B'). The units derived from component B') comprise units derived from components B1') and B2'), and optionally units derived from component B3').

[0059] The polymerization of components A') and B') forms a copolyamide as a copolymer, which may be a random copolymer, as well as a block copolymer.

[0060] In a block copolymer, blocks of units derived from component B') and blocks of units derived from component A') are formed. These alternate. In a random copolymer, units derived from component A') alternate with units derived from component B'). The alternation is random. For example, two units derived from component B') are followed by one unit derived from component A'), which is then followed by a unit derived from component B'), which is then followed by a unit containing three units derived from component A').

[0061] It is preferred if at least one copolyamide is a random copolymer.

[0062] The preparation of at least one copolyamide preferably comprises the following steps: I) polymerizing components A') and B') to obtain at least one first copolyamide; II) pelletizing the at least one first copolyamide obtained in step I) to obtain at least one pelletized copolyamide; III) extracting the at least one pelletized copolyamide obtained in step II) with water to obtain at least one extracted copolyamide; IV) drying the at least one extracted copolyamide obtained in step III) at a temperature (TT) to obtain at least one copolyamide; Includes.

[0063] The polymerization in step I) can be carried out in any reactor known to those skilled in the art. Stirred tank reactors are preferred. To improve reaction control, it is also possible to use auxiliaries known to those skilled in the art, such as antifoaming agents such as polydimethylsiloxane (PDMS).

[0064] In step II), the at least one first copolyamide obtained in step I) can be pelletized by any method known to those skilled in the art, such as strand pelletizing or underwater pelletizing.

[0065] The extraction in step III) can be carried out by any method known to those skilled in the art.

[0066] During the extraction of step III), by-products typically formed during the polymerization of components A') and B') in step I) are extracted from the at least one pelletized copolyamide.

[0067] In step IV), the at least one extracted copolyamide obtained in step III) is dried. Drying methods are known to those skilled in the art. According to the present invention, the at least one extracted copolyamide is dried at a temperature (T T ) is dried at temperature (T T ) is preferably equal to the glass transition temperature (T G(C) ) and the melting temperature (T M(C) ) lower.

[0068] Drying in step IV) is typically carried out for a period in the range of 1 to 100 hours, preferably in the range of 2 to 50 hours, particularly preferably in the range of 3 to 40 hours.

[0069] Drying in step IV) is believed to further increase the molecular weight of the at least one copolyamide.

[0070] The at least one copolyamide typically has a glass transition temperature (T G(C) ) has a glass transition temperature (T G(C) ) is, 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, as determined according to ISO 11357-2:2014.

[0071] In the context of the present invention, the glass transition temperature (T G(C) ) is the glass transition temperature (T) of the dry copolyamide according to ISO 11357-2:2014 G(C) ) based on

[0072] In the context of the present invention, "dry" should be understood to mean that the at least one copolyamide contains less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight of water, based on the total weight of the at least one copolyamide. More preferably, "dry" should be understood to mean that the at least one copolyamide is free of water, and most preferably that the at least one copolyamide is free of solvent.

[0073] Additionally, the at least one copolyamide typically has a melting temperature (T M(C) ) at least one copolyamide has a melting temperature (T M(C) ) is, for example, in the range of 150 to 210°C, preferably in the range of 160 to 205°C, particularly preferably in the range of 160 to 200°C, as determined in accordance with ISO 11357-3:2014.

[0074] The at least one copolyamide generally has a viscosity number (VN) in the range of 150 to 300 ml / g, determined in a 0.5 wt. % solution of the at least one copolyamide in a 1:1 weight ratio mixture of phenol / o-dichlorobenzene. (C) )

[0075] The viscosity number (VN) of at least one copolyamide (C) ) is preferably in the range of 160 to 290 mL / g, particularly preferably in the range of 170 to 280 mL / g, determined in a 0.5% by weight solution of at least one copolyamide in a 1:1 weight ratio mixture of phenol / o-dichlorobenzene.

[0076] Component A') According to the invention, component A') is at least one lactam.

[0077] In the context of the present invention, "at least one lactam" is understood to mean either exactly one lactam or a mixture of two or more lactams.

[0078] Lactams are known per se to those skilled in the art. According to the invention, lactams having 4 to 12 carbon atoms are preferred.

[0079] In the context of the present invention, "lactam" is to be understood to mean a cyclic amide having preferably 4 to 12 carbon atoms in the ring, particularly preferably 5 to 8 carbon atoms.

[0080] Suitable lactams are, for example, 3-aminopropanolactam (propio-3-lactam; β-lactam; β-propiolactam), 4-aminobutanolactam (butyro-4-lactam; γ-lactam; γ-butyrolactam), aminopentanolactam (2-piperidinone; δ-lactam; δ-valerolactam), 6-aminohexanolactam (hexano-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanolactam (heptano-7-lactam; ζ-lactam; ζ-heptanolactam). tam), 8-aminooctanolactam (octano-8-lactam; η-lactam; η-octanolactam), 9-aminononanolactam (nonano-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam (decano-10-lactam; ω-decanolactam), 11-aminoundecanolactam (undecano-11-lactam; ω-undecanolactam) and 12-aminododecanolactam (dodecano-12-lactam; ω-dodecanolactam).

[0081] Therefore, the present invention also provides a process, wherein component A') is selected from the group consisting of 3-aminopropanolactam, 4-aminobutanolactam, 5-aminopentanolactam, 6-aminohexanolactam, 7-aminoheptanolactam, 8-aminooctanolactam, 9-aminononanolactam, 10-aminodecanolactam, 11-aminoundecanolactam and 12-aminododecanolactam.

[0082] The lactam may be unsubstituted or at least monosubstituted. When at least monosubstituted lactams are used, the nitrogen atom and / or ring carbon atoms may be C- to C 10 -Alkyl, C5- to C6-cycloalkyl and C5- to C 10 -aryl.

[0083] Appropriate C1-~C 10 -Alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. A suitable C5- to C6-cycloalkyl substituent is, for example, cyclohexyl. Preferred C5- to C6-cycloalkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. 10 The aryl substituent is phenyl or anthranyl.

[0084] It is preferred to use unsubstituted lactams, with γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam) being preferred, with δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam) being particularly preferred, with ε-caprolactam being particularly preferred.

[0085] Monomer mixture (M) According to the 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 -Contains diamines.

[0086] In the context of the present invention, a monomer mixture (M) is to be understood to mean a mixture of two or more monomers, at least components B1′) and B2′) being present in the monomer mixture (M).

[0087] In the context of the present invention, "component B1')" and "at least one C 32 ~C 40The terms "component B2')" and "at least one C4-C6 dimer acid" are used interchangeably and therefore have the same meaning. 12 The same applies to the terms "-diamine". These terms are likewise used synonymously in the context of the present invention and therefore have the same meaning.

[0088] The monomer mixture (M) comprises, for example, in the range of 45 to 55 mol % of component B1') and in the range of 45 to 55 mol % of component B2'), in each case based on the sum of the molar percentages of components B1') and B2'), preferably based on the total amount of substances of the monomer mixture (M).

[0089] It is preferred if component B') comprises in the range of 47 to 53 mol % of component B1') and in the range of 47 to 53 mol % of component B2'), in each case based on the sum of the molar percentages of components B1') and B2'), preferably based on the total amount of substances of component B').

[0090] It is particularly preferred if component B') comprises in the range of 49 to 51 mol % of component B1') and in the range of 49 to 51 mol % of component B2'), in each case based on the sum of the molar percentages of components B1') and B2'), preferably based on the total amount of substances of component B').

[0091] The mole percentages of components B1') and B2') present in component B') typically add up to 100 mole %.

[0092] Component B') is a component B3'), at least one C4-C 20 - It may further comprise a diacid.

[0093] In the context of the present invention, "component B3')" and "at least one C4-C 20 The terms "-diacid" are used synonymously and therefore have the same meaning.

[0094] If component B') further comprises component B3'), it is preferred if component B') comprises in each case 25 to 54.9 mol % of component B1'), 45 to 55 mol % of component B2'), and 0.1 to 25 mol % of component B3'), based on the total amount of substances of component B').

[0095] It is then particularly preferred if component B') comprises component B1') in the range of 13 to 52.9 mol %, component B2') in the range of 47 to 53 mol % and component B3') in the range of 0.1 to 13 mol %, in each case based on the total amount of substances of component B').

[0096] It is then most preferred if component B') comprises component B1') in the range of 7 to 50.9 mol %, component B2') in the range of 49 to 51 mol %, and component B3') in the range of 0.1 to 7 mol %, in each case based on the total amount of substances of component B').

[0097] When component B') further comprises component B3'), the mole percentages of components B1'), B2') and B3') typically add up to 100 mole %.

[0098] The monomer mixture (M) may further contain water.

[0099] Components B1') and B2') and optionally B3') of component B') can react with each other to give amides. This reaction is known per se to those skilled in the art. Component B') can therefore contain components B1'), B2') and optionally B3') in fully reacted, partially reacted or unreacted form. It is preferred if component B') contains components B1'), B2') and optionally B3') in unreacted form.

[0100] In the context of the present invention, therefore, "in unreacted form" means that component B1') is reacted with at least one C 32 ~C 40 - as a dimer acid, component B2') has at least one C4-C 12- diamine, optionally component B3') having at least one C4-C 20 -diacid should be understood to mean that it exists as a diacid.

[0101] If components B1') and B2') and optionally B3') have at least partially reacted, components B1') and B2') and optionally B3') are therefore at least partially in amide form.

[0102] component B1') According to the invention, component B1') comprises at least one C 32 ~C 40 -dimer acid.

[0103] In the context of the present invention, "at least one C 32 ~C 40 -dimer acid" has just one C 32 ~C 40 -dimer acid or two or more C 32 ~C 40 -dimer acid mixtures.

[0104] Dimer acids are also called dimer fatty acids. 32 ~C 40 Dimer acids are known per se to those skilled in the art and are typically prepared by dimerization of unsaturated fatty acids, which dimerization can be catalyzed, for example, by clayey earths.

[0105] At least one C 32 ~C 40 Suitable unsaturated fatty acids for producing -dimer acids are known to those skilled in the art and include, for example, unsaturated C 16 -fatty acids, unsaturated C 18 -Fatty acids and unsaturated C 20 -Fatty acids.

[0106] Therefore, component B1') is an unsaturated C 16 -fatty acids, unsaturated C 18 -Fatty acids and unsaturated C 20-fatty acids, and preferably from unsaturated fatty acids selected from the group consisting of unsaturated C 18 Fatty acids are particularly preferred.

[0107] Suitable unsaturated C 16 The fatty acid is, for example, palmitoleic acid ((9Z)-hexadec-9-enoic acid).

[0108] Suitable unsaturated C 18 Fatty acids include, for example, 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)-octadeca-9,12-dienoic acid), α-linolenic acid ((9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid), γ-linolenic acid ((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid), calendulic acid acid) ((8E,10E,12Z)-octadeca-8,10,12-trienoic acid), punicic acid ((9Z,11E,13Z)-octadeca-9,11,13-trienoic acid), alpha-eleostearic acid ((9Z,11E,13E)-octadeca-9,11,13-trienoic acid) and beta-eleostearic acid ((9E,11E,13E)-octadeca-9,11,13-trienoic acid). Unsaturated C 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)-octadeca-9,12-dienoic acid). 18 Fatty acids are particularly preferred.

[0109] Suitable unsaturated C 20The fatty acid is, for example, selected from the group consisting of gadoleic acid ((9Z)-eicosa-9-enoic acid), ecosenoic acid ((11Z)-eicosa-11-enoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and timnodonic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).

[0110] Component B1') particularly preferably comprises at least one C 36 -dimer acid.

[0111] At least one C 36 -dimer acids are preferably unsaturated C 18 -Produced from fatty acids. 36 the dimer acid is 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)-octadeca-9,12-dienoic acid). 18 It is particularly preferred that it is produced from fatty acids.

[0112] The production of component B1') from unsaturated fatty acids may also form trimer acids and residues of unconverted unsaturated fatty acids may remain.

[0113] The formation of trimer acids is known to those skilled in the art.

[0114] According to the invention, component B1') preferably comprises not more than 0.5% by weight of unreacted unsaturated fatty acids and not more than 0.5% by weight of trimer acid, particularly preferably not more than 0.2% by weight of unreacted unsaturated fatty acids and not more than 0.2% by weight of trimer acid, in each case based on the total weight of component B1').

[0115] Thus, dimer acids (also known as dimerized fatty acids or dimer fatty acids) should generally be understood, particularly in the context of the present invention, to mean mixtures produced by oligomerization of unsaturated fatty acids. They are, for example, mixtures of unsaturated fatty acids, especially those in which the starting material used is unsaturated C 16 -~C 20 Dimer fatty acids can be produced by catalytic dimerization of plant-derived unsaturated fatty acids. The coupling proceeds primarily via the Diels-Alder mechanism, resulting in a mixture of primarily dimer products with alicyclic, linear aliphatic, branched aliphatic, and even C6-aromatic hydrocarbon groups between the carboxylic groups, depending on the number and position of double bonds in the fatty acids used to produce the dimer acid. Depending on the mechanism and / or any subsequent hydrogenation, the aliphatic radicals may be saturated or unsaturated, and the proportion of aromatic groups may vary. The radical between the carboxylic acid groups then contains, for example, 32 to 40 carbon atoms. For production, fatty acids with 18 carbon atoms are preferably used, resulting in a dimer product with 36 carbon atoms. The radicals linking the carboxylic groups of the dimer fatty acids preferably contain no unsaturated bonds and no aromatic hydrocarbon radicals.

[0116] Therefore, in the context of the present invention, the production is preferably carried out by 18 - fatty acids are used, with particular preference being given to using linolenic acid, linoleic acid and / or oleic acid.

[0117] Depending on the reaction regime, the oligomerization results in a mixture containing primarily dimer molecules, but also trimer molecules, as well as monomer molecules and other by-products. Purification by distillation is common. Commercially available dimer acids generally contain at least 80% by weight of dimer molecules, up to 19% by weight of trimer molecules, and up to 1% by weight of monomer molecules and other by-products.

[0118] It is preferable to use dimer acids which constitute to the extent of at least 90% by weight of the dimer fatty acid molecules, preferably to the extent of at least 95% by weight and very particularly preferably to the extent of at least 98% by weight.

[0119] The proportions of monomer, dimer, and trimer molecules and other by-products in the dimer acid can be determined, for example, by gas chromatography (GC). Prior to GC analysis, the dimer acid is converted to the corresponding methyl esters by the boron trifluoride method (see DIN EN ISO 5509), and then analyzed by GC.

[0120] Therefore, in the context of the present invention, the basic feature of "dimer acid" is that its production involves the oligomerization of unsaturated fatty acids. This oligomerization mainly forms dimer products, i.e., preferably in the range of at least 80% by weight, particularly preferably in the range of at least 90% by weight, very particularly preferably in the range of at least 95% by weight, and particularly preferably in the range of at least 98% by weight. Therefore, the fact that oligomerization mainly forms dimer products containing exactly two fatty acid molecules justifies this name, which is in any case general. Therefore, an alternative expression for the related term "dimer acid" is "mixture containing dimerized fatty acids".

[0121] The dimer acids used are commercially available. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 manufactured by Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 manufactured by Croda, Empol 1008, Empol 1012, Empol 1061, and Empol 1062 manufactured by BASF SE, and Unidyme 10 and Unidyme Tl manufactured by Arizona Chemical.

[0122] Component B1') has an acid number in the range of, for example, 190 to 200 mg KOH / g.

[0123] component B2') According to the invention, component B2') comprises at least one C4-C 12 -diamine.

[0124] In the context of the present invention, "at least one C4-C 12 -diamine" has exactly one C4-C 12 -Diamine or two or more C4-C 12 -diamine mixtures.

[0125] In the context of this compound, "C4-C 12 "-diamine" should be understood to mean an aliphatic and / or aromatic compound having 4 to 12 carbon atoms and two amino groups (-NH2 groups). The aliphatic and / or aromatic compounds may be unsubstituted or may further be at least monosubstituted. If the aliphatic and / or aromatic compounds are further at least monosubstituted, they may have 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 per se to those skilled in the art. At least one C4-C 12 The diamine is preferably unsubstituted.

[0126] Suitable components B2') are, for example, selected 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).

[0127] It is preferred if component B2') is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.

[0128] Component B3') According to the invention, component B3') optionally present in component B') is at least one C4-C 20 - is a diacid.

[0129] In the context of the present invention, "at least one C4-C 20 -diacid" is exactly one C4-C 20 -Diacids or two or more C4-C 20 - should be understood to mean any mixture of diacids.

[0130] In the context of the present invention, "C4-C 20 "-diacid" should be understood to mean an aliphatic and / or aromatic compound having 2 to 18 carbon atoms and two carboxyl groups (-COOH groups). The aliphatic and / or aromatic compounds may be unsubstituted or may further be at least monosubstituted. If the aliphatic and / or aromatic compounds are further at least monosubstituted, they may have 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 - The diacid is unsubstituted.

[0131] Suitable components B3') are, for example, selected from the group consisting of butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.

[0132] It is preferred if component B3') is selected from the group consisting of pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.

[0133] Most preferably, component A) is selected from the group consisting of PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA 6 / 6.36, PA610, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T and PA 6T / 66, more preferably selected from PA 6, PA 6.6, PA 66 / 6, PA 6 / 6.6 and mixtures thereof, most preferably selected from PA 6 and PA 66 and mixtures thereof.

[0134] Component B) As component B), the thermoplastic molding composition contains 0.01 to 0.5% by weight, preferably 0.06 to 0.45% by weight, more preferably 0.1 to 0.4% by weight, of at least one of sodium hypophosphite or sodium hypophosphite hydrate, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0135] The sodium hypophosphite and sodium hypophosphite hydrate used as component B) according to the present invention are commercially available. Sodium hypophosphite monohydrate (CAS: 10039-56-2) is most preferred.

[0136] Component C) As component C), the thermoplastic molding composition contains 0.01 to 20% by weight, preferably 0.1 to 18% by weight, more preferably 1 to 17% by weight, most preferably 3 to 16% by weight of at least one polyamide 6I / 6T, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0137] Preferably, component C) comprises units derived from hexamethylenediamine, terephthalic acid and isophthalic acid, in other words, component C) is a copolymer prepared from hexamethylenediamine, terephthalic acid and isophthalic acid.

[0138] More preferably, component C) comprises units derived from hexamethylenediamine, terephthalic acid, and isophthalic acid. Preferably, it is a random copolymer. The polyamide 6I / 6T used as component C) contains isophthalic acid units (6I units) and terephthalic acid units (6T units). Preferably, the molar ratio of 6I units to 6T units is in the range of 1:1 to 3:1, more preferably in the range of 1.5:1 to 2.5:1, and most preferably in the range of 1.8:1 to 2.3:1.

[0139] Polyamide 6I / 6T is an amorphous copolyamide.It is known in the art that when polyamide 6I / 6T is mainly based on PA6T, the resulting polyamide is semi-crystalline (often referred to as PA6T / 6I).In contrast, when polyamide 6I / 6T is mainly based on PA6I (i.e., more than 55% isophthalic acid; often referred to as PA6I / 6T), the resulting polymer is amorphous (see Kohan, Melvin I.: Nylon Plastics Handbook, Carl Hanser Verlag, Munich Vienna New York, 1995, p, page 373; Stephanie Djukic et al., Heliyon 6 (2020) e03857; https: / / en.wikipedia.org / wiki / Polyphthalamide).

[0140] "Amorphous" in the context of the present invention means that the pure polyamide 6I / 6T does not have any melting point in differential scanning calorimetry (DSC) measured according to ISO 11357-1:2017:02.

[0141] Polyamide 6I / 6T typically has a glass transition temperature (T) in the range of 100 to 150°C, preferably 115 to 135°C, and more preferably 120 to 130°C. G ) The glass transition temperature (T G ) is determined by differential scanning calorimetry. For the determination, according to the invention, a first heating run (H1), then a cooling run (C) and then a second heating run (H2) are measured on a sample of polyamide 6I / 6T (starting weight approx. 8.5 g). The heating rate in the first heating run (H1) and the second heating run (H2) is 20 K / min, and the cooling rate in the cooling run (C) is likewise 20 K / min. In the region of the glass transition of polyamide 6I / 6T, a step is obtained in the second heating run (H2) on the DSC diagram. The glass transition temperature (T) of polyamide 6I / 6T G ) corresponds to the temperature at half the step height in the DSC diagram.

[0142] The MVR (275°C / 5 kg) (Melt Volume Flow Rate) is preferably in the range of 50 ml / 10 min to 150 ml / 10 min, more preferably in the range of 95 ml / 10 min to 105 ml / 10 min (Melt Volume Flow Rate (MVR) is determined according to EN ISO 1133-1:2011, Procedure A).

[0143] The polyamide 6I / 6T used as component C) according to the invention preferably has an amino end group concentration (AEG) in the range from 35 to 45 mmol / kg, particularly preferably in the range from 35 to 42 mmol / kg.

[0144] To determine the amino end group concentration (AEG), 1 g of polyamide 6I / 6T is dissolved in 30 ml of a phenol / methanol mixture (phenol:methanol volume ratio 75:25) and then subjected to potentiometric titration with 0.2 N aqueous hydrochloric acid solution.

[0145] The polyamide 6I / 6T used as component C) according to the invention generally has a carboxyl end group concentration (CEG) preferably in the range of 60 to 300 mmol / kg, more preferably in the range of 80 to 200 mmol / kg.

[0146] The carboxyl end group concentration (CEG) was determined by NMR of HFIP-d2.

[0147] Commercially available polyamides 6I / 6T suitable as component C) according to the invention are Zytel® HTN301 (formerly Selar® PA3426R) from DuPont with a molar ratio of 6I:6T of 2.2:1, Grivory G21 from EMS with a molar ratio of 6I:6T of 2.1:1, and Grivory G16 from EMS with a molar ratio of 6I:6T of 1.9:1.

[0148] Component D) As component D), the thermoplastic molding composition contains 0 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.05 to 2% by weight, of a colorant or a mixture of two or more colorants, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0149] Suitable colorants are pigments or dyes, for example inorganic or organic pigments or dyes.

[0150] Suitable inorganic pigments are, for example, ultramarine blue, cobalt aluminate, e.g. Heucodur Blue 552 from Heubach GmbH, bismuth vanadate, iron oxide, titanium dioxide, zinc sulfide, zinc oxide, cerium sulfide, in particular cerium(III) sulfide [CAS 12014-93-6], cerium / lanthanum sulfide, in particular cerium(III) / lanthanum(III) sulfide [CAS 12014-93-6; CAS 12031-49-1], tin titanium zinc oxide [CAS 923954-49-8].

[0151] Suitable organic colorants are, for example, phthalocyanines, benzimidazoles, such as Keyplast FL OR YF and Ni-2-hydroxy-naphthyl-benzimidazole (Pigment Orange 86, [CAS 42844-93-9] from Milliken), for example PV Fast Orange 6RL from Heubach GmbH, pyridinium-azo-benzimidazole [CAS 72102-84-2], or the condensation product of 5,6-diamino-1,3-dihydro-2H-benzimidazol-2-one with benzo[de]isochroman-1,3-dione, Pigment Yellow 192 [CAS 56279-27-7], perylenes, anthraquinones, in particular 1,8-dichloroanthracene-9,10-dione with benzenethiol (Solvent Yellow 163, [CAS 13676-91-0]), condensation products with 10,10'-oxybis-12H-phthaloperin-12-one (Solvent Orange 111, [CAS 203576-97-0]) from Lanxess Deutschland GmbH, Cologne, for example Macrolex Orange HT, 14H-anthra[2,1,9-m,n,a]thioxanthen-14-one, for example Hostasol Red GG (Solvent Orange 63, [CAS 16294-75-0]) from Heubach GmbH, 2-octadecyl-1H-thioxantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, for example Hostasol Yellow 3G (Solvent Yellow 98, [CAS 16294-75-0]) from Heubach GmbH. 12671-74-8]) or 12H-phthaloperin-12-one (Solvent Orange 60, [CAS 6925-69-5]).

[0152] Polyamide molding compositions used for high-voltage components are of particular interest in the present invention, and since ISO 6469-3 suggests that such high-voltage components should be colored orange, orange colorants, or mixtures of two or more colorants that result in an orange color, are preferred in the thermoplastic polyamide molding compositions according to the present invention.

[0153] Thus, if present, the thermoplastic molding composition according to the invention preferably comprises an orange colorant or a mixture of two or more colorants which produce an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produce an orange color, having a color tone corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system. More preferably, component D) is an orange colorant or a mixture of two or more colorants which produce an orange color, having a color tone corresponding to the color number RAL 2003 in the RAL color system.

[0154] Preferred colorants D) are therefore colorants and mixtures of colorants which result in the colors RAL 2003, RAL 2008 and RAL 2011, preferably cerium(III) sulfide (CeS) [CAS 12014-93-6], known as CI® Pigment Orange 75, cerium(III) sulfide / lanthanum(III) sulfide (CeS / LaS) ([CAS 12014-93-6; CAS 12031-49-1], e.g. CI® Pigment Orange 78) and tin titanium zinc oxide [CAS 923954-49-8], e.g. Sicopal Orange K2430 from BASF SE.

[0155] CI® Pigment Orange 75 and CI® Pigment Orange 78 are commercially available, for example, as Neolor® Orange H and Neolor® light Orange H from Baotou Hongbo Te Technology Co Ltd.

[0156] CI stands for Color Index and is a dual classification system. The primary descriptor is the Color Index Common Name (often abbreviated CIGN). The other descriptor is the Color Index Constitution Number (often abbreviated CICN), which is related to the chemical structure. In the above, CIGN is used to describe the appropriate colorant.

[0157] The CIGN describes commercial products by their recognized class of use, their hue, and serial number (which simply reflects the chronological order in which the associated colorant type was registered in the Color Index).

[0158] Component D) is generally used directly as a powder or in the form of a paste, masterbatch, molding or concentrate comprising component D). Preferably, component D) is used in the form of a powder.

[0159] Component E) It is also important for high-voltage components, especially those in electric vehicles, to be able to be identified in order to identify them with additional information such as serial numbers, manufacturer characteristics, installation information or safety-related information. A suitable means of identifying polymer-based components is laser engraving (see https: / / de.wikipedia.org / wiki / Laserbeschriftung), preferably using a solid-state laser with a Nd:YAG or Nd:YVO4 crystal with a wavelength of 1064 nm, 532 nm or 355 nm, with a laser with a wavelength of 1064 nm being particularly preferred. As component E), the thermoplastic molding composition contains 0 to 5 wt. %, preferably 0.01 to 3 wt. %, more preferably 0.05 to 2 wt. %, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G), and optionally H), of a laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably a pigment system containing antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide, or a mixture thereof. Examples of mixed oxides are inorganic mixed oxides containing antimony trioxide, titanium dioxide, tin oxide, ferrous oxide, and / or zinc oxide, such as antimony tin oxide or mixed oxides of titanium dioxide, tin oxide, and / or zinc oxide.

[0160] In one embodiment of the present invention, the laser engraving additive is antimony-free.

[0161] Glimmer, in the sense of the present invention, has the following composition: DG 2-3 [T4O 10 ]X2 is a group of minerals including During the ceremony, D is ammonium (NH4 + ), barium, cesium, calcium, potassium, sodium, rubidium, G is aluminum, chromium, iron (Fe 2+ , Fe 3+), lithium, magnesium, titanium, vanadium, zinc, T = Aluminum, Beryllium, Boron, Iron (Fe 3+ ), silicium, X = anion: Cl - , O 2- , O.H. - , F - , S2 - is.

[0162] The oxides mentioned above may be surface modified, for example, by a coating containing antimony, ferrous oxide, tin oxide, and / or zinc oxide, e.g., TiO particles coated with an antimony-doped tin dioxide layer (Sn,Sb)O or calcined antimony / tin mixed oxide, in which the antimony concentration is higher at the surface than in the particle as a whole. See, for example, DE 102015009854 A1 and EP 1377522 A1.

[0163] Other suitable laser marking additives are, for example, tin orthophosphate, barium titanate, copper hydroxyphosphate, copper orthophosphate, copper potassium diphosphate, copper hydroxide, and anthraquinone.

[0164] The above laser marking additives are commercially available or can be obtained by methods known to those skilled in the art.

[0165] The laser marking additive may be used directly as a powder or in the form of a paste or masterbatch, molding or concentrate. Those skilled in the art will understand that the term "masterbatch" herein refers to a plastic additive in the form of granules with a higher content of laser marking additive than in the final application.

[0166] Component F) As component F), the thermoplastic molding composition contains 0 to 60% by weight, preferably 0 to 55% by weight, more preferably 0 to 50% by weight, of at least one fibrous and / or particulate filler, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0167] Preferably, component F) comprises glass fibers and is present in an amount of 5 to 60% by weight, more preferably 10 to 55% by weight, most preferably 15 to 50% by weight, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0168] When component F) is present, the maximum amount of component A) is reduced by the minimum amount of component F), so that the total amount of components A) through H) is still 100% by weight.

[0169] It is also possible to use a mixture of two or more different fibrous and / or particulate fillers.

[0170] Fibrous or particulate fillers F) that may be mentioned are carbon fibres, glass beads, for example solid or hollow glass beads, glass fibres, or powdered glass, amorphous quartz glass, borosilicate aluminium glass with an alkali content of about 1% (E glass), amorphous silica, quartz flour, alkaline earth metal silicates, in particular calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or crushed quartz, mica, phlogopite, barium sulphate, feldspar, wollastonite, montmorillonite, and at least one fibrous and / or particulate filler from the group consisting of cellulose ether, 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, aluminum oxide, plaster, zirconium oxide, antimony oxide, clay, silica-alumina, sericite, diatomaceous earth, silica stone, carbon black, glassy hollow microspheres (Shirasu® balloons), red oxide, zinc oxide and mixtures thereof.

[0171] Other fillers that may be mentioned are lamellar or acicular fillers, the amount of which, if present, is preferably 0.1 to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and Laponite®. The lamellar nanofillers are organically modified by conventional methods to provide good compatibility with organic binders. The addition of lamellar or acicular fillers to the thermoplastic molding compositions of the present invention results in a further increase in mechanical strength.

[0172] For the purposes of the present invention, an acicular mineral filler is a mineral filler having strongly developed needle-like characteristics. An example is acicular wollastonite. The mineral preferably has an L / D (length to diameter) ratio of 8:1 to 35:1, preferably 8:1 to 11:1. The mineral filler may optionally be pretreated with the above-mentioned silane compounds, but pretreatment is not required.

[0173] The preferred fibrous or particulate filler F) is glass fiber. Glass fibers are generally chopped fibers, also called short fibers, having a length in the range of 0.1 to 1 mm, long fibers having a length in the range of 1 to 50 mm, and continuous fibers having a length l of more than 50 mm. Continuous fibers are used in fiber-reinforced plastics in the form of rovings or fabrics.

[0174] Powdered glass fibers are also available, with the length of the glass fibers after milling typically ranging from 70 to 200 μm.

[0175] Glass fibres in the form of roving or chopped glass as described above are particularly preferred.

[0176] More preferred glass fibers for use as component F) are chopped long glass fibers having an average starting length in the range of 1 to 50 mm, more preferably in the range of 1 to 10 mm, and most preferably in the range of 2 to 7 mm, as determined by laser diffraction-granulometry (laser granulometry / laser diffraction measurement) according to ISO 13320. Most preferred glass fibers for use as component F) have an average fiber diameter in the range of 7 to 18 μm, more preferably in the range of 9 to 15 μm, as determined by laser diffraction measurement according to ISO 13320.

[0177] In a preferred embodiment, the glass fibers preferably used as component F) are modified with a suitable size system or adhesion promoter / adhesion promoter system. To improve compatibility with thermoplastics, it is preferred to use a silane-based size system or adhesion promoter.

[0178] Suitable silane compounds have the general formula: (X-(CH2) n ) k -Si-(OC m H 2m+1 ) 4-k and X is -NH2, HO-, carboxyl, [ka] or [ka] and n is an integer of 2 to 10, preferably 3 to 4, m is an integer of 1 to 5, preferably 1 to 2; k is an integer of 1 to 3, and is preferably 1.

[0179] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and the corresponding silanes containing a glycidyl or carboxyl group as the substituent X.

[0180] For the modification of glass fibers for preferred use as component F), adhesion promoters, preferably silane compounds of formula (II), are preferably used in amounts of 0.01 to 2% by weight, more preferably 0.025 to 1.5% by weight, most preferably 0.05 to 1% by weight, in each case based on 100% by weight of component F).

[0181] The glass fibers preferably used as component F) may be shorter in the composition as a result of processing to give the thermoplastic molding composition than the glass fibers originally used. The arithmetic mean length of the glass fibers after processing is therefore often only in the range of 150 μm to 300 μm, as determined by high-resolution X-ray computed tomography.

[0182] Those skilled in the art will distinguish between different types of glass fibres, some of which are listed here by way of example (https: / / polser.com / en / frp / fibreglass-types). [Table 1]

[0183] Glass fibers in the form of E-glass are particularly preferred. They can be used as rovings or commercially available chopped glass, with suitable rovings and chopped glass fibers being described above. The E-glass fibers are modified with a suitable size system or adhesion promoter / adhesion promoter system. To improve compatibility with thermoplastics, it is preferred to use a silane-based size system or adhesion promoter. Suitable silane compounds are described above.

[0184] Further, as component F), a d in the range of 5 to 250 μm, preferably in the range of 10 to 150 μm, more preferably in the range of 15 to 80 μm, most preferably in the range of 16 to 25 μm, determined by laser diffraction measurement according to ISO 13320. 90 It is possible to use non-fibrous and non-foamed ground glass having a particle size distribution having a 90 Regarding the values, their determination and their significance, see Chemie Ingenieur Technik (72) pp. 273-276, 3 / 2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which d 90 The value is the particle size (volume distribution) below which 90% of the particle mass falls.

[0185] According to the present invention, it is preferred if the non-fibrous and non-expanded ground glass has a particulate, non-cylindrical shape and a length to thickness ratio, determined by laser diffraction measurements according to ISO 13320, of less than 5, preferably less than 3, more preferably less than 2. It will be understood that a value of 0 is not possible.

[0186] Non-foamed and non-fibrous ground glass is further characterized in that it generally does not have a glass geometry typical of fibrous glass having a cylindrical or elliptical cross section with a length-to-diameter ratio (L / D ratio) greater than 5, as determined by laser diffraction measurements according to ISO 13320.

[0187] Non-foamed and non-fibrous ground glass is preferably obtained by grinding glass in a mill, preferably a ball mill, more preferably by subsequent sieving (sifting or sieving). In one embodiment, preferred starting materials for grinding non-fibrous and non-foamed ground glass for use as component F) also include glass waste, especially produced as an undesirable by-product and / or off-spec primary product (referred to as off-spec material) in the manufacture of glass products. These include waste glass, recycled glass, and broken glass, especially in the manufacture of window glass or bottle glass, and in the manufacture of glass containing fillers and reinforcing agents, especially in the form of molten glass. Although the glass may be colored, non-colored glass is preferred as the starting material for use as component F).

[0188] Component G) As component G), the thermoplastic molding composition contains 0 to 55% by weight, preferably 0 to 35% by weight, more preferably 0 to 25% by weight, of at least one flame retardant additive, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0189] If the thermoplastic molding composition comprises at least one flame retardant additive, said at least one flame retardant additive is present in an amount of 1 to 55% by weight, more preferably 2 to 35% by weight, most preferably 3 to 25% by weight, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0190] When component G) is present, the maximum amount of component A) is reduced by the minimum amount of component G), so that the total amount of components A) through H) is still 100% by weight.

[0191] It is also possible to use a mixture of two or more flame retardant additives.

[0192] Component G) is at least one halogen-free and / or at least one halogen-containing flame retardant, preferably phosphazenes, aliphatic or aromatic esters of phosphoric or polyphosphoric acids, metal phosphinates or phosphinates other than component B), bromine-containing flame retardants, chlorine-containing flame retardants, flame-retardant melamine compounds, benzoguanidine compounds or salts thereof, allantoin compounds or salts thereof, glycoluril or salts thereof, cyanoguanidine, metal oxides such as antimony trioxide, antimony pentoxide and / or sodium antimonate, phosphorus such as red phosphorus, dicarboxylic acids of the formula [ka] (In the formula, R 1 ~R 4 represent, independently of one another, halogen or hydrogen, provided that at least one radical R 1 ~R 4 represents a halogen, x=1 to 3, preferably 1 or 2; m=1 to 9, preferably 1 to 3, 6, or 9, particularly 1 to 3; n=2 to 3, M = alkaline earth metals, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg), and functional polymers comprising 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeat units and poly(2,6-dimethyl-1,4-phenylene oxide) (PPPO).

[0193] As component G), the thermoplastic molding material can, for example, comprise 1.0 to 10.0% by weight, preferably 2.0 to 6.0% by weight, in particular 3.0 to 5.0% by weight, of at least one phosphazene of the general formula (IX) or (X) as flame retardant.

[0194] The minimum amount of this component G), if present, is at least 1.0% by weight, preferably 2.0% by weight, especially 3.0% by weight.

[0195] The maximum amount of this component G) is 10.0% by weight, preferably 6.0% by weight, particularly preferably 5.0% by weight.

[0196] "Phosphazene" refers to a cyclic phosphazene of the general formula (IX): [ka] (wherein m is an integer of 3 to 25, and R 4 and R 4’ are the same or different, C1 to C 20 -Alkyl-, C6-C 30 -Aryl-, C6-C 30 -Arylalkyl- or C6-C 30 -representing alkyl-substituted aryl) or a linear phosphazene of general formula (X): [ka] (wherein n represents 3 to 1000, X represents -N=P(OPh)3 or -N=P(O)OPh, and Y represents -P(OPh)4 or -P(O)(OPh)2.) should be understood to mean

[0197] The preparation of such phosphazenes is described in EP-A-0945478.

[0198] Formula (XI) of the formula P3N3C 36 Cyclic phenoxyphosphazene [ka] or a linear phenoxyphosphazene according to formula (XII) [ka] is particularly preferred.

[0199] The phenyl radical may be optionally substituted. Phosphazenes in the context of the present application are described in Mark, JE, Allcock, HR, West, R., Inorganic Polymers, Prentice Hall, 1992, pages 61 to 141.

[0200] Preferably used as component G) are cyclic phenoxyphosphazenes having at least three phenoxyphosphazene units. Corresponding phenoxyphosphazenes are described, for example, in US Patent Application Publication No. 2010 / 0261818, paragraphs

[0051] to

[0053] . In particular, reference may be made to formula (I) therein. Corresponding cyclic phenoxyphosphazenes are further described in EP Patent Application Publication No. 2100919, in particular in paragraphs

[0034] to

[0038] . Preparation can be carried out as described in EP Patent Application Publication No. 2100919, paragraph

[0041] . In one embodiment of the present invention, the phenyl group in the cyclic phenoxyphosphazene is C 1~4 - alkyl radicals. Preference is given to the case where pure phenyl radicals are involved.

[0201] For further description of cyclic phosphazenes, see Römpp Chemie Lexikon, 9th ed., keyword "phosphazene". Preparation is carried out, for example, via cyclophosphazene obtained from PCl5 and NH4Cl, in which the chlorine group is replaced by a phenoxy group by reaction with phenol.

[0202] Cyclic phenoxyphosphazene compounds can be prepared, for example, as described in Allcock, H.R., Phosphorus-Nitrogen Compounds (Academic Press, 1972), and Mark, J.E., Allcock, H.R., West, R., Inorganic Polymers (Prentice Hall, 1992).

[0203] Component G) is preferably a mixture of cyclic phenoxyphosphazenes having three and four phenoxyphosphazene units. The weight ratio of rings containing three phenoxyphosphazene units to rings containing four phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may be present as well, but in smaller amounts. A suitable cyclic phenoxyphosphazene is available from Fushimi Pharmaceutical Co., Ltd. under the name Rabitle® FP-100. It is a matte white / yellowish solid with a melting point of 110°C, a phosphorus content of 13.4%, and a nitrogen content of 6.0%. The proportion of rings containing three phenoxyphosphazene units is at least 80.0% by weight.

[0204] The thermoplastic molding composition can contain, for example, 1.0 to 6.0% by weight, preferably 2.5 to 5.5% by weight, in particular 3.0 to 5.0% by weight, of at least one aliphatic or aromatic ester of phosphoric or polyphosphoric acid as flame retardant.

[0205] In this case, particularly solid, non-migrating phosphate esters with a melting point between 70°C and 150°C are preferred. This results in a product that is easy to measure and has significantly less migration in the molding compound. Particularly preferred examples are commercially available phosphate esters, such as PX-200 (CAS: 139189-30-3) manufactured by Daihachi, or Sol-DP manufactured by ICL-IP. Further phosphate esters with appropriate substitution of the phenyl group are conceivable if this allows the desired melting range to be achieved. The general structural formula, depending on the substitution pattern at the ortho- or para-position on the aromatic ring, is as follows: [ka] or [ka] or [ka] During the ceremony, R 1=H, methyl, ethyl or isopropyl, but preferably H. n=0 to 7, preferably 0. R 2~6 =H, methyl, ethyl or isopropyl, but preferably methyl. 6 is R 4 and R 5 It is preferably the same as m=may be, but need not be, the same and is between 1, 2, 3, 4 and 5, but is preferably 2. R"= can be H, methyl, ethyl or cyclopropyl, but is preferably methyl and H.

[0206] The PX-200 is given as a specific example. [ka]

[0207] It is particularly preferred if at least one aromatic ester of polyphosphoric acid is used, such as is available, for example, from Daihachi Chemical under the name PX-200.

[0208] Furthermore, as component G), the thermoplastic molding composition according to the invention can comprise, for example, 5.0 to 30.0% by weight, preferably 10.0 to 25.0% by weight, in particular 12.0 to 20.0% by weight, for example about 16.0% by weight, of at least one metal phosphinate or phosphinate salt, as described below as flame retardant.

[0209] A preferred example of a flame retardant for component G) is a metal phosphinate derived from a hypophosphorous acid other than component B). For example, a metal salt of hypophosphorous acid containing Mg, Ca, Al, or Zn as the metal can be used. Aluminum hypophosphite is particularly preferred here.

[0210] Phosphinates of formula (I) or / and diphosphinates of formula (II) or polymers thereof are also suitable, [ka] During the ceremony, R 1 , R 2 are identical or different and represent hydrogen, C1-C6-alkyl, linear or branched chain, and / or aryl; R 3 is C1~C 10 -Alkylene, straight or branched chain, C6-C 10 -arylene, -alkylarylene or -aryl-alkylene; M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base; m=1 to 4; n=1 to 4; x=1 to 4, preferably m=3 and x=3.

[0211] Preferably, R 1 , R 2 are the same or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

[0212] Preferably, R 3 represents methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

[0213] Particularly preferably, R 1 , R 2 is hydrogen, methyl, or ethyl, and M is Al, with Al hypophosphite being particularly preferred.

[0214] The preparation of phosphinate is preferably carried out by precipitating the corresponding metal salt from aqueous solution.However, phosphinate can also be precipitated in the presence of suitable inorganic metal oxide or sulfide (white pigment, such as TiO2, SnO2, ZnO, ZnS, SiO2) as support material.Therefore, this can obtain a surface-modified pigment that can be used as a laser-markable flame retardant for thermoplastic polyester.

[0215] It is preferred to use metal salts of substituted phosphinic acids in which, compared to hypophosphorous acid, one or two hydrogen atoms are replaced by phenyl, methyl, ethyl, propyl, isobutyl, or isooctyl, or the R'-CH-OH radical is replaced by R'-hydrogen, phenyl, or tolyl. The metals are preferably Mg, Ca, Al, Zn, Ti, or Fe. Aluminum diethylphosphinate (DEPAL) is particularly preferred.

[0216] For a description of phosphinates or diphosphinates, reference can be made to DE-A-19960671 as well as DE-A-4430932 and DE-A-19933901.

[0217] Further suitable flame retardants are, for example, halogen-containing flame retardants.

[0218] Suitable halogen-containing flame retardants are preferably brominated compounds, such as brominated diphenyl ether, brominated trimethylphenylindane (FR 1808 from DSB) tetrabromobisphenol A and hexabromocyclododecane.

[0219] Further suitable brominated flame retardants have the structure [ka] and brominated oligocarbonate (BC 52 or BC 58 from Great Lakes) having the formula:

[0220] Particularly relevant is the formula, [ka] where n>4.

[0221] Preferred brominated compounds include those of the formula: [ka] Further included are oligomeric reaction products (n>3) of tetrabromobisphenol A with epoxides having the formula: (e.g., FR 2300 and 2400 from DSB).

[0222] Brominated oligostyrenes preferably used as flame retardants have an average degree of polymerization (number average) of 3 to 90, preferably 5 to 60, as measured by vapor pressure osmometry in toluene. Cyclic oligomers are also suitable. In a preferred embodiment of the present invention, the brominated oligomeric styrene has formula I shown below, where R represents hydrogen or an aliphatic radical, in particular an alkyl radical, such as CH2 or C2H5, and n represents the number of repeating chain building blocks. R 1 may be H, or bromine, or a fragment of a conventional free radical former. [ka]

[0223] The value n can be 1 to 88, preferably 3 to 58. The brominated oligostyrene contains 40.0 to 80.0% by weight, preferably 55.0 to 70.0% by weight, of bromine. Products consisting primarily of polydibromostyrene are preferred. These materials are meltable without decomposition and are soluble, for example, in tetrahydrofuran. They can be prepared by cyclic bromination of optionally aliphatically hydrogenated styrene oligomers, such as those obtained by thermal polymerization of styrene (DT-OS 25 37 385), or by free-radical oligomerization of suitable brominated styrenes. Flame retardants can also be prepared by ionic oligomerization of styrene followed by bromination. The amount of brominated oligostyrene required to impart flame retardancy to polyamides depends on the bromine content. The bromine content in the molding materials according to the present invention is generally 2.0 to 30.0% by weight, preferably 5.0 to 12.0% by weight.

[0224] The brominated polystyrene according to the invention is typically obtained by the process described in EP-A-047549. [ka]

[0225] The commercially available brominated polystyrenes obtained by this method are primarily ring-substituted tribrominated products, with n' (see III) generally having a value of 125 to 1500, which corresponds to a molecular weight of 42,500 to 235,000, preferably 130,000 to 135,000.

[0226] The bromine content (based on the content of ring-substituted bromine) is generally at least 50.0% by weight, preferably at least 60.0% by weight, especially 65.0% by weight.

[0227] Commercially available powder products generally have glass transition temperatures between 160°C and 200°C and are available, for example, from Albemarle under the designation SAYTEX® HP-7010 and from Ferro Corporation under the designation Pyrocheck® PB 68.

[0228] Mixtures of brominated oligostyrenes and brominated polystyrenes can also be used in the molding compositions according to the invention, the mixing ratio being freely selectable.

[0229] Suitable halogen-containing flame retardants are preferably ring-brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxide oligomer or brominated bisphenol A polycarbonate.

[0230] Chlorine-containing flame retardants are also suitable, with Declorane Plus® manufactured by OxyChem being preferred.

[0231] In one embodiment of the present invention, no halogen-containing flame retardants are used in the thermoplastic molding compositions according to the invention.

[0232] Flame-retardant melamine compounds suitable as component G) in the context of the present invention are melamine compounds which, when added to glass-fiber-filled polyamide molding compositions, reduce the flammability and influence the burning behavior in a flame-retardant manner, thus leading to improved properties in the UL 94 test and the glow-wire test.

[0233] The melamine compound is for example selected from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon or melamine cyanurate or mixtures thereof.

[0234] Melamine cyanurates which are preferentially suitable according to the invention are reaction products of preferably equimolar amounts of melamine (formula I) and cyanuric acid / isocyanuric acid (formulas Ia and Ib).

[0235] [ka]

[0236] This can be obtained, for example, by reacting an aqueous solution of the starting compound at 90 to 100°C. 50 is 1.5 to 7 μm, d 99 It is a white powder with a particle size of less than 50 μm.

[0237] Further suitable compounds (often also referred to as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, primary phosphate, secondary phosphate and secondary pyrophosphate, melamine neopentyl glycol borate. According to the invention, the molding material preferably does not contain polymeric melamine phosphate (CAS numbers 56386-64-2 or 218768-84-4).

[0238] This should be understood to mean polyphosphate melamine salts of 1,3,5-triazine compounds having an average condensation degree n of 20 to 200 and a 1,3,5-triazine content of 1,3,5-triazine compounds selected from the group consisting of melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, and diaminophenyltriazine of 1.1 to 2.0 moles per mole of phosphorus atom. Preferably, the n value of such salts is generally 40 to 150, and the ratio of 1,3,5-triazine compounds per mole of phosphorus atom is preferably 1.2 to 1.8. Furthermore, the pH of a 10 wt. % aqueous slurry of the salts prepared according to EP 1095030 is generally above 4.5, preferably at least 5.0. The pH is typically determined by adding 25 g of salt and 225 g of clean water to a 300 ml beaker at 25° C., stirring the resulting aqueous slurry for 30 minutes, and then measuring the pH. The n value, or number-average degree of condensation, can be determined by P solid-state NMR. J.R. van Wazer, C.F. Callis, J. Shoolery, and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956, discloses that the number of adjacent phosphate groups confers unique chemical shifts that allow clear differentiation between orthophosphates, pyrophosphates, and polyphosphates.

[0239] Suitable guanidine salts are: CAS number Guanidine carbonate 593-85-1 Guanidine cyanurate prim. 70285-19-7 Guanidine phosphate prim. 5423-22-3 Guanidine phosphate sec. 5423-23-4 Guanidine sulfate prim. 646-34-4 Guanidine sulfate sec. 594-14-9 Guanidine pentaerythritol borate sodium Guanidine neopentyl glycol borate sodium and Urea Phosphate Green 4861-19-2 Urea cyanurate 57517-11-0 Ammeline 645-92-1 Ammelide 645-93-2 Melem 1502-47-2 Melon 32518-77-7

[0240] In the context of the present invention, "compound" should be understood to mean, for example, benzoguanamine itself and its adducts / salts, but also nitrogen-substituted derivatives and its adducts / salts.

[0241] Ammonium polyphosphate (NH4PO3) n wherein n is about 200 to 1000, preferably 600 to 800, and tris(hydroxyethyl)isocyanurate (THEIC) of formula IV [ka] or aromatic carboxylic acids Ar(COOH), which may be present in mixture with one another. m Also suitable are their reaction products with: wherein Ar represents a mono-, bi- or tricyclic aromatic six-membered ring system and m is 2, 3 or 4.

[0242] Examples of suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, prenitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acid, and anthracenecarboxylic acid.

[0243] The preparation is carried out according to the method of EP-A-584567 by reaction of tris(hydroxyethyl)isocyanurate with an acid, its alkyl ester or its halide.

[0244] Such reaction products are mixtures of monomeric and oligomeric esters, which may be crosslinked. The degree of oligomerization is typically from 2 to about 100, preferably from 2 to 20. The reaction products of THEIC and / or its reaction products with phosphorus-containing nitrogen compounds, especially (NH4PO3) n Alternatively, it is preferable to use a mixture of melamine pyrophosphate or polymeric melamine phosphate. For example, (NH4PO3) n The mixing ratio of THEIC is preferably 90.0-50.0:10.0-50.0, particularly 80.0-50.0:50.0-20.0% by weight based on the mixture of such compounds.

[0245] Also suitable flame retardants are benzoguanidine compounds of formula V: [ka] In the formula, R, R' represent a linear or branched alkyl radical having 1 to 10 carbon atoms, preferably hydrogen, in particular its adducts with phosphate, borate and / or pyrophosphate.

[0246] Allantoin compounds of formula VI and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid, [ka] (wherein R and R′ are as defined in Formula V). and glycolurils of formula VII or salts thereof with the above acids. [ka] wherein R is as defined in Formula V. is also preferred.

[0247] Suitable products are commercially available or available according to DE-A 196 14 424.

[0248] Cyanoguanidines (formula VIII) that can be used according to the invention can be obtained, for example, by reacting calcium cyanamide with carbonic acid and dimerizing the resulting cyanamide at pH 9 to pH 10 to give cyanoguanidine.

[0249] [ka]

[0250] The commercially available product is a white powder with a melting point of 209°C to 211°C.

[0251] It is particularly preferred to use melamine cyanurate (for example Melapur® MC25 from BASF SE).

[0252] Additionally, it is possible to use separate metal oxides such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides. For a description of pentabromobenzyl acrylate and antimony trioxide or antimony pentoxide, reference can be made to EP-A-0 624 626.

[0253] It is also possible to use phosphorus, for example red phosphorus, as a flame retardant, which can be used, for example, in the form of a masterbatch.

[0254] formula [ka] Also contemplated are dicarboxylic acids of the formula: During the ceremony, R 1 ~R 4 represent, independently of one another, halogen or hydrogen, provided that at least one radical R 1 ~R 4 represents a halogen, x=1 to 3, preferably 1 or 2; m=1 to 9, preferably 1 to 3, 6, or 9, particularly 1 to 3; n=2 to 3, M = alkaline earth metals, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg.

[0255] Preferred dicarboxylates are those containing the radical R 1 ~R 4 as radicals R independently of one another contain Cl or bromine or hydrogen, particularly preferably all radicals R 1 ~R 4 is Cl or / and Br.

[0256] The metal M is preferably Be, Mg, Ca, Sr, Ba, Al, Zn, or Fe.

[0257] Such dicarboxylates are commercially available or can be prepared according to the methods described in US Pat. No. 3,354,191.

[0258] Functional polymers can also be used as component G). These may be, for example, flame-retardant polymers. Such polymers are described, for example, in U.S. Pat. No. 8,314,202 and contain 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeating units. A further suitable functional polymer for increasing the amount of carbon residue is poly(2,6-dimethyl-1,4-phenylene oxide) (PPPO).

[0259] Component H) As component H), the thermoplastic molding composition contains 0 to 25% by weight, preferably 0 to 20% by weight, more preferably 0 to 15% by weight, of at least one further additive, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0260] If further additives are used, the minimum amount is preferably 0.1 wt %, more preferably 0.25 wt %, most preferably 0.4 wt %.

[0261] When component H) is present, the maximum amount of component A) is reduced by the minimum amount of component H), so that the total amount of components A) through H) is still 100% by weight.

[0262] It is also possible to use a mixture of two or more additives.

[0263] The thermoplastic molding compositions of the invention can comprise as component H) conventional processing aids, further stabilizers, oxidation retardants, agents for counteracting thermal and UV degradation, lubricants and mold release agents, colorants other than those mentioned as component D), nucleating agents, plasticizers, elastomeric polymers, etc.

[0264] The molding composition according to the invention may contain, as component H1), 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, in particular 0.1 to 1% by weight, of at least one lubricant.

[0265] Preference is given to salts of Al, alkali metals or alkaline earth metals, or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably 12 to 44 carbon atoms.

[0266] The metal ions are preferably alkaline earth metals and Al or Zn, with Ca being particularly preferred.

[0267] Preferred metal salts are calcium stearate and calcium montanate, and aluminum distearate.

[0268] It is also possible to use mixtures of different salts in any desired mixing ratio.

[0269] The carboxylic acids may be monobasic or dibasic. Examples of carboxylic acids 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 also montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0270] The aliphatic alcohol may be monohydric to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.

[0271] The fatty amines may be monobasic to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are, correspondingly, glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

[0272] It is also possible to use mixtures of different esters or amides, or mixtures of esters and amides, combined in any desired ratio.

[0273] As component H2), the molding materials according to the invention may preferably comprise from 0.01% to 3% by weight, particularly preferably from 0.02 to 2% by weight, in particular from 0.05 to 1.0% by weight, of at least one heat stabilizer, based on the total weight of the composition.

[0274] The heat stabilizer is preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites and mixtures thereof.

[0275] As component H2) 0.05 to 3% by weight, preferably 0.1 to 2% by weight, in particular 0.1 to 1% by weight of at least one sterically hindered phenol antioxidant can be used.

[0276] This component H2) preferably has a molecular weight of more than 500 g / mol, more preferably more than 1000 g / mol. Furthermore, component H should preferably exhibit high thermal stability, for example a maximum weight loss of 5%, more preferably a maximum weight loss of 2%, measured at 300°C under nitrogen in a TGA (thermogravimetric analysis) experiment (40°C to 120°C at 10°C / min, isothermal at the latter temperature for 15 minutes, followed by 120°C to 600°C at 20°C / min).

[0277] Component H2) preferably contains at least one branched C 3~12 -has at least one, more preferably at least two phenolic groups substituted with alkyl groups, the substituted phenolic groups being covalently bonded to the structure of component H2).

[0278] Suitable sterically hindered phenols H2) are in principle all compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring. The bulky group can be, for example, a branched C 3~12 - alkyl group, preferably branched C 3~6 -alkyl group, more preferably an isopropyl or tert-butyl group.

[0279] For example, the expression [ka] It is preferred to use a compound of the formula During the ceremony, R 1 and R 2 is an alkyl group, a substituted alkyl group, or a substituted triazole group, and the radical R 1 and R 2 may 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. R 1 ~R 3 At least one of the is preferably a bulky group as defined above.

[0280] Antioxidants of the above type are described, by way of example, in DE-A-2 702 661 (US Pat. No. 4,360,617).

[0281] Another group of preferred sterically hindered phenols is provided by those derived from substituted phenylcarboxylic acids, in particular substituted phenylpropionic acids, which preferably have at least one bulky group on the phenyl group, and which contain at least one, preferably two, covalently bonded substituted phenylcarboxylic acid units in their structure, and which preferably have at least one bulky group on the phenyl group.

[0282] Preferred phenylcarboxylic acids are phenyl-C 1~12 -carboxylic acid, more preferably phenyl-C 2~6 The phenyl group is preferably a phenol group having at least one bulky group on the phenol ring, as described above. Therefore, the sterically hindered phenol is preferably a C 1~12 -alkanecarboxylic acids, more preferably linear C 2~6 -Covalently bonded to alkanecarboxylic acids.

[0283] Particularly preferred compounds of this class have the formula [ka] is a compound of In the formula, R 4 , R 5 , R 7 and R 8 are, independently of one another, optionally substituted C1-C8 alkyl groups (at least one of which is a bulky group), and R 6 R is a divalent aliphatic radical having 1 to 10 carbon atoms, the main chain of which may also have a CO bond.4 ~R 8 At least one of is a bulky group as defined above.

[0284] Preferred compounds corresponding to these formulas are: [ka] (Irganox® 245 from BASF SE) [ka] (Irganox® 259 manufactured by BASF SE).

[0285] Examples of sterically hindered phenols include all of the following:

[0286] 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010 from BASF SE), distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 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-distearylthiotriazylamine, 2-(2'-hydroxy-3' -hydroxy-3',5'-di-tert-butylphenyl)-5-chloro-benzotriazole, 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.

[0287] Compounds which have proven 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 (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate] and also N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098) and the above-mentioned products Irganox® 245 and Irganox® 1010 from BASF SE, which have particularly good compatibility.

[0288] In some cases, sterically hindered phenols having one or less sterically hindering group ortho to the phenolic hydroxy group have been found to be particularly advantageous, especially when assessing colorfastness on storage in diffuse light over extended periods of time.

[0289] Furthermore, it is advantageous to use sterically hindered phenolic antioxidants that have a sufficiently high molecular weight, preferably above 500 g / mol, especially above 1000 g / mol, and that preferably also exhibit high thermal stability with less than 2% decomposition up to 300°C under nitrogen atmosphere, as measured by TGA (thermogravimetric analysis).

[0290] The molding composition of the invention may comprise, as component H2), 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, in particular 0.1 to 1% by weight, of at least one copper stabilizer, preferably a Cu(I) halide, in particular in a mixture with an alkali metal halide, preferably KI, in particular in a ratio of 1:4, or a sterically hindered phenol, or a mixture thereof.

[0291] Preferred salts of monovalent copper used are cuprous acetate, cuprous chloride, cuprous bromide and cuprous iodide, which the material contains in an amount of 5 to 500 ppm, preferably 10 to 250 ppm, of copper, based on the polyamide.

[0292] Advantageous properties are particularly obtained when copper is present in a molecular distribution in the polyamide. This is achieved when 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. For example, a typical concentrate consists of 79-95 wt. % polyamide and 21-5 wt. % copper iodide or a mixture of copper bromide and potassium iodide. The copper concentration in the solid homogeneous solution is preferably 0.3-3 wt. %, more preferably 0.5-2 wt. %, based on the total weight of the solution. The molar ratio of cuprous iodide to potassium iodide is 1-11.5, preferably 1-5.

[0293] Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular PA6.

[0294] According to a preferred embodiment of the present invention, the molding composition does not contain copper, in particular copper stabilizers such as Cu / (I) halides, and combinations of Cu(I) halides with alkali metal halides.

[0295] More preferably, the thermoplastic molding composition of the present invention is free of metal halides.Metal halide-free systems, so-called electricity-friendly systems, are of great interest due to the increasing trend towards electric mobility, electrification and connections in almost all industries.

[0296] Therefore, the thermoplastic molding composition is preferably free of metal halides, in particular Cu halides and alkali metal halides.

[0297] UV stabilizers that may be mentioned as component H3) are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, the amount of which is generally up to 2% by weight, based on the molding composition. Nigrosine can also be used.

[0298] Materials which can be used as nucleating agents, component H4), are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and preferably talc.

[0299] The molding composition of the invention may contain, as component H5), 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight of at least one plasticizer.

[0300] Suitable plasticizers are described in Kunststoff-Handbuch, Band VI Polyamide, Carl Hanser Verlag Munchen 1966, section 3.4.2.1.b), pages 238 and 239, in connection with Table 7. They can be divided into aromatic hydroxy compounds, sulfonamides, and further plasticizers such as lactams, lactones, alcohols, etc.

[0301] Suitable plasticizers include, for example, poly(trimethylene ether) glycol (PPD), preferably having a number average molecular weight of 255, and poly(trimethylene ether) glycol benzoate (PPDB), N-butylbenzenesulfonamide (NBBS), polyethylene glycol dibenzoate (M n =410), poly(1,2-propylene glycol) dibenzoate (M n =400), monomeric amides, specifically sulfonamides, such as N-alkylarylsulfonamides, p-alkylbenzenesulfonamides and guanidine-based compounds, mixtures of lactam compounds and polyethylene glycols, aromatic esters of poly(trimethylene ether) glycols having a number average molecular weight of 1000 or less, or compounds of general formula (1).

[0302] R1-O-(CH2CH2-O-) n R2(1) In the formula, n=1 to 10, R1 and R2 are independently H, C 1~12 - alkyl, phenyl or tolyl, It has a boiling point above 250°C.

[0303] Preferred plasticizers of general formula (1) are based on triethylene glycol, tetraethylene glycol, pentaethylene glycol or mixtures thereof. Tetraethylene glycol is most preferred. Thus, n most preferably has a value between 3.8 and 4.2, most preferably 4.

[0304] 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. Therefore, in a preferred embodiment, the thermoplastic molding composition contains a compound of formula (1) as a plasticizer when a plasticizer is present as component H5).

[0305] As component H6), the molding composition according to the invention can contain 1 to 45% by weight, preferably 2 to 40% by weight, of at least one elastomeric polymer.

[0306] Component H6) can be selected from all elastomeric polymers, impact modifiers, elastomers or rubbers suitable for polyamide molding compositions.

[0307] Preferably, component H6) is b1) ethylene as component B1); C 3~12 -olefins, C 1~12 copolymers with at least one comonomer selected from alkyl (meth)acrylates, (meth)acrylic acid and maleic anhydride, b2) Polyethylene or polypropylene as component B2) is selected from Components B1) and B2) may be further grafted with maleic anhydride, preferably from ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butyl acrylate copolymer, copolymers of ethylene and / or propylene with maleic anhydride and mixtures thereof.

[0308] These elastomeric polymers (often also called impact modifiers, elastomers, or rubbers) are very common copolymers, preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and acrylates and / or methacrylates having 1 to 18 carbon atoms in the alcohol component.

[0309] Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, vol. 14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pages 392 to 406, and in the monograph by C.B. Bucknall, Toughened Plastics (1977, Applied Science Publishers, London, UK).

[0310] Examples of suitable elastomers are available from Lyondellbasell under the names Lucalen A2540D and Lucalen A2700M. Lucalen A2540D is a low density polyethylene with butyl acrylate comonomer. It has a density of 0.923 g / cm at a butyl acrylate proportion of 6.5 wt. %. 3 It has a density of 10.2g, a Vicat softening temperature of 85°C and a melting temperature of 103°C.

[0311] Lucalen A2700M is a low density polyethylene that also contains butyl acrylate comonomer. It has a density of 0.924 g / cm 3 It has a density of 1000, a Vicat softening temperature of 60°C, and a melting temperature of 95°C.

[0312] Exxelor™ VA 1801 polymer resin from ExxonMobil is a semi-crystalline ethylene copolymer with medium viscosity functionalized with maleic anhydride by reactive extrusion. The polymer backbone is fully saturated. The density is 0.880 g / cm. 3 The proportion of maleic anhydride is typically in the range of 0.5 to 1.0% by weight.

[0313] Carbon black or nigrosine may be used, for example, as a colorant other than those listed under D) and E).

[0314] As component H7), the inventive molding composition can comprise 0.1 to 3% by weight, preferably 0.2 to 2.5% by weight, of at least one flow promoter, based on the total amount of components A), B), C), optionally D), optionally E), optionally F), optionally G) and optionally H).

[0315] Examples of suitable flow promoters are macromolecules such as polymers containing branched, hyperbranched or dendritic moieties, typically functional groups such as -NH2, -OH, -COOH or -COOCH3.

[0316] The polymer may be, for example, a polyamide-based polymer or a polyester.

[0317] Examples are CYD-701, CYD-C600, CYD-819, CYD-816A (all Weihai CY Dendrimer Technology Co, Ltd.), Hyper C100 (Wuhan HyperBranched Polymers Science Technology Co., Ltd.), TER-PA9 manufactured by TER HELL & Co. GmbH, and Bruggolen TP-P1507 and TP-P1810 manufactured by L. Brueg-ge-mann GmbH & Co. KG.

[0318] Dendrimers consist of two types of structural units: terminal units on the spherical surface and dendritic units in the interior. Dendrimers are therefore structurally well-defined. Hyperbranched polymers, on the other hand, have three types of structural units: dendritic units, linear units, and terminal units. While terminal units are always located at the ends, dendritic and linear units are randomly distributed within the polymer framework, resulting in an irregular structure.

[0319] composition The compositions according to the invention are characterized by a very high color stability, especially at high temperatures, which is obtained by using a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate (component B)) and ii) at least one polyamide 6I / 6T (component C)).

[0320] The weight ratio of component B) to component C) is preferably 1:15-100, more preferably 1:20-90, and most preferably 1:22-80.

[0321] The thermoplastic molding composition of the present invention therefore a) as component A), 10 to 99.98 wt. %, preferably 20 to 85 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component C), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA 66 / 6 and / or PA 6 / 6.36; b) as component B), 0.01 to 0.5 wt. %, preferably 0.06 to 0.45 wt. %, more preferably 0.1 to 0.4 wt. % of at least one of sodium hypophosphite or sodium hypophosphite hydrate; c) as component C), 0.01 to 20 wt. %, preferably 0.1 to 18 wt. %, more preferably 1 to 17 wt. %, most preferably 3 to 16 wt. % of at least one polyamide 6I / 6T, preferably in which the molar ratio of 6I units to 6T units in the polyamide 6I / 6T is in the range of 1:1 to 3:1, more preferably in the range of 1.5:1 to 2.5:1, most preferably in the range of 1.8:1 to 2.3:1; d) as component D), 0 to 5% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.5 to 2.5% by weight of a colorant or a mixture of two or more colorants, preferably an orange colorant or a mixture of two or more colorants which produces an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produces an orange color, having shades corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably having shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system, e) as component E), 0 to 5 wt. %, preferably 0.1 to 3.5 wt. %, more preferably 0.5 to 2.5 wt. % of at least one laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably at least one pigment system comprising antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof; f) as component F), 0 to 60% by weight, preferably 10 to 55% by weight, more preferably 15 to 50% by weight of at least one fibrous and / or particulate filler, preferably glass fibers, more preferably modified with a size system or an adhesion promoter / adhesion promoter system, and most preferably modified with a silane-based size system or an adhesion promoter / adhesion promoter system; g) as component G), 0 to 55 wt. %, preferably 1 to 35 wt. %, more preferably 2 to 25 wt. % of at least one flame retardant additive; h) as component H), 0 to 25 wt. %, preferably 0.1 to 20 wt. %, more preferably 0.25 to 15 wt. % of at least one further additive; Including, The total weight percentages of components A) to H) is 100% by weight.

[0322] Suitable and preferred components A), B), C), D), E), F), G) and H) and the amounts of said components in the thermoplastic molding composition of the invention are described above.

[0323] The thermoplastic molding compositions of the invention are either filled compositions, i.e. compositions comprising 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 20 to 50% by weight, of at least one fibrous and / or particulate filler as component F), or unfilled compositions, i.e. compositions comprising 0% by weight of fibrous and / or particulate filler as component F).

[0324] In one embodiment, the thermoplastic molding composition of the present invention comprises: a) as component A), 10 to 89.98 wt. %, preferably 20 to 85 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component C), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA 66 / 6 and / or PA 6 / 6.36; b) as component B), 0.01 to 0.5 wt. %, preferably 0.06 to 0.45 wt. %, more preferably 0.1 to 0.4 wt. % of at least one of sodium hypophosphite or sodium hypophosphite hydrate, preferably sodium hypophosphite; c) as component C), 0.01 to 20 wt. %, preferably 0.1 to 18 wt. %, more preferably 1 to 17 wt. %, most preferably 3 to 16 wt. % of at least one polyamide 6I / 6T, preferably having a molar ratio of 6I units to 6T units in the polyamide 6I / 6T in the range of 1:1 to 3:1, more preferably in the range of 1.5:1 to 2.5:1, most preferably in the range of 1.8:1 to 2.3:1, d) as component D), 0 to 5% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.5 to 2.5% by weight of a colorant or a mixture of two or more colorants, preferably an orange colorant or a mixture of two or more colorants which produces an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produces an orange color, having shades corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably having shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system, e) as component E), 0 to 5 wt. %, preferably 0.1 to 3.5 wt. %, more preferably 0.5 to 2.5 wt. % of at least one laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably at least one pigment system comprising antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof; f) as component F), 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 20 to 50% by weight of at least one fibrous and / or particulate filler, preferably glass fibers, more preferably modified with a size system or an adhesion promoter / adhesion promoter system, and most preferably modified with a silane-based size system or an adhesion promoter / adhesion promoter system; g) as component G), 0 to 55 wt. %, preferably 1 to 35 wt. %, more preferably 2 to 25 wt. % of at least one flame retardant additive; h) as component H), 0 to 25 wt. %, preferably 0.1 to 20 wt. %, more preferably 0.25 to 15 wt. % of at least one further additive; Including, The total weight percentage of components A) to H) is 100% by weight. It is a filling composition.

[0325] Suitable and preferred components A), B), C), D), E), F), G) and H) and the amounts of said components in the thermoplastic molding composition of the invention are described above.

[0326] Because of their color stability, especially at high temperatures, the thermoplastic molding compositions of the present invention are particularly useful for providing colored articles, preferably orange colored articles, used, for example, in providing high voltage systems.

[0327] Therefore, the composition of the thermoplastic molding composition of the present invention is more preferably a) as component A), 10 to 99.98 wt. %, preferably 20 to 85 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component C), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA 66 / 6 and / or PA 6 / 6.36; b) as component B), 0.01 to 0.5 wt. %, preferably 0.06 to 0.45 wt. %, more preferably 0.1 to 0.4 wt. % of at least one of sodium hypophosphite or sodium hypophosphite hydrate; c) as component C), 0.01 to 20 wt. %, preferably 0.1 to 18 wt. %, more preferably 1 to 17 wt. %, most preferably 3 to 16 wt. % of at least one polyamide 6I / 6T, preferably in which the molar ratio of 6I units to 6T units in the polyamide 6I / 6T is in the range of 1:1 to 3:1, more preferably in the range of 1.5:1 to 2.5:1, most preferably in the range of 1.8:1 to 2.3:1; d) as component D), 0.1 to 5% by weight, preferably 0.2 to 3.5% by weight, more preferably 0.5 to 2.5% by weight of a colorant or a mixture of two or more colorants, preferably an orange colorant or a mixture of two or more colorants which produces an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produces an orange color, having shades corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably having shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system, e) as component E), 0 to 5 wt. %, preferably 0.1 to 3.5 wt. %, more preferably 0.5 to 2.5 wt. % of at least one laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably at least one pigment system comprising antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof; f) as component F), 0 to 60% by weight, preferably 10 to 55% by weight, more preferably 15 to 50% by weight of at least one fibrous and / or particulate filler, preferably glass fibers, more preferably modified with a size system or an adhesion promoter / adhesion promoter system, and most preferably modified with a silane-based size system or an adhesion promoter / adhesion promoter system; g) as component G), 0 to 55 wt. %, preferably 1 to 35 wt. %, more preferably 2 to 25 wt. % of at least one flame retardant additive; h) as component H), 0 to 25 wt. %, preferably 0.1 to 20 wt. %, more preferably 0.25 to 15 wt. % of at least one further additive; Including, The total weight percentages of components A) to H) is 100% by weight.

[0328] Suitable and preferred components A), B), C), D), E), F), G) and H) and the amounts of said components in the thermoplastic molding composition of the invention are described above.

[0329] In one embodiment, the thermoplastic molding composition of the present invention comprises: a) as component A), 10 to 89.98 wt. %, preferably 20 to 85 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component C), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA 66 / 6 and / or PA 6 / 6.36; b) as component B), 0.01 to 0.5 wt. %, preferably 0.06 to 0.45 wt. %, more preferably 0.1 to 0.4 wt. % of at least one of sodium hypophosphite or sodium hypophosphite hydrate; c) as component C), 0.01 to 20 wt. %, preferably 0.1 to 18 wt. %, more preferably 1 to 17 wt. %, most preferably 3 to 16 wt. % of at least one polyamide 6I / 6T, preferably having a molar ratio of 6I units to 6T units in the polyamide 6I / 6T in the range of 1:1 to 3:1, more preferably in the range of 1.5:1 to 2.5:1, most preferably in the range of 1.8:1 to 2.3:1, d) as component D), 0.1 to 5% by weight, preferably 0.2 to 3.5% by weight, more preferably 0.5 to 2.5% by weight of a colorant or a mixture of two or more colorants, preferably an orange colorant or a mixture of two or more colorants which produces an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produces an orange color, having shades corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably having shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system, e) as component E), 0 to 5 wt. %, preferably 0.1 to 3.5 wt. %, more preferably 0.5 to 2.5 wt. % of at least one laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably at least one pigment system comprising antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof; f) as component F), 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 20 to 50% by weight of at least one fibrous and / or particulate filler, preferably glass fibers, more preferably modified with a size system or an adhesion promoter / adhesion promoter system, and most preferably modified with a silane-based size system or an adhesion promoter / adhesion promoter system; g) as component G), 0 to 55 wt. %, preferably 1 to 35 wt. %, more preferably 2 to 25 wt. % of at least one flame retardant additive; h) as component H), 0 to 25 wt. %, preferably 0.1 to 20 wt. %, more preferably 0.25 to 15 wt. % of at least one further additive; Including, The total weight percentage of components A) to H) is 100% by weight. It is a filled coloring composition.

[0330] Suitable and preferred components A), B), C), D), E), F), G) and H) and the amounts of said components in the thermoplastic molding composition of the invention are described above.

[0331] The thermoplastic molding compositions of the present invention can be prepared in a manner known per se by mixing the starting components A), B), C), and optionally D), optionally E), optionally F), optionally G), and optionally H) in conventional mixing equipment, such as a screw-based extruder, a Brabender mixer, or a Banbury mixer, and then extruding. After extrusion, the extrudate can be cooled and pelletized. It is also possible to premix the individual components and then add the remaining starting materials individually and / or in the form of a mixture. The barrel temperature is generally between 230 and 330°C.

[0332] Purpose These materials are suitable for the production of moldings, fibers, films and extrusions, preferably moldings, which are more preferably pigmented, most preferably orange pigmented.

[0333] The present invention therefore further relates to a molded or extruded article, preferably a molded article, more preferably a colored molded article, most preferably an orange-colored molded article made with the thermoplastic molding composition according to the invention or obtained by the process according to the invention.

[0334] The thermoplastic molding compositions of the present invention can be used in the electrical and electronic fields, for example, to produce plugs, plug parts, plug connectors, membrane switches, printed circuit board modules, microelectronic components, coils, I / O plug connectors, plugs for printed circuit boards (PCBs), plugs for flexible printed circuits (FPCs), plugs for flexible integrated circuits (FFCs), high-speed plug connections, terminal strips, connector plugs, device connectors, cable harness components, circuit mounts, circuit mount parts, three-dimensional injection molded circuit mounts, electrical connection elements, and mechatronic components.

[0335] Since the preferred thermoplastic molding compositions of the present invention are colored orange, the molded or extruded article is in one preferred embodiment a high-voltage component, in particular a high-voltage component of an electric vehicle, more preferably selected from the group consisting of electrical or electronic equipment covers, control devices, fuse covers / housings, relays, battery cell modules, fuse holders, fuse plugs, terminals, cable holders or sheaths, in particular sheaths for high-voltage busbars and high-voltage distributor busbars.

[0336] The method preferably comprises: i) mixing components A), B), C) and optionally D), optionally E), optionally F), optionally G) and optionally H); ii) extruding the composition obtained in step i) to obtain strands; iii) cooling the strands obtained in step ii) until they are pelletizable, pelletizing, and optionally drying; iv) subjecting the pelletized strands obtained in step iii) to further processing, preferably by extrusion methods including injection molding or profile extrusion; Includes.

[0337] The inventors have found that by using a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate and ii) at least one polyamide 6I / 6T, it is possible to obtain polyamide compositions with very high color stability, in particular at high temperatures.The present invention therefore further relates to the use of a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate and ii) at least one polyamide 6I / 6T for improving the color stability, in particular at high temperatures, of thermoplastic polyamide molding compositions comprising at least one polyamide different from polyamide 6I / 6T. [Example]

[0338] The following ingredients were used: Component A1: Polyamide-66 (Stabamid® 23 AE1-K from BASF SE) having a viscosity number of 120-128 ml / g, determined as a 0.5 wt. % solution in 96 wt. % sulfuric acid at 25°C according to ISO 307:2019 Component A2: Polyamide-66 (Ultramid® A24 from BASF SE) having a viscosity number of 115-135 ml / g, determined as a 0.5 wt. % solution in 96 wt. % sulfuric acid at 25°C according to ISO 307:2019 Component A3: Polyamide 6I / 6T (Grivory® G21 Natural from EMS) having a relative viscosity of 1.47 to 1.57, determined as a 0.5 wt. % solution in m-kresol at 20°C according to ISO 307:2019 Component B: Commercially available polyamide glass fiber (standard E glass fiber) with a length of 4.5 mm and a diameter of 10 μm Ingredient C: Commercially available calcium stearate (CAS: 1592-23-0) Component D1: Irganox® 1098 commercially available from BASF SE Ingredient D2: Commercially available sodium hypophosphite monohydrate (CAS: 10039-56-2) Component E: Pigment mixture to achieve RAL 2003 Component F: Exolit® OP 1400 commercially available from Clariant Plastics and Coatings (Deutschland) GmbH

[0339] Preparation of granules: The natural color polyamide granules were dried at 80°C to a moisture content of less than 0.1% by weight, and all other ingredients were premixed in a tumble mixer for 10 minutes. In the next step, the dried polyamide granules were melt extruded with the dry blended ingredients using a twin-screw extruder with a diameter of 25 mm and an L / D ratio of 44. The extruder was run for 240 minutes using a flat temperature profile. -1The machine was operated at a rotation speed of 1000 rpm, a throughput of 16 kg / h, and a cylinder temperature of 280°C-310°C. The resulting strand was cooled in a water bath and granulated. The resulting granules were injection molded in an injection molding machine at a melt temperature of 290°C and a tool temperature of 80°C. The yellowness index (YI) was calculated according to DIN 6167:1980 using a colorimeter with a 45°:0° geometry. Color difference ΔE* ab For the calculation of , the color was measured using a colorimeter, de:8° geometry (SCI: specular component included), according to DIN 53236:2018, method B. The calculation method used was in accordance with DIN EN ISO 11664-4:2012, i.e., that describing the CIE 1976 L*a*b* color space. L*=Lightness; +Lighter; -Darker a*=color component; +reddish; -greenish b* = color component; + yellowish; - blueish C* ab = Saturation (uncolored / colored); h ab = Hue angle (0~360°). By evaluating all of ΔL*, Δa* and Δb*, the color difference ΔE* ab occurs.

[0340] The results before and after heat treatment at 120°C for up to 1000 hours are shown in the table below: Heat aging experiments were carried out in a standard laboratory oven in air at elevated temperatures as shown in the table below. [Table 2] [Table 3] [Table 4] [Table 5]

[0341] The above examples show that superior results were obtained by using a combination of at least one of sodium hypophosphite and sodium hypophosphite hydrate with at least one polyamide 6I / 6T compared to the use of sodium hypophosphite alone.

Claims

1. a) as component A) 10 to 99.98 wt. % of at least one thermoplastic polyamide different from component C), b) as component B), 0.01 to 0.5 wt. % of at least one of sodium hypophosphite or sodium hypophosphite hydrate; c) as component C), 0.01 to 20% by weight of at least one polyamide 6I / 6T, d) as component D), 0 to 5% by weight of a colorant or a mixture of two or more colorants, preferably an orange colorant or a mixture of two or more colorants which produces an orange color, particularly preferably an orange colorant or a mixture of two or more colorants which produces an orange color, having shades which correspond to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011 in the RAL color system, very particularly preferably to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system, e) as component E), 0-5 wt. % of at least one laser marking additive, preferably a metal oxide or a mixture of two or more metal oxides, more preferably at least one pigment system comprising antimony trioxide, titanium dioxide, glimmer, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof; f) as component F), 0 to 60 wt. % of at least one fibrous and / or particulate filler; g) as component G), 0 to 55 wt. % of at least one flame retardant additive; h) as component H), 0 to 25% by weight of at least one further additive; Including, The sum of the weight percentages of components A) to H) is 100% by weight; Thermoplastic molding composition.

2. 2. The thermoplastic molding composition according to claim 1, wherein component A) is selected from aliphatic and semi-aromatic polyamides, preferably PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA 6 / 636, PA 610, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T and PA 6T / 66 and mixtures thereof, more preferably PA 6, PA 66, PA 66 / 6, PA 6 / 66, PA 6 / 636 and mixtures thereof, most preferably PA 6 and PA 66 and mixtures thereof.

3. 3. Thermoplastic molding composition according to claim 1, wherein the amount of component B) is from 0.06 to 0.45% by weight, preferably from 0.1 to 0.4% by weight.

4. 4. Thermoplastic molding composition according to claim 1, wherein component C) consists of units derived from hexamethylenediamine, terephthalic acid and isophthalic acid, preferably in a molar ratio of 6I units to 6T units in the range from 1:1 to 3:1, more preferably in the range from 1.5:1 to 2.5:1, particularly preferably in the range from 1.8:1 to 2.3:

1.

5. 5. The thermoplastic molding composition according to claim 1, wherein component D) is an orange colorant or a mixture of two or more colorants that produce an orange color, achieving a color tone that corresponds to color number RAL 2003 in the RAL color system.

6. Component F) is preferably selected from the group consisting of carbon fibers, glass beads, for example solid or hollow glass beads, glass fibers, powdered glass, amorphous quartz glass, borosilicate aluminum glass with an alkali content of about 1%, amorphous silica, quartz flour, alkaline earth metal silicates, in particular calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or crushed quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, hectorite, 6. The thermoplastic molding composition according to claim 1, wherein the thermoplastic polymer is selected from the group consisting of cellulose acetate, cellulose acetate, cellulose ether, cellulose ether, cellulose ether, cellulose ether, cellulose acetate ...

7. Component G) is at least one halogen-free and / or at least one halogen-containing flame retardant, preferably phosphazenes, aliphatic or aromatic esters of phosphoric or polyphosphoric acids, metal phosphinates or phosphinates, bromine-containing flame retardants, chlorine-containing flame retardants, flame-retardant melamine compounds, benzoguanidine compounds or salts thereof, allantoin compounds or salts thereof, glycoluril or salts thereof, cyanoguanidine, metal oxides such as antimony trioxide, antimony pentoxide and / or sodium antimonate, phosphorus such as red phosphorus, dicarboxylic acids of the formula 【Chemical 1】 (In the formula, R １ ~R ４ represent, independently of one another, halogen or hydrogen, provided that at least one radical R １ ~R ４ represents a halogen, x=1 to 3, preferably 1 or 2; m=1 to 9, preferably 1 to 3, 6, 9, in particular 1 to 3; n=2 to 3, M = alkaline earth metals, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg), and functional polymers comprising 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeat units and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), A thermoplastic molding composition according to any one of claims 1 to 6.

8. A method for producing a thermoplastic molding composition according to any one of claims 1 to 7, comprising the step of mixing components A), B), C) and optionally D), optionally E), optionally F), optionally G) and optionally H).

9. Use of the thermoplastic molding composition according to any one of claims 1 to 7 or obtained by the method according to claim 8 for producing more preferably coloured, most preferably orange-coloured, mouldings, fibres, films and extruded mouldings, preferably moulded articles.

10. A molded or extruded article made from a thermoplastic molding composition according to any one of claims 1 to 7 or obtained by the method according to claim 8.

11. 11. The molded or extruded article of claim 10 which is a high voltage component.

12. 12. The high voltage component according to claim 11, selected from the group consisting of covers for electrical or electronic equipment, control devices, covers / housings for fuses, relays, battery cell modules, fuse holders, fuse plugs, terminals, cable holders or sheaths, in particular sheaths for high voltage bus bars and high voltage distributor bus bars.

13. A method for producing a molded or extruded article as defined in any one of claims 10 to 12 by injection molding or extrusion of a thermoplastic molding composition as defined in any one of claims 1 to 7 or a thermoplastic molding composition obtained by the method as defined in claim 8.

14. i) mixing components A), B), C) and optionally D), optionally E), optionally F), optionally G) and optionally H); ii) extruding the composition obtained in step i) to obtain strands; iii) cooling the strands obtained in step ii) until they are pelletizable, pelletizing, and optionally drying; iv) subjecting the pelletized strands obtained in step iii) to further processing, preferably by extrusion methods including injection molding or profile extrusion; 14. The method of claim 13, comprising:

15. Use of a combination of i) at least one of sodium hypophosphite or sodium hypophosphite hydrate and ii) at least one polyamide 6I / 6T to improve the color stability of a thermoplastic polyamide molding composition comprising at least one polyamide different from polyamide 6I / 6T.

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