Thermoplastic moulding Composition-2 With Improved Color Stability

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) a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom and as component D) at least one acid scavenger; a process for producing the thermoplastic moulding composition according to the invention, comprising the step of mixing the components A), B), C) and D); the use of a thermoplastic moulding composition according to the invention for producing moulded articles, fibers, films and extruded articles, preferably moulded articles, which are more preferably coloured and which are most preferably orange; a molded or extruded article, the molded or extruded article being made from the thermoplastic molding composition of the present invention; the molded or extruded articles of the invention are high voltage components; a process for producing a molded or extruded article according to the invention by injection molding or extrusion of a thermoplastic molding composition according to the invention; the present invention relates to the use of a thermoplastic molding composition comprising i) at least one thermoplastic polyamide, ii) at least one of sodium hypophosphite or sodium hypophosphite hydrate, and at least one acid scavenger in a thermoplastic molding composition comprising i) at least one thermoplastic polyamide, ii) at least one of sodium hypophosphite or sodium hypophosphite hydrate, and iii) a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom.

Description

[0001] manual

[0002] The present invention relates to a thermoplastic molding composition comprising at least one thermoplastic polyamide as component A), at least one of sodium hypophosphite or sodium hypophosphite hydrate as component B), a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom as component C) and at least one acid scavenger as component D); a process for producing the thermoplastic molding composition of the invention, the process comprising the steps of mixing these components A), B), C) and D); the use of the thermoplastic molding composition of the invention for producing molded articles, fibers, films and extruded articles, preferably molded articles, the molded articles being more preferably colored and the The molded article is most preferably orange; a molded or extruded article made from the thermoplastic molding composition of the present invention; the molded or extruded article of the present invention is a high voltage component; a method for producing the molded or extruded article of the present invention by injection molding or extruding the thermoplastic molding composition of the present invention; and use of at least one acid scavenger in a thermoplastic molding composition for improving the odor of the thermoplastic molding composition, the thermoplastic molding composition comprising i) at least one thermoplastic polyamide, ii) at least one of sodium hypophosphite or sodium hypophosphite hydrate, and iii) a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom.

[0003] Among engineering plastics, polyamides are important materials, especially in the field of automotive applications, as these polyamides have good mechanical and electrical properties as well as high chemical resistance. With the transition from internal combustion engines (ICE) to electric engines, at least partially (hybrid vehicles [HEV, PHEV, BEV REX]) or completely (electric vehicles [BEV, FCEV]), new requirements are placed on the emerging materials used in automotive applications. For example, while in conventional cars with an internal combustion engine (ICE) as their only propulsion device, a 12V on-board voltage system is usually sufficient, hybrid vehicles and electric vehicles with electric motors as drive units require significantly higher voltages. Engineers need to meet strict design parameters such as dielectric strength, creep, tracking resistance and the ability to color-code the various electrical systems. The orange color chosen for the high-voltage systems and the main battery charging path helps operators and rescue teams to achieve safe operation during maintenance or in the event of an accident. It is crucial that the orange color is maintained throughout the service life of the hybrid or electric vehicle.

[0004] Because polyamides are generally susceptible to thermo-oxidative degradation, they turn yellow when thermal treatment occurs. This can also affect the color of the product, for example, orange products.

[0005] In the art, it is suggested to delay thermo-oxidative degradation by adding known heat stabilizers, including H donors, hydroperoxide decomposers, alkyl radical scavengers and metal deactivators. An overview of different types of heat stabilizers can be found in Chapter 1 (pages 3-19) of Plastic Additives Handbook edited by Hans Zweifel (fifth edition, Carl Hanser Verlag, Munich). A frequently used system is a hindered phenolic antioxidant, optionally in combination with an organic triaryl phosphite. By using certain phosphorus compounds, improved color (i.e. reduced yellowness) can be further obtained in polyamides. Phosphorus compounds act as color stabilizers for polyamides by reducing the extent of oxidation and thermal degradation, and can be added during polymerization or in the batching step. As a phosphorus compound, sodium hypophosphite can be used (see European patent application "Thermoplastic moulding compositions having an improved colour stability" filed on the same day as the present application by the same applicant).

[0006] Many colorants, including those that produce orange, include sulfur that is not exclusively covalently bonded, i.e., can release hydrogen sulfide (e.g., zinc sulfide, cerium sulfide, cerium sulfide / lanthanum sulfide) in the presence of acidic compounds (e.g., degradation products of sodium hypophosphite). Hydrogen sulfide causes a strong odor and also poses a serious environmental and health hazard.

[0007] However, the problem of hydrogen sulfide release in polyamide compositions comprising compounds comprising at least one non-covalently bonded sulfur atom (e.g., colorants such as zinc sulfide, cerium sulfide, cerium / lanthanum sulfide) and acidic compounds (e.g., derived from sodium hypophosphite) has not been addressed in the related art.

[0008] This combination of compounds present in the polyamide composition comprising at least one non-covalently bonded sulfur atom occurs in particular in colored (especially orange) polyamide compositions, since many colorants contain compounds capable of releasing hydrogen sulfide under acidic conditions.

[0009] It was therefore an object of the present application to provide thermoplastic molding compositions, in particular pigmented thermoplastic molding compositions, which have high color stability, in particular at high temperatures, and which contain no or reduced hydrogen sulfide odor.

[0010] This object is achieved by a thermoplastic molding composition comprising

[0011] a) as component A) 10% to 99.97% by weight of at least one thermoplastic polyamide different from component E),

[0012] b) 0.01% to 0.5% by weight of at least one of sodium hypophosphite or sodium hypophosphite hydrate as component B),

[0013] c) 0.01 to 5% by weight of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, particularly preferably in the RAL color system corresponding to the color numbers RAL 2001, RAL 2003,

[0014] RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL

[0015] 2011, and very particularly preferably the shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system as component C),

[0016] d) from 0.01% to 2% by weight of at least one acid scavenger as component D),

[0017] e) 0 to 20% by weight of at least one polyamide 6I / 6T as component E),

[0018] f) 0 to 5% by weight of at least one laser engraving additive, preferably at least one pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, glitter, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F),

[0019] g) 0 to 60% by weight of at least one fibrous and / or particulate filler as component G),

[0020] g) from 0% to 55% by weight of at least one flame retardant additive as component H), and

[0021] i) 0% to 25% by weight of at least one further additive as component I),

[0022] The total weight percentage of components A) to I) is 100 weight %.

[0023] In the case of sodium hypophosphite monohydrate, the amount of component B) calculated as sodium is 0.002% to 0.11% by weight. In the case of sodium hypophosphite, the amount of sodium is 0.0026% to 0.13% by weight.

[0024] This object is further achieved by a process for producing the thermoplastic molding composition of the invention, which comprises the steps of mixing components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0025] The object is further achieved by using the thermoplastic molding compositions of the invention or the thermoplastic molding compositions obtainable by the process of the invention for producing fibers, foils, moldings and extruded articles.

[0026] The object is further achieved by fibers, foils, molded articles or extruded articles made from the thermoplastic molding composition of the invention or the thermoplastic molding composition obtainable by the process of the invention.

[0027] The object is further achieved by a process for producing the inventive fibers, foils, molded or extruded articles by injection molding, extrusion or blow molding of the inventive thermoplastic molding composition or by a thermoplastic molding composition obtainable by the inventive process.

[0028] This object is further achieved by the use of at least one acid scavenger in a thermoplastic molding composition for improving the odor of the thermoplastic molding composition, the thermoplastic molding composition comprising i) at least one thermoplastic polyamide, ii) at least one of sodium hypophosphite or sodium hypophosphite hydrate, and iii) a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom.

[0029] The inventors discovered the following:

[0030] Polyamide compositions with very high color stability can be obtained by using at least one of sodium hypophosphite or sodium hypophosphite hydrate. However, if at least one colorant containing at least one non-covalently bonded sulfur atom is present in the composition, for example a sulfide, such as zinc sulfide, cerium sulfide, cerium sulfide / lanthanum sulfide, hydrogen sulfide is released due to acidic components generated, for example, during the melt batching process in the presence of sodium hypophosphite, thereby causing a strong odor and also constituting a serious environmental and health hazard. It has been found that the release of hydrogen sulfide can be suppressed by adding an acid scavenger to the polyamide composition.

[0031] Improved "color stability" in the meaning of this application means improved color stability during storage. Color stability is tested by observing the YI (yellowness index) value of the uncolored product or the ΔE (color distance) value of the colored product at specified time intervals and elevated temperatures.

[0032] The thermoplastic molding compositions of the invention are particularly suitable for providing orange compositions for high voltage applications, in particular in automobiles.

[0033] In the case of an orange thermoplastic molding composition of the invention, after 1000 h at 120° C., the color distance ΔE is preferably <20, preferably ΔE<10, more preferably ΔE<5, based on the L*a*b coordinates of the color numbers starting with “2” in the RAL color card.

[0034] The thermoplastic molding compositions of the invention are particularly suitable for / as high-voltage components, especially high-voltage components in automotive applications.

[0035] According to the invention, the term "high voltage" is understood to mean an operating voltage of >30 V (direct current) or >20 V (alternating current), preferably >60 V (direct current) or >30 V (alternating current). Thus, a "high voltage component" according to the invention is a component which is subjected to an operating (working) voltage of >30 V, preferably >60 V (direct current) or >20 V, preferably >30 V (alternating current), preferably a component for an electric vehicle.

[0036] According to ISO 6469-3:2021, the outer coverings of cables and wiring harnesses for high-voltage circuits not within an enclosure or behind a barrier should be marked with orange.

[0037] In the context of the present invention, "at least one" means exactly one or a mixture of two or more different components.

[0038] Component A)

[0039] As component A), the thermoplastic molding composition contains 10% to 99.97% by weight, preferably 20% to 85% by weight, more preferably 30% to 75% by weight, of at least one thermoplastic polyamide different from component E), as mentioned below, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0040] If components E, F, G, H or I 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 E, F, G, H or I or combinations thereof.

[0041] The polyamide (A) of the molding composition of the invention generally has a viscosity value of 90 ml / g to 350 ml / g, preferably 100 ml / g to 240 ml / g. The viscosity values ​​(VN) of the polyamides and polyamide compositions according to the invention are determined in sulfuric acid (96 wt. % [m / m] sulfuric acid at 25° C. containing 0.5 % [m / v] polyamide) according to EN ISO 307:2019, unless otherwise stated.

[0042] Preferred are semicrystalline or amorphous polyamides having a molecular weight (weight average) of at least 5000, such as described by way of 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.

[0043] Examples of these polymers are polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam; and polyamides obtained by reacting dicarboxylic acids with diamines.

[0044] Dicarboxylic acids that can be used are alkanedicarboxylic acids and aromatic dicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms. Merely by way of example, those dicarboxylic acids that may be mentioned here are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic acid and / or isophthalic acid.

[0045] Particularly suitable diamines are alkane diamines having 6 to 12, in particular 6 to 8, carbon atoms, and also meta-xylylenediamine, bis[4-aminophenyl]methane, bis[4-aminocyclohexyl]methane, 2,2-bis[4-aminophenyl]propane, 2,2-bis[4-aminocyclohexyl]propane and 1,5-diamino-2-methylpentane.

[0046] Preferred polyamides are hexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam, and also PA 6 / 66 copolyamides, in particular with a proportion of 5 to 95% by weight of caprolactam units (e.g. C31 from BASF SE).

[0047] Other suitable polyamides are obtainable from ω-aminoalkylnitriles, for example aminocapronitrile (PA 6) and adiponitrile, and hexamethylenediamine (PA 66) in the presence of water by so-called direct polymerization, as described, for example, in DE-A 10313681, EP-A 1198491 and EP 0 922 065.

[0048] Mention may also be made of polyamides obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (PA 46). Processes for the preparation of polyamides of this structure are described, for example, in EP-A 38094, EP-A 38582 and EP-A 39524.

[0049] Other suitable examples are polyamides obtainable by copolymerization of two or more of the abovementioned monomers, and mixtures of two or more polyamides in any desired mixing ratio. Particularly preferred are mixtures of PA 66 with other polyamides, in particular blends of PA 6 and PA 66, and PA6 / 66 copolyamides and PA 66 / 6 copolyamides.

[0050] Other copolyamides that have proven particularly advantageous are semiaromatic copolyamides, such as PA 6 / 6T and PA 66 / 6T, wherein the triamine content of these is preferably less than 0.5% by weight, preferably less than 0.3% by weight (cf. EP-A 299 444). Other high temperature resistant polyamides are known from EP-A 1 994 075 (PA 6T / 6I / MXD6).

[0051] The processes described in EP-A 129 195 and EP-A 129 196 can be used for preparing the preferably semiaromatic copolyamides having a low triamine content.

[0052] The following non-exhaustive list includes the abovementioned polyamides A) and further polyamides A) which can be used for the purposes of the present invention, and the monomers comprised:

[0053] AB polymer:

[0054] PA 4 Pyrrolidone

[0055] PA 6 ε-caprolactam

[0056] PA 7 Enantholactam

[0057] PA 8 Capryllactam

[0058] PA 9 9-aminononanoic acid

[0059] PA 11 11-Aminoundecanoic acid

[0060] PA 12 Lauryl Lactam

[0061] AA / BB polymer:

[0062] PA 46 Tetramethylenediamine, Adipic Acid

[0063] PA 66 Hexamethylenediamine, Adipic Acid

[0064] PA 69 Hexamethylenediamine, Azelaic acid

[0065] PA 610 Hexamethylenediamine, Sebacic acid

[0066] PA 612 Hexamethylenediamine, decanedicarboxylic acid

[0067] PA 613 Hexamethylenediamine, Undecanedicarboxylic Acid

[0068] PA 1212 1,12-Dodecanediamine, decanedicarboxylic acid

[0069] PA 1313 1,13-Diaminotridecane, undecanedicarboxylic acid

[0070] PA 6T Hexamethylenediamine, terephthalic acid

[0071] PA MXD6 m-phenylenediamine, adipic acid

[0072] AA / BB polymer:

[0073] PA 6I Hexamethylenediamine, Isophthalic acid

[0074] PA 6-3-T Trimethylhexamethylenediamine, terephthalic acid

[0075] PA 6 / 6.36 (see below)

[0076] PA 6 / 6T (see PA 6 and PA 6T)

[0077] PA 6 / 66 (see PA 6 and PA 66)

[0078] PA 6 / 12 (See PA 6 and PA 12)

[0079] PA 66 / 6 / 610 (see PA 66, PA 6 and PA 610)

[0080] PA 6I / 6T (See PA 6I and PA 6T)

[0081] PA PACM 12 diaminodicyclohexylmethane, laurolactam

[0082] PA 6I / 6T / PACM as PA 6I / 6T+diaminodicyclohexylmethane

[0083] PA 12 / MACMI lauryl lactam, dimethyl diamino dicyclohexyl methane, isophthalic acid

[0084] PA 12 / MACMT lauryl lactam, dimethyl diamino dicyclohexyl methane, terephthalic acid

[0085] PA PDA-T phenylenediamine, terephthalic acid

[0086] 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.

[0087] Most preferred are PA 6, PA 66, PA 6 / 66 and PA 66 / 6 as well as PA 6 / 636, or mixtures thereof. Most preferred are PA 6, PA 66 or mixtures thereof.

[0088] Suitable copolyamides consist of:

[0089] A1) 20.0% to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine,

[0090] A2) 0 to 50.0% by weight of units derived from ε-caprolactam,

[0091] A3) 0 to 80.0% by weight of units derived from adipic acid and hexamethylenediamine,

[0092] A4) 0 to 40.0% by weight of other polyamide-forming monomers,

[0093] The proportion of component A2) or A3) or A4) or a mixture thereof is at least 10.0% by weight.

[0094] Component A1) comprises from 20.0% to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

[0095] Besides the units deriving from terephthalic acid and hexamethylenediamine, the copolyamide optionally comprises units deriving from ε-caprolactam and / or units deriving from adipic acid and hexamethylenediamine and / or units deriving from further polyamide-forming monomers.

[0096] 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 acid, such as 3-tert-butylisophthalic acid, polycyclic dicarboxylic acids, for example 4,4'-diphenyldicarboxylic acid and 3,3'-diphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid and 3,3'-diphenylmethanedicarboxylic acid, 4,4'-sulfodiphenylcarboxylic acid and 3,3'-sulfodiphenylcarboxylic acid, 1,4-naphthalene dicarboxylic acid or 2,6-naphthalene dicarboxylic acid, phenoxyterephthalic acid, particular preference being given to isophthalic acid.

[0097] Furthermore, the polyamide-forming monomers A4) may be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or alicyclic diamines having 4 to 16 carbon atoms, and aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of these types are suberic acid, azelaic acid and sebacic acid as representatives of aliphatic dicarboxylic acids; 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2-(4,4'-diaminodicyclohexylpropane) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane as representatives of diamines or m-xylylenediamine as representatives of diamines and caprolactam, enantholactam, w-aminoundecanoic acid and laurolactam as representatives of lactams / aminocarboxylic acids.

[0098] Examples of such copolyamides are described more particularly in DE-A 10 2009 011668.

[0099] As component A), the thermoplastic molding material may comprise at least one copolyamide produced by polymerization of the components

[0100] A') 15 to 84% by weight of at least one lactam,

[0101] B') 16 to 85 wt. % of a monomer mixture (M) comprising

[0102] B1') at least one C 32 -C 40 -Dimer acid and

[0103] B2') at least one C4-C 12 - diamine,

[0104] The percentages by weight of components A') and B') are in each case based on the sum of the percentages by weight of components A') and B').

[0105] 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.

[0106] The same applies to the terms “component B′)” and “monomer mixture (M)”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.

[0107] According to the invention, at least one copolyamide is produced by polymerization of 15 to 84% by weight of component A') and 16 to 85% by weight of component B'), preferably by polymerization of 40 to 83% by weight of component A') and 17 to 60% by weight of component B'), and particularly preferably by polymerization of 60 to 80% by weight of component A') and 20 to 40% by weight of component B'), wherein the weight percentages of components A') and B') are each based on the sum of the weight percentages of components A') and B').

[0108] The sum of the weight percentages of components A') and B') is preferably 100 weight %.

[0109] It should be understood that the weight percentages of components A') and B') are related to the weight percentages of components A') and B') before polymerization (i.e., when components A') and B') have not yet reacted with each other). During the polymerization of components A') and B'), the weight ratio of components A') and B') can be optionally changed.

[0110] According to the invention, at least one copolyamide is produced by the polymerization of components A') and B'). The polymerization of components A') and B') is known to those skilled in the art. The polymerization of components A') and B') is generally a condensation reaction. During the condensation reaction, component A') reacts with components B1') and B2') present in component B') and optionally with component B3') 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 generally at least partially in open-chain form, i.e., in amino acid form.

[0111] 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 triphenyl phosphite.

[0112] 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') include units derived from components B1') and B2') and optionally from component B3').

[0113] The polymerization of components A') and B') forms a copolyamide as a copolymer. The copolymer may be a random copolymer. It may also be a block copolymer.

[0114] In block copolymers, blocks of units derived from component B') and blocks of units derived from component A') are formed. These occur in an alternating order. In random copolymers, units derived from component A') alternate with units derived from component B'). This alternation is random. For example, two units derived from component B') may be followed by a unit derived from component A'), followed by a unit derived from component B'), and then a unit comprising three units derived from component A').

[0115] It is preferred when the at least one copolyamide is a random copolymer.

[0116] The production of at least one copolyamide preferably comprises the following steps:

[0117] I) polymerizing components A') and B') to obtain at least a first copolyamide,

[0118] II) pelletizing the at least one first copolyamide obtained in step I) to obtain at least one pelletized copolyamide,

[0119] III) extracting with water at least one pelletized copolyamide obtained in step II) to obtain at least one extracted copolyamide,

[0120] IV) drying the at least one extracted copolyamide obtained in step III) at a temperature (TT) to obtain at least one copolyamide,

[0121] The polymerization in step I) can be carried out in any reactor known to the person skilled in the art. A stirred tank reactor is preferred. It is also possible to use auxiliary agents known to the person skilled in the art, for example defoamers such as polydimethylsiloxane (PDMS), to improve the reaction management.

[0122] In step II), the at least one first copolyamide obtained in step I) can be pelletized by any method known to the person skilled in the art, for example by strand pelletization or underwater pelletization.

[0123] The extraction in step III) can be achieved by any method known to those skilled in the art.

[0124] During the extraction in step III), by-products which are usually formed during the polymerization of components A′) and B′) in step I) are extracted from the at least one pelletized copolyamide.

[0125] In step IV), the at least one extracted copolyamide obtained in step III) is dried. Drying processes are known to those skilled in the art. According to the invention, the at least one extracted copolyamide is dried at a temperature (TT). The temperature (TT) is preferably above the glass transition temperature (T G(C) ), and is lower than the melting temperature (T M(C) ).

[0126] The drying in step IV) is generally carried out for a period of time in the range from 1 hour to 100 hours, preferably in the range from 2 hours to 50 hours and particularly preferably in the range from 3 hours to 40 hours.

[0127] The drying in step IV) is believed to further increase the molecular weight of the at least one copolyamide.

[0128] At least one copolyamide generally has a glass transition temperature (T G(C) The glass transition temperature (T ) is determined according to ISO 11357-2:2014, for example in the range of 20° C. to 50° C., preferably in the range of 23° C. to 47° C., and particularly preferably in the range of 25° C. to 45° C. G(C) ).

[0129] In the context of the present invention, the glass transition temperature (T G(C) ) based on the glass transition temperature (T G(C) ).

[0130] In the context of the present invention, "dry" is understood to mean that the at least one copolyamide contains less than 1% by weight, preferably less than 0.5% by weight, and particularly preferably less than 0.1% by weight of water, based on the total weight of the at least one copolyamide. "Dry" is more preferably understood to mean that the at least one copolyamide contains no water, and most preferably the at least one copolyamide contains no solvent.

[0131] Furthermore, at least one copolyamide generally has a melting temperature (T M(C) The melting temperature (T ) of the at least one copolyamide is determined according to ISO 11357-3:2014, for example in the range of 150° C. to 210° C., preferably in the range of 160° C. to 205° C., and particularly preferably in the range of 160° C. to 200° C. M(C) ).

[0132] The at least one copolyamide generally has a viscosity value (VN ) in the range of 150 ml / g to 300 ml / g, measured in a 0.5% by weight solution of the at least one copolyamide in a phenol / o-dichlorobenzene mixture in a weight ratio of 1:1. (C) ).

[0133] The viscosity value (VN) of the at least one copolyamide measured in a 0.5% by weight solution of the at least one copolyamide in a phenol / o-dichlorobenzene mixture in a weight ratio of 1:1 is (C) ) is preferably in the range of 160 mL / g to 290 mL / g, and particularly preferably in the range of 170 mL / g to 280 mL / g.

[0134] Component A')

[0135] According to the invention, component A') is at least one lactam.

[0136] In the context of the present invention, "at least one lactam" is understood to mean precisely one lactam or a mixture of 2 or more lactams.

[0137] Lactams per se are known to the person skilled in the art. According to the invention, lactams having 4 to 12 carbon atoms are preferred.

[0138] In the context of the present invention, "lactam" is understood to mean a cyclic amide having preferably 4 to 12 carbon atoms, particularly preferably 5 to 8 carbon atoms in the ring.

[0139] Suitable lactams are, for example, selected from the group consisting of: 3-aminopropanol lactam (propan-3-lactam; β-lactam; β-propiolactam), 4-aminobutyrolactam (butyron-4-lactam; γ-lactam; γ-butyrolactam), aminovalerolactam (2-piperidone; δ-lactam; δ-valerolactam), 6-aminocaprolactam (capro-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanolactam (heptano-7-lactam; ζ-lactam; ζ-heptanolactam), 8-aminooctanolactam (octano-8-lactam; η-lactam; η-octanolactam), 9-aminononanolactam (nonano-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam (decan-10-lactam; ω-decanolactam), 11-aminoundecanolactam (undecane-11-lactam; ω-undecanolactam) and 12-aminododecanolactam (dodecane-12-lactam; ω-dodecanolactam).

[0140] The present invention therefore also provides a process, wherein component A') is selected from the group consisting of 3-aminopropiolactam, 4-aminobutyrolactam, 5-aminovalerolactam, 6-aminocaprolactam, 7-aminoheptanolactam, 8-aminooctanolactam, 9-aminononanolactam, 10-aminodecanolactam, 11-aminoundecanolactam and 12-aminododecanolactam.

[0141] The lactam may be unsubstituted or at least monosubstituted. If at least monosubstituted lactams are used, the nitrogen atom and / or its ring carbon atoms may carry one, two or more substituents selected independently of one another from the group consisting of: C1-alkyl to C 10 -alkyl, C5-cycloalkyl to C6-cycloalkyl and C5-aryl to C 10 -Aryl.

[0142] Suitable C1-alkyl groups to C 10 -alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Suitable C5-cycloalkyl to C6-cycloalkyl substituents are, for example, cyclohexyl. Preferred C5-aryl to C6- 10 The -aryl substituent is phenyl or anthracenyl.

[0143] Preference is given to using unsubstituted lactams, preferably γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam). Particular preference is given to δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam), ε-caprolactam being particularly preferred.

[0144] Monomer mixture (M)

[0145] 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 -diamine.

[0146] In the context of the present invention, a monomer mixture (M) is understood to mean a mixture of two or more monomers, wherein at least components B1′) and B2′) are present in the monomer mixture (M).

[0147] In the context of the present invention, the terms "component B1')" and "at least one C 32 -C 40 -dimer acid" are used synonymously and therefore have the same meaning. The same applies to the terms "component B2')" and "at least one C4-C 12-diamine". These terms are also used synonymously in the context of the present invention and therefore have the same meaning.

[0148] The monomer mixture (M) comprises, for example, in the range from 45 mol % to 55 mol % of component B1′) and in the range from 45 mol % 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).

[0149] It is preferred when component B') comprises component B1') in the range of 47 mol % to 53 mol % and component B2') in the range of 47 mol % to 53 mol %, 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').

[0150] Particularly preferred is when component B') comprises a component B1') in the range of 49 mol % to 51 mol % and a component B2') in the range of 49 mol % to 51 mol %, 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').

[0151] The sum of the molar percentages of components B1′) and B2′) present in component B′) generally amounts to 100 mol %.

[0152] Component B') may additionally comprise component B3'), at least one C4-C 20 -Diacid.

[0153] In the context of the present invention, the terms "component B3')" and "at least one C4-C 20 -diacid" are used synonymously and therefore have the same meaning.

[0154] When component B') additionally comprises component B3'), preferably when component B') comprises component B1') in a range of 25 mol % to 54.9 mol %), component B2') in a range of 45 mol % to 55 mol % and component B3') in a range of 0.1 mol % to 25 mol %, in each case based on the total amount of substances of component B').

[0155] Particular preference is given to component B′) when it then comprises component B1′) in a range from 13 mol % to 52.9 mol %, component B2′) in a range from 47 mol % to 53 mol % and component B3′) in a range from 0.1 mol % to 13 mol %, in each case based on the total amount of substances of component B′).

[0156] Most preferably, component B') then comprises component B1') in a range from 7 mol% to 50.9 mol%, component B2') in a range from 49 mol% to 51 mol% and component B3') in a range from 0.1 mol% to 7 mol%, in each case based on the total amount of substances of component B').

[0157] When component B′) additionally comprises component B3′), the sum of the molar percentages of components B1′), B2′) and B3′) is generally 100 mol %.

[0158] The monomer mixture (M) may also contain water.

[0159] Components B1') and B2') and optionally B3') of component B') can react with each other to obtain amides. This reaction itself is known to those skilled in the art. Therefore, component B') can contain components B1'), B2') and optionally B3') in fully reacted form, in partially reacted form or in unreacted form. It is preferred when component B') contains components B1'), B2') and optionally B3') in unreacted form.

[0160] In the context of the present invention, "in unreacted form" is therefore understood to mean that component B1') is present as at least one C 32 -C 40 - dimer acid is present and component B2') as at least one C4-C 12 -diamine is present and optionally component B3') as at least one C4-C 20 -Presence of diacids.

[0161] If components B1′) and B2′) and optionally B3′) have been at least partially reacted, components B1′) and B2′) and optionally B3′) are therefore at least partially in the form of amides.

[0162] Component B1')

[0163] According to the invention, component B1′) is at least one C 32 -C 40 -Dimer acid.

[0164] In the context of the present invention, "at least one C 32 -C 40 "-dimer acid" is understood to mean precisely a C 32 -C 40 - dimer acid or two or more C 32 -C 40 - A mixture of dimer acids.

[0165] Dimer acid is also called dimer fatty acid. 32 -C 40 -Dimer acids are known per se to the person skilled in the art and are generally produced by dimerization of unsaturated fatty acids. This dimerization can be catalyzed by clay, for example.

[0166] To produce at least one C 32 -C 40 Suitable unsaturated fatty acids for the dimer acid are known to the person skilled in the art and are, for example, unsaturated C 16 -Fatty acids, unsaturated C 18 - Fatty acids and unsaturated C 20 -fatty acid.

[0167] Therefore, it is preferred when component B1′) is derived from unsaturated fatty acids selected from the group consisting of: unsaturated C 16 -Fatty acids, unsaturated C 18 - Fatty acids and unsaturated C 20 - fatty acids, of which unsaturated C 18 - Fatty acids are particularly preferred.

[0168] For example, suitable unsaturated C 16 - The fatty acid is palmitoleic acid ((9Z)-hexadec-9-enoic acid).

[0169] Suitable unsaturated C 18 - fatty acids are selected from the group consisting of petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), linoleic acid ((9Z,12Z)-octadec-9,12-dienoic acid), α-linolenic acid ((9Z,12Z,15Z)-octadec-9,12,15-trienoic acid), γ-linolenic acid ((6Z, 9Z,12Z)-octadecane-6,9,12-trienoic acid), calendula acid ((8E,10E,12Z)-octadecane-8,10,12-trienoic acid), punicic acid ((9Z,11E,13Z)-octadecane-9,11,13-trienoic acid), α-eleostearic acid ((9Z,11E,13E)-octadecane-9,11,13-trienoic acid) and β-eleostearic acid ((9E,11E,13E)-octadecane-9,11,13-trienoic acid). Particularly preferred are unsaturated C selected from the group consisting of 18 - Fatty acids: petroselinic acid ((6Z)-octadec-6-enoic acid), oleic acid ((9Z)-octadec-9-enoic acid), elaidic acid ((9E)-octadec-9-enoic acid), vaccenic acid ((11E)-octadec-11-enoic acid), linoleic acid ((9Z,12Z)-octadec-9,12-dienoic acid).

[0170] Suitable unsaturated C 20 - fatty acids, for example, selected from the group consisting of gadoleic acid ((9Z)-eicos-9-enoic acid), eicosenoic acid ((11Z)-eicos-11-enoic acid),

[0171] Arachidonic acid ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) and eicosapentaenoic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa-5,8,11,14,17-pentaenoic acid).

[0172] Component B1') is particularly preferably at least one C 36 -Dimer acid.

[0173] At least one C 36 - The dimer acid is preferably composed of unsaturated C 18 - fatty acids are produced. 36 - dimer acid selected from the group consisting of

[0174] C 18 - The fatty 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)-octadec-9,12-dienoic acid).

[0175] The production of component B1′) from unsaturated fatty acids may also result in the formation of trimer acids, and residues of unconverted unsaturated fatty acids may also remain.

[0176] The formation of trimer acids is known to those skilled in the art.

[0177] According to the invention, component B1′) preferably contains not more than 0.5% by weight of unreacted unsaturated fatty acids and not more than 0.5% by weight of trimer acids, particularly preferably not more than 0.2% by weight of unreacted unsaturated fatty acids and not more than 0.2% by weight of trimer acids, in each case based on the total weight of component B1′).

[0178] Thus, dimer acids (also called dimerized fatty acids or dimerized fatty acids) are to be understood as meaning, in general and in particular in the context of the present invention, mixtures produced by the oligomerization of unsaturated fatty acids. They are produced, for example, by catalytic dimerization of plant-derived unsaturated fatty acids, the starting materials used being in particular unsaturated C 16 -Fatty acids to C 20-fatty acid. Bonding is mainly carried out by Diels-Alder (Diels-Alder) mechanism, and according to the quantity and position of double bonds in the fatty acid for producing dimer acid, what is produced is mainly a mixture of dimer products with alicyclic, linear aliphatic, branched aliphatic and C6-aromatic hydrocarbon groups between the carboxyl groups. According to mechanism and / or any subsequent hydrogenation, the aliphatic group can be saturated or unsaturated, and the ratio of the aromatic group can also change. Then, for example, the group between the carboxylic acid group comprises 32 to 40 carbon atoms. Production preferably uses a fatty acid with 18 carbon atoms, so that the dimer product has 36 carbon atoms. The group connecting the carboxyl group of the dimer fatty acid preferably does not include unsaturated bonds and aromatic hydrocarbon groups.

[0179] In the context of the present invention, the production is therefore preferably carried out using C 18 - Fatty acids. Particular preference is given to using linolenic acid, linoleic acid and / or oleic acid.

[0180] According to reaction management, oligomerization described above provides the mixture that mainly comprises dimer molecule, trimer molecule and monomer molecule and other by-products.It is conventional to purify by distillation.Commercial dimer acid comprises the dimer molecule of at least 80 wt %, the trimer molecule of 19 wt % at the most, and the monomer molecule and other by-products of 1 wt % at most usually.

[0181] Preference is given to using dimer acids which consist of dimer fatty acid molecules to an extent of at least 90% by weight, preferably to an extent of at least 95% by weight and very particularly preferably to an extent of at least 98% by weight.

[0182] The proportion of monomer molecules, dimer molecules and trimer molecules and other byproducts in the dimer acid can be determined by, for example, gas chromatography (GC). Before GC analysis, the dimer acid is converted into the corresponding methyl ester by the boron trifluoride method (see DIN EN ISO 5509) and then analyzed by GC.

[0183] Therefore, in the context of the present invention, the essential feature of "dimer acid" is that its production comprises the oligomerization of unsaturated fatty acids. This oligomerization mainly forms dimer products, i.e. preferably to the extent of at least 80% by weight, particularly preferably at least 90% by weight, very particularly preferably at least 95% by weight, and in particular at least 98% by weight. Therefore, the fact that the oligomerization mainly forms dimer products containing precisely two fatty acid molecules justifies this designation, which is common in any case. Therefore, an alternative expression of the related term "dimer acid" is "a mixture containing dimerized fatty acids".

[0184] The dimer acid to be used is available as a commercial product. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976, and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 from Croda, Empol 1008, Empol 1012, Empol 1061, and Empol 1062 from BASF SE, and Unidyme 10 and Unidyme T1 from Arizona Chemical.

[0185] Component B1′) has, for example, an acid number in the range from 190 mg KOH / g to 200 mg KOH / g.

[0186] Component B2')

[0187] According to the invention, component B2') is at least one C4-C 12 -diamine.

[0188] In the context of the present invention, "at least one C4-C 12 "-diamine" is understood to mean precisely a C4-C 12 - diamine or two or more C4-C 12 - A mixture of diamines.

[0189] In the context of the compounds of the invention, "C4-C12-diamine" is understood to be an aliphatic and / or aromatic compound having four to twelve carbon atoms and two amino groups (-NH2 groups). The aliphatic and / or aromatic compound may be unsubstituted or otherwise at least monosubstituted. If the aliphatic and / or aromatic compound is otherwise at least monosubstituted, the aliphatic and / or aromatic compound may carry one, two or more substituents which do not participate in the polymerization of components A') and B'). Such substituents are, for example, alkyl or cycloalkyl substituents. These are known per se to the person skilled in the art. At least one C4-C12-diamine is preferably an aliphatic and / or aromatic compound. 12 The -diamines are preferably unsubstituted.

[0190] Suitable component B2′) is, 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 (undemethylenediamine) and 1,12-diaminododecane (dodecamethylenediamine).

[0191] It is preferred when component B2′) is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.

[0192] Component B3')

[0193] According to the invention, component B3') optionally present in component B') is at least one C4-C 20 -Diacid.

[0194] In the context of the present invention, "at least one C4-C 20 "-diacid" is understood to mean precisely a C4-C 20 -diacid or two or more C4-C 20 - A mixture of diacids.

[0195] In the context of the present invention, "C4-C 20 "-diacid" is understood to be an aliphatic and / or aromatic compound having two to eighteen carbon atoms and two carboxyl groups (-COOH groups). The aliphatic and / or aromatic compound may be unsubstituted or additionally at least monosubstituted. If the aliphatic and / or aromatic compound is additionally at least monosubstituted, the aliphatic and / or aromatic compound may carry one, two or more substituents which do not participate in the polymerization of components A') and B'). Such substituents are, for example, alkyl or cycloalkyl substituents. These are known to the person skilled in the art. Preferably, at least one C4-C 20 -diacids are unsubstituted.

[0196] Suitable components B3′) are selected, for example, from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.

[0197] It is preferred when component B3′) is selected from the group consisting of glutaric acid (gum acid), adipic acid (fatty acid), sebacic acid (sebacic acid) and dodecanedioic acid.

[0198] 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, PA 610, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T and PA 6T / 66, more preferably PA 6, PA 6.6, PA 66 / 6, PA 6 / 6.6 and mixtures thereof, and most preferably PA 6 and PA 66 and mixtures thereof.

[0199] Component B)

[0200] 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), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0201] Sodium hypophosphite and sodium hypophosphite hydrate used as component B) according to the invention are commercially available. Most preferred is sodium hypophosphite monohydrate (CAS: 10039-56-2).

[0202] Component C)

[0203] As component C), based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I), the thermoplastic molding composition contains 0.01 to 5% by weight, preferably 0.05 to 3% by weight, more preferably 0.1 to 2% by weight, of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, particularly preferably in the RAL color system corresponding to the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011. 2011, and very particularly preferably the chromaticities corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system.

[0204] In the meaning of the present invention, sulfur-containing colorants comprising at least one non-covalently bonded sulfur atom generally comprise at least one ionically bonded sulfur atom. Thus, in the presence of acidic compounds, component C) is able to release hydrogen sulfide.

[0205] Those skilled in the art are aware of the above-mentioned types of bonds (covalent and ionic).

[0206] Ionic bonds are the result of the attraction between ions. Ions are formed when atoms lose or gain electrons. These types of bonds are commonly formed between metals and nonmetals.

[0207] In case of covalent bonding, one atom shares one or more pairs of electrons with another atom and a bond is formed. This type of bonding is commonly seen between two non-metals. Covalent bonds can be non-polar covalent bonds or polar covalent bonds. In case of non-polar covalent bonds, the electrons are equally shared between the two atoms. In polar covalent bonds, the electrons are unequally distributed between the atoms.

[0208] Suitable colorants are pigments or dyes, for example inorganic pigments or organic pigments or dyes.

[0209] Suitable inorganic pigments and organic colorants are described below, with the proviso that at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom is present in the thermoplastic molding composition of the invention.

[0210] 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) sulfide / lanthanum(III) sulfide [CAS 12014-93-6; CAS 12031-49-1], tin titanium zinc oxide [CAS 923954-49-8].

[0211] Suitable organic colorants are, for example, phthalocyanines, benzimidazoles, for example, Keyplast FL OR YF from Milliken and Ni-2-hydroxy-naphthyl-benzimidazole (Pigment Orange 86, [CAS 42844-93-9]), for example PVFast Orange 6RL from Heubach GmbH, pyridinium-azo-benzimidazole [CAS 72102-84-2] or condensation products 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], perylene, anthraquinone, in particular condensation products of 1,8-dichloroanthracene-9,10-dione and benzenethiol (Solvent Yellow 163, [CAS 13676-91-0]), 10,10′-oxybis-12H-phthalipyrin-12-one (Solvent Orange 111, [CAS 203576-97-0]), for example, Macrolex Orange HT from Lanxess Deutschland GmbH, Cologne, 14H-anthra[2,1,9-m,n,a]thioxanthen-14-one, for example, Hostasol Red GG from Heubach GmbH (Solvent Orange 63, [CAS 16294-75-0]), 2-octadecyl-1H-thioxantho[2,1,9-def]isoquinoline-1,3(2H)-dione, for example, Hostasol Yellow HT from Heubach GmbH 3G (Solvent Yellow 98, [CAS 12671-74-8]) or 12H-phthalidin-12-one (Solvent Orange 60, [CAS 6925-69-5]).

[0212] Since according to the invention polyamide molding compositions for high-voltage components are of particular interest and, according to the recommendations of ISO 6469-3, such high-voltage components should be orange in color, preference is given in the thermoplastic polyamide molding compositions according to the invention to orange colorants comprising at least one non-covalently bonded sulfur atom or mixtures of two or more colorants leading to an orange color comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom.

[0213] Therefore, the thermoplastic molding composition according to the invention preferably comprises an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants leading to an orange color comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, particularly preferably in a chromaticity 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, and very particularly preferably in a chromaticity corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system. More preferably, component C) is an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants leading to an orange color comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom having a chromaticity corresponding to the color number RAL 2003 in the RAL color system.

[0214] Therefore, preferred colorants C) are colorants comprising at least one non-covalently bonded sulfur atom or colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably cerium sulfide, in particular cerium (III) sulfide (Ce2S3) [CAS 12014-93-6], referred to as RAL 2003, RAL 2008 and RAL 2011. Pigment Orange 75), cerium (III) sulfide / lanthanum (III) sulfide (Ce2S3 / La2S3) ([CAS 12014-93-6; CAS 12031-49-1], for example, Pigment Orange 78), zinc sulfide and tin titanium zinc oxide [CAS 923954-49-8], for example Sicopal Orange K2430 from BASF SE, wherein the tin titanium zinc oxide is used together with at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom.

[0215] More preferred colorants C) are cerium-containing sulfides, in particular cerium (III) sulfide (Ce2S3) [CAS-Nr.12014-93-6; known as CI Pigment Orange 75], cerium (III) sulfide / lanthanum (III) sulfide (Ce2S3 / La2S3) [CAS-Nr.12014-93-6; CAS-Nr.12031-49-1; known as CI Pigment Orange 78 or zinc sulfide. Most preferred are cerium (III) sulfide / lanthanum (III) sulfide (CI Pigment Orange 78) and zinc sulfide.

[0216] Pigment Orange 75 and Pigment Orange 78 is commercially available, for example, from Chemikos, Dr. Oliver Schmitt, Karlsruhe, Germany, or as a Orange H and light Orange H.

[0217] CI means Color Index and is a dual classification system [https: / / www.chemikos.de / cersulfid-orange-pigmente]. The primary descriptor is the Color Index General Name (usually abbreviated as CIGN). Another descriptor is the Color Index Constituent Number (usually abbreviated as CICN) associated with the chemical structure. Above, CIGN is used to describe suitable colorants.

[0218] The CIGN describes a commercial product by its recognized usage category, its hue and a serial number which simply reflects the chronological order in which the relevant colorant types were registered in the Color Index.

[0219] Component C) is usually used directly as a powder or in the form of a paste, masterbatch, compact or concentrate comprising component C). Preferably, component C) is used in the form of a powder.

[0220] Component D)

[0221] As component D), the thermoplastic molding composition contains 0.01 to 2% by weight, preferably 0.02 to 1.8% by weight, more preferably 0.03 to 1.5% by weight, of at least one acid scavenger, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0222] "Acid scavenger" within the meaning of the present invention refers to a compound or composition which consumes, depletes or reacts with acidic components normally generated during compounding, which inhibit the generation of hydrogen sulfide in the environment of the thermoplastic molding composition of the present invention.

[0223] Acid scavengers suitable for use in the present invention include:

[0224] At least one organic or inorganic base, preferably at least one inorganic base, more preferably selected from the group consisting of oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide-hydroxides, oxide-hydroxide-carbonates, hydroxide-silicates or hydroxide-borates of at least one element selected from the group consisting of alkali metals, alkaline earth metals, elements of the boron group (Group 13 of the IUPAC version of the Periodic Table of the Elements), zinc and tin; salts of fatty acids; hydrotalcites; ricinoleates; and mixtures thereof.

[0225] Examples of acid scavengers according to the present invention are:

[0226] Magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate, zinc stannate, calcium stearate, zinc stearate, calcium lactate, calcium stearoyl lactylate, zinc ricinoleate, natural and synthetic hydrotalcites such as magnesium aluminum hydrotalcites and mixtures thereof. Preferred acid scavengers for use in the present invention are magnesium aluminum hydrotalcites, for example known as HYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYHYDROXYL ... 713. Zinc stannate and lanthanum carbonate.

[0227] Component E)

[0228] As component E), the thermoplastic molding composition contains 0 to 20% by weight, preferably 0.01 to 18% by weight, more preferably 0.1 to 17% by weight, most preferably 1 to 16% by weight, of at least one polyamide 6I / 6T, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0229] Preferably, component E) comprises units derived from hexamethylenediamine, derived from terephthalic acid and derived from isophthalic acid. In other words, component E) is a copolymer prepared from hexamethylenediamine, terephthalic acid and isophthalic acid.

[0230] More preferably, component E) consists of units derived from hexamethylenediamine, derived from terephthalic acid and derived from isophthalic acid. It is preferably a random copolymer. Polyamide 6I / 6T used as component E) 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.

[0231] 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 will be semi-crystalline (usually described as PA6T / 6I). In contrast, when polyamide 6I / 6T is mainly based on PA6I (i.e., more than 55% isophthalic acid; usually described as PA6I / 6T), the resulting polymer will be amorphous (see Kohan, Melvin I.: Nylon Plastics Handbook, Carl Hanser Verlag, Munich Vienna NewYork, 1995, p, p. 373; Stephanie Djukic et al., Heliyon 6 (2020) e03857; https: / / en.wikipedia.org / wiki / Polyphthalamide).

[0232] “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.

[0233] Glass transition temperature (T G ) is generally in the range of 100°C to 150°C, preferably 115°C to 135°C, more preferably 120°C to 130°C. The glass transition temperature (T G ) is determined by differential scanning calorimetry. For the determination, according to the invention, a polyamide 6I / 6T sample (starting weight of about 8.5 g) is subjected to a first heating run (H1), then a cooling run (C) and subsequently a second heating run (H2). The heating rate in the first heating run (H1) and the second heating run (H2) is 20 K / min; 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) in the DSC diagram. The glass transition temperature (T G ) corresponds to the temperature at half the step height in the DSC diagram.

[0234] 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).

[0235] The polyamide 6I / 6T used according to the invention as component E) has an amino end group concentration (AEG) preferably in the range from 35 to 45 mmol / kg and particularly preferably in the range from 35 to 42 mmol / kg.

[0236] To determine the amino end group concentration (AEG), 1 g of polyamide 6I / 6T was dissolved in 30 ml of a phenol / methanol mixture (phenol:methanol volume ratio 75:25) and then titrated potentiometrically with 0.2 N aqueous hydrochloric acid solution.

[0237] The polyamide 6I / 6T used according to the invention as component E) generally has a carboxyl end group concentration (CEG) preferably in the range of 60 to 300 mmol / kg and more preferably in the range of 80 to 200 mmol / kg.

[0238] Carboxyl end group concentration (CEG) was determined by HFIP-d2 with NMR

[0239] A suitable commercially available polyamide 6I / 6T as component E) according to the invention is DuPont's HTN301 (formerly PA3426R), wherein the molar ratio of 6I:6T is 2.2:1, Grivory G21, EMS, wherein the molar ratio of 6I:6T is 2.1:1, and Grivory G16, EMS, wherein the molar ratio of 6I:6T is 1.9:1.

[0240] Component F)

[0241] Also important for high-voltage components, in particular in electric vehicles, is the possibility of identification, in order to identify these components with additional information, such as serial numbers, manufacturer characteristics, installation information or safety-related information. A suitable method for identifying components imparted to polymers is laser engraving (see https: / / de.wikipedia.org / wiki / Laserbeschriftung), preferably using a solid-state laser with a wavelength of 1064 nm, 532 nm or 355 nm with a Nd:YAG or Nd:YV04 crystal, particularly preferably using a laser with a wavelength of 1064 nm. As component F), the thermoplastic molding composition contains 0 to 5% by weight, preferably 0 to 3% by weight, more preferably 0.1 to 2% by weight, of a laser engraving additive, preferably a pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, micro-brightness, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F), based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I). 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.

[0242] In one embodiment of the invention, the laser engraving additive is free of antimony.

[0243] Shimmer in the meaning of the present invention is a group of minerals that generally contain the following composition:

[0244] DG 2-3 [T4O 10 ]X2

[0245] in

[0246] D represents ammonium (NH4 + ), barium, cesium, calcium, potassium, sodium, rubidium

[0247] G stands for aluminum, chromium, iron (Fe 2+ , Fe 3+ ), lithium, magnesium, titanium, vanadium, zinc

[0248] T=aluminum, beryllium, boron, iron (Fe 3+ ),silicon

[0249] X=anion:Cl - , O 2- OH - 、F - , S 2-

[0250] The above oxides can be surface-modified, for example, by a coating comprising antimony, ferrous oxide, tin oxide and / or zinc oxide, for example, TiO2 particles coated on the surface with an antimony-doped tin dioxide layer (Sn, Sb)O2 or calcined antimony / tin mixed oxide, wherein the antimony concentration at the surface is greater than the antimony concentration of the particle as a whole. See, for example, DE102015009854 A and EP1377522 A2.

[0251] Other suitable laser engraving additives are, for example, tin orthophosphate, barium titanate, copper hydroxyphosphate, copper orthophosphate, potassium copper diphosphate, copper hydroxide and anthraquinone.

[0252] The above-mentioned laser engraving additives are commercially available or can be obtained by methods known to those skilled in the art.

[0253] The laser engraving additive can be used directly as a powder, or in the form of a paste or masterbatch, compact or concentrate. A person skilled in the art will understand that the term "masterbatch" means a plastic additive in granular form, where the content of the laser engraving additive is higher than in the final application.

[0254] Component G)

[0255] As component G), 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 fiber and / or particulate filler, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0256] Preferably, component G) comprises glass fibers and is present in an amount of 5 to 60 wt. %, more preferably 10 to 55 wt. %, most preferably 15 to 50 wt. %, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0257] If 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) to I) is still 100% by weight.

[0258] It is also possible to use mixtures of two or more different fiber and / or particulate fillers.

[0259] Fibrous or particulate fillers G) that may be mentioned are at least one fiber and / or particulate filler from the following group: carbon fibers, glass beads, for example solid or hollow glass beads or glass fibers, ground glass, amorphous quartz glass, aluminoborosilicate glass with an alkali content of 1% (E glass), amorphous silicon dioxide, quartz powder, alkaline earth metal silicates, in particular calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, feldspar, barium sulfate, wollastonite, montmorillonite, pseudoboehmite of the formula AIO(OH), magnesium carbonate, talc, aramid fibers, potassium titanate fibers, barium carbonate, alkaline earth metal oxides, metal fibers, ceramic fibers, titanium dioxide, aluminum oxide, gypsum, zirconium oxide, antimony oxide, clay, silicon dioxide-alumina, sericite, diatomaceous earth, silica, carbon black, hollow glass microspheres ( Balloon), red oxide, zinc oxide and mixtures thereof.

[0260] Other fillers that may be mentioned are lamellar or acicular fillers, the amount of these fillers, if present, preferably being from 0.1% to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite and The lamellar nanofiller is organically modified by the prior art method to make it compatible with the organic binder. Adding lamellar or needle-shaped fillers to the thermoplastic molding composition of the present invention further improves the mechanical strength.

[0261] For the purposes of the present invention, needle-shaped mineral fillers are mineral fillers with strongly developed needle-shaped features. An example is needle-shaped 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 can optionally be pretreated with the above-mentioned silane compounds, but pretreatment is not necessary.

[0262] Preferred fiber or particle fillers G) are glass fibers. Glass fibers are usually chopped fibers, also called short fibers, with a length in the range of 0.1 mm to 1 mm, long fibers with a length in the range of 1 mm to 50 mm, and continuous fibers with a length of 1>50 mm. Continuous fibers are used in the form of rovings or fabrics in fiber-reinforced plastics.

[0263] Milled glass fibers are also available, the milled glass fibers typically having a length in the range of 70 μm to 200 μm.

[0264] Particularly preferred are glass fibers in the form of rovings or chopped glass as described above.

[0265] More preferred glass fibers for use as component G) are chopped long glass fibers having an average starting length in the range of 1 mm to 50 mm, more preferably in the range of 1 mm to 10 mm, most preferably in the range of 2 mm to 7 mm, as determined by laser diffraction-particle size analysis (laser particle size determination / laser diffraction) according to ISO 13320. The most preferred glass fibers for use as component G) have an average starting length in the range of 7 μm to 18 μm, as determined by laser diffraction according to ISO 13320.

[0266] The average fiber diameter is in the range of 10 μm and more preferably in the range of 9 μm to 15 μm.

[0267] In a preferred embodiment, the glass fibers preferably used as component G) are modified with a suitable size system or adhesion promoter / adhesion promoter system. Preferably, silane-based size systems or adhesion promoters are used to improve the compatibility with thermoplastics.

[0268] Suitable silane compounds have the following general formula:

[0269] (X-(CH2) n ) k -Si-(OC m H 2m+1 ) 4-k

[0270] X is -NH2, HO-, carboxyl,

[0271] N is an integer from 2 to 10, preferably from 3 to 4,

[0272] M is an integer of 1 to 5, preferably 1 to 2, and

[0273] K is an integer from 1 to 3, preferably 1.

[0274] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and the corresponding silanes which comprise as substituent X a glycidyl group or a carboxyl group.

[0275] For the modification of the glass fibers used preferably as component G), adhesion promoters, preferably silane compounds of the formula (II), are preferably used in amounts of 0.01% to 2% by weight, more preferably in amounts of 0.025% to 1.5% by weight and most preferably in amounts of 0.05% to 1% by weight, in each case based on 100% by weight of component F).

[0276] As a result of processing to give the thermoplastic molding composition, the glass fibers preferably used as component G) may be shorter in the composition than the glass fibers originally used. Thus, the arithmetic mean value of the length of the glass fibers after processing, determined by high-resolution X-ray computed tomography, is generally only in the range of 150 μm to 300 μm.

[0277] The person skilled in the art distinguishes between different types of glass fibers, some of which are listed here, for example (https: / / polser.com / en / frp / fibreglass-types):

[0278]

[0279] Particularly preferred are glass fibers in the form of E-glass. These can be used as rovings or in the form of commercially available chopped glass, wherein suitable rovings and chopped glass fibers are as described above. The E-glass fibers are modified with suitable sizing systems or adhesion promoters / adhesion promoter systems. Preferably, silane-based sizing systems or adhesion promoters are used to improve compatibility with thermoplastics. Suitable silane compounds are as described above.

[0280] It is also possible to use as component G) a particle size distribution determined by laser diffraction according to ISO 13320 having 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. 90 Non-fibrous and non-foamed ground glass. About d 90 For 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 this document, d 90 The value is the particle size below which 90% of the particle mass lies (volume distribution).

[0281] According to the invention, it is preferred when the non-fibrous and non-foamed ground glass has a granular, non-cylindrical shape and has a length to thickness ratio of less than 5, preferably less than 3, more preferably less than 2, determined by laser diffraction according to ISO 13320. It should be understood that a value of zero is not possible.

[0282] The non-foamed and non-fiber milled glass is further characterized in that it generally does not have the glass geometry of a typical fiber glass, a cylindrical or elliptical cross section with an aspect ratio (L / D ratio) greater than 5 as determined by laser diffraction according to ISO 13320.

[0283] The non-foam and non-fiber ground glass is preferably obtained by grinding glass with a mill, preferably a ball mill, more preferably by subsequent sieving or screening. In one embodiment, the preferred starting material for grinding the non-fiber and non-foam ground glass used as component G) also includes glass waste produced as unwanted by-products and / or unqualified primary products (referred to as unqualified materials), especially in the production of glass products. These especially include waste glass, recycled glass and cullet obtained especially in the form of so-called melt blocks, especially when producing windows or bottle glass, and when producing glass containing fillers and reinforcing agents. Glass can be colored, but preferably colorless glass as the starting material used as component G).

[0284] Component H)

[0285] As component H), 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), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0286] In case the thermoplastic molding composition comprises at least one flame retardant additive, the 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), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0287] If 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) to I) is still 100% by weight.

[0288] It is also possible to use mixtures of two or more flame retardant additives.

[0289] Component H) is at least one halogen-free flame retardant and / or at least one halogen-containing flame retardant, preferably at least one member selected from the group consisting of phosphazenes, aliphatic or aromatic esters of phosphoric acid or polyphosphoric acid, 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

[0290]

[0291] in

[0292] R 1 To R 4 independently of one another represent halogen or hydrogen, provided that at least one radical R 1 To R 4 represents halogen,

[0293] x=1 to 3, preferably 1, 2

[0294] m=1 to 9, preferably 1 to 3, 6, 9, especially 1 to 3

[0295] n=2 to 3

[0296] M = alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg,

[0297] Functional polymers comprising 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeating units and poly(2,6-dimethyl-1,4-phenylene ether) (PPPO).

[0298] As component H), the thermoplastic molding material can comprise, for example, 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 formula (IX) or (X) as flame retardant.

[0299] The minimum amount of this component H) (if present) is at least 1.0% by weight, preferably 2.0% by weight, in particular 3.0% by weight.

[0300] The maximum amount of this component H) is 10.0% by weight, preferably 6.0% by weight and particularly preferably 5.0% by weight.

[0301] "Phosphazene" is understood to mean a cyclic phosphazene of the general formula (IX)

[0302]

[0303] wherein m is an integer from 3 to 25, and R 4 and R 4’ Same or different and represents C1-C 20 -alkyl-, C6-C 30 -Aryl-, C6-C 30 -Arylalkyl or C6-C 30 -alkyl-substituted aryl or a linear phosphazene of formula (X)

[0304]

[0305] wherein n represents 3 to 1000 and X represents -N=P(OPh)3 or -N=P(O)OPh, and Y represents -P(OPh)4 or -P(O)(OPh)2.

[0306] The preparation of such phosphazenes is described in EP-A 0 945 478.

[0307] Particularly preferred is the formula (XI) P3N3C 36 Cyclic phenoxyphosphazene

[0308]

[0309] or a linear phenoxyphosphazene according to formula (XII)

[0310]

[0311] The phenyl group 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.

[0312] Preferably used as component H) is a cyclic phenoxyphosphazene having at least three phenoxyphosphazene units. For example, the corresponding phenoxyphosphazenes are described in paragraphs

[0051] to

[0053] of US2010 / 0261818. Reference may be made to formula (I) therein. The corresponding cyclic phenoxyphosphazenes are further described in EP-A-2 100 919, in particular in paragraphs

[0034] to

[0038] thereof. The preparation can be carried out as described in paragraph

[0041] of EP-A-2 100 919. In one embodiment of the invention, the phenyl groups in the cyclic phenoxyphosphazene may be C 1-4 -Alkyl substitution is preferred when pure phenyl groups are involved.

[0313] For further description of cyclic phosphazenes, please refer to Chemie Lexikon, 9th edition, keyword "phosphazene". The preparation is carried out, for example, via cyclophosphazenes obtainable from PCl5 and NH4Cl, in which the chlorine groups in the cyclophosphazenes have been replaced by phenoxy groups by reaction with phenol.

[0314] Cyclic phenoxyphosphazene compounds can be prepared, for example, as described in Allcock, HR, Phosphorus-Nitrogen Compounds (Academic Press, 1972) and Mark, JE, Allcock, HR, West, R., Inorganic Polymers (Prentice Hall, 1992).

[0315] Component H) is preferably a mixture of cyclic phenoxyphosphazenes having three and four phenoxyphosphazene units. The weight ratio of rings comprising three phenoxyphosphazene units to rings comprising four phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may also be present, but in smaller amounts. Suitable cyclic phenoxyphosphazenes are available from Fushimi Pharmaceutical Co., Ltd. under the name FP-100 was obtained. This was a matt 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 was at least 80.0% by weight.

[0316] The thermoplastic molding material can, for example, contain 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 acid or polyphosphoric acid as a flame retardant, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0317] Particularly preferred in this context are solid, non-migrating phosphoric acid esters with a melting point between 70° C. and 150° C. This results in products that are easy to meter and exhibit significantly less migration in the molding material. Particularly preferred examples are the commercially available phosphoric acid esters PX-200 (CAS: 139189-30-3) from Daihachi, or Sol-DP from ICL-IP. Other phosphoric acid esters with appropriate substitution of phenyl groups are possible when this allows the preferred melting range to be achieved. Depending on the substitution pattern in the ortho or para position on the aromatic ring, the general structural formula is as follows:

[0318]

[0319]

[0320] in

[0321] R 1 =H, methyl, ethyl or isopropyl, but preferably H.

[0322] n=0 to 7, but preferably 0.

[0323] R 2-6 =H, methyl, ethyl or isopropyl, but preferably methyl. 6 Preferred with R 4 and R 5 same.

[0324] m=can be, but needs to be different, and is between 1, 2, 3, 4 and 5, but preferably 2.

[0325] R" = can be H, methyl, ethyl or cyclopropyl, but methyl and H are preferred.

[0326] Taking the PX-200 as a specific example:

[0327]

[0328] It is particularly preferred when at least one aromatic ester of polyphosphoric acid is used. Such aromatic polyphosphates are available, for example, from Daihachi Chemical under the name PX-200.

[0329] Furthermore, as component H), the thermoplastic molding material according to the invention can contain, 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 as described below as a flame retardant, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0330] Examples of preferred flame retardants of component H) in addition to component B) are metal phosphinates derived from hypophosphorous acid. For example, metal salts of hypophosphorous acid with Mg, Ca, Al or Zn as metal can be used. Particularly preferred here is aluminum hypophosphite.

[0331] Also suitable are phosphinic acid salts of the formula (I) and / or diphosphinic acid salts of the formula (II) or polymers thereof.

[0332]

[0333] in

[0334] R 1 , R 2 are identical or different and represent hydrogen, linear or branched C1-C6-alkyl and / or aryl;

[0335] R 3 Indicates a straight or branched C1-C 10 -alkylene, C6-C 10-arylene, -alkylarylene or -aryl-alkylene;

[0336] M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi,

[0337] Sr, Mn, Li, K and / or protonated nitrogen bases;

[0338] m=1 to 4; n=1 to 4; x=1 to 4, preferably m=3, x=3.

[0339] 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.

[0340] Preferably, R 3 represents a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a tert-butylene group, an n-pentylene group, an n-octylene group or an n-dodecylene group, a phenylene group or a naphthylene group; a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group or a tert-butylnaphthylene group; a phenylmethylene group, a phenylethylene group, a phenylpropylene group or a phenylbutylene group.

[0341] Particularly preferably, R 1 , R 2 is hydrogen, methyl, ethyl, and M is Al, particularly preferably aluminum hypophosphite.

[0342] The production of the phosphinate is preferably carried out by precipitation of the corresponding metal salt from an aqueous solution. However, the phosphinate can also be precipitated in the presence of suitable inorganic metal oxides or sulfides (white pigments, such as TiO2, SnO2, ZnO, ZnS, SiO2) as support materials. This thus provides surface-modified pigments which can be used as laser-markable flame retardants for thermoplastic polyesters.

[0343] It is preferred when using metal salts of substituted phosphinic acids in which, compared to hypophosphorous acid, one or two hydrogen atoms have been replaced by phenyl, methyl, ethyl, propyl, isobutyl, isooctyl, or the group R'-CH-OH has been replaced by R'-hydrogen, phenyl, tolyl. The metal is preferably Mg, Ca, Al, Zn, Ti, Fe. Diethylaluminum phosphinate (DEPAL) is particularly preferred.

[0344] With regard to the description of phosphinates or diphosphinates, reference is made to DE-A 199 60 671 as well as DE-A 44 30 932 and DE-A 199 33 901.

[0345] Further suitable flame retardants are, for example, halogen-containing flame retardants.

[0346] Suitable halogen-containing flame retardants are preferably brominated compounds, such as brominated diphenyl ether, brominated trimethylphenylindane (FR 1808 from DSB), tetrabromobisphenol A and hexabromocyclododecane.

[0347] Another suitable brominated flame retardant is the brominated oligomeric carbonate (BC 52 or BC58 from Great Lakes) which has the following structural formula:

[0348]

[0349] Particularly suitable are polypentabromobenzyl acrylates where n>4 (eg FR 1025 from ICL-IP) having the formula:

[0350]

[0351] Preferred brominated compounds also include oligomeric reaction products of tetrabromobisphenol A with epoxides (n>3) (eg, FR 2300 and 2400 from DSB), which have the formula:

[0352]

[0353] The brominated oligostyrenes preferably used as flame retardants have an average degree of polymerization (number average) of 3 to 90, preferably 5 to 60, measured by vapor pressure osmometry in toluene. Cyclic oligomers are also suitable. In a preferred embodiment of the invention, the brominated oligostyrenes have the formula I shown below, in which R represents hydrogen or an aliphatic group, in particular an alkyl group, such as CH2 or C2H5, and n represents the number of repeating chain structural units. R 1 It can be H or bromine or a fragment of a conventional free radical former:

[0354]

[0355] The value n can be from 1 to 88, preferably from 3 to 58. The brominated oligostyrene contains 40.0% to 80.0% by weight, preferably 55.0% to 70.0% by weight of bromine. Preferred is a product consisting mainly of polydibromostyrene. These substances can be melted without decomposition and are soluble in, for example, tetrahydrofuran. The substance can be prepared by ring bromination (optionally aliphatic hydrogenation) of styrene oligomers, which are obtained, for example, by thermal polymerization of styrene (according to DT-OS25 37385) or by free radical oligomerization of suitable brominated styrene. The production of flame retardants can also be achieved by ionic oligomerization of styrene and subsequent bromination. The amount of brominated oligostyrene necessary to impart flame retardant properties to polyamide depends on the bromine content. The bromine content in the molding material according to the present invention is from 2.0% to 30.0% by weight, preferably from 5.0% to 12.0% by weight.

[0356] The brominated polystyrene according to the invention is generally obtained by the process described in EP-A 047 549:

[0357]

[0358] The brominated polystyrenes obtainable by this process and commercially available are predominantly ring-substituted tribrominated products. n' (see III) generally has a value of 125 to 1500, which corresponds to a molecular weight of 42500 to 235000, preferably 130000 to 135000.

[0359] 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 and in particular 65.0% by weight.

[0360] Commercially available powdered products generally have a glass transition temperature of 160° C. to 200° C. and are available, for example, from Albemarle under the name HP-7010 was obtained from Ferro Corporation under the name PB 68 obtained.

[0361] Mixtures of brominated oligostyrenes with brominated polystyrenes can also be used in the molding materials according to the invention, the mixing ratio being freely selectable.

[0362] Suitable halogen-containing flame retardants are preferably ring-brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxide oligomer or brominated bisphenol A polycarbonate.

[0363] Chlorine-containing flame retardants are also suitable, preferably Decoran from OxyChem

[0364] In one embodiment of the invention, no halogen-containing flame retardants are used in the thermoplastic molding materials according to the invention.

[0365] In the context of the present invention, a flame retardant melamine compound suitable as component H) is a melamine compound which, when added to glass-fiber-filled polyamide molding materials, reduces the flammability and influences the burning behavior in a flame-retardant manner, leading to improved performance in the UL 94 test and the glow-wire test.

[0366] The melamine compound is for example selected from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, cyanuramide or melamine cyanurate or mixtures thereof.

[0367] Melamine cyanurates which are preferably suitable according to the invention are reaction products of melamine (formula I) and cyanuric acid / isocyanuric acid (formulas Ia and Ib) in preferably equimolar amounts.

[0368]

[0369] It is obtained, for example, by reacting an aqueous solution of the starting compounds at 90° C. to 100° C. Commercially available products are 50 1.5 to 7 μm and d 99 White powder with a particle size of less than 50 μm.

[0370] Further suitable compounds (also generally described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalates, phosphate prim., phosphate sec. and pyrophosphate sec., melamine neopentyl glycol borate. According to the invention, the molding material preferably does not contain polymerized melamine phosphate (CAS No. 56386-64-2 or 218768-84-4).

[0371] This is understood to mean melamine polyphosphates of 1,3,5-triazine compounds, whose average degree of condensation n is from 20 to 200 and whose 1,3,5-triazine content is from 1.1 mol to 2.0 mol of 1,3,5-triazine compounds selected from the group consisting of melamine, melam, melem, cyanuric acid amide, ammeline, ammeline, 2-ureidomelamine, acetoguanamine, benzoguanamine and diaminophenyltriazine per mole of phosphorus atom. Preferably, the n value of such salts is generally from 40 to 150, and the ratio of 1,3,5-triazine compounds per mole of phosphorus atom is preferably from 1.2 to 1.8. In addition, the pH of a 10% by weight aqueous slurry of the salt prepared according to EP-B 1095 030 is generally greater than 4.5 and preferably at least 5.0. The pH is usually 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 above n value (number average degree of condensation) can be determined by 31P solid-state NMR. JR van Wazer, CF Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956 disclosed that the number of adjacent phosphate groups gives a unique chemical shift, which allows a clear distinction between orthophosphates, pyrophosphates and polyphosphates.

[0372] Suitable guanidine salts are

[0373]

[0374]

[0375] In the context of the present invention, "compounds" are understood to mean not only, for example, benzoguanamine itself and its adducts / salts, but also nitrogen-substituted derivatives and their adducts / salts.

[0376] Also suitable is ammonium polyphosphate (NH4PO3) n , wherein n is about 200 to 1000, preferably 600 to 800, and tris(hydroxyethyl)isocyanurate (THEIC) of formula IV

[0377]

[0378] or with aromatic carboxylic acid Ar(COOH) m wherein Ar represents a monocyclic, bicyclic or tricyclic aromatic six-membered ring system and m is 2, 3 or 4.

[0379] Examples of suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, benzilic acid, pyromellitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalene dicarboxylic acid, and anthracenecarboxylic acid.

[0380] According to the process of EP-A 584 567, production is carried out by reaction of tris(hydroxyethyl)isocyanurate with acids, their alkyl esters or their halides.

[0381] Such reaction products are mixtures of monomers and oligoesters, which may also be crosslinked. The degree of oligomerization is generally from 2 to about 100, preferably from 2 to 20. Preference is given to using THEIC and / or its reaction products with phosphorus-containing nitrogen compounds, in particular (NH4PO3) n or mixtures of melamine pyrophosphate or polymerized melamine phosphates. For example, (NH4PO3) n The mixing ratio with THEIC is preferably 90.0 to 50.0:10.0 to 50.0, in particular 80.0 to 50.0:50.0 to 20.0, % by weight, based on the mixture of such compounds.

[0382] Likewise suitable flame retardants are benzoguanidine compounds of the formula V

[0383]

[0384] Therein R, R′ denotes a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, preferably hydrogen, and in particular adducts thereof with phosphoric acid, boric acid and / or pyrophosphoric acid.

[0385] Also preferred are allantoin compounds of formula VI,

[0386]

[0387] wherein R and R' are as defined in formula V, and salts thereof with phosphoric acid, boric acid and / or pyrophosphoric acid, and glycoluril of formula VII or salts thereof with the above acids

[0388]

[0389] wherein R is as defined in Formula V.

[0390] According to DE-A 196 14 424, suitable products are commercially available or obtainable.

[0391] Cyanoguanidine (formula VIII) which can be used according to the invention can be obtained, for example, by reacting calcium cyanamide with carbonic acid, the resulting cyanamide dimerizing at pH 9 to pH 10 to provide cyanoguanidine.

[0392] CaNCN+H2O CO2→H2N-CN+CaCO3

[0393]

[0394] The commercially available product is a white powder having a melting point of 209 to 211°C.

[0395] Particular preference is given to using melamine cyanurate (e.g. MC25).

[0396] It is also possible to use individual 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 is made to EP-A 0 624 626.

[0397] Phosphorus (eg red phosphorus) can also be used as a flame retardant. Red phosphorus can be used, for example, in the form of a masterbatch.

[0398] Also considered are dicarboxylic acids of the formula:

[0399]

[0400] in

[0401] R 1 To R 4 independently of one another represent halogen or hydrogen, provided that at least one radical R 1 To R 4 represents halogen,

[0402] x=1 to 3, preferably 1, 2

[0403] m=1 to 9, preferably 1 to 3, 6, 9, especially 1 to 3

[0404] n=2 to 3

[0405] M = alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg.

[0406] Preferred dicarboxylates contain, independently of one another, Cl or Br or H as radical R 1 To R 4 , particularly preferably all radicals R 1 To R 4 It is Cl and / or Br.

[0407] As the metal M, Be, Mg, Ca, Sr, Ba, Al, Zn and Fe are preferred.

[0408] Such dicarboxylates are commercially available or can be prepared according to the method described in US 3,354,191.

[0409] Functional polymers can also be used as component H). These can be, for example, flame retardant polymers. Such polymers are described, for example, in US 8,314,202 and contain repeating units of 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone. Another suitable functional polymer for increasing the amount of residual carbon is poly(2,6-dimethyl-1,4-phenylene ether) (PPPO).

[0410] Component I)

[0411] As component I), 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), D), optionally E), optionally F), optionally G), optionally H) and optionally I),

[0412] If further additives are used, the minimum amount is preferably 0.1 wt.-%, more preferably 0.25 wt.-%, most preferably 0.4 wt.-%, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0413] If component I) is present, the maximum amount of component A) is reduced by the minimum amount of component I) so that the total amount of components A) to I) is still 100% by weight.

[0414] It is also possible to use mixtures of two or more additives.

[0415] The thermoplastic molding compositions of the invention may comprise as component I) customary processing aids, further stabilizers, oxidation retarders, agents for preventing thermal and UV decomposition, lubricants and mold release agents, colorants other than the colorants mentioned as component C), nucleating agents, plasticizers, elastomeric polymers, etc.

[0416] The molding compositions of the invention can comprise, as component I1), 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, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0417] 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.

[0418] The metal ions are preferably alkaline earth metals and Al, particularly preferably Ca or Mg.

[0419] Preferred metal salts are calcium stearate and calcium montanate, and aluminum stearate.

[0420] It is also possible to use mixtures of the various salts in any desired mixing ratios.

[0421] The carboxylic acids may be monobasic or dibasic. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, heptadecanoic acid, dodecanedioic acid, behenic acid, and particular preference is given to stearic acid, capric acid and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0422] The fatty alcohols may be monohydric to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preferably glycerol and pentaerythritol.

[0423] The aliphatic amines may be monobasic or tribasic. Examples of these aliphatic amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are, respectively, glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate and pentaerythritol tetrastearate.

[0424] It is also possible to use mixtures of various esters or amides, or combinations of esters and amides in any desired mixing ratio.

[0425] As component I2), the molding material according to the invention may contain preferably 0.01% to 3% by weight, particularly preferably 0.02% to 2% by weight, in particular 0.05% to 1.0% by weight, of at least one heat stabilizer, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0426] The heat stabilizer is preferably selected from the group consisting of copper compounds, aromatic secondary amines, hindered phenols, phosphites, phosphonites, and mixtures thereof.

[0427] As component I2), 0.05 to 3% by weight, preferably 0.1 to 2% by weight, in particular 0.1 to 1% by weight, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I), of at least one sterically hindered phenol antioxidant can be used.

[0428] This component I2) preferably has a molecular weight of more than 500 g / mol, more preferably more than 1000 g / mol. In addition, component I) should preferably exhibit a high thermal stability, for example a maximum weight loss of 5%, more preferably a maximum weight loss of 2%, measured in a TGA (thermogravimetric analysis) experiment at 300° C. under nitrogen (from 40° C. to 120° C. at 10° C. / min, isothermal at the latter temperature for 15 minutes, then from 120° C. to 600° C. at 20° C. / min).

[0429] Component I2) preferably has at least one, more preferably at least two, branched C 3-12 The phenolic groups substituted with alkyl groups act as steric hindering groups. The substituted phenolic groups are covalently linked to the structure of component I2).

[0430] Suitable sterically hindered phenols I2) are in principle all compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring. 3-12 -alkyl group, preferably branched C 3-6 - an alkyl group, more preferably an isopropyl or tert-butyl group.

[0431] Preferably, compounds of the formula:

[0432]

[0433] in:

[0434] R 1 and R 2 is an alkyl group, a substituted alkyl group or a substituted triazole group, and wherein the group R 1 and R 2 can be the same or different, and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group. The alkyl and alkoxy residues preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The substituents are preferably C 1-12 -alkyl, more preferably C 1-6 -alkyl, most preferably C 1-4 -alkyl. 1 To R 3 At least one of is preferably a bulky group as defined above.

[0435] Antioxidants of the aforementioned type are described, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).

[0436] Another group of preferred hindered phenols is provided by those radicals derived from substituted phenylcarboxylic acids, in particular derived from substituted phenylpropionic acids, said radicals preferably having at least one bulky group on the phenyl group. Said radicals contain in their structure at least one, preferably two, covalently linked substituted phenylcarboxylic acid units, which preferably have at least one bulky group on the phenyl group.

[0437] The preferred phenyl carboxylic acid is phenyl-C 1-12 -carboxylic acid, more preferably phenyl-C 2-6 As mentioned above, the phenyl group is preferably a phenol group having at least one bulky group on the phenol ring. Therefore, the above-mentioned hindered phenol is preferably C 1-12 -alkanecarboxylic acid, more preferably straight chain C 2-6 -Alkane carboxylic acid is covalently linked.

[0438] Particularly preferred compounds of this type are those of the formula

[0439]

[0440] Where R 4 , R 5 , R 7 and R 8 are independently C1-C8-alkyl groups, which themselves may have substituents (at least one of these groups is a bulky group), and R 6 R is a divalent aliphatic group having 1 to 10 carbon atoms and whose main chain may further have a CO bond. 4 To R 8 At least one of is a bulky group as defined above.

[0441] Preferred compounds corresponding to these formulae are

[0442]

[0443] As examples of hindered phenols, all of the following should be mentioned:

[0444] 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (from BASF SE 1010), 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid distearyl ester, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-yl methyl ester, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazolylamine, 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.

[0445] Compounds which have proven to be particularly effective and which are therefore preferably used are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( 259), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] and N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamamide ( 1098) and the above-mentioned products from BASF SE 245 and 1010, they have particularly good applicability.

[0446] In certain cases, sterically hindered phenols having not more than one sterically hindering group in the ortho position relative to the phenolic hydroxyl group have proven to be particularly advantageous; in particular when assessing color fastness during storage over a long period of time in diffuse light.

[0447] Furthermore, it is advantageous to use sterically hindered phenolic antioxidants which also have a sufficiently high molecular weight, preferably a molecular weight of more than 500 g / mol, in particular more than 1000 g / mol. Furthermore, they preferably exhibit a high thermal stability measured by TGA (thermogravimetric analysis), with a degradation of less than 2% up to 300° C. under a nitrogen atmosphere.

[0448] The molding compositions of the invention can comprise, as component I2), 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, in particular 0.1 to 1% by weight, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I), of at least one copper stabilizer (preferably Cu(I) halide), in particular as a mixture with an alkali metal halide (preferably KI), in particular in a ratio of 1:4 or a mixture of a sterically hindered phenol, or mixtures thereof.

[0449] Preferred monovalent copper salts used are cuprous acetate, cuprous chloride, cuprous bromide and cuprous iodide. The material contains these in an amount of 5 ppm to 500 ppm of copper, preferably 10 ppm to 250 ppm, based on the polyamide.

[0450] Advantageous properties are particularly obtained if the copper is present in the polyamide in molecular distribution. The above-mentioned advantageous properties can be achieved if a concentrate containing polyamide, a monovalent copper salt and an alkali metal halide is added to the molding composition in the form of a solid, homogeneous solution. For example, a typical concentrate consists of 79% to 95% by weight of polyamide and 21% to 5% by weight of a mixture of cuprous iodide or cuprous bromide and potassium iodide. The copper concentration in the solid homogeneous solution is preferably 0.3% to 3% by weight, in particular 0.5% to 2% by weight, based on the total weight of the solution, and the molar ratio of cuprous iodide to potassium iodide is 1 to 11.5, preferably 1 to 5.

[0451] Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular PA6.

[0452] According to a preferred embodiment of the invention, the molding composition is free of copper, in particular free of copper stabilizers such as Cu / (I) halides, and combinations of Cu(I) halides with alkali metal halides.

[0453] More preferably, the thermoplastic molding composition of the invention is free of metal halides.Systems free of metal halides, so-called electro-friendly systems, are of great interest since electromobility, electrification and connectivity are a growing trend in almost all industries.

[0454] The thermoplastic molding composition is therefore preferably free of metal halides, in particular Cu halides and alkali metal halides.

[0455] UV stabilizers which may be mentioned as component I3) are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, the amounts used being generally up to 2% by weight, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I). Aniline black may also be used.

[0456] Materials component I4) which can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc.

[0457] The molding compositions of the invention may comprise, as component I5), 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, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0458] Suitable plasticizers are described in Kunststoff-Handbuch, Band V Polyamide, Carl Hanser Verlag München 1966, Section 3.4.2.1.b) on pages 238 and 239 in conjunction with Table 7. They can be divided into aromatic hydroxy compounds, sulfonamides and further plasticizers such as lactams, lactones, alcohols and the like.

[0459] Suitable plasticizers are, for example, poly(trimethylene ether) glycol (PPD), preferably poly(trimethylene ether) glycol (PPD) 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, in particular sulfonamides, for example, 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 the general formula (1).

[0460] R1-O-(CH2CH2-O-) n R2 (1)

[0461] Where n = 1 to 10

[0462] R1 and R2 are independently H, C 1-12 - alkyl, phenyl or tolyl,

[0463] It has a boiling point of over 250°C.

[0464] Preferred plasticizers of formula (1) are based on triethylene glycol, tetraethylene glycol, pentaethylene glycol or mixtures thereof. Tetraethylene glycol is most preferred. Therefore, n most preferably has a value of 3.8 to 4.2, most preferably 4.

[0465] Tetraethylene glycol is nontoxic and has high plasticizing efficiency. Compared with sulfonamide and lactam, only half the amount of tetraethylene glycol is needed to achieve the same plasticizing effect and the reduction of the same glass transition temperature. Therefore, in a preferred embodiment, in the presence of a plasticizer as component 15), the thermoplastic molding composition comprises a compound of formula (1) as a plasticizer.

[0466] As component I6), the molding composition of the invention may comprise 1% to 45% by weight, preferably 2% to 40% by weight, of at least one elastomeric polymer, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0467] Component I6) can be chosen from all elastomeric polymers, impact modifiers, elastomers or rubbers which are suitable for polyamide molding compositions.

[0468] Preferably component I6) is selected from

[0469] b1) Copolymers of ethylene and at least one comonomer selected from the group consisting of

[0470] C 3-12 -Olefin, (meth)acrylic acid C 1-12 - alkyl esters, (meth)acrylic acid and maleic anhydride as component B1),

[0471] b2) polyethylene or polypropylene as component B2),

[0472] Components B1) and B2) may also be grafted with maleic anhydride, preferably from ethylene-propylene rubbers, ethylene-propylene-diene rubbers, ethylene-butyl acrylate copolymers, copolymers of ethylene and / or propylene and maleic anhydride and mixtures thereof.

[0473] These elastomeric polymers (also often called impact modifiers, elastomers or rubbers) are typically copolymers, preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutylene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylates and / or methacrylates having 1 to 18 carbon atoms in the alcohol component.

[0474] Such polymers are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pp. 392 to 406 and in the monograph by CB Bucknall, Toughened Plastics (Applied Science Publishers, London, UK, 1977).

[0475] Examples of suitable elastomers are available, for example, from Lyondellbasell under the names Lucalen A2540D and Lucalen A2700M. Lucalen A2540D is a low density polyethylene containing butyl acrylate comonomer. It has a molecular weight of 0.923 g / cm 3 The density and Vicat softening temperature of 85°C, and the melting temperature is 103°C when the proportion of butyl acrylate is 6.5% by weight.

[0476] Lucalen A2700M is a low density polyethylene that also contains butyl acrylate comonomer. It has a molecular weight of 0.924 g / cm 3 density, a Vicat softening temperature of 60°C and a melting temperature of 95°C.

[0477] Exxelor polymer resin from ExxonMobil TM VA 1801 is a semi-crystalline ethylene copolymer functionalized with maleic anhydride by reactive extrusion and has a medium viscosity. The polymer backbone is fully saturated. The density is 0.880 g / cm 3 , and the proportion of maleic anhydride is usually in the range of 0.5 wt % to 1.0 wt %.

[0478] In addition to the colorants mentioned under C) and F), carbon black or aniline black, for example, are used as colorants.

[0479] As component I7), the molding composition of the invention may comprise 0.1 to 3% by weight, preferably 0.2 to 2.5% by weight, of at least one flow enhancer, based on the total amount of components A), B), C), D), optionally E), optionally F), optionally G), optionally H) and optionally I).

[0480] Examples of suitable flow enhancers are branched, hyperbranched or dendritic components, typically macromolecules such as polymers containing functional groups such as -NH2, -OH, -COOH or -COOCH3.

[0481] The macromolecule may be, for example, a polyamide-based polymer or a polyester.

[0482] Examples are CYD-701, CYD-C600, CYD-819, CYD-816A (all Weihai CY Dendrimer Technology Co, Ltd.), HyPer C100 (Wuhan HyPer Branched Polymers Science Technology Co., Ltd.), TER-PA9 from TER HELL & Co. GmbH and Bruggolen TP-P1507 and TP-P1810 from L. Brüg-ge-mann GmbH & Co. KG.

[0483] Dendrimers consist of two types of structural units: terminal units on the spherical surface and dendritic units in the interior. Therefore, dendrimers are well-defined in structure. On the other hand, hyperbranched polymers have three types of structural units: dendritic units, linear units, and terminal units. The terminal units are always located at the ends, whereas the dendritic units and linear units are randomly distributed within the macromolecular framework, resulting in an irregular structure.

[0484] Composition

[0485] The composition according to the invention is characterized by a very high color stability, in particular at high temperatures, whereby the odor of the composition is reduced or absent, which is obtained by using a combination of i) at least one sodium hypophosphite or sodium hypophosphite hydrate (component B)) and ii) at least one acid scavenger (component D)) in the presence of at least one sulfur-containing colorant containing at least one non-covalently bonded sulfur atom (component C)).

[0486] Therefore, the thermoplastic molding composition of the present invention comprises

[0487] a) 10 to 99.97 wt. %, preferably 20 to 85 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component E) as component A), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA

[0488] 66 / 6 and / or PA 6 / 6.36;

[0489] 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 as component B),

[0490] c) 0.01 to 5% by weight of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, as component C),

[0491] d) 0.01 to 2% by weight, preferably 0.02 to 1.8% by weight, more preferably 0.03 to 1.5% by weight, of at least one acid scavenger as component D),

[0492] e) 0 to 20 wt.-%, preferably 0.01 to 18 wt.-%, more preferably 0.1 to 17 wt.-%, most preferably 1 to 16 wt.-% of at least one polyamide 6I / 6T as component E), preferably 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 and most preferably in the range of 1.8:1 to 2.3:1;

[0493] f) 0 to 5% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.5 to 2.5% by weight, of at least one laser engraving additive, preferably at least one pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, glitter, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F),

[0494] g) 0 to 60 wt. %, preferably 10 to 55 wt. %, more preferably 15 to 50 wt. % of at least one fiber and / or particle filler as component G), preferably glass fibers, these glass fibers are more preferably modified with a size system or an adhesion promoter / adhesion promoter system, which adhesion promoter / adhesion promoter system is further most preferably based on silanes,

[0495] h) 0% to 55% by weight, preferably 1% to 35% by weight, more preferably 2% to 25% by weight, of at least one flame retardant additive as component H), and

[0496] i) 0 to 25% by weight, preferably 0.1 to 20% by weight, more preferably 0.25 to 15% by weight, of at least one further additive as component I),

[0497] The total weight percentage of components A) to I) is 100 weight %.

[0498] Suitable and preferred components A), B), C), D), E), F), G), H) and I) and the amounts of said components in the thermoplastic molding compositions according to the invention are as stated above.

[0499] The thermoplastic molding composition of the invention is a filled composition, i.e. comprises as component G) 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 20 to 50% by weight, of at least one fiber and / or particle filler, or is an unfilled composition, i.e. comprises as component G) 0% by weight of fiber and / or particle filler.

[0500] In one embodiment, the thermoplastic molding composition of the present invention is a filled composition comprising

[0501] a) 10 to 89.97 wt. %, preferably 20 to 80 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component D) as component A), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA

[0502] 66 / 6 and / or PA 6 / 6.36;

[0503] 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 as component B),

[0504] c) 0.01 to 5% by weight of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, as component C),

[0505] d) 0.01 to 2% by weight, preferably 0.02 to 1.8% by weight, more preferably 0.03 to 1.5% by weight, of at least one acid scavenger as component D),

[0506] e) 0 to 20 wt.-%, preferably 0.01 to 18 wt.-%, more preferably 0.1 to 17 wt.-%, most preferably 1 to 16 wt.-% of at least one polyamide 6I / 6T as component E), preferably 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 and most preferably in the range of 1.8:1 to 2.3:1;

[0507] f) 0 to 5% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.5 to 2.5% by weight, of at least one laser engraving additive, preferably at least one pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, glitter, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F),

[0508] g) 10 to 60 wt. %, preferably 15 to 55 wt. %, more preferably 20 to 50 wt. % of at least one fiber and / or particulate filler as component G), preferably glass fibers, these glass fibers are more preferably modified with a size system or an adhesion promoter / adhesion promoter system, which adhesion promoter / adhesion promoter system is further most preferably based on silanes,

[0509] h) 0% to 55% by weight, preferably 1% to 35% by weight, more preferably 2% to 25% by weight, of at least one flame retardant additive as component H), and

[0510] i) 0 to 25% by weight, preferably 0.1 to 20% by weight, more preferably 0.25 to 15% by weight, of at least one further additive as component I),

[0511] The total weight percentage of components A) to I) is 100 weight %.

[0512] Suitable and preferred components A), B), C), D), E), F), G), H) and I) and the amounts of said components in the thermoplastic molding compositions according to the invention are as stated above.

[0513] Due to their color stability, in particular at high temperatures, the thermoplastic molding compositions of the invention can be used in particular for providing colored products, preferably orange products, which are used, for example, for providing high-voltage systems.

[0514] Therefore, the thermoplastic molding composition of the present invention more preferably comprises

[0515] a) 10 to 99.97 wt. %, preferably 20 to 85 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component E) as component A), most preferably component A) is PA 6, PA66, PA 6 / 66,

[0516] PA 66 / 6 and / or PA 6 / 6.36;

[0517] 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 as component B),

[0518] c) 0.01 to 5% by weight of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, particularly preferably in the 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 and very particularly preferably in the shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system as component C),

[0519] d) 0.01 to 2% by weight, preferably 0.02 to 1.8% by weight, more preferably 0.03 to 1.5% by weight, of at least one acid scavenger as component D),

[0520] e) 0 to 20 wt.-%, preferably 0.01 to 18 wt.-%, more preferably 0.1 to 17 wt.-%, most preferably 1 to 16 wt.-% of at least one polyamide 6I / 6T as component E), preferably 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 and most preferably in the range of 1.8:1 to 2.3:1;

[0521] f) 0 to 5% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.5 to 2.5% by weight, of at least one laser engraving additive, preferably at least one pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, glitter, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F),

[0522] g) 0 to 60 wt. %, preferably 10 to 55 wt. %, more preferably 15 to 50 wt. % of at least one fiber and / or particle filler as component G), preferably glass fibers, these glass fibers are more preferably modified with a size system or an adhesion promoter / adhesion promoter system, which adhesion promoter / adhesion promoter system is further most preferably based on silanes,

[0523] h) 0% to 55% by weight, preferably 1% to 35% by weight, more preferably 2% to 25% by weight, of at least one flame retardant additive as component H), and

[0524] i) 0 to 25% by weight, preferably 0.1 to 20% by weight, more preferably 0.25 to 15% by weight, of at least one further additive as component I),

[0525] The total weight percentage of components A) to I) is 100 weight %.

[0526] Suitable and preferred components A), B), C), D), E), F), G), H) and I) and the amounts of said components in the thermoplastic molding compositions according to the invention are as stated above.

[0527] In one embodiment, the thermoplastic molding composition of the present invention is a filled and colored composition comprising

[0528] a) 10 to 89.97 wt. %, preferably 20 to 80 wt. %, more preferably 30 to 75 wt. % of at least one thermoplastic polyamide different from component D) as component A), most preferably component A) is PA 6, PA 66, PA 6 / 66, PA 66 / 6 and / or PA 6 / 6.36;

[0529] 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 as component B),

[0530] c) 0.01 to 5% by weight of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, particularly preferably in the RAL color system with the color numbers RAL 2001, RAL 2003, RAL 2004, RAL 2007, RAL 2008, RAL 2009, RAL 2010 and RAL 2011.

[0531] 2011, and very particularly preferably the shades corresponding to the color numbers RAL 2003, RAL 2008 and RAL 2011 in the RAL color system as component C),

[0532] d) 0.01 to 2% by weight, preferably 0.02 to 1.8% by weight, more preferably 0.03 to 1.5% by weight, of at least one acid scavenger as component D),

[0533] e) 0 to 20 wt.-%, preferably 0.01 to 18 wt.-%, more preferably 0.1 to 17 wt.-%, most preferably 1 to 16 wt.-% of at least one polyamide 6I / 6T as component E), preferably 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 and most preferably in the range of 1.8:1 to 2.3:1;

[0534] f) 0 to 5% by weight, preferably 0.1 to 3.5% by weight, more preferably 0.5 to 2.5% by weight, of at least one laser engraving additive, preferably at least one pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, glitter, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F),

[0535] g) 10 to 60 wt. %, preferably 15 to 55 wt. %, more preferably 20 to 50 wt. % of at least one fiber and / or particulate filler as component G), preferably glass fibers, these glass fibers are more preferably modified with a size system or an adhesion promoter / adhesion promoter system, which adhesion promoter / adhesion promoter system is further most preferably based on silanes,

[0536] h) 0% to 55% by weight, preferably 1% to 35% by weight, more preferably 2% to 25% by weight, of at least one flame retardant additive as component H), and

[0537] i) 0 to 25% by weight, preferably 0.1 to 20% by weight, more preferably 0.25 to 15% by weight, of at least one further additive as component I),

[0538] The total weight percentage of components A) to I) is 100 weight %.

[0539] Suitable and preferred components A), B), C), D), E), F), G), H) and I) and the amounts of said components in the thermoplastic molding compositions according to the invention are as stated above.

[0540] The thermoplastic molding compositions of the invention can be produced by methods known per se, by mixing the starting components A), B), C), D) and optionally E), optionally F), optionally G), optionally H) and optionally I) in conventional mixing equipment, such as screw-based extruders, Brabender mixers or Banbury mixers, and then extruding them. 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 separately and / or likewise in the form of a mixture. The barrel temperature is generally 230° C. to 330° C.

[0541] application

[0542] These materials are suitable for producing mouldings, fibres, films and extruded articles, preferably mouldings, the mouldings more preferably being coloured and the mouldings most preferably being orange.

[0543] Therefore, the present invention further relates to a molded or extruded article, preferably a molded article, more preferably a colored molded article, most preferably an orange molded article, made from the thermoplastic molding composition according to the invention or obtained by the process according to the invention.

[0544] The thermoplastic molding composition of the present invention can be used in the electrical and electronic fields to produce, for example, 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 connectors, terminal strips, connector plugs, device connectors, cable harness assemblies, circuit mounts, circuit mount assemblies, three-dimensional injection molded circuit mounts, electrical connection elements, and electromechanical assemblies.

[0545] Since the preferred thermoplastic molding composition of the present invention is orange, in a preferred embodiment, the molded or extruded article is a high voltage component, especially a high voltage component for an electric vehicle. The high voltage component is selected from the group consisting of: a cover for an electrical or electronic device, a control device, a cover or housing for a fuse, a relay, a battery cell module, a fuse holder, a fuse plug, a terminal, a cable bracket or a sheath, especially a sheath for a high voltage busbar and a high voltage distributor busbar.

[0546] The method further comprises

[0547] i) mixing components A), B), C), D) and optionally E), optionally F), optionally G), optionally H) and optionally I),

[0548] ii) extruding the composition obtained in step i) to obtain a strand,

[0549] iii) cooling the strands obtained in step ii) until they can be granulated, granulating and optionally drying, and

[0550] iv) further processing the pelletized strands obtained in step iii) preferably by injection molding or extrusion methods, including profile extrusion.

[0551] The inventors have found that by using at least one acid scavenger, a polyamide composition comprising a combination of sodium hypophosphite or sodium hypophosphite hydrate and at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom can be obtained, having very high color stability, especially at high temperatures, and without or with reduced hydrogen sulfide odor.

[0552] The present invention therefore further relates to the use of at least one acid scavenger in a thermoplastic molding composition for improving the odor of the thermoplastic molding composition, the thermoplastic molding composition comprising i) at least one thermoplastic polyamide, ii) at least one of sodium hypophosphite or sodium hypophosphite hydrate, and iii) a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom. Example

[0553] The following components were used:

[0554] Component A1: with a A24) Polyamide-66 having a viscosity of 115 ml / g to 135 ml / g, measured at 25° C. in 0.5% by weight of 96% by weight sulfuric acid solution

[0555] Component A2: with ISO 307:2019 (from EMS G21 Natural) Polyamide 6I / 6T with a relative viscosity of 1.47-1.57 measured in 0.5% m-cresol solution at 20°C

[0556] Component B: Commercially available glass fibers for polyamide having a length of 4.5 mm and a diameter of 10 μm (standard E glass fibers)

[0557] Component C: Commercially available calcium stearate (CAS: 1592-23-0)

[0558] Component D1: Commercially available from BASF SE 1098

[0559] Component D2: Commercially available sodium hypophosphite monohydrate (CAS: 10039-56-2)

[0560] Component E1: Commercially available zinc sulfide (CAS: 1314-98-3)

[0561] Component E2: A pigment mixture comprising at least one sulfur-containing colorant containing at least one non-covalently bonded sulfur atom, in order to obtain an orange color in RAL 2003

[0562] Component F1: Commercially available hydrotalcite ([carbonate (2-)] hexadecanoic acid bis (aluminum) hexa-magnesium 713, CAS: 11097-59-9), sold under the trade name 713 is known from BASF SE.

[0563] Component F2: Commercially available zinc oxide (CAS: 1314-13-2)

[0564] Component F3: commercially available zinc stannate (CAS: 12036-37-2), sold under the trade name S known from William Blythe Ltd.

[0565] Component F4: commercially available anhydrous zinc borate (CAS: 12767-90-7), sold under the trade name 500 Known from Nordmann, Rassmann GmbH

[0566] Component F5: commercially available zinc borate hydrate (CAS: 138265-88-0), sold under the trade name ZB is known from Nordmann, Rassmann GmbH

[0567] Component F6: Zinc ricinoleate commercially available under the trade name TEGO PY 88TQ known from Evonik

[0568] Component F7: commercially available surface-modified magnesium hydroxide (CAS: 1309-42-8), sold under the trade name H-5IV known from Martinswerke

[0569] Component F8: Commercially available lanthanum carbonate (CAS: 587-26-8)

[0570] Preparation of particles:

[0571] 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 drum mixer for 10 minutes. In the next step, the dried polyamide granules were melt extruded together with the dried blended ingredients using a twin screw extruder with a diameter of 25 mm and an L / D ratio of 44. The extruder was heated at 240 min. -1 The system was operated at a rotation speed of 1000 rpm, a throughput of 16 kg / h and a barrel temperature of 280°C to 310°C with a flat temperature profile. The obtained strands were cooled in a water bath, pelletized and packed in aluminum foil bags. After several days of storage, the bags were reopened and the smell / odor was verified.

[0572]

[0573] The above examples illustrate that hydrogen sulfide formation, and therefore hydrogen sulfide odor, can be inhibited by using an acid scavenger in a polyamide composition comprising a combination of sodium hypophosphite and at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom (typically present in the colorant or colorant mixture).

Claims

1. A thermoplastic molding composition comprising a) as component A) 10% to 99.97% by weight of at least one thermoplastic polyamide different from component E), b) 0.01% to 0.5% by weight of at least one of sodium hypophosphite or sodium hypophosphite hydrate as component B), c) 0.01 to 5% by weight of a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom, preferably an orange colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom which lead to an orange color, as component C), d) from 0.01% to 2% by weight of at least one acid scavenger as component D), e) 0 to 20% by weight of at least one polyamide 6I / 6T as component E), f) 0% to 5% by weight of at least one laser engraving additive, Preferably at least one pigment system comprising a metal oxide or a mixture of two or more metal oxides, more preferably antimony trioxide, titanium dioxide, tin oxide, ferrous oxide, zinc oxide, aluminum oxide, bismuth trioxide or mixtures thereof as component F), g) 0% to 60% by weight of at least one fiber and / or particulate filler as component G), g) 0% to 55% by weight of at least one flame retardant additive as component H), and i) 0% to 25% by weight of at least one further additive as component I), The total weight percentage of components A) to I) is 100 weight %.

2. The thermoplastic molding composition according to claim 1, wherein component A) is selected from aliphatic and semiaromatic polyamides, preferably PA 6, PA 66, PA 46, PA 6 / 66, PA 66 / 6, PA 6 / 636, PA610, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 66, PA 9T and PA 6T / 66 and mixtures thereof, more preferably PA 6, PA 66, PA 66 / 6, PA 6 / 66, PA6 / 636 and mixtures thereof, and most preferably PA 6 and PA 66 and mixtures thereof.

3. The thermoplastic molding composition according to claim 1 or 2, wherein the amount of component B) is 0.06% to 0.45% by weight, preferably 0.1% to 0.4% by weight.

4. Thermoplastic molding composition according to any one of claims 1 to 3, wherein component D) is at least one organic or inorganic base, preferably at least one inorganic base, more preferably selected from the group consisting of oxides, hydroxides, carbonates, silicates, borates, stannates, mixed oxide-hydroxides, oxide-hydroxide-carbonates, hydroxide-silicates or hydroxide-borates of at least one element selected from the group consisting of alkali metals, alkaline earth metals, elements of the boron group (Group 13 of the IUPAC version of the Periodic Table of the Elements), zinc and tin; salts of fatty acids; hydrotalcites; ricinoleates; and mixtures thereof.

5. The thermoplastic molding composition according to any one of claims 1 to 4, wherein component E) consists of units derived from hexamethylenediamine, derived from terephthalic acid and derived from isophthalic acid, 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 particularly preferably in the range of 1.8:1 to 2.3:

1.

6. The thermoplastic molding composition according to any one of claims 1 to 5, wherein component G) is selected from the group consisting of carbon fibers, glass beads, for example solid or hollow glass beads, glass fibers, ground glass, amorphous quartz glass, aluminoborosilicate glass with an alkali content of about 1%, amorphous silicon dioxide, quartz powder, alkaline earth metal silicates, in particular calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, gold Mica, barium sulfate, feldspar, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, hectorite, laponite, pseudo-boehmite of formula AIO(OH), magnesium carbonate, talc, aramid fiber, potassium titanate fiber, barium carbonate, alkaline earth metal oxides, metal fiber, ceramic fiber, titanium dioxide, aluminum oxide, gypsum, zirconium oxide, antimony oxide, clay, silica-alumina, sericite, diatomaceous earth, silica, carbon black, glass hollow microspheres, red oxide, zinc oxide and mixtures thereof.

7. Thermoplastic molding composition according to any one of claims 1 to 6, wherein component H) is at least one halogen-free flame retardant and / or at least one halogen-containing flame retardant, preferably at least one member selected from the group consisting of phosphazenes, aliphatic or aromatic esters of phosphoric acid or polyphosphoric acid, 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 in R 1 To R 4 independently of one another represent halogen or hydrogen, provided that at least one radical R 1 to R 4 represents halogen, x=1 to 3, preferably 1 or 2, m=1 to 9, preferably 1 to 3, 6, 9, especially 1 to 3, n = 2 or 3, M = alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg, Functional polymers comprising 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone repeating units and poly(2,6-dimethyl-1,4-phenylene ether) (PPO).

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

9. Use of the thermoplastic molding composition according to any one of claims 1 to 7 or obtained by the process according to claim 8 for producing molded articles, fibers, films and extruded articles, preferably molded articles, the molded articles are more preferably colored and the molded articles are most preferably orange.

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

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

12. A high-voltage component according to claim 11, wherein the high-voltage component is selected from the group consisting of: covers for electrical or electronic devices, control devices, covers or housings for fuses, relays, battery cell modules, fuse holders, fuse plugs, terminals, cable supports or sheaths, in particular sheaths for high-voltage busbars and high-voltage distributor busbars.

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

14. The method according to claim 13, comprising: i) mixing components A), B), C), D) and optionally E), optionally F), optionally G), optionally H) and optionally I), ii) extruding the composition obtained in step i) to obtain a strand, iii) cooling the strands obtained in step ii) until they can be granulated, granulating and optionally drying, and iv) further processing the pelletized strands obtained in step iii) preferably by injection molding or extrusion methods, including profile extrusion.

15. Use of at least one acid scavenger in a thermoplastic molding composition for improving the odor of the thermoplastic molding composition, the thermoplastic molding composition comprising i) at least one thermoplastic polyamide, ii) at least one of sodium hypophosphite or sodium hypophosphite hydrate, and iii) a colorant comprising at least one non-covalently bonded sulfur atom or two or more colorants comprising at least one sulfur-containing colorant comprising at least one non-covalently bonded sulfur atom.

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