Thermoplastic molding composition and molded article

Abstract

The invention relates to a thermoplastic molding composition and a molded article. The thermoplastic molding composition comprises: A. a mixture of at least one polyamide A1, at least one polyphenylene ether A2 and optionally a compatibilizer A3 and optionally an olefin and / or vinyl aromatic polymer A4; B. 10-60 wt% of a glass filler, the glass composition of which comprises at least 10 wt% of boron oxide and up to 15 wt% of the sum of magnesium oxide and calcium oxide; C. 1-8 wt% of an LDS additive; D. 0-5 wt% of additives other than components A, B and C; wherein the mixture is in each case based on the sum of components M and A4. The composition A consists of 80-100 wt.-% of a mixture M of components A1, A2 and A3 and 0-20 wt.-% of a component A4, and the sum of components M and A4 is 100 wt.-% of the mixture A; wherein, based in each case on the sum of components A1 to A3, the mixture M comprises 36-92 wt.-% of component A2, 8-60 wt.-% of component A1 and 0-4 wt.-% of component A3, and the sum of components A1 to A3 is 100 wt.-% of the mixture M, and the sum of components A to D is 100 wt.-% of the molding composition.

Description

Technical Field

[0001] The present invention relates to glass fiber reinforced thermoplastic molding compositions based on polyamide and polyphenylene ether having low relative permittivity and low dielectric loss factor, as well as moldings made from these molding compositions and their use. The molding compounds also contain LDS additives, and the moldings made from these molding compounds can be selectively metallized after local irradiation. Background Art

[0002] Plastic molding compositions having low relative permittivity and low dielectric loss factor are advantageously used for manufacturing housings, housing parts or other components of devices that communicate via electromagnetic waves with a frequency of 0.3 GHz to 300 GHz, because their use avoids significant impairment of the transmission and reception performance of these devices.

[0003] Devices that communicate via such electromagnetic waves are used in various areas, for example in telecommunications, consumer electronics or household appliances, in particular transmitting and receiving devices, mobile phones, tablets, laptops, navigation devices, surveillance cameras, cameras, sensors, diving computers, audio systems, remote controls, loudspeakers, headphones, radios, televisions, kitchen appliances, door openers or door openers, control units for central locking systems in vehicles, vehicle keys for keyless start, temperature measuring and temperature display devices, measuring devices and control units.

[0004] The polyamide molding compositions described in EP 3 330 319 A1 are said to have a relative permittivity of no greater than 3.5 at a frequency of 2.45 GHz. In addition to specific mixtures of aliphatic polyamides and amorphous or microcrystalline polyamides, the molding compounds contain a glass filler and an additive consisting of glass containing 0 to 12% by weight of alkali metal oxides and alkaline earth metal oxides. Regardless of the composition, all working and comparative examples exhibit a relative permittivity greater than 3.2. No information is provided regarding the dielectric loss factor and metallization properties.

[0005] EP 3 560 987 A1 describes a glass fiber reinforced molding composition having high tensile strength and high impact strength together with low dielectric constant and low dielectric loss factor. The molding compound comprises 10% to 90% by weight of glass fibers and 90% to 10% by weight of plastics, the composition of the glass fibers being described in more detail. Compared to E-glass, the glass fibers comprise significantly less alkaline earth metal oxides, but contain a higher content of boron oxide, which reduces the dielectric constant to 4.8 and the dielectric loss factor to 0.0015 (all measured at 10 GHz). As shown in the disclosed embodiments, improved dielectric properties can also be applied to polyamide molding compounds. However, for a molding compound of PA6 and 50% by weight of glass fibers, a relative permittivity of 3.39 and a dielectric loss factor of 0.0109 were determined to be optimal. Information on the metallization of the molding compound is not provided.

[0006] EP 2 291 444 describes laser direct structuring (LDS) molding compounds with a high dielectric constant of at least 4 and a low dielectric loss tangent of at most 0.01. The molding compounds comprise a base resin, an LDS additive, and a ceramic filler with a dielectric constant ≥ 25. Examples show Dk values ​​ranging from 4.1 to 6.8 for molding compounds based on polyamide and polyphenylene ether. However, the dielectric loss tangent of the molding compounds described in the examples is not disclosed. Summary of the Invention

[0007] Based on this, one object of the present invention is to provide thermoplastic molding compositions that, in addition to having a low relative permittivity of less than 3.0 and a low dielectric loss tangent of less than 0.008, can also be easily processed by injection molding and, in particular, exhibit good injection shrinkage and warpage / deformation behavior. Furthermore, the thermoplastic molding compositions should have good mechanical properties; preferably, the molding compositions should have a stress at break of at least 70 MPa and a tensile modulus of at least 4000 MPa. Furthermore, the molding compounds should exhibit good metallization properties after partial laser irradiation.

[0008] This object is achieved by the thermoplastic molding compound according to the invention, which consists of the following components:

[0009] (A) a mixture of at least one polyamide (A1), at least one polyphenylene ether (A2) and optionally a compatibilizer (A3) and optionally an olefin and / or vinyl aromatic polymer (A4);

[0010] (B) 0 to 60 weight percent of a glass filler having a glass composition comprising at least 10.0 weight percent boron oxide and up to 15 weight percent of the sum of magnesium oxide and calcium oxide;

[0011] (C) 1 wt % to 8 wt % LDS additive;

[0012] (D) 0 to 5 wt% of additives other than components (A), (B), and (C);

[0013] wherein the mixture (A) comprises from 80 to 100% by weight of the mixture (M) of components (A1), (A2) and (A3) and from 0 to 20% by weight of component (A4), based in each case on the sum of components (M) and (A4), and wherein the sum of components (M) and (A4) is 100% by weight of the mixture (A);

[0014] and wherein the mixture (M) consists of 36 to 92% by weight of component (A2), 8 to 60% by weight of component (A1) and 0 to 4% by weight of component (A3), based in each case on the sum of components (A1) to (A3), and wherein the sum of components (A1) to (A3) is 100% by weight of the mixture (M);

[0015] and wherein the sum of components (A) to (D) is 100% by weight of the molding composition.

[0016] As can be seen from the above, regarding the composition of mixture (A), components (A1) to (A3) collectively account for 80% to 100% by weight of mixture (A), and the content of component (A4) in mixture (A) is 0% to 20% by weight. The mixture of components (A1), (A2), and (A3) is referred to as component (M). In addition to components (A1) to (A4), mixture (A) does not contain any other components.

[0017] The thermoplastic molding composition according to the present invention and the molded article made therefrom have a relative permittivity of less than 3.0 and a dielectric loss factor (DLF) of less than 0.008. The relative permittivity and DLF were measured in accordance with IEC 61189-2-721 (2015) on an 80 mm × 80 mm × 3 mm flat plate using a split-post dielectric resonator (SPDR) from QWED, Poland, at a measurement frequency of 2.45 GHz and a measurement temperature of 23°C.

[0018] Good mechanical properties are understood to mean that the molding compound according to the present invention has a tensile modulus of at least 4000 MPa, preferably at least 5000 MPa, and / or a stress at break of at least 70 MPa, preferably at least 75 MPa, and / or an elongation at break of at least 1.5%, preferably at least 1.8%. Here, the tensile modulus, stress at break, and elongation at break are determined according to ISO 527 (2012).

[0019] Good metallization within the meaning of the present invention means that a molding (flat 60 mm x 60 mm x 2 mm) injection-molded from the thermoplastic molding composition of the invention can be fully metallized in a copper plating bath after partial irradiation with an Nd:YAG laser (FOBA DP50 laser, wavelength = 1064 nm, irradiation width = 50 μm, speed = 4 m / s). To this end, during the laser structuring process, 16 adjacent 10 mm x 10 mm areas were irradiated on the surface of the molding, whereby the pulse frequency (5 kHz, 6 kHz, 7 kHz and 8 kHz) and the current intensity (24 amperes to 25.5 amperes) of the laser were varied. The cleaned molding was then metallized in a reducing copper plating bath (MacDermid MID-Copper 100B1) for 20 to 30 minutes.

[0020] In this context, sufficient metallization means that copper is deposited in at least 14 areas with an average thickness of at least 3 μm. DETAILED DESCRIPTION

[0021] Surprisingly, it has been found that the above-mentioned object is achieved by a thermoplastic molding composition consisting of:

[0022] (A) a mixture of at least one polyamide (A1), at least one polyphenylene ether (A2) and optionally a compatibilizer (A3) and optionally an olefin and / or vinyl aromatic polymer (A4);

[0023] (B) 10% to 60% by weight of a glass filler having a glass composition comprising at least 10.0% by weight of boron oxide and up to 15% by weight of magnesium oxide and calcium oxide combined;

[0024] (C) 1 to 8 wt% of additives other than components (A), (B), and (C);

[0025] (D) 0 to 5 wt% of additives;

[0026] wherein the mixture (A) consists of 80 to 100% by weight of a mixture (M) of components (A1), (A2) and (A3) and 0 to 20% by weight of component (A4), based in each case on the sum of components (M) and (A4), and wherein the sum of components (M) and (A4) is 100% by weight of the mixture (A);

[0027] and wherein the mixture (M) consists of 36 to 92% by weight of component (A2), 8 to 60% by weight of component (A1) and 0 to 4% by weight of component (A3), based in each case on the sum of components (A1) to (A3), and wherein the sum of components (A1) to (A3) is 100% by weight of the mixture (M);

[0028] and wherein the sum of components (A) to (D) is 100% by weight of the molding composition.

[0029] The content of mixture (A) in the molding composition is obtained as the difference between the sum of the contents of (B) to (D) and 100% by weight of the total molding composition.

[0030] Preferably, mixture (A) is present in the molding composition in a proportion of 34% to 82.9% by weight, particularly preferably 39% to 78.8% by weight, based on the total weight of the molding composition (total of A to D).

[0031] The proportion of component (B), based in each case on the sum of (A) to (D), is preferably from 15% to 55% by weight, particularly preferably from 18% to 52% by weight.

[0032] The proportion of component (C), based in each case on the sum of (A) to (D), is preferably from 2% to 6% by weight, particularly preferably from 3% to 5% by weight.

[0033] The proportion of component (D) is preferably 0.1% to 5% by weight, particularly preferably 0.2% to 4% by weight, based in each case on the sum of (A) to (D).

[0034] As studies have shown, glass-fiber-reinforced molding compounds whose polymer matrix consists solely of polyamide have excessively high relative permittivity and excessively high dielectric loss factors, even when so-called "low-DK glass fibers" are used as reinforcing fibers. In contrast, molding compounds with a polyphenylene ether matrix exhibit excessively high warpage / deformation, particularly high shrinkage values, and process more poorly. Molding compositions whose polymer component consists of a 1:1 mixture of polyamide and polyphenylene ether and are reinforced with glass fibers consisting of E-glass also exhibit excessive permittivity and dielectric losses, particularly in the presence of LDS additives with high relative permittivity.

[0035] Terminology Definition

[0036] For the purposes of the present invention, the term "polyamide" (abbreviated PA) is understood as a general term encompassing homopolyamides and copolyamides. The selected spellings and abbreviations for polyamides and their monomers correspond to those specified in ISO Standard 16396-1 (2015, (D)). The abbreviations used here are used synonymously with the IUPAC names of the monomers hereinafter. Specifically, the following monomer abbreviations appear: T or TPS for terephthalic acid, I or IPS for isophthalic acid, MACM for bis(4-amino-3-methylcyclohexyl)methane (also known as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, CAS No. 6864-37-5), PACM for bis(4-aminocyclohexyl)methane (also known as 4,4'-diaminodicyclohexylmethane, CAS No. 1761-71-3), and TMDC for bis(4-amino-3,5-dimethylcyclohexyl)methane (also known as 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, CAS No. 65962-45-0). For hexamethylenediamine (also known as hexamethylenediamine), the abbreviation HMDA is used.

[0037] In contrast to semicrystalline polyamides, amorphous polyamides exhibit no or only a very low, barely detectable heat of fusion. In dynamic differential scanning calorimetry (DSC) according to ISO 11357-2 (2013), amorphous polyamides preferably exhibit a heat of fusion of less than 5 J / g, particularly preferably no more than 3 J / g, and most preferably between 0 J / g and 1 J / g at a heating rate of 20 K / min. Due to their amorphous nature, amorphous polyamides do not have a melting point.

[0038] In addition to a glass transition temperature, microcrystalline polyamides also have a melting point. However, they have a morphology in which the crystals are so small that a sheet made therefrom with a thickness of 2 mm is still transparent, i.e., its light transmittance, measured according to ASTM D1003-13 (2013), is at least 90% and its haze is at most 3%. In differential scanning calorimetry (DSC) according to ISO 11357-2 (2013), microcrystalline polyamides exhibit a heat of fusion of preferably 5 J / g to 50 J / g, particularly preferably 5 J / g to 22 J / g, and most preferably 5 J / g to 20 J / g at a heating rate of 20 K / min.

[0039] In addition to the glass transition temperature, the semi-crystalline polyamide has a distinct melting point and, in dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013), exhibits a heat of fusion of more than 25 J / g, particularly preferably more than 30 J / g, most preferably from 30 J / g to 80 J / g at a heating rate of 20 K / min.

[0040] Relative permittivity and dielectric loss factor

[0041] Permittivity (ε) is an indicator of the behavior of a molecule when it is introduced into an electric field. It is expressed by the equation ε = ε r ·ε0 will be the relative permittivity (ε r ) is related to the vacuum permittivity (ε0). r ) represents the amount that depends on the material and is the quotient of the permittivity (ε) and the vacuum permittivity (ε0). In addition to the type of material, the relative permittivity (ε r ) also depends on the frequency of the electric field and the temperature.

[0042] The dielectric loss factor indicates the extent of electromagnetic wave propagation losses in electrical components such as capacitors or in substances such as plastic molding compounds. Losses here refer to energy that is converted electrically or electromagnetically and dissipated as heat. These losses attenuate the electromagnetic waves. To express the loss factor more precisely, consider a capacitor connected to a voltage source with a sinusoidal voltage curve over time. A phase shift occurs between the voltage and current in such a capacitor. The phase shift of an ideal lossless capacitor is For true lossy capacitors, the phase shift is less than the loss angle δ of 90°, and the dielectric loss factor (DLF) is equal to tan δ. Therefore, the dielectric loss factor is a measure of the amount of energy absorbed by an insulating material in an alternating electric field and converted into heat loss. Materials with high loss factors are unsuitable for use as insulation or housing materials in high-frequency applications. Relative permittivity and dielectric loss factor are preferably determined according to IEC 61189-2-721 (2015).

[0043] Component (A)

[0044] The thermoplastic molding composition according to the invention comprises as polymer components a mixture (A) of at least one polyamide (A1), at least one polyphenylene ether (A2) and optionally a compatibilizer (A3) and optionally an olefinic and / or vinylaromatic polymer (A4).

[0045] In this case, the mixture (A) consists of 80% to 100% by weight of the mixture (M) of components (A1) to (A3) and 0% to 20% by weight of component (A4), the sum of components (M) and (A4) being 100% by weight of the mixture (A) in each case, based on the sum of components (M) and (A4).

[0046] The mixture (M) consists of 36% to 92% by weight of component (A2), 8% to 60% by weight of component (A1), 0% to 4% by weight of component (A3), based in each case on the sum of components (A1) to (A3).

[0047] Component (A1) is preferably present in the mixture (M) in a proportion of 10% to 48% by weight, particularly preferably 10% to 45% by weight, based on the sum of (A1) to (A3).

[0048] Component (A2) is preferably present in the mixture (M) in a proportion of 48% to 89.9% by weight, particularly preferably 52% to 89.8% by weight, based on the sum of (A1) to (A3).

[0049] Component (A3) is preferably present in the mixture (M) in a proportion of 0.1% to 4% by weight, particularly preferably 0.2% to 3% by weight, based on the sum of (A1) to (A3).

[0050] Preferably, component (A4) is present in mixture (A) in a proportion of 0% to 20% by weight, based on the sum of (M) and (A4). Particularly preferably, mixture (A) does not contain component (A4). In other words, mixture (A) particularly preferably consists solely of components (A1) to (A3).

[0051] Component (A1)

[0052] One embodiment of the present invention provides preferred aliphatic polyamides as component (A1). In particular, the aliphatic polyamide is preferably selected from the group consisting of PA 46, PA 6, PA 66, PA 6 / 66, PA 10, PA 11, PA 12, PA 516, PA 610, PA 612, PA 614, PA 616, PA 618, PA 1010, PA 1012, PA 1014, PA 1016, PA 1018, PA 1212, and mixtures thereof. Aliphatic polyamides having an N / C ratio (N=nitrogen / C=carbon) of greater than or equal to 8 are particularly preferred because these polyamides have lower water absorption and, therefore, exhibit less change in dielectric properties in humid environments. In particular, the aliphatic polyamides PA 610, PA 612, PA 1010, PA 12, and PA 616 are preferred.

[0053] According to another embodiment of the present invention, amorphous polyamide or microcrystalline polyamide is preferred as component (A1). In particular, the amorphous polyamide or microcrystalline polyamide is preferably selected from the group consisting of PA 6I / 6T, PA MACM9, PAMACM10, PA MACM12, PA MACM13, PA MACM14, PA MACM16, PA MACM17, PA MACM18, PA PACM10, PA PACM12, PA PACM13, PA PACM14, PA PACM16, PA PACM17, PA PACM18, PA TMDC10, PATMDC12, PA TMDC13, PA TMDC14, PA TMDC16, PA TMDC17, PA TMDC18, PA MACM10 / 10, PAMACMI / 12, PA MACMT / 12, PA 6I / MACMI / MACMT, PA MACMI / MACMT / 12, PA MACMI / MACMT / MACM12 / 12, PA6I / 6T / MACMI / MACMT / 12, PA 6I / 6T / MACMI, PAMACMI / MACM36, PA MACMT / MACM36, PA MACMI / MACM12, PA MACMT / MACM12, PA MACM6 / 11, PAMACM10 / 10, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACM18 / PACM18 and mixtures thereof, of which PA 6I / 6T, PA MACM12, PA MACM14, PA TMDC12, PA TMDC14, PA MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA MACMI / MACMT / 12, PA MACMI / MACMT / MACM12, PA are preferred. 6I / 6T / MACMI / MACMT / 12, PA MACM10 / 10, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACM18 / PACM18 and mixtures thereof. Most preferred are PA 6I / 6T, PA MACM12, PA MACMI / 12, PA MACMI / MACMT / 12, PA MACMI / MACMT / MACM12, PAMACM12 / PACM12 and mixtures thereof.

[0054] According to another preferred embodiment, a semicrystalline partially aromatic polyamide is preferred as component (A1). The glass transition temperature of the semicrystalline partially aromatic polyamide is preferably from 90°C to 150°C, preferably from 110°C to 140°C, and in particular from 115°C to 135°C. The melting point of the semicrystalline partially aromatic polyamide is from 255°C to 330°C, preferably from 270°C to 325°C, and in particular from 280°C to 320°C. Preferably, the semicrystalline partially aromatic polyamide of component (A1) has a melting enthalpy of 25 J / g to 80 J / g, preferably from 30 J / g to 70 J / g, as determined by dynamic differential scanning calorimetry (DSC) according to ISO 11357-2 (2013).

[0055] Preferred partially aromatic, partially crystalline polyamides are made from:

[0056] (a): dicarboxylic acids: 30 to 100 mol %, in particular 50 to 100 mol %, of terephthalic acid and 0 to 70 mol %, in particular 0 to 50 mol %, of at least one aliphatic dicarboxylic acid having 6 to 16 carbon atoms, and / or 0 to 70 mol %, in particular 0 to 50 mol %, of at least one cycloaliphatic dicarboxylic acid having 8 to 20 carbon atoms, and / or 0 to 50 mol % of isophthalic acid, in each case based on the total amount of dicarboxylic acids,

[0057] (b): Diamines: Based on the total amount of diamines, 80 mol % to 100 mol % of at least one aliphatic diamine having 4 to 18 carbon atoms, preferably having 6 to 12 carbon atoms, and 0 mol % to 20 mol % of at least one cycloaliphatic diamine, preferably having 6 to 20 carbon atoms, such as PACM, MACM, IPDA and / or 0 mol % to 20 mol % of at least one aromatic aliphatic diamine, such as MXDA and PXDA, and optionally

[0058] (c): Aminocarboxylic acid and / or lactam: each having 6 to 12 carbon atoms.

[0059] According to a preferred embodiment, the semicrystalline, partially aromatic polyamide of component (A1) is based on at least 55 mol %, in particular at least 65 mol %, of terephthalic acid and at least 80 mol %, preferably at least 90 mol %, particularly preferably at least 95 mol %, of aliphatic diamines having 4 to 18 carbon atoms, preferably having 6 to 12 carbon atoms, and optionally further based on aliphatic, cycloaliphatic and aromatic dicarboxylic acids and lactams and / or aminocarboxylic acids.

[0060] According to another preferred embodiment, the aliphatic dicarboxylic acid (which can be used in addition to terephthalic acid) of the partially aromatic polyamide, for example component (A1), is selected from the group consisting of adipic acid, succinic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and dimer fatty acids (36 carbon atoms). Adipic acid, sebacic acid, and dodecanedioic acid are particularly preferred. Therefore, in addition to terephthalic acid, preferably used dicarboxylic acids are isophthalic acid, adipic acid, sebacic acid, and dodecanedioic acid, or mixtures of these dicarboxylic acids. In particular, polyamides (A1) based solely on terephthalic acid as dicarboxylic acid are preferred.

[0061] According to another preferred embodiment, the aliphatic diamine of the partially aromatic polyamide of component (A1) is selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine or a mixture of these diamines, of which 1,6-hexanediamine, 1,10-decanediamine, 1,12-dodecanediamine or a mixture of these diamines is preferred, and 1,6-hexanediamine and 1,10-decanediamine are particularly preferred. In addition to the aliphatic diamine, cycloaliphatic and / or aromatic aliphatic diamines may be substituted in a concentration of 0 mol % to 20 mol %, based on the total amount of diamines.

[0062] Further preferably, the polyamide (A1) is formed from the following components:

[0063] (a): dicarboxylic acids: in each case, based on the total amount of dicarboxylic acids present, 50 to 100 mol % of terephthalic acid, 0 to 50 mol % of aliphatic dicarboxylic acids preferably having 6 to 12 carbon atoms, and / or cycloaliphatic dicarboxylic acids preferably having 8 to 20 carbon atoms, and / or isophthalic acid;

[0064] (b): Diamines: 80 mol % to 100 mol % of at least one aliphatic diamine having 4 to 18 carbon atoms, preferably having 6 to 12 carbon atoms, based on the total content of diamines present; 0 mol % to 20 mol % of cycloaliphatic diamines, preferably having 6 to 20 carbon atoms, such as, for example, PACM, MACM, IPDA and / or araliphatic diamines, such as MXDA and PXDA, wherein the mole percentage content of dicarboxylic acid in the high-melting polyamide is 100%, the mole percentage content of diamine is 100%, and optionally

[0065] (c): aminocarboxylic acids and / or lactams comprising lactams preferably having 6 to 12 carbon atoms and / or aminocarboxylic acids preferably having 6 to 12 carbon atoms.

[0066] Although components (a) and (b) are preferably used in approximately equimolar proportions, the concentration of (c) is preferably up to 30% by weight, preferably up to 20% by weight, particularly preferably up to 15% by weight, based in each case on the sum of (a) to (c).

[0067] Suitable cycloaliphatic dicarboxylic acids are cis- and / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3-dicarboxylic acid (CHDA). The aliphatic diamines commonly used may be substituted with other diamines in minor amounts of up to 20 mol %, preferably up to 15 mol %, and in particular up to 10 mol %, based on the total amount of diamine. Examples of cycloaliphatic diamines that can be used include cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane (BAC), isophoronediamine (IPDA), norbornanedimethylamine, 4,4'-diaminodicyclohexylmethane (PACM), 2,2-(4,4'-diaminodicyclohexyl)propane (PACP), and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM). Examples of aromatic aliphatic diamines include m-xylylenediamine (MXDA) and p-xylylenediamine (PXDA).

[0068] In addition to the dicarboxylic acids and diamines mentioned, lactams and / or aminocarboxylic acids can also be used as polyamide-forming components (component (c)). Suitable compounds include, for example, caprolactam (CL), α,ω-aminocaproic acid, α,ω-aminononanoic acid, α,ω-aminoundecanoic acid (AUA), laurolactam (LL), and α,ω-aminododecanoic acid (ADA). The concentration of aminocarboxylic acids and / or lactams used with components (A1a) and (A1b) is up to 20% by weight, preferably up to 15% by weight, and particularly preferably up to 12% by weight, based on the sum of components (A1a) to (A1c). Lactams or α,ω-amino acids having 4, 6, 7, 8, 11, or 12 carbon atoms are particularly preferred. These are the lactam pyrrolidin-2-one (4 C atoms), ε-caprolactam (6 C atoms), enantholactam (7 C atoms), capryllactam (8 C atoms), laurolactam (12 C atoms), and the α,ω-amino acids 1,4-aminobutyric acid, 1,6-aminocaproic acid, 1,7-aminoheptanoic acid, 1,8-aminooctanoic acid, 1,11-aminoundecanoic acid, and 1,12-aminododecanoic acid, respectively. In a particularly preferred embodiment, component (A1) does not contain caprolactam or aminocaproic acid or any aminocarboxylic acid or lactam.

[0069] Regulators in the form of monocarboxylic acids or monoamines can be added to the batch and / or the pre-precondensate (before post-condensation) to control the molecular weight, relative viscosity, flowability or MVR. Suitable aliphatic, cycloaliphatic or aromatic monocarboxylic acids or monoamines as regulators are acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid, 2-(3,5-di-tert-butyl-4-hydroxybenzylthio)acetic acid, 3,3 -bis(3-tert-butyl-4-hydroxyphenyl)butanoic acid, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, 3-(cyclohexylamino)-propylamine, methylcyclohexylamine, dimethylcyclohexylamine, benzylamine, 2-phenylethylamine, 2,2,6,6-tetramethylpiperidin-4-amine, 1,2,2,6,6-pentamethylpiperidin-4-amine, 4-amino-2,6-di-tert-butylphenol, etc. The regulator can be used alone or in combination. Other monofunctional compounds that can react with amino or acid groups, such as anhydrides, isocyanates, acyl halides or esters, can also be used as regulators. The usual amount of the regulator is 10 to 200 mmol per kilogram of polymer.

[0070] Specific representatives of the semicrystalline partially aromatic polyamide (A1) are: PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, PA6T / 6, PA 6T / 6I, PA 6T / 6I / 6, PA 6T / 66, 6T / 610, 6T / 612, PA 6T / 10T, PA 6T / 10I, PA 9T, PA10T, PA 12T, PA 10T / 10I, PA 10T / 106, PA 10T / 610, PA 10T / 612, PA 10T / 66, PA 10T / 6, PA10T / 1010, PA 10T / 1012, PA 10T / 12, PA 10T / 11, PA 6T / 9T, PA 6T / 12T, PA 6T / 10T / 6I, PA6T / 6I / 6, PA 6T / 6I / 12, and mixtures thereof. Particularly preferably, the partially aromatic polyamide of component (A1) is selected from the group consisting of PA6T / 6I, PA 6T / 10T, PA 6T / 10T / 6I6T / 10T / 6I, and mixtures thereof. Preference is given to polyamide (A1) containing 6T units, in particular at least 10% by weight of 6T units.

[0071] Therefore, according to the present invention, the following partially aromatic copolyamides are particularly preferred as polyamide (A1):

[0072] semi-crystalline polyamides 6T / 6I having 55 to 75 mol % of hexamethylene terephthalamide units and 25 to 45 mol % of hexamethylene isophthalamide units;

[0073] semi-crystalline polyamide 6T / 6I having 62 to 73 mol % of hexamethylene terephthalamide units and 25 to 38 mol % of hexamethylene isophthalamide units;

[0074] semicrystalline polyamides prepared from a mixture of at least 50 mol % of terephthalic acid and at most 50 mol % of isophthalic acid, in particular 100 mol % of terephthalic acid and at least two diamines selected from the group consisting of hexamethylenediamine, nonanediamine, methyloctanediamine and decanediamine;

[0075] Semicrystalline polyamides prepared from a mixture of 70 mol % to 100 mol % of terephthalic acid and 0 mol % to 30 mol % of isophthalic acid and hexamethylenediamine and dodecanediamine;

[0076] semicrystalline polyamides prepared from a mixture of at least 50 mol % of terephthalic acid and not more than 50 mol % of dodecanedioic acid with at least two diamines selected from the group consisting of hexamethylenediamine, nonanediamine, methyloctanediamine and decanediamine;

[0077] semicrystalline polyamides 6T / 10T having from 10 to 60 mol%, preferably from 10 to 40 mol%, of hexamethyleneterephthalamide (6T) units and from 40 to 90 mol%, preferably from 60 to 90 mol%, of decamethyleneterephthalamide (10T) units; semicrystalline polyamides 6T / 10T / 6I having from 50 to 90 mol%, preferably from 50 to 70 mol%, of hexamethyleneterephthalamide (6T) units and from 5 to 45 mol%, preferably from 10 to 30 mol%, of hexamethyleneisophthalamide (6I) units and from 5 to 45 mol%, preferably from 20 to 40 mol% of decamethyleneterephthalamide (10T) units.

[0078] Solution viscosity η of polyamide (A1) rel Determined in accordance with ISO 307 (2007) on a 0.5 g polymer solution in 100 ml m-cresol at 20° C., preferably 1.3 to 2.7, particularly preferably 1.4 to 2.3 and particularly preferably 1.5 to 2.0.

[0079] Component (A2)

[0080] Thus, the polyphenylene ethers used according to the present invention are known. They are prepared by conventional methods from phenols disubstituted in the ortho position with alkyl groups by oxidative coupling (see U.S. Patents 3,661,848, 3,378,505, 3,306,874, 3,306,875, and 3,639,656). Catalysts based on heavy metals such as copper, manganese, or cobalt are typically used in combination with other substances (e.g., secondary amines, tertiary amines, halogens, or combinations thereof).

[0081] Suitable polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether or copolymers, such as copolymers containing 2,3,6-trimethylphenol, and mixtures thereof. Preferred is poly(2,6-dimethyl-1,4-phenylene) ether, optionally in combination with 2,3,6-trimethylphenol units. The polyphenylene ether can be used in the form of a homopolymer, copolymer, graft copolymer, block copolymer or ionomer.

[0082] Suitable polyphenylene ethers generally have an intrinsic viscosity, measured in chloroform at 25° C., preferably between 0.1 dl / g and 0.6 dl / g. This corresponds to a molecular weight (Mn) (number average) of 3,000 to 40,000 grams per mole and a weight average molecular weight (Mw) of 5,000 to 80,000 grams per mole. Combinations of high-viscosity and low-viscosity polyphenylene ethers can be used. The ratio of the two polyphenylene ethers of different viscosities depends on the viscosity and the desired physical properties.

[0083] In order to improve the compatibility between components (A1) and (A2), in a preferred embodiment, the polyphenylene ethers used are modified so that they preferably contain carbonyl, carboxyl, carboxylic acid, anhydride, amide, imide, carboxylate, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups (covalently bonded). Preferably, for this purpose, the unmodified polyphenylene ether (A2) is modified with α,β-unsaturated dicarbonyl compounds having polymerizable double bonds, monomers containing amide or lactam groups (A3), optionally in combination with free radical initiators (A3), such as peroxides, in particular dibenzoyl peroxide, as described, for example, in EP 0 654 505 A1.

[0084] Component (A3)

[0085] To improve the compatibility of components (A1) and (A2), a compatibilizer may be used in the form of a functional compound that interacts with the polyphenylene ether, the polyamide, or both. The interaction may be chemical (e.g., by grafting) and / or physical (e.g., by influencing the surface properties of the dispersed phase).

[0086] In a preferred embodiment of the present invention, the compatibilizer further comprises a free radical initiator, which is preferably an organic peroxide or an azo compound. That is, in this embodiment, the compatibilizer is graft polymerized in the presence of the free radical initiator.

[0087] In a particularly preferred embodiment, the compatibilizer is used in the absence of a free radical initiator.

[0088] Compatibilizers can be functional compounds containing at least one carboxylic acid, carboxylic anhydride, epoxy, ester, amide, or imide group, preferably double-bonded to an olefin. Examples include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, methylmaleic acid, methylmaleic anhydride, itaconic acid, itaconic anhydride, butenylsuccinic acid, butenylsuccinyl, tetrahydrophthalic acid, tetrahydrophthalic anhydride, N-phenylmaleimide, citric acid, malic acid, and 2-hydroxynonadecane-1,2,3-tricarboxylic acid, monoesters or diesters of the above acids with C1- to C12-alcohols (such as methanol or ethanol), monoamides or diamides of the above acids (which may be substituted on the nitrogen with an alkyl or aryl group having up to 12 carbon atoms), and salts with alkali or alkaline earth metals (such as calcium and potassium). Particularly preferred are maleic acid, fumaric acid, maleic anhydride, and citric acid. The compatibilizer can be added alone or in combination with an optional free radical initiator, or added directly during the blend preparation, or the polyphenylene ether and / or polyamide can be functionalized with the compatibilizer in a separate step.

[0089] Suitable free radical initiators (starters) include, for example, 1,1-di-tert-butyl-peroxy-3,3,5-trimethylcyclohexane, tert-butyl-peroxyisopropyl carbonate, tert-butyl-peroxy-3,3,5-trimethylhexanoate, tert-butyl peracetate, tert-butyl perbenzoate, n-butyl 4,4-di-tert-butyl-peroxyvalerate, 2,2-di-tert-butyl-peroxybutane, dicumyl peroxide, tert-butylcumyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, di-tert-butyl peroxide, and azoisobutyronitrile. Preferred free radical initiators are organic peroxides, particularly dicumyl peroxide.

[0090] Therefore, component (A3) comprises a compatibilizer or a mixture of a compatibilizer and a free radical initiator. The total amount of compatibilizer and free radical initiator is 0% to 4% by weight, preferably 0.1% to 4% by weight, and particularly preferably 0.2% to 3% by weight, based on the total of (A1) to (A3). The free radical initiator is preferably 0% to 1% by weight, particularly preferably 0.05% to 0.8% by weight, based on the total of (A1) to (A3).

[0091] In a preferred embodiment, the compatibilizer is graft polymerized without the addition of a free-radical initiator, ie component (A3) preferably does not comprise a free-radical initiator.

[0092] Component (A4)

[0093] Besides the polyamide (A1), the polyphenylene ether (A2) and optionally the compatibilizer (A3), the blend (A) according to the invention may contain from 0% to 20% by weight of vinylaromatic and / or olefinic polymers (A4).

[0094] The olefin polymers are homopolyolefins or copolyolefins, particularly preferably polymers based on ethylene, propylene and butene or copolymers thereof and copolymers with other α-olefin monomers, in particular 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene.

[0095] The vinyl aromatic polymer is preferably polystyrene or a copolymer of styrene with other monomers having at least one olefinic double bond, for example α-olefins, ethylene, propylene and butylene, or acrylic acid or an acrylate ester or butadiene. Particularly preferred are block copolymers having at least one block composed of a vinyl aromatic monomer (block A) and at least one block composed of an olefin monomer (block B), as is present, for example, in styrene block copolymers.

[0096] The olefin and / or vinyl aromatic polymer used as component (A4) may be or may comprise natural rubber, polybutadiene, polyisoprene, polyisobutylene, copolymers of butadiene and / or isoprene with styrene or styrene derivatives and other comonomers, hydrogenated copolymers and / or copolymers formed by grafting or copolymerization with anhydrides, (meth)acrylic acid and its esters. Polymer (A4) may also be a grafted rubber having a crosslinked elastomeric core composed of butadiene, isoprene or an alkyl acrylate and a grafted shell of polystyrene, nonpolar or polar olefin homopolymers and copolymers (e.g. ethylene-propylene rubber, ethylene-propylene-diene rubber and ethylene-octene rubber or ethylene-vinyl acetate rubber), or nonpolar or polar olefin homopolymers and copolymers formed by grafting or copolymerization with anhydrides, (meth)acrylic acid and its esters. Polymer (A4) can also be a carboxylic acid functionalized copolymer, such as poly(ethylene-co-(meth)acrylic acid) or poly(ethylene-co-1-olefin-co-(meth)acrylic acid), wherein the 1-olefin is an olefin having more than 4 atoms or an unsaturated (meth)acrylate, including those copolymers in which the acid groups are partially neutralized by metal ions.

[0097] Component (A4) is advantageously selected from the group consisting of polystyrene, polybutadiene-polystyrene graft copolymers, styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-butadiene-styrene block copolymers (SBS), styrene-styrene-butadiene-styrene block copolymers (SSBS), ethylene / propylene copolymers, ethylene / propylene / diene copolymers (EPDM), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-octene copolymers, ethylene-propylene-butene copolymers, ethylene-propylene-hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-hexene copolymers, ethylene-propylene-diene terpolymers, and blends of these polymeric materials. Particularly preferably, these polymers (A4) are grafted with acrylic acid, methacrylic acid or maleic anhydride, the degree of grafting being from 0.1% to 4.0% by weight, based on the grafted polymer (A4).

[0098] Furthermore, the mixture (A) preferably comprises at least one vinyl aromatic polymer and optionally at least one polyolefin as component (A4). It is particularly preferred that the mixture (A) comprises at least 5% by weight, in particular at least 10% by weight, of vinyl aromatic polymer, based in each case on the total amount of (A).

[0099] Preferably, the olefin and / or vinyl aromatic polymer (A4) is selected from the group consisting of styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-butadiene-styrene block copolymers (SBS), styrene-styrene-butadiene-styrene block copolymers (SSBS), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-octene copolymers, ethylene-propylene-butene copolymers, ethylene-propylene-hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-hexene copolymers, ethylene-propylene-diene terpolymers and blends of these polymeric materials.

[0100] Furthermore, the olefin and / or vinylaromatic polymer (A4) of the molding composition is preferably grafted with carboxylic acid or carboxylic anhydride groups, particularly preferably with acrylic acid, methacrylic acid or maleic anhydride, and / or the degree of grafting is preferably from 0.1% to 4.0% by weight, particularly preferably from 0.4% to 2.5% by weight and especially preferably from 0.5% to 2.0% by weight, in each case based on the grafted polymer (A4).

[0101] Component (B) is a glass-based filler present in the polyamide molding composition in an amount of 10 to 60% by weight. The filler can be fibrous or particulate, either alone or in a mixture. Thus, component (B) can comprise a fibrous filler (reinforcer) or a particulate filler, or a mixture of a reinforcing agent and a particulate filler. For the purposes of the present invention, the terms glass-based filler and glass filler are used synonymously.

[0102] According to the invention, a glass filler (B) based on glass is used, the glass composition of which comprises at least 10% by weight of boron oxide and at most 15% by weight of the sum of magnesium oxide and calcium oxide, based on the composition of the glass.

[0103] According to a preferred embodiment of the present invention, the glass filler is based on glass having a total magnesium oxide and calcium oxide content of 2 to 14 wt%, more preferably 4 to 12 wt%, based on the glass composition.

[0104] According to a further preferred embodiment of the invention, the glass filler is based on a glass which, based on the glass composition, contains 12% to 24% by weight, particularly preferably 15% to 22% by weight, of boron oxide.

[0105] The glass filler is preferably selected from the group consisting of fibers, ground fibers, particles, flakes, spheres, hollow spheres and mixtures thereof, particularly preferably from the group consisting of fibers, particles, flakes and mixtures thereof. More particularly preferably, the glass filler is glass fiber. Very particularly preferably, component (B) is a glass fiber having a non-circular cross-section and an axial ratio of the major cross-sectional axis to the minor cross-sectional axis of 2 to 6, more preferably 3 to 5.

[0106] The glass filler can be surface treated. This can be carried out with a suitable sizing system or bonding promoter system. For this reason, a system such as based on fatty acid, wax, silane, titanate, polyamide, carbamate (urethane), polyurethane (polyurethane), polyhydroxy ether, epoxide, nickel or its combination or mixture can be used. Preferably, the glass filler is surface treated with aminosilane, epoxysilane, polyamide or its mixture.

[0107] If fibers are selected as the glass filler of component (B), the glass fibers are preferably selected from the group consisting of chopped fibers, continuous fibers, and mixtures thereof, wherein the fibers may have a circular or non-circular cross-section. Non-circular glass fibers or non-circular glass fibers are also called flat glass fibers and may have an oval, elliptical, angular, rectangular, or nearly rectangular cross-section.

[0108] The chopped glass fibers preferably have a fiber length of 1 mm to 25 mm, preferably 1.5 mm to 20 mm, more preferably 2 mm to 12 mm, most preferably 2 mm to 8 mm.

[0109] The chopped glass fibers preferably have a diameter of 5 μm to 20 μm, preferably 5 μm to 15 μm, particularly preferably 6 μm to 12 μm.

[0110] If glass fibers are used as continuous fibers (rovings), they preferably have a diameter of at most 20 μm, preferably at most 18 μm, particularly preferably from 5 μm to 17 μm.

[0111] In the case of flat glass fibers, the aspect ratio, i.e., the ratio of the main cross-sectional axis to the minor cross-sectional axis, is 2 to 8, preferably 2 to 6, and particularly preferably 3 to 5. The length of the cross-sectional axis of the flat glass fibers is 3 to 40 μm. Preferably, the length of the minor cross-sectional axis is 3 to 20 μm, particularly preferably 4 to 10 μm, and the length of the main cross-sectional axis is 6 to 40 μm, particularly preferably 12 to 30 μm.

[0112] For the reinforcement of the polyamide molding compositions of the invention, it is also possible to use mixtures of fibers having a circular (round) and a non-circular (flat) cross section.

[0113] If glass spheres or glass particles are chosen as glass filler (B), their average volume diameter (D50), measured by laser diffraction according to ASTM B 822-10 (2010), is preferably 0.3 to 100 μm, particularly preferably 5 to 80 μm, and particularly preferably 17 to 70 μm.

[0114] Furthermore, the glass filler preferably has a relative permittivity of not more than 7, particularly preferably not more than 5, and a dielectric loss tangent of preferably not more than 0.0040, particularly preferably not more than 0.0030, which are measured in accordance with IEC 61189-2-721 (2015) using a glass plate (80 mm x 80 mm x 3 mm) made of glass with the glass filler, with a split post dielectric resonator (SPDR) from QWED, Poland, at a frequency of 2.45 GHz and a temperature of 23° C.

[0115] According to a preferred embodiment of the invention, component (B) is present in the polyamide molding composition in an amount of preferably 15% to 55% by weight, particularly preferably 18% to 52% by weight, these amounts relating to the sum of components (A) to (D).

[0116] According to a preferred embodiment of the present invention, component (B) consists exclusively of a glass filler selected from the group consisting of glass fibers, milled glass fibers, glass granules, glass flakes, glass beads, hollow glass beads or combinations thereof, the glass filler consisting of glass in which the sum of the magnesium oxide and calcium oxide contents is from 2% to 14% by weight and the boron oxide (BO) content is from 12% to 24% by weight, based in each case on the composition of the glass. Particularly preferably, the glass filler is formed entirely of glass fibers.

[0117] In a particularly preferred embodiment, component (B) is selected as a glass filler, particularly preferably as glass fibers, the glass of which has the following composition: 52.0% to 57.0% by weight of silicon dioxide, 13.0% to 17.0% by weight of aluminum oxide, 15.0% to 22.0% by weight of boron oxide, 2.0% to 6.0% by weight of magnesium oxide, 2.0% to 6.0% by weight of calcium oxide, 1.0% to 4.0% by weight of titanium dioxide, 0% to 1.5% by weight of fluorine, and 0% to 0.6% by weight of basic oxides.

[0118] Preferably, the proportion of component (C), based in each case on the molding compound (the sum of components (A) to (D)), is 2% to 6% by weight, preferably 3% to 5% by weight.

[0119] Component (C) is preferably an LDS additive having a non-zero absorption coefficient for UV, VIS or IR radiation, which forms metal nuclei under the influence of electromagnetic radiation, preferably laser radiation, which promote and / or enable and / or improve the deposition of a metal layer during the chemical metallization process for producing conductor tracks at the irradiated points on the molding surface. The LDS additive preferably has an absorption capacity in the visible and infrared radiation range with an absorption coefficient of at least 0.05, preferably at least 0.1, in particular at least 0.2, and / or preferably provides an absorber that transfers the radiation energy to the LDS additive.

[0120] Component (C) is preferably an LDS additive having a median particle size (D50) of 50 nm to 10,000 nm, preferably 200 nm to 5,000 nm, particularly preferably 300 nm to 4,000 nm, and / or an aspect ratio of at most 10, particularly preferably at most 5. The D50 value given as a measure of the particle size is a measure of the median particle size, wherein 50% by volume of the sample is finer and a further 50% of the sample is coarser than the D50 value (median).

[0121] Preferably, component (D) is an LDS (Laser Direct Structuring) additive selected from the group of metal oxides, in particular so-called spinels having the general formula AB2O4, in which A is a metal cation with a valence of 2 and B is a metal cation with a valence of 3. The metal cation A is preferably selected from the group consisting of magnesium, copper, cobalt, zinc, tin, iron, manganese and nickel, and combinations thereof, and the metal cation B is preferably selected from the group consisting of manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum and chromium, and combinations thereof.

[0122] In particular, the LDS additive is preferably a copper-iron spinel, a copper-containing magnesium-aluminum oxide, a copper-chromium-manganese mixed oxide, a copper-manganese-iron mixed oxide, optionally each having oxygen vacancies, or copper salts and oxides, such as, in particular, copper(I) oxide, copper(II) oxide, basic copper phosphate, copper sulfate, and metal complexes, in particular chelate complexes of copper, tin, nickel, cobalt, silver and palladium, or mixtures of these systems, and / or in particular selected from the group consisting of copper-chromium-manganese mixed oxide, copper-manganese-iron mixed oxide, copper chromium oxide, copper tungstate, zinc iron oxide, cobalt chromium oxide, cobalt aluminum oxide, magnesium aluminum oxide, and mixtures thereof and / or surface-treated / or oxygen-deficient forms. Possible systems are, for example, those described in WO-A-2000 / 35259 or Kunststoffe 92 (2002) 11, pages 2-7.

[0123] Also preferred as component (C) are LDS (Laser Direct Structuring) additives selected from the group consisting of tin-based metal oxides, mixed metal oxides, metal hydroxides, and metal sulfides. Particularly preferred are tin oxide and doped tin oxides, where the doping can be with antimony, bismuth, molybdenum, aluminum, titanium, silicon, iron, copper, silver, palladium, and cobalt. Tin oxide doped with antimony, titanium, or copper is particularly preferred. Furthermore, mixtures of tin oxide and at least one other metal oxide, particularly antimony oxide, are preferred as LDS additives. Other metal oxides include colorless, highly refractive metal oxides, such as, in particular, titanium dioxide, antimony(III) oxide, zinc oxide, tin oxide, and / or zirconium dioxide, as well as colored metal oxides, such as chromium oxide, nickel oxide, copper oxide, cobalt oxide, and especially iron oxide (Fe2O3, Fe3O4). Mixtures of tin oxide and antimony(III) oxide are particularly preferred.

[0124] Preferably, the doped tin oxide or metal oxide mixture or tin oxide is formed in the form of a layer on a flaky substrate, in particular a phyllosilicate, such as synthetic or natural mica, talc, kaolin, glass flakes or silicon dioxide flakes. Mica or mica flakes are particularly preferred as substrates for the metal oxide. In addition, flaky metal oxides such as flaky iron oxide, aluminum oxide, titanium dioxide, silicon dioxide, LCP (liquid crystal polymer), holographic pigments or coated graphite flakes are also suitable as substrates.

[0125] Particularly preferred are LDS additives based on mica, wherein the mica surface is coated with metal-doped tin oxide. Antimony-doped tin oxide is particularly preferred. Examples of commercially available LDS additives according to the invention are: Lazerflair LS820, LS825, LS830, and Minatec 230A-IR from Merck, Stanostat CP40W, Stanostat CP15G, or Stanostat CP5C from Keeling & Walker, and Fabulase 322S, 330, 350, and 352 from Budenheim.

[0126] Particularly preferred LDS additives are copper chromite, copper tungstate, copper hydroxide phosphate and antimony-doped tin oxide, the latter preferably being used in combination with mica. Copper tungstate is very particularly preferred.

[0127] The thermoplastic molding composition according to the invention comprises, as component (D), 0 to 5% by weight of at least one additive, which component (D) is different from components (A), (B) and (C).

[0128] According to a preferred embodiment, the molding compositions of the invention comprise as component (D) 0.1 to 5% by weight, preferably 0.2 to 4% by weight, based on the sum of components (A) to (D), of at least one additive.

[0129] According to a preferred embodiment, the additives of component (D) are selected from the group consisting of stabilizers, antioxidants, antiozonants, processing stabilizers, processing aids, viscosity improvers, light stabilizers, UV stabilizers, UV absorbers, inorganic heat stabilizers, in particular inorganic heat stabilizers based on copper halides and alkali halides, organic heat stabilizers, optical brighteners, crystallization accelerators, crystallization retarders, flow aids, lubricants, slip agents, release agents, colorants, in particular dyes, inorganic pigments, organic pigments, marking agents and mixtures thereof.

[0130] According to a particularly preferred embodiment, the molding composition of the invention comprises at least one processing aid as component (D), preferably present in a proportion of 0 to 2% by weight, particularly preferably 0.1 to 2.0% by weight, and especially preferably 0.1 to 1.5% by weight, most preferably 0.2 to 1.0% by weight, based in each case on the total weight of components (A) to (D). Preferred metal salts are aluminum (Al), alkali metals, alkaline earth metal salts, esters or amides of fatty acids containing 10 to 44 carbon atoms, preferably 14 to 44 carbon atoms, preferably the metal ions sodium (Na), magnesium (Mg), calcium (Ca) and Al, particularly preferably Ca or Mg. Particularly preferred metal salts are magnesium stearate, calcium stearate and calcium montmorillonate, and aluminum stearate. The fatty acids may be monovalent or divalent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixtures of fatty acids having 30 to 40 carbon atoms).

[0131] According to a further preferred embodiment, the molding composition according to the invention comprises as component (D) at least one heat stabilizer, which is preferably present in a proportion of 0% to 3% by weight, particularly preferably 0.1% to 2.0% by weight, in each case based on the total weight of components (A) to (D).

[0132] According to a preferred embodiment, the heat stabilizer is selected from the group consisting of:

[0133] Compounds of monovalent or divalent copper, for example salts of monovalent or divalent copper with inorganic or organic acids or monovalent or divalent phenols, oxides of monovalent or divalent copper, or complexes of copper salts with ammonia, amines, amides, lactams, cyanides or phosphine, preferably copper(I) or Cu(II) salts of hydrohalic acids, copper(I) or Cu(II) salts of hydrocyanic acid or copper salts of aliphatic carboxylic acids. Particularly preferred are the monovalent copper compounds CuCl, CuBr, CuI, CuCN and Cu2O, and the divalent copper compounds CuCl2, CuSO4, CuO, copper(II) acetate or copper(II) stearate. Advantageously, the copper compound is used in combination with other metal halides, in particular alkaline halides (e.g. NaI, KI, NaBr, KBr), the molar ratio of metal halide to copper halide being 0.5 to 20, preferably 1 to 10 and particularly preferably 3 to 7.

[0134] Stabilizers based on aromatic secondary amines, the content of these stabilizers is preferably 0.1% to 2% by weight, preferably 0.2% to 0.5% by weight

[0135] Stabilizers based on sterically hindered phenols, the content of these stabilizers preferably being from 0.1% to 1.5% by weight, preferably from 0.2% to 0.6% by weight, and

[0136] Phosphites and phosphonites, and

[0137] Mixtures of the above stabilizers.

[0138] Examples of stabilizers based on aromatic secondary amines which can be used according to the invention are adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linol, Naugard 445, N,N′-dinaphthyl-p-phenylenediamine, N-phenyl-N′-cyclohexyl-p-phenylenediamine or mixtures thereof.

[0139] Suitable sterically hindered phenols are, in principle, all compounds having a phenol structure which has at least one sterically demanding group on the phenol ring. Preferred examples of stabilizers based on sterically hindered phenols that can be used according to the invention are N,N′-hexamethylene-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionamide, bis-(3,3-bis-(4′-hydroxy-3′-tert-butylphenyl)-butyric acid) glycol ester, 2,1′-thioethyl-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate), 4-4′-butylidene-bis-(3-methyl-6-tert-butylphenol), triethylene glycol-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionate or mixtures of two or more of these stabilizers.

[0140] Preferred phosphites and phosphonites are triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6- Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris-(tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-bisphenylene diphosphonite, 6-isooctyloxy-2,4,8, 10-tetra-tert-butyl-12H-dibenzo-[d,g]-1,3,2-dioxaphosphocine, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz-[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g] -1,3,2-dioxaphosphocene, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite. In particular, tris[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butyl)-phenyl-5-methyl]phenylphosphite and tris(2,4-di-tert-butylphenyl)phosphite (Irgafos168) are preferred.

[0141] Preferred embodiments of heat stabilizers include combinations of organic heat stabilizers, particularly a combination of Irgafos 168 and Irganox 1010, or a combination of HOSTANOX O 3P (bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butyric acid diol ester) and SANDOSTAB P-EPQ (tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphite). Heat stabilizers based solely on CuI and KI are particularly preferred.

[0142] Examples of oxidation retarders and heat stabilizers include phosphites and other amines (eg triacetonediamine), hydroquinone, variously substituted representatives of these groups and mixtures thereof, in concentrations up to 1% by weight, based on the weight of components (A) to (D).

[0143] Various substituted resorcinols, salicylates, benzotriazoles, triazines and benzophenones are mentioned as UV stabilizers, which are generally used in amounts of up to 2% by weight, based on the weight of the molding composition.

[0144] Inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide, and carbon black and / or graphite, and furthermore organic pigments, such as phthalocyanines, quinacridones, perylenes, and dyes, such as nigrosine and anthraquinones, can be added as colorants. However, it is preferred that the molding composition according to the invention contains neither carbon black nor graphite, i.e., the molding composition according to the invention is preferably free of carbon black and graphite.

[0145] In a particularly preferred embodiment, the thermoplastic molding composition according to the invention comprises:

[0146] (A) a mixture of 34% to 82.9% by weight of at least one polyamide (A1), at least one polyphenylene ether (A2) and a compatibilizer (A3);

[0147] (B) 15 to 55 weight percent glass fibers having a glass composition comprising 12 to 24 weight percent boron oxide and 2 to 14 weight percent of the combined total of magnesium oxide and calcium oxide;

[0148] (C) 2 to 6 wt% of an LDS additive selected from the group consisting of copper chromium oxide, copper tungstate, copper oxide, copper hydroxide phosphate, tin hydroxide phosphate, tin phosphate, copper phosphate, basic copper phosphate and basic tin phosphate or mixtures thereof, preferably copper tungstate;

[0149] (D) 0.1 to 5 wt% of additives other than (A), (B), and (C);

[0150] The mixture (A) consists of 52 to 89.8% by weight of component (A2), 10 to 45% by weight of component (A1), 0.2 to 3% by weight of component (A3), based in each case on the sum of components (A1) to (A3), the sum of components (A1) to (A3) being 100% by weight of the mixture (A); and the sum of (A) to (D) being 100% by weight of the molding composition.

[0151] The molding compositions according to the invention have good mechanical properties, can be easily metallized after irradiation, and are characterized by a low relative permittivity of less than 3.0 and a low dielectric loss factor of less than 0.008.

[0152] A preferred variant for producing the molding composition according to the invention is that, in a first step, a mixture comprising components (A1) to (A4) is provided. To this end, components (A2), (A3) and optionally (A4) can first be metered into the feed section of an extruder and mixed at a temperature in the range of 220° C. to 340° C. The mixture is then added to a side feeder. Component (A) is then introduced via a side feeder into the molten mixture of components (A2), (A3) and optionally (A4) in the housing of the extruder downstream of the feed. Alternatively, components (A1) to (A4) can also be metered into the feeder of the extruder and mixed in the extruder at a temperature of 220° C. to 340° C. In both variants, components (C) and / or (D) can also be included, with these components preferably being metered into the feed. Then, in a second extrusion step, mixture (A) and components (C) and (D) or a mixture of (A), (C) and (D) are metered into the feed of the extruder and melted at a temperature of 220° C. to 340° C., while component (B) is fed into the extruder housing downstream of the feed via a side feeder and mixed with the melt present.

[0153] Another preferred method for preparing the molding composition is to meter components (A1) to (A4), (C), and (D) into the feed of an extruder and melt and mix them in a first extruder section at a temperature of 220° C. to 340° C. Component (B) is then introduced into the melt via a side feeder and mixed with the other components in a second extruder section. The molding compound is then discharged and, after cooling, pelletized. Underwater pelletization is preferred for high filler contents.

[0154] The present invention furthermore comprises a molded article which comprises or preferably consists of the above-described thermoplastic molding composition according to the invention.

[0155] The molded body is preferably a component, housing, or housing part of a device that communicates via electromagnetic waves having a frequency of 0.3 GHz to 300 GHz.

[0156] In particular, the molded article is selected from the group consisting of transmitting and receiving devices, mobile phones, tablet computers, laptop computers, navigation devices, surveillance cameras, cameras, sensors, diving computers, audio systems, remote controls, loudspeakers, headphones, radios, televisions, household appliances, kitchen appliances, door openers or door openers, vehicle central locking operating devices, keyless start vehicle keys, temperature measuring or temperature indicating devices, components, housings or housing parts of measuring and control devices.

[0157] Example

[0158] Measurement method:

[0159] Within the scope of this application, the following measurement methods are used:

[0160] Relative viscosity

[0161] The relative viscosity is determined according to ISO 307 (2007) at 20° C. For this purpose, 0.5 g of polymer particles are weighed into 100 ml of m-cresol. The relative viscosity (RV) is calculated according to Chapter 11 of the standard as RV=t / t0.

[0162] Glass transition temperature (Tg) and melting point (Tm)

[0163] The particles were subjected to glass transition temperature and melting point determination according to ISO 11357-2 and ISO 11357-3 (2013). Differential scanning calorimetry (DSC) was performed at a heating rate of 20 K / min for each of the three heatings. After the first heating, the sample was cooled at a rate of 20 K / min, and the melting point was determined during the subsequent heating (second heating). The sample was then quenched in dry ice, and the glass transition temperature (Tg) was determined during the third heating. The temperature at the maximum peak is indicated as the melting point. The midpoint of the glass transition region was determined according to the "half-height" method, which shows the glass transition temperature (Tg).

[0164] Tensile modulus

[0165] The tensile modulus was determined according to ISO 527 (2012) at 23°C and a tensile speed of 1 mm / min on ISO tensile bars (type A1, mass 170x20 / 10x4) prepared according to standard ISO / CD 3167 (2003).

[0166] Breaking stress and breaking elongation

[0167] The tensile stress at break and the elongation at break were determined according to ISO 527 (2012) at 23°C at a tensile speed of 5 mm / min on ISO tensile bars type A1 (mass 170 mm x 20 / 10 mm x 4 mm) with reinforcement, which were prepared according to standard: ISO / CD 3167 (2003).

[0168] Relative permittivity and dielectric loss factor (DLF)

[0169] Relative permittivity (εr) and dielectric loss factor (DLF) were measured in accordance with IEC 61189-2-721 (2015) on an 80 mm x 80 mm x 3 mm flat plate with a film gate using a split post dielectric resonator (SPDR) from QWED, Poland (a brochure containing information related to the measurements is available at www.qwed.eu). The measurement frequency was 2.45 GHz and the measurement temperature was 23°C.

[0170] Molding shrinkage

[0171] Plaques (type D2, 60 mm x 60 mm x 2 mm, film gate) for determining mold shrinkage were prepared according to ISO 294-3 (2002) and Amendment 1 (2006). After 14 days of storage under standard conditions (23°C, 50% relative humidity) according to ISO 294-4 (2001), the actual injection shrinkage in the longitudinal and transverse directions relative to the mold cavity dimensions and the flow direction of the molding compound melt was determined. The arithmetic mean of the measurements on five plaques is shown. The ratio of the injection shrinkage along and across the flow direction of the molding compound is also known as warpage or deformation.

[0172] Laser structuring and metallization capabilities

[0173] To evaluate the metallization behavior, injection molded parts (60 mm × 60 mm × 2 mm plates) were structured using an Nd:YAG laser and then metallized in an electroless copper plating bath. During the laser structuring process, 16 adjacent 10 mm × 10 mm areas were irradiated on the surface of the molded parts. Laser structuring was performed using a FOBA DP50 laser at a speed of 4 m / s, a wavelength of 1064 nm, and an irradiation width of approximately 50 μm. Both the pulse frequency and pulse width were adjusted. Both the pulse frequency and current intensity of the laser were varied. The laser diode current was set to 24.0 amps, 24.5 amps, 25.0 amps, and 25.5 amps for specific pulse frequencies of 5 kHz, 6 kHz, 7 kHz, and 8 kHz, respectively. After laser structuring, the molded parts were cleaned to remove residues from the laser process. The molded parts were subjected to an ultrasonic bath, followed by a surfactant and then deionized water. The cleaned moldings were then metallized in a reducing copper plating bath (MacDermid MID-Copper 100B1) for 20 to 30 minutes.

[0174] Metallization evaluation

[0175] o: The average copper deposit thickness is at least 3 μm in fewer than 14 areas;

[0176] +: The average copper deposition thickness is at least 3 μm in 14 or 15 areas;

[0177] ++: The average copper deposition thickness is at least 3 μm in all 16 areas;

[0178] For the purposes of the present invention, sufficient metallization means that copper is deposited in at least 14 areas with an average thickness of at least 3 μm.

[0179] Colorability:

[0180] F: The molding composition can be colored with colors other than black, for example yellow, orange, red or blue.

[0181] S: Molding compound is black and cannot be pigmented in other colors.

[0182] Glass composition of glass fiber

[0183] The glass composition of glass fillers, in particular of glass fibers, was determined using the following determination methods: optical emission spectrometry with inductively coupled plasma (ICP OES) according to DIN 51086-2:2004, titrimetric determination of the boron oxide content according to ISO 21078-1:2008, X-ray fluorescence melt digestion method according to ISO 12677:2003, determination of fluorine after high-temperature hydrolysis according to DIN 51084:2008.

[0184] Preparation of polyamide molding compounds

[0185] For Examples B1 to B9 according to the invention and Comparative Example VB4, the various compounds (A) were first prepared. To this end, the corresponding amounts of polyphenylene ether (A2) and compatibilizer (A3) were metered into the feed zone of a Werner & Pfleiderer ZSK 25 twin-screw extruder according to Tables 2 and 3, and the polyamide component (A1) was introduced into the melt via six barrel zones of a side feeder before the discharge. For the polyamide 1 example, the temperature of the first zone was set at 70°C, while the temperature of the remaining shells was set at 260°C to 290°C; for the polyamide 2 example, the temperature of the remaining shells was set at 290°C to 320°C. A rotation speed of 300 rpm and a rate of 10 kg / h were used, and degassing was carried out at atmospheric pressure. The strands were cooled in a water bath, cut, and the resulting pellets were dried at 100°C under vacuum (30 mbar) for 24 hours. The blend (A), the dry granules of polyamide or polyphenylene ether, and the additives (C) and (D) were then mixed together to form a dry blend in the proportions shown in Tables 2 and 3. This mixture was homogenized using a drum mixer for approximately 20 minutes. The molding compositions were prepared on a Werner & Pfleiderer ZSK 25 twin-screw extruder in the proportions shown in Tables 2 and 3. The dry blend was metered into the feeder via a gravimetric feeder. The glass fiber (B) was metered into a side feeder via a gravimetric feeder, which delivered six housing units of the glass fiber (B) into the melt upstream of the mold. The temperature of the first housing was set at 80°C, while the temperatures of the remaining housings were set at 260°C to 280°C for Examples B1 to B3, B7, B8, VB1, and VB2, and at 280°C to 310°C for Examples B4 to B6, B9, VB3, and VB4. A rotation speed of 250 rpm and a throughput of 15 kg / h were used with atmospheric degassing. The strands were cooled in a water bath, cut and the resulting granules were dried at 110° C. under vacuum (30 mbar) for 24 h to a water content below 0.1% by weight.

[0186] Preparation of test samples

[0187] The test specimens were produced on an Arburg injection molding machine, Model Allrounder 420C 1000-250. For Examples B1-B3, B7, B8, VB1, and VB2, a barrel temperature of 260°C to 280°C and a mold temperature of 80°C were used, while for Examples B4-B6, B9, VB3, and VB4, a barrel temperature of 290°C to 320°C and a mold temperature of 120°C were used. Unless otherwise stated, the test specimens were used under dry conditions; to this end, they were stored in a dry environment, i.e., on silica gel, at room temperature for at least 48 hours after injection molding.

[0188] Table 1 Materials used in Examples and Comparative Examples

[0189]

[0190]

[0191] RP: relative permittivity; DLF: dielectric loss factor

[0192] Table 2: Results

[0193]

[0194] 1) Relative to the sum of components (A) to (D)

[0195] 2) Relative to the sum of components (A1) to (A3); A4 = 0% by weight.

[0196] 3) Deformation rate = ratio of transverse injection shrinkage to longitudinal injection shrinkage

[0197] Table 3: Results

[0198]

[0199]

[0200] 1) Relative to the sum of components (A) to (D)

[0201] 2) relative to the sum of components (A1) to (A3);

[0202] 3) Deformation rate = ratio of transverse injection shrinkage to longitudinal injection shrinkage.

Claims

1. A thermoplastic molding composition consisting of the following components: A) a mixture of at least one polyamide A1, at least one polyphenylene ether A2 and optionally a compatibilizer A3 and optionally an olefin and / or vinyl aromatic polymer A4; B) 10 to 60 wt% of a glass filler, wherein the glass filler has a glass composition comprising 52.0 to 57.0 wt% of silicon dioxide, 13.0 to 17.0 wt% of aluminum oxide, 15.0 to 21.5 wt% of boron oxide, 2.0 to 6.0 wt% of magnesium oxide, 2.0 to 6.0 wt% of calcium oxide, 1.0 to 4.0 wt% of titanium dioxide, 0 to 1.5 wt% of fluorine, and 0 to 0.6 wt% of a basic oxide; C) 1 to 8 wt% of an LDS additive; D) 0% to 5% by weight of additives other than component A, component B, and component C; wherein the mixture A consists of 80% to 100% by weight of a mixture M of component A1, component A2 and component A3 and 0% to 20% by weight of component A4, each based on the sum of component M and component A4, and wherein the sum of component M and component A4 is 100% by weight of the mixture A; and wherein the mixture M consists of 52% to 89.8% by weight of the component A2, 10% to 45% by weight of the component A1 and 0.2% to 3% by weight of the component A3, based in each case on the sum of the components A1 to A3, and wherein the sum of the components A1 to A3 is 100% by weight of the mixture M; and the sum of the components A to D is 100% by weight of the thermoplastic molding composition.

2. The thermoplastic molding composition according to claim 1, characterized in that The glass filler B is selected from the group consisting of fibers, particles, flakes, balls or combinations thereof.

3. The thermoplastic molding composition according to claim 2, characterized in that The ball is a hollow ball.

4. The thermoplastic molding composition according to claim 2, characterized in that The fibers are glass fibers.

5. Thermoplastic molding composition according to claim 4, characterized in that The glass fiber has a non-circular cross section and an axis ratio of a major cross-sectional axis to a minor cross-sectional axis in a range of 2 to 6.

6. The thermoplastic molding composition according to claim 2, characterized in that The glass filler B is selected from milled fibers.

7. The thermoplastic molding composition according to claim 5, characterized in that An axis ratio of the major cross-sectional axis to the minor cross-sectional axis is in the range of 3 to 5.

8. The thermoplastic molding composition according to claim 1 or 2, characterized in that The at least one polyamide A1 is selected from the group consisting of PA 46, PA 6, PA 66, PA 6 / 66, PA 10, PA 11, PA 12, PA 516, PA 610, PA 612, PA 614, PA 616, PA 618, PA 1010, PA 1012, PA 1014, PA 1016, PA 1018, PA 1212 and mixtures thereof; and / or a semicrystalline partially aromatic polyamide selected from the group consisting of PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 6, PA 6T / 66, PA 6T / 610, PA 6T / 612, PA 6T / 10T, PA 6T / 10I, PA 9T, PA 10T, PA 12T, PA 10T / 10I, PA10T / 106, PA10T / 610, PA10T / 612, PA10T / 66, PA10T / 6, PA10T / 1010, PA10T / 1012, PA10T / 12, PA10T / 11, PA 6T / 9T, PA 6T / 12T, PA 6T / 10T / 6I, PA 6T / 6I / 6, PA 6T / 6I / 12 and their mixtures;and / or an amorphous polyamide or microcrystalline polyamide selected from the group consisting of PA 6I / 6T, PA MACM9, PA MACM10, PAMACM12, PA MACM13, PA MACM14, PA MACM16, PA MACM17, PA MACM18, PA PACM10, PA PACM12, PA PACM13, PA PACM14, PA PACM16, PA PACM17, PA PACM18, PA TMDC10, PA TMDC12, PATMDC13, PA TMDC14, PA TMDC16, PA TMDC17, PA TMDC18, PA MACM10 / 10, PA MACMI / 12, PAMACMT / 12, PA 6I / MACMI / MACMT, PA MACMI / MACMT / MACM12, PA MACMI / MACMT / MACM12 / 12, PA 6I / 6T / MACMI / MACMT / 12, PA 6I / 6T / MACMI, PA MACMI / MACM36, PAMACMT / MACM36, PA MACMI / MACM12, PA MACMT / MACM12, PA MACM6 / 11, PA MACM10 / 10, PAMACM12 / PACM12, PA MACM14 / PACM14, PA MACM18 / PACM18 and their mixtures. ; 9. The thermoplastic molding composition according to claim 8, characterized in that The at least one polyamide A1 is selected from the group consisting of the following as aliphatic polyamide: PA 610, PA 612, PA1010, PA12 and PA616; and / or a semicrystalline partially aromatic polyamide selected from the group consisting of the following: PA 6T / 6I, PA 6T / 10T, PA 6T / 10T / 6I; and / or an amorphous or microcrystalline polyamide selected from the group consisting of the following: PA 6I / 6T, PA MACM12, PAMACM14, PA TMDC12, PA TMDC14, PA MACMI / 12, PA 6I / 6T / MACMI / MACMT, PA MACMI / MACMT / 12, PA MACMI / MACMT / MACM12, PA 6I / 6T / MACMI / MACMT / 12, PA MACM10 / 10, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACM18 / PACM18 and mixtures thereof.

10. The thermoplastic molding composition according to claim 1 or 2, characterized in that The at least one polyphenylene ether of component A2 is selected from the group consisting of poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, or copolymers or mixtures thereof.

11. The thermoplastic molding composition according to claim 1 or 2, characterized in that The component A3 is selected as a compatibilizer, or a mixture of a compatibilizer and a free radical initiator.

12. Thermoplastic molding composition according to claim 11, characterized in that The compatibilizer is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, methylmaleic acid, methylmaleic anhydride, itaconic acid, itaconic anhydride, butenylsuccinic acid, butenylsuccinic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, N-phenylmaleimide, citric acid, malic acid and 2-hydroxynonadecane-1,2,3-tricarboxylic acid, monoesters or diesters of the aforementioned acids with C1- to C12-alcohols, monoamides or diamides of the aforementioned acids, which monoamides or diamides may be substituted on nitrogen by alkyl or aryl groups having up to 12 carbon atoms, the aforementioned acids and the aforementioned The salts of the mentioned monoamides or diamides with alkali metals or alkaline earth metals, and mixtures thereof; and the free radical initiator is selected from the group consisting of: 1,1-di-tert-butyl-peroxy-3,3,5-trimethylcyclohexane, tert-butyl-peroxy-isopropyl carbonate, tert-butyl-peroxy-3,3,5-trimethylhexanoate, tert-butyl peracetate, tert-butyl perbenzoate, 4,4-di-tert-butyl-peroxy-n-butyl valerate, 2,2-di-tert-butyl-peroxy-butane, diisopropyl benzene peroxide, tert-butyl isopropyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, di-tert-butyl peroxide, and mixtures thereof.

13. Thermoplastic molding composition according to claim 12, characterized in that The C1- to C12-alcohol is methanol or ethanol; the alkali metal or alkaline earth metal is calcium and potassium.

14. Thermoplastic molding composition according to claim 1 or 2, characterized in that The olefin and / or vinyl aromatic polymer A4 is selected from the group consisting of styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene-styrene block copolymers, styrene-styrene-butadiene-styrene block copolymers, polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-octene copolymers, ethylene-propylene-butene copolymers, ethylene-propylene-hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly(ethylene-vinyl acetate), ethylene-ethyl acrylate copolymers, ethylene-hexene copolymers, ethylene-propylene-diene terpolymers and mixtures of these polymeric materials; and / or is grafted with carboxylic acid or carboxylic anhydride groups, with a grafting degree of 0.1% to 4.0% by weight, based on the grafted polymer A4.

15. The thermoplastic molding composition according to claim 1 or 2, characterized in that The olefin and / or vinyl aromatic polymer A4 is selected from the group consisting of styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene-styrene block copolymers, styrene-styrene-butadiene-styrene block copolymers, polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-octene copolymers, ethylene-propylene-butene copolymers, ethylene-propylene-hexene copolymers, ethylene-propylene-methylhexadiene copolymers, poly(ethylene-vinyl acetate), ethylene-ethyl acrylate copolymers, ethylene-hexene copolymers, ethylene-propylene-diene terpolymers and mixtures of these polymeric materials; and / or is grafted with acrylic acid, methacrylic acid or maleic anhydride, with a degree of grafting of 0.1% to 4.0% by weight, based on the grafted polymer A4.

16. The thermoplastic molding composition according to claim 14, characterized in that The degree of grafting is from 0.4% to 2.5% by weight.

17. The thermoplastic molding composition according to claim 14, characterized in that The degree of grafting is 0.5 wt % to 2.0 wt %.

18. The thermoplastic molding composition according to claim 15, characterized in that The degree of grafting is from 0.4% to 2.5% by weight.

19. The thermoplastic molding composition according to claim 15, characterized in that The degree of grafting is 0.5 wt % to 2.0 wt %.

20. The thermoplastic molding composition according to claim 1 or 2, characterized in that Component C comprises or is completely formed from at least one LDS additive based on copper and / or tin selected from the group consisting of metal oxides, metal phosphates.

21. Thermoplastic molding composition according to claim 20, characterized in that The metal phosphate is a basic metal phosphate and / or a metal hydroxide phosphate.

22. The thermoplastic molding composition according to claim 20, characterized in that The component C comprises or is entirely composed of at least one LDS additive selected from the group consisting of tin oxide; metal or metal oxide doped tin oxide; mica coated with metal oxide; mica coated with antimony doped tin oxide; a mixture of tin oxide and antimony oxide and optionally other metal oxides; spinel; copper chromium oxide; copper tungstate; copper oxide; copper hydroxide; copper hydroxide phosphate; copper phosphate; basic copper phosphate; copper tin phosphate; basic copper tin phosphate; tin phosphate; basic tin phosphate; antimony doped tin oxide; or mixtures or combinations thereof.

23. Thermoplastic molding composition according to claim 22, characterized in that The metal or metal oxide doped tin oxide is antimony doped tin oxide.

24. The thermoplastic molding composition according to claim 20, characterized in that The component C comprises or is entirely formed of at least one LDS additive selected from the group consisting of antimony-doped tin oxide in combination with mica.

25. Thermoplastic molding composition according to claim 1 or 2, characterized in that The LDS additive of component C is selected from the group consisting of copper chromium oxide, copper tungstate, copper oxide, copper hydroxide phosphate, tin hydroxide phosphate, tin phosphate, copper phosphate, basic copper phosphate and tin phosphate, or a mixture thereof.

26. Thermoplastic molding composition according to claim 25, characterized in that The LDS additive of component C is selected from copper tungstate.

27. The thermoplastic molding composition according to claim 1 or 2, characterized in that The additive of component D is selected from the group consisting of stabilizers, anti-aging agents, antiozonants, processing aids, optical brighteners, crystallization accelerators, crystallization retarders, and mixtures thereof.

28. Thermoplastic molding composition according to claim 27, characterized in that The additives of component D are selected from the group consisting of processing stabilizers, light stabilizers, inorganic heat stabilizers, organic heat stabilizers, antioxidants, flow aids, lubricants, slip agents, mold release agents, colorants, and mixtures thereof.

29. The thermoplastic molding composition according to claim 27, characterized in that The additives of component D are selected from the group consisting of UV stabilizers, UV absorbers, inorganic heat stabilizers based on copper halides and alkaline halides, dyes, inorganic pigments, organic pigments and mixtures thereof.

30. The thermoplastic molding composition according to claim 27, characterized in that The additive of component D is selected from viscosity improvers and marking agents.

31. The thermoplastic molding composition according to claim 1 or 2, characterized in that Based on the sum of components A to D, component A is present in a proportion ranging from 34% by weight to 82.9% by weight; and / or based on the sum of components A to D, component B is present in a range of 15% by weight to 55% by weight; and / or based on the sum of components A to D, component C is present in a range of 2 wt % to 6 wt %, and / or based on the sum of components A to D, component D is present in a range of 0.1 wt % to 5 wt %.

32. Thermoplastic molding composition according to claim 31, characterized in that Based on the sum of components A to D, component A is present in a proportion ranging from 39% by weight to 78.8% by weight; and / or based on the sum of components A to D, component B is present in a proportion ranging from 18% by weight to 52% by weight; and / or based on the sum of components A to D, component C is present in a range of 3 wt % to 5 wt %, and / or based on the sum of components A to D, component D is present in a range of 0.2 wt % to 4 wt %.

33. A molded article comprising the thermoplastic molding composition according to any one of claims 1 to 32.

34. A molded article consisting of the thermoplastic molding composition according to any one of claims 1 to 32.

35. The molded article according to claim 33 or 34, characterized in that The molded article is selected from components of a device that communicates with electromagnetic waves having a frequency of 0.3 GHz to 300 GHz.

36. The molded article according to claim 35, characterized in that The molded article is selected from housings of devices that communicate with electromagnetic waves having a frequency of 0.3 GHz to 300 GHz.

37. The molded article according to claim 35, wherein The molded article is selected from housing parts of a device that communicates with electromagnetic waves having a frequency of 0.3 GHz to 300 GHz.

38. The molded article according to claim 35, wherein The molded article is selected from the group consisting of components of transmitting and receiving devices, cameras, sensors, audio systems, household appliances, door opening devices, operating devices for vehicle central locking systems, temperature measuring devices or temperature indicating devices and control devices.

39. The molded article according to claim 35, wherein The molded article is selected from the group consisting of components for mobile phones, tablet computers, laptop computers, navigation devices, surveillance cameras, diving computers, remote controls, speakers, headphones, radios, televisions, kitchen appliances, door openers, keyless start vehicle keys, and measuring devices.

40. The molded article according to claim 35, wherein The molded article is selected from the group consisting of: housings for transmitting and receiving devices, cameras, sensors, audio systems, household appliances, door openers, operating devices for vehicle central locking systems, temperature measuring devices or temperature indicating devices, and control devices.

41. The molded article according to claim 35, wherein The molded article is selected from the group consisting of: housings for mobile phones, tablet computers, laptop computers, navigation devices, surveillance cameras, diving computers, remote controls, speakers, headphones, radios, televisions, kitchen appliances, door openers, keyless start vehicle keys, and measuring devices.

42. The molded article according to claim 35, wherein The molded article is selected from the group consisting of: housing parts for transmitting and receiving devices, cameras, sensors, audio systems, household appliances, door openers, operating devices for vehicle central locking systems, temperature measuring devices or temperature indicating devices, and control devices.

43. The molded article according to claim 35, wherein The molded article is selected from the group consisting of mobile phones, tablet computers, laptop computers, navigation devices, surveillance cameras, diving computers, remote controls, speakers, headphones, radios, televisions, kitchen appliances, door openers, keyless start vehicle keys, housing parts for measuring devices.

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