Polyamide molding compound with low dielectric loss factor

Abstract

To provide a thermoplastic molding compound that has at least 5.0 of a relative dielectric constant and less than 0.008 of a low dielectric loss factor; in particular, has excellent injection shrinkage and warp / distortion behaviors; and has excellent mechanical properties.SOLUTION: A thermoplastic molding composition includes: (A) a mixture consisting of at least one polyamide A1 and at least one polyphenylene ether A2, and as optional components, a compatibilizer A3 and an olefinic and / or vinyl aromatic polymer A4; (B) 10-40 wt.% of a glass filler having a specific component; (C) 20-50 wt.% of a salt of titanic acid, a salt of tin acid, a salt of zirconic acid, or a mixture of them; (D) 1-8 wt.% of an LDS additive; and (E) 0-5 wt.% of an additive other than the components (A), (B), (C) and (D).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to glass fiber reinforced thermoplastic molding compounds based on polyamides and polyphenylene ethers, which have high dielectric constants and low dielectric loss factors, as well as moldings made from these molding compounds and their use.The molding compounds also contain LDS additives, and moldings made from them can be selectively metallized after partial irradiation. [Background technology]

[0002] Plastic molding compounds having a high dielectric constant and a low dielectric loss factor are advantageously used in the manufacture of housings, housing parts, or other components of devices that communicate via electromagnetic waves having frequencies between 0.3 and 300 GHz, since their use can avoid significant impairment of the transmission and reception characteristics of these devices.

[0003] Such devices communicating via electromagnetic waves are used in various fields, for example in telecommunications, consumer electronics or the home, in particular in transceiver devices, mobile phones, tablets, laptops, navigation devices, surveillance cameras, photo cameras, sensors, dive computers, audio systems, remote controls, speakers, headphones, radios, televisions, kitchen appliances, door or gate openers, control units for central locking systems in vehicles, keyless-go vehicle keys, temperature measuring and display devices, measuring and control units, temperature display devices, measuring and control devices.

[0004] The polyamide molding compounds described in EP 3330319 A1 are said to have a dielectric constant of 3.5 or less at a frequency of 2.45 GHz. These molding compounds contain a specific mixture of aliphatic and amorphous or microcrystalline polyamides, as well as a glass filler consisting of glass with an alkali and alkaline earth oxide content of 0 to 12 wt. %, and additives. All examples and comparative examples, regardless of composition, have a dielectric constant of less than 4.0. No information on dielectric loss factor or metallization is provided.

[0005] European Patent Application Publication No. 3560987A1 describes glass fiber-reinforced molding compounds with high tensile and impact strength combined with low dielectric constant and low dielectric loss factor. The molding compounds contain 10 to 90% by weight of glass fiber and 90 to 10% by weight of plastic, with the composition of the glass fiber being more precisely specified. Compared to E-glass, the described glass fiber contains significantly less alkaline earth oxides but a relatively high content of boron oxide, lowering the dielectric constant to 4.8 and the dielectric loss factor to 0.0015, respectively, determined at 10 GHz. As the disclosed examples show, the improved dielectric properties can also be applied to polyamide molding compounds. However, a dielectric constant of less than 4.0 and a dielectric loss factor of at least 0.0109 have been determined for molding compounds with PA6 and 50% by weight of glass fiber. No information is provided regarding the metallization properties of the molding compounds.

[0006] EP 2291444 A1 describes laser direct structuring (LDS) molding compounds with a high dielectric constant of at least 4 and a low dielectric loss factor of up to 0.01. These molding compounds contain a base resin, an LDS additive, and a ceramic filler with a dielectric constant of ≥ 25. The examples show molding compounds based on polyamides and polyphenylene ethers with DKs ranging from 4.1 to 6.8. However, the dielectric loss factors of the molding compounds described in the examples are not disclosed. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] European Patent Application Publication No. 3330319A1 [Patent Document 2] European Patent Application Publication No. 3560987A1 [Patent Document 3] European Patent Application Publication No. 2291444 Summary of the Invention [Problem to be solved by the invention]

[0008] Based on the above, one objective of the present invention was to provide a thermoplastic molding compound that, in addition to having a dielectric constant of at least 5.0 and a low dielectric loss factor of less than 0.008, can also be easily processed by injection molding and exhibits particularly good injection shrinkage and warpage / distortion behavior. Furthermore, the thermoplastic molding compound should have good mechanical properties, preferably a stress at break of at least 70 MPa and a tensile modulus of at least 5000 MPa. Furthermore, the molding compound should have good metallization properties after laser irradiation.

[0009] This challenge consists 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 olefinic and / or vinyl aromatic polymer (A4); (B) 10 to 40 wt. % of a glass filler having a glass composition containing at least 10.0 wt. % of boron oxide and up to 15 wt. % of magnesium oxide and calcium oxide in total; (C) 20 to 50% by weight of titanic acid salts, stannic acid salts, zirconic acid salts, and mixtures thereof; (D) 1-8 wt% LDS additive; (E) 0 to 5 wt. % of additives other than components (A), (B), (C), and (D); It consists of the mixture (A) comprises 80 to 100% by weight of a mixture (M) of components (A1), (A2) and (A3), and 0 to 20% by weight of component (A4), in each case based on the total of components (M) and (A4), where the total of components (M) and (A4) is 100% by weight of the mixture (A); the mixture (M) comprises 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), in each case based on the total of components (A1) to (A3), where the total of components (A1) to (A3) is 100% by weight of the mixture (M); The total of (B) and (C) is in the range of 35 to 70% by weight, based on the total of components (A) to (E), where the total of components (A) to (E) is 100% by weight of the molding composition; The problem is solved by a thermoplastic molding compound according to claim 1.

[0010] Dependent claims 2 to 13 relate to advantageous embodiments of the thermoplastic molding composition according to the invention. Furthermore, according to claim 14, moldings are provided from the thermoplastic molding composition according to the invention, and claims 15 and 16 relate to special moldings.

[0011] Regarding the composition of mixture (A), as described above, components (A1), (A2), and (A3) together 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). Mixture (A) does not contain any other components other than components (A1) to (A4).

[0012] The thermoplastic molding compositions according to the invention and the moldings produced therefrom have a dielectric constant of at least 5.0 and a dielectric loss factor (DLF) of less than 0.008, measured in accordance with IEC 61189-2-721 (2015) on a plate of 80 x 80 x 3 mm at a measuring frequency of 2.45 GHz and a temperature of 23°C using a split post dielectric resonator (SPDR) manufactured by QWED (Poland).

[0013] By good mechanical properties, it is understood that the molding compound according to the invention has a tensile modulus of at least 5000 MPa, preferably at least 6000 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 0.8%, preferably at least 0.9%, wherein the tensile modulus, stress at break and elongation at break are determined in accordance with ISO 527 (2012).

[0014] In the context of the present invention, "satisfactory metallization" means that a molding (60 x 60 x 2 mm plate) injection-molded from a thermoplastic molding compound according to the invention can be fully metallized in a copper plating bath after partial irradiation with an Nd:YAG laser (FOBA DP 50 laser, wavelength = 1064 nm, irradiation width = 50 μm, speed = 4 m / s). For this purpose, 16 adjacent 10 x 10 mm areas are irradiated on the surface of the molded part during laser structuring, whereby both the laser pulse frequency (5, 6, 7, and 8 kHz) and the current intensity (24-25.5 amperes) are varied. The cleaned molding is then metallized for 20-30 minutes in a reduction copper plating bath (MacDermid MID-Copper 100 B1). "Fully metallized" here means that copper is deposited in at least 14 areas to an average thickness of at least 3 μm. [Means for solving the problem]

[0015] Surprisingly, the above-mentioned problem is solved by a thermoplastic molding composition, which comprises (A) a mixture of at least one polyamide (A1), at least one polyphenylene ether (A2) and optionally a compatibilizer (A3), and optionally an olefinic and / or vinyl aromatic polymer (A4); (B) 10 to 40 wt. % of a glass filler having a glass composition containing at least 10.0 wt. % of boron oxide and up to 15 wt. % of magnesium oxide and calcium oxide in total; (C) 20 to 50% by weight of titanic acid salts, stannic acid salts, zirconic acid salts, and mixtures thereof; (C) 1-8 wt% LDS additive; (D) 0 to 5 wt. % of additives other than components (A), (B), (C), and (D); It consists of the mixture (A) comprises 80 to 100% by weight of a mixture (M) of components (A1), (A2) and (A3), and 0 to 20% by weight of component (A4), in each case based on the total of components (M) and (A4), where the total of components (M) and (A4) is 100% by weight of the mixture (A); the mixture (M) comprises 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), in each case based on the total of components (A1) to (A3), where the total of components (A1) to (A3) is 100% by weight of the mixture (M); The total of (B) and (C) is in the range of 35 to 70% by weight based on the total of components (A) to (E), where the total of components (A) to (E) is 100% by weight of the molding composition. It has been found that a solution is provided by a thermoplastic molding composition.

[0016] The content of the mixture (A) in the molding composition is the difference between the total of the contents (B) to (E) and 100% by weight of the entire molding composition.

[0017] Preferably, component (A) of the molding compound is present in an amount of 24 to 57.9% by weight, particularly preferably 31 to 51.8% by weight, based on the total weight of the molding compound (components (A) to (E)).

[0018] The proportion of component (B) is preferably in the range of 15 to 35% by weight, particularly preferably 18 to 32% by weight, based on the total of components (A) to (E) in any case.

[0019] The proportion of component (C) is preferably in the range of 25 to 45% by weight, particularly preferably 30 to 42% by weight, based on the total of components (A) to (E) in any case.

[0020] The total proportion of component (B) and component (C) is preferably in the range of 40 to 65% by weight, particularly preferably in the range of 45 to 60% by weight, based on the total of components (A) to (E).

[0021] The proportion of component (D) is preferably in the range of 2 to 6% by weight, particularly preferably in the range of 3 to 5% by weight, based on the total of components (A) to (E) in any case.

[0022] The proportion of component (E) is preferably in the range of 0.1 to 5% by weight, particularly preferably 0.2 to 4% by weight, based on the total of (A) to (E) in any case.

[0023] As the investigations carried out have shown, glass-fiber-reinforced molding compounds whose polymer matrix consists solely of polyamide have too high a dielectric loss factor, even when so-called "low DK glass fibers" are used as reinforcing fibers. In contrast, molding compounds with a polyphenylene ether matrix exhibit too high a warpage, especially too high a shrinkage value, and are poorly processable. Molding compounds with a polymer component formed from a 1:1 mixture of polyamide and polyphenylene ether and reinforced with glass fibers consisting of E-glass also exhibit excessive dielectric loss.

[0024] Definition of Terms For the purposes of the present invention, the term "polyamide" (abbreviation PA) is understood as a generic term encompassing homopolyamides and copolyamides. The spellings and abbreviations chosen for polyamides and their monomers correspond to those specified in ISO standard 16396-1 (2015(D)). The abbreviations used therein will be used below as synonyms of the IUPAC names of the monomers. In particular, the following abbreviations occur for the monomers: T or TPS for terephthalic acid, I or IPS for isophthalic acid, MACM for bis(4-amino-3-methyl-cyclohexyl)methane (also known as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, CAS number 6864-37-5), PACM for bis(4-amino-cyclohexyl)methane (also known as 4,4'-diaminodicyclohexylmethane, CAS number 1761-71-3), TMDC for bis(4-amino-3,5-dimethylcyclohexyl)methane (also known as 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, CAS number 65962-45-0). For 1,6-hexanediamine (also known as hexamethylenediamine), the abbreviation HMDA is used.

[0025] Compared to semi-crystalline polyamides, amorphous polyamides exhibit no or very low, barely detectable heat of fusion. At a heating rate of 20 K / min in dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013), amorphous polyamides preferably exhibit a heat of fusion of less than 5 J / g, particularly preferably 3 J / g or less, and most preferably 0 to 1 J / g. Because amorphous polyamides are amorphous, they do not have a melting point.

[0026] Microcrystalline polyamides have a melting point in addition to a glass transition temperature. However, they have such small crystallites that a 2 mm thick sheet made from them remains transparent, i.e., its light transmittance is at least 90% and its haze is at most 3% as measured according to ASTM D 1003-13 (2013). Microcrystalline polyamides preferably exhibit a heat of fusion of 5 to 25 J / g, particularly preferably 5 to 22 J / g, and most preferably 5 to 20 J / g at a heating rate of 20 K / min in dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013).

[0027] In addition to the glass transition temperature, the semi-crystalline polyamide has a well-defined melting point and exhibits a heat of fusion of preferably more than 25 J / g, particularly preferably more than 30 J / g, most preferably 30 to 80 J / g at a heating rate of 20 K / min in dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013).

[0028] Dielectric constant and loss factor. The dielectric constant (ε) is a measure of the behavior of a molecule when placed in an electric field. The dielectric constant is ε = ε r The relative permittivity (ε r ) and the dielectric constant of a vacuum (ε0). r ) is a material-dependent quantity and is the quotient of the dielectric constant (ε) and the dielectric constant of a vacuum (ε0). In addition to the type of material, the relative dielectric constant (ε r ) also depends on the frequency of the electric field and on the temperature.

[0029] The dielectric loss factor indicates the magnitude of losses in the propagation of electromagnetic waves in electrical components such as capacitors or materials such as plastic molding compounds. Losses here refer, for example, to the energy converted electrically or electromagnetically and dissipated as heat. These losses result in attenuation of electromagnetic waves. For a more accurate representation of the loss factor, consider a capacitor connected to a voltage source with a sinusoidal voltage curve over time. A phase shift φ occurs between the voltage and current across such a capacitor. An ideal lossless capacitor would have a phase shift of φ = 90°. In a practical lossy capacitor, the phase shift is less than 90° by the loss angle δ, and the dielectric loss factor is equal to tan δ. Therefore, the dielectric loss factor is a measure of the amount of energy an insulating material absorbs in an AC electric field and converts it into dissipated heat. Materials with high dielectric loss tangents are unsuitable for use as insulating or housing materials in high-frequency applications. The dielectric constant and dielectric loss factor are preferably determined in accordance with IEC 61189-2-721(2015).

[0030] Component (A) 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 vinyl aromatic polymer (A4).

[0031] In this case, 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 total of components (M) and (A4), where the total of components (M) and (A4) is 100% by weight of the mixture (A).

[0032] The mixture (M) consists in each case 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 on the total of components (A1) to (A3).

[0033] Preferably, component (A1) is present in 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).

[0034] Preferably, component (A2) is present in 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).

[0035] Preferably, component (A3) is present in 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).

[0036] Preferably, component (A4) is present in mixture (A) in a proportion of 0 to 20% by weight, based on the total of components (M) and (A4), and particularly preferably, mixture (A) does not contain component (A4), i.e., mixture (A) particularly preferably consists only of components (A1) to (A3).

[0037] Ingredient (A1) According to one embodiment of the present invention, aliphatic polyamides are preferred as component (A1). In particular, aliphatic polyamides selected from the group consisting of PA46, PA6, PA66, PA6 / 66, PA10, PA11, PA12, PA516, PA610, PA612, PA614, PA616, PA618, PA1010, PA1012, PA1014, PA1016, PA1018, PA1212, and mixtures thereof are preferred. Aliphatic polyamides with an N / C ratio (N = nitrogen / C = carbon) of 8 or more are particularly preferred because they have low water absorption and therefore little change in dielectric properties in humid environments. In particular, aliphatic polyamides PA610, PA612, PA1010, PA12, and PA616 are preferred.

[0038] According to a further embodiment of the present invention, amorphous or microcrystalline polyamides are preferred as component (A1). In particular, amorphous or microcrystalline polyamides are preferably PA 6I / 6T, PA MACM9, PA MACM10, 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, PA TMDC12, PA TMDC13, PA TMDC14, PA TMDC16, PA TMDC17, PA TMDC18, PA MACM10 / 10, PA MACMI / 12, PA MACMT / 12, PA 6I / MACMI / MACMT, PA MACMI / MACMT / 12, PA MACMI / MACMT / MACM12, PA MACMI / MACMT / MACM12 / 12, PA 6I / 6T / MACMI / MACMT / 12, PA 6I / 6T / MACMI, PA MACMI / MACM36, PA MACMT / MACM36, PA MACMI / MACM12, PA MACMT / MACM12, PA MACM6 / 11 PA MACM10 / 10, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACM18 / PACM18, and mixtures thereof, selected from the group consisting of 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 6I / 6T / MACMI / MACMT / 12, PA MACM10 / 10, PA MACM12 / PACM12, PA The preferred polyolefins are selected from the group consisting of 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, PA MACM12 / PACM12, and blends thereof.

[0039] According to a further preferred embodiment, semi-crystalline partially aromatic polyamides are preferred as component (A1). The semi-crystalline partially aromatic polyamides preferably have a glass transition temperature in the range of 90 to 150°C, preferably in the range of 110 to 140°C, and in particular in the range of 115 to 135°C. The melting point of the semi-crystalline partially aromatic polyamides is in the range of 255 to 330°C, preferably in the range of 270 to 325°C, and in particular in the range of 280 to 320°C. Preferably, the semi-crystalline partially aromatic polyamide of component (A1) has a melting enthalpy in the range of 25 to 80 J / g, preferably in the range of 30 to 70 J / g, determined by DSC according to ISO 11357 (2013).

[0040] In this context, preferred semi-aromatic, semi-crystalline polyamides are (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, (b) Diamines: based on the total amount of diamines, 80-100 mol % of at least one aliphatic diamine having 4-18 carbon atoms, preferably 6-12 carbon atoms, and 0-20 mol % of at least one cycloaliphatic diamine having preferably 6-20 carbon atoms, such as PACM, MACM, IPDA, and / or 0-20 mol % of at least one araliphatic diamine, such as MXDA and PXDA, and optionally (c) Aminocarboxylic acids and / or lactams, each having 6 to 12 carbon atoms It is made from

[0041] According to a preferred embodiment, the semicrystalline, partially aromatic polyamide of component (A1) is formed on the basis of at least 55 mol %, in particular at least 65 mol %, of terephthalic acid and at least 80 mol %, preferably at least 90 mol %, in particular at least 95 mol % of an aliphatic diamine having 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and, if desired, further aliphatic, cycloaliphatic and aromatic dicarboxylic acids, and further lactams and / or aminocarboxylic acids.

[0042] According to a further preferred embodiment, the aliphatic dicarboxylic acids, for example, of the partially aromatic polyamides of component (A1), which can be used in addition to terephthalic acid, are selected from the group consisting of adipic acid, succinic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, brassylic acid, tetradecanedicarboxylic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and dimer fatty acids (36 C atoms). Adipic acid, sebacic acid, and dodecanedicarboxylic acid are particularly preferred. Accordingly, dicarboxylic acids preferably used in addition to terephthalic acid are isophthalic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, or mixtures of such dicarboxylic acids. In particular, polyamides (A1) based solely on terephthalic acid as the dicarboxylic acid are preferred.

[0043] According to a further 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 such diamines, with 1,6-hexanediamine, 1,10-decanediamine, 1,12-dodecanediamine, or a mixture of such diamines being preferred, and 1,6-hexanediamine and 1,10-decanediamine being particularly preferred. In addition to the aliphatic diamines, cycloaliphatic and / or araliphatic diamines can be substituted at a concentration of 0 to 20 mol % based on the total amount of diamines.

[0044] More preferably, the polyamide (A1) is formed from the following components: (a): dicarboxylic acids: 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, in each case based on the total content of dicarboxylic acids present; (b): Diamines: based on the total content of diamines present, 80 to 100 mole % of at least one aliphatic diamine having 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms; 0 to 20 mole % of cycloaliphatic diamines, such as PACM, MACM, IPDA, and / or araliphatic diamines, such as MXDA and PXDA, preferably having 6 to 20 carbon atoms (in the fire-resistant polyamide, the percent molar content of dicarboxylic acids is 100% and the percent molar content of diamines is 100%), and optionally: (c): An aminocarboxylic acid and / or a lactam, preferably a lactam having 6 to 12 carbon atoms and / or an aminocarboxylic acid, preferably having 6 to 12 carbon atoms.

[0045] Components (a) and (b) are preferably used in approximately equimolar amounts, while the concentration of (c) is preferably at most 30% by weight, preferably at most 20% by weight, in particular at most 15% by weight, in each case based on the sum of (a) to (c).

[0046] Suitable alicyclic dicarboxylic acids include cis- and / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3-dicarboxylic acid (CHDA). The commonly used aliphatic diamines mentioned above can be replaced with small amounts of other diamines, based on the total amount of diamines, of 20 mol% or less, preferably 15 mol% or less, and particularly 10 mol% or less. Examples of alicyclic 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). Araliphatic diamines include m-xylylenediamine (MXDA) and p-xylylenediamine (PXDA).

[0047] In addition to the dicarboxylic acids and diamines mentioned above, lactams and / or aminocarboxylic acids can also be used as polyamide-forming components (component (c)). Suitable compounds are, 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 the aminocarboxylic acid and / or lactam used together with components (A1_a) and (A1_b) is up to 20% by weight, preferably up to 15% by weight, and particularly preferably up to 12% by weight, based on the total of components (A1a) to (A1c). Lactams or α,ω-amino acids having 4, 6, 7, 8, 11, or 12 carbon atoms are particularly preferred. The lactams are pyrrolidin-2-one (4 C atoms), ε-caprolactam (6 C atoms), enantholactam (7 C atoms), capryllactam (8 C atoms), and laurinlactam (12 C atoms), and the α,ω-amino acids are 1,4-aminobutanoic acid, 1,6-aminohexanoic 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.

[0048] To control the molecular weight, relative viscosity, flowability, or MVR, regulators in the form of monocarboxylic acids or monoamines can be added to the batch and / or precondensate (before postcondensation). Aliphatic, cycloaliphatic, or aromatic monocarboxylic acids or monoamines suitable as regulators are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid, 2-(3,5-di-tert-butyl-4-hydroxybenzylthio)acetic acid, 3,3-bis(3-tert-butyl-4-hydroxyphenyl)propanoic acid, 2-(3,5-di-tert-butyl-4-hydroxybenzylthio)acetic acid, 3,3-bis(3-tert-butyl-4-hydroxyphenyl)propanoic acid, 2-(3,5-di-tert-butyl-4-hydroxybenzylthio)acetic acid, 2-(3,5-di ... Examples of suitable modifiers include 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, and 4-amino-2,6-di-tert-butylphenol. Modifiers can be used individually or in combination. Other monofunctional compounds capable of reacting with amino or acid groups, such as anhydrides, isocyanates, acid halides, or esters, can also be used as modifiers. The typical amount of modifier used is between 10 and 200 mmol / kg of polymer.

[0049] Specific representative examples of semi-crystalline partially aromatic polyamides (A1) are PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 6, PA 6T / 66, 6T / 610, 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 Particularly preferred are the partially aromatic polyamides of component (A1) selected from the group consisting of PA 6T / 6I, PA 6T / 10T, PA 6T / 10T / 6I, and mixtures thereof. Polyamides (A1) containing 6T units, especially at least 10% by weight of 6T units, are preferred.

[0050] According to the invention, the following partially aromatic copolyamides are therefore particularly preferred as polyamide (A1): semicrystalline polyamide 6T / 6I containing 55-75 mol% hexamethylene terephthalamide units and 25-45 mol% hexamethylene isophthalamide units; · semicrystalline polyamide 6T / 6I containing 62-73 mol% hexamethylene terephthalamide units and 25-38 mol% hexamethylene isophthalamide units; semicrystalline polyamides prepared from at least 50 mol % of terephthalic acid and up to 50 mol % of isophthalic acid, in particular 100 mol % of terephthalic acid, and a mixture of at least two diamines selected from the group consisting of hexamethylenediamine, nonanediamine, methyloctanediamine, and decanediamine; · semicrystalline polyamides prepared from 70-100 mol% terephthalic acid and 0-30 mol% isophthalic acid with a mixture of hexamethylenediamine and decanediamine; semicrystalline polyamides prepared from at least 50 mol % of terephthalic acid and not more than 50 mol % of dodecanedioic acid and a mixture of at least two diamines selected from the group consisting of hexamethylenediamine, nonanediamine, methyloctanediamine and decanediamine; semicrystalline polyamide 6T / 10T having 10 to 60 mol %, preferably 10 to 40 mol %, of hexamethylene terephthalamide (6T) units and 40 to 90 mol %, preferably 60 to 90 mol %, of decamethylene terephthalamide (10T) units; Semicrystalline polyamides 6T / 10T / 6I having 50 to 90 mol %, preferably 50 to 70 mol %, of hexamethylene terephthalamide (6T) units and 5 to 45 mol %, preferably 10 to 30 mol % of hexamethylene isophthalamide (6I) units and 5 to 45 mol %, preferably 20 to 40 mol % of decamethylene terephthalamide (10T) units. The polyamide (A1) preferably has a solution viscosity η in the range of 1.3 to 2.7, particularly preferably in the range of 1.4 to 2.3, and most particularly preferably in the range of 1.5 to 2.0, measured in accordance with ISO 307 (2007) on a solution of 0.5 g of polymer in 100 ml of m-cresol at a temperature of 20°C. rel It has.

[0051] Ingredients (A2) The polyphenylene ethers used in 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. Pat. Nos. 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 in combination with other substances such as secondary amines, tertiary amines, halogens, or combinations thereof are commonly used in the preparation.

[0052] 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 containing 2,3,6-trimethylphenol, and blends thereof. Poly(2,6-dimethyl-1,4-phenylene) ether, optionally in combination with 2,3,6-trimethylphenol units, is preferred. Polyphenylene ethers can be used in the form of homopolymers, copolymers, graft copolymers, block copolymers, or ionomers.

[0053] Suitable polyphenylene ethers preferably have an intrinsic viscosity in the range of 0.1 to 0.6 dL / g, as measured in chloroform at 25°C. This corresponds to a molecular weight (Mn) (number average) of 3,000 to 40,000 g / mol and a weight average molecular weight (Mw) of 5,000 to 80,000 g / mol. A high-viscosity polyphenylene ether and a low-viscosity polyphenylene ether can be used in combination. The ratio of the two polyphenylene ethers with different viscosities depends on the viscosity and the desired physical properties.

[0054] To improve the compatibility between component (A1) and component (A2), in a preferred embodiment, the polyphenylene ether used is modified to contain, preferably covalently bonded, carbonyl, carboxyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam, or halobenzyl groups. Preferably, for this purpose, unmodified polyphenylene ether (A2) is modified with an α,β-unsaturated dicarbonyl compound, an amide- or lactam-containing monomer having a polymerizable double bond (A3), optionally in combination with a radical starter (A3), such as a peroxide, especially dibenzoyl peroxide, as described, for example, in EP 0 654 505 A1.

[0055] Ingredients (A3) To improve the compatibility of components (A1) and (A2), compatibilizers can be used in the form of functional compounds that interact with the polyphenylene ether, the polyamide, or both. The interaction can be chemical (e.g., by grafting) and / or physical (e.g., by affecting the surface properties of the dispersed phase).

[0056] In a preferred embodiment of the present invention, the compatibilizer further comprises a radical initiator, which is preferably an organic peroxide or an azo compound, i.e., in this embodiment, the compatibilizer is graft polymerized in the presence of the free radical initiator.

[0057] In a particularly preferred embodiment, the compatibilizer is used without a free radical initiator.

[0058] The compatibilizer may be a functional compound containing at least one carboxylic acid, carboxylic anhydride, epoxy, ester, amide, or imide group, preferably in combination with an olefinic double bond. Examples include 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; mono- or diesters of the aforementioned acids with C1-C12 alcohols such as methanol or ethanol; mono- or diamides of the aforementioned acids, optionally substituted on the nitrogen with alkyl or aryl groups having up to 12 carbon atoms; and salts with alkali or alkaline earth metals such as calcium and potassium. Maleic acid, fumaric acid, maleic anhydride, and citric acid are particularly preferred. The compatibilizer, alone or in combination with an optional free radical initiator, may be added directly during blend preparation, or the polyphenylene ether and / or polyamide may be functionalized with the compatibilizer in a separate step.

[0059] Suitable radical initiators are, for example: 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-valeric acid n-butyl ester, 2,2-di-tert-butyl-peroxy-butane, dicumyl peroxide, tert-butyl-cumyl peroxide, 1,3-bis(tert-butyl-peroxyisopropyl)benzene, di-tert-butyl peroxide and azoisobutyronitrile.As the radical initiator, organic peroxides are preferred, and dicumyl peroxide is particularly preferred.

[0060] Thus, component (A3) comprises a compatibilizer or a mixture of a compatibilizer and a radical initiator. The compatibilizer and radical initiator are present in a total amount of 0 to 4 wt. %, preferably 0.1 to 4 wt. %, and particularly preferably 0.2 to 3 wt. %, based on the sum of (A1) to (A3). The radical initiator is preferably present in a range of 0 to 1 wt. %, and particularly preferably 0.05 to 0.8 wt. %, based on the sum of (A1) to (A3).

[0061] In a preferred embodiment, the compatibilizer is graft polymerized without the addition of a free radical initiator, ie, component (A3) preferably does not contain a free radical initiator.

[0062] Ingredients (A4) The blend (A) according to the invention may contain, in addition to the polyamide (A1), the polyphenylene ether (A2) and the optional compatibilizer (A3), 0 to 20% by weight of a vinyl aromatic polymer and / or an olefinic polymer (A4).

[0063] The olefin polymers are homopolyolefins or copolyolefins, particularly preferably polymers based on ethylene, propylene and butylene or copolymers thereof, and copolymers with other α-olefin monomers, in particular 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene.

[0064] The vinyl aromatic polymer is preferably polystyrene or a copolymer of styrene with another monomer having at least one olefinic double bond, such as the α-olefins ethylene, propylene, and butylene, or acrylic acid or acrylic acid esters, or butadiene. Particularly preferred are block copolymers having at least one block (Block-A) formed from a vinyl aromatic monomer and at least one block (Block-B) formed from an olefinic monomer, such as those present in styrene block copolymers.

[0065] The olefinic and / or vinylaromatic polymers used as component (A4) may be or contain 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 acid anhydrides, (meth)acrylic acid, and their esters. Polymer (A4) may also be a crosslinked elastomeric core consisting of butadiene, isoprene, or alkyl acrylate, with a graft shell of polystyrene, non-polar or polar olefin homopolymers and copolymers, such as ethylene-propylene, ethylene-propylene-diene, and ethylene-octene or ethylene-vinyl acetate rubber, or non-polar or polar olefin homopolymers and copolymers formed by grafting or copolymerization with acid anhydrides, (meth)acrylic acid, and their esters. Polymer (A4) may also be a carboxylic acid functionalized copolymer, such as poly(ethene-co-(meth)acrylic acid) or poly(ethene-co-1-olefin-co-(meth)acrylic acid) (wherein the 1-olefin is an alkene or an unsaturated (meth)acrylic acid ester having more than four atoms), including copolymers in which the acid groups are partially neutralized with metal ions.

[0066] Component (A4) is polystyrene, polybutadiene-polystyrene graft copolymer, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene-styrene block copolymer (SBS), styrene-styrene-butadiene-styrene block copolymer (SSBS), ethylene / propylene copolymer, ethylene / propylene / diene copolymer (EPDM), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene Advantageously, the polymer (A4) is selected from the group consisting of 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 0.1 to 4.0% by weight, based on the grafted polymer (A4).

[0067] It is further preferred that the mixture (A) comprises as component (A4) at least one vinyl aromatic polymer and optionally at least one polyolefin. It is particularly preferred if the mixture (A) contains at least 5% by weight, in particular at least 10% by weight, of vinyl aromatic polymer, in each case based on the total amount of (A).

[0068] Preferably, the olefinic 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-butylene copolymers, styrene ... The polymeric material is selected from the group consisting of ethylene copolymer, ethylene-methylhexadiene copolymer, propylene-methylhexadiene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-hexene copolymer, ethylene-propylene-methylhexadiene copolymer, poly(ethylene-vinyl acetate) (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-hexene copolymer, ethylene-propylene-diene terpolymer, and blends of these polymeric materials.

[0069] Furthermore, it is preferred if the olefinic and / or vinyl aromatic polymer (A4) of the molding composition is grafted with carboxylic acid or carboxylic acid anhydride groups, particularly preferably with acrylic acid, methacrylic acid or maleic anhydride, the degree of grafting being in each case preferably from 0.1 to 4.0% by weight, particularly preferably from 0.4 to 2.5% by weight, and even more particularly preferably from 0.5 to 2.0% by weight, based on the grafted polymer (A4).

[0070] Component (B) is a glass-based filler present in the polyamide molding composition in an amount of 10 to 40% by weight. The filler can be both fibrous and particulate, either individually or as a mixture. Thus, component (B) can contain a fibrous filler (reinforcing agent) or a particulate filler, or a mixture of a reinforcing agent and a particulate filler. For the purposes of this invention, the terms glass-based filler, glass filler, or glass filler are used synonymously.

[0071] According to a preferred embodiment of the invention, component (B) is present in the polyamide molding composition in an amount of preferably 15 to 35% by weight, particularly preferably 18 to 32% by weight, these amounts being stated relative to the sum of components (A) to (E).

[0072] According to the invention, a glass filler (B) is used which is based on a glass whose composition comprises at least 10% by weight of boron oxide and a maximum of 15% by weight in total of magnesium oxide and calcium oxide.

[0073] According to a preferred embodiment of the invention, the glass filler is based on a glass composition, the glass composition being based on a glass with a magnesium oxide and calcium oxide content of 2 to 14% by weight, more preferably 4 to 12% by weight in total.

[0074] According to another preferred embodiment of the invention, the glass filler is based on a glass whose composition comprises 12 to 24% by weight, particularly preferably 15 to 22% by weight, of boron oxide.

[0075] The glass filler is preferably selected from the group consisting of fibers, milled fibers, particles, flakes, spheres, hollow spheres, and mixtures thereof, and is preferably composed of fibers, particles, flakes, and mixtures thereof. More particularly preferably, the glass filler is glass fiber. Most particularly preferred as glass fiber is glass fiber having a non-circular cross section and an axial ratio of the major cross section axis to the minor cross section axis in the range of 2 to 6, preferably 3 to 5.

[0076] The glass filler may be surface-treated. This can be achieved using a suitable sizing or adhesion promoter system. For example, systems based on fatty acids, waxes, silanes, titanates, polyamides, urethanes, polyurethanes, polyhydroxyethers, epoxides, nickel, or combinations or mixtures thereof can be used for this purpose. Preferably, the glass filler is surface-treated with aminosilanes, epoxysilanes, polyamides, or mixtures thereof.

[0077] When 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, and the fibers may have a circular or non-circular cross section. Non-circular or non-circular glass fibers, also called flat glass fibers, may have an elliptical, oblong, angular, rectangular, or nearly rectangular cross section.

[0078] The chopped glass fibers preferably have a fiber length of 1 to 25 mm, preferably 1.5 to 20 mm, more preferably 2 to 12 mm, and most preferably 2 to 8 mm.

[0079] The chopped glass fibers preferably have a diameter of 5 to 20 μm, preferably 5 to 15 μm, particularly preferably 6 to 12 μm.

[0080] If the 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 5 to 17 μm.

[0081] In the case of flat glass fibers, the aspect ratio, i.e., the ratio of the major cross-sectional axis to the minor cross-sectional axis, is 2 to 8, preferably 2 to 6, and particularly preferably 3 to 5. The cross-sectional axis of the flat glass fiber has a length of 3 to 40 μm. Preferably, the length of the minor cross-sectional axis is 3 to 20 μm, more preferably 4 to 10 μm, and the length of the major cross-sectional axis is 6 to 40 μm, more preferably 12 to 30 μm.

[0082] Blends of fibers having circular (round) and non-circular (flat) cross sections may also be used to reinforce the polyamide molding compounds of the present invention.

[0083] If glass beads or glass particles are selected as the glass filler (B), their average volume diameter (D50), measured by laser diffraction in accordance with ASTM B 822-10 (2010), is preferably 0.3 to 100 μm, particularly preferably 5 to 80 μm, and even more particularly preferably 17 to 70 μm.

[0084] Furthermore, the glass filler preferably has a relative permittivity of at most 7, particularly preferably at most 5, and a dielectric loss factor of at most 0.0040, particularly preferably at most 0.0030, determined in accordance with IEC 61189-2-721 (2015) at a frequency of 2.45 GHz and a temperature of 23°C using a split post dielectric resonator (SPDR) from QWED, Poland, based on a glass plate (80 x 80 x 3 mm) made from the glass of the glass filler.

[0085] According to a preferred embodiment of the present invention, component (B) consists solely of a glass filler selected from the group consisting of glass fibers, crushed glass fibers, glass particles, glass flakes, glass spheres, hollow glass spheres, or combinations thereof, and the glass filler consists of glass having a total content of magnesium oxide and calcium oxide in the range of 2 to 14 wt % and a boron oxide (BO) content in the range of 12 to 24 wt % based on the composition of each glass. Particularly preferably, the glass filler is formed entirely of glass fibers.

[0086] In a particularly preferred embodiment, component (B) is selected as a glass filler, particularly preferably glass fiber, the glass having 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, 0 to 0.6% by weight of alkali oxides.

[0087] To improve the dielectric properties, component (C) is added to the molding composition according to the invention in a proportion of 20 to 50% by weight, preferably 25 to 45% by weight, particularly preferably 30 to 42% by weight, in each case based on the molding composition (sum of A to E). Component (C) preferably has a high relative permittivity of at least 100 or at least 500 and preferably a dielectric loss factor of at most 0.02 or at most 0.01, determined at a frequency of 2.45 GHz.

[0088] According to the present invention, metal salts of titanate, stannate, and zirconate, as well as mixtures thereof, are used as component (C). The aforementioned metal salts can be present individually or in the form of mixtures or as solid solutions, preferably as mixed crystals. Metal titanates are particularly preferred, with the metal being selected from the group consisting of barium, strontium, calcium, magnesium, lead, zirconium, manganese, neodymium, bismuth, hafnium, tin, zinc, and mixtures thereof. The aforementioned metals may be present in the titanate singly or in combinations of two or three metals.

[0089] Specific examples of such metal salts include barium titanate, strontium titanate, calcium titanate, magnesium titanate, neodymium titanate, bismuth titanate, lead titanate, nickel titanate, zinc titanate, barium stannate, strontium stannate, calcium stannate, magnesium stannate, neodymium stannate, bismuth stannate, lead stannate, nickel stannate, zinc stannate, barium zirconate, strontium zirconate, calcium zirconate, magnesium zirconate, neodymium zirconate, bismuth zirconate, lead zirconate, nickel zirconate, and zinc zirconate. Particularly preferred metal titanates may contain a portion of metal stannate and metal zirconate to improve dielectric properties.

[0090] Combinations of two or three metal titanates, metal stannates, and metal zirconates are particularly preferred, preferably including at least one metal titanate, such as barium titanate and strontium titanate, barium titanate and neodymium titanate, barium titanate, strontium titanate, and barium stannate, barium titanate, strontium titanate, and magnesium zirconate, barium titanate, and calcium titanate, and strontium titanate and magnesium titanate.

[0091] Particularly preferred as component (C) are barium titanate, strontium titanate, barium strontium titanate, and barium neodymium titanate. For barium strontium titanate and barium neodymium titanate, it is particularly preferred that the molar fraction of barium is in the range of 55 to 85% based on the metal titanate.

[0092] Component (C) is preferably used as a powder in which 90% by volume of the particles have a diameter of less than 10 μm, preferably less than 5 μm, and 50% by volume of the particles have a diameter of less than 5 μm, preferably 2.5 μm, determined in accordance with ISO 13320 (2009) using a Malvern Mastersizer 2000 instrument.

[0093] Preferably, the proportion of component (D) is in the range from 2 to 6% by weight, preferably in the range from 3 to 5% by weight, based in each case on the molding composition (sum of A to E).

[0094] Component (D) is preferably an LDS (Laser Direct Structuring) additive with a non-zero absorption coefficient for UV, VIS or IR radiation, which under the action of electromagnetic radiation, preferably laser radiation, forms metal nuclei which facilitate and / or enable and / or improve the deposition of a metal layer for producing conductor tracks at the irradiation points on the molding surface in a chemical metallization process, this LDS additive preferably having 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 comprising an absorber which transfers the radiation energy to the LDS additive.

[0095] Component (D) is preferably an LDS additive having a median particle size (D50) in the range of 50 to 10,000 nanometers, preferably 200 to 5,000 nanometers, particularly preferably 300 to 4,000 nanometers, and / or an aspect ratio of at most 10, in particular at most 5. The D50 value given as a measure of particle size is a measure of the median particle size, such that 50 volume percent of the sample is finer than the D50 value (median) and the other 50% of the sample is coarser than the D50 value (median).

[0096] Preferably, component (D) is an LDS additive selected from the group of metal oxides, in particular so-called spinels having the general chemical formula AB2O4, where A is a divalent metal cation and B is a trivalent metal cation. In this context, metal cation A is preferably selected from the group consisting of magnesium, copper, cobalt, zinc, tin, iron, manganese, and nickel, and combinations thereof, and metal cation B is preferably selected from the group consisting of manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum, and chromium, and combinations thereof.

[0097] In particular, the LDS additive is preferably copper-iron spinel, copper-containing aluminum magnesium oxide, copper-chromium-manganese mixed oxide, optionally with oxygen vacancies, or copper salts and oxides, such as copper-manganese-iron mixed oxide with copper(I) oxide, copper(II) oxide, basic copper phosphate, copper sulfate, and metal complex compounds, in particular chelate complexes of copper, tin, nickel, cobalt, silver, and palladium, or mixtures of such systems, and / or is particularly selected from the following group: copper-chromium-manganese mixed oxide, copper-manganese-iron mixed oxide, copper chromate, copper tungstate, iron zinc oxide, chromium-cobalt oxide, aluminum cobalt oxide, aluminum magnesium oxide, and mixtures and / or surface-treated and / or oxygen-deficient forms thereof. Possible systems are, for example, those described in WO 2000 / 35259 or Kunststoffe 92 (2002) 11, pp. 2-7.

[0098] Also preferred as component (D) are LDS additives selected from the group consisting of metal oxides, mixed metal oxides, metal hydroxide oxides, and tin-based metal sulfide oxides. Tin oxide and doped tin oxide are particularly preferred, with antimony, bismuth, molybdenum, aluminum, titanium, silicon, iron, copper, silver, palladium, and cobalt being doped. Tin oxide doped with antimony, titanium, or copper is particularly preferred. Furthermore, mixtures of tin oxide with at least one additional metal oxide, especially antimony oxide, are preferred as LDS additives. As additional metal oxides, both colorless, highly refractive metal oxides, such as titanium dioxide, antimony(III) oxide, zinc oxide, tin oxide, and / or zirconium dioxide, and colored metal oxides, such as chromium oxide, nickel oxide, copper oxide, cobalt oxide, and especially iron oxide (Fe2O3, Fe3O4), are used. In particular, mixtures of tin oxide and antimony(III) oxide are preferred.

[0099] Preferably, the doped tin oxide or metal oxide mixture or tin oxide is formed as a layer on a plate-like substrate, particularly a layered silicate such as synthetic or natural mica, talc, kaolin, glass platelets, or silicon dioxide platelets. Mica or mica flakes are particularly preferred as substrates for metal oxides. Also contemplated as substrates are plate-like metal oxides such as plate-like iron oxide, aluminum oxide, titanium dioxide, silicon dioxide, LCP (liquid crystal polymer), holographic pigments, and coated graphite platelets.

[0100] Particularly preferred are mica-based LDS additives, in which 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 present invention include Lazerflair LS 820, LS 825, LS 830, and Minatec 230 A-IR from Merck, Stanostat CP40W, Stanostat CP15G, and Stanostat CP5C from Keeling & Walker, and Fabulase 322S, 330, 350, and 352 from Budenheim.

[0101] Particularly preferred LDS additives are copper chromite, copper tungstate, copper hydroxide phosphate and antimony-doped tin oxide, the latter preferably used in combination with mica. Copper tungstate is very particularly preferred.

[0102] The polyamide molding composition according to the invention contains, as component (E) different from components (A), (B), (C) and (D), 0 to 5% by weight of at least one additive.

[0103] According to a preferred embodiment, the molding composition according to the invention contains 0.1 to 5% by weight, preferably 0.2 to 4% by weight, of at least one additive as component (E), based on the sum of components (A) to (E).

[0104] According to a preferred embodiment, the additives of component (E) are selected from the group consisting of stabilizers, antioxidants, antiozonants, processing stabilizers, processing aids, viscosity modifiers, 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, mold release agents, colorants, in particular dyes, inorganic pigments, organic pigments, marking agents and mixtures thereof.

[0105] According to a particularly preferred embodiment, the molding composition according to the invention contains at least one processing aid as component (E), the latter being present in a proportion of preferably 0 to 2% by weight, particularly preferably 0.1 to 2.0% by weight, particularly preferably 0.1 to 1.5% by weight, and most particularly preferably 0.2 to 1.0% by weight, in each case based on the total weight of components (A) to (E). Preferred metal salts are salts of Al, alkali metals, alkaline earth metals, esters or amides of fatty acids containing 10 to 44 carbon atoms, preferably 14 to 44 carbon atoms; preferred metal ions are Na, Mg, Ca, and Al, with Ca or Mg being particularly preferred. Particularly preferred metal salts are magnesium stearate, calcium stearate, calcium montanate, and aluminum stearate. The fatty acids may be mono- or divalent. Examples are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferred stearic acid, capric acid and montanic acid (mixtures of fatty acids having 30 to 40 carbon atoms).

[0106] According to a further preferred embodiment, the molding composition according to the invention contains as component (E) 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 (E).

[0107] According to a preferred embodiment, the heat stabilizer is selected from the group consisting of: Monovalent or divalent copper compounds, such as salts of monovalent or divalent copper with inorganic or organic acids or monovalent or divalent phenols, monovalent or divalent copper oxides, or complex compounds of copper salts with ammonia, amines, amides, lactams, cyanides, or phosphines, preferably hydrohalic acids, Cu(I) or Cu(II) salts of hydrocyanic acid, or copper salts of aliphatic carboxylic acids. Particularly preferred monovalent copper compounds are CuCl, CuBr, CuI, CuCN, and CuO, and particularly preferred divalent copper compounds are CuCl, CuSO, CuO, copper(II) acetate, or copper(II) stearate. Advantageously, copper compounds are used in combination with additional metal halides, especially alkali halides such as NaI, KI, NaBr, or KBr, with the molar ratio of metal halide to copper halide being 0.5 to 20, preferably 1 to 10, and particularly preferably 3 to 7; stabilizers based on secondary aromatic amines, preferably present in an amount of 0.1 to 2, preferably 0.2 to 0.5% by weight; stabilizers based on sterically hindered phenols, preferably present in an amount of 0.1 to 1.5, preferably 0.2 to 0.6% by weight; Phosphites and phosphonites, and A mixture of the above stabilizers.

[0108] Examples of stabilizers based on secondary aromatic amines that can be used according to the invention are the adduct of phenylenediamine with acetone (Naugard A), the adduct of phenylenediamine with linoleic acid, Naugard 445, N,N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine or mixtures thereof.

[0109] Suitable sterically hindered phenols are in principle all compounds with a phenol structure that has at least one sterically bulky group on the phenol ring.Preferred examples of stabilizers based on sterically hindered phenols that can be used according to the present invention are N,N'-hexamethylene-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionamide, bis-(3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)-butanoic 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 a mixture of two or more of these stabilizers.

[0110] Preferred phosphites and phosphonites include triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylphentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol 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, tris Examples include tearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10 tetra-tert-butyl-12H-dibenzo-[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo-[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. Particularly preferred are tris[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butyl)-phenyl-5-methyl]phenyl phosphite and tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168).

[0111] A preferred embodiment of the heat stabilizer is a combination of organic heat stabilizers, in particular Irgafos 168 and Irganox 1010 or HOSTANOX O 3P (bis[3,3-bis-(4'hydroxy-3'-tert-butyl-phenyl)butanoic acid glycol ester] with SANDOSTAB P-EPQ (tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonite). In particular, heat stabilization based solely on CuI and KI is preferred.

[0112] Examples of oxidation retarders and thermal stabilizers include phosphites and other amines (e.g., triacetone diamine), hydroquinone, various substituted representatives of these groups, and mixtures thereof, in concentrations of up to 1% by weight based on the weight of components (A) through (D).

[0113] Various substituted resorcinols, salicylates, benzotriazoles, benzotriazines and benzophenones are cited as UV stabilizers, and are generally used in amounts up to 2% by weight based on the weight of the molding composition.

[0114] Inorganic pigments such as titanium dioxide, ultramarine, iron oxide and carbon black and / or graphite, as well as organic pigments such as phthalocyanines, quinacridones, perylenes, and dyes such as nigrosine and anthraquinones can be added as colorants. However, it is preferred if the molding composition according to the invention does not contain carbon black or graphite, i.e. the molding composition according to the invention is preferably free of carbon black and graphite.

[0115] In a particularly preferred embodiment, the thermoplastic molding composition according to the invention comprises (A) 24 to 57.9 wt. % of a mixture of at least one polyamide (A1), at least one polyphenylene ether (A2) and a compatibilizer (A3); (B) 15 to 35 wt. % glass fibers having a glass composition containing 12 to 24 wt. % boron oxide and 2 to 14 wt. % magnesium oxide and calcium oxide in total; (C) 25 to 45 weight percent of a metal titanate selected from the group consisting of barium titanate, strontium titanate, barium strontium titanate, and barium neodymium titanate; (D) 2-6 wt. % of an LDS additive selected from the group consisting of copper chromate, copper tungstate, copper oxide, copper hydroxide phosphate, stannic hydroxide phosphate, tin hydroxide, copper phosphate, basic copper phosphate, and tin phosphate, or mixtures thereof, preferably selected as copper tungstate; (E) 0.1 to 5 wt. % of an additive other than (A), (B), (C), and (D); It consists of the mixture (A) comprises 52 to 89.8% by weight of component (A2), 10 to 45% by weight of component (A1), and 0.2 to 3% by weight of component (A3), in each case based on the total of components (A1) to (A3), where the total of components (A1) to (A3) is 100% by weight of the mixture (A); The total of (B) and (C) is in the range of 40 to 65% by weight, based on the total of (A) to (E), where the total of components (A) to (E) is 100% by weight of the molding composition.

[0116] The molding compounds according to the invention have good mechanical properties, can be easily metallized after irradiation, and are characterized by a relative dielectric constant of at least 5.0 and a low dielectric loss factor (DLF) of less than 0.008.

[0117] In a preferred variant of the production of molding compounds according to the invention, a mixture containing components (A1) to (A4) is provided in a first step. To this end, components (A2), (A3), and optionally (A4) can be initially metered into the feed section of an extruder and mixed at a temperature in the range of 220 to 340°C. The mixture is then fed into a side feeder. Component (A1) can then be introduced by the side feeder into the molten mixture formed from components (A2) to (A4) in the extruder housing downstream of the feed section. Alternatively, components (A1) to (A4) can be metered into the feeder of the extruder and mixed therein at a temperature of 220 to 340°C. In both variants, components (D) and / or (E) can also be included, which are preferably metered into the feed section. In the second extrusion step, mixture (A) and components (D) and (E), or a mixture of (A), (D) and (E), can then be metered into the feed section of the extruder and melted at a temperature of 220-340°C, while components (B) and (C) are fed via side feeders into the extruder housing downstream of the feed section and mixed with the melt present.

[0118] Another preferred method for producing molding compounds is to meter components (A1) through (A4), (D), and (E) into the feed section of an extruder, melt and mix them in the first extruder section at a temperature of 220°C to 340°C, and then feed components (B) and (C) into the melt via a side feeder and mix them with the other components in the second extruder section. The molding compound is then discharged and granulated after cooling. Underwater pelletization is preferred when the filler content is high.

[0119] Furthermore, the present invention comprises moldings which contain or preferably consist of the thermoplastic molding composition according to the invention described above.

[0120] The molded article is preferably a component, housing, or housing part of a device that communicates using electromagnetic waves having a frequency of 0.3 to 300 GHz.

[0121] In particular, the molding is selected from the group consisting of transceiver devices, mobile phones, tablets, laptops, navigation devices, surveillance cameras, photo cameras, sensors, diving computers, audio systems, remote controls, speakers, headphones, radio sets, television sets, domestic appliances, kitchen appliances, door or gate openers, operating devices for central locking of vehicles, keyless-go vehicle keys, temperature measurement or temperature display devices, components of measuring and control devices, housings or housing parts. DETAILED DESCRIPTION OF THE INVENTION

[0122] Measurement method: The following measurement methods were used within the scope of this application: Relative Viscosity The relative viscosity (RV) was measured at 20°C according to ISO 307 (2007). For this purpose, 0.5 g of polymer granules were weighed into 100 ml of m-cresol. The relative viscosity (RV) was calculated according to section 11 of the standard as RV = t / t0.

[0123] Glass transition temperature (Tg) and melting point (Tm) The glass transition temperature and melting point were determined on the granules according to ISO 11357-2 and -3 (2013). Differential scanning calorimetry (DSC) was performed at a heating rate of 20 K / min for each of three heats. After the first heat, the sample was cooled at a rate of 20 K / min, and the melting point was determined during the subsequent heat (second heat). The sample was then quenched in dry ice, and the glass transition temperature (Tg) was determined during the third heat. The temperature of the peak maximum was taken as the melting point. The glass transition temperature (Tg) was determined as the midpoint of the glass transition region using the "half height" method.

[0124] Tensile modulus The tensile Young's modulus was determined according to ISO 527 (2012) on ISO tensile bars (type A1, dimensions 170 × 20 / 10 × 4) prepared according to the standard ISO / CD 3167 (2003) at a pulling rate of 1 mm / min at 23 °C.

[0125] Stress at break and elongation at break The determination of the tensile stress at break and the elongation at break was carried out according to ISO 527 (2012) on ISO tensile bars, type A1 (dimensions 170 x 20 / 10 x 4 mm), prepared according to the standard ISO / CD 3167 (2003), at a pulling speed of 5 mm / min at 23 °C.

[0126] Dielectric constant and dielectric loss factor (DLF) Measurements of the dielectric constant εr and dielectric loss factor (DLF) were carried out according to IEC 61189-2-721(2015) on an 80 x 80 x 3 mm plate with a film gate using a split post dielectric resonator (SPDR) from QWED, Poland (brochure containing measurement information available at www.qwed.eu). The measurement frequency was 2.45 GHz and the measurement temperature was 23 °C.

[0127] Mold shrinkage Plates for determining splash shrinkage (type D2, 60 x 60 x 2 mm, film gate) were prepared according to ISO 294-3 (2002) and Amendment 1 (2006). Injection shrinkage was determined according to ISO 294-4 (2001) for the cavity size longitudinal and transverse to the direction of flow of the molding compound melt after storing the sheets for 14 days in a standard climate (23 °C, 50% relative humidity). The arithmetic mean of the measurements on five plates is shown. The ratio of injection shrinkage along the flow direction of the molding compound to the injection shrinkage across the flow direction is also called warpage or distortion.

[0128] Laser Structuring and Metallization To evaluate the metallization behavior, injection-molded parts (60 × 60 × 2 mm plates) were patterned using an Nd:YAG laser and subsequently metallized in an electroless copper plating bath. During laser structuring, 16 adjacent 10 × 10 mm areas were irradiated on the molded part surface. Laser structuring was performed using a FOBA DP50 laser at a wavelength of 1064 nm and an irradiation width of approximately 50 μm at a speed of 4 m / s. Both the pulse frequency and pulse width were adjusted. Both the laser pulse frequency and current intensity were varied. For specific pulse frequencies of 5, 6, 7, and 8 kHz, the laser diode current was set to 24.0, 24.5, 25.0, and 25.5 amperes, respectively. Following laser structuring, the molded parts were subjected to a cleaning process to remove laser process residues. The molded parts were subsequently subjected to ultrasonic baths using surfactants and deionized water. The cleaned extrusions were then metallized in a reduction copper plating bath (MacDermid MID-Copper 100 B1) for 20-30 minutes.

[0129] Metallization rating: o: copper was deposited to an average thickness of at least 3 μm in fewer than 14 areas; +: in 14 or 15 areas, copper was deposited with an average thickness of at least 3 μm; ++: In all 16 areas, copper was deposited to an average thickness of at least 3 μm; For purposes of this invention, fully metallized means that copper is deposited to an average thickness of at least 3 μm in at least 14 areas.

[0130] Glass composition of glass filler The glass composition of the glass fillers, especially the glass fibers, was determined using the following determination methods: inductively coupled plasma optical emission spectroscopy (ICP OES) according to DIN 51086-2:2004, titrimetric determination of the boron oxide content according to ISO 21078-1:2008, X-ray fluorescence fusion digestion according to ISO 12677:2003, fluorine determination after pyrohydrolysis according to DIN 51084:2008.

[0131] Preparation of polyamide molding compounds For Examples B1 to B3 according to the invention, various compounds (A) were first prepared. To this end, the respective amounts of polyphenylene ether (A2) and compatibilizer (A3) according to Table 2 were metered into the feed zone of a twin-screw extruder, type ZSK 25, manufactured by Werner & Pfleiderer. The polyamide component (A1) was introduced into the melt via a side feeder 6-barrel zone before discharge. The temperature of the first housing was set to 70°C, while the temperatures of the remaining housings were set to 260-290°C for the polyamide-1 examples and 290-320°C for the polyamide-2 examples. A speed of 300 rpm and a throughput of 10 kg / h were used, with atmospheric degassing applied. The strands were cooled in a water bath, chopped, and the resulting granules were dried in a vacuum (30 mbar) at 100°C for 24 hours. The dry granules of blend (A), polyamide, or polyphenylene ether were then mixed with additives (C), (D), and (E) to form a dry blend in the proportions shown in Table 2. This mixture was homogenized for approximately 20 minutes using a tumble mixer. Molding compounds were produced in the proportions shown in Table 2 using a twin-screw extruder, model FED 26 MTS, manufactured by Feddem GmbH & Co. KG. The dry blend was metered into the feeder via a metering feeder. Glass fiber (B) was metered into a side feeder via a metering feeder, which conveyed the glass fiber (B) to the melt in the six housing units upstream of the die. The temperature of the first housing was set at 80°C, and the temperatures of the remaining housings were set at 260-280°C for Examples B2, B3, and VB2, and 280-310°C for Examples B1 and VB2. A speed of 250 rpm and a throughput of 15 kg / h were used, and atmospheric degassing was applied. The strands were cooled by underwater pelletizing, cut, and the resulting pellets were dried in vacuum (30 mbar) at 110° C. for 24 hours to a moisture content of less than 0.1% by weight.

[0132] Preparation of test specimens The test specimens were prepared on an Arburg injection molding machine, model Allrounder 420C 1000-250. For Examples B2, B3, and VB2, an elevated cylinder temperature of 260°C to 280°C and a molding temperature of 80°C were used, while for Examples B1 and VB1, a cylinder temperature of 290°C to 320°C and a molding temperature of 120°C were used. Unless otherwise stated, the test specimens were used dry. For this purpose, the test specimens were stored for at least 48 hours after injection molding in a dry environment, i.e., on silica gel at room temperature.

[0133] Table 1 Materials used in the Examples and Comparative Examples JPEG0007805109000001.jpg179125

[0134] Table 2: Results JPEG0007805109000002.jpg179165

Claims

1. 1. A thermoplastic molding composition comprising: A 24 to 57.9% by weight of a mixture of at least one polyamide A1, at least one polyphenylene ether A2 and a compatibilizer A3, and optionally an olefinic and / or vinyl aromatic polymer A4; B 10-40 wt. % of a glass filler whose glass composition comprises at least 10.0 wt. % of boron oxide and a maximum of 15 wt. % in total of magnesium oxide and calcium oxide; C 20-50 wt. % of a titanic acid salt, a stannic acid salt, a zirconic acid salt, or a mixture thereof; D 1-8 wt. % of an LDS additive; E 0 to 5% by weight of additives other than components A, B, C and D; It consists of 80 to 100% by weight of mixture A consists of mixture M of components A1, A2 and A3 and 0 to 20% by weight of component A4, in each case based on the sum of components M and A4, with the sum of components M and A4 being 100% by weight of mixture A; the mixture M comprises 48 to 89.9% by weight of component A2, 10 to 48% by weight of component A1, and 0.1 to 4% by weight of component A3, in each case based on the total of components A1 to A3, with the total of components A1 to A3 being 100% by weight of the mixture M, the sum of B and C is in the range of 35 to 70% by weight, based on the sum of components A to E, where the sum of components A to E is 100% by weight of the molding composition; Thermoplastic molding composition.

2. component A1 is present in the mixture M in a proportion of 10 to 45% by weight, based on the sum of components A1 to A3, component A2 is present in the mixture M in a proportion of 52 to 89.8% by weight, based on the sum of A1 to A3, component A3 is present in the mixture M in a proportion of 0.2 to 3% by weight, based on the sum of A1 to A3; and mixture A consists only of components A1 to A3; The thermoplastic molding composition of claim 1.

3. The glass filler B is The glass composition is a magnesium oxide and calcium oxide content in total of 2 to 14% by weight, particularly preferably 4 to 12% by weight, based on the composition of the glass; and / or 12 to 24% by weight, particularly preferably 15 to 22% by weight, of boron oxide, based on the composition of the glass; Contains or or 52.0 to 57.0% by weight of silica, 13.0 to 17.0% by weight of aluminum oxide, 15.0 to 21.5% 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, 0 to 0.6% by weight of alkali oxide; 3. The thermoplastic molding composition according to claim 1, based on a glass comprising:

4. The glass filler B is From the group consisting of fibers, crushed fibers, particles, flakes, spheres, hollow spheres, or combinations of the foregoing; or As glass fibers; or Glass fibers having a non-circular cross section and an axial ratio of the major cross section axis to the minor cross section axis in the range of 2 to 6, preferably 3 to 5, 4. The thermoplastic molding composition according to claim 3, characterized in that it is selected from the group consisting of:

5. and / or the at least one polyamide A1 is selected as an aliphatic polyamide 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, with PA610, PA 612, PA 1010, PA12, and PA 616 being preferred; and / or As semi-crystalline partially aromatic polyamides, PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, PA 6T / 6, PA 6T / 6I, PA 6T / 6I / 6, PA 6T / 66, 6T / 610, 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 mixtures thereof, with PA 6T / 6I, PA 6T / 10T, PA 6T / 10T / 6I and mixtures thereof being preferred; and / or As amorphous or microcrystalline polyamides, PA 6I / 6T, PA MACM9, PA MACM10, 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, PA TMDC12, PA TMDC13, PA TMDC14, PA TMDC16, PA TMDC17, PA TMDC18, PA MACM10 / 10, PA MACMI / 12, PA MACMT / 12, PA 6I / MACMI / MACMT, PA selected from the group consisting of MACMI / MACMT / 12, PA MACMI / MACMT / MACM12, PA MACMI / MACMT / MACM12 / 12, PA 6I / 6T / MACMI / MACMT / 12, PA 6I / 6T / MACMI, PA MACMI / MACM36, PA MACMT / MACM36, PA MACMI / MACM12, PA MACMT / MACM12, PA MACM6 / 11, PA MACM10 / 10, PA MACM12 / PACM12, PA MACM14 / PACM14, PA MACM18 / PACM18, and mixtures thereof; 5. Thermoplastic molding compositions according to claim 1, characterized in that 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 are preferred.

6. 6. Thermoplastic molding composition according to claim 1, characterized in that the 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.

7. Component A3 is compatibilizers, or a mixture of a compatibilizer and a radical initiator, the compatibilizer is preferably 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, mono- or diesters of the aforementioned acids with C1-C12-alcohols such as methanol or ethanol, mono- or diamides of the aforementioned acids optionally carrying an alkyl or aryl group having up to 12 carbon atoms on the nitrogen, salts with alkali metals or alkaline earth metals such as calcium and potassium, and mixtures thereof, 7. Thermoplastic molding composition according to any one of claims 1 to 6, characterized in that the radical initiator is preferably 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-trimethylhexoate, tert-butyl-peracetate, tert-butyl-perbenzoate, 4,4-di-tert-butyl-peroxy-valeric acid n-butyl ester, 2,2-di-tert-butyl-peroxy-butane, dicumyl peroxide, tert-butyl-cumyl peroxide, 1,3-bis(tert-butyl-peroxyisopropyl)benzene, di-tert-butyl peroxide.

8. the olefinic 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 grafted with carboxylic acid or carboxylic anhydride groups, and / or grafted with acrylic acid, methacrylic acid or maleic anhydride, the degree of grafting being 0.1 to 4.0, preferably 0.4 to 2.5, particularly preferably 0.5 to 2.0% by weight, based on the grafted polymer A4. Thermoplastic molding composition according to any one of claims 1 to 7, characterized in that it is grafted with acrylic acid, methacrylic acid or maleic anhydride, the degree of grafting being 0.1 to 4.0, preferably 0.4 to 2.5, particularly preferably 0.5 to 2.0% by weight, based on the grafted polymer A4.

9. Component C is a metal titanate, said metal being selected from the group consisting of barium, strontium, calcium, magnesium, lead, zirconium, manganese, neodymium, bismuth, hafnium, tin, and zinc, said metals being present alone or in combination in the titanate; 9. The thermoplastic molding composition according to claim 1, wherein the metal titanate is selected from the group consisting of barium titanate, strontium titanate, barium strontium titanate and barium neodymium titanate.

10. 10. The thermoplastic composition according to any one of claims 1 to 9, wherein component D comprises at least one LDS additive based on copper and / or tin selected from the following group: metal oxides, metal phosphates, basic metal phosphates and / or metal hydroxide phosphates.

11. 11. The thermoplastic molding composition according to any one of claims 1 to 10, characterized in that component D comprises at least one LDS additive selected from the following group: tin oxide, tin oxide doped with a metal or metal oxide, antimony-doped tin oxide, mica coated with a metal oxide, mica coated with antimony-doped tin oxide, mixtures of tin oxide and antimony oxide, optionally with other metal oxides, spinel, copper chromate, 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 and combinations thereof.

12. the LDS additive of component D is selected from the group consisting of copper chromate, copper tungstate, copper oxide, copper hydroxide phosphate, stannic hydroxide phosphate, tin phosphate, copper phosphate, basic copper phosphate, and tin phosphate, or mixtures thereof; 12. Thermoplastic molding composition according to claim 1, characterized in that it is selected as copper tungstate or copper tungstate.

13. 13. Thermoplastic molding composition according to any one of claims 1 to 12, characterized in that the additives of component E are selected from the group consisting of stabilizers, antiaging agents, antioxidants, antiozonants, processing stabilizers, processing aids, viscosity modifiers, 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, leveling agents, mold release agents, colorants, in particular dyes, inorganic pigments, organic pigments, marking agents and mixtures thereof.

14. Component B is present in the range of 15 to 35 wt. %, based on the total of components A through E; and / or Component C is present in the range of 25 to 45 wt. % based on the total of components A through E; and / or Components B and C are present in the range of 40 to 65% by weight, based on the total of components A through E; and / or Component D is present in the range of 2 to 6 wt. %, based on the total of components A through E; and / or 14. Thermoplastic molding composition according to any one of claims 1 to 13, characterized in that component E is present in the range of 0.1 to 5% by weight, based on the sum of components A to E.

15. Component A is present in the range of 31 to 51.8% by weight based on the total of components A to E, and / or Component B is present in the range of 18 to 32 wt. %, based on the total of components A through E; and / or Component C is present in the range of 30 to 42 wt. % based on the total of components A through E; and / or Components B and C are present in the range of 45 to 60% by weight, based on the total of components A through E; and / or Component D is present in the range of 3 to 5 wt. %, based on the total of components A through E; and / or 15. Thermoplastic molding composition according to any one of claims 1 to 14, characterized in that component E is present in the range of 0.2 to 4% by weight, based on the sum of components A to E.

16. A molded article comprising a molding composition according to any one of claims 1 to 15.

17. 17. The molded article according to claim 16, wherein the molded article is a component, a housing, or a housing part of a device that communicates by electromagnetic waves having a frequency of 0.3 to 300 GHz.

18. 18. The molded article according to claim 17, characterized in that it is selected from the group consisting of transceiver devices, mobile phones, tablets, laptops, navigation devices, surveillance cameras, photo cameras, sensors, diving computers, audio systems, remote controls, speakers, headphones, radio equipment, television equipment, domestic appliances, kitchen appliances, door or gate openers, operating devices for central locking systems of vehicles, keyless-go vehicle keys, temperature measurement or temperature display devices, components, housings or housing parts of measuring and control devices.

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