Polyamide molding compound with low dielectric loss

Abstract

To provide a thermoplastic molding composition that has less than 3.0 of a low relative dielectric constant and less than 0.008 of a low dielectric loss factor; has excellent injection shrinkage and warp / distortion behaviors; and has excellent mechanical properties, wherein a molding compound thereof has excellent metalizing properties after partial laser irradiation.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) 10-60 wt.% of a glass filler with a glass composition including at least 10 wt.% of boron oxide, and a total of at most 15 wt.% of magnesium oxide and calcium oxide; (C) 1-8 wt.% of an LDS additive; and (D) 0-5 wt.% of an additive other than the components (A), (B), and (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a glass fiber reinforced thermoplastic molding composition based on polyamide and polyphenylene ether having a low relative dielectric constant and a low dielectric loss factor, and to moldings produced from these molding compositions and their use. The molding compounds also contain an LDS additive, and moldings produced therefrom can be selectively metallized after partial irradiation.

Background Art

[0002] Plastic molding compositions having a low relative 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 from 0.3 to 300 GHz, because by their use, significant impairment of the transmission and reception characteristics of these devices can be avoided.

[0003] Devices that communicate via such electromagnetic waves are used in various fields, for example, telecommunications, household appliances or in the home, particularly in transmitting and receiving 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 vehicle central locking systems, keyless go vehicle keys, temperature measurement and display devices, measuring devices and control units.

[0004] The polyamide molding compositions described in European Patent Application Publication No. 330 319A1 (Patent Document 1) are said to have a dielectric constant of 3.5 or less at a frequency of 2.45 GHz. In addition to specific mixtures of aliphatic and amorphous or microcrystalline polyamides, these molding compounds contain a glass filler consisting of glass with an alkali oxide and alkaline earth oxide content of 0 to 12% by weight, and additives. All examples and comparative examples, regardless of composition, have a dielectric constant greater than 3.2. Information regarding dielectric loss and metallization properties is not provided.

[0005] European Patent Application Publication No. 3 560 987A1 (Patent Document 2) describes a glass fiber reinforced molding composition having high tensile and impact strength in combination with low dielectric constant and low dielectric loss. This molding compound comprises 10-90 wt% glass fiber and 90-10 wt% plastic, with the composition of the glass fiber being more specifically defined. Compared to E-glass, the described glass fiber contains significantly less alkaline earth oxides but has a relatively high boron oxide content, resulting in a dielectric constant of 4.8 and a dielectric loss of 0.0015, determined at 10 GHz, respectively. As the disclosed example shows, the improved dielectric properties can also be applied to polyamide molding compounds. However, in the molding compound of PA6 and 50 wt% glass fiber, a relative dielectric constant of 3.39 and a dielectric loss of at most 0.0109 are determined. Information regarding the metallization properties of the molding compound is not provided.

[0006] European Patent Application Publication No. 2291444 (Patent Document 3) describes laser direct structuring (LDS) molding compounds having a high dielectric constant of at least 4 and a low dielectric loss of up to 0.01. These molding compounds contain a base resin, an LDS additive, and a ceramic filler having a dielectric constant ≥ 25. Examples show molding compounds based on polyamide and polyphenylene ether having a DK in the range of 4.1 to 6.8. However, the dielectric loss of the molding compounds described in the examples is 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 [Overview of the project] [Problems that the invention aims to solve]

[0008] Based on this, one objective of the present invention was to provide a thermoplastic molded composition that, in addition to having a low dielectric constant of less than 3.0 and a low dielectric loss of less than 0.008, can be well processed by injection molding and exhibits particularly good injection shrinkage and warping / strain behavior. Furthermore, the thermoplastic molded composition should have good mechanical properties, preferably having a breaking stress of at least 70 MPa and a tensile modulus of at least 4000 MPa. In addition, the molded compound should have good metallization properties after partial laser irradiation.

[0009] This challenge involves 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-based and / or vinyl aromatic polymer (A4); (B) Glass filler comprising 0-60% by weight of boron oxide with a glass composition of at least 10.0% by weight, and a total of up to 15% by weight of magnesium oxide and calcium oxide; (C) 1-8% by weight of LDS additive; (D) Additives other than components (A), (B), and (C) in an amount of 0-5% by weight; It consists of, In all cases, the mixture (A) consists of 80-100% by weight of a mixture (M) of components (A1), (A2), and (A3), and 0-20% by weight of component (A4), based on the sum of components (M) and (A4), where the sum of components (M) and (A4) is 100% by weight of the mixture (A); In all cases, the mixture (M) consists of 36-92% by weight of component (A2), 8-60% by weight of component (A1), and 0-4% by weight of component (A3), based on the sum of components (A1) to (A3), where the sum of components (A1) to (A3) is 100% by weight of the mixture (M). The sum of components (A) through (D) is 100% by weight of the molded composition; This is solved by the thermoplastic molding compound described in claim 1.

[0010] Dependent claims 2 to 12 relate to advantageous embodiments of the thermoplastic molding composition according to the present invention. Furthermore, according to claim 13, a molded article is provided from the thermoplastic molding composition according to the present invention, and claims 14 and 15 relate to special molded articles.

[0011] Regarding the composition of mixture (A), as described above, components (A1) to (A3) together account for 80-100% by weight of mixture (A), and the content of component (A4) in mixture (A) is 0-20% by weight. The mixture of components (A1), (A2), and (A3) is called component (M). Mixture (A) does not contain any other components besides components (A1) to (A4).

[0012] The thermoplastic molding composition according to the present invention, and the molded articles produced therefrom, have a relative permittivity of less than 3.0 and a dielectric loss (DLF) of less than 0.008. Here, the relative permittivity and DLF are measured on an 80 × 80 × 3 mm plate, at a measurement frequency of 2.45 GHz and a temperature of 23 °C, using a split post dielectric resonator (SPDR) manufactured by QWED (Poland), in accordance with IEC 61189-2-721 (2015).

[0013] Due to its excellent mechanical properties, the molded compound according to the present invention will be understood to have a tensile modulus of at least 4000 MPa, preferably at least 5000 MPa, and / or a breaking stress 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, breaking stress, and breaking elongation are determined according to ISO 527 (2012).

[0014] In the sense of the present invention, "successfully metallizable" means that a molded product (plate 60 × 60 × 2 mm) injection-molded from the thermoplastic molding compound according to the present invention can be sufficiently 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, velocity = 4 m / sec). For this purpose, 16 adjacent 10 × 10 mm areas are irradiated on the surface of the molded part during laser structuring, thereby changing both the laser pulse frequency (5, 6, 7, and 8 kHz) and current intensity (24~25.5 Amp). The cleaned molded product is then metallized in a reduced copper plating bath (MacDermid MID-Copper 100 B1) for 20~30 minutes.

[0015] Sufficient metallization here means that copper is deposited in at least 14 regions with an average thickness of at least 3 μm. [Means for solving the problem]

[0016] Surprisingly, the above problem is solved by a thermoplastic molding composition, (A) A mixture of at least one polyamide (A1), at least one polyphenylene ether (A2), and optionally a compatibilizer (A3), and optionally an olefin-based and / or vinyl aromatic polymer (A4); (B) Glass filler comprising 10-60% by weight, with a glass composition of at least 10.0% by weight of boron oxide and a total of up to 15% by weight of magnesium oxide and calcium oxide; (C) 1 to 8% by weight of LDS additives other than components (A), (B), and (C); (D) 0 to 5% by weight of additives; and consists of In all cases, based on the total of component (M) and (A4), assuming the total of component (M) and (A4) is 100% by weight of the mixture (A), it 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); In all cases, based on the total of components (A1) to (A3), assuming the total of components (A1) to (A3) is 100% by weight of the mixture (M), it 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), The total of components (A) to (D) is 100% by weight of the molding composition; It has been found to be solved by the thermoplastic molding composition.

[0017] [[ID= 16]] The content of mixture (A) in the molding composition is obtained as the difference between the total of contents (B) to (D) and 100% by weight of the entire molding composition.

[0018] Preferably, component (A) is present in the molding composition at a ratio of 34 to 82.9% by weight, particularly preferably 39 to 78.8% by weight, based on the total weight of the molding composition (the total of components A to D).

[0019] The proportion of component (B) is, in all cases, based on the total of (A) to (D), preferably in the range of 15 to 55% by weight, particularly preferably in the range of 18 to 52% by weight.

[0020] The proportion of component (C) is, in all cases, based on the total of (A) to (D), preferably in the range of 2 to 6% by weight, particularly preferably in the range of 3 to 5% by weight.

[0021] The proportion of component (D) is preferably in the range of 0.1 to 5% by weight, and particularly preferably in the range of 0.2 to 4% by weight, based on the sum of (A) to (D) in all cases.

[0022] As the studies conducted show, glass fiber-reinforced molding compounds with a polymer matrix consisting solely of polyamide exhibit excessively high dielectric constant and dielectric loss, 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 warp / strain, particularly excessively high shrinkage values, and very poor processability. Molding compositions in which the polymer portion is formed by a 1:1 blend of polyamide and polyphenylene ether and reinforced with glass fibers made of E-glass also exhibit excessive dielectric constant and dielectric loss, especially in the presence of LDS additives with high dielectric constant.

[0023] For the purposes of this 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 therein are used below as synonyms for the IUPAC names of the monomers. In particular, the following abbreviations arise for 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), and 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). The abbreviation HMDA is used for 1,6-hexanediamine (also called hexamethylenediamine).

[0024] Compared to semicrystalline polyamides, amorphous polyamides exhibit no heat of fusion, or a very low, almost undetectable heat of fusion. At a heating rate of 20 K / min, measured by dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013), amorphous polyamides exhibit a heat of fusion of preferably 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.

[0025] Microcrystalline polyamides have a melting point in addition to a glass transition temperature. However, they are in a form where the crystallites are small enough that a 2 mm thick sheet made from them is still transparent, i.e., their light transmittance is at least 90% and their haze is at most 3%, as measured according to ASTM D 1003-13 (2013). In dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013), microcrystalline polyamides exhibit a heat of fusion of preferably 5-25 J / g, particularly preferably 5-22 J / g, and most preferably 5-20 J / g at a heating rate of 20 K / min.

[0026] In addition to the glass transition temperature, semicrystalline polyamides have a distinct melting point and exhibit a heat of fusion of preferably greater than 25 J / g, particularly preferably greater than 30 J / g, and most preferably 30-80 J / g, at a heating rate of 20 K / min as measured by dynamic differential scanning calorimetry (DSC) according to ISO 11357 (2013).

[0027] Relative permittivity and dielectric loss. The permittivity (ε) is an indicator of the behavior of a molecule when placed in an electric field. This is expressed by the following relationship: relative permittivity (ε) r It is related to the dielectric constant of vacuum (ε0). ε = ε r ·ε0. Relative permittivity (ε r ) represents a material-dependent quantity and is the quotient between the dielectric constant (ε) and the dielectric constant of vacuum (ε0). In addition to the type of material, the relative permittivity (ε) r ) also depends on the frequency and temperature of the electric field.

[0028] The dielectric loss rate indicates the magnitude of loss in the propagation of electromagnetic waves in electrical components such as capacitors, or in materials such as plastic molding compounds. Here, loss refers to energy that is converted electrically or electromagnetically and dissipated as heat. These losses attenuate electromagnetic waves. For a more accurate representation of the loss rate, consider a capacitor connected to a voltage source with a sinusoidal voltage curve over time. A phase shift φ occurs between voltage and current across such a capacitor. An ideal, lossless capacitor has a phase shift of φ = 90°. In a real lossy capacitor, the phase shift is less than 90° by the loss angle δ, and the dielectric loss rate (DLF) is equal to tanδ. Therefore, the dielectric loss rate is a measure of the amount of energy absorbed by an insulating material in an AC field and converted into heat loss. Materials with high dielectric loss tangents are unsuitable as insulating or housing materials in high-frequency applications. The relative permittivity and dielectric loss rate are preferably determined according to IEC 61189-2-721 (2015).

[0029] Ingredient (A) The thermoplastic molding composition according to the present invention comprises a mixture (A) consisting of at least one polyamide (A1), at least one polyphenylene ether (A2), an optional compatibilizer (A3), and an optional olefin-based and / or vinyl aromatic polymer (A4) as polymer components.

[0030] In this case, mixture (A) consists of 80-100% by weight of mixture (M) of components (A1) to (A3) and 0-20% by weight of component (A4), based on the sum of components (M) and (A4) in all cases, with the sum of components (M) and (A4) being 100% by weight of mixture (A).

[0031] In all cases, the mixture (M) consists of 36-92% by weight of component (A2), 8-60% by weight of component (A1), and 0-4% by weight of component (A3), based on the sum of components (A1) to (A3).

[0032] Preferably, component (A1) is 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).

[0033] Preferably, component (A2) is 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).

[0034] Preferably, component (A3) is 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).

[0035] Preferably, component (A4) is present in mixture (A) in a proportion of 0 to 20% by weight based on the sum of component (M) and (A4), and particularly preferably, mixture (A) does not contain component (A4). That is, mixture (A) particularly preferably consists only of components (A1) to (A3).

[0036] Ingredients (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 higher are particularly preferred because these polyamides have low hygroscopicity and therefore less change in dielectric properties under high humidity conditions. In particular, aliphatic polyamides PA610, PA612, PA1010, PA12, and PA616 are preferred.

[0037] According to further embodiments 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 group is selected from 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.

[0038] In a more preferred embodiment, a semi-crystalline partially aromatic polyamide is preferred as component (A1). The semi-crystalline, partially aromatic polyamide has a glass transition temperature preferably in the range of 90 to 150°C, preferably in the range of 110 to 140°C, and particularly in the range of 115 to 135°C. The melting point of the semi-crystalline, partially aromatic polyamide is in the range of 255 to 330°C, preferably in the range of 270 to 325°C, and particularly 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, as determined by DSC according to ISO 11357 (2013).

[0039] Preferred partially aromatic partially crystalline polyamides are: (a) Dicarboxylic acids: In all cases, 30 to 100 mol%, particularly 50 to 100 mol%, of terephthalic acid and 0 to 70 mol%, particularly 0 to 50 mol%, of at least one aliphatic dicarboxylic acid having 6 to 16 carbon atoms, and / or 0 to 70 mol%, particularly 0 to 50 mol%, of at least one alicyclic dicarboxylic acid having 8 to 20 carbon atoms, and / or 0 to 50 mol%, of isophthalic acid, (b) Diamines: Based on the total amount of diamines, 80 to 100 mol% of at least one aliphatic diamine having 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and 0 to 20 mol% of at least one alicyclic diamine having 6 to 20 carbon atoms, preferably PACM, MACM, IPDA, and / or 0 to 20 mol% of at least one aromatic aliphatic 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.

[0040] According to a preferred embodiment, the semicrystalline, partially aromatic polyamide of component (A1) is formed based on at least 55 mol%, particularly at least 65 mol%, of terephthalic acid, and at least 80 mol%, preferably at least 90 mol%, particularly at least 95 mol%, of an aliphatic diamine having 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and optionally, further aliphatic, alicyclic and aromatic dicarboxylic acids, and further lactams and / or aminocarboxylic acids.

[0041] In a more preferred embodiment, the aliphatic dicarboxylic acid of the partially aromatic polyamide component (A1) that can be used in addition to terephthalic acid is selected from the group consisting of adipic acid, succinic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, brassic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, octadecanediic acid, and dimer fatty acids (36 carbon atoms). Adipic acid, sebacic acid, and dodecanediic acid are particularly preferred. Therefore, the dicarboxylic acids that are preferably used in addition to terephthalic acid are isophthalic acid, adipic acid, sebacic acid, and dodecanediic acid, or mixtures of such dicarboxylic acids. In particular, polyamide (A1) based solely on terephthalic acid as the dicarboxylic acid is preferred.

[0042] In a more 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 aliphatic diamines, alicyclic and / or aromatic aliphatic diamines may be substituted at concentrations of 0 to 20 mol% based on the total amount of diamines.

[0043] More preferably, the polyamide (A1) is formed from the following components: (a): Dicarboxylic acids: In any case, based on the total amount of dicarboxylic acids present, 50 to 100 mol% terephthalic acid, 0 to 50 mol% of aliphatic dicarboxylic acids, preferably having 6 to 12 carbon atoms, and / or alicyclic dicarboxylic acids, preferably having 8 to 20 carbon atoms, and / or isophthalic acid; (b): Diamines: Based on the total content of diamines present, 80 to 100 mol% of at least one aliphatic diamine having 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms; 0 to 20 mol% of alicyclic diamines having 6 to 20 carbon atoms, e.g., PACM, MACM, IPDA, and / or aromatic aliphatic diamines, e.g., MXDA and PXDA (in high melting point polyamides, the percent molar content of dicarboxylic acid is 100%, and the percent molar content of diamine is 100%), and optionally: (c): Aminocarboxylic acid and / or lactam, preferably a lactam having 6 to 12 carbon atoms and / or preferably an aminocarboxylic acid having 6 to 12 carbon atoms.

[0044] Components (a) and (b) are preferably used in approximately equimolar proportions, but the concentration of (c) is preferably up to 30% by weight, preferably up to 20% by weight, and especially up to 15% by weight, based on the sum of (a) through (c) in all cases.

[0045] Suitable alicyclic 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 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 especially 10 mol% or less. Examples of alicyclic diamines that can be used are 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).

[0046] 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 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 the aminocarboxylic acid and / or lactam used with components (A1_a) and (A1_b) is a maximum of 20% by weight, preferably a maximum of 15% by weight, and particularly preferably a maximum of 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 include pyrrolidine-2-one (4 carbon atoms), ε-caprolactam (6 carbon atoms), enanthlactam (7 carbon atoms), capryllactam (8 carbon atoms), and laurinlactam (12 carbon atoms), and the α,ω-amino acids include 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. In a particularly preferred embodiment, component (A1) does not contain caprolactam or aminocaproic acid, or any aminocarboxylic acid or lactam.

[0047] To control molecular weight, relative viscosity or fluidity, or MVR, modifiers in the form of monocarboxylic acids or monoamines can be added to the batch and / or pre-condensed (before post-condensation). Suitable aliphatic, alicyclic, or aromatic monocarboxylic acids or monoamines as modifiers include 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 Examples of 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-tetramethylpiperidine-4-amine, 1,2,2,6,6-pentamethylpiperidine-4-amine, and 4-amino-2,6-di-tert-butylphenol. These modifiers can be used individually or in combination. Other monofunctional compounds that can react 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 polymer.

[0048] 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 The partially aromatic polyamide of component (A1) is preferably selected from the group consisting of PA 6T / 6I, PA 6T / 10T, PA 6T / 10T / 6I, and mixtures thereof. A polyamide (A1) containing 6T units, particularly at least 10% by weight of 6T units, is preferred.

[0049] Therefore, according to the present invention, the following partially aromatic copolyamides are 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; A semi-crystalline polyamide prepared from a mixture of at least 50 mol% terephthalic acid and up to 50 mol% isophthalic acid, particularly 100 mol% terephthalic acid, and at least two diamines selected from the group consisting of hexamethylenediamine, nonanediamine, methyloctanediamine, and decanediamine; A semi-crystalline polyamide prepared from a mixture of 70-100 mol% terephthalic acid and 0-30 mol% isophthalic acid, along with hexamethylenediamine and decanediamine; A semi-crystalline polyamide prepared from a mixture of at least 50 mol% terephthalic acid and 50 mol% or less dodecanediic acid, and at least two diamines selected from the group consisting of hexamethylenediamine, nonanediamine, methyloctanediamine, and decanediamine; Semicrystalline polyamide 6T / 10T having 10-60 mol%, preferably 10-40 mol%, of hexamethylene terephthalamide (6T) units and 40-90 mol%, preferably 60-90 mol%, of decamethylene terephthalamide (10T) units; semicrystalline polyamide 6T / 10T / 6I having 50-90 mol%, preferably 50-70 mol%, of hexamethylene terephthalamide (6T) units and 5-45 mol%, preferably 10-30 mol%, of hexamethylene isophthalamide (6I) units and 5-45 mol%, preferably 20-40 mol%, of decamethylene terephthalamide (10T) units. Polyamide (A1) is measured according to ISO 307 (2007) at a temperature of 20°C when a solution of 0.5 g of the polymer in 100 ml of m-cresol has a solution viscosity η preferably in the range of 1.3 to 2.7, particularly preferably in the range of 1.4 to 2.3, and even more preferably in the range of 1.5 to 2.0. rel It holds.

[0050] Ingredients (A2) The polyphenylene ethers used in accordance with the present invention are known in themselves. They are prepared by conventional methods from phenols disubstituted at the ortho position with alkyl groups by oxidative coupling (see U.S. Patents No. 3,661,848, 3378,505, 3306,874, 3306,875 and 3639,656). Catalysts based on heavy metals such as copper, manganese, or cobalt, combined with other substances such as secondary amines, tertiary amines, halogens, or combinations thereof, are commonly used in the preparation.

[0051] Suitable polyphenylene ethers include copolymers such as 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 those containing 2,3,6-trimethylphenol, and blends thereof. Optionally, poly(2,6-dimethyl-1,4-phenylene) ether combined 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.

[0052] A suitable polyphenylene ether generally has an intrinsic viscosity, preferably in the range of 0.1 to 0.6 dl / g, measured in chloroform at 25°C. This corresponds to a molecular weight Mn (number mean) of 3,000 to 40,000 g / mol and a weight-average molecular weight Mw of 5,000 to 80,000 g / mol. High-viscosity and low-viscosity polyphenylene ethers can be used in combination. The ratio of the two polyphenylene ethers of different viscosities depends on the viscosity and the desired physical properties.

[0053] To improve compatibility between component (A1) and component (A2), in preferred embodiments, the polyphenylene ethers used are modified to contain carbonyl, carboxyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam, or halobenzyl groups, which are preferably covalently bonded. Preferably, the unmodified polyphenylene ether (A2) is modified for this purpose with an α,β-unsaturated dicarbonyl compound, an amide group having a polymerizable double bond, or a lactam group-containing monomer (A3), optionally combined with a radical starter (A3), such as a peroxide, particularly dibenzoyl peroxide.

[0054] Ingredients (A3) To improve the compatibility between components (A1) and (A2), the compatibilizer can be used in the form of a functional compound that interacts with polyphenylene ether, polyamide, or both. The interaction may be chemical (e.g., by grafting) and / or physical (e.g., by affecting the surface properties of the dispersed phase).

[0055] In preferred embodiments of the present invention, the compatibilizer further comprises a radical initiator, which is preferably an organic peroxide or azo compound. That is, in these embodiments, the compatibilizer is graft polymerized in the presence of a free radical initiator.

[0056] In a particularly preferred embodiment, the compatibilizer is used without a free radical initiator.

[0057] The compatibilizer may be a functional compound containing at least one carboxylic acid, carboxylic acid anhydride, epoxy, ester, amide, or imide group, preferably in combination with an olefin double bond. Examples include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, methyl maleic acid, methyl maleic anhydride, itaconic acid, itaconic anhydride, butenyl succinic acid, butenyl succinic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride N-phenylmaleimide, citric acid, malic acid, and 2-hydroxynonadecane-1,2,3-tricarboxylic acid, mono or diesters of the above acids with C1-C12 alcohols such as methanol or ethanol, mono 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 metals or alkaline earth metals such as calcium and potassium. Maleic acid, fumaric acid, maleic anhydride, and citric acid are particularly preferred. The compatibilizer may be added directly during blend preparation, either alone or in combination with an optional radical initiator, or the polyphenylene ether and / or polyamide may be functionalized with the compatibilizer in a separate step.

[0058] Suitable radical initiators include, for example, 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-valerate 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. Organic peroxides are preferred as radical initiators, and dicumyl peroxide is particularly preferred.

[0059] Therefore, 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% by weight, preferably 0.1 to 4% by weight, and particularly preferably 0.2 to 3% by weight, based on the sum of (A1) to (A3). The radical initiator is present in a total amount of 0 to 1% by weight, and particularly preferably 0.05 to 0.8% by weight, based on the sum of (A1) to (A3).

[0060] In preferred embodiments, the compatibilizer is graft polymerized without the addition of a free radical initiator; that is, component (A3) preferably does not contain a free radical initiator.

[0061] Ingredients (A4) Blend (A) according to the present invention may contain 0 to 20% by weight of a vinyl aromatic polymer and / or olefin polymer (A4), in addition to a polyamide (A1), a polyphenylene ether (A2), and an optional compatibilizer (A3).

[0062] Olefin polymers include homopolyolefins or copolyolefins, particularly preferably polymers or copolymers thereof based on ethylene, propylene, and butylene, as well as copolymers with other α-olefin monomers, especially 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene.

[0063] The vinyl aromatic polymer is preferably a copolymer of polystyrene, or styrene with other monomers having at least one olefinic double bond, such as α-olefin ethylene, propylene and butylene, or acrylic acid or acrylic acid ester or butadiene. Block copolymers having at least one block (block-A) formed from vinyl aromatic monomers and at least one block (block-B) formed from olefinic monomers, such as those present in styrene block copolymers, are particularly preferred.

[0064] The olefin-based and / or vinyl aromatic polymer used as component (A4) may be or may contain copolymers formed by grafting or copolymerization with natural rubber, polybutadiene, polyisoprene, polyisobutylene, butadiene and / or isoprene and styrene or styrene derivatives and other comonomers, hydrogenated copolymers and / or acid anhydrides, (meth)acrylic acid and their esters. Polymer (A4) may also be a graft rubber having a graft shell of polystyrene, nonpolar or polar olefin homopolymers and copolymers, such as ethylene-propylene-, ethylene-propylene-diene and ethylene-octene or ethylene-vinyl acetate rubber, or nonpolar or polar olefin homopolymers and copolymers formed by grafting or copolymerization with acid anhydrides, (meth)acrylic acid and its esters. The 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) (where 1-olefin is an alkene or an unsaturated (meth)acrylic acid ester having more than four atoms), and includes copolymers in which the acid groups are partially neutralized with metal ions.

[0065] The components (A4) are 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 ethylene-propylene copolymer, ethylene-butene 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 copolymer, and blends thereof are advantageously selected from the group consisting of these polymer materials. Particularly preferred are these polymers (A4) 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).

[0066] The mixture (A) is more preferably comprising at least one vinyl aromatic polymer and optionally at least one polyolefin as component (A4). In any case, it is particularly preferable that the mixture (A) contains at least 5% by weight, and especially at least 10% by weight, of the vinyl aromatic polymer based on the total amount of (A).

[0067] Preferably, the olefin-based and / or vinyl aromatic polymer (A4) is 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), polyethylene (PE), polypropylene (PP), polybutadiene (PB), poly-4-methylpentene, ethylene-propylene copolymer, ethylene- The polymers are selected from the group consisting of ethylene-methylhexadiene copolymers, propylene-methylhexadiene copolymers, ethylene-octen 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 copolymers, and blends thereof.

[0068] Furthermore, it is preferable that the olefin-based and / or vinyl aromatic polymer (A4) of the molded composition is grafted with a carboxylic acid or carboxylic acid anhydride group, and the grafting is particularly preferably carried out with acrylic acid, methacrylic acid or maleic anhydride, and / or the degree of grafting is in any case preferably 0.1 to 4.0% by weight, particularly preferably 0.4 to 2.5% by weight, and even more preferably 0.5 to 2.0% by weight, based on the grafted polymer (A4).

[0069] Component (B) is a glass-based filler present in the polyamide molding compound at a concentration of 10-60% by weight. The filler may be fibrous or particulate, individually or as a mixture. Thus, component (B) may contain fibrous filler (reinforcement agent), particulate filler, or a mixture of reinforcement agent and particulate filler. For the purposes of this invention, the terms glass-based filler and glass filler are used synonymously.

[0070] According to the present invention, a glass filler (B) is used, which is based on a glass composition and whose glass composition comprises at least 10% by weight of boron oxide and a total of up to 15% by weight of magnesium oxide and calcium oxide.

[0071] According to a preferred embodiment of the present invention, the glass filler is based on a glass composition, wherein the glass composition contains a total of 2 to 14% by weight, more preferably 4 to 12% by weight, of magnesium oxide and calcium oxide.

[0072] According to another preferred embodiment of the present invention, the glass filler is based on a glass composition, wherein the glass composition is based on glass containing 12 to 24% by weight, particularly preferably 15 to 22% by weight, of boron oxide.

[0073] The glass filler is preferably selected from the group consisting of fibers, crushed fibers, particles, flakes, spheres, hollow spheres, and mixtures thereof, and is particularly preferably consisting of fibers, particles, flakes, and mixtures thereof. More preferably, the glass filler is glass fiber. Most preferably, component (B) is glass fiber having a non-circular cross-section and an axial ratio of long cross-sectional axis to short cross-sectional axis in the range of 2 to 6, more preferably 3 to 5.

[0074] The glass filler may be surface-treated. This can be done using an appropriate sizing or adhesion promoter system. For example, systems based on fatty acids, waxes, silanes, titanates, polyamides, urethanes, polyurethanes, polyhydroxy ethers, epoxides, nickel, or combinations or mixtures thereof can be used for this purpose. Preferably, the glass filler is surface-treated with aminosilane, epoxysilane, polyamide, or a mixture thereof.

[0075] When fibers are selected as glass fillers for 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 cross-section or a non-circular cross-section. Non-circular or non-circular glass fibers are also called flat glass fibers and may have an elliptical, oblong, square, rectangular, or substantially rectangular cross-sectional area.

[0076] 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.

[0077] The chopped glass fibers preferably have a diameter of 5 to 20 μm, preferably 5 to 15 μm, and particularly preferably 6 to 12 μm.

[0078] When glass fibers are used as continuous fibers (rovings), they preferably have a diameter of up to 20 μm, preferably up to 18 μm, and particularly preferably 5 to 17 μm.

[0079] In the case of flat glass fibers, the aspect ratio, i.e., the ratio of the long cross-sectional axis to the short 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 short cross-sectional axis is 3 to 20 μm, more preferably 4 to 10 μm, and the length of the long cross-sectional axis is 6 to 40 μm, more preferably 12 to 30 μm.

[0080] The polyamide molding compound of the present invention can also be reinforced using a blend of fibers having circular (round) and non-circular (flat) cross-sections.

[0081] When glass beads or glass particles are selected as glass fillers (B), their average volume diameter (D50) is preferably 0.3 to 100 μm, particularly preferably 5 to 80 μm, and even more preferably 17 to 70 μm, as measured by laser diffraction according to ASTM B 822-10 (2010).

[0082] Furthermore, the glass filler is made using a glass plate (80 × 80 × 3 mm) made from the glass of the glass filler, and is measured using a split post dielectric resonator (SPDR) manufactured by QWED, Poland, at a frequency of 2.45 GHz and a temperature of 23 °C, and has a relative permittivity of preferably up to 7, particularly preferably up to 5, and a dielectric loss of preferably up to 0.0040, particularly preferably up to 0.0030, according to IEC 61189-2-721 (2015).

[0083] According to a preferred embodiment of the present invention, component (B) is present in the polyamide molded composition in an amount preferably 15 to 55% by weight, and particularly preferably 18 to 52% by weight, these amounts being relative to the sum of components (A) to (D).

[0084] 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 beads, hollow glass beads, or combinations thereof, wherein the glass filler is made of glass having a total magnesium oxide and calcium oxide content in the range of 2 to 14% by weight and a boron oxide (B2O3) content in the range of 12 to 24% by weight, based on the glass composition. Particularly preferably, the glass filler is formed entirely from glass fibers.

[0085] In a particularly preferred embodiment, component (B) is selected as a glass filler, particularly preferably glass fiber, the glass comprising the following composition: 52.0-57.0% by weight of silicon dioxide, 13.0-17.0% by weight of aluminum oxide, 15.0-22.0% by weight of boron oxide, 2.0-6.0% by weight of magnesium oxide, 2.0-6.0% by weight of calcium oxide, 1.0-4.0% by weight of titanium dioxide, 0-1.5% by weight of fluorine, and 0-0.6% by weight of alkali oxide.

[0086] Preferably, the proportion of component (C) is in the range of 2 to 6% by weight, preferably 3 to 5% by weight, based on the molded compound (the sum of components (A) to (D)).

[0087] Component (C) is preferably an LDS additive having a non-zero absorption coefficient for UV, VIS, or IR radiation, which forms a metallic nucleus under the action of electromagnetic radiation, preferably laser radiation, the metallic nucleus promoting and / or enabling and / or improving the deposition of a metallic layer for producing conductive tracks at the irradiation point on the molded surface in a chemical metallization process. The LDS additive preferably comprises an absorbent having the ability to absorb in the visible and infrared radiation range and / or transferring radiant energy to the LDS additive, with an absorption coefficient of at least 0.05, preferably at least 0.1, and particularly at least 0.2.

[0088] Component (C) is an LDS additive having a median particle size (D50) in the range of 50 to 10,000 nanometers, preferably 200 to 5,000 nanometers, and particularly preferably 300 to 4,000 nanometers, and / or an aspect ratio of up to 10, particularly up to 5. The D50 value given as a measure of particle size is a measure of median particle size, where 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).

[0089] Preferably, component (C) is an LDS (Laser Direct Structuring) additive selected from the group of metal oxides, particularly a so-called spinel having the general chemical formula AB2O4, where A is a divalent metal cation and B is a trivalent metal cation. 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.

[0090] In particular, LDS additives are preferably copper-iron spinel, copper-containing aluminum magnesium oxide, copper-chromium-manganese mixed oxide, optionally each having oxygen vacancies, or copper salts and oxides, such as copper(I) oxide, copper(II) oxide, copper-manganese-iron mixed oxide, or basic copper phosphate, copper sulfate, and metal complex compounds, particularly chelate complexes of copper, tin, nickel, cobalt, silver, and palladium or mixtures of such systems, and / or are particularly selected from the following group: copper-chromium-manganese mixed oxide, copper-manganese-iron mixed oxide, copper chromate, copper tungstate, zinc iron oxide, chromium cobalt oxide, aluminum cobalt oxide, aluminum magnesium oxide, and mixtures thereof, and / or surface treatment forms and / or oxygen-vacuated forms. Possible systems are, for example, those described in International Publication No. 2000 / 35259 or Kunststoffe 92(2002)11, pp 2-7.

[0091] Furthermore, preferred component (C) is an LDS (Laser Direct Structuring) additive 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, and antimony, bismuth, molybdenum, aluminum, titanium, silicon, iron, copper, silver, palladium, and cobalt can be used for doping. In particular, tin oxide doped with antimony, titanium, and copper is preferred. Moreover, a mixture of tin oxide and at least one further metal oxide, particularly antimony oxide, is preferred as an LDS additive. As the further metal oxide, both colorless high refractive index metal oxides such as 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 particularly iron oxide (Fe2O3, Fe3O4), can be used. In particular, a mixture of tin oxide and antimony(III) oxide is preferred.

[0092] Preferably, doped tin oxide or a mixture of metal oxides or tin oxide is formed as a layer on a plate-like substrate, particularly on layered silicates such as synthetic or natural mica, talc, kaolin, glass plates, or silicon dioxide plates. Mica or mica flakes are particularly preferred as substrates for metal oxides. 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 plates can also be considered as substrates.

[0093] Mica-based LDS additives are particularly preferred, with the mica surface coated with metal-doped tin oxide. Antimond-doped tin oxide is especially preferred. Examples of commercially available LDS additives according to the present invention include Merck's Lazerflair LS 820, LS 825, LS 830 and Minatec 230 A-IR, Keeling & Walker's Stanostat CP40W, Stanostat CP15G or Stanostat CP5C, and Budenheim's Fabulase 322S, 330, 350 and 352.

[0094] Particularly preferred LDS additives are copper chromate, copper tungstate, copper hydroxide phosphate, and antimond-doped tin oxide, the latter of which is preferably used in combination with mica. Copper tungstate is especially preferred.

[0095] The thermoplastic molding composition according to the present invention contains at least one additive in an amount of 0 to 5% by weight as component (D), which is different from components (A), (B), and (C).

[0096] According to a preferred embodiment, the molding composition according to the present invention contains at least one additive as component (D) in an amount of 0.1 to 5% by weight, preferably 0.2 to 4% by weight, based on the total of components (A) to (D).

[0097] According to a preferred embodiment, the additives of component (D) are selected from the group consisting of stabilizers, antioxidants, ozone inhibitors, processing stabilizers, processing aids, viscosity modifiers, light stabilizers, UV stabilizers, UV absorbers, inorganic heat stabilizers, particularly inorganic heat stabilizers based on copper halides and alkali halides, organic heat stabilizers, fluorescent whitening agents, crystallization accelerators, crystallization retarders, flow aids, lubricants, slip agents, mold release agents, colorants, particularly dyes, inorganic pigments, organic pigments, marking agents, and mixtures thereof.

[0098] In a particularly preferred embodiment, the molding composition according to the present invention contains at least one processing aid as component (D), the latter present in any case in a proportion 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 preferably 0.2 to 1.0% by weight, based on the total weight of components (A) to (D). 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, with metal ions Na, Mg, Ca, and Al being preferred, and Ca or Mg being particularly preferred. Particularly preferred metal salts are magnesium stearate, calcium stearate, calcium montana, and aluminum stearate. The fatty acid may be monovalent or divalent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanediic acid, behenic acid, and particularly preferred stearic acid, capric acid, and montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0099] In a more preferred embodiment, the molding composition according to the present invention contains at least one heat stabilizer as component (D), which is present in any case in a proportion preferably of 0 to 3% by weight, and particularly preferably of 0.1 to 2.0% by weight, based on the total weight of components (A) to (D).

[0100] According to a preferred embodiment, the heat stabilizer is selected from the group consisting of: • Compounds of monovalent or divalent copper, for example, salts of monovalent or divalent copper with an inorganic or organic acid, or a monovalent or divalent phenol, oxides of monovalent or divalent copper, or salts of copper, with ammonia, amines, amides, lactams, cyanides, or phosphines, preferably Cu(I) or Cu(II) salts of hydrohalides, hydrocyanides, or copper salts of aliphatic carboxylic acids. Particularly preferred monovalent copper compounds are CuCl, CuBr, CuI, CuCN, and Cu2O, while particularly preferred divalent copper compounds are CuCl2, CuSO4, CuO, copper(II) acetate, or copper(II) stearate. Advantageously, the copper compounds are used in combination with further metal halides, particularly alkali halides, such as Na, KI, NaBr, and KBr, where the molar ratio of metal halide to copper halide is 0.5 to 20, preferably 1 to 10, and particularly preferably 3 to 7. • A stabilizer based on a secondary aromatic amine is 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, more preferably 0.2 to 0.6% by weight, and • Phosphite and phosphonite, and • A mixture of the above-mentioned stabilizers.

[0101] Examples of stabilizers based on secondary aromatic amines that can be used in accordance with the present invention include adducts of phenylenediamine and acetone (Naugard A), adducts of phenylenediamine and linol, Naugard 445, N,N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, or mixtures thereof.

[0102] Suitable sterically hindered phenols are, in principle, all compounds having a phenol structure with 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'-thioethylbis-(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.

[0103] Preferred phosphites and phosphonites include triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol 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, and Listeryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10tetra-tert-butyl-12H-dibenzo-[d,g]-1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo-[d,g]-1,3,2-dioxaphosphosine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. In particular, 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) are preferred.

[0104] Preferred embodiments of the heat stabilizer include organic heat stabilizers, particularly Irgafos168 and a combination of Irganox1010 or HOSTANOX O 3P (bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butanoate glycol ester) and SANDOSTAB P-EPQ (tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonite). Heat stabilization based solely on CuI and KI is particularly preferred.

[0105] Examples of oxidation retarders and heat stabilizers include phosphites and other amines (e.g., triacetone diamine), hydroquinones, various substituted representatives of these groups, and mixtures thereof, in concentrations of up to 1% by weight based on the weight of components (A) to (D).

[0106] Various substituted resorcinols, salicylates, benzotriazoles, benzotriazines, and benzophenones are listed as UV stabilizers, and these are generally used in amounts up to 2% by weight based on the weight of the molding composition.

[0107] Inorganic pigments such as titanium dioxide, ultramarine, iron oxide, and carbon black and / or graphite, as well as organic pigments such as phthalocyanine, quinacridone, and perylene, and dyes such as nigrosine and anthraquinone can be added as colorants. However, it is preferable that the molding composition according to the present invention does not contain carbon black or graphite; that is, the molding composition according to the present invention preferably does not contain carbon black or graphite.

[0108] In a particularly preferred embodiment, the thermoplastic molding composition according to the present invention is (A) A mixture of at least one polyamide (A1), at least one polyphenylene ether (A2), and a compatibilizer (A3) in an amount of 34 to 82.9% by weight; (B) Glass fibers comprising 15-55% by weight, with a glass composition of 12-24% by weight of boron oxide and a total of 2-14% by weight of magnesium oxide and calcium oxide; (C) 2-6% by weight of an LDS additive selected from the group consisting of copper chromate, copper tungstate, copper oxide, copper hydroxide phosphate, tin hydroxide phosphate, tin hydroxide, copper phosphate, basic copper phosphate, and tin phosphate, or mixtures thereof, preferably selected as copper tungstate; (D) Additives other than (A), (B), and (C) in an amount of 0.1 to 5% by weight; Includes, In all cases, the mixture (A) consists of 52-89.8% by weight of component (A2), 10-45% by weight of component (A1), and 0.2-3% by weight of component (A3), with the sum of components (A1) to (A3) being 100% by weight of the mixture (A), and the sum of components (A) to (D) being 100% by weight of the molded composition.

[0109] The molding compound according to the present invention has good mechanical properties, can be easily metallized after irradiation, and is characterized by a low dielectric constant of less than 3.0 and a low dielectric loss rate of less than 0.008.

[0110] A preferred variation of the production of the molded composition according to the present invention is that in a first step, a mixture containing components (A1) to (A4) is provided. For this purpose, components (A2), (A3) and optionally (A4) can first be metered and supplied to the feed section of an extruder and mixed at a temperature in the range of 220 to 340°C. The mixture is then supplied to a side feeder. The side feeder can then introduce component (A1) into the molten mixture formed from components (A2), (A3) and optionally (A4) in the extruder housing downstream of the feed section. Alternatively, components (A1) to (A4) can also be metered and supplied to the extruder feeder and mixed in the extruder at a temperature of 220 to 340°C. In both variations, components (C) and / or (D) can be further included, which are preferably metered and supplied to the feed section. In the second extrusion step, mixture (A) and components (C) and (D), or a mixture of (A), (C) and (D), can then be metered and supplied to the feed section of the extruder and melted at a temperature of 220-340°C, while component (B) is supplied via a side feeder to the extruder housing downstream of the feed section and mixed with the existing molten material.

[0111] Another preferred method for producing the molded compound is to meter and feed components (A1), (A4), (C), and (D) 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, then introduce component (B) into the molten material via a side feeder and mix it with the other components in the second extruder section. The molded compound is then released and granulated after cooling. Pelletization in water is preferred when the filler content is high.

[0112] Furthermore, the present invention includes a thermoplastic molding composition according to the present invention as described above, or preferably a molded article comprising this molding composition.

[0113] This molded body 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.

[0114] In particular, molded products are selected from the group consisting of transceivers, mobile phones, tablets, laptops, navigation devices, surveillance cameras, photo cameras, sensors, diving computers, audio systems, remote controls, speakers, headphones, radio sets, television sets, household appliances, kitchen appliances, door or gate openers, operating devices for central locking of vehicles, keyless go vehicle keys, temperature measuring or temperature display devices, components of measuring and control devices, housings or housing components.

[0115] Measurement method: The following measurement methods were used within the scope of this application: Relative viscosity Relative viscosity was measured at 20°C according to ISO 307 (2007). For this purpose, 0.5 g of polymer granules was weighed into 100 ml of m-cresol. Relative viscosity (RV) was calculated according to Section 11 of the standard, using the formula RV = t / t0. Glass transition temperature (Tg) and melting point (Tm)

[0116] The glass transition temperature and melting point were determined for 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 the three heating cycles. 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 rapidly cooled in dry ice, and the glass transition temperature (Tg) was determined during the third heating. The temperature at which the peak maximum was reached was defined as the melting point. The glass transition temperature (Tg) was defined as the midpoint of the glass transition region and determined by the "half height" method.

[0117] Tensile modulus The tensile modulus was determined according to ISO 527 (2012) and ISO / CD 3167 (2003) standards for an ISO tensile bar (Type A1, size 170 × 20 / 10 × 4) at a tensile speed of 1 mm / min at 23°C.

[0118] Stress at fracture and elongation at fracture The tensile stress and elongation at fracture were determined according to ISO 527 (2012) and ISO / CD 3167 (2003) standards for ISO tensile bars, type A1 (size 170 × 20 / 10 × 4 mm), at a tensile speed of 5 mm / min at 23°C.

[0119] Relative permittivity and dielectric loss (DLF) Relative permittivity εr and dielectric loss (DLF) were measured using a split-post dielectric resonator (SPDR) manufactured by QWED, Poland (a brochure containing measurement information is available at www.qwed.eu) on an 80 × 80 × 3 mm plate with a film gate, in accordance with IEC 61189-2-721 (2015). The measurement frequency was 2.45 GHz and the measurement temperature was 23 °C.

[0120] Molding shrinkage A plate for determining molding shrinkage (Type D2, 60 × 60 × 2 mm, film gate) was prepared according to ISO 294-3 (2002) and Correction 1 (2006). Injection shrinkage was determined according to ISO 294-4 (2001) with respect to cavity size in the longitudinal and transverse directions relative to the flow direction of the molding compound molten material, after storing the sheets for 14 days in a standard climate (23°C, 50% relative humidity). The arithmetic mean of the measurements from five plates is shown. The ratio of injection shrinkage along the flow direction of the molding compound to injection shrinkage across the flow direction is also called warp or distortion.

[0121] Laser structuring and metallization properties: To evaluate the metallization behavior, injection-molded parts (plates 60 × 60 × 2 mm) were structured using an Nd:YAG laser and subsequently metallized in an electroless copper plating bath. During laser structuring, 18 adjacent 10 × 10 mm regions were irradiated on the surface of the molded part. Laser structuring was performed using a FOBA DP50 laser at a wavelength of 1064 nm and a pulse width of approximately 50 μm at a speed of 4 m / s. Both 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 continuously subjected to an ultrasonic bath using a surfactant and deionized water. Next, the cleaned molded material was metallized in a reducing copper plating bath (MacDermid MID-Copper 100 B1) for 20-30 minutes.

[0122] Evaluation of metallization: o: In fewer than 14 regions, copper was deposited with an average thickness of at least 3 μm; +: In 14 or 15 regions, copper was deposited with an average thickness of at least 3 μm; In all ++:16 regions, copper was deposited with an average thickness of at least 3 μm; For the purposes of the present invention, sufficient metallization means that copper is deposited in at least 14 regions with an average thickness of at least 3 μm.

[0123] Colorability: F: The molding compound can be colored in colors other than black, such as yellow, orange, red, or blue. S: The molding compound is black and cannot be colored in any other color.

[0124] Glass composition of glass filler The glass composition of glass fillers, particularly glass fibers, was determined using the following methods: inductively coupled plasma atomic emission spectroscopy (ICP OES) according to DIN 51086-2:2004, titration determination of boron oxide content according to ISO 21078-1:2008, X-ray fluorescence melting decomposition according to ISO 12677:2003, and determination of fluorine after thermal hydrolysis according to DIN 51084:2008.

[0125] Preparation of polyamide molding compounds For Examples B1 to B9 and Comparative Example VB4 according to the present invention, various compounds (A) were first prepared. For this purpose, according to Tables 2 and 3, the respective amounts of polyphenylene ether (A2) and compatibilizer (A3) were metered and fed into the feed zone of a Werner & Pfleiderer twin-screw extruder, type ZSK 25, and the polyamide component (A1) was introduced into the molten material via a side feeder 6 barrel zone before discharge. The temperature of the first zone was set to 70°C, and the temperature of the remaining housings was set to 260-290°C for the polyamide-1 example and 290-320°C for the polyamide-2 example. Degassing was applied using a speed of 300 rpm and a volume of 10 kg / hour. The strands were cooled in a water bath, cut, and the resulting granules were dried in a vacuum (30 mbar) at 100°C for 24 hours. Next, dry granules of blend (A), polyamide, or polyphenylene ether were mixed with additives (C) and (D) to form dry blends in the proportions shown in Tables 2 and 3. This mixture was homogenized in a tumble mixer for approximately 20 minutes. Molding compounds were produced in proportions shown in Tables 2 and 3 using a twin-screw extruder of Werner & Pfleiderer type ZSK 25. The dry blend was metered and fed into feeders via a metering feeder. Glass fibers (B) were metered and fed into side feeders via a metering feeder, and the side feeders supplied the glass fibers (B) to the molten material in the six housing units upstream of the die. The temperature of the first housing was set to 80°C, and the temperatures of the remaining housings were set to 260-280°C for Examples B1 to B3, B7, B8, VB1 and VB2, and to 280-310°C for Examples B4 to B6, B9, VB3 and VB4. Degassing was performed using a speed of 250 rpm and a processing rate of 15 kg / hour, with atmospheric degassing. The strands were cooled in a water bath, cut, and the resulting granules were dried in a vacuum (30 mbar) at 110°C for 24 hours to reduce the moisture content to less than 0.1% by weight.

[0126] Preparation of test specimens Test specimens were prepared using an Arburg Allrounder 420C 1000-250 injection molding machine. Examples B1 to B3, B7, B8, VB1 and VB2 used a rise cylinder temperature of 260°C to 280°C and a molding temperature of 80°C, while Examples B4 to B6, B9, VB3 and VB4 used a cylinder temperature of 290°C to 320°C and a molding temperature of 120°C. Unless otherwise specified, test specimens were used in a dry state. For this purpose, after injection molding, the test specimens were stored in a dry environment, i.e., on silica gel at room temperature for at least 48 hours.

[0127] Table 1: Materials used in the examples and comparative examples JPEG0007840643000001.jpg249170

[0128] Table 2: Results JPEG0007840643000002.jpg146170

[0129] Table 3: Results JPEG0007840643000003.jpg152170

Claims

1. A thermoplastic molding composition, A) A mixture of at least one polyamide A1, at least one polyphenylene ether A2 and a compatibilizer A3, and optionally an olefin-based and / or vinyl aromatic polymer A4; B) Glass fillers comprising 10 to 60% by weight of a glass composition containing at least 10% by weight of boron oxide and a total of up to 15% by weight of magnesium oxide and calcium oxide; C) 1-8% by weight of LDS additive; D) Additives other than components A, B, and C, in an amount of 0 to 5% by weight; It consists of, Based on the sum of each component M and A4, assuming that the sum of components M and A4 is 100% by weight of mixture A, then 80 to 100% by weight of mixture A consists of mixture M of components A1, A2, and A3, and 0 to 20% by weight consists of component A4; In all cases, the mixture M consists of 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, with the sum of components A1 to A3 being 100% by weight of the mixture M. The sum of components A to D is 100% by weight of the molded composition; Thermoplastic molding composition.

2. The thermoplastic molding composition according to claim 1, characterized in that the glass filler B is based on a glass composition containing, based on the glass composition, a total of 2 to 14% by weight of magnesium oxide and calcium oxide; and / or based on the glass composition, 12 to 24% by weight of boron oxide; or a glass containing 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, and 0 to 0.6% by weight of alkali oxide.

3. The thermoplastic molding composition according to claim 2, characterized in that the glass filler B is selected from the group consisting of fibers, crushed fibers, particles, flakes, spheres, hollow spheres, or combinations thereof; or as glass fibers; or as glass fibers having a non-circular cross-section and having an axial ratio of long cross-sectional axes to short cross-sectional axes in the range of 2 to 6.

4. The at least one polyamide A1 is selected from the group consisting of aliphatic polyamides 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 as semicrystalline 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 Selected from the group consisting of 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, and / or as amorphous or microcrystalline polyamide, 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,A thermoplastic molding composition according to any one of claims 1 to 3, characterized by being selected from the group consisting of 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. The thermoplastic molding composition according to any one of claims 1 to 4, 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.

6. Component A3 is selected as a compatibilizer, or a mixture of a compatibilizer and a free radical initiator, wherein the compatibilizer is selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, methyl maleic acid, methyl maleic anhydride, itaconic acid, itaconic anhydride, butenyl succinic acid, butenyl succinic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride N-phenylmaleimide, citric acid, malic acid and 2-hydroxynonadecane-1,2,3-tricarboxylic acid, mono or diesters of the above acids with C1-C12 alcohols, mono 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, salts with alkali metals or alkaline earth metals, and mixtures thereof. The thermoplastic molding composition according to any one of claims 1 to 5, characterized in that the 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-trimethylhexoate, tert-butyl-peracetate, tert-butyl-perbenzoate, 4,4-di-tert-butyl-peroxy-valerate 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 mixtures thereof.

7. The olefin-based and / or vinyl aromatic polymer A4 is styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-styrene-butadiene-styrene block copolymer, polyethylene, polypropylene, polybutadiene, poly-4-methylpentene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-methylhexadiene copolymer, propylene-methylhexadiene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene A thermoplastic molding composition according to any one of claims 1 to 6, characterized in that it is selected from the group consisting of n-hexene copolymer, ethylene-propylene-methylhexadiene copolymer, poly(ethylene-vinyl acetate), ethylene-ethyl acrylate copolymer, ethylene-hexene copolymer, ethylene-propylene-diene copolymer, and mixtures thereof, and / or grafted with a carboxylic acid or carboxylic acid anhydride group, and / or grafted with acrylic acid, methacrylic acid or maleic anhydride, wherein the degree of grafting is 0.1 to 4.0% by weight, based on grafted polymer A4.

8. The molding composition according to any one of claims 1 to 7, characterized in that component C comprises or is entirely formed by 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.

9. A molding composition according to any one of claims 1 to 8, characterized in that component (C) comprises or is entirely formed by at least one LDS additive selected from the following group: tin oxide, tin oxide doped with metal or metal oxide, antimond-doped tin oxide, mica coated with metal oxide, mica coated with antimond-doped tin oxide, mixtures of tin oxide and antimony oxide, and optionally mixtures of 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, antimond-doped tin oxide, or mixtures and combinations thereof.

10. The molding composition according to any one of claims 1 to 9, characterized in that the LDS additive of component C is selected from the group consisting of copper chromate, copper tungstate, copper oxide, copper hydroxide phosphate, tin hydroxide phosphate, tin phosphate, copper phosphate, basic copper phosphate, and tin phosphate, or a mixture thereof, or is selected as copper tungstate.

11. The thermoplastic molding composition according to any one of claims 1 to 10, characterized in that the additive of component D is selected from the group consisting of stabilizers, anti-aging agents, antioxidants, ozone inhibitors, processing stabilizers, processing aids, viscosity modifiers, light stabilizers, UV stabilizers, UV absorbers, inorganic heat stabilizers, inorganic heat stabilizers based on copper halides and alkali halides, organic heat stabilizers, fluorescent whitening agents, crystallization accelerators, crystallization retarders, flow aids, lubricants, slip agents, mold release agents, colorants, dyes, inorganic pigments, organic pigments, marking agents, and mixtures thereof.

12. A thermoplastic molding composition according to any one of claims 1 to 11, characterized in that the proportion of component A is in the range of 34 to 82.9% by weight based on the sum of components A to D, and / or component B is in the range of 15 to 55% by weight based on the sum of components A to D, and / or component C is in the range of 2 to 6% by weight based on the sum of components A to D, and / or component D is in the range of 0.1 to 5% by weight based on the sum of components A to D.

13. A molded article comprising the molding composition according to any one of claims 1 to 12.

14. The molded article according to claim 13, characterized in that it is selected from components, housings, or housing parts of a device that communicates using electromagnetic waves having a frequency of 0.3 to 300 GHz.

15. The molded article according to claim 14, characterized in that the molded article is selected from the group consisting of transceivers, mobile phones, tablets, laptops, navigation devices, surveillance cameras, photo cameras, sensors, diving computers, audio systems, remote controls, speakers, headphones, radio sets, television sets, household appliances, kitchen appliances, door or gate openers, operating devices for vehicle central locking systems, keyless go vehicle keys, temperature measuring or temperature display devices, components of measuring devices and control devices, housings or housing components.

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