POLYAMIDE COMPOSITIONS

Description

[0001] The present invention relates to reinforced compositions and products to be produced therefrom based on at least one polyamide containing at least one aluminium salt of an organophosphorus compound of general formula (I) and aluminium hypophosphite, a process for its manufacture and its uses. State of the art

[0002] Due to their good mechanical stability, chemical resistance, and processability, polyamides are an important material for applications such as in motor vehicles, components for the electrical and electronics industry, and household appliances. When polyamides are used near live electrical components, flame-retardant materials are frequently employed to counteract the risk of fire caused by overheated wires or contacts. Depending on the application, not only good self-extinguishing properties, but also, in particular, a UL94 V-0 classification according to Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances," pp. 14-18, Northbrook 1998, are important. ,but also low flammability is required. For example, IEC 60335-1 prescribes a glow wire test according to IEC 60695-2-11 on the finished part for components in unattended household appliances located within 3 mm of live parts with currents >0.2 A. In this test, no flame may be visible for more than 2 seconds at a glow wire temperature of 750°C. Experience shows that test results on the finished part do not directly correspond to test results obtained according to IEC 60695-2-13 on a defined circular plate at the same glow wire temperature, due to the undefined geometry of finished parts or metal contacts that impede heat flow. Furthermore, according to IEC 60695-2-13, a test specimen is still considered unignited if it exhibits a flame for less than 5 seconds.According to IEC60695-2-13, the classification "GWIT 775°C" is awarded if 3 test plates measured consecutively at 750°C show no flame appearance for > 5 seconds.

[0003] To ensure that a material does not exhibit a flame with a burning time longer than 2 seconds, even at a glow wire temperature of 750°C, regardless of the geometry, there is an increasing demand for materials that have a larger safety margin in a plate test according to IEC60695-2-13, i.e., that they also pass a GWIT above 775°C in addition to meeting the standard requirements of IEC60335-1.

[0004] In the field of polyamides, halogen-free solutions are increasingly in demand recently. This is due not only to ecological reasons, but also to the fact that halogen-free flame-retardant polyamides generally exhibit lower density and higher tracking resistance according to IEC 60112-2010 compared to halogen-containing systems. Both of these factors play a particularly important role in drive systems for electromobility.

[0005] However, high impact strength combined with high strength and stiffness is also essential for widespread use in technical applications, allowing the designer to create material-saving, and therefore weight-saving and resource-saving, component designs.

[0006] The desire for maximum design freedom and thus higher complexity of component geometry, combined with the cost-driven need for automatable and easily integrated series production processes, increasingly demands materials that can also be welded using the laser transmission welding process. [https: / / de.wikipedia.org / wiki / Laserdurchstrahlschwei%C3%9Fen] to join together. For a laser-transparent joining partner, this requires a high transmittance at the laser wavelength used. The latter is a major challenge, especially with flame-retardant polyamides, since flame retardants scatter or even absorb the laser light, as is the case, for example, with antimony trioxide, which is used as a synergist in halogenated flame retardants. State of the art

[0007] To improve flame retardancy, polyamides are treated with flame retardants. EP 1 702 007 B1 describes polyamide 6 compositions with 30 wt% glass fiber reinforced and flame-retardant aluminum hypophosphite in Table 2. Only the combination of aluminum hypophosphite with sorbitan dioleate (Example 5), or the combination of aluminum hypophosphite with Irganox® < 1098 and ethylenediamine distearate (Example 7), achieve a V0 classification in the UL 94 test at wall thicknesses of 1.6 mm and 3.2 mm, respectively; at 0.8 mm, only a V2 classification is achieved. GWIT 775 / 3 mm and GWIT 775 / 2 mm are only reported as "passed" for polyamide 6 in Example 7 when using Irganox® < 1098 and ethylenediamine distearate. The test results for 30 wt% glass fiber reinforced polyamide 66 in Table 3 of EP 1 702 007 B1 are comparable to those for polyamide 6. Example 1 in Table 3 shows a polyamide reinforced with 30 wt% glass fiber.-% glass fiber reinforced and aluminum hypophosphite reinforced polyamide 66, which achieves a V0 classification in the UL 94 test at 3.2 mm and at 1.6 mm. A V0 classification in the UL 94 test at 0.8 mm, as well as the GWIT tests 775 / 3 mm and 775 / 2 mm, is only achieved with 30 wt% glass fiber reinforced and aluminum hypophosphite flame-retardant polyamide 66 compositions, which also contain three (!) additional components: ethylenediamine distearate, Irganox® < 1098, and polydimethylsiloxane.

[0008] Therefore, compositions of EP 1 702 007 B1 do not meet the requirements of the applicable household appliance standard IEC 60335-1 for glow wire testing when wall thicknesses are less than or equal to 1 millimeter.

[0009] Based on the prior art, the object of the present invention was therefore to provide halogen-free, flame-retardant, reinforced polyamide compositions with the potential for UL94 V0 classification, especially with regard to applications and products for electromobility, household appliances, and the electronics and electrical sectors, while simultaneously exhibiting very good performance in the glow wire ignition test – even with wall thicknesses ≤ 1 millimeter – very good impact strength, and, in particular, high laser transmission for use in laser transmission welding, and at least without any deterioration compared to the UL 94 results. ( Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pp. 14 - 18 Northbrook 1998 ) and GWIT results of EP 1 702 007 B1 show.

[0010] It has now been surprisingly found that the combination of at least one phosphorus-containing aluminum salt of the general formula (I) wherein R stands for C 1 -C 12 -alkyl, with aluminium hypophosphite in reinforced polyamide-based polymer compositions and products made therefrom, fulfills the above-mentioned complex task.

[0011] The IZOD impact strength according to DIN EN ISO 180, used within the scope of the present invention to obtain mechanical properties, can be applied to rigid thermoplastic injection molding and extrusion compounds, thermosetting materials and thermotropic liquid crystalline polymers, as well as to filled and reinforced materials. The impact energy absorbed during fracture is used to determine this strength. EC of an unnotched test specimen relative to the initial cross-sectional area of ​​the test specimen, according to the following equation: a iU = E c h ⋅ b with a iU = Impact strength, h= Thickness and b = Width.

[0012] The test specimens to be used here can be produced according to the relevant molding compound standard or by pressing and injection molding, or taken from multi-purpose test specimens (DIN EN ISO 527 [2]). The dimensions of the unnotched test specimen according to DIN EN ISO 3167, type A, used in the scope of the present invention are: Länge l = 80 ± 2 mm Breite b = 10 , 0 ± 0 , 2 mm Dicke h = 4 , 0 ± 0 , 2 mm

[0013] See also: https: / / wiki.polymerservice-merseburg.de / index.php / Schlagbiegeversuch

[0014] According to the invention, high laser transmission is defined as a laser transmission of at least 30%, preferably at least 40%, and particularly preferably at least 50%, measured on plates with a thickness of 0.75 mm using the LPKF TMG3 transmission meter from LPKF Laser & Electronics AG, Garbsen, Germany, at a laser wavelength of 980 nm. The LPKF TMG3 transmission meter is a certified, traceable, calibrated measuring instrument. Its measurement capability has been demonstrated within the framework of a statistical measurement system analysis (MSA). The device also complies with the requirements of Automotive standard IATF 16949 and is therefore directly qualified for standard-compliant quality assurance. The measurements within the scope of the present invention are based on the DVS Guideline 2243 (01 / 2014) "Laser beam welding of thermoplastic materials"The measurements are performed using round plates with a diameter of 80 mm and a thickness of 0.75 mm in the near-infrared (NIR) range. The LPKF TMG3 transmission meter from LPKF Laser & Electronics AG is calibrated before the measurements using a measurement standard generated according to DIN EN ISO / IEC 17025. Within the scope of the present invention, the measurements are performed at a laser wavelength of 980 nm.

[0015] The designation of polyamides (PA) used in the present application complies with the international standard ISO 1874-1, where the first digit(s) indicate the number of carbon atoms in the starting diamine and the last digit(s) indicate the number of carbon atoms in the dicarboxylic acid. If only one number is given, as in the case of PA6, this means that an α,ω-aminocarboxylic acid or the lactam derived from it, in the case of PA6, ε-caprolactam, was used as the starting material. Subject of the invention

[0016] The invention relates to polymer compositions containing A) to 100 mass parts polyamide, preferably PA 6 or PA 66, B) 2 to 100 mass parts, preferably 5 to 60 mass parts, particularly preferably 7 to 40 mass parts, particularly preferably 8 to 20 mass parts of at least one aluminium salt of general formula (I) wherein R represents C 1 -C 12 alkyl, preferably methyl, ethyl, isopropyl or iso-butyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, most preferably methyl, and C) 5 to 120 mass parts, preferably 7 to 80 mass parts, particularly preferably 8 to 60 mass parts, particularly preferably 10 to 50 mass parts of aluminum hypophosphite and D) 3 to 300 mass parts, preferably 5 to 200 mass parts, particularly preferably 15 to 120 mass parts, particularly preferably 20 to 90 mass parts of at least one filler and / or reinforcing agent.

[0017] The present invention also relates to the useof 2 to 100 mass fractions, preferably 5 to 60 mass fractions, particularly preferably 7 to 40 mass fractions, particularly preferably 8 to 20 mass fractions of at least one aluminium salt of general formula (I) wherein R represents C1-C12 alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, most preferably methyl, and 5 to 120 mass parts, preferably 7 to 80 mass parts, particularly preferably 8 to 60 mass parts, particularly preferably 10 to 50 mass parts of aluminum hypophosphite, each based on 100 mass parts of polyamide, preferably PA 6 or PA 66, which is reinforced with 3 to 300 mass parts, preferably 5 to 200 mass parts, particularly preferably 15 to 120 mass parts, particularly preferably 20 to 90 mass parts of at least one filler and / or reinforcing agent, for the production of laser-transparent compositions or products, preferably also with a GWIT at 0.75 mm wall thickness of at least 800 °C.

[0018] The preparation of polyamide-based polymer compositions according to the invention for use in electromobility, household appliances, and the electronics and electrical sectors is carried out by mixing the components A), B), C), and D) used as starting materials in at least one mixing tool in the mass ratios specified above. This mixing process yields molding compounds based on the polymer compositions according to the invention as intermediate products. These molding compounds can consist exclusively of components A), B), C), and D), or can additionally contain at least one further component. If laser-transparent polymer compositions are to be provided, further components must be selected such that laser-absorbing additives are not required.

[0019] Furthermore, the present invention relates to a Proceedingsfor the production of molding compounds according to the invention, wherein component A) 100 mass parts of polyamide, preferably PA 6 or PA 66, with B) 2 to 100 mass fractions, preferably 5 to 60 mass fractions, particularly preferably 7 to 40 mass fractions, particularly preferably 8 to 20 mass fractions of at least one aluminium salt of general formula (I) wherein R represents C1-C12 alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, most preferably methyl, and C) 5 to 120 mass parts, preferably 7 to 80 mass parts, particularly preferably 8 to 60 mass parts, particularly preferably 10 to 50 mass parts of aluminum hypophosphite with D) 3 to 300 mass parts, preferably 5 to 200 mass parts, particularly preferably 15 to 120 mass parts, particularly preferably 20 to 90 mass parts of at least one filler and / or reinforcing agent, and optionally with further additives, in at least one mixing unit and finally processed by injection molding. Preferably, the components are kneaded, compounded, extruded, or rolled to form a molding compound.This mixing is preferably carried out at a temperature in the range of 240 to 275°C for polyamide 6 and 260 to 275°C for polyamide 66, particularly preferably by compounding on a co-rotating twin-screw extruder or Buss kneader. It can be advantageous to premix individual components.

[0020] For the avoidance of doubt, it should be noted that the scope of the present invention encompasses all listed general or preferred definitions and parameters in any combination. This applies in particular to the specified mass fractions with regard to the polymer compositions, the use(s) described according to the invention, and the processes described according to the invention. The standards cited in this application refer to the version in force on the filing date of this invention. Further preferred embodiments of the invention

[0021] In a further preferred embodiment, the invention further relates to polymer compositions comprising, in addition to components A) to D), at least one further of components B), C) and D) different component E), preferably to 0.01 to 100 mass fractions, particularly preferably to 0.05 to 50 mass fractions, most preferably to 0.1 to 30 mass fractions, each based on 100 mass fractions of component A) with the proviso that laser absorbers are omitted to maintain laser transparency. Component A)

[0022] The components to be used as component A) within the scope of the present inventions according to the invention PolyamidePolyamides can be produced using various methods and synthesized from different building blocks. A multitude of processes are known for the production of polyamides, whereby, depending on the desired end product, different monomer building blocks, various chain regulators to adjust a target molecular weight, or even monomers with reactive groups for subsequent post-treatments can be used.

[0023] The technically relevant processes for the production of polyamides mostly involve polycondensation in the melt. In this context, the hydrolytic polymerization of lactams is also understood as polycondensation.

[0024] Suitable starting materials include aliphatic and / or aromatic dicarboxylic acids such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines such as tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Caprolactams, especially ε-caprolactam, are particularly preferred. Copolyamides consisting of several of the aforementioned monomers are also included.

[0025] Preferred polyamides are semi-crystalline polyamides that can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids. Particularly preferred semi-crystalline polyamides are those with a melting point of less than or equal to 275°C.

[0026] The PA6 [CAS No. 25038-54-4] to be used as component A) according to the invention preferably has a ISO 307 The viscosity number to be determined in a 0.5 wt% solution in 96 wt% sulfuric acid at 25°C is in the range of 80 to 180 ml / g, particularly preferably in the range of 85 to 160 ml / g and most preferably in the range of 90 to 135 ml / g. Polyamide 6, preferably to be used as component A) according to the invention, is available, for example, as Durethan® < B24 from Lanxess Deutschland GmbH, Cologne.

[0027] Preferably, a polyamide 66 [CAS No. 32131-17-2] to be used as component A) has a ISO 307The viscosity number to be determined in a 0.5 wt% solution in 96 wt% sulfuric acid at 25°C is in the range of 80 to 180 ml / g, most preferably a viscosity number in the range of 100 to 165 ml / g, and particularly preferably in the range of 110 to 140 ml / g. The polyamide 66 to be used as component A) according to the invention is available, for example, as Ultramid® < A24E01 from BASF SE, Ludwigshafen.

[0028] The polyamide used as component A) according to the invention can also be used in a mixture with at least one other polyamide and / or at least one other polymer. Preferred other polymers are selected from the group consisting of polyethylene, polypropylene, and acrylonitrile butadiene styrene copolymer (ABS). In the case of the use of at least one further polyamide or at least one other polymer, this is preferably or optionally carried out with the use of at least one compatibilizer.

[0029] The polyamide to be used as component A) can have conventional additives, preferably demolding agents, stabilizers and / or flow aids known to those skilled in the art, already added to the melt. Component B)

[0030] As component B) to be used according to the invention, at least one aluminium salt of the general formula (I) is used, wherein R stands for C 1 -C 12 -alkyl, preferably for Methyl, Ethyl, Isopropyl or iso-Butyl, tert-Butyl or n-Butyl, particularly preferably for Ethyl or Methyl, most preferably for Methyl.

[0031] These aluminum salts of organic phosphorus compounds with the general formula (I), which are to be used as component B) within the scope of the present invention, can be prepared by various processes and synthesized from different building blocks. Within the scope of the present invention, the following process is used to prepare compound (1a) with R = methyl:

[0032] A reaction vessel is charged with 83 g of methylphosphonic acid and heated to 120°C. An intermediate prepared from 50 g of methylphosphonic acid and 35.4 g of aluminum tris(isopropoxide) is added to the reaction vessel in the presence of water. The resulting solution, containing an intermediate of methylphosphonic acid and aluminum methylphosphonate in a molar ratio of 5:1, is heated to 240°C with mechanical stirring. Stirring is continued at 240°C for approximately 30 minutes until a solid forms. Subsequently, 500 ml of water are added, and this mixture is stirred for 16 h, during which time a uniform slurry is formed. The product is then filtered, washed with 750 ml, and dried. The result is 64.3 g of the product of formula (1a), to be used as component B), as fine, colorless crystals in a yield of 93%. The empirical formula (1a) represents repeating monomer units (ieCoordination units) of a coordination polymer that exists in crystalline form.

[0033] Further methods, in particular for R ≠ Methyl, can be found in WO 2020 / 132075 A1, the contents of which are fully encompassed by the present invention.

[0034] Component B) according to formula (1a) is particularly preferred, with a molar ratio of phosphorus to aluminum of 4:1, to be determined by ICP-OES elemental analysis, wherein needle-shaped crystals are particularly preferred. See Example 3 in WO 2021 / 076169 A1 and for ICP-OES see: https: / / www.itmc.rwth-aachen.de / go / id / gden Component C)

[0035] Component C) of the compositions according to the invention contains aluminum hypophosphite [CAS No. 7784-22-7]. Aluminum hypophosphite used according to the invention can be obtained under the name Phoslite® < IP-A from Italmatch, Genoa, Italy. CN103145110 A discloses a manufacturing process for aluminum hypophosphite. The manufacturing process comprises the following steps: a) preparing a sodium hypophosphite solution; b) preparing an aluminum nitrate solution; and c) uniformly mixing the sodium hypophosphite solution with the aluminum nitrate solution, adjusting the pH to 2–6, and heating to form the desired product, aluminum hypophosphite.The aluminum hypophosphite can be used directly as a powder or preferably also in the form of a polyamide masterbatch, with the use as a masterbatch being preferred and the use as a masterbatch with polyamide 6 as a carrier material being particularly preferred, and in turn an aluminum hypophosphite content between 34 and 56 wt%, in particular between 39 and 51 wt% in the polyamide 6 masterbatch being especially preferred. Component D)

[0036] The polymer compositions according to the invention contain at least one component D). Filler and / or reinforcing agent. Mixtures of two or more different fillers and / or reinforcing agents can also be used.

[0037] Preferably, component D) comprises at least one filler and / or reinforcing material from the group consisting of carbon fibers [CAS No. 7440-44-0], glass spheres or solid or hollow glass spheres, glass fibers, ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E-glass) [CAS No. 65997-17-3], amorphous silica [CAS No. 7631-86-9], quartz flour [CAS No. 14808-60-7], calcium silicate [CAS No. 1344-95-2], calcium metasilicate [CAS No. 10101-39-0], magnesium carbonate [CAS No. 546-93-0], kaolin [CAS No. 1332-58-7], calcined kaolin [CAS No. 92704-41-1], chalk [CAS No. 1317-65-3], kyanite [CAS No. 1302-76-7], powdered or ground quartz [CAS No. 14808-60-7], mica [CAS No. 1318-94-1], phlogopite [CAS No. 12251-00-2], barium sulfate [CAS No. 7727-43-7], feldspar [CAS No. 68476-25-5], wollastonite [CAS No. 13983-17-0], montmorillonite [CAS No. 67479-91-8], pseudoboehmite of the formula AIO(OH), magnesium carbonate [CAS No. 12125-28-9] and talc [CAS No. 14807-96-6] used.

[0038] Among the fibrous fillers or reinforcing materials, glass fibers and wollastonite are particularly preferred, with glass fibers being especially preferred. In the case of a laser-absorbing component or product, carbon fibers can also be used as a filler or reinforcing material.

[0039] Particularly preferred is the use of glass as a filler and / or reinforcing material in component D). Preferably, glass conforming to DIN 1259-1 is used. Most preferred is the use of solid or hollow glass spheres, glass fibers, ground glass, or aluminum borosilicate glass with an alkali content of 1% (E-glass) [CAS No. 65997-17-3].

[0040] Regarding the optical fibers, the expert distinguishes according to "http: / / de.wikipedia.org / wiki / Faser-Kunststoff-Verbund"Cut fibers, also known as short fibers, have a length of 0.1 to 1 mm; long fibers have a length of 1 to 50 mm; and continuous fibers have a length L > 50 mm. Short fibers are preferably used in injection molding and can be processed directly with an extruder. Long fibers can also be processed in extruders. Continuous fibers are used as rovings or woven fabrics in fiber-reinforced plastics. Products made with continuous fibers achieve the highest stiffness and strength values. Ground glass fibers are also available, with a typical length after grinding of 70 to 200 µm.

[0041] According to the invention, glass fibers preferably used as component D) are cut long glass fibers with an average initial length in the range of 1 to 50 mm, particularly preferably in the range of 1 to 10 mm, and most preferably in the range of 2 to 7 mm.

[0042] Preferred optical fibers to be used as component D) have a mean fiber diameter in the range of 7 to 18 µm, particularly preferably in the range of 9 to 15 µm. Scanning electron microscopy (SEM) can be used as a possible method for determining the fiber diameters. (https: / / de.wikipedia.org / wiki / Rasterelektronenmikroskop).

[0043] The glass fibers preferably used as component D) are, in a preferred embodiment, equipped with a suitable sizing system or an adhesion promoter or adhesion promoter system. A silane-based sizing system or adhesion promoter is preferably used. Particularly preferred silane-based adhesion promoters for treating the glass fibers preferably used as component D) are silane compounds of the general formula (II) (X-(CH₂)q)k-Si-(O-CrH₂R+I)4-k (II) wherein X for NH2, carboxyl, HO or qin formula (II) represents an integer from 2 to 10, preferably 3 to 4; rin formula (II) represents an integer from 1 to 5, preferably 1 to 2; and kin formula (II) represents an integer from 1 to 3, preferably 1.

[0044] Particularly preferred adhesion promoters are silane compounds from the group consisting of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl or a carboxyl group as substituent X in formula (II), wherein carboxyl groups are particularly preferred.

[0045] For the treatment of the glass fibers to be preferably used as component D), the adhesion promoter, preferably the silane compounds according to formula (II), is preferably used in amounts of 0.05 to 2 wt.%, particularly preferably in amounts of 0.25 to 1.5 wt.% and most preferably in amounts of 0.5 to 1 wt.%, each based on 100 wt.% component D).

[0046] The glass fibers preferably used as component D) may be shorter in the composition or product than the originally used glass fibers due to processing. Thus, the arithmetic mean of the glass fiber length, determined by high-resolution X-ray computed tomography, is often only in the range of 150 µm to 300 µm after processing.

[0047] According to "http: / / www.rg.de / wiki / Glasfasern"Glass fibers are produced using melt spinning processes (nozzle drawing, rod drawing, and nozzle blowing). In the nozzle drawing process, the hot glass mass flows through hundreds of nozzle holes in a platinum spinning plate, utilizing gravity. The elementary fibers can be drawn to unlimited lengths at a speed of 3–4 km / minute.

[0048] Experts distinguish between different types of fiberglass, some of which are listed here: E-glass, the most widely used material with an optimal price-performance ratio (E-glass from R&G) with a composition according to https: / / www.rg.de / wiki / Glasfasern53-55% SiO₂, 14-15% Al₂O₃, 6-8% B₂O₃, 17-22% CaO, <5% MgO, <1% K₂O or Na₂O and approx. 1% other oxides; H-glass, hollow glass fibers for reduced weight (R&G hollow glass fiber fabric 160 g / m²< and 216 g / m²<); R, S-glass, for increased mechanical requirements (S2-glass from R&G); D-glass, borosilicate glass for increased electrical requirements; C-glass, with increased chemical resistance; quartz glass, with high temperature resistance.

[0049] Further examples can be found at "http: / / de.wikipedia.org / wiki / Glasfaser".E-glass fibers have become the most important type for reinforcing plastics. The "E" in E-glass stands for electrical glass, as it was originally used primarily in the electrical industry. E-glass is produced by melting pure quartz glass with additives of limestone, kaolin, and boric acid. In addition to silicon dioxide, it contains varying amounts of different metal oxides. The composition determines the properties of the products. According to the invention, at least one type of glass fiber from the group consisting of E-glass, H-glass, R,S-glass, D-glass, C-glass, and quartz glass is preferably used, with E-glass glass being particularly preferred.

[0050] E-glass fibers are the most widely used reinforcing material. Their strength properties are comparable to those of metals (e.g., aluminum alloys), although the specific gravity of laminates containing E-glass fibers is lower than that of the metals. E-glass fibers are non-combustible, heat-resistant up to approximately 400°C, and resistant to most chemicals and weathering.

[0051] Preferably, needle-shaped mineral fillers are also used as component D). According to the invention, needle-shaped mineral fillers are defined as mineral fillers with a pronounced needle-shaped character. Wollastonite is a preferred needle-shaped mineral filler used as component D). Preferably, the needle-shaped mineral filler has a length-to-diameter ratio, determined by high-resolution X-ray computed tomography, in the range of 2:1 to 35:1, particularly preferably in the range of 3:1 to 19:1, and especially preferably in the range of 4:1 to 12:1. The mean particle size of the needle-shaped mineral fillers, which can be determined, for example, by scanning electron microscopy, is preferably less than 20 µm, particularly preferably less than 15 µm, and especially preferably less than 10 µm.

[0052] However, non-fibrous and non-foamed ground glass with a properties determined by laser diffractometry according to is also preferred as component D). ISO 13320 The particle size distribution to be determined is determined using a d90 in the range of 5 to 250 µm, preferably in the range of 10 to 150 µm, particularly preferably in the range of 15 to 80 µm, and most preferably in the range of 16 to 25 µm. Regarding the d90 values, their determination, and their significance, reference is made to Chemie Ingenieur Technik (72) pp. 273-276, 3 / 2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d90 value is the particle size below which 90% of the particle count lies. For laser diffraction particle size determination or laser diffractometry according to the standard ISO 13320, see: https: / / de.wikipedia.org / wiki / Laserbeugungs-artikelgr%C3%B6%C3%9Fenanalyse

[0053] According to the invention, preferably the non-fibrous and non-foamed ground glass is of a particulate, non-cylindrical shape with a length-to-thickness ratio of less than 5, preferably less than 3, and particularly preferably less than 2, which can be determined, for example, by scanning electron microscopy. The value zero is of course excluded.

[0054] The non-foamed and non-fibrous ground glass to be used as component D) in one embodiment is further characterized in that it does not have the glass geometry typical for fibrous glass with a cylindrical or oval cross-section and a length-to-diameter ratio (L / D ratio) greater than 5, which can be determined, for example, by scanning electron microscopy.

[0055] The non-foamed and non-fibrous ground glass to be used as component D) in one embodiment according to the invention is preferably obtained by grinding glass with a mill, preferably a ball mill, and particularly preferably with subsequent classification or sieving. Preferred starting materials for grinding the non-fibrous and non-foamed ground glass to be used as component D) in one embodiment also include glass waste, such as that which arises in particular during the manufacture of glass products as an undesired by-product and / or as a main product that does not meet specifications (so-called off-spec material). This includes in particular waste, recycled, and broken glass, such as that which can arise particularly during the manufacture of window or bottle glass, as well as during the manufacture of glass-containing fillers and reinforcing materials, especially in the form of so-called melt cakes.The glass can be colored, but uncolored glass is preferred as the starting material for use as component D). Component E)

[0056] Component E) is at least one further component different from components B), C) and D). AdditivePreferred additives to be used as component E) are antioxidants, thermostabilizers, UV stabilizers, gamma-ray stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, lubricants and / or demolding agents, components for reducing water absorption, flow aids or elastomer modifiers, chain-extending additives, flame retardants or colorants different from components B), C), and D). The additives can be used alone or in mixtures or in the form of masterbatches. In the case of laser-transparent products, the additives to be used as component E) must be selected so that no laser absorbers, such as carbon black, are used. Laser-absorbing additives are sufficiently known to those skilled in the art.

[0057] Preferred Thermostabilizersof component E) are sterically hindered phenols, in particular those containing at least one 2,6-di-tert-butylphenyl group and / or 2-tert-butyl-6-methylphenyl group, particularly preferred N,N '-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide] [CAS No. 23128-74-7], for example available as Irganox 1098 from BASF, Ludwigshafen, Germany, furthermore phosphites, hypophosphites, in particular sodium hypophosphite NaH 2 PO 2, hydroquinones, aromatic secondary amines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, 3,3'-thiodipropionic acid esters as well as various substituted representatives of these groups or their mixtures.

[0058] In one embodiment, copper salts, preferably in combination with sodium hypophosphite (NaH₂PO₄), can also be used as thermostabilizers for component E). Preferably, copper(I) iodide [CAS No. 7681-65-4] and / or copper(triphenylphosphino) iodide [CAS No. 47107-74-4] are used as the copper salt. Preferably, the copper salts are used in combination with sodium hypophosphite (NaH₂PO₄) or with at least one alkali iodide. Potassium iodide [CAS No. 7681-11-0] is preferred as the alkali iodide.

[0059] Thermostabilizers to be used as component E) are preferably used in amounts of 0.01 to 2 mass fractions, particularly preferably in amounts of 0.05 to 1 mass fraction, in each case based on 100 mass fractions of component A).

[0060] to be used as component E) UV stabilizersPreferably substituted resorcinols, salicylates, benzotriazoles and benzophenones, HALS derivatives ("Hindered Amine Light Stabilizers") containing at least one 2,2,6,6-tetramethyl-4-piperidyl unit or benzophenones are used.

[0061] UV stabilizers to be used as component E) are preferably used in amounts of 0.01 to 2 mass fractions, particularly preferably in amounts of 0.1 to 1 mass fraction, in each case based on 100 mass fractions of component A).

[0062] to be used as component E) colorantPreferably inorganic pigments are used, in particular ultramarine blue, bismuth vanadate, iron oxide, titanium dioxide, zinc sulfide, tin-titanium-zinc oxides [CAS No. 923954-49-8], furthermore organic colorants, preferably phthalocyanines, quinacridones, benzimidazoles, in particular Ni-2-hydroxy-napthyl-benzimidazole [CAS No. 42844-93-9] and / or pyrimidine azo-benzimidazole [CAS No. 72102-84-2] and / or Pigment Yellow 192 [CAS No. 56279-27-7], also Perylene, Anthraquinones, in particular CI Solvent Yellow 163 [CAS No. 13676-91-0], whereby this list is not exhaustive and whereby the selection of colorants must be made with particular consideration of the requirements for laser transmission or laser absorption behavior.

[0063] In one embodiment, preferably in the case of a laser-absorbing component or product, carbon black and / or nigrosine are also used as colorants.

[0064] to be used as component E) Nucleating agent Sodium or calcium phenylphosphinate, aluminium oxide or silicon dioxide, and especially talc, are preferably used, although this list is not exhaustive.

[0065] to be used as component E) Flow aidsCopolymers of at least one α-olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol are preferably used. Copolymers in which the α-olefin is composed of ethene and / or propene and the methacrylic acid ester or acrylic acid ester contains linear or branched alkyl groups with 6 to 20 carbon atoms as the alcohol component are particularly preferred. Acrylic acid (2-ethyl)hexyl ester is especially preferred. Copolymers suitable as flow aids are characterized not only by their composition but also by their low molecular weight. Accordingly, for the compositions to be protected from thermal degradation according to the invention, copolymers are particularly suitable that have a minimum molecular weight index (MFI) of at least 100 g / 10 min, preferably at least 150 g / 10 min, and most preferably at least 300 g / 10 min, measured at 190°C and a load of 2.16 kg.The MFI, Melt Flow Index, is used to characterize the flow of a thermoplastic melt and is subject to the standards ISO 1133 or ASTM D 1238. A copolymer of ethene and acrylic acid (2-ethyl)hexyl ester with an MFI of 550, known as Lotryl® < 37EH550, is particularly preferred as a flow aid.

[0066] to be used as component E) chain-extending additivesDi- or multifunctional branching or chain-extending additives containing at least two branching or chain-extending functional groups per molecule are preferably used as hydrolysis stabilizers. Low-molecular-weight or oligomeric compounds are preferred as branching or chain-extending additives, provided they have at least two chain-extending functional groups per molecule that can react with primary and / or secondary amino groups, and / or amide groups, and / or carboxylic acid groups. Preferably, chain-extending functional groups are isocyanates, alcohols, blocked isocyanates, epoxides, maleic anhydride, oxazolines, oxazines, or oxazolones, with epoxides being preferred.

[0067] Particularly preferred di- or multifunctional branching or chain-extending additives are diepoxides based on diglycidyl ethers (bisphenol and epichlorohydrin), on amine epoxy resin (aniline and epichlorohydrin), on diglycidyl esters (cycloaliphatic dicarboxylic acids and epichlorohydrin) individually or in mixtures, as well as 2,2-bis[p-hydroxyphenyl]-propane diglycidyl ether, bis-[p-(N-methyl-N-2,3-epoxy-propylamino)-phenyl]-methane and epoxidized fatty acid esters of glycerol, containing at least two epoxide groups per molecule.

[0068] Particularly preferred di- or multifunctional branching or chain-extending additives are glycidyl ethers, most preferably bisphenol A diglycidyl ethers [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, as well as most preferably epoxidized soybean oil [CAS No. 8013-07-8] and / or epoxidized linseed oil.

[0069] Preferably to be used as component E) Plasticizers These include phthalic acid dioctyl esters, phthalic acid dibenzyl esters, phthalic acid butylbenzyl esters, hydrocarbon oils or N-(n-butyl)benzenesulfonamide.

[0070] Preferably to be used as component E) Elastomer modifiers include, among other things, one or more graft polymers of E.1 5 to 95 wt.%, preferably 30 to 90 wt.%, of at least one vinyl monomer and E.2 95 to 5 wt.%, preferably 70 to 10 wt.% of one or more graft bases with glass transition temperatures < 10°C, preferably < 0°C, particularly preferably < -20°C, wherein the wt.% refer to 100 wt.% elastomer modifier.

[0071] The graft base E.2 generally has a mean particle size d50 value of 0.05 to 10 µm, preferably 0.1 to 5 µm, particularly preferably 0.2 to 1 µm, which can be determined by laser diffractometry according to ISO 13320.

[0072] Monomers to E.1 are preferably mixtures of E.1.1 50 to 99 wt% vinyl aromatics and / or core-substituted vinyl aromatics, in particular styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and / or methacrylic acid (C1-C8) alkyl esters, in particular methyl methacrylate, ethyl methacrylate) and E.1.2 1 to 50 wt.% vinyl cyanides, in particular unsaturated nitriles such as acrylonitrile and methacrylonitrile, and / or (meth)acrylic acid (C 1 -C 8 )-alkyl esters, in particular methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives, in particular anhydrides and imides of unsaturated carboxylic acids, in particular maleic anhydride or N-phenyl maleimide, wherein the wt.% refer to 100 wt.% elastomer modifier.

[0073] Preferred monomers E.1.1 are to be selected from at least one of the monomers styrene, α-methylstyrene, and methyl methacrylate; preferred monomers E.1.2 are to be selected from at least one of the monomers acrylonitrile, maleic anhydride, glycidyl methacrylate, and methyl methacrylate. Particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.

[0074] Suitable graft bases for the graft polymers used in the elastomer modifiers include, for example, diene rubbers, EPDM rubbers (i.e., those based on ethylene / propylene and, if applicable, diene), as well as acrylate, polyurethane, silicone, chloroprene, and ethylene / vinyl acetate rubbers. EPDM stands for ethylene-propylene-diene rubber.

[0075] Preferred graft bases E.2 are diene rubbers, in particular based on butadiene, isoprene, etc., or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with further copolymerizable monomers, in particular according to E.1.1 and E.1.2, provided that the glass transition temperature of component E.2 is <10°C, preferably <0°C, particularly preferably <-10°C.

[0076] Particularly preferred graft bases E.2 are ABS polymers (emulsion, bulk and suspension ABS) where ABS stands for acrylonitrile butadiene styrene, as described, for example, in DE-A 2 035 390 or in DE-A 2 248 242 or in Ullmann, Encyclopedia of Technical Chemistry, Vol. 19 (1980), pp. 277-295. The gel content of the graft base E.2 is preferably at least 30 wt.%, particularly preferably at least 40 wt.% (measured in toluene).

[0077] The elastomer modifiers or graft polymers to be used as component E) are produced by radical polymerization, preferably by emulsion, suspension, solution or bulk polymerization, in particular by emulsion or bulk polymerization.

[0078] Particularly suitable grafting rubbers are also ABS polymers, which are produced by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US-A 4 937 285.

[0079] Since, as is known, the graft monomers are not necessarily completely grafted onto the graft base during the grafting reaction, according to the invention, graft polymers are also understood to be products that are obtained by (co)polymerization of the graft monomers in the presence of the graft base and are produced during the work-up.

[0080] Suitable acrylic rubbers are also based on graft bases E.2, which preferably consist of polymers of acrylic acid alkyl esters, optionally with up to 40 wt%, based on E.2, other polymerizable, ethylene-unsaturated monomers. Preferred polymerizable acrylic acid esters include C1-C8 alkyl esters, preferably methyl, ethyl, butyl, n-octyl, and 2-ethylhexyl esters; halogenated alkyl esters, preferably halogenated C1-C8 alkyl esters, such as chloroethyl acrylate, glycidyl esters, and mixtures of these monomers. Graft polymers with butyl acrylate as the core and methyl methacrylates as the shell, in particular Paraloid® < EXL2300, Dow Corning Corporation, Midland, Michigan, USA, are especially preferred.

[0081] As an alternative to ethylene-unsaturated monomers, monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

[0082] Particularly preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylene unsaturated groups.

[0083] Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloyl hexahydro-s-triazine, and triallylbenzenes. The amount of crosslinked monomers is preferably 0.02 to 5 wt.%, and in particular 0.05 to 2 wt.%, based on the graft base E.2.

[0084] For cyclic crosslinking monomers with at least 3 ethylene unsaturated groups, it is advantageous to limit the amount to less than 1 wt% of the graft base E.2.

[0085] Preferred "other" polymerizable, ethylene-unsaturated monomers, which, in addition to the acrylic acid esters, may optionally serve to prepare the graft base E.2, are acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C1-C6 alkyl ethers, methyl methacrylate, glycidyl methacrylate, and butadiene. Preferred acrylate rubbers as graft base E.2 are emulsion polymers having a gel content of at least 60 wt%.

[0086] Other preferably suitable grafting bases according to E.2 are silicone rubbers with grafting-active sites, as described in DE-A 3 704 657 , DE-A 3 704 655 , DE-A 3 631 540 and DE-A 3 631 539 are described.

[0087] Preferred graft polymers containing a silicone component are those comprising methyl methacrylate or styrene-acrylonitrile as a shell and a silicone / acrylate graft as a core. The styrene-acrylonitrile preferably used as a shell is Metablen® < SRK200. The methyl methacrylate preferably used as a shell is Metablen® < S2001, Metablen® < S2030, or Metablen® < SX-005. Metablen® < S2001 is particularly preferred. The products sold under the trade name Metablen® < are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.

[0088] For crosslinking, monomers with more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

[0089] Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylene unsaturated groups.

[0090] Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloyl hexahydro-s-triazine, and triallylbenzenes. The amount of crosslinked monomers is preferably 0.02 to 5 wt.%, and in particular 0.05 to 2 wt.%, based on the graft base E.2.

[0091] For cyclic crosslinking monomers with at least 3 ethylene unsaturated groups, it is advantageous to limit the amount to less than 1 wt% of the graft base E.2.

[0092] Preferred "other" polymerizable, ethylene-unsaturated monomers, which, in addition to the acrylic acid esters, may optionally serve to prepare the graft base E.2, are acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C1-C6 alkyl ethers, methyl methacrylate, glycidyl methacrylate, and butadiene. Preferred acrylate rubbers as graft base E.2 are emulsion polymers having a gel content of at least 60 wt%.

[0093] In addition to elastomer modifiers based on graft polymers, non-graft polymer-based elastomer modifiers can also be used, which have glass transition temperatures < 10°C, preferably < 0°C, and particularly preferably < -20°C. These preferably include elastomers with a block copolymer structure as well as thermoplastic meltable elastomers, in particular EPM, EPDM and / or SEBS rubbers (EPM = ethylene-propylene copolymer, EPDM = ethylene-propylene-diene rubber and SEBS = styrene-ethene-butene-styrene copolymer).

[0094] to be used as component E) Lubricants and / or demolding agentsare preferably long-chain fatty acids, in particular stearic acid or behenic acid, their salts, in particular Ca or Zn stearate, as well as their ester derivatives, in particular those based on pentaerythritol, in particular fatty acid esters of pentaerythritol or amide derivatives, in particular ethylene bis stearylamide, montan waxes as well as low molecular weight polyethylene or polypropylene waxes.

[0095] Montan waxes within the meaning of the present invention are mixtures of straight-chain saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms.

[0096] According to the invention, sliding and / or demolding agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms with aliphatic saturated alcohols or amides of amines with 2 to 40 carbon atoms with unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms are particularly preferred, or metal salts of saturated or unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms are used instead of the carboxylic acids.

[0097] Particularly preferred as component E) are the lubricating and / or demolding agents to be selected from the group consisting of pentaerythritol tetrastearate [CAS No. 115-83-3], ethylene bis-stearylamide, calcium stearate, and ethylene glycol dimontanate. Calcium stearate [CAS No. 1592-23-0] or ethylene bis-stearylamide [CAS No. 110-30-5] is particularly preferred. Ethylene bis-stearylamide (Loxiol® < EBS from Emery Oleochemicals) is especially preferred.

[0098] Component E) preferably to be used Hydrolysis stabilizers or components for reducing water absorption The polyesters are preferably polybutylene terephthalate and / or polyethylene terephthalate, with polyethylene terephthalate being particularly preferred. The polyesters are preferably used in concentrations of 5 to 20 wt% and particularly preferably in concentrations of 7 to 15 wt%, in each case based on the total polymer composition and provided that the sum of all wt% of the polymer composition always equals 100 wt%.

[0099] As component E), further components preferably to be used Flame retardants Components B) and C) contain various mineral flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants.

[0100] In an alternative embodiment, flame retardants that negatively affect the laser transmission of a product based on polymer compositions according to the invention can also be used, provided that the need requires it, taking into account the disadvantages due to the loss of laser transparency.

[0101] Among mineral flame retardants, magnesium hydroxide is particularly preferred. Magnesium hydroxide [CAS No. 1309-42-8] may be contaminated due to its origin and method of manufacture. Typical impurities include, for example, silicon-, iron-, calcium-, and / or aluminum-containing species, which may be incorporated into the magnesium hydroxide crystals, for instance, in the form of oxides. The magnesium hydroxide used as a mineral flame retardant may be uncoated or coated. Preferably, the magnesium hydroxide used as a mineral flame retardant is coated with sizing based on stearates or aminosiloxanes, particularly preferably with aminosiloxanes.

[0102] Magnesium hydroxide, preferably used as a mineral flame retardant, has a composition determined by laser diffractometry according to ISO 13320The mean particle size d50 to be determined is in the range of 0.5 µm to 6 µm, wherein a d50 in the range of 0.7 µm to 3.8 µm is preferred and a d50 in the range of 1.0 µm to 2.6 µm is particularly preferred.

[0103] According to the invention, suitable mineral flame retardants to be used as component E) are magnesium hydroxide types, in particular Magnifin ®< H5IV from Martinswerk GmbH, Bergheim, Germany or Hidromag ®< Q2015 TC from Penoles, Mexico City, Mexico.

[0104] Preferred nitrogen-containing flame retardants to be used as component E) are the reaction products of trichlorotriazine, piperazine, and morpholine according to CAS No. 1078142-02-5, in particular MCA PPM Triazine HF from MCA Technologies GmbH, Biel-Benken, Switzerland, as well as melamine cyanurate and condensation products of melamine, in particular melem, melam, melon, or higher-condensed compounds of this type. Preferred inorganic nitrogen-containing compounds are ammonium salts.

[0105] Furthermore, salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives, in particular aluminum hydroxide or Ca-Mg carbonate hydrates, may also be used. ( DE-A 4 236 122 ) Flame retardants are used as component E).

[0106] Suitable for use as flame retardants in component E) are also flame retardant synergists from the group of oxygen-, nitrogen-, or sulfur-containing metal compounds. Zinc-free compounds are preferred, in particular molybdenum oxide, magnesium oxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, magnesium nitride, calcium phosphate, calcium borate, magnesium borate, or mixtures thereof.

[0107] Furthermore, zinc-containing compounds can also be used as flame retardants for component E), if required. These preferably include zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide and zinc nitride, or mixtures thereof.

[0108] In addition, calcium stannate and calcium hydroxystannate can also be used as flame retardants for component E) if required.

[0109] Flame retardants used as component E) are preferably aluminum salts of phosphonic acid. According to Wikipedia, phosphonic acid is the substance with the molecular formula H₃PO₃ [CAS No. 13598-36-2]. (http: / / de.wikipedia.org / wiki / Phosphons%C3%A4ure)Understood. The salts of phosphonic acid are called phosphonates. Phosphonic acid can exist in two tautomeric forms, one of which has a lone pair of electrons on the phosphorus atom and the other of which has a doubly bonded oxygen atom to the phosphorus (P=O). The tautomeric equilibrium lies entirely on the side of the form with the doubly bonded oxygen atom. According to A.F. Holleman, E. Wiberg: Textbook of Inorganic Chemistry. 101st edition. Walter de Gruyter, Berlin / New York 1995, ISBN 3-11-012641-9, p. 764, the terms "phosphorous acid" and "phosphites" should only be used for the tautomeric species with a lone pair of electrons on the phosphorus atom. Previously, the terms "phosphorous acid" and "phosphites" were also used for the tautomeric forms with oxygen doubly bonded to phosphorus, so that in the present invention the terms phosphonic acid and phosphorous acid or phosphonates and phosphites are used synonymously.

[0110] Preferably, at least one of the aluminum salts of phosphonic acid from the group is used. primary aluminum phosphonate [Al(H₂PO₃)₃], basic aluminum phosphonate [Al(OH)H₂PO₃)₂·2H₂O], Al₂(HPO₃)₃•xAl₂O₃•nH₂O with x in the range of 2.27 to 1 and n in the range of 0 to 4, Al₂(HPO₃)₃•(H₂O)q of formula (III) where q represents 0, 1, 2, 3 or 4, in particular aluminum phosphonate tetrahydrate [Al₂(HPO₃)₃•4H₂O] or secondary aluminum phosphonate [Al₂(HPO₃)₃], Al₂Mz(HPO₃)y(OH)v•(H₂O)w of formula (IV) where M represents alkali metal ion(s) and z in the range of 0.01 to 1.5, y in the range of 2.63 - 3.5, v in the range of 0 to 2 and w in the range of 0 to 4, and Al 2 (HPO 3 ) u (H 2 PO 3 ) t • (H 2 O) s of formula (V) wherein u is in the range of 2 to 2.99, t in the range of 2 to 0.01 and s in the range of 0 to 4, wherein in formula (IV) z, y and v and in formula (V) u and t only take such numbers that the corresponding aluminium salt of phosphonic acid as a whole is uncharged, selected.

[0111] Preferred alkali metals in formula (IV) are sodium and potassium.

[0112] The described aluminum salts of phosphonic acid exhibit high laser transmission in polyamides and can be used individually or in mixtures.

[0113] Particularly preferred aluminum salts of phosphonic acid are selected from the group Primary aluminum phosphonate [Al(H₂PO₃)₃], secondary aluminum phosphonate [Al₂(HPO₃)₃], basic aluminum phosphonate [Al(OH)H₂PO₃)₂·2H₂O], aluminum phosphonate tetrahydrate [Al₂(HPO₃)₃·4H₂O], and Al₂(HPO₃)₃·xAl₂O₃·nH₂O, with x in the range of 2.27 to 1 and n in the range of 0 to 4. Particularly preferred are secondary aluminum phosphonate [Al₂(HPO₃)₃], CAS No. 71449-76-8], and secondary aluminum phosphonate tetrahydrate [Al₂(HPO₃)₃·4H₂O], CAS No. 156024-71-4], in particular secondary aluminium phosphonate [Al 2 (HPO 3 ) 3 ].

[0114] Preferred phosphorus-containing flame retardants other than components B) and C) are further organic metal phosphinates, red phosphorus, other inorganic metal hypophosphites, other metal phosphonates, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO derivatives), resorcinol bis-(diphenyl phosphate) (RDP) including oligomers, bisphenol A bis-diphenyl phosphate (BDP) including oligomers, melamine pyrophosphate, melamine polyphosphate, melamine poly(aluminum phosphate), melamine poly(zinc phosphate) or phenoxyphosphazene oligomers and mixtures thereof.

[0115] Furthermore, preferably phosphorus-containing flame retardants to be used as component E) are at least a phosphinic acid salt of formula (VI) and / or at least one diphosphinic acid salt of formula (VII) and / or their polymers. Phosphinic acid salts of formula (VI) and diphosphinic acid salts of formula (VII) are also referred to as phosphinates within the scope of the present invention.

[0116] Preferably, M in formulas (VI) or (VII) represents aluminum, zinc, titanium, or magnesium. Preferably, R<1, R<2 in formulas (VI) and (VII) are the same or different and represent C1-C6 alkyl, linear or branched, and / or phenyl. Particularly preferably, R1, R2 are the same or different and represent methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and / or phenyl.

[0117] Preferably, R 3< in formula (VII) means methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylpropylene, or phenylbutylene. Particularly preferably, R 3< means phenylene or naphthylene. Suitable phosphinates are described in WO-A 97 / 39053, the contents of which, with respect to the phosphinates, are included in the present application. Particularly preferred phosphinates within the meaning of the present invention are aluminium and zinc salts of dimethyl phosphinate, ethyl methyl phosphinate, diethyl phosphinate and methyl n-propyl phosphinate, as well as mixtures thereof.

[0118] Preferably, m in formula (VI) represents 2 and 3, particularly preferably 3.

[0119] Preferably, n in formula (VII) represents 1 and 3, particularly preferably 3.

[0120] Preferably, x in formula (VII) represents 1 and 2, and especially 2.

[0121] In particular, aluminium tris(diethylphosphinate) is preferred as component E1), which is available as Exolit ®< OP1230 from Clariant SE, Muttenz, Switzerland.

[0122] Other flame retardants to be used as component E) are carbon formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyetherketones, as well as anti-drip agents, in particular tetrafluoroethylene polymers.

[0123] The flame retardants to be used as component E) can be added in pure form, as well as via masterbatches or compacts.

[0124] Furthermore, as component E), halogenated flame retardants can also be used if required, taking into account the disadvantages, including the loss of halogen-free properties. Preferred halogenated flame retardants are commercially available organic halogen compounds, particularly preferably ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabrombenzyl acrylate, brominated polystyrene, or brominated polyphenylene ethers, which can be used alone or in combination with synergists, especially antimony trioxide or antimony pentoxide. Among the halogenated flame retardants, brominated polystyrene is particularly preferred. Brominated polystyrene is preferably used in a concentration of 10–30 wt.%, and particularly preferably in a concentration of 15–25 wt.%.% used, each in relation to the total composition, wherein at least one of the other components is reduced to such an extent that the sum of all weight percent always equals 100.

[0125] Brominated polystyrene is commercially available in various product grades. Examples include Firemaster® < PBS64 from Lanxess, Cologne, Germany, and Saytex® < HP-3010 from Albemarle, Baton Rouge, USA.

[0126] In the case of a laser-absorbing component, at least one component can be used as component E), albeit with the loss of the property of high laser transmission. Laser absorber Selected from the group consisting of antimony trioxide, tin oxide, tin orthophosphate, barium titanate, aluminum oxide, copper hydroxyphosphate, copper orthophosphate, potassium copper diphosphate, copper hydroxide, antimony tin oxide, bismuth trioxide, and anthraquinone are used. Tin oxide, antimony trioxide, or antimony tin oxide are particularly preferred. Antimony trioxide is most preferred.

[0127] The laser absorber, in particular the antimony trioxide, can be used directly as a powder or in the form of masterbatches. Preferred masterbatches are those based on polyamide and / or polyolefins, preferably polyethylene. The laser absorber can be used individually or as a mixture of several laser absorbers.

[0128] Laser absorbers can absorb laser light of a specific wavelength. In practice, this wavelength lies in the range of 157 nm to 10.6 µm. Examples of lasers of these wavelengths are described in WO2009 / 003976 A1, the content of which is included in the present application. Preferably, Nd:YAG lasers, with which wavelengths of 1064, 532, 355 and 266 nm can be achieved, or CO₂ lasers are used. Preferred polymer compositions

[0129] Polymer compositions containing polymers are particularly preferred. A) to 100 mass parts PA 6 or PA 66, B) 2 to 100 mass parts, preferably 5 to 60 mass parts, particularly preferably 7 to 40 mass parts, particularly preferably 8 to 20 mass parts of aluminium methylphosphonate of formula (1a) C) 5 to 120 mass fractions, preferably 7 to 80 mass fractions, particularly preferably 8 to 60 mass fractions, particularly preferably 10 to 50 mass fractions of aluminum hypophosphite, and D) 3 to 300 mass fractions, preferably 5 to 200 mass fractions, particularly preferably 15 to 120 mass fractions, particularly preferably 20 to 90 mass fractions of glass fibers.

[0130] Polymer compositions containing polymers are particularly preferred. A) to 100 mass parts PA 6 or PA 66, B) 2 to 100 mass parts, preferably 5 to 60 mass parts, particularly preferably 7 to 40 mass parts, particularly preferably 8 to 20 mass parts of aluminium methylphosphonate of formula (1a) C) 5 to 120 mass fractions, preferably 7 to 80 mass fractions, particularly preferably 8 to 60 mass fractions, particularly preferably 10 to 50 mass fractions of aluminum hypophosphite, D) 3 to 300 mass fractions, preferably 5 to 200 mass fractions, particularly preferably 15 to 120 mass fractions, particularly preferably 20 to 90 mass fractions of glass fibers, and E) 0.01 to 100 mass fractions, preferably 1 to 80 mass fractions, particularly preferably 3 to 50 mass fractions, particularly preferably 4 to 30 mass fractions of aluminum tris(diethylphosphinate). Preferred process variants

[0131] Furthermore, a preferred subject matter of the present invention is a Proceedings for the production of molding compounds according to the invention, by combining the components A) 100 mass parts PA 6 or PA 66 with B) 2 to 100 mass parts, preferably 5 to 60 mass parts, particularly preferably 7 to 40 mass parts, particularly preferably 8 to 20 mass parts of aluminium methylphosphonate of formula (1a) and C) 5 to 120 mass parts, preferably 7 to 80 mass parts, particularly preferably 8 to 60 mass parts, particularly preferably 10 to 50 mass parts of aluminum hypophosphite, as well as D) 3 to 300 mass parts, preferably 5 to 200 mass parts, particularly preferably 15 to 120 mass parts, particularly preferably 20 to 90 mass parts of glass fibers and optionally with further additives in at least one mixing unit and finally processed by injection molding. Preferably, the components are kneaded, compounded, extruded, or rolled to form a molding compound. This mixing preferably takes place at a temperature in the range of 240 to 275°C for polyamide 6 and 260 to 275°C for polyamide 66, particularly preferably by compounding on a co-rotating twin-screw extruder or Buss kneader. It may be advantageous to premix individual components.

[0132] A particularly preferred subject matter of the present invention is a Proceedings for the production of molding compounds according to the invention, wherein the components A) 100 mass parts PA 6 or PA 66 with B) 2 to 100 mass parts, preferably 5 to 60 mass parts, particularly preferably 7 to 40 mass parts, particularly preferably 8 to 20 mass parts of aluminium methylphosphonate of formula (1a) C) 5 to 120 mass fractions, preferably 7 to 80 mass fractions, particularly preferably 8 to 60 mass fractions, particularly preferably 10 to 50 mass fractions of aluminum hypophosphite, D) 3 to 300 mass fractions, preferably 5 to 200 mass fractions, particularly preferably 15 to 120 mass fractions, particularly preferably 20 to 90 mass fractions of glass fibers and with E) 0.01 to 100 mass fractions, preferably 1 to 80 mass fractions, particularly preferably 3 to 50 mass fractions, particularly preferably 4 to 30 mass fractions of aluminum tris(diethylphosphinate) and optionally with further additives in at least one mixing unit and finally processed by injection molding.

[0133] The injection molding process is characterized by the fact that the raw material, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity and injected under pressure into a temperature-controlled cavity. After the mass has cooled (solidified), the injection-molded part is demolded. One distinguishes

[0134] 1. Plasticizing / Melting 2. Injection phase (filling process) 3. Holding phase (due to thermal contraction during crystallization) 4. Demolding.

[0135] An injection molding machine consists of a clamping unit, the injection unit, the drive, and the control system. The clamping unit includes fixed and movable mounting plates for the mold, an end plate, as well as columns and the drive for the movable mold mounting plate (toggle joint or hydraulic clamping unit).

[0136] An injection unit comprises the electrically heated cylinder, the screw drive (motor, gearbox), and the hydraulics for moving the screw and injection unit. The injection unit's function is to melt, meter, inject, and compress the powder or granules (due to contraction). The problem of melt backflow within the screw (leakage) is solved by non-return valves.

[0137] In the injection mold, the flowing molten metal is dissolved, cooled, and thus the product to be manufactured is produced. This always requires two mold halves. The following functional complexes are distinguished in injection molding: Gating system, mold-forming inserts, venting, machine and force absorption, demolding system and motion transmission, temperature control

[0138] The present invention therefore also relates to products obtainable by injection molding of the compositions according to the invention. Preferred uses

[0139] A preferred aspect of the invention is also the use of polymer compositions containing A) to 100 mass fractions of PA 6 or PA 66, B) 2 to 100 mass fractions, preferably 5 to 60 mass fractions, particularly preferably 7 to 40 mass fractions, particularly preferably 8 to 20 mass fractions of at least one aluminium salt of general formula (I) wherein R represents C1-C12 alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, most preferably methyl, and C) 5 to 120 mass parts, preferably 7 to 80 mass parts, particularly preferably 8 to 60 mass parts, particularly preferably 10 to 50 mass parts of aluminum hypophosphite and D) 3 to 300 mass parts, preferably 5 to 200 mass parts, particularly preferably 15 to 120 mass parts, particularly preferably 20 to 90 mass parts of at least one filler and / or reinforcing agent for the manufacture of products for use in motor vehicles, in components for the electrical and electronics industry or in household appliances.

[0140] The use of polymer compositions containing is particularly preferred. A) to 100 mass parts PA 6 or PA 66, B) 2 to 100 mass parts, preferably 5 to 60 mass parts, particularly preferably 7 to 40 mass parts, particularly preferably 8 to 20 mass parts of aluminium methylphosphonate of formula (1a) C) 5 to 120 mass fractions, preferably 7 to 80 mass fractions, particularly preferably 8 to 60 mass fractions, particularly preferably 10 to 50 mass fractions of aluminum hypophosphite, D) 3 to 300 mass fractions, preferably 5 to 200 mass fractions, particularly preferably 15 to 120 mass fractions, particularly preferably 20 to 90 mass fractions of glass fibers and E) 0.01 to 100 mass fractions, preferably 1 to 80 mass fractions, particularly preferably 3 to 50 mass fractions, particularly preferably 4 to 30 mass fractions of aluminum tris(diethylphosphinate) for the manufacture of products for use in motor vehicles, in components for the electrical and electronics industry or in household appliances.

[0141] The present invention also relates to the use from 2 to 100 mass fractions, preferably 5 to 60 mass fractions, particularly preferably 7 to 40 mass fractions, particularly preferably 8 to 20 mass fractions of aluminium methylphosphonate of formula (1a) and 5 to 120 mass fractions, preferably 7 to 80 mass fractions, particularly preferably 8 to 60 mass fractions, particularly preferably 10 to 50 mass fractions of aluminum hypophosphite, as well as 3 to 300 mass fractions, preferably 5 to 200 mass fractions, particularly preferably 15 to 120 mass fractions, particularly preferably 20 to 90 mass fractions of glass fibers, each based on 100 mass fractions of PA 6 or PA 66, for the production laser-transparent compositions or products, preferably with a GWIT at a wall thickness of at least 800 °C at 0.75 mm.

[0142] Particularly preferred is the use of 2 to 100 mass fractions, preferably 5 to 60 mass fractions, particularly preferably 7 to 40 mass fractions, particularly preferably 8 to 20 mass fractions of aluminium methylphosphonate of formula (1a) and 5 to 120 mass parts, preferably 7 to 80 mass parts, particularly preferably 8 to 60 mass parts, particularly preferably 10 to 50 mass parts of aluminum hypophosphite, as well as 3 to 300 mass parts, preferably 5 to 200 mass parts, particularly preferably 15 to 120 mass parts, particularly preferably 20 to 90 mass parts of glass fibers and 0.01 to 100 mass parts, preferably 1 to 80 mass parts, particularly preferably 3 to 50 mass parts, particularly preferably 4 to 30 mass parts of aluminum tris(diethylphosphinate), for the production laser-transparent compositions or products, preferably with a GWIT at a wall thickness of at least 800 °C. Examples

[0143] To demonstrate the improvements in properties described according to the invention, corresponding polyamide 6-based polymer compositions were first prepared by compounding. The individual components according to Table I were mixed in a twin-screw extruder (ZSK 25 Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany)) at temperatures in the range of 240 to 275°C, extruded as a strand, cooled until granulation was possible, and granulated. During this process, the glass fibers were added to the rear (near the nozzle) section of the extruder using a side extruder. After drying (generally two days at 80°C in a vacuum drying oven), the granules were injection molded at temperatures in the range of 250 to 260°C to form standard test specimens for the respective tests. The standard test specimens were injection molded on an Arburg 320-210-500 injection molding machine. Process for the production of the aluminium methylphosphonate used as component B).

[0144]

[0145] A reaction vessel was charged with 83 g of methylphosphonic acid and heated to 120°C. An intermediate prepared from 50 g of methylphosphonic acid and 35.4 g of aluminum tris(isopropoxide) was added to the reaction vessel in the presence of water. The resulting solution, containing an intermediate of methylphosphonic acid and aluminum methylphosphonate in a molar ratio of 5:1, was heated to 240°C with mechanical stirring. Stirring was continued at 240°C for approximately 30 minutes until a solid formed. Subsequently, 500 ml of water were added, and this mixture was stirred for 16 h, during which time a uniform slurry was formed. The product was then filtered, washed with 750 ml, and dried. The result was 64.3 g of the product of formula (1a), to be used as component B), as fine, colorless crystals in a yield of 93%.

[0146] The Glow wire resistanceThe glow wire ignition temperature (GWIT) was determined according to DIN EN 60695-2-13. The GWIT test specifies the glow wire ignition temperature that is 25 K (or 30 K for temperatures in the range of 900°C to 960°C) higher than the maximum glow wire temperature that does not ignite in three consecutive tests, even during the exposure time of the glow wire. Ignition is defined as a flame with a burning time of ≥ 5 seconds. Round plates with a diameter of 80 mm and a thickness of 0.75 mm were used for the tests.

[0147] The Laser transparency The samples examined within the scope of the present invention were examined in accordance with the DVS Guideline 2243 (01 / 2014) "Laser beam welding of thermoplastic materials"Measurements were taken using round plates with a diameter of 80 mm and a thickness of 0.75 mm in the near-infrared (NIR) range with the LPKF TMG3 transmission meter from LPKF Laser & Electronics AG, Garbsen, Germany, which had previously been calibrated with a measurement standard produced according to DIN EN ISO / IEC 17025, at a laser wavelength of 980 nm; see: LPKF AG 101016-DE: "Simple transmission measurement for plastics LPKF TMG3".

[0148] The Flame retardancy The test specimen, measuring 125 mm • 13 mm • 0.75 mm, was tested according to the UL94V method. ( Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pp. 14 - 18 Northbrook 1998 ) certainly.

[0149] The Impact resistance According to ISO180-A, the following was obtained after IZOD on test specimens with dimensions of 80 mm • 10 mm • 4 mm. Starting materials:

[0150] Component A): Polyamide 6 (Durethan® < B24, Lanxess Deutschland GmbH, Cologne, Germany) with a viscosity number of 105 ml / g measured according to ISO 307 in a 0.5 wt% solution in 96 wt% sulfuric acid at 25°C, Component B): Aluminium methylphosphonate of formula (1a) Component C): Aluminum hypophosphite, [CAS No. 7784-22-7] (Phoslite IP-A, from Italmatch, Genova, Italy), Component D): Cut glass fiber CS 7997D from Lanxess Deutschland GmbH, Cologne, Germany [average fiber diameter 10 µm, average fiber length 4.5 mm, E-glass], Component E / 1): Aluminium tris(diethylphosphinate), [CAS No. 225789-38-8] (Exolit ®< OP1230 of Clariant SE, Muttenz, Switzerland), Table I Starting materials Example 1 Example 2 Component A / 1 [Mass fraction] 100 100 Component B / 1 [Mass fraction] 18,1 18,1 Component C / 1 [Mass fraction] 38,4 27,1 Component D / 1 [Mass fraction] 67,7 67,7 Component E / 1 [Mass fraction] 11,3 UL94 at 0.75mm [Class] V0 V0 GWIT at 0.75mm [°C] ≥ 800 ≥ 800 IZOD kJ / m²< ] ≥ 45 LPKF laser transmission [%] ≥ 45 ≥ 45

[0151] Component details in Table I in mass fractions based on 100 mass fractions of component A1

[0152] Table I shows that the inventive example 1 achieves both a very high GWIT of at least 800°C and a V0 classification in the UL94 test at wall thicknesses or test specimen thicknesses of 0.75mm.

[0153] In addition, it offers excellent laser transparency of at least 45% and good impact strength of at least 45 kJ / m 2< as determined according to DIN EN ISO 180.

Claims

1. Polymer compositions containing A) per 100 parts by mass of polyamide 6 or polyamide 66, B) 2 to 100 parts by mass of at least one aluminium salt of general formula (I) wherein R represents C1-C12-alkyl, C) 5 to 120 parts by mass of aluminium hypophosphite and D) 3 to 300 parts by mass of at least one filler and / or reinforcer.

2. Polymer compositions according to Claim 1, characterized in that R in formula (I) represents methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl.

3. Polymer compositions according to Claim 1, characterized in that R in formula (I) represents ethyl or methyl.

4. Polymer compositions according to Claim 1, characterized in that R in formula (I) represents methyl.

5. Polymer compositions according to one or more of Claims 1 to 4, characterized in that the component D) employed is at least one filler and / or reinforcer from glass, preferably according to DIN1259-1, particularly preferably solid or hollow glass spheres, glass fibres, ground glass or aluminium borosilicate glass having an alkali metal content of 1% (E-glass) [CAS No. 65997-17-3].

6. Polymer compositions according to one or more of Claims 1 to 4, characterized in that the component D) employed is glass fibres.

7. Polymer compositions according to Claim 6, characterized in that the glass fibres are employed with a size system or a silane-based adhesion promoter.

8. Polymer compositions according to Claim 7, characterized in that the glass fibres are treated with a silane compound of general formula (II)         (X-(CH2)q)k-Si-(O-CrH2r+1)4-k     (II) wherein X represents NH2-, carboxyl, HO or q in formula (II) represents an integer from 2 to 10, preferably 3 to 4, r in formula (II) represents an integer from 1 to 5, preferably 1 to 2, and k in formula (II) represents an integer from 1 to 3, preferably 1.

9. Polymer compositions according to Claim 8, characterized in that the glass fibres are treated with an adhesion promoter from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes containing a glycidyl or a carboxyl group as substituent X in formula (II).

10. Products, especially products for electromobility, for household appliances and in the field of electronics and electricals, based on polymer compositions according to one or more of Claims 1 to 9.

11. Process for producing products, characterized in that it comprises mixing or blending the component A) 100 parts by mass of polyamide 6 or polyamide 66 with B) 2 to 100 parts by mass of at least one aluminium salt of general formula (I) wherein R represents C1-C12-alkyl, and C) 5 to 120 parts by mass of aluminium hypophosphite with D) 3 to 300 parts by mass of at least one filler and / or reinforcer and optionally with further additives in at least one mixing unit and finally subjecting the mixture to injection moulding.

12. Use of 2 to 100 parts by mass of at least one aluminium salt of general formula (I) wherein R represents C1-C12-alkyl, and 5 to 120 parts by mass of aluminium hypophosphite in each case based on 100 parts by mass of polyamide 6 or polyamide 66 which is reinforced with 3 to 300 parts by mass of at least one filler and / or reinforcer for production of laser-transparent compositions or products.

13. Use according to Claim 12, characterized in that the laser-transparent compositions or products also have a GWIT at 0.75 mm wall thicknesses of at least 800°C.