Creep-resistant polyester composition

Abstract

The present invention relates to the use of an aluminum salt of an organophosphorus compound according to formula (I), (I) to achieve a CTI A of 600 according to IEC 60112-2010 in polyester-based products, as well as to flame-retardant and creep-resistant polyester-based compositions and articles producible therefrom based on at least one aluminum salt of an organophosphorus compound of general formula (I) and at least one organophosphinate and / or at least one diphosphinate, and to a process for the preparation thereof.

Description

[Technical field]

[0001] The present invention relates to an aluminum salt of an organophosphorus compound of formula (I) for achieving a CTI A of 600 according to IEC 60112-2010 in or for a polyester-based product.

[0002] [ka]

[0003] and flame-retardant and tracking-resistant polyester-based compositions and products producible therefrom, as well as processes for their production, based on at least one polyester comprising at least one aluminum salt of an organophosphorus compound of general formula (I) and at least one organophosphinic acid salt and / or at least one diphosphinic acid salt. [Background technology]

[0004] Polyesters, preferably polyalkylene terephthalates or polycycloalkylene terephthalates, in particular polybutylene terephthalates (PBT), are important materials for use, for example, in automobiles, in electrical and electronics industrial parts or in household appliances, because they have good mechanical stability, low water absorption and good processability. Particularly noteworthy are, among other things, the electrical insulating properties, which, unlike, for example, polyamides, are largely preserved even at high operating temperatures and in the presence of moisture, as is particularly relevant for applications in fast-charging electric vehicles. Thus, in applications of polyesters near current-conducting parts, flame-retardant materials are often employed to counter the risk of fire caused by overheated conductors or contacts. Good self-extinguishing characteristics, in particular UL94 V-0 classification according to Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pages 14-18, Northbrook, 1998, are especially required.

[0005] In addition to the current ever-increasing demand for the use of halogen-free flame retardants for environmental reasons, features required for industrial adoption include high impact toughness combined with strength and stiffness in polyester-based products, relatively low density and relatively high tracking resistance according to IEC 60112-2010.

[0006] The demand for maximum design freedom and therefore even greater complexity of the geometrical shape of the components, together with the cost-effective need for mass production processes that are easy to automate and can be easily integrated, also requires materials that can ideally be joined together by laser transmission welding [https: / / de.wikipedia.org / wiki / Laserdurchstrahlschwei%C3%9Fen]. For the laser-transparent joined partners, high laser transmission at the laser wavelength employed is required. This is a major challenge, especially for products based on flame-retardant polyesters, because the flame retardants scatter or even absorb the laser light, as is the case for example with some nitrogen-containing flame retardant synergists, and also with antimony trioxide, which is commonly used as a synergist in particular with halogen-containing flame retardants.

[0007] Prior Art WO2021 / 076169A1 discloses in Table 4 a polymer composition comprising polybutylene terephthalate, glass, aluminum methylphosphonate and melam.

[0008] DE 102017215776 A1 teaches in example 4 a composition comprising 50% by weight of polybutylene terephthalate, 30% by weight of glass fibres and 20% by weight of the flame retardant combination FM4, which is composed of an aluminium salt of diethylphosphinic acid comprising 10 mol % aluminium ethylbutylphosphinate and 5 mol % aluminium ethylphosphonate produced by the method according to US 7,420,007 B2.

[0009] WO2012 / 139990A1 discloses a reinforced thermoplastic molding material based on polyalkylene terephthalate that is tracking-resistant and flame-retardant, which, in addition to a flame retardant consisting of a nitrogen-containing or phosphorus-containing compound, also contains a polyolefin from the group of polyethylene, polypropylene and polypropylene copolymers.While these are characterized by high tracking resistance, the use of polyolefin as an additional polymer runs the risk of reducing the advantages typical of polyalkylene terephthalate, in particular the high surface tension and high color stability under thermal stress, because the use of polyolefin, especially polyethylene, in particular in polyalkylene terephthalate formulations also increases the risk of residues in the injection mold.

[0010] EP3067388A1 discloses flame-retardant polyester-based molding materials containing aluminum tris(diethylphosphinate) and melamine cyanurate, where an improvement in tracking resistance was achieved by adding barium sulfate. However, the addition of solids that are not meltable under injection molding conditions, such as barium sulfate, leads to a deterioration of the mechanical properties and also to a reduction in the laser transmittance, which is undesirable, for example, especially in applications for laser transmission welding. Moreover, in the case of PBT, only EP3067388A1 was able to achieve a V-1 classification according to UL94. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] WO2021 / 076169A1 [Patent Document 2] DE102017215776A1 [Patent Document 3] US7,420,007B2 [Patent Document 4] WO2012 / 139990A1 [Patent Document 5] EP3067388A1 [Patent Document 6] WO2020 / 132075A1

Patent document 7

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Patent document 16

Non-licensed literature

[0012] [Non-licensed document 1] Underwriters Laboratories Inc.Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pages 14~18, Northbrook, 1998 [Non-licensed document 2] Kunststoff-Handbuch, volume VIII, pages 695~743, Karl Hanser Verlag, Munich 1973 [Non-licensed document 3] Chemie Ingenieur Technik (volume 72) pages 273~276, 3 / 2000, Wiley-VCH Verlags GmbH, Weinheim, 2000

Non-licensed Document 4

[0013] Starting from the prior art, it is the object of the present invention to provide a flame-retardant, tracking-resistant and glass fiber-reinforced polyester-based thermoplastic molding material for achieving good mechanical properties while achieving a V-0 classification according to UL94 at wall thicknesses of more than 0.8 mm without the use of polyolefins and barium sulfate, preferably without the use of nitrogen-containing, especially melamine-based synergists. According to the present invention, high tracking resistance is understood to mean achieving a CTI A of 600 according to IEC 60112-2010. This improved tracking resistance should ideally not have a negative effect on the laser transmission and thus should not prevent or make impossible the use in laser transmission welding. In the context of the present invention, good mechanical properties mean, in particular, high values ​​in the Izod impact strength, which can be determined according to DIN EN ISO 180. [Means for solving the problem]

[0014] Surprisingly, the phosphorus-containing aluminum salt of the general formula (I)

[0015] [ka]

[0016] (Wherein, R is C1-C 12 - represents alkyl) It has now been found that, in polyester-based products and in reinforced polyester-based compositions, together with at least one organometallic phosphinate or diphosphinate, they achieve a CTI A of 600 according to IEC 60112-2010, and that the products producible therefrom achieve the complex objectives of the invention in terms of flame retardancy, mechanical properties and in particular also laser transparency, when the mass fraction of the aluminium salt of general formula (I) is less than the mass fraction of the organometallic phosphinate or diphosphinate that can be employed.

[0017] Surprisingly, it was also found that the phosphorus-containing aluminum salt of general formula (I) allowed the test to be carried out, deviating from the IEC 60112-2010 standard, not with 50 drops on each of five test specimens (250 drops), but rather in a more severe manner, with 100 drops on each of three test specimens (300 drops in total), and that the average number of drops until failure of the material due to a tracking current >0.5 A or ignition and subsequent continuous flame on the polyester-based test specimens was significantly higher than the average number for the comparative example not containing the phosphorus-containing aluminum salt of general formula (I).

[0018] Izod impact strength The Izod impact strength according to DIN EN ISO 180, which is used in the context of the present invention to obtain the mechanical parameters, can be used not only for rigid thermoplastic injection- and extrusion-molded materials, thermosetting materials and thermotropic liquid crystal polymers, but also for filled and reinforced materials. Breakage E of unnotched test specimens C The impact energy absorbed during the impact is given by the following equation:

[0019]

number

[0020] (where a / u = impact strength, h = thickness and b = width) is related to the original cross-sectional area of ​​the test specimen according to

[0021] The test specimens which can be used here can be produced according to the corresponding molding compound standards or by pressing and injection moulding, or can be taken from the multipurpose test specimen (DIN EN ISO 527[2]). The dimensions of the unnotched test specimens which are used in the context of the present invention according to DIN EN ISO 3167, type A, are length l=(80±2) mm; width b=(10.0±0.2) mm; thickness h=(4.0±0.2) mm. https: / / wiki.polymerservice-merseburg.de / index.php / Schlagbiegeversuch

[0022] Laser Transmittance According to the invention, high laser transmission is understood to mean a transmission of at least 8%, preferably at least 9%, when measured on a plate having a thickness of 1.5 mm at a laser wavelength of 980 nm using an LPKF TMG3 transmission measuring device available from LPKF Laser & Electronics AG, Garbsen, Germany. The transmission measuring device LPKF TMG3 is an approved, traceable calibrated measuring device. Its performance has been demonstrated in the context of a statistical measurement system analysis (MSA). The device further corresponds to the specifications of the automotive standard IATF 16949 and thus directly meets the requirements for standard-compliant quality assurance. The measurements in connection with the present invention are carried out in accordance with DVS guideline 2243 (01 / 2014) "Laserstrahlschweissen thermoplastischer Kunststoffe (Laser beam welding of thermoplastics)" using test specimens having the dimensions 125 mm x 13 mm x 1.5 mm in the near infrared (NIR) range. Prior to the measurement, a transmission measuring device LPKF TMG3 available from LPKF Laser & Electronics AG is calibrated with a measurement standard drawn up in accordance with DIN EN ISO / IEC 17025. In the context of the present invention, the measurement is carried out at a laser wavelength of 980 nm.

[0023] Tracking resistance According to https: / / de.wikipedia.org / wiki / Kriechstromfestigkeit, tracking resistance describes the dielectric strength (tracking path) of the surface of an insulating material, especially upon exposure to moisture and pollutants. It defines the maximum tracking current that can occur in a defined test configuration (electrode distance, electrode shape) under standardized test conditions (defined voltage, conductive layer material). Tracking resistance is reported in CTI values ​​(Comparative Tracking Index). The CTI value indicates the highest voltage in volts (V) at which the investigated material does not show any tracking when 50 drops of a standardized electrolyte solution (A or B, hence KA or KB value) are applied. The measurements are performed on the surface, dropping small drops between two platinum electrodes every 30 ± 5 seconds. The failure criterion is a tracking current > 0.5 A or ignition of the component. Details on how to measure the CTI value are specified in IEC 60112.

[0024] The polyester-based composition according to the invention should also ultimately exhibit a V-0 classification, determinable by method UL94V (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pages 14 to 18, Northbrook, 1998) as regards the UL94 V-0 classification specified in WO2021 / 076169A1, at a maximum thickness of 0.8 mm, or at least show no substantial decrease compared to the prior art.

[0025] In the context of the present invention, "alkyl" shall be understood to mean a linear or branched saturated hydrocarbon group. In some embodiments, an alkyl group having 1 to 6 carbon atoms is employed. This may be referred to as a "lower alkyl group". Preferred alkyl groups are methyl (Me), ethyl (Et), propyl, especially n-propyl and isopropyl, butyl, especially n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl groups, especially n-pentyl, isopentyl, neo-pentyl and hexyl groups, etc. The term polyakylene is defined similarly.

[0026] For clarity, it should be noted that the scope of the present invention includes all the specified definitions and parameters stated as generalized or preferred ranges in any desired combination. This particularly relates to the mass fractions specified for the compositions according to the present invention, the uses described according to the present invention and the methods described according to the present invention. The specifications described within the scope of this application refer to the version applicable at the filing date of the present invention. An aryl group (abbreviated Ar) is an organic chemical group that has an aromatic basic structure. Thus, aryl is a general description for a monovalent group of atoms derived from an aromatic hydrocarbon by removing a hydrogen atom attached to the ring. Most aryl groups are derived from benzene (C6H6), and the simplest aryl group is the phenyl group (Ph), (-C6H5). Aryl groups can occur either as molecular fragments or as unstable free radicals.

[0027] Subject of the Invention The present invention relates to aluminium salts of general formula (I) for achieving a CTI A of 600 according to IEC 60112-2010 in or for polyester-based products, preferably for or for polyalkylene terephthalate- or polycycloalkylene terephthalate-based products, in particular for or for polybutylene terephthalate (PBT), polyethylene terephthalate (PET) or poly-1,4-cyclohexanedimethanol terephthalate-based products.

[0028] [ka]

[0029] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl For clarity, it should be noted that for polybutylene terephthalate (PBT), polyethylene terephthalate (PET) or poly-1,4-cyclohexanedimethanol terephthalate based products is synonymous with in polybutylene terephthalate (PBT), polyethylene terephthalate (PET) or poly-1,4-cyclohexanedimethanol terephthalate based products.

[0030] First, the present invention provides A) for 100 parts by mass of polyalkylene terephthalate or polycycloalkylene terephthalate, B) 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass of at least one aluminum salt of the general formula (I)

[0031] [ka]

[0032] (Wherein, R is C1-C 12 -alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl and very particularly preferably methyl, and C) 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass, and particularly preferably 10 to 50 parts by mass of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof,

[0033] [ka]

[0034] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and D) 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 10 to 120 parts by mass, and particularly preferably 15 to 90 parts by mass of at least one glass-based filler and / or reinforcing agent Including, However, this relates to a composition in which component B) is present in a lower mass fraction than component C).

[0035] The invention also provides products based on the compositions according to the invention, in particular products for electromobility, products for household appliances and products in the electronics and electrical sectors.

[0036] The preparation of polyalkylene terephthalate or polycycloalkene terephthalate-based compositions, in particular PBT, PET or poly-1,4-cyclohexanedimethanol terephthalate-based compositions for use in electromobility products, in household appliances and in products of the electronics and electrical sectors, is carried out by mixing components A), B), C) and D) which can be used as starting materials in at least one mixing device in the above-mentioned mass fraction ratios. This mixing produces molding materials based on the composition according to the invention as intermediate products. These molding materials can consist exclusively of components A), B), C) and D) or can further comprise at least one further component E). If a laser-transparent composition is provided, the further component E) is selected so that laser-absorbing additives are avoided.

[0037] The present invention relates to a process for producing products, preferably products for electromobility, for household appliances and products in the electronics and electrical sectors, comprising reacting 100 parts by weight of component A) with a polyalkylene terephthalate or polycycloalkene terephthalate, in particular with polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, B) 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass of at least one aluminum salt of the general formula (I)

[0038] [ka]

[0039] (Wherein, R is C1-C 12 -alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl and very particularly preferably methyl, and C) 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass, and particularly preferably 10 to 50 parts by mass of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof,

[0040] [ka]

[0041] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can simultaneously assume only integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; D) 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 10 to 120 parts by mass, particularly preferably 15 to 90 parts by mass of at least one glass-based filler and / or reinforcing agent; The method further comprises the steps of mixing or blending in at least one mixing device, optionally with further additives, and finally processing the resulting mixture by injection molding, with the proviso that component B) is employed in a lower mass fraction than component C).

[0042] The components are preferably kneaded, compounded, extruded or rolled into a molding material. The mixing is preferably carried out at temperatures in the range of 230° C. to 300° C., particularly preferably by compounding in a co-rotating twin-screw extruder or a Buss kneader. It may be advantageous to premix the individual components.

[0043] The injection molding process is characterized in that the raw material, preferably in pellet form, is melted (plasticized) in a heated cylindrical cavity as the injection molding material is injected under pressure into the temperature-controlled cavity. After the material cools (solidifies), the injection molded part is demolded.

[0044] A distinction is made between the following: 1.Plastification / Melting 2. Injection stage (filling operation) 3. Pressure holding stage (due to thermal contraction during crystallization) 4. Release

[0045] The injection molding equipment consists of a clamping unit, an injection unit, a drive means, and a controller. The clamping unit includes fixed and movable clamping plates, end plates and tie bars for the mold, and a drive means (toggle joint or hydraulic clamping unit) for the movable mold clamping plates.

[0046] The injection unit includes an electrically heatable barrel, a drive for the screw (motor, transmission) and hydraulics to move the screw and the injection unit. The task of the injection unit is to melt, meter, inject and apply holding pressure (by shrinkage) to the powder / pellet material. The problem of backflow of the melt in the screw (leakage flow) is solved by a backflow barrier.

[0047] In the injection mould, the incoming melt is then separated and cooled and the product to be produced is thus produced. Two mould halves are always required for this purpose. In injection moulding the following functional complexes are distinguished: - Runner System - Molded inserts - Ventilation - Mounting machine and force absorption - Release system and motion transmission - Temperature control

[0048] The present invention therefore also relates to products obtainable by injection molding of the compositions according to the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] In a further preferred embodiment, the present invention further relates to a composition and to a product based on this composition which comprises not only components A) to D) but also at least one further additive of component E), which is different from components B), C) and D), preferably in an amount of 0.01 to 100 parts by weight, particularly preferably in an amount of 0.05 to 50 parts by weight and very particularly preferably in an amount of 0.1 to 30 parts by weight, based on 100 parts by weight of component A), with the proviso that laser-absorbing additives are avoided if retention of laser transparency is required.

[0050] Component A) The polyalkylene terephthalates or polycycloalkylene terephthalates that can be used as component A) according to the present invention can be produced in various processes and synthesized from various units, and in certain use cases, can be made into materials with a specially adjusted combination of properties, either alone or in combination with processing aids, stabilizers, polymeric alloy partners (e.g. elastomers) or reinforcing materials (e.g. mineral fillers or glass fibers) and optionally further additives. Blends with some proportions of other polymers are also suitable, in which case one or more compatibilizers can be optionally employed. The properties of the polymer can be improved by the addition of elastomers, if required.

[0051] Preferred polyalkylene terephthalates or polycycloalkylene terephthalates can be prepared by known methods from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms (Kunststoff-Handbuch, Vol. VIII, pp. 695-743, Karl Hanser Verlag, Munich 1973).

[0052] Preferred polyalkylene terephthalates or polycycloalkylene terephthalates contain, based on the dicarboxylic acid, at least 80 mol %, preferably at least 90 mol %, of terephthalic acid groups and, based on the diol component, at least 80 mol %, preferably at least 90 mol %, of 1,4-cyclohexanedimethanol and / or ethylene glycol and / or propane-1,3-diol (in the case of polypropylene terephthalate) and / or butane-1,4-diol groups.

[0053] Preferred polyalkylene terephthalates or polycycloalkylene terephthalates may contain not only terephthalic acid groups, but also up to 20 mol % of other aromatic dicarboxylic acid groups having 8 to 14 carbon atoms or aliphatic dicarboxylic acid groups having 4 to 12 carbon atoms, in particular phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid groups.

[0054] Preferred polyalkylene terephthalates or polycycloalkylene terephthalates are 1,4-cyclohexanedimethanol / ethylene glycol / propane-1,3-diol / butane-1,4-diol, but also up to 20 mol % of other aliphatic diols having 3 to 12 carbon atoms, or up to 20 mol % of cycloaliphatic diols having 6 to 21 carbon atoms, preferably propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-2,4-diol, 2-methylpent ... 2-ethylpropane-1,3-diol, 2-ethylpropane-1,3-diol, 2-ethylpropane-1,3-diol, 2-ethylpropane-1,3-diol, 2-ethylpropane-1,3-diol, 2- The groups may also include hexane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2,2,4-trimethylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di(β-hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis(3-β-hydroxyethoxyphenyl)propane and 2,2-bis(4-hydroxypropoxyphenyl)propane.

[0055] Particularly preferred are polyalkylene terephthalates or polycycloalkylene terephthalates which are produced exclusively from terephthalic acid and its reactive derivatives, especially its dialkyl esters, and 1,4-cyclohexanedimethanol and / or ethylene glycol and / or propane-1,3-diol and / or butane-1,4-diol, particularly preferred are poly-1,4-cyclohexanedimethanol terephthalate, polyethylene terephthalate and polybutylene terephthalate, and mixtures thereof.

[0056] Preferred polyalkylene terephthalates or polycycloalkylene terephthalates also include copolyesters made from at least two of the abovementioned acid components and / or at least two of the abovementioned alcohol components. A particularly preferred copolyester is poly(ethylene glycol / butane-1,4-diol) terephthalate.

[0057] The polyalkylene terephthalate or polycycloalkylene terephthalate has a viscosity of 30 to 150 cm when measured in phenol / o-dichlorobenzene (1:1 parts by mass) at 25°C. 3 / g, preferably 40 to 130 cm 3 / g, particularly preferably 50 to 100 cm 3 / g. The intrinsic viscosity IV, also known as the Staudinger index or intrinsic viscosity, is proportional to the average molecular mass according to the Marchouinck equation and is an extrapolation of the viscosity number VN when the polymer concentration is taken to be zero. It can be predicted by a series of measurements or through the use of suitable approximations (e.g. Billmeyer). VN [ml / g] is obtained from the measurement of the solution viscosity in a capillary viscometer, e.g. the Ubbelohde viscometer. The solution viscosity is a measure of the average molecular weight of the plastic. The determination is made on the dissolved polymer, employing different solvents (formic acid, m-cresol, tetrachloroethane, phenol, 1,2-dichlorobenzene, etc.) and concentrations. The viscosity number VN allows the control of the processing and use properties of the plastic. Thermal stresses, ageing processes or the influence of chemicals, weather and light on the polymer can be investigated through comparative measurements. This process is standardized for general-purpose plastics and, in the context of the present invention, by DIN ISO 1628-5 for polyesters. See also http: / / de.wikipedia.org / wiki / Viskosimetrie and http: / / de.wikipedia.org / wiki / Mark-Houwink-Gleichung.

[0058] According to the invention, the polyalkylene terephthalates or polycycloalkylene terephthalates employable as component A) can also be employed in mixtures with other polyesters and / or further polymers.

[0059] The polyalkylene terephthalates or polycycloalkylene terephthalates that can be employed as component A) can be blended with customary additives, especially release agents, in the melt during compounding, where the skilled person understands that "compounding" means the plastics industry term synonymous with plastics processing and refers to the final processing process for plastics by blending additive substances (fillers, additives, etc.) for specific optimization of the property profile. Compounding is preferably carried out in an extruder, particularly preferably a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, a planetary multi-screw extruder or a co-compounder, and includes the process operations of conveying, melting, dispersing, mixing, degassing and pressure build-up.

[0060] It is preferred if the polyester which can be employed as component A) is a polyalkylene terephthalate or a polycycloalkylene terephthalate, particularly preferably polyethylene terephthalate (PET) [CAS number 25038-59-9] or polybutylene terephthalate [CAS number 24968-12-5], especially polybutylene terephthalate (PBT).

[0061] Alternatively, polyesters which can be employed as component A) are polycycloalkylene terephthalates, in particular poly-1,4-cyclohexanedimethanol terephthalate [CAS number 25037-99-4].

[0062] Component B) As components B) which can be employed according to the invention, aluminum salts of the general formula (I)

[0063] [ka]

[0064] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl It is preferable to adopt the following.

[0065] These aluminum salts of organophosphorus compounds of general formula (I) which can be employed as component B) can be produced by different processes and can be synthesized from different units. In the context of the present invention, the production of compound (Ia) (wherein R=methyl) which can be preferably employed according to the present invention employs the following process:

[0066] [ka]

[0067] A reaction vessel is charged with 83 g of methylphosphonic acid and heated to 120° C. An intermediate product made 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 methylphosphonic acid and aluminum methylphosphonate as intermediate products in a molar ratio of 5:1 is heated to 240° C. with mechanical stirring. Stirring is continued at 240° C. for about 30 minutes until a solid is formed. Then, 500 ml of water is added and the resulting mixture is stirred for 16 hours to form a homogeneous slurry. The product is finally separated by filtration, washed with 750 ml of water, and dried. This results in 64.3 g of product of formula (Ia), most preferably product of formula (Ia) that can be employed as component B), as fine colorless crystals with a yield of 93%. Empirical formula (Ia) represents the monomer repeat unit (i.e., coordination unit) of the coordination polymer present in crystalline form.

[0068] Further processes, particularly for R≠methyl, can be derived from WO2020 / 132075A1, the contents of which are hereby incorporated in their entirety into the present invention.

[0069] Particularly preferred is component B) according to formula (Ia) in which the molar ratio of phosphorus to aluminum, determinable by ICP-OES elemental analysis, is 4:1, and needle-shaped crystals are particularly preferred. In this regard, see Example 1 of WO2021 / 076169A1. For ICP-OES, see: https: / / www.itmc.rwth-aachen.de / go / id / gden

[0070] Component C) As component C), the composition according to the invention comprises at least one phosphinic acid salt of formula (II)

[0071] [ka]

[0072] and / or at least one diphosphinic acid salt of formula (III)

[0073] [ka]

[0074] and / or polymers thereof. In the context of the present invention, the phosphinic acid salts of formula (II) and the diphosphinic acid salts of formula (III) are also called phosphinic acid salts.

[0075] M in formula (II) or (III) preferably represents aluminum or zinc. 1 , R 2 are the same or different and denote linear or branched C-C-alkyl and / or phenyl. 1 , R 2 are identical or different and denote methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

[0076] In formula (III), R 3It is preferred that R represents 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, phenylethylene, phenylpropylene or phenylbutylene. 3 Particularly preferred is when represents phenylene or naphthylene.Suitable phosphinates are described in WO-A97 / 39053, the contents of which regarding phosphinates are hereby incorporated into the present application.In the context of the present invention, particularly preferred phosphinates are the aluminum and zinc salts of dimethylphosphinate, ethylmethylphosphinate, diethylphosphinate and methyl-n-propylphosphinate, and mixtures thereof.

[0077] In formula (II), m preferably represents 2 and 3, particularly preferably 3.

[0078] In formula (III), n preferably represents 1 and 3, particularly preferably 3.

[0079] In formula (III), x preferably represents 1 and 2, particularly preferably 2.

[0080] Very particularly preferably employed as component C) is aluminum tris(diethylphosphinate) [CAS number 225789-38-8], which is available, for example, under the trade names Exolit® OP1230 or Exolit® OP1240 from Clariant International Ltd., Muttenz, Switzerland.

[0081] According to the invention, component B) is employed in a lower mass fraction than component C).

[0082] Component D) The polymer composition according to the invention comprises as component D) at least one glass-based filler and / or reinforcing agent. It is also possible to employ mixtures of two or more different glass-based fillers and / or reinforcing agents.

[0083] Glasses according to DIN 1259-1 are preferably used as component D). It is very particularly preferable to use glass as solid or hollow glass spheres, glass fibers, crushed glass or aluminum borosilicate glass (E glass) with an alkali metal content of 1% [CAS number 65997-17-3].

[0084] Concerning the glass fibres which can preferably be employed according to the invention, the skilled person distinguishes according to "http: / / de.wikipedia.org / wiki / Faser-Kunststoff-Verbund" between chopped fibres, also called short fibres, having a length in the range of 0.1-1 mm, long fibres, having a length in the range of 1-50 mm and continuous fibres, having a length L>50 mm. Short fibres are preferably employed in injection moulding and are suitable for direct processing with an extruder. Long fibres can likewise be further processed in an extruder. Continuous fibres are used as rovings or fabrics in fibre-reinforced plastics. Products containing continuous fibres achieve the highest stiffness and strength values. Furthermore, crushed glass fibres are provided, the length of which after crushing is usually in the range of 70-200 μm.

[0085] The glass fibers, particularly preferably the glass fibers which can be employed according to the invention as component D), are chopped long glass fibers having an average initial length in the range from 1 to 50 mm, particularly preferably in the range from 1 to 10 mm and very particularly preferably in the range from 2 to 7 mm, the initial length referring to the length before any processing, in particular the length in the compounder.

[0086] Preferred glass fibers that can be employed as component D) have an average fiber diameter in the range of 7 to 18 μm, particularly preferably in the range of 9 to 15 μm. A possible process for determining the fiber diameter that can be employed is scanning electron microscopy (SEM) (https: / / de.wikipedia.org / wiki / Rasterelektronenmikroskop).

[0087] In a preferred embodiment, the glass fibres which can preferably be employed as component D) are treated with a suitable size system or adhesion promoter / adhesion promoter system. It is preferred to employ a silane-based size system / adhesion promoter. Particularly preferred silane-based adhesion promoters for the treatment of glass fibres which can preferably be employed as component D) are silane compounds of the general formula (IV) (X-(CH2) q ) k -Si-(O-CrH 2r+1 ) 4-k (IV) (In the formula, X is NH2, carboxyl, HO, or

[0088] [ka]

[0089] represents In formula (IV), q represents an integer of 2 to 10, preferably 3 to 4. In formula (IV), r represents an integer of 1 to 5, preferably 1 to 2; In formula (IV), k represents an integer of 1 to 3, preferably 1.

[0090] Particularly preferred adhesion promoters are silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group or a carboxyl group as the substituent X in formula (IV), in which the carboxyl group is very particularly preferred.

[0091] The treatment of glass fibers which can preferably be employed as component D) comprises employing an adhesion promoter, preferably a silane compound of the formula (IV), preferably in an amount of 0.05% to 2% by weight, particularly preferably in an amount of 0.25% to 1.5% by weight and very particularly preferably in an amount of 0.5% to 1% by weight, based in each case on 100% by weight of component D).

[0092] The glass fibers preferably employable as component D) may be shorter in the composition or product as a result of processing to produce the composition or product than the glass fibers originally employed. Thus, the arithmetic mean of the glass fiber length, determinable by high-resolution X-ray computer tomography after processing, is often in the range of only 150 μm to 300 μm.

[0093] According to http: / / www.rg.de / wiki / Glasfasern, glass fibers are produced by melt spinning processes (die drawing, bar drawing, and die blowing). In the die drawing process, the hot glass composition flows under the influence of gravity through hundreds of die holes in a platinum spinning plate. The basic threads can be drawn to unlimited lengths at speeds of 3-4 km / min.

[0094] Those skilled in the art distinguish between various types of glass fibers, some of which are listed below, for example: · E-glass, the most commonly used material with an optimal price / performance ratio (E-glass available from R & G), has a composition according to https: / / www.rg.de / wiki / Glasfasern of 53-55% SiO2, 14-15% Al2O3, 6-8% B2O3, 17-22% CaO, <5% MgO, <1% K2O / Na2O and about 1% other oxides; H-glass, hollow glass fibre for mass reduction (R&G hollow glass fibre fabric 160g / m 2 and 216 g / m 2 ) R, S glass, for high mechanical demands (S2 glass available from R & G) D-glass, a borosilicate glass for high electrical demands; C glass, with high chemical resistance; Quartz glass, high temperature resistant.

[0095] Further examples can be found at http: / / de.wikipedia.org / wiki / Glasfaser. For plastic reinforcement, E-glass fibres have achieved the greatest importance. The "E" in E-glass stands for electrical glass, as it was originally used specifically in the electrical industry.

[0096] For the production of E-glass, a glass melt is produced from pure quartz with the addition of limestone, kaolin and boric acid. These contain, in addition to silicon dioxide, different amounts of various metal oxides. The composition determines the properties of the product. According to the invention, it is preferred to employ at least one glass fiber from the group of E-glass, H-glass, R, S-glass, D-glass, C-glass and quartz glass, particularly preferably glass fibers made of E-glass.

[0097] Glass fibres made from E-glass are the most widely used reinforcing material. The strength properties correspond to those of metals (e.g. aluminium alloys) and the specific gravity of laminates containing E-glass fibres is lower than that of metals. E-glass fibres are non-combustible, heat-resistant up to about 400°C and resistant to most chemical and weathering influences.

[0098] However, it is also preferred to employ as component D) non-fibrous, non-foamed ground glass having a d90 value 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, very particularly preferably in the range of 16 to 25 μm, with a particle size distribution determinable by laser diffraction according to ISO 13320. With regard to the d90 values, reference is made to their determination and their meaning in Chemie Ingenieur Technik (vol. 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 particles lie.

[0099] According to the invention, non-fibrous, non-foamed ground glass is preferred, which is a non-cylindrical particulate having a length to thickness ratio, as can be determined by scanning electron microscopy, of less than 5, preferably less than 3, particularly preferably less than 2. This of course excludes the value of zero.

[0100] Also in one embodiment, the non-foamed, non-fibrous ground glass that can be employed as component D) is characterized in that it does not have a glass shape typical of fibrous glass having a cylindrical or elliptical cross section with a length to diameter ratio (L / D ratio) greater than 5, as can be determined by scanning electron microscopy.

[0101] In one embodiment, the non-foamed, non-fibrous ground glass that can be used as component D) according to the present invention is preferably obtained by grinding the glass using a mill, preferably using a ball mill, particularly preferably followed by sifting / sieving. In one embodiment, the starting material preferred for grinding the non-fibrous, non-foamed ground glass that can be used as component D) also includes glass waste, for example glass waste that is generated in particular in the production of glass products as an unwanted by-product and / or as off-spec product. This includes in particular waste glass, recycled glass and broken glass, which can occur, for example, in the production of window or bottle glass and in the production of glass-containing fillers and reinforcements, in particular in the form of so-called melt cake. The glass can be colored, but uncolored glass is preferred for use as a starting material for use in component D).

[0102] Component E) The component E) employed is preferably selected from at least one further additive different from components B), C) and D), with the proviso that laser-absorbing additives are avoided if laser transparency needs to be maintained.Preferred additives that can be employed as component E) include antioxidants, heat stabilizers, UV stabilizers, gamma light stabilizers, hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, lubricants and / or release agents, flow aids or elastomer modifiers, chain-extending additives, flame retardants different from components B) and C), and fillers and reinforcing agents or colorants different from component D).The additives can be employed alone or in the form of blends / masterbatches.In the case of laser-transparent products, the additives that can be employed as component E) are selected so that no laser absorbers, such as, in particular, carbon black, are employed.Laser-absorbing additives are well known to those skilled in the art.

[0103] Preferably, the heat stabilizers employable as component E) are selected from the group of sulfur-containing stabilizers, in particular the sulfides, dialkylthiocarbamates or thiodipropionic acid, and also from the group of copper salts (here in particular copper(I) iodide, which are preferably employed in combination with potassium iodide and / or sodium hypophosphite NaH2PO2), sterically hindered amines, in particular tetramethylpiperidine derivatives, aromatic secondary amines, in particular diphenylamines, hydroquinones, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as sterically hindered phenols and aliphatic or aromatic substituted phosphites, and variously substituted representatives of these groups.

[0104] The sterically hindered phenol is preferably one having at least one 3-tert-butyl-4-hydroxy-5-methylphenyl and / or at least one 3,5-di(tert-butyl-4-hydroxyphenyl) unit, and examples thereof include 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][CAS number 35074-77-2] (Irganox® 259, available from BASF SE, Ludwigshafen, Germany), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][CAS number 6683-19-8] (Irganox® 1010, available from BASF SE, Ludwigshafen, Germany), and the like. Particularly preferred are ADK Stab® AO 80, available from Adeka-Palmerole SAS, Mulhouse, France, and 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane [CAS number 90498-90-1]. ADK Stab® AO 80 is a commercial product available from Adeka-Palmerole SAS, Mulhouse, France.

[0105] Among the aliphatic or aromatic substituted phosphites preferably employed are bis(2,4-dicumylphenyl)pentaerythritol diphosphite [CAS number 154862-43-8], available under the trade name Doverphos® S9228 from Dover Chemical Corp., Dover, USA, and tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4′-diylbisphosphonate [CAS number 38613-77-3], available, for example, as Hostanox® P-EPQ from Clariant International Ltd., Muttenz, Switzerland.

[0106] The heat stabilizers which can be employed as component E) are preferably employed in amounts of 0.01 to 2 parts by weight, particularly preferably 0.05 to 1 part by weight, based in each case on 100 parts by weight of component A).

[0107] UV stabilizers which can be employed as component E) preferably include substituted resorcinols, salicylates, benzotriazoles and HALS derivatives (hindered amine light stabilizers) containing at least one 2,2,6,6-tetramethyl-4-piperidyl unit, or benzophenones.

[0108] The UV stabilizers which can be employed as component E) are preferably employed in amounts of 0.01 to 2 parts by weight, particularly preferably 0.1 to 1 part by weight, based in each case on 100 parts by weight of component A).

[0109] The colorants employed, which can be employed as component E), are preferably selected from inorganic pigments, in particular ultramarine blue, bismuth vanadate, iron oxide, titanium dioxide, zinc sulfide, tin titanium zinc oxide [CAS number 923954-49-8], also organic dyes, preferably phthalocyanines, quinacridones, benzimidazoles, in particular Ni-2-hydroxy-naphthyl-benzimidazole [CAS number 42844-93-9] and / or pyrimidine-azo-benzimidazole [CAS number 72102-84-2] and / or Pigment Yellow 192 [CAS number 56279-27-7], furthermore perylenes, anthraquinones, in particular CI Solvent Yellow 163 [CAS number 13676-91-0], this list being non-exhaustive, the selection of the colorants being made in particular taking into account the requirements of the laser transmission / laser absorption behavior.

[0110] In certain embodiments, and preferably in the case of laser absorbing components, the dyes employed may also include carbon black and / or nigrosine.

[0111] Nucleating agents which can be employed as component E) preferably include sodium or calcium phenylphosphinate, aluminum oxide or silicon dioxide, and very particularly preferably talc, this list being non-exhaustive.

[0112] The flow aids employed, which can be employed as component E), preferably comprise copolymers of at least one α-olefin and at least one methacrylic or acrylic ester of an aliphatic alcohol. Particular preference is given to copolymers in which the α-olefin comprises ethene and / or propene units and the methacrylic or acrylic ester comprises, as the alcohol component, a linear or branched alkyl group having 6 to 20 carbon atoms. 2-Ethylhexyl acrylate is especially preferred. Copolymers suitable as flow aids are distinguished not only by their composition but also by their low molecular weight. Thus, copolymers suitable for the composition according to the invention are, in particular, copolymers having an MFI of at least 100 g / 10 min, preferably at least 150 g / 10 min, particularly preferably at least 300 g / 10 min, measured at 190° C. and a load of 2.16 kg. The MFI, i.e. the melt flow index, is used to characterize the flow of thermoplastic melts and is the subject of standards ISO 1133 or ASTM D 1238. It is particularly preferable to employ as flow aid a copolymer of ethene and 2-ethylhexyl acrylate having an MFI of 550, known as Lotryl® 37EH550.

[0113] As chain extension additives and hydrolysis stabilizers that can be employed as component E), it is preferred to employ bifunctional or polyfunctional branching or chain extension additives that contain at least two branching or chain extension functional groups per molecule. The branching or chain extension additives are preferably low molecular weight oligomeric or polymeric compounds that have at least two chain extension functional groups per molecule that can react with alcohol groups and / or amide groups and / or carboxylic acid groups. The chain extension functional groups are preferably isocyanates, carbodiimides, alcohols, epoxides, maleic anhydrides, oxazolines, oxazines and oxazolones, with epoxides and carbodiimides being particularly preferred.

[0114] Particularly preferred di- or polyfunctional branching or chain extension additives are the glycidyl ether series (bisphenols and epichlorohydrin), aminoepoxy resin series (aniline and epichlorohydrin), diglycidyl ester series (cycloaliphatic dicarboxylic acids and epichlorohydrin) diepoxides, individually or as mixtures, as well as 2,2-bis[p-hydroxyphenyl]propane glycidyl ether, bis[p-(N-methyl-N-2,3-epoxypropylamino)phenyl]methane, and also epoxidized fatty acid esters of glycerol containing at least two epoxy groups per molecule.

[0115] Particularly preferred bi- or polyfunctional branching or chain extension additives are glycidyl ethers, especially very preferably bisphenol A glycidyl ether [CAS number 98460-24-3] or epoxidized fatty acid esters of glycerol, also especially very preferably epoxidized soybean oil [CAS number 8013-07-8] and / or epoxidized linseed oil [CAS number 8016-11-3], very especially preferably carbodiimides, where polymeric carbodiimides, such as poly-2,4,6-triisopropyl-1,3-dicarbodiimide and carbodiimides containing pentaerythrityl units, in particular 14,14',15,15'-tetradehydro-7,7'-spirobi[dibenzo[b,g][1,9,4,6]dioxadiazacyclododecine], [CAS number 1231148-36-9], are particularly preferred within the class of carbodiimides.

[0116] Plasticizers which can be preferably employed as component E) are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N-(n-butyl)benzenesulfonamide.

[0117] Preferred elastomer modifiers which may be employed as component E) include one or more of the following graft polymers, among others: E.1 5% to 95% by weight, preferably 30% to 90% by weight, of at least one vinyl monomer, and E.2 95% to 5% by weight, preferably 70% to 10% by weight, of one or more graft substrates having a glass transition temperature <10° C., preferably <0° C., particularly preferably <-20° C. Here, the mass percentages are based on 100 mass % of the elastomer modifier.

[0118] The graft substrate E.2 generally has a mean particle size d50 value, determinable by laser diffraction according to ISO 13320, of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm.

[0119] The monomers according to E.1 are preferably mixtures of E.1.1 50% to 99% by weight of vinyl aromatics and / or ring-substituted vinyl aromatics, in particular styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and / or (C1-C8)-alkyl methacrylates, in particular methyl methacrylate or ethyl methacrylate, and E.1.2 1% to 50% by weight of vinyl cyanide, preferably unsaturated nitriles, in particular acrylonitrile and methacrylonitrile, and / or (C1-C8)-alkyl (meth)acrylates, 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 Here, the mass percentages of E.1.1 and E.1.2 are based on 100 mass % of the elastomer modifier.

[0120] Preferred monomers E.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, and preferred monomers E.1.2 are 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.

[0121] Suitable graft substrates E.2 for the graft polymers that can be employed in the elastomer modifier include, for example, diene rubbers, EPDM rubbers, i.e. those based on ethylene / propylene, and optionally dienes, as well as acrylates, polyurethanes, silicones, chloroprene and ethylene / vinyl acetate rubbers, where EPDM stands for ethylene-propylene-diene rubber.

[0122] Preferred graft substrates E.2 are diene rubbers, especially those based on butadiene, isoprene, etc., or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers, especially monomers 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.

[0123] Particularly preferred graft substrates E.2 are ABS polymers (emulsion, bulk and suspension ABS), ABS standing for example for acrylonitrile-butadiene-styrene as described in DE-A 2 035 390 or DE-A 2 248 242 or Ullmann, Enzyklopadie der Technischen Chemie, Vol. 19 (1980), pp. 277 to 295. The gel content of the graft substrate E.2 is preferably at least 30% by weight, particularly preferably at least 40% by weight (measured in toluene).

[0124] The elastomer modifiers / graft polymers which can be employed as component E) are produced by free radical polymerization, preferably by emulsion, suspension, solution or bulk polymerization, in particular by emulsion or bulk polymerization.

[0125] Particularly suitable graft rubbers also include ABS polymers produced by redox initiation with an initiator system composed of an organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.

[0126] Since, as is well known, in a grafting reaction the grafting monomer is not necessarily completely grafted onto the graft substrate, according to the invention graft polymer shall also be understood to mean the product resulting from the (co)polymerization of the grafting monomer in the presence of the graft substrate and co-obtained by work-up.

[0127] Likewise suitable acrylic rubbers are based on the graft substrate E.2, which is preferably a polymer of alkyl acrylate, optionally with up to 40% by weight, based on E.2, of other polymerizable ethylenically unsaturated monomers. Preferred polymerizable acrylic esters include C1-C8-alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C1-C8-alkyl esters, such as chloroethyl acrylate, glycidyl esters, and mixtures of these monomers. Particularly preferred in this context are graft polymers with butyl acrylate as the core and methyl methacrylate as the shell, in particular Paraloid® EXL2300, Dow Corning Corporation, Midland, Michigan, USA.

[0128] Crosslinking can be achieved by copolymerizing monomers having more than one polymerizable double bond as a replacement for ethylenically unsaturated monomers.Preferred crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms with unsaturated monohydric alcohols having 3 to 12 carbon atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, preferably trivinyl cyanurate and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzene; and also triallyl phosphate and diallyl phthalate.

[0129] Particularly preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds having at least three ethylenically unsaturated groups.

[0130] Very particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzene. The amount of crosslinking monomer is preferably 0.02% to 5% by weight, in particular 0.05% to 2% by weight, based on the graft substrate E.2.

[0131] For cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit their amount to less than 1% by weight of the graft substrate E.2.

[0132] Preferred "other" polymerizable ethylenically unsaturated monomers which can optionally be used in addition to the acrylic esters to produce the graft substrate E.2 are acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl C1-C6-alkyl ethers, methyl methacrylate, glycidyl methacrylate, butadiene. Preferred acrylic rubbers as graft substrate E.2 are emulsion polymers having a gel content of at least 60% by weight.

[0133] Further suitable graft substrates according to E.2 which are particularly suitable are silicone rubbers which have graft active sites, as described in DE-A 3704657, DE-A 3704655, DE-A 3631540 and DE-A 3631539.

[0134] A preferred graft polymer containing a silicone moiety is a graft polymer containing methyl methacrylate or styrene-acrylonitrile as the shell and silicone / acrylate graft as the core. A preferred styrene-acrylonitrile that can be used as the shell is Metablen® SRK200. A preferred methyl methacrylate that can be used as the shell is Metablen® S2001 or Metablen® S2030 or Metablen® SX-005. It is particularly preferred to use Metablen® S2001. Products with the trade name Metablen® are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.

[0135] Crosslinking can be achieved by copolymerizing monomers having more than one polymerizable double bond. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms with unsaturated monohydric alcohols having 3 to 12 carbon atoms or with saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, preferably trivinyl cyanurate and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzene; and also triallyl phosphate and diallyl phthalate.

[0136] Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds having at least three ethylenically unsaturated groups.

[0137] Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzene. The amount of crosslinking monomer is preferably 0.02% to 5% by weight, in particular 0.05% to 2% by weight, based on the graft substrate E.2.

[0138] For cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit their amount to less than 1% by weight of the graft substrate E.2.

[0139] Preferred "other" polymerizable ethylenically unsaturated monomers which can optionally be used in addition to the acrylic esters to produce the graft substrate E.2 are acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl C1-C6-alkyl ethers, methyl methacrylate, glycidyl methacrylate, butadiene. Preferred acrylic rubbers as graft substrate E.2 are emulsion polymers having a gel content of at least 60% by weight.

[0140] Other materials which can likewise be used together with the elastomer modifiers based on graft polymers are elastomer modifiers not based on graft polymers, which have a glass transition temperature <10° C., preferably <0° C., particularly preferably <−20° C. These preferably include elastomers with block copolymer structures, as well as thermoplastically 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).

[0141] The lubricants and release agents which can be employed as component E) are preferably selected from the group of long chain fatty acids, salts of long chain fatty acids, ester derivatives of long chain fatty acids and montan wax.

[0142] Preferred long chain fatty acids are stearic acid or behenic acid. Preferred salts of long chain fatty acids are Ca, Mg, Al or Zn stearates. Preferred ester derivatives of long chain fatty acids are those based on pentaerythritol, especially the C 16 -C 18 Fatty acid ester [CAS number 68604-44-4] or [CAS number 85116-93-4].

[0143] In the context of the present invention, montan wax is a mixture of linear saturated carboxylic acids with a chain length of 28 to 32 carbon atoms. According to the present invention, it is particularly preferred to employ lubricants and / or release agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols having 2 to 40 carbon atoms and metal salts of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms, with pentaerythritol tetrastearate, calcium stearate [CAS number 1592-23-0] and / or ethylene glycol dimontanate, here especially Licowax® E [CAS number 74388-22-0] available from Clariant, Muttenz, Basle being very particularly preferred, and pentaerythritol tetrastearate [CAS number 115-83-3], for example available as Loxiol® P861 from Emery Oleochemicals GmbH, Dusseldorf, Germany being very particularly preferred.

[0144] Preferably, further flame retardants which can be employed as component E) are mineral flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants different from components B) and C).

[0145] In an alternative embodiment, it is also possible to employ flame retardants as laser absorbers, which have a negative impact on the laser transmittance of products based on the polymer composition according to the invention, if required and taking into account the drawback of loss of laser transparency.

[0146] Among the mineral flame retardants, magnesium hydroxide is particularly preferred.

[0147] However, in alternative embodiments, it is also possible to employ nitrogen-containing flame retardants and flame retardant synergists as the flame retardant of component E) if necessary.Preferred nitrogen-containing flame retardants that can be employed as component E) are reaction products of trichlorotriazine, piperazine and morpholine according to CAS number 1078142-02-5, in particular MCA PPM Triazine HF available from MCA Technologies GmbH, Biel-Benken, Switzerland, as well as melamine cyanurate or condensates of melamine, in particular milem, melam, melon or more highly concentrated compounds of this type.Preferred inorganic nitrogen-containing compounds are ammonium salts.

[0148] It is furthermore also possible to employ salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives, in particular aluminium hydroxide or Ca Mg carbonate hydrate (DE-A 4236122), as flame retardants employable in component E).

[0149] Also suitable for use as flame retardants of component E) are flame retardant synergists from the group of oxygen-, nitrogen- or sulfur-containing metal compounds. Preference is given to zinc-free compounds, 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, among which calcium carbonate is very particularly preferred. The calcium carbonates which can be preferably employed have an average particle size (d50) in the range of 0.5 μm to 10 μm, determinable by laser diffraction according to ISO 13320, preferably a d50 in the range of 0.7 μm to 5 μm, particularly preferably a d50 in the range of 1.0 μm to 3 μm. A suitable measuring device for determining the d50 of calcium carbonate is, for example, the Mastersizer® 2000 available from Malvern Panalytical GmbH, Kassel, Germany.

[0150] However, in alternative embodiments, where required, zinc-containing compounds may also be utilized as flame retardants in component E), preferably including zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide, and zinc nitride, or mixtures thereof.

[0151] However, in alternative embodiments, it is also possible to employ calcium stannate or calcium hydroxystannate as the flame retardant of component E), if required.

[0152] However, the flame retardant employed, which can be employed as component E), different from components B) and C), also preferably comprises an inorganic aluminum salt of phosphonic acid. Phosphonic acid is understood to mean a substance with empirical formula H3PO3 [CAS number 13598-36-2], according to Wikipedia (http: / / de.wikipedia.org / wiki / Phosphons%C3%A4ure). The salts of phosphonic acid are known as phosphonates. Phosphonic acids can exist in two tautomeric forms, one of which has a free electron pair on the phosphorus atom and the other has a double-bonded oxygen (P=O) to the phosphorus. The tautomeric equilibrium is entirely on the side of the form with the double-bonded oxygen. According to AF Holleman, E. Wiberg: Lehrbuch der Anorganischen Chemie. 101st edition, Walter de Gruyter, Berlin / New York 1995, ISBN3-11-012641-9, page 764, the terms "phosphorous acid" and "phosphite" should be used only for tautomeric species with a free electron pair on phosphorus. However, the terms "phosphorous acid" and "phosphite" were also once used for tautomeric forms with oxygen double-bonded to phosphorus, and therefore, in the present invention, the terms "phosphonic acid" and "phosphorous acid", as well as the terms "phosphonate" and "phosphite" are used synonymously with each other.

[0153] Preferred aluminium salts of phosphonic acids are one or more selected from the following group: Primary aluminum phosphonate [Al(H2PO3)3], Basic aluminum phosphonate [Al(OH)H2PO3)2·2H2O], Al2(HPO3)3·xAl2O3·nH2O, where x is in the range of 2.27 to 1 and n is in the range of 0 to 4; Al2(HPO3)3·(H2O) of formula (V) q where q is 0, 1, 2, 3 or 4, in particular aluminium phosphonate tetrahydrate [Al2(HPO3)3·4H2O] or secondary aluminium phosphonate [Al2(HPO3)3], AlM of formula (VI) z (HPO3) y (OH) v (H2O) w (wherein M represents an alkali metal ion, z is in the range of 0.01 to 1.5, y is in the range of 2.63 to 3.5, v is in the range of 0 to 2, and w is in the range of 0 to 4), Al2(HPO3) of formula (VII) u (H2PO3) t (H2O) (wherein, u is in the range of 2 to 2.99, t is in the range of 2 to 0.01, and s is in the range of 0 to 4). z, y and v in formula (VI) and u and t in formula (VII) can assume only values ​​such that the corresponding aluminum phosphonate is uncharged as a whole.

[0154] Preferred alkali metals M in formula (VI) are sodium and potassium.

[0155] Particularly preferred aluminum salts of phosphonic acids are selected from the following 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, where x is in the range of 2.27 to 1 and n is in the range of 0 to 4.

[0156] Secondary aluminum phosphonate [Al2(HPO3)3], [CAS number 71449-76-8] and secondary aluminum phosphonate tetrahydrate [Al2(HPO3)3·4H2O], [CAS number 156024-71-4] are very particularly preferred, secondary aluminum phosphonate [Al2(HPO3)3] being especially preferred.

[0157] Preferred further phosphorus-containing flame retardants different from components B) and C) further comprise further organometallic phosphinates, red phosphorus, inorganic metal hypophosphites, further metal phosphonates, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO derivatives), resorcinol bis(diphenyl phosphate) (RDP) including oligomers, bisphenol A bis(diphenyl phosphate) (BDP) including oligomers, melamine pyrophosphate, melamine polyphosphate, melamine poly(aluminium phosphate), melamine poly(zinc phosphate) or phenoxyphosphazene oligomers and mixtures thereof.

[0158] Further flame retardants which can be employed as component E) are char-formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyetherketones, and anti-drip agents, especially tetrafluoroethylene polymers.

[0159] The flame retardants employable as component E) can be added in pure form and as masterbatches or compression molded products.

[0160] However, in alternative embodiments, if necessary, it is also possible to employ halogen-containing flame retardants, especially taking into account the drawbacks of the loss of halogen-free properties of the flame retardant.Preferred halogen-containing 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, polypentabromobenzyl acrylate, brominated polystyrene or brominated polyphenylene ether, which can be used alone or in combination with a synergist, and especially when the drawbacks to laser transmittance need to be taken into account due to the specific use, antimony trioxide or antimony pentoxide, among which the halogen-containing flame retardants tetrabromobisphenol A epoxy oligomer and tetrabromobisphenol A oligocarbonate are particularly preferred.

[0161] In alternative embodiments, if required by the particular use, it is also possible to employ further fillers and reinforcing agents different from component D), possibly taking into account disadvantages to the laser transmittance.

[0162] These are preferably carbon fibres [CAS number 7440-44-0], calcium silicate [CAS number 1344-95-2], calcium metasilicate [CAS number 10101-39-0], magnesium carbonate [CAS number 546-93-0], kaolin [CAS number 1332-58-7], calcined kaolin [CAS number 92704-41-1], chalk [CAS number 1317-65-3], kyanite [CAS number 1302-76-7], powdered or ground quartz [CAS number 14808-60-7], mica [CAS number No. 1318-94-1], phlogopite [CAS No. 12251-00-2], feldspar [CAS No. 68476-25-5], wollastonite [CAS No. 13983-17-0], montmorillonite [CAS No. 67479-91-8], pseudoboehmite of formula AlO(OH), magnesium carbonate [CAS No. 12125-28-9] and talc [CAS No. 14807-96-6], and, if required, also one or more fillers and / or reinforcing agents from the group barium sulfate [CAS No. 7727-43-7].

[0163] Among the fibrous fillers or reinforcing agents different from component D), wollastonite is particularly preferred. In the case of laser-absorbing components / products, carbon fibers can also be employed as reinforcing material.

[0164] In the case of laser-absorbing components, at least one laser absorber selected from the group consisting of antimony trioxide, tin oxide, tin orthophosphate, barium titanate, aluminum oxide, copper hydroxyphosphate, copper orthophosphate, copper potassium diphosphate, copper hydroxide, antimony tin oxide, bismuth trioxide and anthraquinone can be employed as component E), albeit with the loss of the property of high laser transmittance. Particularly preferred are tin oxide, antimony trioxide or antimony tin oxide. Particularly preferred is antimony trioxide.

[0165] The laser absorber, especially antimony trioxide, can be employed as powder or in the form of a masterbatch. Preferred masterbatches are those based on polyamide and / or polyolefin, preferably polyethylene. Antimony trioxide is very particularly preferably employed in the form of a polyamide 6 based masterbatch.

[0166] The laser absorbers may be employed individually or as a mixture of two or more laser absorbers.

[0167] The laser absorber is capable of absorbing laser light of a specific wavelength. In practice, this wavelength is in the range of 157 nm to 10.6 μm. Examples of lasers of these wavelengths are described in WO2009 / 003976A1. It is preferable to employ Nd:YAG lasers (which can achieve wavelengths of 1064, 532, 355 and 266 nm) and CO2 lasers.

[0168] Further preferred uses The present invention preferably comprises: B) Aluminum salts of general formula (I) for achieving a CTI A of 600 in or for polyester-based products according to IEC 60112-2010

[0169] [ka]

[0170] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl wherein 1 to 80 parts by weight, preferably 2 to 60 parts by weight, particularly preferably 3 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, of the aluminum salt of formula (I) are employed per 100 parts by weight of a polyalkylene terephthalate or polycycloalkylene terephthalate employable as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate.

[0171] The present invention particularly preferably relates to B) aluminum methylphosphonates of the formula (Ia) for achieving a CTI A of 600 in or for polyester-based products according to IEC 60112-2010

[0172] [ka]

[0173] wherein 1 to 80 parts by weight, preferably 2 to 60 parts by weight, particularly preferably 3 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, of the aluminum salt of formula (Ia) are employed per 100 parts by weight of a polyalkylene terephthalate or polycycloalkylene terephthalate employable as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate.

[0174] The present invention preferably relates to B) aluminum salts of general formula (I) for achieving a CTI A of 600 according to IEC 60112-2010 in polyester-based products.

[0175] [ka]

[0176] (Wherein, R is C1-C 12- alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of an aluminum salt of formula (I), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0177] [ka]

[0178] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; In formula (III), n, x and m can simultaneously assume only integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole. with the proviso that component B) is employed in a lower mass fraction than component C).

[0179] The present invention particularly preferably relates to a method for achieving a CTI A of 600 in accordance with IEC 60112-2010 in or for polyester-based products, B) Aluminum methylphosphonate of formula (Ia)

[0180] [ka]

[0181] The use of 1 to 800 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0182] [ka]

[0183] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14-aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; In formula (III), n, x and m can simultaneously assume only integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole. with the proviso that component B) is employed in a lower mass fraction than component C).

[0184] The present invention particularly preferably relates to a method for achieving a CTI A of 600 in accordance with IEC 60112-2010 in or for polyester-based products, B) Aluminum methylphosphonate of formula (Ia)

[0185] [ka]

[0186] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass, and particularly preferably 10 to 50 parts by mass of aluminum tris(diethylphosphinate) with the proviso that component B) is employed in a lower mass fraction than component C).

[0187] The present invention preferably relates to a method for achieving a CTI A of 600 according to IEC 60112-2010 in or for polyester-based products, B) Aluminum salts of general formula (I)

[0188] [ka]

[0189] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of an aluminum salt of formula (I), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0190] [ka]

[0191] (In the formula, R 1 , R 2are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of at least one glass-based filler and / or reinforcing agent which can be employed as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0192] The present invention particularly preferably relates to a polyester-based product for achieving a CTI A of 600 according to IEC 60112-2010, B) Aluminum methylphosphonate of formula (Ia)

[0193] [ka]

[0194] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0195] [ka]

[0196] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of at least one glass-based filler and / or reinforcing agent which can be employed as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0197] The present invention particularly preferably relates to a method for achieving a CTI A of 600 according to IEC 60112- in or for polyester-based products, B) Aluminum methylphosphonate of formula (Ia)

[0198] [ka]

[0199] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0200] [ka]

[0201] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of glass fibers that can be used as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0202] The present invention particularly preferably relates to a method for achieving a CTI A of 600 in accordance with IEC 60112-2010 in or for polyester-based products, B) Aluminum methylphosphonate of formula (Ia)

[0203] [ka]

[0204] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of aluminum tris(diethylphosphinate) as component C), and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of at least one glass-based filler and / or reinforcing agent which can be employed as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0205] The present invention particularly preferably relates to a method for achieving a CTI A of 600 in accordance with IEC 60112-2010 in or for polyester-based products, B) Aluminum methylphosphonate of formula (Ia)

[0206] [ka]

[0207] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of aluminum tris(diethylphosphinate) as component C), and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of glass fibers that can be used as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0208] The present invention preferably relates to a method for achieving a laser transmission of at least 8% in or for a polyester-based product, determinable according to IEC 60112-2010 CTI A 600 and DVS guideline 2243 (01 / 2014), at a wall thickness of 1.5 mm, B) Aluminum salts of general formula (I)

[0209] [ka]

[0210] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of an aluminum salt of formula (I), The use is based on 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate.

[0211] The present invention particularly preferably relates to a method for achieving a laser transmission of at least 8% in or for polyester-based products, determinable in accordance with IEC 60112-2010 CTI A 600 and DVS guideline 2243 (01 / 2014), at a wall thickness of 1.5 mm, B) Aluminum methylphosphonate of formula (Ia)

[0212] [ka]

[0213] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), The use is based on 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate.

[0214] The present invention preferably relates to a method for achieving a laser transmission of at least 8% in or for a polyester-based product, determinable according to IEC 60112-2010 CTI A 600 and DVS guideline 2243 (01 / 2014), at a wall thickness of 1.5 mm, B) Aluminum salts of general formula (I)

[0215] [ka]

[0216] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of an aluminum salt of formula (I), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0217] [ka]

[0218] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; In formula (III), n, x and m can simultaneously assume only integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole. with the proviso that component B) is employed in a lower mass fraction than component C).

[0219] The present invention particularly preferably relates to a method for achieving a laser transmission of at least 8% in or for polyester-based products, determinable in accordance with IEC 60112-2010 CTI A 600 and DVS guideline 2243 (01 / 2014), at a wall thickness of 1.5 mm, B) Aluminum methylphosphonate of formula (Ia)

[0220] [ka]

[0221] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0222] [ka]

[0223] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; In formula (III), n, x and m can simultaneously assume only integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole. with the proviso that component B) is employed in a lower mass fraction than component C).

[0224] The present invention preferably relates to a method for achieving a laser transmission of at least 8% in or for a polyester-based product, determinable according to IEC 60112-2010 CTI A 600 and DVS guideline 2243 (01 / 2014), at a wall thickness of 1.5 mm, B) Aluminum salts of general formula (I)

[0225] [ka]

[0226] (Wherein, R is C1-C 12 - alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl, very particularly preferably methyl The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of an aluminum salt of formula (I), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0227] [ka]

[0228] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of at least one glass-based filler and / or reinforcing agent which can be employed as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0229] The present invention particularly preferably relates to a method for achieving a laser transmission of at least 8% in or for polyester-based products, determinable in accordance with IEC 60112-2010 CTI A 600 and DVS guideline 2243 (01 / 2014), at a wall thickness of 1.5 mm, B) Aluminum methylphosphonate of formula (Ia)

[0230] [ka]

[0231] The use of 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of the aluminum salt of formula (Ia), Per 100 parts by weight of polyalkylene terephthalates or polycycloalkylene terephthalates available as component A), in particular polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, particularly preferably 10 to 50 parts by weight of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof which can be used as component C).

[0232] [ka]

[0233] (In the formula, R 1 , R 2 are the same or different and represent linear or branched C1-C6-alkyl, and / or C6-C 14 -aryl, R 3 is a straight or branched C1-C 10 -Alkylene, C6-C 10 -arylene or C1-C6-alkyl-C6-C 10 -Arylene or C6-C 10 -aryl-C1-C6-alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer of 1 to 3; x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, particularly preferably 15 to 90 parts by weight of at least one glass-based filler and / or reinforcing agent which can be employed as component D). with the proviso that component B) is employed in a lower mass fraction than component C).

[0234] The invention finally provides the use of the composition according to the invention for producing products, preferably products for electromobility, products for household appliances and products in the electronics and electrical sector.

[0235] Further preferred compositions The present invention relates to A) For 100 parts by mass of polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, B) 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of aluminum methylphosphonate of the formula (Ia)

[0236] [ka]

[0237] C) 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass of aluminum tris(diethylphosphinate), and D) 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 10 to 120 parts by mass, particularly preferably 15 to 90 parts by mass of glass fibers with the proviso that component B) is present in a lower mass fraction than component C).

[0238] As component A) polybutylene terephthalate and as component B) aluminum methylphosphonate of the formula (Ia),

[0239] [ka]

[0240] Very particularly preferred are compositions which employ aluminum tris(diethylphosphinate) as component C) and glass fibres as component D).

[0241] More preferred method The present invention relates to a process for producing products, preferably products for electromobility, products for household appliances and products in the electronics and electrical sectors, comprising the steps of: mixing 100 parts by weight of component A) polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate, B) 1 to 80 parts by mass, preferably 2 to 60 parts by mass, particularly preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass of aluminum methylphosphonate of the formula (Ia)

[0242] [ka]

[0243] C) 5 to 120 parts by mass, preferably 7 to 80 parts by mass, particularly preferably 8 to 60 parts by mass of aluminum tris(diethylphosphinate), and D) 3 to 300 parts by mass, preferably 5 to 200 parts by mass, particularly preferably 10 to 120 parts by mass, particularly preferably 15 to 90 parts by mass of glass fibers and optionally further additives in at least one mixing device, and finally processing the resulting mixture by injection molding, with the proviso that component B) is employed in a lower mass fraction than component C).

[0244] As component A) polybutylene terephthalate and as component B) aluminum methylphosphonate of the formula (Ia),

[0245] [ka]

[0246] Very particularly preferred is a process which employs aluminum tris(diethylphosphinate) as component C) and glass fibres as component D). EXAMPLES

[0247] To demonstrate the corresponding property improvements described by the present invention, polyalkylene terephthalate or polycycloalkylene terephthalate-based polymer compositions were first prepared by compounding. To this end, the components according to Table I were mixed in a twin-screw extruder (ZSK 25 Compounder, available from Coperion Werner & Pfleiderer, Stuttgart, Germany) at temperatures ranging from 260°C to 290°C, extruded, cooled until pelletizable, and pelletized. After drying for 2 hours, typically at 120°C in a vacuum drying cabinet, the pelletized material was processed by injection molding at temperatures ranging from 260°C to 290°C using an Arburg 320-210-500 injection molding machine to produce standard test samples for each test.

[0248] The preparation of aluminum methylphosphonate of formula (Ia) employed as component B) in the examples and comparative examples was carried out according to Example 1 of WO2021 / 076169A1.

[0249] [ka]

[0250] Tracking resistance Test samples having dimensions of 60 mm x 40 mm x 4 mm were used with test solution A at a test voltage of 600 V to determine the tracking resistance ("tracking index") according to IEC 60112-2010.

[0251] The test was run in a more severe manner, using 100 drops each on three test specimens (300 drops total), rather than 50 drops each on five test specimens (250 drops) as a deviation from the standard test, to determine the average number of drops until failure of the material occurred due to a tracking current >0.5A on the test specimen or ignition and subsequent continuous flame.

[0252] Laser Transparency In the context of the present invention, the laser transparency of the investigated samples was measured using a transmission measuring device LPKF TMG3 available from LPKF Laser & Electronics AG, Garbsen, Germany, previously calibrated with a measurement standard made according to DIN EN ISO / IEC 17025, in accordance with DVS guideline 2243 (01 / 2014) "Laserstrahlschweissen thermoplastischer Kunststoffe" (Laser beam welding of thermoplastics) at a laser wavelength of 980 nm in the near infrared (NIR) range on test samples having dimensions 125 mm x 13 mm x 1.5 mm. See LPKF AG 101016-DE: "Einfache Transmissionsmessung fur Kunststoffe LPKF TMG3" (Simple Transmission Measurement for Plastics LPKF TMG3).

[0253] Flame retardant The flame retardancy of test specimens having dimensions 125 mm·13 mm·0.75 mm was determined according to method UL94V (Underwriters Laboratories Inc. Standard of Safety, "Test for Flammability of Plastic Materials for Parts in Devices and Appliances", pp. 14-18, Northbrook, 1998).

[0254] Izod impact resistance The Izod impact resistance was determined according to ISO 180-A on test specimens having dimensions 80 mm x 10 mm x 4 mm.

[0255] Bending strength and outer fiber strain were obtained from bending tests according to ISO178 for test specimens with dimensions 80 mm x 10 mm x 4 mm.

[0256] Starting materials: Component A / 1): Linear polybutylene terephthalate (intrinsic viscosity 93 cm (measured at 25 ° C. in phenol: 1,2-dichlorobenzene = 1: 1) 3 / g and Pocan® B1300 in a 3:2 ratio. Both Pocan® types are commercially available products from Lanxess Deutschland GmbH, Cologne, Germany. Component B / 1): Aluminum methylphosphonate of formula (Ia) prepared according to WO2021 / 076169A1, Example 1 Component C / 1): Aluminum tris(diethylphosphinate), [CAS number 225789-38-8] (Exolit® OP1240, available from Clariant SE, Muttenz, Switzerland) Component D / 1): Chopped glass fibers CS 7967D, available from Lanxess Deutschland GmbH, Cologne, Germany [average fiber diameter 10 μm, average fiber length 4.5 mm, E-glass (DIN 1259), silane size] Component E): As further additives of component E), the following components were employed in the examples, which are customarily used in flame-retardant thermoplastic polyesters: Anti-drip additive: Polytetrafluoroethylene, [CAS number 9002-84-0] (Dyneon® PA 5932, available from Dyneon GmbH & Co KG, Neuss, Germany) Heat stabilizer: tetrakis(2,4-di-tert-butylphenyl)-1,1-biphenyl-4,4'-diylbisphosphonite [CAS number 38613-77-3] (Hostanox® P-EPQ, available from Clariant International Ltd., Muttenz, Switzerland) Release agent: pentaerythritol tetrastearate (PETS) [CAS number 115-83-3] (Loxiol® VPG 861, Cognis Deutschland GmbH, Dusseldorf, Germany) The further additives employed (component E) correspond in type and amount in each case to the corresponding comparative examples and examples, ie a total of 1.0 part by weight. Component X / 1): Melamine cyanurate, (Melapur® MC25, BASF SE, Ludwigshafen, Germany)

[0257] [Table 1]

[0258] The ingredients in Table I are reported in parts by weight based on 100 parts by weight of ingredient A1.

[0259] Table I shows that only Example 1 of the present invention exhibits UL94 classification V0 at 0.75 mm and achieves a CTI A of 600V under much more stringent conditions compared to the standard test using 100 drops on each of three test samples (300 drops in total), while also demonstrating a laser transmission significantly greater than 8% for the 1.5 mm thick test sample.

[0260] Example 1 also exhibits better mechanical performance as evidenced, for example, by higher values ​​for Izod impact strength and better outer fiber strain compared to the formulation containing a nitrogen-containing flame retardant (Comparative Example 1).

Claims

1. A) for 100 parts by mass of polyalkylene terephthalate or polycycloalkylene terephthalate, B) 1 to 80 parts by weight, preferably 2 to 60 parts by weight, particularly preferably 3 to 30 parts by weight, and especially preferably 5 to 20 parts by weight, of at least one aluminum salt of the general formula (I) 【Chemistry 1】 (Wherein, R is C 1 -C 12 -alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl and very particularly preferably methyl, C) 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, and especially preferably 10 to 50 parts by weight, of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof, 【Chemistry 2】 (In the ceremony R 1 , R 2 are the same or different, linear or branched C 1 -C 6 -alkyl and / or C 6 -C 14 -aryl, R 3 is a straight or branched C 1 -C 10 -Alkylene, C 6 -C 10 -Arylene or C 1 -C 6 -Alkyl-C 6 -C 10 -Arylene or C 6 -C 10 -Aryl-C 1 -C 6 - represents alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer from 1 to 3, x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and D) 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, and especially preferably 15 to 90 parts by weight, of at least one glass-based filler and / or reinforcing agent, provided that component B) is present in a lower mass fraction than component C).

2. 2. The composition according to claim 1, characterized in that polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate is adopted as component A).

3. 3. The composition according to claim 1, characterized in that tris(diethylphosphinate)aluminum is employed as component C).

4. 4. The composition according to claim 1, characterized in that glass fibers are employed as component D).

5. Polybutylene terephthalate as component A) and aluminum methylphosphonate of formula (Ia) 【Chemistry 3】 5. The composition according to claim 1 , characterized in that it employs as component B), tris(diethylphosphinate)aluminum as component C) and glass fibres as component D).

6. 6. Products based on a composition according to any one of claims 1 to 5, preferably products for electromobility, products for household appliances and products in the electronics and electrical sector.

7. 1. A method for producing a product, preferably a product for electromobility, a product for household appliances and products in the electronics and electrical sector, comprising the steps of: Component A) 100 parts by weight of polyalkylene terephthalate or polycycloalkene terephthalate, B) 1 to 80 parts by weight, preferably 2 to 60 parts by weight, particularly preferably 3 to 30 parts by weight, and especially preferably 5 to 20 parts by weight, of at least one aluminum salt of the general formula (I) 【Chemistry 4】 (Wherein, R is C 1 -C 12 -alkyl, preferably methyl, ethyl, isopropyl or isobutyl, tert-butyl or n-butyl, particularly preferably ethyl or methyl and very particularly preferably methyl, C) 5 to 120 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 8 to 60 parts by weight, and very particularly preferably 10 to 50 parts by weight, of at least one organic phosphinic acid salt of the formula (II) and / or at least one diphosphinic acid salt of the formula (III) and / or a polymer thereof 【Chemistry 5】 (In the formula, R 1 , R 2 are the same or different, linear or branched C 1 -C 6 -alkyl and / or C 6 -C 14 -aryl, R 3 is a straight or branched C 1 -C 10 -Alkylene, C 6 -C 10 -Arylene or C 1 -C 6 -Alkyl-C 6 -C 10 -Arylene or C 6 -C 10 -Aryl-C 1 -C 6 - represents alkylene, M represents aluminum, zinc or titanium; m represents an integer from 1 to 4; n represents an integer from 1 to 3, x represents 1 and 2; n, x and m in formula (III) can only simultaneously assume integers such that the diphosphinic acid salt of formula (III) is uncharged as a whole; and D) 3 to 300 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 to 120 parts by weight, and especially preferably 15 to 90 parts by weight, of at least one glass-based filler and / or reinforcing agent, mixing or blending in at least one mixing device, optionally with further additives, and finally processing the resulting mixture by injection molding, with the proviso that component B) is employed in a lower mass fraction than component C).

8. 8. The process according to claim 7, characterized in that polybutylene terephthalate, polyethylene terephthalate or poly-1,4-cyclohexanedimethanol terephthalate is employed as component A).

9. 9. The process according to claim 7 or 8, characterized in that tris(diethylphosphinate)aluminum is employed as component C).

10. 10. The method according to claim 7, characterized in that glass fibres are employed as component D).

11. Polybutylene terephthalate as component A) and aluminum methylphosphonate of formula (Ia) 【Chemistry 6】 11. The method according to claim 7, characterized in that as component B) aluminum tris(diethylphosphinate) is employed as component C) and glass fibres as component D).

12. Use of a composition according to any one of claims 1 to 5 for producing products, preferably products for electromobility, products for household appliances and products in the electronics and electrical sectors.

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