POLYAMIDE-BASED PRODUCTS

Description

[0001] The present invention relates to polyamide-based products based on compositions containing at least one sterically hindered phenol, at least one phosphinic acid derivative, at least one 3-thiopropionate and 4,4'-bis(phenylisopropyl)diphenylamine and the use of the latter as an additive for the production of polyamide-based products with improved retention of elongation at break, improved color stability and simultaneously improved UV stability after thermal aging compared to polyamide-based products based on compositions containing at least one sterically hindered phenol, at least one phosphinic acid derivative and at least one 3-thiopropionate.

[0002] While the internal combustion engine was the dominant drive concept for many years, the search for alternative drive concepts has also led to new requirements regarding material selection. Electromobility plays a key role in this, where the internal combustion engine is partially replaced in hybrid vehicles or completely replaced in electric vehicles by one or more electric motors, which typically draw their electrical energy from batteries or fuel cells. While conventional vehicles with an internal combustion engine as their sole drive system typically manage with a 12V electrical system, hybrid and electric vehicles with electric motors as their drive unit require significantly higher voltages.This poses a serious additional hazard potential for the immediate area and surroundings of such live components, which is playing an increasingly important role in technical specifications and standards. Clear marking of these high-voltage hazard zones is crucial to prevent unintentional contact with people, especially drivers or mechanics. In this context, clear color coding, particularly orange, of polyamide-based products in high-voltage applications is especially important.The German statutory accident insurance DGUV describes the term high voltage in its information BGI / GUV-I 8686 on "Qualification for work on vehicles with high-voltage systems", especially in hybrid and fuel cell technology as well as electric vehicles, encompassing voltages >60 V and <1500V for DC voltage and >30V and 1000V for AC voltage.

[0003] However, polyamide-based products are subject to degradation when exposed to external influences, particularly light, UV radiation, heat, or adverse weather conditions. Degradation occurs especially as a result of exposure to high temperatures. The result of such degradation is generally perceived as a loss of mechanical properties, particularly impact strength, elongation at break, and especially discoloration. Degradation processes in the form of undesirable discoloration are particularly undesirable in the case of colored polyamide-based products, especially orange-colored polyamide-based products in high-voltage applications, as a clear and consistent color identification over the service life, e.g., in motor vehicles, is not guaranteed in such cases. Discoloration is also undesirable in applications in the visible spectrum involving contact with UV radiation.Examples of such applications outside the automotive sector include, in the household sector, hair dryers or hair straighteners, which are designed in white or light pastel shades for aesthetic reasons.

[0004] Applications of polyamide-based products in the automotive sector, particularly in e-mobility applications, especially in high-voltage applications such as charging plugs, require not only stiffness measured by the modulus of elasticity, but also good impact strength and elongation at break. Polyamide-based products used in high-voltage applications can be subjected to high mechanical forces during installation, removal, and use in vehicles and must not break. Maintaining impact strength and elongation at break throughout the vehicle's service life must also be ensured.

[0005] The prior art solution for improving the impact strength of polyamide-based compositions is the use of amorphous plastics such as ABS or elastomers in polyamide-based blends, as described in the Plastics Handbook 3 / 4, Technical Thermoplastics, Polyamides, Karl Hansen Verlag, Munich, Vienna, 1998, p. 16 and pp. 148-150. Such polymers, which are used in other polymers, particularly polyamides, to increase impact strength, are referred to in technical terminology as modifiers or impact modifiers and are therefore also to be referred to as impact modifiers according to the invention. Suitable impact modifiers used in polyamides include ethylene propylene rubbers (EPM, EPR) or ethylene propylene diene rubbers (EPDM), styrene-containing elastomers, e.g., SEBS, SBS, SEPS, or acrylate rubbers.Nitrile rubbers (NBR, H-NBR), silicone rubbers, EVA, and microgels, as described in WO 2005 / 033185 A1, are also suitable as impact modifiers. Investigations within the framework of... Dissertation by S. Moll on "Investigation of the effects of thermal oxidative stress on the emission behavior of ABS and PP and the correlation with the degree of aging" out of 2016 However, studies have shown that poly(acrylonitrile butadiene styrene) "ABS" discolors under thermal-oxidative stress. Furthermore, it is known to those skilled in the art from Kunststoffhandbuch 3 / 4, Technische Thermoplastike, Polyamides (Karl Hansen Verlag, Munich, Vienna, 1998, p. 16 and p. 157) that adding an impact modifier reduces stiffness, measured by the modulus of elasticity (E-modulus), also sometimes called the tensile modulus. Therefore, the impact modifiers described in the prior art and typically used in polyamide appear unsuitable, especially if color-coded polyamide-based components are not intended to discolor.

[0006] Impact strength is calculated as the ratio of impact energy to the cross-sectional area of ​​the specimen (unit: kJ / m²). Various types of impact bending tests are used to determine impact strength, such as the Charpy test, the 2-way impact test, and the 2-way impact test. DIN EN ISO 179, or according to Izod DIN EN ISO 180, Impact strength can be determined. Within the scope of the present invention, impact strength is measured according to... ISO180-1U on injection-molded test specimens (80·10·4 mm 3< ) at 23°C in the freshly injected state.

[0007] Those skilled in the art will know from PH Selden, Glass Fiber Reinforced Plastics, pages 324-325, chapter "Glass Fiber Reinforced Thermoplastics" by K. Schlichting, Springer Verlag Berlin 1967, that the glass fiber content influences the impact strength of a polyamide composition. Since reinforcing materials, especially glass fibers, themselves influence the impact strength of polyamides, comparative statements within the scope of the present invention always refer to compositions or products with the same content of reinforcing materials, especially glass fibers. This statement also applies to methods and uses according to the invention.

[0008] The elongation at break (unit of measurement %) represents an indicator of the deformability of a plastic and is according to DIN EN ISO 527The last recorded strain value before a stress drop to less than or equal to 10% of the tensile strength value occurs. The elongation at break is measured according to the present invention. DIN EN ISO 527 on injection-molded test specimens (170·10·4 mm 3< ), tensile bar type 1A) at 23°C in the freshly injected state.

[0009] In summary, the requirements for polyamide-based products for e-mobility applications, particularly in high-voltage applications, are diverse. For automotive applications, both color coding and mechanical properties, especially impact strength and elongation at break, must be guaranteed throughout the vehicle's service life. As explained above, the use of impact modifiers discussed in the prior art is not suitable for satisfactorily meeting all these requirements for polyamides.

[0010] Compositions according to European application 20177768.7 and the 3-thiopropionate used therein are suitable for the production of impact-resistant polyamide-based products with improved color stability after thermal aging. However, these products exhibit insufficient UV stability, and the retention of elongation at break after 500 h of thermal aging at 150°C is unsatisfactory for applications in the automotive and household sectors.

[0011] The object of the present invention was therefore to provide polyamide-based compositions or products made therefrom which, in addition to improved impact strength measured according to ISO180-1UIn comparison to polyamide compositions not modified with impact modifier, they exhibit good aging behavior in the form of improved color retention or color stability after hot air aging, as well as improved UV stability, and also good aging behavior in the form of sufficient retention of impact strength and, above all, elongation at break after hot air aging.

[0012] According to the invention, good aging behavior in the form of improved color retention or improved color stability after hot air aging is understood to mean that the color difference ΔE is calculated according to DIN EN ISO 11664-4After hot air storage for over 500 hours at 150°C, the color difference is small, preferably in the range of 0 to 20, and particularly preferably in the range of 0 to 15. The color difference ΔE is a dimensionless quantity. The smaller the value, the smaller the color difference from a given initial value. A color difference ΔE = 0 therefore corresponds to no change in color, but rather to a constant color.

[0013] According to the invention, good aging behavior in the form of improved UV stability is understood to mean that the color difference ΔE is calculated according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2AThe color difference is low over 200 hours at 80°C, 340 nm, and 1.55 W / m² without irrigation; preferably, the color difference ΔE is in the range of 0 to 30, and particularly preferably, the color difference ΔE is in the range of 0 to 20. In this case as well, the color difference ΔE is a dimensionless quantity. The smaller the value, the smaller the color difference from a given initial value. A color difference ΔE = 0 therefore corresponds not to a change in color, but to a constant color.

[0014] According to the invention, good aging behavior in the form of sufficient retention of impact strength after hot air aging is understood to mean that the impact strength measured after ISO180-1U After hot air aging for over 500 hours at 150°C, the value does not decrease by more than 30% compared to the time at 0 hours.

[0015] According to the invention, good aging behavior in the form of sufficient retention of elongation at break after hot air aging is understood to mean that the elongation at break is measured after DIN EN ISO 527 After hot air aging for over 500 hours at 150°C, the value does not decrease by more than 30% compared to the time at 0 hours.

[0016] The subject matter of the present invention is Compositions and based thereon Products containing a) at least one polyamide, preferably polyamide 6 or polyamide 66, b) at least one sterically hindered phenol, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate, and e) 4,4'-bis(phenylisopropyl)diphenylamine with the proviso that for every 100 mass fractions of component a) 0.03 to 3 mass fractions, preferably 0.05 to 1 mass fractions of component b), 0.05 to 5 mass fractions, preferably 0.25 to 1 mass fractions, of component c), 0.05 to 5 mass fractions, preferably 0.2 to 1 mass fractions, of component d) and 0.05 to 5 mass fractions, preferably 0.1 to 1 mass fractions, of component e) are used.

[0017] The ammonium ion NH₄⁺ for R' in formula (I) is a cation that forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0018] Surprisingly, polyamide-based products according to the invention, containing in addition to the polyamide the components b), c), d) and e), show a higher impact strength measured according to ISO180-1U compared to polyamide-based products not modified with 4,4'-bis(phenylisopropyl)diphenylamine but containing components b), c) and d).

[0019] Surprisingly, products according to the invention also exhibit good aging behavior in the form of improved color retention and stability after hot air aging, as well as sufficient retention of impact strength and elongation at break after hot air aging, compared to polyamide-based products containing only components b), c), and d). Furthermore, polyamide-based products according to the invention show improved UV stability compared to compositions containing components b), c), and d), but not 4,4'-bis(phenylisopropyl)diphenylamine.The diverse requirements for polyamide-based products for applications in e-mobility, but also in household appliances, are thus met simultaneously by the use of components b), c), d) and e), both in unreinforced and in reinforced, preferably glass fiber reinforced, products.

[0020] The invention also relates to the use of 4,4'-bis(phenylisopropyl)diphenylamine to maintain impact strength measured according to ISO180-1U and / or the elongation at break measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 after UV storage according to DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0021] According to the invention, good aging behavior in the form of color retention or color stability after hot air aging is present when the color change ΔE is smaller compared to polyamide-based products containing components b), c), and d), but without component e), where the color difference ΔE is a dimensionless quantity and the smaller the value, the smaller the color difference from an initial value, with a color difference ΔE = 0 corresponding to no color change, but rather to a constant color. Preferably, the color change ΔE is in the range of 0 to 20, particularly preferably in the range of 0 to 15.

[0022] The invention further relates to the use containing mixtures a) at least one polyamide, preferably polyamide 6 or polyamide 66, b) at least one sterically hindered phenol, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, and d) at least one 3-thiopropionate, and e) 4,4'-bis(phenylisopropyl)diphenylamine (antioxidant 445), for the manufacture of polyamide-based products, preferably for the manufacture of polyamide-based products with retention of impact strength measured according to ISO180-1U and / or maintenance of elongation at break measured after ISO 527 calculated after hot air aging over 500h at 150°C and / or color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or color retention according to DIN EN ISO 11664-4 after UV storage according to DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation, provided that for every 100 mass fractions of at least one polyamide to be used as component a), preferably polyamide 6 or polyamide 66, 0.03 to 3 mass fractions, preferably 0.05 to 1 mass fraction, of component b), 0.05 to 5 mass fractions, preferably 0.25 to 1 mass fraction, of component c), 0.05 to 5 mass fractions, preferably 0.2 to 1 mass fraction, of component d) and 0.05 to 5 mass fractions, preferably 0.1 to 1 mass fraction, of component e) are used.

[0023] The invention also relates to a Proceedings to maintain impact strength measured according to ISO180-1Uand / or to maintain elongation at break measured according to ISO 527 after hot air aging for over 500 h at 150°C and / or to maintain color according to DIN EN ISO 11664-4 after hot air storage for over 500 h at 150°C and / or to maintain color according to DIN EN ISO 11664-4 after UV storage according to DIN ISO 4892-2A for over 200 h at 80°C, 340 nm and 1.55 W / m² without spraying of polyamide-based products, by adding 0.05 to 5 mass fractions, preferably 0.1 to 1 mass fraction, of 4,4'-bis(phenylisopropyl)diphenylamine as component e) to a) 100 mass fractions of a polyamide to be used as component a) b) 0.03 to 3 mass fractions, preferably 0.05 to 1 mass fractions of at least one sterically hindered phenol, c) 0.05 to 5 mass fractions, preferably 0.25 to 1 mass fractions of at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, and d) uses 0.05 to 5 mass fractions, preferably 0.2 to 1 mass fractions of at least one 3-thiopropionate.

[0024] The ammonium ion NH₄⁺< for R', defined in formula (I) of the present invention, is a cation that forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0025] For the avoidance of doubt, it should be noted that within the scope of the present invention, with regard to the compositions, products, uses and methods according to the invention, the impact strength test according to ISO 180-1U (Izod) as well as the elongation at break test according to ISO 527 on injection-molded after DIN EN ISO 1874-2 The test was and is to be carried out on specified test specimens in the freshly molded state at 23°C in order to determine the values ​​before heat aging. The freshly molded state, also known as "dry as molded," is defined in the DIN EN ISO 1874-2 defined.

[0026] For the sake of clarity, it should also be noted that within the scope of the present invention, the testing of the aging behavior with regard to the compositions, products, uses and methods according to the invention is carried out in the form of maintaining the impact strength by storing injection-molded parts according to DIN EN ISO 1874-2The impact strength of the test specimens was determined in a Binder FP115 material testing chamber with circulating air at temperatures of 150°C for 500 hours. The impact strength of the test specimens produced according to the present invention was therefore determined both before (in the freshly injected state) and after storage according to the specified parameters. ISO 180-1U The elongation at break was determined at 23°C and the difference value calculated. Within the scope of the present invention, the elongation at break was measured on these specimens both before (in the freshly injected state) and after heat aging according to the present invention. ISO 527 determined to ascertain the percentage received.

[0027] The Lab color space (also: CIELAB, CIEL*a*b*, Lab colors) describes all perceptible colors. It uses a three-dimensional color space in which the brightness value L* is perpendicular to the color plane (a,b). The L* axis describes the brightness (luminance) of the color with values ​​from 0 to 100. In the representation, it is perpendicular to the a*b* plane at the origin. It can also be called the neutral gray axis, because all achromatic colors (shades of gray) are contained between the endpoints black (L*=0) and white (L*=100). In analogy to Ewald Hering's opponent-process theory, the a-coordinate indicates the hue and color intensity between green and red, and the b-coordinate indicates the hue and color intensity between blue and yellow. The larger the positive a and b values, and the smaller the negative a and b values, the more intense the hue. If a=0 and b=0, there is an achromatic hue on the brightness axis.In typical software implementations, L* can take values ​​between 0 and 100, and a and b can be varied between -128 and 127. The discoloration of polymer-based products due to oxidative damage to the polymer matrix can be determined by measuring the color difference ΔE over storage time at high temperature. The color difference ΔE between two color stimuli is calculated according to the equation ΔE = [(ΔL*)² + (Δa*)² + (Δb*)²] 1 / 2< according to... DIN EN ISO 11664-4 calculated. As explained above, the color difference ΔE is a dimensionless quantity. The smaller the value, the smaller the color difference from a given initial value. A color difference ΔE = 0 therefore corresponds to no change in color, but rather to a constant color.

[0028] For clarification, it should therefore be noted that, within the scope of the present invention, the testing of the aging behavior with regard to the inventive compositions, the inventive products, the inventive uses, and the inventive methods in the form of improved color retention / improved color stability is carried out by storing injection-molded sheets measuring 60 mm x 40 mm x 4 mm in a Binder FP115 model material testing chamber with circulating air at temperatures of 150°C, hereinafter referred to as hot air aging. As a measure of discoloration, the color difference ΔE of injection-molded products based on inventive polymer compositions before and after hot air aging is determined within the scope of the present invention by measuring the color values ​​L*a*b*. ΔE = ΔL ∗ 2 + Δa ∗ 2 + Δb ∗ 2 1 / 2

[0029] Thus, according to the invention, good aging behavior in the form of improved color retention or improved color stability after hot air aging is characterized by the fact that the color change ΔE is smaller compared to polyamide-based products containing components b), c), and d), but without component e), and preferably lies in the range of 0 to 20, particularly in the range of 0 to 15. The color values ​​L*a*b* of the samples are determined within the scope of the present invention on plates measuring 60 mm x 40 mm x 4 mm, and from these, according to... DIN EN ISO 11664-4 The color difference ΔE is calculated.

[0030] For clarification, it should also be noted that within the scope of the present invention, the testing of the aging behavior with regard to the compositions, products, uses, and methods according to the invention, in the form of improved UV stability compared to polyamide-based products containing components b), c), and d), but without component e), is carried out by storing injection-molded plates of 60 mm x 40 mm x 4 mm in a QUV rapid weathering device from Q-Lab, based on the DIN ISO 4892-2AUV curing, hereinafter referred to as UV storage, is carried out for over 200 hours at 80°C, 340 nm, and 1.55 W / m² without irrigation. Within the scope of the present invention, the color difference ΔE of injection-molded products based on polymer compositions according to the invention is determined before and after 200 hours of UV curing by measuring the color values ​​L*a*b*. As already explained above, the color difference ΔE is a dimensionless quantity. The smaller the value, the smaller the color difference from a baseline value. A color difference ΔE = 0 therefore corresponds to no change in color, but rather to a constant color. ΔE = ΔL ∗ 2 + Δa ∗ 2 + Δb ∗ 2 1 / 2

[0031] Thus, according to the invention, good aging behavior in the form of improved UV stability after UV storage in a QUV rapid weathering device is characterized by the fact that the color change ΔE in products according to the invention is smaller than in comparison to polyamide-based products containing components b), c) and d) but without component e) and the color difference ΔE is in the range of 0 to 30, particularly preferably in the range of 0 to 20.

[0032] The color values ​​L*a*b* of the samples are determined within the scope of the present invention on plates measuring 60mm • 40mm • 4mm and from these according to DIN EN ISO 11664-4 The color difference ΔE is calculated.

[0033] For the avoidance of doubt, it should also be noted that the scope of the present invention encompasses all the general or preferred definitions and parameters listed in any combination with regard to the compositions, products, uses, and methods according to the invention. This applies in particular to the quantities of the individual components to be used in the methods and uses claimed within the scope of this application. The standards cited within the scope of this application refer to the version in force on the filing date of this invention. Unless otherwise stated, percentages are percentages by weight.

[0034] Finally, for the sake of clarity, it should be noted that only unreinforced products according to the invention can be compared with unreinforced products based on prior art compositions. Likewise, only reinforced, preferably glass fiber reinforced, products according to the invention can be compared with reinforced, preferably glass fiber reinforced, products based on prior art compositions. Preferred embodiments

[0035] In a further preferred embodiment, the invention relates to Compositions as well as Polyamide-based products containing, in addition to components a), b), c), d) and e), at least one f) Filler or reinforcing agent to 5 to 185 mass fractions, preferably to 5 to 100 mass fractions, each based on 100 mass fractions of component a).

[0036] In a particularly preferred embodiment, the invention relates to Compositions as well as Polyamide-based productscontaining, in addition to components a), b), c), d) and e), at least f) glass fibers as Reinforcing material to 5 to 185 mass fractions, preferably to 5 to 100 mass fractions, each based on 100 mass fractions of component a).

[0037] In this case, the preferred subject matter of the present invention is Compositions and based thereon Products containing a) at least one polyamide, preferably polyamide 6 or polyamide 66, b) at least one sterically hindered phenol, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate, e) 4,4'-bis(phenylisopropyl)diphenylamine (antioxidant 445), and f) at least one filler or reinforcing material, preferably glass fibers, with the proviso that for every 100 mass fractions of component a), 0.03 to 3 mass fractions, preferably 0.05 to 1 mass fractions of component b), 0.05 to 5 mass fractions, preferably 0.25 to 1 mass fractions, of component c), 0.05 to 5 mass fractions, preferably 0.2 to 1 mass fractions, of component d), 0.05 to 5 mass fractions, preferably 0.1 to 1 mass fractions, of component e), and 5 to 185 mass fractions, preferably 5 to 100 mass fractions, of component f) are used.

[0038] For the avoidance of doubt, it should be noted in this case that, within the scope of the present invention, all fillers and reinforcing materials as well as the quantities mentioned herein relate to both the compositions according to the invention and the polyamide-based products to be manufactured therefrom, in particular polyamide-based products in high-voltage applications, in the automotive sector or in the household sector, as well as to the uses and processes according to the invention.

[0039] The ammonium ion NH₄⁺ for R' in formula (I) is a cation that forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0040] The invention therefore also relates to the use containing mixtures a) at least one polyamide, preferably polyamide 6 or polyamide 66, b) at least one sterically hindered phenol, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate, e) 4,4'-bis(phenylisopropyl)diphenylamine (antioxidant 445), and f) at least one filler or reinforcing material, preferably glass fibers, for the manufacture of polyamide-based products, preferably for the manufacture of polyamide-based products with retention of impact strength measured according to ISO180-1U and / or maintenance of elongation at break measured after ISO 527 calculated after hot air aging over 500h at 150°C and / or color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or color retention according to DIN EN ISO 11664-4 after UV storage according to DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation, provided that for every 100 mass fractions of at least one polyamide to be used as component a), preferably polyamide 6 or polyamide 66, 0.03 to 3 mass fractions, preferably 0.05 to 1 mass fraction, of component b), 0.05 to 5 mass fractions, preferably 0.25 to 1 mass fraction, of component c), 0.05 to 5 mass fractions, preferably 0.2 to 1 mass fraction, of component d), 0.05 to 5 mass fractions, preferably 0.1 to 1 mass fraction, of component e), and 5 to 185 mass fractions, preferably 5 to 100 mass fractions, of component f) are used.

[0041] The ammonium ion NH₄⁺< for R' is a cation that forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0042] The invention also relates to a Proceedingsto maintain impact strength measured according to ISO 180-1U and / or to maintain elongation at break measured according to ISO 527 after hot air aging for over 500 h at 150°C and / or to maintain color according to DIN EN ISO 11664-4 after hot air storage for over 500 h at 150°C and / or to maintain color according to DIN EN ISO 11664-4 after UV storage according to DIN ISO 4892-2A for over 200 h at 80°C, 340 nm and 1.55 W / m² without spraying of polyamide-based products by e) 0.05 to 5 mass fractions of 4,4'-bis(phenylisopropyl)diphenylamine as a component of a) 100 mass fractions of a polyamide to be used as component a), b) 0.03 to 3 mass fractions of at least one sterically hindered phenol, c) 0.05 to 5 mass fractions of at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, and d) employs 0.05 to 5 mass fractions of at least one 3-thiopropionate and 5 to 185 mass fractions, preferably 5 to 100 mass fractions, of at least one filler or reinforcing material, preferably glass fibers, as component f).

[0043] The ammonium ion NH₄⁺ for R' in formula (I) is a cation that forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0044] In a further embodiment, the invention relates to Compositions as well as Polyamide-based products containing, in addition to components a), b), c), d), e) and f), or instead of f), at least one component other than components b), c), d), e) and f). Flame retardantsg) to 3 to 100 mass fractions, preferably to 5 to 80 mass fractions, particularly preferably to 10 to 50 mass fractions, each based on 100 mass fractions of component a).

[0045] For the avoidance of doubt, it should be noted that within the scope of the present invention, all flame retardants to be used as component g) and the quantities mentioned herein relate to both the compositions and the polyamide-based products to be manufactured therefrom, in particular polyamide-based products in high-voltage applications, as well as to the uses and processes according to the invention.

[0046] In a further embodiment, the invention relates to Compositions as well as Polyamide-based products containing, in addition to components a), b), c), d), e) and f), or instead of f) and / or g), at least one component other than components b), c), d), e), f) and g). Additiveh) to 0.01 to 80 mass fractions, preferably to 0.05 to 50 mass fractions, particularly preferably to 0.1 to 30 mass fractions, each based on 100 mass fractions of component a).

[0047] For the avoidance of doubt, it should be noted that within the scope of the present invention, all additives to be used as component h) and the quantities mentioned herein relate to both the polyamide-based compositions and the polyamide-based products to be produced therefrom, in particular polyamide-based products in high-voltage applications, and are also applicable to the uses and methods according to the invention. Component a)

[0048] The components to be used as component a) according to the invention PolyamidePolyamides can be produced using various methods and synthesized from different building blocks. A multitude of processes have become known for the production of polyamides, whereby, depending on the desired end product, different monomer building blocks, various chain regulators to adjust a target molecular weight, or even monomers with reactive groups for subsequent post-treatments can be used.

[0049] The technically relevant processes for the production of polyamides mostly involve polycondensation in the melt. In this context, the hydrolytic polymerization of lactams is also understood as polycondensation.

[0050] Suitable starting materials include aliphatic and / or aromatic dicarboxylic acids such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines such as tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Caprolactams, especially ε-caprolactam, are particularly preferred. Copolyamides consisting of several of the aforementioned monomers are also included.

[0051] Preferred polyamides to be used as component a) are semi-crystalline polyamides which can be produced starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.

[0052] Semicrystalline polyamides, also known as semicrystalline polyamides, are characterized according to DE 10 2011 084 519 A1 by the fact that the enthalpy of fusion is in the range of 4 to 25 J / g, measured using the DSC method according to ISO 11357 during the second heating and integration of the melting peak.

[0053] Particularly preferred polyamides are polyamide 6, polyamide 66, polyamide 46 and / or partially aromatic copolyamides. Preferred partially aromatic copolyamides are PA6T / 6, PA6T / 66, PA6T / 61 or PA6T / 6I / 66.

[0054] The designation of the polyamides used in the present application complies with the international standard ISO 1874-1,where the first digit(s) indicate the number of carbon atoms in the starting diamine and the last digit(s) indicate the number of carbon atoms in the dicarboxylic acid. If only one number is given, as in the case of PA6, this means that an α,ω-aminocarboxylic acid or the lactam derived from it, in the case of PA6, ε-caprolactam, was used as the starting material.

[0055] The PA6 [CAS No. 25038-54-4], which according to the invention is preferably used as component a), preferably has a ISO 307 The viscosity number to be determined in a 0.5 wt% solution in 96 wt% sulfuric acid at 25°C is in the range of 80 to 180 ml / g, particularly preferably in the range of 85 to 170 ml / g and most preferably in the range of 90 to 160 ml / g. According to the invention, polyamide 6, preferably to be used as component a), is available, for example, as Durethan® < B29 from Lanxess Deutschland GmbH, Cologne.

[0056] Preferably, a polyamide 66 [CAS No. 32131-17-2] to be used as component a) has a according to ISO 307 The viscosity number to be determined in a 0.5 wt% solution in 96 wt% sulfuric acid at 25°C is in the range of 80 to 180 ml / g, most preferably in the range of 85 to 170 ml / g, and particularly preferably in the range of 90 to 160 ml / g. The polyamide 66 to be used as component a) according to the invention is available, for example, as Ultramid® < A27E01 from BASF SE, Ludwigshafen.

[0057] The polyamide to be used as component a) according to the invention can also be used in a mixture with at least one other polyamide, as a copolyamide, and / or at least one other polymer, provided that the additional polymer used does not negatively affect the discoloration after long-term storage in hot air at up to 150°C. In the case of the use of at least one additional polyamide or at least one other polymer, this is preferably or optionally carried out with the use of at least one compatibilizer.

[0058] The polyamide to be used as component a) can already have conventional additives, preferably demolding agents, stabilizers and / or flow aids known to those skilled in the art, added to it in the melt. Component b)

[0059] to be used as component b) according to the invention sterically hindered phenolsare compounds with a phenolic structure that have at least one sterically demanding group in the form of a tert-butyl group in the immediate vicinity of the phenolic OH group on the phenolic ring. According to "http: / / de.wikipedia.org / wiki / Sterische_Hinderung" In organic chemistry, steric hindrance refers to the influence of a molecule's spatial dimensions on the course of a reaction. The term was first coined in 1894 by Victor Meyer to describe the observation that some reactions proceed very slowly or not at all when large, bulky groups are present in the vicinity of the reacting atoms. A well-known example of the influence of steric hindrance, or a sterically demanding group, is the presence of very bulky molecules. tert- butyl groups.

[0060] Preferred are sterically hindered phenols of general formula (II), where R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms, and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group.

[0061] Phenols of general formula (II) are particularly preferred. where R 1< and R 2< each represent a tert-butyl group and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

[0062] Preferred sterically hindered phenols are also compounds of formula (II), where R 1< represents a methyl group and R 2< represents a substituted alkyl group and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

[0063] Particularly favored sterically hindered phenols are also compounds of formula (II), where R 1< represents a methyl group and R 2< represents a tert-butyl group and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

[0064] Preferred phenols of formula (II) are described in DE-A 27 02 661, the content of which is fully encompassed by the present application.

[0065] Another group of sterically hindered phenols, preferably used as component b), is derived from substituted benzenecarboxylic acids, in particular from substituted benzenepropionic acids. Particularly preferred compounds from this class are compounds of formula (III). wherein R 4< , R 5< , R 7< and R 8< independently represent C 1 -C 8 alkyl groups which may in turn be substituted and at least one of which is a sterically demanding group, and R 6< represents a bridging diamine, preferably ethylenediamine or hexamethylenediamine, a diol, preferably glycol, hexanediol or an ethylene glycol oligomer.

[0066] Symmetrical compounds of formula (III) are preferably used in which R 4< = R 7< and R 5< = R 8<, wherein at least R 4< and R 7< are sterically demanding groups and R 6< is a bridging diamine, preferably ethylenediamine or hexamethylenediamine, a diol, preferably glycol, hexanediol or an ethylene glycol oligomer.

[0067] Particularly preferred are symmetrical compounds of formula (III) in which R 4< = R 7< and R 5< = R 8<, wherein R 4< and R 7< are sterically demanding groups and R 5< and R 8< are methyl groups and R 6< is a bridging diamine, preferably ethylenediamine or hexamethylenediamine, a diol, preferably glycol, hexanediol or an ethylene glycol oligomer.

[0068] Symmetrical compounds of formula (III) are particularly preferred in which R 4< and R 7< are tert-butyl groups and R 5< and R 8< are methyl groups and R 6< is a bridging diamine, preferably ethylenediamine or hexamethylenediamine, a diol, preferably glycol, hexanediol or an ethylene glycol oligomer.

[0069] Particularly preferred compounds to be used as component b) are those of general formula (IV) wherein R< , R< 5< independently represent C1-C8 alkyl groups, which may themselves be substituted, and of which at least one is a sterically demanding group, and R< 6< represents a bridging tetraalcohol derivative, preferably pentraerythritol, a pentaerythritol derivative, or a tetraamine. Compounds of formula (IV) are preferably used in which R< = methyl and R< 5< = ter-butyl and R< 6< represents a bridging tetraalcohol, preferably pentraerythritol, or a pentaerythritol derivative, or a tetraamine.

[0070] Particularly preferred compounds to be used as component b) are those of the general formula (V) wherein R< 1< and R< 2< independently represent C1-C8 alkyl groups, which may themselves be substituted and at least one of which is a sterically demanding group. Compounds of the general formula (V) are particularly preferred, wherein R< 1< represents methyl and R< 2< represents tert-butyl.

[0071] In particular, preferred compounds of formula (II) are compounds of the series Triethylenglycol-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionat (Irganox ®< 245 der BASF SE, [CAS No. 36443-68-2]); Hexamethylen-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat] (Irganox ®< 259 der BASF SE, [CAS No. 35074-77-2]); N,N'-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamid] (Irganox ®< 1098 der BASF SE, [CAS No. 23128-74-7]): 3,9-Bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]-undecan (Sumilizer ®< GA-80 der Sumitomo Chemical Co. Ltd., [CAS No. 90498-90-1]); Tetrakis[methylen-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methan (Songnox ®< 1010 der Songwon Industrial Group, [CAS No. 6683-19-8]); Thiodiethylen-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionat] (Songnox ®< 1035 der Songwon Industrial Group [CAS No. 41484-35-9]); 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzen (Songnox ®< 1330 der Songwon Industrial Group [CAS No.1709-70-2]); 1,2-Bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoly)hydrazine (Songnox® < 1024 of the Songwon Industrial Group [CAS No. 32687-78-8]); .

[0072] Particularly preferred sterically hindered phenols to be used as component b) are selected from the group consisting of 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate], pentaerythril-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate], 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene, 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine.

[0073] According to the invention, and especially preferably, component b) 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 No. 90498-90-1 ], which is available as Sumilzer ®< GA80 from Sumitomo Chemical Co., Ltd., is used. Component c)

[0074] Component c) uses at least one phosphinic acid derivative of the general formula (I). where R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group.

[0075] If R represents a hydrogen atom, it is hypophosphoric acid; if R represents an alkyl, cycloalkyl or aryl group, it is phosphinic acid, wherein the alkyl, cycloalkyl or aryl group preferably comprises up to 12 carbon atoms.

[0076] If R represents an alkyl, cycloalkyl, or aryl group, salts and esters of phosphinic acid are preferably used. Salts of phosphinic acid are preferred, and these may also be hydrates of the salts. Alkali and alkaline earth metal salts, as well as metal salts of group 12 or 13 of the periodic table of phosphinic acid, are particularly preferred, and these may also be hydrates of the salts.

[0077] If R is a hydrogen atom, the compound is hypophosphoric acid. Salts and esters of hypophosphoric acid are preferably used. Alkali and alkaline earth metal salts, salts with ammonium ions as the cation, and metal salts of hypophosphoric acid from group 12 or 13 of the periodic table are particularly preferred. Alkali metal salts of hypophosphoric acid are especially preferred, and these may also be hydrates of the salts.

[0078] The ammonium ion NH₄⁺ for R' in formula (I) is a cation that forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0079] Sodium hypophosphite [CAS No. 7681-53-0] or sodium hypophosphite monohydrate [CAS No. 10039-56-2] is particularly preferred as component c). Sodium hypophosphite and sodium hypophosphite monohydrate are commercially available from, among others, Sigma-Aldrich. Component d)

[0080] Component d) is preferably 3-thiopropionates of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms.

[0081] Preferably, 3-thiopropionates of general formula (VII) are used as component d), where R2 represents an alkyl group with 4 to 20 carbon atoms.

[0082] According to the invention, pentaerythrityltetrakis(3-dodecylthiopropionate) with CAS No. 29598-76-3 and available from Rialon Corporation, China, under the trade name Rianox ®< 412S is particularly preferred as component d). Component e)

[0083] According to the invention, component e) is the secondary amine 4,4'-bis(phenylisopropyl)diphenylamine (antioxidant 445) with CAS No. 10081-67-1 of formula (VIII).

[0084] Component e) is commercially available, among other places, from OKA-Tec GmbH under the trade name Okabest ®< AO445. Component f)

[0085] Component f) will be at least one Filler or reinforcing agentused. Mixtures of two or more different fillers or reinforcing agents can also be used.

[0086] Preferably, at least one filler or reinforcing material is selected from the group consisting of carbon fibers [CAS No. 7440-44-0], glass spheres or solid or hollow glass spheres, glass fibers, ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E-glass) [CAS No. 65997-17-3], amorphous silica [CAS No. 7631-86-9], quartz flour [CAS No. 14808-60-7], calcium silicate [CAS No. 1344-95-2], calcium metasilicate [CAS No. 10101-39-0], magnesium carbonate [CAS No. 546-93-0], kaolin [CAS No. 1332-58-7], calcined kaolin [CAS No. 92704-41-1], chalk [CAS No. 1317-65-3], kyanite [CAS No. 1302-76-7], powdered or ground quartz [CAS No. 14808-60-7], mica [CAS No. 1318-94-1], phlogopite [CAS No. 12251-00-2], barium sulfate [CAS No. 7727-43-7], feldspar [CAS No. 68476-25-5], wollastonite [CAS No. 13983-17-0], montmorillonite [CAS No. 67479-91-8], pseudoboehmite of the formula AIO(OH), magnesium carbonate [CAS No. 12125-28-9] and talc [CAS No. 14807-96-6] used.

[0087] Among the fibrous fillers or reinforcing materials, glass fibers and wollastonite are particularly preferred, with glass fibers being especially preferred. Carbon fibers can also be used as fillers or reinforcing materials.

[0088] Regarding the optical fibers, the expert distinguishes according to "http: / / de.wikipedia.org / wiki / Faser-Kunststoff-Verbund"Cut fibers, also known as short fibers, have a length of 0.1 to 1 mm; long fibers have a length of 1 to 50 mm; and continuous fibers have a length L > 50 mm. Short fibers are primarily used in injection molding and can be processed directly with an extruder. Long fibers can also be processed in extruders and are widely used in fiber spraying. Long fibers are frequently added to thermosets as a filler. Continuous fibers are used as rovings or woven fabrics in fiber-reinforced plastics. Products made with continuous fibers achieve the highest stiffness and strength values. Ground glass fibers are also available, with a typical length after grinding of 70 to 200 µm.

[0089] According to the invention, glass fibers preferably used as component f) are cut long glass fibers with a surface area determined by laser diffractometry prior to incorporation into molding compounds. ISO 13320 The mean initial length to be determined is in the range of 1 to 50 mm, particularly preferably in the range of 1 to 10 mm, and most preferably in the range of 2 to 7 mm. For laser diffraction particle size determination / laser diffractometry according to the standard. ISO 13320 see: https: / / de.wikipedia.org / wiki / Laserbeugungs-Partikelgr%C3%B6%C3%9Fenanalyse Preferred optical fibers to be used as component f) have a profile determined by laser diffraction according to ISO 13320 The mean fiber diameter to be determined is in the range of 7 to 18 µm, particularly preferably in the range of 9 to 15 µm.

[0090] The fillers to be used as component f), preferably glass fibers, are in a preferred embodiment equipped with a suitable sizing system or an adhesion promoter or adhesion promoter system. A silane-based sizing system or adhesion promoter is preferably used. Particularly preferred silane-based adhesion promoters for the treatment of component e), especially for the treatment of glass fibers, are silane compounds of the general formula (IX) (X-(CH₂)q)k-Si-(O-CrH₂R+I)4-k (IX) wherein X stands for NH2, carboxyl, HO, or other pigments. qin formula (IX) represents an integer from 2 to 10, preferably 3 to 4, rin formula (IX) represents an integer from 1 to 5, preferably 1 to 2 and kin formula (IX) represents an integer from 1 to 3, preferably 1. Particularly preferred adhesion promoters are silane compounds from the group consisting of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl or a carboxyl group as substituent X in formula (IX), wherein carboxyl groups are particularly preferred.

[0091] For the treatment of the fillers to be used as component f), preferably glass fibers, the adhesion promoter, preferably the silane compounds according to formula (IX), is used preferably in amounts in the range of 0.05 to 2 wt.%, particularly preferably in amounts in the range of 0.25 to 1.5 wt.% and most preferably in amounts in the range of 0.5 to 1 wt.%, in each case based on 100 wt.% component f).

[0092] The glass fibers preferably used as component f) may be shorter in the composition or product than the originally used glass fibers due to processing. Thus, the arithmetic mean of the glass fiber length, determined by high-resolution X-ray computed tomography, is often only in the range of 150 µm to 300 µm after processing.

[0093] According to "http: / / www.rg.de / wiki / Glasfasern" Glass fibers are produced using melt spinning processes (nozzle drawing, rod drawing, and nozzle blowing). In the nozzle drawing process, the hot glass mass flows through hundreds of nozzle holes in a platinum spinning plate, utilizing gravity. The elementary fibers can be drawn to unlimited lengths at a speed of 3–4 km / minute.

[0094] Experts distinguish between different types of fiberglass, some of which are listed here: E-glass, the most widely used material with an optimal price-performance ratio (E-glass from R&G) H-glass, hollow glass fibers for reduced weight (R&G hollow glass fiber fabric 160 g / m²< and 216 g / m²<) R, S-glass, for increased mechanical requirements (S2-glass from R&G) D-glass, borosilicate glass for increased electrical requirements C-glass, with increased chemical resistance Quartz glass, with high temperature resistance

[0095] Further examples can be found at "http: / de.wikipedia.org / wiki / Glass fiber".E-glass fibers have become the most important type for reinforcing plastics. E stands for electrical glass, as it was originally used primarily in the electrical industry. E-glass is produced by melting pure quartz glass with additives of limestone, kaolin, and boric acid. In addition to silicon dioxide, it contains varying amounts of different metal oxides. The composition determines the properties of the products. According to the invention, at least one type of glass fiber from the group consisting of E-glass, H-glass, R,S-glass, D-glass, C-glass, and quartz glass is preferably used, with E-glass glass being particularly preferred.

[0096] E-glass fibers are the most widely used reinforcing material. Their strength properties are comparable to those of metals (e.g., aluminum alloys), although the specific gravity of laminates containing E-glass fibers is lower than that of the metals. E-glass fibers are non-combustible, heat-resistant up to approximately 400°C, and resistant to most chemicals and weathering.

[0097] Preferably, needle-shaped mineral fillers are also used as component f). According to the invention, needle-shaped mineral fillers are defined as mineral fillers with a pronounced needle-shaped character. Wollastonite is a preferred needle-shaped mineral filler used as component f). The needle-shaped mineral filler preferably has a length-to-diameter ratio (L / D) of 2:1 to 35:1, determined by high-resolution X-ray computed tomography, particularly preferably in the range of 3:1 to 19:1, and especially preferably in the range of 4:1 to 12:1. The mean particle size of the needle-shaped mineral fillers, determined by high-resolution X-ray computed tomography, is preferably less than 20 µm, particularly preferably less than 15 µm, and especially preferably less than 10 µm.

[0098] However, non-fibrous and non-foamed ground glass with a properties determined by laser diffractometry according to is also preferred as component f). ISO 13320 The particle size distribution to be determined is determined using a d90 in the range of 5 to 250 µm, preferably with a d90 in the range of 10 to 150 µm, particularly preferably with a d90 in the range of 15 to 80 µm, and most preferably with a d90 in the range of 16 to 25 µm. Regarding the d90 values, their determination, and their significance, reference is made to Chemie Ingenieur Technik (72) pp. 273-276, 3 / 2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d90 value is the particle size below which 90% of the particle quantity lies.

[0099] Preferably according to the invention, the non-fibrous and non-foamed ground glass is of a particulate, non-cylindrical shape and has, prior to processing into molding compounds, a structure determined by laser diffractometry according to ISO 13320The length-to-diameter ratio L / D to be determined must be less than 5, preferably less than 3, and particularly preferably less than 2. The value zero is of course excluded.

[0100] The non-foamed and non-fibrous ground glass, which is particularly preferably used as component f) in one embodiment, is further characterized in that it does not have the glass geometry typical of fibrous glass with a cylindrical or oval cross-section with a shape determined by laser diffractometry prior to processing into molding compounds. ISO 13320 has a length-to-diameter ratio (L / D ratio) greater than 5.

[0101] The non-foamed and non-fibrous ground glass, which is particularly preferred as component f) in one embodiment according to the invention, is preferably obtained by grinding glass with a mill, preferably a ball mill, and particularly preferably with subsequent classification or sieving. Preferred starting materials for grinding the non-fibrous and non-foamed ground glass, which is used as component f) in one embodiment, also include glass waste, such as that which arises in particular during the manufacture of glass products as an undesired by-product and / or as a main product that does not meet specifications (so-called off-spec material). This includes in particular waste, recycled, and broken glass, such as that which can arise in particular during the manufacture of window or bottle glass, as well as during the manufacture of glass-containing fillers and reinforcing materials, especially in the form of so-called melt cakes.The glass may be colored, but uncolored glass is preferred as the starting material for use as component f). Component g)

[0102] In a preferred embodiment, at least one flame retardant is used as component g). Flame retardants These include various mineral flame retardants, nitrogen-containing flame retardants, or phosphorus-containing flame retardants.

[0103] Among the mineral flame retardants to be used as component g), magnesium hydroxide is particularly preferred. Magnesium hydroxide [CAS No. 1309-42-8] may be contaminated due to its origin and manufacturing process. Typical impurities include, for example, silicon-, iron-, calcium-, and / or aluminum-containing species, which may be incorporated into the magnesium hydroxide crystals, for instance, in the form of oxides. The magnesium hydroxide used as a mineral flame retardant may be uncoated or coated. A coating promotes the mechanical bond between the polymer (matrix) and the component to be coated, thus improving quality. Preferably, the magnesium hydroxide used as a mineral flame retardant is coated with sizing based on stearates or aminosiloxanes, particularly preferably with aminosiloxanes.Magnesium hydroxide, preferably used as a mineral flame retardant, has been tested for consistency before processing into a molding compound by laser diffractometry according to . ISO 13320 The mean particle size d50 to be determined is in the range of 0.5 µm to 6 µm, wherein a d50 in the range of 0.7 µm to 3.8 µm is preferred and a d50 in the range of 1.0 µm to 2.6 µm is particularly preferred.

[0104] Preferred mineral flame retardants according to the invention are magnesium hydroxide types, in particular Magnifin ®< H5IV from Martinswerk GmbH, Bergheim, Germany or Hidromag ®< Q2015 TC from Penoles, Mexico City, Mexico.

[0105] Preferred nitrogen-containing flame retardants to be used as component g) are the reaction products of trichlorotriazine, piperazine, and morpholine according to CAS No. 1078142-02-5, in particular MCA PPM Triazine HF from MCA Technologies GmbH, Biel-Benken, Switzerland, as well as melamine cyanurate and condensation products of melamine, in particular melem, melam, melon, or higher-condensed compounds of this type. Preferred inorganic nitrogen-containing compounds are ammonium salts.

[0106] Furthermore, salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives, in particular aluminum hydroxide or Ca-Mg carbonate hydrates, may also be used. ( DE-A 4 236 122 ) be used.

[0107] Flame retardant synergists from the group of oxygen-, nitrogen-, or sulfur-containing metal compounds are also suitable for use as component g). Zinc-free compounds are preferred, in particular molybdenum oxide, magnesium oxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, magnesium nitride, calcium phosphate, calcium borate, magnesium borate, or mixtures thereof.

[0108] In an alternative embodiment, zinc-containing compounds can also be used as component g), if required. These preferably include zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide and zinc nitride, or mixtures thereof.

[0109] Preferred phosphorus-containing flame retardants to be used as component g) are organic metal phosphinates, aluminum salts of phosphonic acid, red phosphorus, inorganic metal hypophosphites, metal phosphonates, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO derivatives), resorcinol bis-(diphenyl phosphate) (RDP) including oligomers, bisphenol A bis-diphenyl phosphate (BDP) including oligomers, melamine pyrophosphate, melamine polyphosphate, melamine poly(aluminum phosphate), melamine poly(zinc phosphate) or phenoxyphosphazene oligomers and mixtures thereof.

[0110] A preferred organic metal phosphinate is aluminum tris(diethyl phosphinate). A preferred inorganic metal hypophosphite is aluminum hypophosphite.

[0111] Other flame retardants to be used as component g) are carbon formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyetherketones, as well as anti-drip agents, in particular tetrafluoroethylene polymers.

[0112] The flame retardants to be used as component g) can be added in pure form, as well as via masterbatches or compacts of component a).

[0113] In an alternative embodiment, component g) can also be a flame retardant, but also – if required, taking into account the disadvantages of the

[0114] Loss of halogen-free flame retardants – halogen-containing flame retardants are used. 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, polypentabrombenzyl acrylate, brominated polystyrene, or brominated polyphenylene ethers, which can be used alone or in combination with synergists, with brominated polystyrene being particularly preferred among the halogen-containing flame retardants. Brominated polystyrene is preferably used at 10–30 wt.%, particularly preferably at 15–25 wt.%, in each case based on the total composition, wherein at least one of the other components is reduced to such an extent that the sum of all wt. percent always equals 100.

[0115] In another alternative embodiment, antimony trioxide and antimony pentoxide can also be used as flame retardant synergists - if required and taking into account the hazard classification according to H351.

[0116] Brominated polystyrene is commercially available in various product grades. Examples include Firemaster® < PBS64 from Lanxess, Cologne, Germany, and Saytex® < HP-3010 from Albemarle, Baton Rouge, USA.

[0117] Among the flame retardants to be used as component g), aluminium tris(diethylphosphinate)] [CAS No. 225789-38-8] and the combination of aluminium tris(diethylphosphinate) and melamine polyphosphate or the combination of aluminium tris(diethylphosphinate) and at least one aluminium salt of phosphonic acid are particularly preferred, the latter combination being especially preferred.

[0118] In the case of combinations of aluminium tris(diethylphosphinate) and melamine polyphosphate or of aluminium tris(diethylphosphinate) and at least one aluminium salt of phosphonic acid, the proportion of aluminium tris(diethylphosphinate) is preferably in the range of 40 to 90 mass parts, particularly preferably in the range of 50 to 80 mass parts, and most preferably in the range of 60 to 70 mass parts, in each case based on 100 mass parts of the combination of aluminium tris(diethylphosphinate) and melamine polyphosphate or of the combination of aluminium tris(diethylphosphinate) and at least one aluminium salt of phosphonic acid.

[0119] The aluminum tris(diethylphosphinate) preferably used as component g) is known to those skilled in the art as Exolit® < OP1230 or Exolit® < OP1240 from Clariant International Ltd., Muttenz, Switzerland. Melamine polyphosphate is commercially available in various product grades. Examples include Melapur® < 200 / 70 from BASF, Ludwigshafen, Germany, and Budit® < 3141 from Budenheim, Budenheim, Germany.

[0120] Preferred aluminium salts of phosphonic acid to be used as component g) are to be selected from the group primary aluminum phosphonate [Al(H₂PO₃)₃], basic aluminum phosphonate [Al(OH)H₂PO₃)₂·2H₂O], Al₂(HPO₃)₃·xAl₂O₃·nH₂O with x in the range of 2.27 to 1 and n in the range of 0 to 4, Al₂(HPO₃)₃·(H₂O)q of formula (X) with q in the range of 0 to 4, in particular aluminum phosphonate tetrahydrate [Al₂(HPO₃)₃·4H₂O] or secondary aluminum phosphonate [Al₂(HPO₃)₃], Al₂Mz(HPO₃)y(OH)v·(H₂O)w of formula (XI) wherein M denotes alkali metal ion(s) and z in the range of 0.01 to 1.5, y in the range from 2.63 - 3.5, v in the range of 0 to 2 and w in the range of 0 to 4, and Al 2 (HPO 3 ) u (H 2 PO 3 ) t · (H 2 O) s of formula (XII), 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, wherein in formula (XI) z, y and v and in formula (XII) u and t can only take such numbers that the corresponding aluminium salt of phosphonic acid as a whole is uncharged.

[0121] Preferred alkali metals M in formula (XI) are sodium and potassium.

[0122] The described aluminum salts of phosphonic acid can be used individually or in a mixture.

[0123] Particularly preferred aluminium salts of phosphonic acid to be used as component g) are selected from the group primary aluminum phosphonate [Al(H2PO3)3], secondary aluminum phosphonate [Al2(HPO3)3], basic aluminum phosphonate [Al(OH)H2PO3)2 ·2H2O], aluminum phosphonate tetrahydrate [Al2(HPO3)3 ·4H2O] and Al2(HPO3)3 • xAl2O3 • nH2O with x in the range of 2.27 to 1 and n in the range of 0 to 4.

[0124] Particularly preferred are secondary aluminium phosphonate Al 2 (HPO 3 ) 3 [CAS No. 71449-76-8] and secondary aluminium phosphonate tetrahydrate Al 2 (HPO 3 ) 3 ·4H 2 O [CAS No. 156024-71-4], especially preferred is secondary aluminium phosphonate Al 2 (HPO 3 ) 3 .

[0125] The preparation of aluminum salts of phosphonic acid to be used as component g) according to the invention is described, for example, in WO 2013 / 083247 A1. It is typically carried out by reacting an aluminum source, preferably aluminum isopropoxide, aluminum nitrate, aluminum chloride, or aluminum hydroxide, with a phosphorus source, preferably phosphonic acid, ammonium phosphonate, or alkali phosphonate, and optionally with a template in a solvent at 20 to 200°C for a period of up to 4 days. For this purpose, the aluminum source and phosphorus source are mixed, heated under hydrothermal conditions or under reflux, filtered, washed, and dried. Preferred templates are 1,6-hexanediamine, guanidine carbonate, or ammonia. The preferred solvent is water. Component h)

[0126] Component h) is at least one further component, different from components b), c), d), e), f) and g). AdditivePreferred additives to be used as component h) are antioxidants, thermostabilizers, UV stabilizers, gamma-ray stabilizers, water absorption reducers or hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, lubricants and / or demolding agents, water absorption reducers, flow agents, chain-extending additives, colorants, or laser absorbers. The additives can be used alone or in mixtures or in the form of masterbatches.

[0127] Preferred ThermostabilizersComponent h) consists of various sterically hindered phenols from component b), in particular those containing at least one 2,6-di-tert-butylphenyl group and / or 2-tert-butyl-6-methylphenyl group, furthermore phosphites, hydroquinones, aromatic secondary amines different from component e), substituted resorcinols, salicylates, benzotriazoles and benzophenones, 3,3'-thiodipropionic acid esters as well as variously substituted representatives of these groups or their mixtures.

[0128] Thermostabilizers to be used as component h) are preferably used in a mass fraction of 0.01 to 2, particularly preferably in a mass fraction of 0.05 to 1, each based on 100 mass fractions of component a).

[0129] Component h) to be used UV stabilizersPreferably substituted resorcinols, salicylates, benzotriazoles and benzophenones, HALS derivatives ("Hindered Amine Light Stabilizers") containing at least one 2,2,6,6-tetramethyl-4-piperidyl unit or benzophenones are used. UV stabilizers to be used as component h) are preferably added at a mass fraction of 0.01 to 2 parts, particularly preferably at a mass fraction of 0.1 to 1 part, based on 100 parts by mass of component a).

[0130] Component h) to be used colorantIn one embodiment, inorganic pigments are preferably used, particularly ultramarine blue, bismuth vanadate [CAS No. 14059-33-7], iron oxide [CAS No. 1309-37-1], titanium dioxide [CAS No. 13463-67-7 (rutile) or CAS No. 1317-70-0 (anatase)], barium sulfate [CAS No. 7727-43-7], zinc sulfide [CAS No. 1314-98-3], or sulfides containing cerium. Preferred sulfides containing cerium are cerium(III) sulfide (Ce₂S₃) [CAS No. 12014-93-6], also known as CI Pigment Orange 75, or Cerium(III) sulfide / Lanthanum(III) sulfide (Ce₂S₃ / La₂S₃) [CAS No. 12014-93-6; CAS No. 12031-49-1], also known as CI Pigment Orange 78. Barium sulfate is particularly preferred. Titanium dioxide, also known as Pigment White 6 or CI 77891, is also particularly preferred.

[0131] also to be used as component h) according to the invention colorantPigment systems based on inorganic mixed oxides containing titanium dioxide, tin oxide, and zinc oxide are also preferably used. A pigment system based on inorganic mixed oxides containing titanium dioxide, tin oxide, and zinc oxide, which is preferably used as component h) according to the invention, is known from EP 0 113 229 B1, as is its preparation. The content of EP 0 113 229 B1 is fully encompassed by the present description. According to EP 0 113 229 B1, the proportions of the tin, titanium, zinc, and oxygen content in a pigment system to be used as component g) according to the invention are preferably represented by the general formula (XIII) (TiO 2 ) c SnO(ZnO) d (SnO) e , (XIII) wherein c is in the range of 0.3 to 6.2, d is in the range of 0.04 to 6.2, and e is in the range of 0 to 7.

[0132] Preferably, a pigment system of general formula (XIII) to be used as component h) contains 300 to 6000 parts of alkali metal residues per million parts of the entire complex or pigment system. According to the invention, a pigment system to be used as component h) based on inorganic mixed oxides of titanium dioxide, tin oxide, and zinc oxide can be used individually or in a mixture with at least one other inorganic mixed oxide of titanium dioxide, tin oxide, and zinc oxide. In particular, a pigment system of general formula (XIII) of CAS No. 923954-49-8, or CI Pigment Orange 82 [CAS No. 2170864-77-2], or CI Pigment Yellow 216 [CAS No. 817181-98-9] is preferred. Regarding the CI classification, see: https: / / de.wikipedia.org / wiki / Colour_Index.Pigment Orange 82, for example, can be obtained under the name Sicopal® < Orange K2430 from BASF SE, Ludwigshafen, Germany. Pigment Yellow 216, for example, can be obtained under the name Orange 10P340 from Shepherd, Ghent, Belgium.

[0133] The further component h) to be used colorant In one embodiment, organic colorants are preferably used, particularly phthalocyanines, quinacridones, benzimidazoles, especially Ni-2-hydroxy-napthyl-benzimidazole [CAS No. 42844-93-9] and / or pyrimidine azo-benzimidazole [CAS No. 72102-84-2] and / or Pigment Yellow 192 [CAS No. 56279-27-7], also perylene, anthraquinones, in particular CI Solvent Yellow 163 [CAS No. 13676-91-0] and phthaloperins, in particular 10,10'-oxy-bis-12H-phthaloperin-12-one [CAS No. 203576-97-0] and 12H-phthaloperin-12-one [CAS No. 6925-69-5], wherein 10,10'-oxy-bis-12H-phthaloperin-12-one is in particular preferred.

[0134] In an alternative embodiment, carbon black or nigrosine can also be used as the coloring agent of component h), if required.

[0135] In a particularly preferred embodiment, the colorants are used according to the invention in such a way that the color-stable, impact-resistant polyamide-based products are colored "orange", wherein shades that are "similar" to those of the color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 and RAL2011 in the RAL color system are preferred and such shades that are "similar" to the color numbers RAL2003, RAL2008 and RAL2011 are particularly preferred.

[0136] According to the invention, "orange" is understood to mean a color shade that is "similar" to a color shade of a color number beginning with "2" in the RAL color chart. According to the invention, "similar" color shades are those whose color difference in the L*a*b* system has a ΔE of <20, preferably a ΔE <10, and particularly preferably a ΔE <5 to the color in the RAL color chart. For further explanation of the EN ISO 11664-4 defined ΔE see, for example: https: / / de.wikipedia.org / wiki / Delta_E.

[0137] Component h) to be used Nucleating agent The nucleating agents are preferably sodium or calcium phenylphosphinate, aluminum oxide, silicon dioxide, or talc. Talc [CAS No. 14807-96-6], especially microcrystalline talc, is particularly preferred. Talc, also known as talc, is a layered silicate with the chemical composition Mg₃[Si₄O₁₀(OH)₂], which, depending on the modification, crystallizes as Talc-1A in the triclinic or as Talc-2M in the monoclinic crystal system. (http: / / de.wikipedia.org / wiki / Talkum).Talc to be used according to the invention can, for example, be obtained as Mistron ®< R10 from Imerys Talc Group, Toulouse, France (Rio Tinto Group).

[0138] Component h) to be used Flow aidsCopolymers of at least one α-olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol are preferably used. Copolymers in which the α-olefin is composed of ethene and / or propene and the methacrylic acid ester or acrylic acid ester contains linear or branched alkyl groups with 6 to 20 carbon atoms as the alcohol component are particularly preferred. Acrylic acid (2-ethyl)hexyl ester is especially preferred. Copolymers suitable as flow aids are characterized not only by their composition but also by their low molecular weight. Accordingly, copolymers with a minimum molecular weight index (MFI) of at least 100 g / 10 min, preferably at least 150 g / 10 min, and particularly preferably at least 300 g / 10 min, measured at 190°C and a load of 2.16 kg, are particularly suitable for the polymer compositions according to the invention.The MFI, Melt Flow Index, is used to characterize the flow of a thermoplastic melt and is subject to standards. ISO 1133 or ASTM D 1238. In particular, a copolymer of ethene and acrylic acid (2-ethyl)hexyl ester with MFI 550, known as Lotryl ®< 37EH550, is preferably used as a flow aid.

[0139] Component h) to be used chain-extending additivesPreferably, di- or multifunctional branching or chain-extending additives containing at least two branching or chain-extending functional groups per molecule are used. Low-molecular-weight or oligomeric compounds are preferred as branching or chain-extending additives, provided they possess at least two chain-extending functional groups per molecule that can react with primary and / or secondary amino groups, and / or amide groups, and / or carboxylic acid groups. Preferably, chain-extending functional groups include isocyanates, alcohols, blocked isocyanates, epoxides, maleic anhydride, oxazolines, oxazines, and oxazolones, with epoxides being particularly preferred.

[0140] Particularly preferred di- or multifunctional branching or chain-extending additives are diepoxides based on diglycidyl ethers (bisphenol and epichlorohydrin), on amine epoxy resin (aniline and epichlorohydrin), on diglycidyl esters (cycloaliphatic dicarboxylic acids and epichlorohydrin) individually or in mixtures, as well as 2,2-bis[p-hydroxyphenyl]-propane diglycidyl ether, bis-[p-(N-methyl-N-2,3-epoxy-propylamino)-phenyl]-methane and epoxidized fatty acid esters of glycerol, containing at least two epoxide groups per molecule.

[0141] Particularly preferred di- or multifunctional branching or chain-extending additives are glycidyl ethers, most preferably bisphenol A diglycidyl ethers [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, as well as most preferably epoxidized soybean oil [CAS No. 8013-07-8] and / or epoxidized linseed oil.

[0142] preferably to be used as component h) Plasticizers These include phthalic acid dioctyl esters, phthalic acid dibenzyl esters, phthalic acid butylbenzyl esters, hydrocarbon oils or N-(n-butyl)benzenesulfonamide.

[0143] Component h) to be used Lubricants and / or demolding agents are preferably long-chain fatty acids, in particular stearic acid or behenic acid, their salts, in particular Ca or Zn stearate, as well as their ester derivatives, in particular those based on pentaerythritol, in particular fatty acid esters of pentaerythritol or amide derivatives, in particular ethylene bis stearylamide, montan waxes as well as low molecular weight polyethylene or polypropylene waxes.

[0144] Montan waxes within the meaning of the present invention are mixtures of straight-chain saturated carboxylic acids with chain lengths in the range of 28 to 32 carbon atoms.

[0145] According to the invention, sliding and / or demolding agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms with aliphatic saturated alcohols or amides of amines with 2 to 40 carbon atoms with unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms are particularly preferred, or metal salts of saturated or unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms are used instead of the carboxylic acids.

[0146] Particularly preferably, the lubricating and / or demolding agents to be used as component h) are selected from the group consisting of pentaerythritol tetrastearate [CAS No. 115-83-3], ethylene bis-stearylamide, zinc stearate, calcium stearate, and ethylene glycol dimontanate. Zinc stearate [CAS No. 557-05-1], calcium stearate [CAS No. 1592-23-0], or ethylene bis-stearylamide [CAS No. 110-30-5] are used. Zinc stearate [CAS No. 557-05-1] is particularly preferred.

[0147] Component h) preferably to be used Hydrolysis stabilizers or components for reducing water absorption The polyesters are preferably polybutylene terephthalate and / or polyethylene terephthalate, with polyethylene terephthalate being particularly preferred. The polyesters are preferably used in concentrations of 5 to 20 wt% and particularly preferably in concentrations of 7 to 15 wt%, in each case based on the total polymer composition and provided that the sum of all wt% of the polymer composition always equals 100 wt%.

[0148] Component h) preferably to be used Laser absorber The following are selected from the group consisting of tin oxide, tin orthophosphate, barium titanate, aluminum oxide, copper hydroxyphosphate, copper orthophosphate, potassium copper diphosphate, copper hydroxide, bismuth trioxide, tin and / or antimony oxide doped micas and anthraquinone. Tin oxide is particularly preferred.

[0149] In an alternative embodiment, antimony tin oxide, antimony trioxide or antimony pentoxide can also be used as a laser absorber - if required, taking into account the disadvantages with regard to a hazard classification H351.

[0150] The laser absorber can be used directly as a powder or in the form of masterbatches. Preferred masterbatches are those based on polyamide and / or polyolefins, preferably polyethylene. The laser absorber is most preferably used in the form of a polyamide 6-based masterbatch.

[0151] The laser absorber can be used individually or as a mixture of several laser absorbers. Laser absorbers can absorb 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 / 003976 A1. Nd:YAG lasers, with which wavelengths of 1064, 532, 355, and 266 nm can be achieved, and CO₂ lasers are preferred. Particularly preferred compositions / products

[0152] The present invention relates in particular, and especially preferably, to Compositions and to be produced from it Products containing a) at least one polyamide, preferably polyamide 6 or polyamide 66, b) at least one sterically hindered phenol of general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur, and oxygen, or optionally nitrogen, with up to 300 atoms, and R2 represents an alkyl group with 4 to 20 carbon atoms. at least glass fibers, and e) 4,4'-bis(phenylisopropyl)diphenylamine, wherein 38 to 85 wt.%, preferably 65 to 70 wt.% of component a) contains 0.1 to 0.3 wt.% of component b), 0.3 to 1 wt.% of component c), 0.2 to 0.6 wt.% of component d), 0.1 to 1 wt.% of component e), and 15 to 60 wt.%, preferably 25 to 34.4 wt.% of component f), and the sum of all wt. percent always equals 100.

[0153] The present invention relates in particular, and especially preferably, to Compositions and to be produced from it Products containing a) at least one polyamide, preferably polyamide 6 or polyamide 66, b) 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane, c) sodium hypophosphite, d) pentaerythrityltetrakis(3-dodecylthiopropionate), e) 4,4'-bis(phenylisopropyl)diphenylamine and f) glass fibers, wherein, for 38 to 85 wt.%, preferably 65 to 70 wt.% of component a), 0.1 to 0.3 wt.% of component b), 0.3 to 1 wt.% of component c), 0.2 to 0.6 wt.% of component d), 0.1 to 1 wt.% of component e), and 15 to 60 wt.%, preferably 25 to 34.4 wt.% of component f) is used and the sum of all wt.% always equals 100. Particularly preferred uses

[0154] The invention preferably relates to the use of 4,4'-Bis(phenylisopropyl)diphenylamine in combination with b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, to obtain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0155] The invention preferably further relates to the use of 4,4'- Bis(phenylisopropyl)diphenylamine in combination with c) at least one phosphinic acid derivative of the general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, to obtain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0156] The invention preferably further relates to the use of 4,4'- Bis(phenylisopropyl)diphenylamine in combination with d) at least one 3-thiopropionate of the general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, to obtain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0157] The invention preferably further relates to the use of 4,4'- Bis(phenylisopropyl)diphenylamine in combination with b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms, and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group, and c) at least one phosphinic acid derivative of the general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, to obtain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0158] The invention preferably further relates to the use of 4,4'- Bis(phenylisopropyl)diphenylamine in combination with b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms, and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group, and d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, to obtain impact strength measured according to ISO180-1Uand / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0159] The invention preferably further relates to the use of 4,4'- Bis(phenylisopropyl)diphenylamine in combination with c) at least one phosphinic acid derivative of the general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, to obtain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products.

[0160] The invention also relates to the use of the components b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, and e) 4,4'-bis(phenylisopropyl)diphenylamine (antioxidant 445) to maintain impact strength as measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without spraying of polyamide-based products, provided that for every 100 mass fractions of at least one polyamide to be used as component a), 0.03 to 3 mass fractions of component b), 0.05 to 5 mass fractions of component c), 0.05 to 5 mass fractions of component d) and 0.2 to 1 mass fraction of component e) are used.

[0161] In the case of the uses according to the invention, good aging behavior is also understood to mean color retention or retention of color stability after hot air aging compared to polyamide-based products containing components a), b), c) and d), but not component e). Preferably, the color difference ΔE to be determined is calculated according to DIN EN ISO 11664-4After hot air storage for over 500 hours at 150°C, the color difference is small and is particularly preferably in the range of 0 to 20, and most preferably in the range of 0 to 15. In the case of the uses according to the invention, the color difference ΔE is also a dimensionless quantity. The smaller the value, the smaller the color difference from a starting value. A color difference ΔE = 0 therefore corresponds not to a change in color, but to a constant color.

[0162] In the case of the uses according to the invention, good aging behavior in the form of improved UV stability is also to be understood as meaning that the color difference ΔE is calculated according to DIN EN ISO 11664-4 after UV storage according to DIN ISO 4892-2AThe color difference ΔE is low over 200 hours at 80°C, 340 nm and 1.55 W / m² without irrigation, preferably in the range of 0 to 30, and particularly preferably in the range of 0 to 20. In the applications according to the invention, the color difference ΔE is also a dimensionless quantity. The smaller the value, the smaller the color difference from a starting value. A color difference ΔE = 0 therefore corresponds not to a change in color, but to a constant color.

[0163] In the case of the uses according to the invention, good aging behavior in the form of sufficient retention of impact strength after hot air aging is also to be understood as meaning that the impact strength measured after ISO180-1U Before and after hot air aging over 500h at 150°C, the value does not drop by more than 30% compared to the time at 0h.

[0164] Even in the case of the uses according to the invention, sufficient retention of the elongation at break after hot air aging is to be understood as meaning that the elongation at break measured after DIN EN ISO 527 Before and after hot air aging over 500h at 150°C, the value does not drop by more than 30% compared to the time at 0h.

[0165] The invention further preferably relates to the use the components b) at least one sterically hindered phenols the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, preferably 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, preferably sodium hypophosphite, d) at least one 3-thiopropionate of general formula (VII), wherein R2 represents an alkyl group having 4 to 20 carbon atoms, preferably pentaerythrityltetrakis(3-dodecylthiopropionate), and e) 4,4'-bis(phenylisopropyl)diphenylamine for the production of polyamide-based products with retention of impact strength as measured according to ISO180-1U and / or with preservation of the elongation at break measured after ISO 527 Calculated after hot air aging for over 500 hours at 150°C and / or with color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or with color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation compared to products containing a), b), c) and d) and with the provision that for every 100 mass fractions of at least one polyamide to be used as component a), preferably polyamide 6 or polyamide 66, 0.03 to 3 mass fractions of component b), 0.05 to 5 mass fractions of component c), 0.05 to 5 mass fractions of component d) and 0.05 to 5 mass fractions of component e) are used.

[0166] The invention further preferably relates to the use containing mixtures b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, e) 4,4'-bis(phenylisopropyl)diphenylamine and f) glass fibers for the manufacture of polyamide-based products retaining impact strength as measured according to ISO180-1U and / or with preservation of the elongation at break measured after ISO 527 Calculated after hot air aging for over 500 hours at 150°C and / or with color retention according to DIN EN ISO 11664-4calculated after hot air storage for over 500 hours at 150°C and / or with color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation compared to products containing a), b), c) and d) and with the provision that for every 100 mass fractions of at least one polyamide to be used as component a), preferably polyamide 6 or polyamide 66, 0.03 to 3 mass fractions of component b), 0.05 to 5 mass fractions of component c), 0.05 to 5 mass fractions of component d), 0.05 to 5 mass fractions of component e) and 5 to 185 mass fractions of component f) are used.

[0167] The invention further preferably relates to the use from the components b) 3,9-Bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane, c) sodium hypophosphite, d) pentaerythrityltetrakis(3-dodecylthiopropionate) and e) 4,4'-bis(phenylisopropyl)diphenylamine for the production of polyamide-based products with retention of impact strength measured according to ISO180-1U and / or with preservation of the elongation at break measured after ISO 527 Calculated after hot air aging for over 500 hours at 150°C and / or with color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or with color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2 without irrigation compared to products containing a), b), c) and d) and with the The stipulation is that 38 to 85 wt.%, preferably 65 to 70 wt.% of at least one polyamide, preferably polyamide 6 or polyamide 66, 0.1 to 0.3 wt.% of component b), 0.3 to 1 wt.% of component c), 0.2 to 0.6 wt.% of component d), 0.1 to 1 wt.% of component e) and 15 to 60 wt.%, preferably 25 to 34.4 wt.% of the glass fibers to be used as component f) are used, and that the sum of all wt. percent always equals 100. Preferred methods

[0168] The invention ultimately relates to a Proceedings to maintain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation compared to products containing a), b), c) and d) by using mixtures containing b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, and d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, and e) uses 4,4'-bis(phenylisopropyl)diphenylamine in polyamide as component a), preferably polyamide 6 or polyamide 66, with the provision that for every 100 mass parts of component a), 0.03 to 3 mass parts of component b), 0.05 to 5 mass parts of component c), 0.05 to 5 mass parts of component d) and 0.05 to 5 mass parts of component e) are used.

[0169] In the case of the process according to the invention, the ammonium ion NH₄⁺ is also a cation for R', which forms salts with anions similar to alkali metal ions. It is the conjugate acid of the base ammonia (NH₃).

[0170] The invention further relates to a Proceedingsto maintain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation compared to products containing a), b), c) and d) by using mixtures containing b) at least one sterically hindered phenol the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, preferably 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, preferably sodium hypophosphite, and d) a 3-thiopropionate of general formula (VII), wherein R2 represents an alkyl group having 4 to 20 carbon atoms, preferably pentaerythrityltetrakis(3-dodecylthiopropionate), and e) uses 4,4'-bis(phenylisopropyl)diphenylamine in polyamide as component a), preferably polyamide 6 or polyamide 66, with the provision that for every 100 mass parts of component a) 0.03 to 3 mass parts of component b), 0.05 to 5 mass parts of component c), 0.05 to 5 mass parts of component d) and 0.05 to 5 mass parts of component e) are used.

[0171] The invention also relates to a Proceedings to maintain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527 calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2Aover 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation compared to products containing a), b), c), d) and f) by using mixtures containing b) at least one sterically hindered phenol of the general formula (II) wherein R 1< represents a tert-butyl group, R 2< represents an alkyl group with 1 to 9 carbon atoms and R 3< represents an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group, c) at least one phosphinic acid derivative of general formula (I), wherein R represents a hydrogen atom or an alkyl, cycloalkyl or aryl group, and R' represents an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the periodic table of elements, an ammonium ion or a C1-C10 alkyl group, and d) at least one 3-thiopropionate of general formula (VI), wherein R1 represents an alkyl group with 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen with up to 300 atoms and R2 represents an alkyl group with 4 to 20 carbon atoms, and e) uses 4,4'-bis(phenylisopropyl)diphenylaminine in polyamide as component a), preferably polyamide 6 or polyamide 66, with the provision that for every 100 mass parts of component a) and 5 to 185 mass parts of glass fibers to be used as component f), 0.03 to 3 mass parts of component b), 0.05 to 5 mass parts of component c), 0.05 to 5 mass parts of component d) and 0.05 to 5 mass parts of component e) are used.

[0172] The invention ultimately relates to a Proceedings to maintain impact strength measured according to ISO180-1U and / or to maintain the elongation at break, measured according to ISO 527calculated after hot air aging over 500h at 150°C and / or for color retention according to DIN EN ISO 11664-4 calculated after hot air storage for over 500 hours at 150°C and / or for color retention according to DIN EN ISO 11664-4 based on UV storage DIN ISO 4892-2A over 200h at 80°C, 340 nm and 1.55 W / m 2< without irrigation compared to products containing a), b), c), d) and f) by using mixtures containing b) 3,9-Bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]undecane, c) sodium hypophosphite, d) pentaerythrityltetrakis(3-dodecylthiopropionate), and e) 4,4'-Bis(phenylisopropyl)diphenylamine

[0173] in polyamide as component a), preferably polyamide 6 or polyamide 66, with the proviso that for every 100 mass parts of component a) and 5 to 185 mass parts of glass fibers to be used as component f), 0.03 to 3 mass parts of component b), 0.05 to 5 mass parts of component c), 0.05 to 5 mass parts of component d) and 0.05 to 5 mass parts of component e) are used.

[0174] The subject of the present application also includes the Use or processing the molding compounds to be produced from the components to be used according to the invention in the extrusion process, in blow molding processes or in injection molding for the production of products, preferably molded parts or semi-finished products, in particular by means of injection molding.

[0175] Processing methods according to the invention for the production of products by means of extrusion, blow molding or injection molding are carried out at melt temperatures in the range of 230 to 330°C, preferably from 250 to 300°C and optionally additionally at pressures of a maximum of 2500 bar, preferably at pressures of a maximum of 2000 bar, particularly preferably at pressures of a maximum of 1500 bar and most preferably at pressures of a maximum of 750 bar.

[0176] In extrusion, also known as extrusion pressing, solid to viscous thermoplastic molding compounds are continuously forced under pressure out of a shaping opening, preferably called a nozzle, die, or cutting tip. This process produces products with a cross-section equal to the opening and theoretically any length. (http: / / de.wikipedia.org / wiki / Extrusion_(Verfahrenstechnik). The basic process steps of the profile extrusion process, a form of extrusion, are: 1. Plasticizing and supplying the thermoplastic melt in an extruder, 2. Extrusion of the thermoplastic melt strand through a calibration sleeve that has the cross-section of the profile to be extruded, 3. Cooling of the extruded profile in a calibration table, 4. Further transport of the profile with a take-up unit behind the calibration table, 5. Cutting of the previously continuous profile to length in a cutting unit, 6. Collection of the cut profiles on a collection table.

[0177] A description of the profile extrusion of polyamide 6 and polyamide 66 can be found in Kunststoff-Handbuch 3 / 4, Polyamide, Carl Hanser Verlag, Munich 1998, pages 374-384. .

[0178] The blow molding process is used, for example, in http: / / www.blasformen.com / The process is described below. In blow molding, the first step involves drawing in plastic granules through a heated extruder, compacting them, degassing them, heating them, plasticizing them, and homogenizing them into a plastic strand. In the next step, the molten plastic is fed into a die head flanged to the extruder. There, the molten plastic is formed into a tube that exits vertically downwards from a nozzle. The tube diameter is adjusted to the desired part by using mandrels and nozzles of varying sizes, which are flanged to the die head. The tube thickness and the resulting weight of the blow-molded parts are predetermined by selecting different diameter differences between the mandrel and nozzle.

[0179] Injection molding is characterized by the fact that the raw material, i.e., the thermoplastic molding compound to be processed containing the components to be used according to the invention, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity and injected as injection material under pressure into a temperature-controlled cavity. After the compound has cooled (solidified), the injection-molded part is demolded.

[0180] One distinguishes 1. Plasticizing / Melting 2. Injection phase (filling process) 3. Holding phase (due to thermal contraction during crystallization) 4. Demolding.

[0181] An injection molding machine consists of a clamping unit, the injection unit, the drive, and the control system. The clamping unit includes fixed and movable mounting plates for the mold, an end plate, as well as columns and the drive for the movable mold mounting plate (toggle joint or hydraulic clamping unit).

[0182] An injection unit comprises the electrically heated cylinder, the screw drive (motor, gearbox), and the hydraulics for moving the screw and injection unit. The injection unit's function is to melt, meter, inject, and compress the powder or granules (due to contraction). The problem of melt backflow within the screw (leakage) is solved by non-return valves.

[0183] In the injection mold, the flowing melt of the molding compound containing the components to be processed and the components to be inserted according to the invention is dissolved, cooled, and thus the component to be manufactured is produced. At least two mold halves are always necessary for this. The following functional complexes are distinguished in injection molding: Gating system, mold-forming inserts, venting, machine and force absorption, demolding system and motion transmission, temperature control

[0184] In contrast to injection molding, extrusion involves inserting an endless strand of the molding compound used according to the invention into the extruder, where the extruder is a machine for producing products based on thermoplastic molded parts. A distinction is made between single-screw extruders and twin-screw extruders, as well as their respective subgroups: conventional single-screw extruders, conveying single-screw extruders, counter-rotating twin-screw extruders, and co-rotating twin-screw extruders.

[0185] Extrusion plants for the production of profiles consist of: extruder, profile tool, calibration, cooling section, caterpillar and roller take-off, cutting device and tipping trough.

[0186] The present invention therefore also relates to products, preferably molded parts, molded bodies or semi-finished products, obtainable by extrusion or injection molding of the molding compounds according to the invention, comprising at least the components a), b), c), d) and e) and optionally f).

[0187] The preparation of compositions to be used according to the invention for the production of molding compounds for injection molding, extrusion, or blow molding is carried out by mixing the individual components a), b), c), d), and e), and optionally further components, in at least one mixing unit, preferably a compounder, and particularly preferably a co-rotating twin-screw extruder. This mixing process, also referred to as compounding, yields molding compounds as intermediate products, which are provided in the form of powders, granules, or strands for further processing. These molding compounds—also referred to as thermoplastic molding compounds—can consist exclusively of components a), b), c), d), and e), or optionally contain further components, preferably f), g), and / or h).

[0188] Finally, the present invention also relates to the use of products manufactured by extrusion or injection molding from molding compounds containing at least the components a), b), c), d) and e), and optionally f), g) and h), preferably molded parts, molded bodies or semi-finished products, for electrical or electronic components. These products according to the invention can preferably be used in the automotive, electrical, electronics, telecommunications, solar, information technology, and computer industries, as well as in households, sports, medicine, or the entertainment industry. In particular, products according to the invention can be used for applications where long-term color stability is required. Preferred for such applications is the use of molded parts in electrical engineering, household applications, and vehicles, especially high-voltage components in vehicles, particularly in motor vehicles, as well as in hair dryers or hair straighteners.

[0189] The present invention therefore also relates to the use of the thermoplastic molding compounds according to the invention for the production of molded parts and semi-finished products and products to be manufactured therefrom, preferably molded parts for vehicles or for household applications, in particular in the form of high-voltage components, hair dryers or hair straighteners. Examples

[0190] To demonstrate the improvements in properties described according to the invention, corresponding polyamide-based compositions or molding compounds were first produced by compounding. For this purpose, the individual components were mixed in a twin-screw extruder (ZSK 25 Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany)) at temperatures between 270 and 300°C, extruded as a strand, cooled until granulation was possible, and then granulated. After drying, generally for two days at 80°C in a vacuum drying oven, the granules were processed at temperatures between 270 and 290°C into standard test specimens for the respective tests.

[0191] The impact strength according to ISO 180-1U (Izod) and the elongation at break according to ISO 527 were applied to injection-molded parts DIN EN ISO 1874-2 The moisture content of specified test specimens in the freshly molded state is determined at 23°C. The freshly molded state, also known as "dry as moulded", is defined in the DIN EN ISO 1874-2The Lab color space (also: CIELAB, CIEL*a*b*, Lab colors) describes all perceptible colors. It uses a three-dimensional color space in which the lightness value L is perpendicular to the color plane (a,b). The L* axis describes the lightness (luminance) of the color with values ​​from 0 to 100. In the representation, this axis is perpendicular to the a*b* plane at the origin. It can also be called the neutral gray axis, because all achromatic colors (shades of gray) are contained between the endpoints black (L*=0) and white (L*=100). In analogy to Ewald Hering's opponent-process theory, the a-coordinate indicates the hue and color intensity between green and red, and the b-coordinate indicates the hue and color intensity between blue and yellow. The larger the positive a and b values, and the smaller the negative a and b values, the more intense the hue. If a=0 and b=0, there is an achromatic hue on the brightness axis.In typical software implementations, L* can take values ​​between 0 and 100, and a and b can be varied in the range of -128 and 127. The discoloration of polymer-based products due to oxidative damage to the polymer matrix can be determined by measuring the color difference ΔE over storage time at high temperature. The color difference ΔE between two color stimuli was calculated according to the equation ΔE = [(ΔL*)² + (Δa*)² + (Δb*)²] 1 / 2< according to... DIN EN ISO 11664-4 The color difference ΔE is calculated. It is a dimensionless quantity. The smaller the value, the smaller the color difference from a given initial value. A color difference ΔE = 0 therefore corresponds to no change in color, but rather to a constant color.

[0192] The testing of aging behavior in the form of improved color retention or color stability was carried out by storing injection-molded sheets measuring 60 mm x 40 mm x 4 mm in a Binder FP115 material testing chamber with circulating air at temperatures of 150°C, also referred to as hot air aging within the scope of the present invention. As a measure of discoloration, the color difference ΔE of injection-molded products based on polymer compositions according to the invention was determined after hot air aging for 500 hours before and after the hot air aging by measuring the color values ​​L*a*b*. ΔE = ΔL ∗ 2 + Δa ∗ 2 + Δb ∗ 2 1 / 2

[0193] Thus, according to the invention, good aging behavior in the form of improved color retention or improved color stability after hot air aging is characterized by a smaller color change ΔE. The color values ​​L*a*b* of the samples were determined within the scope of the present invention on plates with dimensions of 60 mm × 40 mm × 4 mm and from these, according to... DIN EN ISO 11664-4 The color difference ΔE is calculated.

[0194] The color measurement was performed using the CM-2600d spectrophotometer from Konica Minolta with the CIE standard illuminant D65 in reflection (10° observer angle) with specular component excluded (SCE).

[0195] Within the scope of the present invention, the aging behavior of the inventive compositions, products, uses, and methods was tested in the form of improved UV stability by storing injection-molded plates measuring 60 mm x 40 mm x 4 mm in a QUV rapid weathering device from Q-Lab. DIN ISO 4892-2AUV curing is performed for over 200 hours at 80°C, 340 nm, and 1.55 W / m² without irrigation, hereinafter referred to as UV curing. Within the scope of the present invention, the color difference ΔE of injection-molded products based on polymer compositions according to the invention is determined before and after UV curing for 200 hours by measuring the color values ​​L*a*b*. The color difference ΔE is a dimensionless quantity. The smaller the value, the smaller the color difference from a baseline value. A color difference ΔE = 0 therefore corresponds to no change in color, but rather to a constant color. ΔE = ΔL ∗ 2 + Δa ∗ 2 + Δb ∗ 2 1 / 2

[0196] Thus, according to the invention, good aging behavior in the form of improved UV stability after UV storage is characterized by a smaller color change ΔE compared to polyamide-based products without component e). The color values ​​L*a*b* of the samples were determined within the scope of the present invention on plates with dimensions of 60 mm × 40 mm × 4 mm and from these according to DIN EN ISO 11664-4 The color difference ΔE was calculated. Within the scope of the present invention, the aging behavior was tested in the form of maintaining impact strength and elongation at break by storing injection-molded parts in DIN EN ISO 1874-2 The impact strength was determined according to the specified test specimens in a Binder FP115 material testing chamber with circulating air at temperatures of 150°C. ISO 180-1U and the elongation at break in the tensile test according to ISO 527 The percentage of the product retained was determined at 23°C on these test specimens before (freshly injected) and after storage for over 500 h at 150°C. Starting materials:

[0197] Component a) Polyamide 6 (Durethan® < B29, Lanxess Deutschland GmbH) Component b) 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 No. 90498-90-1, (Sumilizer ® < GA-80, Sumitomo Chemical) Component c) Sodium hypophosphite anhydrous CAS No. 7681-53-0 (Sigma Aldrich, extra pure) Component d) Pentaerythrityltetrakis(3-dodecylthiopropionate), CAS No. 29598-76-3 (Sumilizer®< TP-D, Sumitomo Chemical) Component e) 4,4'-Bis(phenylisopropyl)diphenylamine (Antioxidant 445), CAS No. 10081-67-1 (Okabest®< AO445, OKA-Tec) Component f) Fiber optic cable (CS7928, Lanxess Deutschland GmbH) Table 1: Example 1 See 1 See 2 Component a) Weight % 68,65 68,9 70 Component b) Weight % 0,1 0,2 0 Component c) Weight % 0,65 0,5 0 Component d) Weight % 0,3 0,4 0 Component e) Weight % 0,3 0 0 Component f) Weight % 30 30 30 Color change ΔE after hot air aging 500 h, 150°C 13 24 40 Retention of elongation at break, 23°C, ISO 527-1,2 after hot air aging over 500h at 150°C % 91 84 67 Maintenance of impact strength, ISO180-1U, 23°C, after hot air aging over 500h at 150°C % 49 48 41 Color change ΔE after UV storage, 200h, 80°C, 340 nm, 1.55 W / m²< 20 26 5

[0198] The results in Tab. 1The mixture of components b), c), d), and e) used according to the invention in glass fiber-reinforced polyamide 6-based products according to Example 1 surprisingly exhibits improved color stability in the form of a lower color change ΔE after hot air aging at 150°C for 500 h and after UV storage for 200 h, compared to Comparative Example 1, in which component e) is not used. At the same time, the retention of impact strength and elongation at break after hot air aging at 150°C for 500 h is improved compared to Comparative Example 1. These improvements also apply compared to Comparative Example 2, in which components b), c), d), and e) are not used. "nb" stands for not determined.

Claims

1. Compositions and products based thereon comprising a) at least one polyamide, b) at least one sterically hindered phenol, c) at least one phosphinic acid derivative of the general formula (I) in which R is a hydrogen atom or is an alkyl, cycloalkyl or aryl group, and R' is an alkali metal, an alkaline earth metal, a metal of Group 12 or 13 of the Periodic Table of the Elements, an ammonium ion or a C1-C10-alkyl group, d) at least one 3-thiopropionate, and e) 4,4'-bis(phenylisopropyl)diphenylamine, with the proviso that, per 100 parts by mass of component a), 0.03 to 3 parts by mass of component b), 0.05 to 5 parts by mass of component c), 0.05 to 5 parts by mass of component d) and 0.05 to 5 parts by mass of component e) are used.

2. Compositions and products based thereon according to Claim 1, characterized in that these contain, in addition to components a), b), c), d) and e), also f) at least one filler, preferably glass fibres, in an amount of 5 to 185 parts by mass, based on 100 parts by mass of component a).

3. Compositions and products based thereon according to Claim 1 or 2, characterized in that these contain, in addition to components a), b), c), d) and e) or in addition to components a), b), c), d), e) and f), also at least one flame retardant g) different from components b), c), d), e) and f) in an amount of 3 to 100 parts by mass, based on 100 parts by mass of component a).

4. Compositions and products based thereon according to one or more of Claims 1 to 3, characterized in that polyamide 6, polyamide 66, polyamide -46 and / or semiaromatic copolyamides are used as component a), preferably polyamide 6 or polyamide 66.

5. Compositions and products based thereon according to one or more of Claims 1 to 4, characterized in that sterically hindered phenols of the general formula (II) are used as component b) in which R1 is a tert-butyl group, R2 is an alkyl group having 1 to 9 carbon atoms and R3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

6. Compositions and products based thereon according to Claim 5, characterized in that R1 and R2 in formula (II) are each a tert-butyl group and R3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

7. Compositions and products based thereon according to Claim 5, characterized in that R1 in formula (II) is a methyl group and R2 is a substituted alkyl group and R3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

8. Compositions and products based thereon according to Claim 5, characterized in that R1 in formula (II) is a methyl group and R2 is a tert-butyl group and R3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

9. Compositions and products based thereon according to one or more of Claims 1 to 5, characterized in that component b) comprises compounds of the general formula (V) in which R1 and R2 are independently C1-C8-alkyl groups which may in turn be substituted, and at least one of which is a sterically demanding group.

10. Compositions and products based thereon according to one or more of Claims 1 to 5, characterized in that triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl), hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-1,6-hexanediylbis[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropanamide], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro-[5.5]-undecane, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene or 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine is employed as component b).

11. Compositions and products based thereon according to one or more of Claims 1 to 5, characterized in that sterically hindered phenols to be selected from the group of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylene-bis-(2,6-di-tert.-butylphenol) and 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine are employed as component b).

12. Compositions and products based thereon according to one or more of Claims 1 to 11, characterized in that sodium hypophosphite or sodium hypophosphite monohydrate are employed as component c).

13. Compositions and products based thereon according to one or more of Claims 1 to 12, characterized in that 3-thiopropionates of the general formula (VI) are employed as component d), in which R1 is an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group consisting of the elements carbon, hydrogen, sulfur and oxygen or optionally nitrogen and having up to 300 atoms, and R2 is an alkyl radical having 4 to 20 carbon atoms.

14. Use of mixtures comprising a) at least one polyamide, b) at least one sterically hindered phenol, c) at least one phosphinic acid derivative of the general formula (I) in which R is a hydrogen atom or is an alkyl, cycloalkyl or aryl group, and R' is an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the Periodic Table of the Elements, an ammonium ion or a C1-C10-alkyl group, and d) at least one 3-thiopropionate, and e) 4,4'-bis(phenylisopropyl)diphenylamine, for production of polyamide-based products, preferably for production of polyamide-based products with retention of impact strength measured to ISO180-1U and / or retention of elongation at break measured to ISO 527 after hot air ageing over 500 h at 150°C and / or colour retention calculated in accordance with DIN EN ISO 11664-4 after hot air storage over 500 h at 150°C and / or colour retention calculated in accordance with DIN EN ISO 11664-4 after UV storage in accordance with DIN ISO 4892-2A over 200 h at 80°C, 340 nm and 1.55 W / m2 without irrigation, with the proviso that, per 100 parts by mass of at least one polyamide to be used as component a), preferably nylon-6 or nylon-6,6, 0.03 to 3 parts by mass, preferably 0.05 to 1 part by mass, of component b), 0.05 to 5 parts by mass, preferably 0.25 to 1 part by mass, of component c), 0.05 to 5 parts by mass, preferably 0.2 to 1 part by mass, of component d) and 0.05 to 5 parts by mass, preferably 0.1 to 1 part by mass, of component e) are used.

15. Method of retaining impact strength measured to ISO180-1U and / or of retaining elongation at break measured to ISO 527 after hot air ageing over 500 h at 150°C and / or of colour retention calculated in accordance with DIN EN ISO 11664-4 after hot air storage over 500 h at 150°C and / or of colour retention calculated in accordance with DIN EN ISO 11664-4 after UV storage in accordance with DIN ISO 4892-2A over 200 h at 80°C, 340 nm and 1.55 W / m2 without irrigation, of polyamide-based products, characterized in that e) 0.05 to 5 parts by mass of 4,4'-bis(phenylisopropyl)diphenylamine is used per a) 100 parts by mass of a polyamide to be used as component a), b) 0.03 to 3 parts by mass of at least one sterically inhibited phenol, c) 0.05 to 5 parts by mass of at least one phosphinic acid derivative of the general formula (I) in which R is a hydrogen atom or is an alkyl, cycloalkyl or aryl group, and R' is an alkali metal, an alkaline earth metal, a metal of group 12 or 13 of the Periodic Table of the Elements, an ammonium ion or a C1-C10-alkyl group, and c) 0.05 to 5 parts by mass of at least one 3-thiopropionate.