Flame-retardant plastic products

Abstract

We provide flame-retardant plastic products. [Solution] The present invention relates to flame-retardant plastic products made of polyamide molding compounds comprising at least one phosphinate and / or at least one diphosphinate as a flame retardant, at least one flame retardant synergistic agent, and at least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one; molding compounds necessary for the manufacture of these plastic products; and the use of colorants for use in accordance with the present invention to manufacture flame-retardant polyamide molding compounds or plastic products having high laser transmittance.

Description

[Technical Field]

[0001] The present invention relates to flame-retardant plastic products made of polyamide molding compounds comprising at least one phosphinate and / or at least one diphosphinate as a flame retardant, at least one flame retardant synergist, and at least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one; molding compounds necessary for the manufacture of these plastic products; and the use of colorants for use in accordance with the present invention to manufacture flame-retardant polyamide molding compounds or plastic products having high laser transmittance. [Background technology]

[0002] Due to its excellent mechanical and chemical stability and good processability, polyamide is an important material used, for example, in components for the automotive, electrical and electronic industries, or in household appliances. In applications of polyamide near electrically energized components, flame-retardant materials are often used to counteract the risk of fire caused by overheated wires or contacts. Depending on the application, low ignition properties are also desired, in particular, as is good self-extinguishing ability as classified as UL94 V-0 according to Non-Patent Literature 1.

[0003] In the field of polyamides, the demand for halogen-free solutions is increasing for environmental reasons. Furthermore, polyamides containing halogen-free flame retardants generally reduce the flammability of materials compared to halogen-containing systems, thereby not only delaying the progression of fires but also reducing smoke generation, preventing toxic gases, and simultaneously being environmentally friendly and beneficial to health.

[0004] The demand for maximum design freedom, and consequently for greater complexity in the geometric shapes of components, coupled with cost-driven demands for automatable and easily integrable mass production processes, is increasingly creating a need for materials that can also be joined to each other by laser-transmissive welding processes (see Non-Patent Literature 2). Regarding laser-transmissive joining partners, this requires a high degree of transmittance at the laser wavelength used. The latter poses a significant challenge for flame-retardant polyamides, as flame retardants, such as antimony trioxide used as a flame retardant synergist in halogen-containing flame retardants, scatter or even absorb laser light. An additional challenge in the case of colored polyamides is the colorants used.

[0005] Patent Document 1 describes NIR-absorbing molding compounds that can be used in laser welding processes. Various pigments are used to reduce NIR transmittance in polyamide-containing plastics, including TiO2 pigments with an average particle size of 30 nm to 4.35 μm. Laser-transmitting molding compounds are not specifically described in Patent Document 1.

[0006] In particular, high processing temperatures of >300°C in some cases, such as compounding and injection molding, and especially the presence of additives such as flame retardants, severely limit the selection of suitable colorants in polyamides for orange marking of critical components, particularly for electric drive systems. The color orange for marking the electrical equipment of machines is specified in VDE 0113-1 “Safety of machinery - Electrical equipment of machines - Part 1: General requirements”, section 13.2.4, where it is stipulated that orange should only be used for “excluded circuits” as defined in section 5.3.5. The standard CEI EN 60204-1:2006 (CEI 44-5 “Safety of machinery - Electrical equipment of machines”) states that orange should be used for circuits where the power supply cannot be interrupted by a circuit breaker. Therefore, orange has become established for identifying key components of electric drive systems.

[0007] Furthermore, it should be considered that, especially under extreme demanding conditions such as those encountered in the processing of polyamides, dyes in polyamides tend to cause uneven coloring or discoloration, particularly on surfaces near the injection point of injection-molded products.

[0008] When soluble organic dyes are used in polymers, for example, in the case of isoindoline dyes (as known from Patent Document 2), those skilled in the art are well aware of browning caused by thermal damage to the dye.

[0009] In contrast, undesirable color unevenness can occur if the colorant is not properly mixed, if the colorant and the plastic to be processed are incompatible, or if demixing occurs due to excessive shear during injection molding. Numerous error factors can contribute to such undesirable color unevenness. Examples include equipment-related errors in the mixing screw, a mixing barrel that is too small, faulty color metering, an oversized material hopper, or electrostatic charging of the color or colorant. Material-related error factors include incompatibility between the masterbatch or colorant and the plastic to be processed, insufficient solubility of the colorant in the plastic to be processed, heat sensitivity of the colorant, oversized pellets, or excessive pigment content. Methodological error factors may include excessively low back pressure during injection molding, excessively high screw speed, excessively high or excessively low melting temperature, excessively high or excessively low injection speed, excessively high or excessively low mold temperature, or insufficient or excessive color metering. Finally, the occurrence of color unevenness can also be exacerbated by mold-related error factors such as channel cross-sections that are too small, channels that are too long, improperly placed weld seams, or sections on injection-molded products that are too small for injection molding. In particular, in the case of glass fiber reinforced plastic products, processing polyamide polymer compositions in a manner that reduces or even eliminates streaks, especially in injection molding, with respect to the coexistence of colorants, is therefore a particular challenge for those skilled in the art.

[0010] Patent Document 4 discloses a high-voltage component based on a polymer composition containing at least one polyamide and 10,10'-oxybis-12H-phthaloperin-12-one.

[0011] Finally, (Patent Document 5) describes the L from the color number starting with "2" in the RAL color chart. * a * b *The present invention relates to an electric mobility component having a coordinate color difference ΔE < 20, comprising a polymer composition based on at least one polyamide and a colorant having a median particle size d50 in the range of 1 to 12 μm, as determined by laser diffraction in accordance with ISO 13320, wherein the colorant contains 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one in a ratio of 1:1:0.8 to 1.5 to 1:1.5:0.8 to 1.5, and the colorant is present in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of at least one polyamide in the polymer composition.

[0012] Therefore, starting from the prior art, the present invention aims to provide a plastic product formed from a polyamide polymer composition containing a halogen-free flame retardant, which enables the production of orange plastic products without streaking or browning caused by the polyamide-soluble colorants used, while simultaneously providing a plastic product that has sufficient laser transparency to be processable in downstream laser-based processing processes without degradation compared to the UL 94 results of non-orange-colored samples having the same composition in other respects. [Prior art documents] [Patent Documents]

[0013] [Patent Document 1] International Publication No. 2009 / 066232A1 Pamphlet [Patent Document 2] European Patent No. 0035672B1 [Patent Document 3] European Patent Application Publication No. 3 421 540A1 Specification [Patent Document 4] International Publication No. 2020 / 187702A1 Pamphlet [Patent Document 5] German Utility Model No. 2024 001708 U Specification [Non-patent literature]

[0014] [Non-Patent Document 1] Underwriters Laboratories Inc.Standard of Safety, “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, p.14-18 Northbrook 1998 [Non-Patent Document 2] E. Haberstroh, W.-M. Hoffmann, Laserdurchstrahlschweissen von Kunststoffen-Elastomere und Kunststoffe, KGK-Rubberpoint, 11.2006, p.590-595 [Overview of the Initiative] [Means for solving the problem]

[0015] Surprisingly, it is hereby found that the aforementioned requirements can be satisfied by a plastic product made of a polymer composition comprising at least one polyamide, at least one flame retardant comprising at least one phosphinate and / or at least one diphosphinate and / or polymer thereof, at least one flame retardant synergist, and at least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one. [Modes for carrying out the invention]

[0016] This invention is: a) at least one type of polyamide; b) At least one phosphinate of formula (I) and / or at least one diphosphinate of formula (II) [ka] (wherein R 1 and R 2 are the same or different, and are linear or branched C1-C6-alkyl and / or C6-C 14 -aryl; R 3 is linear or branched C1~C 10 -alkylene, C6~C 10 -arylene or C1-C6-alkyl-C6-C 10 -arylene or C6-C 10 -aryl-C1-C6-alkylene; M is aluminum or zinc; m is an integer of 1 to 4; n is an integer of 1 to 3; and x is 1 or 2; wherein n, x and m in formula (II) can simultaneously only take integer values such that the diphosphinate of formula (II) is uncharged as a whole) at least one flame retardant composed of and / or polymers thereof; c) at least one flame retardant synergist selected from melamine polyphosphate and aluminum phosphonate; and d) at least one colorant in the form of an isomer mixture of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one A plastic product made of a polymer composition comprising the above is provided.

[0017] The present invention preferably a) at least one polyamide, preferably nylon-6 or nylon-6,6; b) at least one phosphinate of formula (I)

Chemical Formula

[0018] The present invention preferably comprises a) at least one polyamide, b) at least one flame retardant, c) at least one flame retardant synergist, and d) at least one colorant, and is derived from the color numbers starting with "2" in the RAL color chart according to the color model of EN ISO 11664-4. * a * b * This relates to plastic products having a color difference ΔE < 20, determined according to the coordinate system DIN 5033 (1979).

[0019] More preferably, the present invention comprises a) at least one polyamide, b) at least one flame retardant, c) at least one flame retardant synergist, and d) at least one colorant, and is derived from a color number starting with "2" in the RAL color chart relating to the color model according to EN ISO 11664-4. * a * b * This invention relates to plastic products having a color difference ΔE < 10 determined according to the coordinate system DIN 5033 (1979), and to polymer compositions necessary for their manufacture.

[0020] More preferably, the present invention comprises a) at least one polyamide, b) at least one flame retardant, c) at least one flame retardant synergist, and d) at least one colorant, and L from the color number starting with "2" in the RAL color chart relating to the color model according to EN ISO 11664-4. * a * b * This relates to plastic products having a color difference ΔE < 5, determined according to the coordinate system DIN 5033 (1979).

[0021] a) For every 100 parts by mass of at least one type of polyamide, 2 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 30 parts by mass of b) at least one flame retardant, c) at least one flame retardant synergistic agent in an amount of 0.2 to 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 0.75 to 35 parts by mass, and d) At least one coloring agent in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one (0.01 to 5 parts by mass) Plastic products using this material are preferred.

[0022] For clarity, it should be noted that the scope of the present invention encompasses all definitions and parameters cited in general or preferred terms, in any desired combination. This is particularly true with respect to the above combinations of described amounts of individual components relating to the polymer compositions and plastic products produced therefrom according to the present invention, and also with respect to the methods and uses claimed in the context of the present invention. The standards cited in the context of this application refer to the most current edition as of the filing date of the present invention. Unless otherwise specified, reported percentages are by weight percentages.

[0023] Laser transmission welding A prerequisite for employing laser transmission welding as a method for joining two plastic molded parts is that the radiation emitted by the laser first penetrates a molded part (also called an NIR-transparent molded part) that has sufficient transparency to the laser light of the NIR wavelength used. For this purpose, the wavelength is preferably in the range of 800 nm to 1200 nm. Transparency is sufficient if the first molded part is at least partially transparent to NIR radiation. This has the effect that the NIR radiation reaches the second molded part to a degree sufficient to allow the two molded parts to be firmly joined by laser welding. Preferably, the first molded part has at least 10% transmittance to NIR radiation, at least partially. Here, "at least partially" means that this specified at least 10% transmittance is satisfied in at least the area corresponding to the welding area. Outside this welding area, the specified at least 10% transmittance is not required. However, it is preferable that the entire molded part that is penetrated by the laser radiation has at least 10% transmittance. NIR radiation penetrating the first molded part eventually reaches the welding area, where it is absorbed by a thin layer of the second molded part, where the NIR-absorbing molded part is in contact with the NIR-transparent molded part. In the thin layer of the second molded part that absorbs the NIR laser light, the laser energy is converted into heat, resulting in melting in the welding area and ultimately joining the NIR-transparent and NIR-absorbing molded parts. Laser transmission welding typically uses lasers in the wavelength range of 800 nm to 1200 nm. For welding thermoplastic resins, Nd:YAG lasers (1064 nm) or high-performance diode lasers (800 to 1000 nm) are commonly used. Several variations of laser welding processes are available to those skilled in the art, all based on the principle of transmission. For example, contour welding is a sequential welding process in which the laser beam is guided along a freely programmable seam contour, or components are moved relative to a fixed laser. In simultaneous welding, the linearly emitted radiation from individual high-performance diodes is positioned along the seam contour being welded. Therefore, the melting and welding of the entire contour occur simultaneously.Semi-simultaneous welding is a combination of contour welding and simultaneous welding. The laser beam is guided along the weld seam contour at a very high speed of over 10 m / s with the help of a galvanometric mirror (scanner). The high speed gradually heats and melts the joining area. Compared to simultaneous welding, it offers greater flexibility in case of changes to the weld seam contour. Mask welding is a process in which a linear laser beam is moved over the parts to be joined. The radiation is selectively shielded by the mask and reaches only the joining surface where welding is to be performed. This process makes it possible to achieve a very precisely positioned weld. These methods are known to those skilled in the art, for example, from “Handbuch Kunststoff-Verbindungstechnik [Handbook of Plastics Joining Technology]” (GWEhrenstein, Hanser, ISBN 3-446-22668-0) and / or DVS Directive 2243 “Laserstrahlschweissen thermoplastischer Kunststoffe [Laser Beam Welding of Thermoplastics]”.

[0024] Preferred variations of laser transmission welding according to the present invention are therefore contour welding, simultaneous welding, semi-simultaneous welding, TWIST® approach, mask welding, radial welding, Globo welding, and hybrid welding.

[0025] While the NIR transparency of various thermoplastic resins can differ, standard thermoplastic resins possess sufficiently high transparency in the NIR region to enable laser welding when suitable process parameters (thickness of the NIR-transparent bonding partner, laser beam intensity, welding process speed, and selection of suitable additives in the thermoplastic resin) are chosen. Due to the low NIR absorption of thermoplastic resins, the bonding partner that absorbs laser light is typically modified with an NIR-absorbing admixture. Particularly suitable for this purpose are pigments that have maximum absorption in the wavelength range of the welding laser. A particularly preferred and widely practiced method is the use of all kinds of soot as the NIR-absorbing pigment. Consequently, NIR-absorbing bonding partners are usually dark to black. If the NIR-transparent bonding partner should have a similar color to the NIR-absorbing partner, the coloring of the NIR-transparent bonding partner should be carried out mainly in the wavelength range perceptible to the human eye (approximately 380-750 nm) to ensure that the impairment of NIR transmittance is minimized. For coloring plastics, two types of colorants are generally available: pigments and soluble dyes (sometimes simply referred to as "dyes"). When soluble dyes are used, they can be distributed to a molecularly dispersed extent within the thermoplastic resin and therefore do not constitute a scattering source for NIR light, thus making it possible to avoid most of the scattering of NIR light by the colorant. Furthermore, the NIR absorption of soluble dyes should be kept to a minimum.

[0026] In the context of the present invention, at least one polymer-soluble dye used for orange identification of polyamide plastic products and further satisfying the requirement of slight impairment of laser transmittance or NIR transmittance is a mixture of isomers in the form of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one. [ka]

[0027] The colorants to be used in accordance with the present invention are preferably available in isomer ratios within the range of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one, ranging from 1:1:0.8 to 1.5 to 1:1.5:0.8 to 1.5, by the method relating to Synthesis Specification 2 in German Utility Model No. 20 2024 001 708 U1. The colorants to be used in accordance with the present invention preferably have a median particle size d50 in the range of 1 to 20 μm, more preferably in the range of 1 to 10 μm, as determined by laser diffraction in accordance with ISO 13320.

[0028] Based on experimental findings in the context of the present invention, the colorants to be used according to the present invention exhibit high NIR transmittance in polyamides, and at the same time do not interact with the flame retardant or flame retardant synergistic agent c) used as component b), and further withstand high processing temperatures and therefore do not show any browning, flame retardant orange polymer compositions and plastic products manufactured therefrom according to the present invention, with at least reduced streaking, can be used in applications where laser transmittance is preferably required. Accordingly, the present invention preferably relates to laser-transparent orange flame retardant products or polymer compositions and plastic products that are bonding partners, in particular those used in electric mobility.

[0029] The colorants to be used according to the present invention, which are in the form of isomer mixtures of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one, can be used directly as a powder, or in the form of a masterbatch, a compact, or a concentrate, and can be used preferably as a masterbatch, and more preferably as a masterbatch in a polyamide matrix.

[0030] Laser transparency In the context of this invention, the laser transmittance determined for a test specimen is derived from the fact that the incident radiation is split into two parts depending on the absorbency and thickness of the plastic part being inspected, and these parts are detectable by measurement.

[0031] According to the present invention, high laser transmittance means a laser transmittance of at least 30%, preferably at least 40%, and more preferably at least 50%, measured on a 0.75 mm thick sample plaque at a laser wavelength of 980 nm using an LPKF TMG3 transmittance measuring instrument manufactured by LPKF Laser & Electronics AG, Garbsen, Germany. The LPKF TMG3 transmittance measuring instrument is a certified, traceable, and calibrated measuring instrument. Its measurement capability has been demonstrated by statistical measurement system analysis (MSA). This instrument further conforms to the specifications of automotive standard IATF 16949 and is therefore directly eligible for quality assurance conforming to standards. In the context of the present invention, a Nd:YAG laser (1064 nm) or a high-performance diode laser (800-1000 nm) is preferably employed. Measurements in the context of this invention are performed in the near-infrared (NIR) using a circular plaque with a diameter of 80 mm and a thickness of 0.75 mm, based on DVS Guideline 2243 (01 / 2014) “Laserstrahlschweissen thermoplastischer Kunststoffe [Laser beam welding of thermoplastics]”. The LPKF TMG3 transmittance measuring instrument manufactured by LPKF Laser&Electronics AG is calibrated before measurement using a measurement standard manufactured in accordance with DIN EN ISO / IEC 17025. Measurements in the context of this invention are performed at a laser wavelength of 980 nm.

[0032] A decrease in transmittance at 980 nm of <3% compared to a plastic sample without the colorant in the form of a mixture of isomers of component d) 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one is rated as +++ in the context of the present invention. A decrease in transmittance at 980 nm within the range of 3% to 5% compared to a plastic sample without the colorant in the form of a mixture of isomers of component d) 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one is rated as ++ in the context of the present invention. A decrease in transmittance at 980 nm within the range of 5% to 10% compared to a plastic sample without the colorant in the form of a mixture of isomers of component d) 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one is evaluated only as positive in the context of the present invention.

[0033] kneading The polymer composition for the manufacture of flame-retardant plastic products according to the present invention is prepared by mixing at least one polyamide to be used as a reactant with b) at least one flame retardant, c) at least one flame retardant synergistic agent, and d) at least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one in the proportions specified above using at least one mixing tool, kneading, and subsequent processing by injection molding, extrusion molding, or blow molding. This yields a polymer composition in the form of a molding material consisting only of the above components, or otherwise containing at least one additional component in addition to these components. The flame-retardant plastic products according to the present invention are therefore preferably injection-molded products, extruded products, or blow-molded products, particularly injection-molded articles.

[0034] The processing of the polyamide in the above process reaches temperatures in the range of the polyamide's melting point. The industrially important and therefore preferred melting points of polyamides according to the present invention are in the range from over 178°C for nylon-12 and over 220°C for nylon-6 to 260°C for nylon-6,6.

[0035] Polyamides are hygroscopic; that is, they absorb moisture from the air. Preferably, the polyamides used, especially those used in pellet form, are dried before injection molding. Drying reduces or, in the best case, prevents air pockets, blister formation, and dimensional inaccuracies.

[0036] The dried polyamide is melted in an injection molding machine. The processing temperature is preferably in the range of 230°C to 310°C, more preferably in the range of 230°C to 280°C, where it can be changed depending on the type of polyamide and specific requirements.

[0037] In the extruder of the injection molding apparatus, the liquefied polyamide is finally injected into the injection mold under high pressure. Injection speed, pressure, and injection volume are important parameters that must be carefully adjusted for the appropriate polyamide to ensure optimal mold filling and surface quality. For the particularly preferred nylon-6 (PA6) according to the present invention, the injection pressure is preferably in the range of 1000 to 2000 bar. However, the exact value may vary depending on the type of material ((glass fiber) reinforced or unreinforced PA6), the geometric shape of the mold, and specific requirements related to the injection molding process. The mold temperature in the injection molding of nylon-6 (PA6) is preferably in the range of 40°C to 120°C, more preferably in the range of 40°C to 80°C. For structural parts where crystallinity is important, a mold temperature in the range of 80 to 120°C is recommended. Thin-walled parts with long flow paths may benefit from higher mold temperatures, while thick-walled parts can be processed better at lower temperatures in the range of 20 to 40°C. The injection speed for nylon-6 (PA6) should generally be high to ensure complete mold filling and prevent voids. However, the injection speed can vary depending on the material and product design. The ideal injection speed depends on various factors such as the material composition (e.g., glass fiber reinforced PA6 may require a slightly lower speed) and the geometric shape of the molded part. It is important to adjust the injection speed to meet the specific requirements of a particular component. For PA6 injection molding, a back pressure in the range of 40-80 bar is considered a guideline value. In addition to the injection speed, screw speed, injection pressure, and holding time are also important to the injection process.

[0038] Surprisingly, the colorants to be used according to the present invention in the form of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and mixtures of isomers of 10,10'-oxybis-12H-phthaloperin-12-one are thermally stable to the extent that they do not brown in the above processing method.

[0039] The flame-retardant plastic product according to the present invention is preferably colored orange with a colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one, with particular preference for shades corresponding to color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 and RAL2011 in the RAL color system, and particularly preference for shades corresponding to color numbers RAL2001, RAL2003, RAL2008, RAL2010 and RAL2011 in the RAL color system.

[0040] The “similar shades” permitted and included in this invention are those starting with the color number “2” in the RAL color chart. * a * b * The system has a color difference of ΔE < 20, preferably ΔE < 10, and more preferably ΔE < 5. For the explanation of ΔE as defined in EN ISO 11664-4, see, for example, https: / / de.wikipedia.org / wiki / Delta_E.

[0041] orange In the context of this invention, orange is considered to mean a color having a color number beginning with "2" in the RAL color chart in the RAL color system as described at https: / / de.wikipedia.org / wiki / RAL-Farbe#Orange. In particular, as of the filing date of this invention, distinctions are made between orange hues as shown in Table 1.

[0042] [Table 1]

[0043] Table 1 shows the instrument-independent CIE L for each RAL value. * a * b* Color value indicated: L * represents brightness, a * This shows the color coordinates on the red-green axis using the D65 standard light with a 10° field of view of a standard observer, and b * This shows the color coordinates on the yellow-blue axis with a standard observer's 10° field of view. The color model is based on EN ISO 11664-4 “Colorimetry-Part 4:CIE 1976 L * a * b * It is standardized in "Colour Space". * a * b * For more information on color spaces (also known as CIELAB), see https: / / de.wikipedia.org / wiki / Lab-Farbraum. Each color in the color space corresponds to a Cartesian coordinate {L}. * a * , b * Defined by color coordinates having}. * b * The coordinate plane was constructed using the theory of opposing colors. Green and red are a * Located at opposite ends of the axis, b * The axis extends from blue to yellow. Complementary colors are opposite each other at an angle of 180°; all achromatic colors are at their center (coordinate origin a). * =0, b * It is located at =0).

[0044] L * The axis represents the brightness (luminance) of a color, with a value from 0 to 100. In the figure, L * The axis is at the origin, a * b * It is perpendicular to the plane. All achromatic colors (hues of gray) are black (L * =0) and white (L * Since it lies between the endpoints of (=100), L * The axis can also be called a neutral gray axis. * The axis shows the green or red component of the color, where negative values ​​represent green and positive values ​​represent red. *The axis shows the blue or yellow component of the color, where negative values ​​represent blue and positive values ​​represent yellow. * The value is approximately in the range of -170 to +100, b * The values ​​range from -100 to +150, with the maximum value being achieved only at medium brightness levels for specific hues. CIELAB color entities have the greatest spread in the medium brightness range, although their height and size vary depending on the color gamut.

[0045] Further Preferred Embodiments of the Invention The present invention preferably relates to L from the color number starting with "2" in the RAL color chart according to EN ISO 11664-4. * a * b * This relates to plastic products having a color difference ΔE < 20, determined according to the coordinate system DIN 5033 (1979).

[0046] The present invention more preferably relates to plastic products characterized by a color tone corresponding to color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010, or RAL2011 in the RAL color system.

[0047] The present invention particularly prefers L from color numbers beginning with "2" in the RAL color chart according to EN ISO 11664-4. * a * b * This relates to injection-molded plastic products having a color difference ΔE < 20, determined according to DIN 5033 (1979) of coordinates.

[0048] The present invention particularly relates to injection-molded plastic products characterized by hues corresponding to color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010, or RAL2011 in the RAL color system.

[0049] In a preferred embodiment, the present invention relates to L from color numbers beginning with "2" in the RAL color chart. * a * b * The present invention relates to a plastic product based on a polymer composition having a coordinate color difference ΔE < 20, and containing, in addition to at least one polyamide, b) at least one flame retardant, c) at least one flame retardant synergistic agent, and d) a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one used as a colorant, and e) at least one filler and / or reinforcing agent. Component e) is preferably used in an amount of 1 to 150 parts by mass, more preferably 5 to 80 parts by mass, and most preferably 10 to 50 parts by mass, based on 100 parts by mass of polyamide in each case.

[0050] In a more preferred embodiment, the present invention relates to L, determined according to DIN 5033 (1979) from color numbers beginning with "2" in the RAL color chart according to EN ISO 11664-4. * a * b * The present invention relates to a plastic product based on a polymer composition having a coordinate color difference ΔE < 20, and containing, in addition to at least one polyamide, b) at least one flame retardant, c) at least one flame retardant synergistic agent, and d) a mixture of isomers in the form of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one used as a colorant, and at least one additive which is component f) additionally or alternatively to component e). Component f) is preferably used in each case in an amount of 0.01 to 80 parts by mass, more preferably 0.05 to 50 parts by mass, and most preferably 0.1 to 30 parts by mass, based on 100 parts by mass of polyamide.

[0051] polyamide The polyamides employed in accordance with the present invention can be produced by different processes and can be synthesized from different units. Numerous methods for preparing polyamides are known, and depending on the desired final product, it is possible to use different monomer units and various chain transfer agents to achieve the desired molecular weight, or monomers having reactive groups for post-treatment intended in later stages.

[0052] Industrially relevant processes for the preparation of polyamides typically proceed via polycondensation in a molten material. In this context, the hydrolysis polymerization of lactams is also considered polycondensation.

[0053] In the context of the present invention, other examples of polyamides include polyarylamides (PARAs) available, for example, as IXEF® 1022, which has 50% glass fiber reinforcement, or IXEF® 2057, which has inorganic reinforcement, manufactured by Solvay Specialty Polymers.

[0054] Useful reactants 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, and terephthalic acid; aliphatic and / or aromatic diamines such as tetramethylenediamine, hexamethylenediamine, nonane-1,9-diamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, isomer diaminodicyclohexylmethane, diaminodicyclohexylpropane, bisaminomethylcyclohexane, phenylenediamine, and xylylenediamine; aminocarboxylic acids such as aminocaproic acid; or corresponding lactams. The use of caprolactam, particularly ε-caprolactam, is especially preferred. Copolyamides of the above-mentioned monomers are also included.

[0055] Preferred polyamides are semicrystalline polyamides that can be prepared from diamines and dicarboxylic acids, and / or lactams or corresponding amino acids having at least five ring members.

[0056] Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-4,6 and / or semi-aromatic copolyamides. Preferred semi-aromatic copolyamides are PA6T / 6, PA6T / 66, PA6T / 6I or PA6T / 6I / 66.

[0057] Particularly preferred polyamides according to the present invention include nylon-6 (PA6) [CAS No. 25038-54-4] and nylon-6,6 (PA66) [CAS No. 25038-54-4], where nylon-6 is particularly preferred.

[0058] In the context of this application, the nomenclature of polyamides corresponds to the international standard ISO 1874-1, where the first number indicates the number of carbon atoms in the starting diamine and the last number indicates the number of carbon atoms in the dicarboxylic acid. When only one number is given, as in the case of PA6, this means that the starting material was an α,ω-aminocarboxylic acid or a lactam derived therefrom, i.e., ε-caprolactam in the case of PA6.

[0059] PA6 [CAS No. 25038-54-4], which can be preferably used according to the present invention, preferably has a viscosity number in the range of 80 to 180 ml / g, particularly preferably in the range of 85 to 160 ml / g, and particularly preferably in the range of 90 to 140 ml / g, which can be determined at 25°C in a 0.5 wt% solution in 96 wt% sulfuric acid, in accordance with ISO 307. Polyamide 6, which can be used as component A) according to the present invention, is available, for example, as Durethan® B26 from Lanxess Deutschland GmbH, Cologne.

[0060] The nylon-6,6 [CAS No. 32131-17-2] that can be preferably used according to the present invention preferably has a viscosity number in the range of 80 to 180 ml / g, particularly preferably in the range of 85 to 160 ml / g, and particularly preferably in the range of 90 to 140 ml / g, which can be determined at 25°C in a 0.5 wt% solution in 96 wt% sulfuric acid in accordance with ISO 307. The polyamide 66 that can be used according to the present invention is available from BASF SE, Ludwigshafen as, for example, Ultramid® A24E01.

[0061] The polyamides used in the polymer composition according to the present invention may also be used in admixtures with at least one other polyamide and / or at least one other polymer. Preferred other polymers are selected from the group of polyethylene, polypropylene, and acrylonitrile-butadiene-styrene copolymer (ABS). If at least one further polyamide or at least one other polymer is used, this is preferably or optionally combined with the use of at least one compatibilizer.

[0062] The polyamide used in the polymer composition according to the present invention may already be mixed in the molten material with conventional additives known to those skilled in the art, preferably release agents, stabilizers, and / or flow aids.

[0063] In the context of this application, the nomenclature of polyamides (PA) corresponds to the international standard ISO 1874-1, where the first number indicates the number of carbon atoms in the starting diamine and the last number indicates the number of carbon atoms in the dicarboxylic acid. When only one number is given, as in the case of PA6, this means that the starting material was an α,ω-aminocarboxylic acid or a lactam derived therefrom, i.e., ε-caprolactam in the case of PA6.

[0064] b) Flame retardants To achieve fire protection classifications such as UL 94 V0 or GWFI 960°C (Glow-Wire Flammability Index), in many cases only a small amount of at least one flame retardant of component b) is required.

[0065] The phosphinate salts that should preferably be used as component b) according to the present invention are dialkylphosphinate salts selected from the group consisting of aluminum methylethylphosphinate, aluminum trisdiethylphosphinate, aluminum isopropylisobutylphosphinate, aluminum isopropyl-tert-butylphosphinate, aluminum diisobutylphosphinate, aluminum trismethylethylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, and mixtures thereof. It is particularly preferable to use aluminum trisdiethylphosphinate or zinc bisdiethylphosphinate. Aluminum trisdiethylphosphinate is particularly preferred. These common colorless flame retardants are sold by Clariant International Ltd, Muttenz, Switzerland under the brand name Exolit®, for example, aluminum trisdiethylphosphinate (DEPAL) in pure form as Exolit® OP1240, or zinc bisdiethylphosphinate as Exolit® OP950. Aluminum trisdiethylphosphinate (DEPAL), which is particularly preferred as component b) in the context of this application, was first described by Clariant GmbH, Frankfurt am Main in International Publication No. 99 / 28327A1 and is registered in the registry database under CAS No. 225789-38-8 and the name "Phosphinic acid, P,P-diethyl-aluminum salt (3:1)".

[0066] c) Flame retardant synergistic agent The flame-retardant effect of flame retardants can be further improved by using synergistic agents to shorten the duration or afterburn time of a fire, or to prevent the dripping of polymers that are melting or burning due to the heat of the fire. For example, Korean Patent No. 890 004 333 B1 teaches those skilled in the art the use of antimony trioxide (Sb2O3) as a synergistic agent in combination with halogen-containing flame retardants. German Patent Application Publication No. 3 808 493 A1 further discloses to those skilled in the art the use of aromatic polyamides and / or polyimidoamides as drip inhibitors, which have a synergistic effect when combined with other conventional flame retardants and mainly prevent the dripping of combustion droplets of aliphatic / alicyclic polyamides.

[0067] According to the present invention, the flame retardant of component b) is used together with c) at least one flame retardant synergistic agent selected from melamine polyphosphate (CAS No. 1312753-42-6 or 218768-84-4) and aluminum phosphonate (CAS No. 2278203-39-5). Melamine polyphosphate is available as Melapur® 200 / 70 from BASFSE, Ludwigshafen, Germany. Aluminum phosphonate is the formula Al2(HPO3)3·(H2O) according to Example 2 of International Publication No. 2013 / 083247A1. q It is available as secondary aluminum phosphonate (where q is in the range of 0 to 4).

[0068] Particularly preferred combinations of components b) and c) are in the form of aluminum trisdiethylphosphinate (DEPAL) and melamine polyphosphate, and aluminum trisdiethylphosphinate (DEPAL) and aluminum phosphonate.

[0069] In the context of the present invention, it has been further found that zinc bis-diethylphosphinate or zinc bis-methylethylphosphinate does not necessarily require a flame retardant synergist. The present invention therefore relates, in preferred embodiments, to plastic products made of a polymer composition comprising a) at least one polyamide, b) at least one flame retardant from zinc bis-diethylphosphinate or zinc bis-methylethylphosphinate, and d) a colorant mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one.

[0070] The flame retardant synergistic agent used as component c) is similarly sold under the brand name Exolit®, for example, by Clariant International Ltd, Muttenz, Switzerland, in the form of a finished mixture with the flame retardant of component b). Examples include: Exolit® OP1311, Exolit® OP1314, Exolit® OP1316, Exolit® OP1400, Exolit® OP1402, Exolit® OP1466, or Exolit® OP1260.

[0071] Further ingredients In a preferred embodiment, the polymer composition includes not only a polyamide and a colorant, but also at least one filler or reinforcing agent. It is also possible to use a mixture of two or more different fillers and / or reinforcing agents.

[0072] Carbon fiber [CAS No. 7440-44-0], glass beads or solid or hollow glass beads or glass fiber or crushed glass, amorphous quartz glass, aluminum borosilicate glass (E glass) with 1% alkali content [CAS No. 65997-17-3], amorphous silica [CAS No. 7631-86-9], quartz powder [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 It is preferable to use at least one filler or reinforcing material from the group consisting of [CAS No. 1302-76-7], powdered or crushed 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], pseudobaumite of formula AlO(OH), magnesium carbonate [CAS No. 12125-28-9], and talc [CAS No. 14807-96-6].

[0073] Particularly preferred fibrous fillers or reinforcing materials include glass fibers and wollastonite, with glass fibers being particularly preferred. With respect to glass fibers, those skilled in the art distinguish between chopped fibers, also called short fibers, having a length in the range of 0.1 to 1 mm; long fibers, having a length in the range of 1 to 50 mm; and continuous fibers, having a length L > 50 mm. Short fibers are preferably used in injection molding and can be processed directly in an extruder. Long fibers can also be processed in an extruder. These fibers are widely used in fiber spraying. Long fibers are frequently added to thermosetting resins as fillers. Continuous fibers are used in fiber-reinforced plastics in the form of rovings or woven fabrics. Products containing continuous fibers achieve the highest stiffness and strength values. Crushed glass fibers are also available, and their length after crushing is typically in the range of 70 to 200 μm.

[0074] The glass fibers preferably used as fillers or reinforcing materials according to the present invention are chopped-length glass fibers having an average starting length in the range of 1 to 50 mm, more preferably in the range of 1 to 10 mm, and most preferably in the range of 2 to 7 mm, as measured by laser diffraction particle size analysis (laser particle size measurement method / laser diffraction method) in accordance with ISO 13320. Regarding laser diffraction particle size measurement / laser diffraction method in accordance with standard ISO 13320: https: / / de.wikipedia.org / wiki / Laserbeugungs-Partikelgr%C3%B6%C3%9Fenanalyse See below.

[0075] Glass fibers may have lower d90 or d50 values ​​in the molded material or manufactured article than the original glass fibers used, particularly as a result of processing to obtain the molded material (compounding) or manufactured article in the injection molding process. Therefore, the arithmetic mean of the glass fiber length after processing is often only in the range of 150 μm to 300 μm, and consequently, the length, width and diameter of fillers and reinforcing materials, particularly glass fibers, described herein refer to the state before any processing, especially before compounding or especially before injection molding.

[0076] Preferred glass fibers that can be used as fillers or reinforcing materials have an average fiber diameter that can be determined by laser diffraction in accordance with ISO 13320, in the range of 7 to 18 μm, more preferably in the range of 9 to 15 μm.

[0077] In a preferred embodiment, the glass fibers, which are preferably usable as a filler or reinforcing material, are modified with a suitable sizing agent system or fixing agent(s). It is preferable to use a sizing agent system or a silane-based fixing agent.

[0078] additives Under the premise of obtaining high laser transmittance, the polymer composition or plastic product according to the present invention contains, in addition to components a), b), c), and d), at least additive e) other than components b), c), and d). Preferably, usable additive e), which includes fillers or reinforcing materials, include antioxidants, (thermal) stabilizers, ultraviolet stabilizers, gamma-ray stabilizers, components that reduce water absorption or hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact resistance modifiers, lubricants and / or release agents, components for reducing water absorption, flow aids or elastomer modifiers, chain extension additives, and colorants other than isomer mixtures in the form of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one. Additives may be used alone, in mixtures, or in the form of a masterbatch.

[0079] Preferred (thermal) stabilizers as additives include sterically hindered phenols (especially those containing at least one 2,6-di-tert-butylphenyl group and / or 2-tert-butyl-6-methylphenyl group), and phosphites, hypophosphites, especially sodium hypophosphate (NaH2PO2), hydroquinone, aromatic secondary amines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, 3,3'-thiodipropionic acid esters, and representative examples of these substituted in various ways or mixtures thereof. Further stabilizers in the context of the present invention include zinc oxide, zinc borate, and calcium stannate or zinc (hydroxy)stannate. The (thermal) stabilizers usable as additives are preferably used in amounts of 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of polyamide in each case.

[0080] Preferred UV stabilizers that can be used as additives include substituted resorcinols, salicylates, benzotriazoles and benzophenones, HALS derivatives containing at least one 2,2,6,6-tetramethyl-4-piperidyl unit ("hindered amine light stabilizers"), or benzophenone. The UV stabilizers that can be used as additives are preferably used in an amount of 0.01 to 2 parts by mass, particularly preferably 0.1 to 1 part by mass, based on 100 parts by mass of polyamide in each case.

[0081] Other colorants that can be used as additives, besides isomer mixtures in the form of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one, are preferably inorganic pigments, especially ultramarine blue, bismuth vanadate, iron oxide, titanium dioxide, zinc sulfide, zinc-titanium-zinc oxide [CAS No. 923954-49-8], and organic dyes, preferably phthalocyanine, quinacridone, benzimidazole, especially nickel 2-hydroxynaphthylbenzimidazole [CAS No. 42844-93-9] and / or pyrimidine-azo-benzimidazole [CAS No. 72102-84-2] and / or pigment yellow 192 [CAS Examples include [No. 56279-27-7], and perylene, anthraquinone, 1,3-dihydro-5,6-bis(((2-hydroxy-1-naphthyl)methylene)amino-2H-benzimidazole-2-onato(2-)-N5,N6,O5,O6)nickel, particularly CI Solvent Yellow 163 [CAS No. 13676-91-0], and this list is not exhaustive. In one embodiment, the colorants used are also carbon black or nigrosine, although this results in a loss of laser transmittance in the laser-absorbing plastic product.

[0082] Suitable nucleating agents that can be used as additives include, but are not exhaustive, sodium phenylphosphinate or calcium phenylphosphinate, aluminum oxide or silicon dioxide, and more preferably talc.

[0083] Preferred plasticizers that can be used as additives include dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oil, or N-(n-butyl)benzenesulfonamide.

[0084] Preferred elastomer modifiers that can be used as additives include: E.1 5% to 95% by weight, preferably 30% to 90% by weight, of at least one vinyl monomer, and E.2 Graft substrates having a glass transition temperature of <10°C, preferably <0°C, more preferably <-20°C, in an amount of 95% to 5% by weight, preferably 70% to 10% by weight of one or more types One or more graft polymers are mentioned, where the weight percentage is based on 100% by weight of the elastomer modifier. The graft substrate E.2 generally has a median particle size d50 value that can be determined by laser diffraction in accordance with ISO 13320, with a particle size of 0.05 to 10 μm, preferably 0.1 to 5 μm, and more preferably 0.2 to 1 μm.

[0085] Monomer E.1 is preferably, E.1.1 50% to 99% by weight of vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds, particularly styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and / or (C1-C8)-alkyl methacrylates, particularly methyl methacrylate, ethyl methacrylate and E.1.2 1% to 50% by weight of vinyl cyanide, particularly unsaturated nitriles such as acrylonitrile and methacrylonitrile, and / or (C1-C8)-alkyl (meth)acrylates, particularly methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, particularly derivatives of maleic anhydride or N-phenylmaleimide, particularly anhydrides and imides. It is a mixture of the following, where the weight percentage is based on 100% by weight of the elastomer modifier.

[0086] Preferred monomer E.1.1 is selected from at least one of styrene, α-methylstyrene, and methyl methacrylate monomer; preferred monomer E.1.2 is selected from at least one of acrylonitrile, maleic anhydride, glycidyl methacrylate, and methyl methacrylate monomer. Particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.

[0087] Suitable graft substrates E.2 for graft polymers usable in elastomer modifiers include, for example, diene rubber, EPDM rubber (i.e., ethylene / propylene and optionally diene-based), and acrylates, polyurethanes, silicones, chloroprene, and ethylene / vinyl acetate rubber. EPDM is ethylene-propylene-diene rubber.

[0088] Preferred graft substrate E.2 is a diene rubber based particularly on butadiene, isoprene, etc., or a mixture of diene rubber or a copolymer of diene rubber, or a mixture of these with further copolymerizable monomers of E.1.1 and E.1.2, wherein the glass transition temperature of component E.2 is <10°C, preferably <0°C, and more preferably <-10°C.

[0089] Lubricants and / or release agents that can be used as additives include long-chain fatty acids, particularly stearic acid or behenic acid, their salts, particularly calcium stearate or zinc stearate, and their ester derivatives, particularly those based on pentaerythritol, particularly fatty acid esters or amide derivatives of pentaerythritol, particularly ethylenebisstearylamide, montan wax, and low molecular weight polyethylene or polypropylene wax. In the context of the present invention, montan wax is a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms.

[0090] Glass fiber reinforced plastic products The present invention relates to a plastic product made of a polymer composition in which, preferably in addition to components a), b), c), and d), an additive e) filler or reinforcing material is used, glass fibers, preferably chopped glass fibers having an average initial length measurable by laser diffraction particle size analysis (laser particle size measurement method / laser diffraction method) in accordance with ISO 13320 in the range of 1 to 50 mm. Preferably, the average initial length of the cut glass fibers determined in accordance with ISO 13320 is in the range of 1 to 10 mm, particularly preferably in the range of 2 to 7 mm.

[0091] In the polymer composition, it is preferable to use 1 to 150 parts by mass, preferably 5 to 80 parts by mass, and more preferably 10 to 50 parts by mass of chopped long glass fibers for every 100 parts by mass of polyamide.

[0092] The chopped long glass fibers preferably have an average fiber diameter that can be determined by laser diffraction in accordance with ISO 13320, in the range of 7 to 18 μm, more preferably in the range of 9 to 15 μm.

[0093] More preferably, the present invention relates to the RAL color chart relating to the color model according to EN ISO 11664-4, starting with L from the color number beginning with "2". * a * b * A plastic product having a color difference ΔE < 20 as determined according to the coordinate system DIN 5033 (1979), comprising at least one polyamide, components b) and c), and a colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one (preferably in a ratio of 1:1:0.8~1.5 to 1:1.5:0.8~1.5, particularly preferably additionally having a median particle size d50 in the range of 1~12 μm as determined by laser diffraction in accordance with ISO 13320), and an ISO This invention relates to plastic products based on a polymer composition containing glass fibers, preferably chopped-length glass fibers, having an average starting length measurable by laser diffraction particle size analysis (laser particle size measurement method / laser diffraction method) in accordance with 13320. The polyamide used is preferably at least nylon-6 or nylon-6,6, particularly nylon-6.

[0094] In particular, these plastic products most preferably contain 1 to 150 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 50 parts by mass, of glass fiber for every 100 parts by mass of at least one polyamide, preferably at least nylon-6 or nylon-6,6, and especially nylon-6.

[0095] process The present invention also relates to a manufacturing process for plastic products, particularly injection-molded plastic products: a) at least one type of polyamide; b) At least one phosphinate of formula (I) and / or at least one diphosphinate of formula (II) [ka] (In the formula, R 1 , R 2 These are identical or different linear or branched C1-C6 alkyl and / or C6-C 14 -Aryl; R 3 This refers to linear or branched chains C1-C 10 -Alkylene, C6~C 10 -Arylene or C1~C6-alkyl-C6~C 10 - Arylene or C6~C 10 -Aryl-C1~C6-alkylenes; M is either aluminum or zinc; m is an integer between 1 and 4; n is an integer from 1 to 3; and x is either 1 or 2; Here, n, x, and m in equation (II) can simultaneously take only integer values ​​such that the diphosphinate of equation (II) as a whole is uncharged. and / or at least one flame retardant comprising those polymers; c) At least one flame retardant synergistic agent selected from melamine polyphosphate and aluminum phosphonate; and d) At least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one The invention also relates to a process of further processing the polymer composition by mixing to obtain a polymer composition, extruding it into strands, cooling it until it can be pelletized, drying and pelletizing it, and then by injection molding, including special methods such as gas injection molding (GIT), water injection molding (WIT), or projectile injection molding (PIT), by extrusion molding methods including profile extrusion molding, or by blow molding.

[0096] The present invention preferably: a) At least one polyamide, preferably nylon-6 or nylon-6,6; b) At least one phosphinate of formula (l) [ka] (In the formula, R 1 , R 2 These are identical or different linear or branched C1-C6 alkyl groups; M is aluminum or zinc, especially aluminum; (m is an integer between 1 and 4) At least one flame retardant comprising: c) At least one flame retardant synergistic agent selected from melamine polyphosphate and aluminum phosphonate; and d) At least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one This relates to plastic products made from polymer compositions containing the following:

[0097] Here: A) 100 parts by mass of at least one polyamide, preferably nylon-6 or nylon-6,6; B) 2 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 30 parts by mass of at least one flame retardant b); C) 0.2 to 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 0.75 to 35 parts by mass of at least one flame retardant synergistic agent c); and D) At least one coloring agent in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one, in an amount of 0.01 to 5 parts by mass. It is preferable to use [this].

[0098] Preferably, the plastic products obtained by the process according to the present invention also have a color number starting with "2" in the RAL color chart relating to the color model according to EN ISO 11664-4. * a * b * Color difference ΔE < 10ΔE determined according to coordinates DIN 5033 (1979), more preferably L from the color number starting with "2" in the RAL color chart relating to the color model according to EN ISO 11664-4 * a * b * The color difference ΔE < 5 is determined according to the coordinate system DIN 5033 (1979).

[0099] The polyamide used is particularly preferably nylon-6.

[0100] The present invention further relates to a process in which, in addition to components a), b), c), and d), e) glass fibers are also used, having an average starting length measurable by laser diffraction particle size analysis (laser particle size measurement / laser diffraction method) in accordance with ISO 13320, in the range of 1 to 50 mm, more preferably in the range of 1 to 10 mm, and even more preferably in the range of 2 to 7 mm.

[0101] Preferably, in the process according to the present invention, 1 to 150 parts by mass of glass fibers, more preferably 5 to 80 parts by mass, still more preferably 10 to 50 parts by mass of glass fibers are used, based on 100 parts by mass of polyamide.

[0102] Also in the process according to the present invention, the glass fibers particularly preferably additionally have an average fiber diameter that can be determined by a laser diffraction method in accordance with ISO 13320 within the range of 7 to 18 μm, more preferably within the range of 9 to 15 μm.

[0103] More preferably, the present invention relates to a process for producing a plastic product in the form of a laser-transparent, orange-colored and flame-retardant product or a joining partner for further processing by laser transmission welding within a wavelength range of 800 nm to 1200 nm. It is preferable to employ an Nd:YAG laser (1064 nm) or a high-power diode laser (800 to 1000 nm) in the laser transmission welding.

[0104] For the sake of clarity, it should be noted that the scope of the present invention encompasses all definitions and parameters that are normally mentioned in the context of electric mobility components, or that are mentioned in preferred ranges in any desired combination of the process according to the present invention.

[0105] Use Preferably, in the present invention, the plastic product is: a) at least one polyamide; b) at least one phosphinate salt of formula (I) and / or at least one diphosphinate salt of formula (II)

Chemical Formula

[0106] Particularly preferably, the present invention relates to use of a colorant comprising an isomer mixture of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one for producing flame-retardant plastic products, wherein the flame-retardant plastic product is: a) at least one polyamide, preferably nylon-6 or nylon-6,6; b) at least one phosphinate of formula (I)

Chemical Formula

[0107] Furthermore, in the context of use according to the present invention, a) for every 100 parts by mass of at least one type of polyamide; 2 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 30 parts by mass of b) at least one flame retardant, c) at least one flame retardant synergistic agent in an amount of 0.2 to 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 0.75 to 35 parts by mass, and d) At least one coloring agent comprising 0.01 to 5 parts by mass of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and a mixture of isomers of 10,10'-oxybis-12H-phthaloperin-12-one The use of is preferable.

[0108] In a preferred embodiment, in the context of use according to the present invention, in addition to components a), b), c), and d), a similarly used component e) glass fiber is used, which has an average starting length determined by laser diffraction particle size analysis (laser particle size measurement / laser diffraction method) in accordance with ISO 13320, in the range of 1 to 50 mm, more preferably in the range of 1 to 10 mm, and even more preferably in the range of 2 to 7 mm.

[0109] Preferably, in the context of use according to the present invention, 1 to 150 parts by mass, more preferably 5 to 80 parts by mass, and even more preferably 10 to 50 parts by mass of glass fibers are used based on 100 parts by mass of polyamide.

[0110] In the context of use according to the present invention, the glass fibers particularly preferably have an average fiber diameter determined by laser diffraction in accordance with ISO 13320, in the range of 7 to 18 μm, more preferably in the range of 9 to 15 μm.

[0111] Preferably, the present invention relates to L from color numbers beginning with "2" in the RAL color chart according to EN ISO 11664-4. * a * b * The present invention relates to the use of colorants in the form of isomer mixtures of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one for the manufacture of plastic products having a color difference ΔE < 20 as determined according to DIN 5033 (1979) of coordinates, wherein these colorants comprise a) at least one polyamide, and the above components b) at least one flame retardant and c) at least one flame retardant synergist.

[0112] Preferably, in the use according to the present invention, the plastic product is an injection-molded plastic product. Preferably, the colorants in the plastic product are in the form of isomer mixtures of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one, and are used in laser transmission welding in the wavelength range of 800 nm to 1200 nm to obtain the plastic product as a laser-transmissive, orange flame-retardant product or bonding partner. Preferably, in the context of this use, an Nd:YAG laser (1064 nm) or a high-performance diode laser (800 to 1000 nm) is employed.

[0113] For clarity, it should be noted that the claimed scope of use includes all definitions and parameters generally enumerated in the context of the above-described plastic products or methods according to the present invention, or in preferred areas in any desired combination. [Examples]

[0114] To demonstrate the improved properties described in accordance with the present invention, the corresponding polyamide polymer compositions were first formed by kneading. For this purpose, the individual components were mixed in a twin-screw extruder (Leistritz LSM 30-34, manufactured by Leistritz AG (Nuremberg, Germany)) at a temperature of 270°C to 300°C, extruded as strands, cooled until pelletizable, and then pelletized. After drying (generally in a vacuum drying cabinet at 80°C for 2 days), the pellets were processed by injection molding at a temperature in the range of 270°C to 290°C to obtain standard test specimens for each test.

[0115] Starting materials: Ingredient a) Nylon-6 (Durethan® B30S, manufactured by Envalior Deutschland GmbH, Duesseldorf, Germany) Components b) and c) Contains Exolit® OP 1311, aluminum trisdiethylphosphinate (CAS No. 225789-38-8), and melamine polyphosphate (CAS No. 1312753-42-6), manufactured by Clariant International Ltd., Muttenz, Switzerland. Component b) and component c') Contains Exolit® OP 1400, aluminum trisdiethylphosphinate (CAS No. 225789-38-8), and aluminum phosphonate (CAS No. 2278203-39-5), manufactured by Clariant International Ltd., Muttenz, Switzerland. Component d') Component colorant relating to International Publication No. 2020 / 187702A1, namely, 10,10'-oxybis-12H-phthaloperine-12-one [CAS No. 203576-97-0] manufactured by Angene International Limited, London. Component d) A colorant in the form of isomers 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one in a 1:1.2:1 ratio, prepared according to the following synthesis specifications, having a median particle size d50 that can be determined by laser diffraction in accordance with ISO 13320 over a 5 μm region:

[0116] Synthesis specifications for component d) Preparation of colorants in the form of isomers 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one in a 1:1.2:1 ratio. 300 g of phenol was melted at 60°C. 45 g (285 mmol) of 1,8-diaminonaphthalene and 3.1 g of 2,6-lutidine (28.5 mmol) were added, and the mixture was stirred for 30 minutes. Next, 45 g (145 mmol) of 4,4-oxydiphthalic anhydride was introduced, and the reaction mixture was stirred for a further 30 minutes. The reaction mixture was then heated to 175°C and held at that temperature for 10 hours, after which the resulting reaction water was removed by distillation. Next, 295 g of methanol was added to the reaction mixture at 175°C, and the temperature of the reaction mixture was lowered to 30°C over 1 hour. The reaction product was isolated on a suction filter and subsequently stirred in 300 g of phenol at 175°C for 45 minutes. Next, 295 g of methanol was added at 175°C, and the temperature of the reaction mixture was lowered to 30°C over 3 hours. The reaction product was isolated on a suction filter, washed first with 440 g of methanol, then with 800 g of water, and dried in a vacuum drying cabinet at 80°C and 150 mbar. The isomer distribution of the dye was determined to be 1:1.2:1, and the median particle size d50 was determined to be 5 μm.

[0117] [Table 2]

[0118] The test results listed in Table 2 show that the embodiment of the present invention for multipurpose test specimens not only achieved the highest fire resistance classification V-0 but also possessed excellent laser transmittance (+++), and that the test specimens were free of streaks after injection molding (+++). After injection molding, the 1A type multipurpose test specimen according to DIN EN ISO 527 had a ΔE < 10 and an RAL of 2001 (red-orange), showing no browning, compared to Comparative Example 1 (RAL 8023).

[0119] Judgment method In the context of the present invention, the isomer distribution of the isomer mixture of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one is determined by HPLC (high-pressure liquid chromatography), and the polymer composition listed in Table 2 or the 60·40·2mm formed therefrom by injection molding is determined. 3 Scale for measuring the color vividness of plastic products in the form of plaques (colorimetric measurement (D65 standard light, CIE 1976 L) * a * b * In Colour Space, C was measured using a d / 8° spectrophotometer in accordance with DIN EN ISO 11664-4. * The values ​​can be cited. HPLC is a liquid chromatography method that not only separates substances but also identifies and quantifies them (determines their exact concentration) via standards. The presence of color unevenness is due to the median particle size d50 of the colorant used in the polymer composition according to the present invention, as determined in accordance with ISO 13320.

[0120] According to the present invention, high laser transmittance means a laser transmittance of at least 30%, preferably at least 40%, and more preferably at least 50%, measured at a laser wavelength of 980 nm using an LPKF TMG3 transmittance analyzer manufactured by LPKF Laser&Electronics AG, Garbsen, Germany, in a sample plaque with a thickness of 0.75 mm. The measurement in the context of the present invention was performed in the near-infrared (NIR) using a circular plaque with a diameter of 80 mm and a thickness of 0.75 mm, based on DVS Guideline 2243 (01 / 2014) “Laserstrahlschweissen thermoplastischer Kunststoffe”. The LPKF TMG3 transmittance analyzer manufactured by LPKF Laser&Electronics AG was calibrated before measurement with a measurement standard manufactured in accordance with DIN EN ISO / IEC 17025. The measurement was performed at a laser wavelength of 980 nm in the context of the present invention.

[0121] A decrease in transmittance at 980 nm of <3% compared to a plastic sample without the colorant in the form of a mixture of isomers of component d) 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one is rated as +++ in the context of the present invention. A decrease in transmittance at 980 nm within the range of 3% to 5% compared to a plastic sample without the colorant in the form of a mixture of isomers of component d) 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one is rated as ++ in the context of the present invention. A decrease in transmittance at 980 nm within the range of 5% to 10% compared to a plastic sample without the colorant in the form of a mixture of isomers of component d) 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one is evaluated only as positive in the context of the present invention.

[0122] The detection of streaks after injection molding is evaluated by visual inspection. "+++" means there are no streaks, "++" means the streaks are reduced, and "-" means streaks are present.

[0123] The detection of browning due to injection molding was achieved by determining the RAL color of the injection-molded product, which is in the form of a 1A type multipurpose test specimen according to DIN EN ISO 527, by comparison with the RAL color chart. The most well-known RAL colors are defined in the RAL Classic System, which includes 213 colors. These are identified by a four-digit number beginning with "RAL" and an arbitrary color name. The RAL color chart is a physical color fan that shows different RAL colors. The color tone of the injection-molded product was determined by visual matching with the chart.

Claims

1. a) At least one type of polyamide; b) At least one phosphinate of formula (I) and / or at least one diphosphinate of formula (II) 【Chemistry 1】 (In the formula, R １ , R ２ C is identical or different, linear or branched. １ ~C ６ - Alkyl and / or C ６ ~C １４ - is an allele; R ３ represents linear or branched C １ to C １０ -alkylene, C ６ to C １０ -arylene, C １ to C ６ -alkyl-C ６ to C １０ -arylene, or C ６ to C １０ -aryl-C １ to C ６ -alkylene; M is aluminum or zinc; m is an integer between 1 and 4; n is an integer from 1 to 3; and x is either 1 or 2; Here, n, x, and m in formula (II) can simultaneously take only integer values ​​such that the diphosphinate in formula (II) as a whole is uncharged. and / or at least one flame retardant comprising those polymers; c) At least one flame retardant synergistic agent selected from melamine polyphosphate and aluminum phosphonate; and d) At least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one Plastic products made from polymer compositions containing the following:

2. The component b) used is at least one phosphinate of formula (I) above. 【Chemistry 2】 (In the formula, R １ , R ２ C is identical or different, linear or branched. １ ~C ６ (It is an alkyl group, M is aluminum or zinc, and m is an integer from 1 to 4.) The plastic product according to claim 1, characterized in that it is the same as the product described in claim 1.

3. In the RAL color chart related to EN ISO 11664-4, L from color numbers starting with "2" ＊ a ＊ b ＊ The plastic product according to claim 1 or 2, characterized by a color difference ΔE < 20 determined according to DIN 5033 (1979) of coordinates.

4. a) For every 100 parts by mass of at least one type of polyamide, the following is used: 2 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 30 parts by mass of b) at least one of the flame retardants, c) at least one of the flame retardant synergistic agents and 0.2 to 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 0.75 to 35 parts by mass d) At least one coloring agent 0.01 to 5 parts by mass A plastic product according to any one of claims 1 to 3, characterized in that it is a plastic product according to any one of claims 1 to 3.

5. The plastic product according to any one of claims 1 to 4, characterized in that component b) the phosphinate is a dialkylphosphinate selected from the group consisting of aluminum methylethylphosphinate, aluminum trisdiethylphosphinate, aluminum isopropylisobutylphosphinate, aluminum isopropyl-tert-butylphosphinate, aluminum diisobutylphosphinate, aluminum trismethylethylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, and mixtures thereof.

6. The plastic product according to any one of claims 1 to 4, characterized in that component b) used is aluminum trisdiethylphosphinate or zinc bisdiethylphosphinate.

7. A plastic product according to any one of claims 1 to 6, characterized by a color tone corresponding to color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010, or RAL2011 in the RAL color system.

8. e) The plastic product according to any one of claims 1 to 7, characterized in that it contains at least one filler and / or reinforcing material, preferably in an amount of 1 to 150 parts by mass based on 100 parts by mass of polyamide.

9. The plastic product according to claim 8, characterized in that the filler and / or reinforcing material is selected from the group consisting of carbon fiber, solid or hollow glass beads, glass fiber, crushed glass, amorphous quartz glass, aluminum borosilicate glass (E glass) having an alkali content of 1%, amorphous silica, quartz powder, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or crushed quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, pseudobohmite of the formula AlO(OH), magnesium carbonate, and talc.

10. The plastic product according to claim 9, characterized in that the filler and / or reinforcing material used is glass fiber having an average starting length in the range of 1 to 50 mm, as determined by laser diffraction particle size analysis in accordance with ISO 13320.

11. The plastic product according to any one of claims 3 to 10, characterized in that it is laser-transparent and used as an orange flame-retardant product or bonding partner, particularly in electric mobility.

12. Preferably, L from a color number starting with "2" in the RAL color chart according to EN ISO 11664-4 ＊ a ＊ b ＊ A process for manufacturing plastic products having a color difference ΔE < 20 determined according to the coordinate system DIN 5033 (1979), a) At least one type of polyamide; b) At least one phosphinate of formula (I) and / or at least one diphosphinate of formula (II) 【Transformation 3】 (In the formula, R １ , R ２ C is identical or different, linear or branched. １ ~C ６ - Alkyl and / or C ６ ~C １４ - is an allele; R ３ C is a straight or branched chain. １ ~C １０ - Alkylene, C ６ ~C １０ - Arylene or C １ ~C ６ -Alkyl-C ６ ~C １０ - Arylene or C ６ ~C １０ -Aryl-C １ ~C ６ - It is alkylene; M is aluminum or zinc; m is an integer between 1 and 4; n is an integer from 1 to 3; and x is either 1 or 2; Here, n, x, and m in formula (II) can simultaneously take only integer values ​​such that the diphosphinate in formula (II) as a whole is uncharged. and / or at least one flame retardant comprising those polymers; c) At least one flame retardant synergistic agent selected from melamine polyphosphate and aluminum phosphonate; and d) At least one colorant in the form of a mixture of isomers of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one, and 10,10'-oxybis-12H-phthaloperin-12-one A manufacturing process comprising: mixing to obtain a polymer composition; extruding it into strands; cooling until pelletizable; drying and pelletizing; and then further processing the polymer composition by injection molding, including special methods such as gas injection, water injection, or projectile injection; extrusion molding, including profile extrusion; or blow molding.

13. A) For every 100 parts by mass of at least one polyamide, preferably nylon-6 or nylon-6,6, B) 2 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 30 parts by mass of at least one of the flame retardants b) C) 0.2 to 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 0.75 to 35 parts by mass of at least one of the flame retardant synergistic agents c), and D) 0.01 to 5 parts by mass of the above-mentioned coloring agent The process according to claim 12, characterized in that the following is used.

14. Use of a colorant containing an isomer mixture in the form of 9,9'-oxybis-12H-phthaloperin-12-one, 9,10-oxybis-12H-phthaloperin-12-one and 10,10'-oxybis-12H-phthaloperin-12-one for the manufacture of flame-retardant plastic products, wherein the flame-retardant plastic products a) At least one type of polyamide; b) At least one phosphinate of formula (I) and / or at least one diphosphinate of formula (II) 【Chemistry 4】 (In the formula, R １ , R ２ C is identical or different, linear or branched. １ ~C ６ - Alkyl and / or C ６ ~C １４ - is an allele; R ３ C is a straight or branched chain. １ ~C １０ - Alkylene, C ６ ~C １０ - Arylene or C １ ~C ６ -Alkyl-C ６ ~C １０ - Arylene or C ６ ~C １０ -Aryl-C １ ~C ６ - It is alkylene; M is aluminum or zinc; m is an integer between 1 and 4; n is an integer from 1 to 3; and x is either 1 or 2; Here, n, x, and m in formula (II) can simultaneously take only integer values ​​such that the diphosphinate in formula (II) as a whole is uncharged. and / or at least one flame retardant comprising those polymers; and c) At least one flame retardant synergistic agent selected from melamine polyphosphate and aluminum phosphonate. Use in cases that include [this].

15. a) For every 100 parts by mass of at least one type of polyamide, 2 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 30 parts by mass of b) at least one of the flame retardants, c) at least one flame retardant synergistic agent in an amount of 0.2 to 50 parts by mass, preferably 0.5 to 40 parts by mass, more preferably 0.75 to 35 parts by mass, and d) At least one coloring agent 0.01 to 5 parts by mass The use according to claim 14, characterized in that the above is used.

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