Flame-retardant plastic products

Abstract

We provide flame-retardant plastic products. [Solution] The present invention relates to flame-retardant plastic products made of polyester 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 polyester molding compounds or plastic products having high laser transmittance.

Description

[Technical Field]

[0001] The present invention relates to flame-retardant plastic products made of polyester 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 polyester molding compounds or plastic products having high laser transmittance. [Background technology]

[0002] Due to its excellent mechanical stability, chemical resistance, and processability, polyester is an important material used, for example, in components for the automotive, electrical and electronic industries, or in household appliances. In applications of polyester near live electrical 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 is also desired, in addition to good self-extinguishing ability, particularly as classified as UL94 V-0 according to Non-Patent Literature 1.

[0003] In the field of polyester, the demand for halogen-free solutions is increasing for environmental reasons, and because polyesters containing halogen-free flame retardants generally reduce the flammability of articles compared to halogen-containing systems, thereby not only delaying the progression of fire but also reducing smoke generation, preventing toxic gases, and being environmentally friendly and beneficial to health. The desire for maximum design freedom, and consequently for greater complexity of 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 transmission welding processes (see Non-Patent Literature 2). Regarding laser-transparent joining partners, this requires a high degree of transmittance at the laser wavelength used. The latter is a major challenge for flame-retardant polyesters because flame retardants scatter or even absorb laser light, such as antimony trioxide used as a flame retardant synergist in halogen-containing flame retardants. An additional challenge in the case of colored polyesters is the colorants used.

[0004] 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 polyester-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.

[0005] In particular, the high processing temperatures of >300°C in some cases, such as kneading and injection molding, and especially the presence of additives such as flame retardants, severely limit the selection of suitable colorants in polyester 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.

[0006] Furthermore, it should be considered that, especially under extreme demanding conditions such as those encountered in the processing of polyester, dyes in polyester tend to cause uneven coloring or discoloration, particularly on surfaces near the injection point of injection-molded products.

[0007] 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.

[0008] 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 may 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 the injection-molded product that are too small for injection molding. In particular, in the case of glass fiber reinforced injection-molded products, reducing, if not eliminating, the streaking, especially in the processing of orange polyester-based molding materials by injection molding, is therefore a particular challenge for those skilled in the art.

[0009] (Patent Document 3) discloses polyester resin compositions colored black with anthraquinone dyes Solvent Blue 104, Solvent Blue 97, and Solvent Yellow 163, a perinone dye Solvent Red 179, and an azomethine dye Solvent Brown 53, which are welded to a second polyester component containing nigrosine to form a test specimen having an overall black appearance. Although a perinone dye in the form of Solvent Red 179 is used in (Patent Document 3), (Patent Document 3) does not address the issue of laser transmittance of orange polyester or the presence of flame retardants. Aside from the fact that the problem addressed in (Patent Document 3) was to produce a visually uniform product by welding two components having a black appearance, the problem of browning due to the effects of heat on the polyester and / or dyes, whether in laser welding or mixing, is not considered in (Patent Document 3).

[0010] Patent Document 4 discloses a high-voltage component based on a polymer composition containing at least one polyester 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 describes an electric mobility component having a coordinate color difference ΔE < 20, comprising a polymer composition based on at least one polyester 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 polyester in the polymer composition.

[0012] Therefore, starting from the prior art, the present invention aims to provide a plastic product formed from a polyester polymer composition containing a halogen-free flame retardant, which enables the production of orange plastic products without streaking or browning caused by the polyester-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 / 187704A1 Pamphlet [Patent Document 5] International Publication No. 2025 / 003531A1 Pamphlet [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, Laser Transmission Welding of Plastics—Elastomers and Plastics, KGK-Rubberpoint, 11.2006, pp. 590-595 Summary of the Invention Means for Solving the Problems

[0015] Surprisingly, it has now been found that the above-described requirements are satisfied by a plastic article made of a polymer composition comprising at least one polyester, at least one flame retardant composed of at least one phosphinate and / or at least one diphosphinate and / or polymers thereof, at least one flame retardant synergist, and 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. Mode for Carrying Out the Invention

[0016] The present invention provides: a) at least one polyester; b) at least one phosphinate of formula (I) and / or at least one diphosphinate of formula (II) Chemical Formula (wherein, R 1 , R 2 are the same or different and are each 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-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 We provide plastic products made from polymer compositions containing the following:

[0017] The present invention preferably: a) at least one type of polyester; 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 either aluminum or zinc; (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:

[0018] More 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 a plastic product having a color difference ΔE < 20 as determined according to DIN 5033 (1979) of coordinates, comprising a) at least one polyester, b) at least one flame retardant, c) at least one flame retardant synergist, and d) at least one colorant.

[0019] More 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 a plastic product having a color difference ΔE < 10 as determined according to DIN 5033 (1979) of coordinates, comprising a) at least one polyester, b) at least one flame retardant, c) at least one flame retardant synergist, and d) at least one colorant.

[0020] Particularly 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 a plastic product having a color difference ΔE < 5 as determined according to DIN 5033 (1979) of coordinates, and comprising a) at least one polyester and the above component b) at least one flame retardant, c) at least one flame retardant synergist, and d) at least one colorant.

[0021] Preferably, a) for every 100 parts by mass of at least one type of polyester, 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 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 At least one coloring agent in the form of a mixture of isomers of d) 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.

[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] The NIR permeability of various thermoplastic resins can differ, but standard thermoplastic resins have suitable process parameters. The NIR-transparent bonding partner has sufficiently high transparency in the NIR region to enable the laser welding process when the thickness of the NIR-transparent bonding partner, the intensity of the laser beam, the speed of the welding process, and the 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. Thus, 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 colorants. 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 identifying the orange color of polyester 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 described in Synthesis Specification 2 of German Utility Model No. 20 2024 001 709 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 colorant to be used according to the present invention exhibits high NIR transmittance in polyester, does not interact with the flame retardant or flame retardant synergistic agent c) used as component b), withstands high processing temperatures, and therefore does not show any browning, it becomes possible to use the flame-retardant orange polymer composition according to the present invention and the plastic products manufactured therefrom, which have at least reduced streaking, in applications where laser transmittance is preferably required.

[0029] Accordingly, the present invention preferably relates to polymer compositions and plastic products that are laser-transparent and orange flame-retardant products or bonding partners, in particular to those used as components for electric drive systems of automobiles, known as electric mobility components.

[0030] 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, may be used directly as a powder, or in the form of a masterbatch, a compact, or a concentrate, and may be used preferably as a masterbatch, and more preferably as a masterbatch in a polyester matrix.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] kneading The polymer composition for the manufacture of flame-retardant plastic products according to the present invention is prepared by mixing at least one polyester 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 molded 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.

[0035] In the processing of polyester in the injection molding, extrusion molding, or blow molding processes described above, the temperature reaches the melting point of the polyester used. The industrially important and therefore preferred melting points of polyester according to the present invention are in the 220°C range for polybutylene terephthalate, in the range of 220-230°C for polycarbonate, and in the range of 235-260°C for polyethylene terephthalate.

[0036] The present invention relates to plastic products based on at least one polyester, particularly polybutylene terephthalate or polycarbonate, which are preferably injected at a melting temperature in the range of 220 to 270°C. Preferably, in injection molding, the injection mold temperature is in the range of 70 to 100°C. In injection molding of at least one polyester, particularly polybutylene terephthalate or polycarbonate, an injection pressure in the range of 60 to 100 MPa is preferably employed.

[0037] 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 enough not to cause browning in the above-described polyester processing method.

[0038] Using 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 L color chart of the RAL color chart was used. * a * b * Plastic products are manufactured with a color difference of ΔE < 20, determined according to EN ISO 11664-4, from color numbers starting with "2" in the system.

[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 in the range of approximately -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 color numbers beginning 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 to use 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 polyester, 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 each case 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 polyester.

[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 polyester, 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 polyester.

[0051] C2-C used as polyester in component a) 10Polyalkylene terephthalate C2-C, which are preferably used as polyesters in the context of the present invention. 10 Polyalkylene terephthalates are reaction products of an alcohol moiety having 2 to 10 carbon atoms in the alcohol moiety and terephthalic acid. 10 Polyalkylene terephthalates are known to those skilled in the art and are extensively described in the literature. They contain an aromatic ring in the main chain derived from terephthalic acid and an aliphatic moiety derived from a dihydroxy compound. The aromatic ring of terephthalic acid may be substituted. Preferred substituents are halogens or C1-C4 alkyl groups. Preferred halogens are chlorine or bromine. Preferred C1-C4 alkyl groups are methyl-, ethyl-, n-propyl-, or n-, i-, or t-butyl groups.

[0052] Preferably usable C2~C 10 Polyalkylene terephthalates can be obtained by reacting aromatic dicarboxylic acids, their esters, or other esterifying derivatives with aliphatic dihydroxy compounds using methods known to those skilled in the art.

[0053] C2~C 10 In the case of polyalkylene terephthalates, up to 30 mol% of the terephthalic acid used in their preparation may be replaced with 2,6-naphthalenedicarboxylic acid, isophthalic acid, or a mixture thereof. Up to 70 mol%, preferably 10 mol% or less, of the terephthalic acid may be replaced with aliphatic or alicyclic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, or cyclohexanedicarboxylic acid.

[0054] Among aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms, particularly ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, hexane-1,4-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, neopentyl glycol, or mixtures thereof are preferred. Particularly preferred polyalkylene terephthalates are derived from alkanediols having 2 to 4 carbon atoms. Of these, polyethylene terephthalate (PET), polypropylene terephthalate, and polybutylene terephthalate (PBT), or mixtures thereof are particularly preferred. Furthermore, PET and / or PBT containing 1% or less by weight, preferably 0.75% or less by weight of hexane-1,6-diol and / or 2-methylpentane-1,5-diol as further monomer units are preferred.

[0055] C2-C used as polyester according to the present invention 10 It is preferable that the polyalkylene terephthalate has a viscosity number that can be determined by ISO 1628, in the range of 50 to 220, preferably in the range of 80 to 160, when measured in a 0.5 wt% solution in a 1:1 wt ratio phenol / o-dichlorobenzene mixture at 25°C.

[0056] C2-C which are preferably used as polyester according to the present invention. 10 The polyalkylene terephthalate preferably has a carboxyl-terminated group content of 100 meq or less per kg of polyester, more preferably 50 meq or less per kg of polyester, and particularly preferably 40 meq or less per kg of polyester. 10 Polyalkylene terephthalates can be prepared, for example, by the process described in German Patent Application Publication No. A44 01 055. The carboxyl-terminated group content is typically determined by a titration process, particularly potentiometry.

[0057] Particularly preferred C2-C when used as polyester10 Polyalkylene terephthalates are prepared using a Ti catalyst. After polymerization, they preferably have a residual Ti content of ≤250 ppm, more preferably <200 ppm, and most preferably <150 ppm.

[0058] C2~C according to the present invention 10 Polybutylene terephthalate (PBT) [CAS No. 24968-12-5], which is preferably used as polyalkylene terephthalate, is prepared from terephthalic acid or its reactive derivatives and butanediol by known methods (Kunststoff-Handbuch [Plastics Handbook], vol. VIII, pp. 695-743, Karl Hanser Verlag, Munich 1973).

[0059] PBT suitable for use as a polyester preferably contains at least 80 mol%, preferably at least 90 mol%, of terephthalic acid groups based on a dicarboxylic acid.

[0060] In one embodiment, the PBT that can be preferably used as a polyester according to the present invention may contain not only terephthalic acid groups, but also 20 mol% or less of other aromatic dicarboxylic acid groups having 8 to 14 carbon atoms or aliphatic dicarboxylic acid groups having 4 to 12 carbon atoms, in particular phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid and 2,5-franzicarboxylic acid groups.

[0061] In one embodiment, the PBT that can be preferably used as a polyester according to the present invention is not only butanediol, but also other aliphatic diols having 3 to 12 carbon atoms in an amount of 20 mol% or less, or alicyclic diols having 6 to 21 carbon atoms in an amount of 20 mol% or less, preferably propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2, It may also contain the groups of 2,4-trimethylpentane-1,3-diol, 2,2,4-trimethylpentane-1,5-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di(β-hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis(3-β-hydroxyethoxyphenyl)propane, and 2,2-bis(4-hydroxypropoxyphenyl)propane.

[0062] PBT, which is preferably used as the polyester, showed a viscosity of 40-170 cm³ in each case, as measured by an Ubbelohde viscometer at 25°C in phenol / o-dichlorobenzene (1:1 parts by weight). 3 Within the range of / g, more preferably 50-150cm 3 Within the range of / g, most preferably 65-135cm 3It has an intrinsic viscosity in accordance with EN-ISO 1628 / 5 within the range of / g. The intrinsic viscosity iV, also called the Staudinger index or intrinsic viscosity, is proportional to the average molecular weight according to the Mark-Hoink equation and is an extrapolation of the viscosity number VN as the polymer concentration approaches zero. The intrinsic viscosity can be estimated from a series of measurements or through the use of a suitable approximation method (e.g., Billmeyer). VN [ml / g] is obtained from the measurement of solution viscosity in a capillary viscometer, such as an Ubbelohde viscometer. Solution viscosity is a measure of the average molecular weight of the plastic. The determination is made on a dissolved polymer, and various solvents (m-cresol, tetrachloroethane, phenol, 1,2-dichlorobenzene, etc.) and concentrations are used. The viscosity number VN makes it possible to monitor the processing and performance characteristics of the plastic. Thermal stress, aging processes, or exposure to chemicals, weathering, and light on the polymer can be investigated by comparative measurements. For further information on this point, see http: / / de.wikipedia.org / wiki / Viskosimetrie and http: / / de.wikipedia.org / wiki / Mark-Houwink-Gleichung.

[0063] PBT, which is preferably usable as a polyester, may also be used in mixtures with other polymers. PBT blends usable according to the present invention are produced by kneading. During such kneading operations, conventional additives, particularly release agents or elastomers, may be further added to the molten material to improve the properties of the blend.

[0064] PBT that is preferably usable in accordance with the present invention is available from Envalior Deutschland GmbH, Duesseldorf under the trade name Pocan® B 1300.

[0065] Component a) Polycarbonate used as polyester The polyesters preferably used in accordance with the present invention may also be at least one thermoplastic resin from the group of polycarbonates.

[0066] The polycarbonate that can be preferably used according to the present invention is a bisphenol of general formula (III) HO-Z-OH (III) (wherein Z is a divalent organic group having 6 to 30 carbon atoms and containing one or more aromatic groups) which is a homopolycarbonate or copolycarbonate based on.

[0067] As the polyester, a bisphenol of formula (IIIa):

Chemical Formula

Chemical Formula

[0068] In a preferred embodiment: when m is 4, Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -; when m is 5, Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -; when m is 6, Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -; and when m is 7, Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -.

[0069] Preferred bisphenols containing general formula (IV) are bisphenols from the group consisting of dihydroxydiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, indanbisphenol, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, bis(hydroxyphenyl)sulfone, bis(hydroxyphenyl)sulfoxide, and α,α'-bis-(hydroxyphenyl)-diisopropylbenzene.

[0070] The derivatives of the above bisphenol, which are preferably obtainable by alkylation or halogenation of the aromatic ring of the above bisphenol, are also preferably usable bisphenols of general formula (IV).

[0071] Particularly preferred bisphenols including general formula (IV) are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) methane, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p / m-diisopropylbenzene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 1,1-bis(4-hydroxyphenyl)- These are 3,3,5-trimethylcyclohexane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (i.e., bisphenol M), α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, and indanbisphenol.

[0072] The bisphenol described by general formula (IV) can be prepared, preferably from the corresponding phenol and ketone, by processes known to those skilled in the art.

[0073] Polycarbonates usable as polyesters can also be prepared by known processes. Preferred processes for preparing polycarbonates include, for example, preparation from bisphenol and phosgene by an interfacial process, or preparation from bisphenol and phosgene by a homogeneous phase process known as the so-called pyridine process, or preparation from bisphenol and carbonate ester by a melt transesterification process. The above-mentioned bisphenol and its preparation process are described, for example, in the monograph H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, pp. 77-98, Interscience Publishers, New York, London, Sydney, 1964, and in U.S. Patent Publication No. 3028635, U.S. Patent Publication No. 3062781, U.S. Patent Publication No. 2999835, U.S. Patent Publication No. 3148172, U.S. Patent Publication No. 2991273, U.S. Patent Publication No. 3271367, U.S. Patent Publication No. 4982014, U.S. Patent Publication No. 2999846, German Patent Publication No. A1570703, German Patent Publication No. A2063 This is described in Specifications No. 050, German Patent Application Publication No. A2 036 052, German Patent Application Publication No. A2 211 956, German Patent Application Publication No. A3 832 396, and French Patent Application Publication No. A1 561 518, as well as in Japanese Unexamined Patent Publications No. 61-62039, 61-62040, and 61-105550.

[0074] 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and its preparations are described, for example, in U.S. Patent Application Publication No. 4982014.

[0075] Indanbisphenol and its preparation are described, for example, in U.S. Patent Application Publication No. 3,288,864, Japanese Unexamined Patent Publication No. 60-035,150, and U.S. Patent Application Publication No. 4,334,106. Indanbisphenol can be prepared, for example, from isopropenylphenol or its derivatives, or from isopropenylphenol dimers or its derivatives, in an organic solvent in the presence of a Friedelcraft catalyst.

[0076] The molten transesterification process is described in H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, pages 44 to 51, Interscience Publishers, New York, London, Sydney, 1964, and in German Patent Application Publication No. A1 031 512.

[0077] In the production of polycarbonates, it is preferable to use raw materials and additives with low levels of impurities. In particular, in the case of production by molten transesterification process, the bisphenol and carbonate derivatives used should ideally be substantially free of alkali metal ions and alkaline earth metal ions. Raw materials of such purity can be obtained, for example, by recrystallization, washing, or distillation of carbonate derivatives, especially carbonate esters and bisphenols.

[0078] The polycarbonate that can be preferably used as a polyester according to the present invention is preferably one with a weight-average molar mass M in the range of 10,000 to 200,000 g / mol, determined by ultracentrifugation (see K. Schilling, Analytische Ultrazentrifugation [Analytical Ultracentrifugation], Nanolytics GmbH, Dallgow, pages 1-15) or by scattered light measurement in accordance with DIN EN ISO 16014-5:2012-10. wIt has the following characteristics. More preferably, the polycarbonate used has a weight-average molar mass in the range of 12,000 to 80,000 g / mol, and particularly preferably a weight-average molar mass in the range of 20,000 to 35,000 g / mol.

[0079] The average molar mass of polycarbonate that can be preferably used as polyester according to the present invention can preferably be adjusted by known methods using an appropriate amount of chain inhibitor. Chain inhibitors can be used individually or as a mixture of different chain inhibitors.

[0080] Preferred chain arresters include both monophenols and monocarboxylic acids. Preferred monophenols are phenol, p-chlorophenol, p-tert-butylphenol, cumylphenol, or 2,4,6-tribromophenol, and long-chain alkylphenols, particularly 4-(1,1,3,3-tetramethylbutyl)phenol or monoalkylphenol / dialkylphenol having a total of 8 to 20 carbon atoms in the alkyl substituent, especially 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol, or 4-(3,5-dimethylheptyl)phenol. Preferred monocarboxylic acids are benzoic acid, alkylbenzoic acid, or halobenzoic acid.

[0081] Particularly preferred chain inhibitors are phenol, p-tert-butylphenol, 4-(1,1,3,3-tetramethylbutyl)phenol, or cumylphenol.

[0082] The amount of chain-stopping agent used is preferably in the range of 0.25 to 10 mol%, based on the sum of the bisphenols used in each case.

[0083] Polycarbonates that can be preferably used as polyesters according to the present invention may be branched in known ways, preferably by incorporating a trifunctional or more trifunctional branching agent. The preferred branching agent has three or more phenolic groups or three or more carboxylic acid groups.

[0084] Particularly preferred branching agents are phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)hepta-2-ene, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)heptane, 1,3,5-tri-(4-hydroxyphenyl)benzene, 1,1,1-tris-(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl These are (nyl)-2-(2,4-dihydroxyphenyl)propane, hexa(4-(4-hydroxyphenylisopropyl)phenyl) terephthalate, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane, and 1,4-bis(4',4”-dihydroxytriphenyl)methylbenzene, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid chloride, 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, trimesyl trichloride, or α,α',α”-tris-(4-hydroxyphenol)-1,3,5-triisopropylbenzene.

[0085] Particularly preferred branching agents are 1,1,1-tris(4-hydroxyphenyl)ethane or 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

[0086] The amount of branching agent used is preferably in the range of 0.05 mol% to 2 mol%, based on the number of moles of bisphenol used.

[0087] In the preparation of polycarbonates by interfacial processes, the branching agent is preferably included in the aqueous alkaline phase initially charged together with bisphenol and a chain arrestor, or added together with a carbonate derivative as a solution in an organic solvent. When a transesterification process is used, the branching agent is preferably weighed together with a dihydroxy aromatic compound or bisphenol.

[0088] The catalysts preferably used in the preparation of polycarbonates that can be preferably used as polyesters according to the present invention by a melt transesterification process are, for example, ammonium salts and phosphonium salts, as described in U.S. Patent Publication No. 3,442,864, Japanese Unexamined Patent Publication No. 47-14742, U.S. Patent Publication No. 5,399,659, or German Patent Publication No. A19,539,290.

[0089] In preferred embodiments, the copolymer can also be used as a polyester. In the context of the present invention, the copolymer is particularly characterized by a weight-average molar mass M, preferably in the range of 10,000 to 200,000 g / mol, more preferably in the range of 20,000 to 80,000 g / mol, as measured by gel chromatography in accordance with DIN EN ISO 16014-5:2012-10 after prior calibration by scattered light measurement or ultracentrifugation. w This is a polydiorganosiloxane-polycarbonate block copolymer having α,ω-bishydroxyaryloxy terminal groups and an average degree of polymerization P in the range of 5 to 100. n, more preferably, the average degree of polymerization P in the range of 20 to 80 n It is preferable that it can be prepared from a polydiorganosiloxane having [a specific characteristic].

[0090] Polycarbonates particularly preferred for use as polyesters include homopolycarbonates based on bisphenol A, homopolycarbonates based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and copolycarbonates based on two monomers, bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (=bisphenol TMC). Polycarbonates that can be preferably used as polyesters according to the present invention are available, for example, from Covestro AG, Leverkusen under the brand name Makrolon®.

[0091] In one embodiment, a polycarbonate usable as a polyester may have conventional additives, particularly release agents, added to the molten material or applied to its surface. The polycarbonate for use as a polyester preferably already contains a release agent before subsequent compounding with other components, where those skilled in the art understand compounding as a plastics industry term, synonymous with plastics processing, referring to the process of finishing a plastic for controlled optimization of its property profile by adding admixtures (fillers, additives, etc.). See https: / / de.wikipedia.org / wiki / Compoundierung. Compounding is preferably carried out in an extruder, more preferably a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, a planetary screw extruder, or a co-compounder, and includes processing operations of conveying, melting, dispersion, mixing, degassing, and pressure building.

[0092] However, in a preferred embodiment, the polyester used may also be a blend of polycarbonate and polyalkylene terephthalate, which are similarly marketed by Covestro AG under the brand name Makroblend®. These are preferably PC-PET blends, PC-PBT blends, or PC-PCT-G blends, where PC refers to polycarbonate, PET refers to polyethylene terephthalate, PBT refers to polybutylene terephthalate, and PCT refers to polycyclohexylene dimethylene terephthalate.

[0093] 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.

[0094] The phosphinate salts that should be preferably 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.

[0095] 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)".

[0096] 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 the 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.

[0097] 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).

[0098] 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.

[0099] 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 polyester, b) at least one flame retardant from zinc bis-diethylphosphinate and 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.

[0100] 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.

[0101] Further ingredients In a preferred embodiment, the filler or reinforcing material to be used additionally as component e) may also be used in the form of a mixture of two or more different fillers and / or reinforcing materials.

[0102] 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].

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] The present invention therefore preferably uses L from color numbers beginning with "2" in the RAL color chart. * a * b * The present invention relates to a plastic product or precursor thereof formed from a polymer composition having a coordinate color difference ΔE < 20, and comprising a) at least one polyester, and the above components b) at least one flame retardant, c) at least one flame retardant synergistic agent, d) at least one colorant, and e) glass fibers which are chopped-length glass fibers having an average initial length in the range of 1 to 50 mm as measured by laser diffraction particle size analysis (laser particle size measurement method or laser diffraction method) in accordance with ISO 13320. Preferably, the average initial length of the chopped-length 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.

[0109] 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 polyester.

[0110] 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.

[0111] The polyester used is preferably at least one type C2-C 10Polyalkylene terephthalate, particularly polybutylene terephthalate (PBT), is used.

[0112] additives Under the premise of obtaining high laser transmittance, the polymer composition or plastic product according to the present invention, in a preferred embodiment, includes, in addition to or instead of, components a), b), c), d), and e), at least one additive f) other than the aforementioned components. Preferred and usable additive f) include antioxidants, (thermal) stabilizers, ultraviolet stabilizers, gamma-ray stabilizers, water absorption reducing components or hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact resistance improvers, lubricants and / or mold 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.

[0113] 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 polyester in each case.

[0114] 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, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of polyester in each example.

[0115] 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.

[0116] 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.

[0117] Preferred plasticizers that can be used as additives include dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oil, or N-(n-butyl)benzenesulfonamide.

[0118] 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 materials. 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] process The present invention also relates to a manufacturing process for plastic products, particularly injection-molded plastic products: a) at least one type of polyester; 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.

[0125] In the process according to the present invention, at least one phosphinate of formula (l) is used. [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, and (m is an integer between 1 and 4) It is preferable to use at least one flame retardant consisting of the following:

[0126] Preferably, in the process according to the present invention, a) At least one type of polyester, preferably at least one type of C2-C 10 For every 100 parts by mass of polyalkylene terephthalate or polycarbonate, 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.

[0127] Preferably, the plastic products obtained by the process according to the present invention are also L from the color numbers beginning with "2" in the RAL color chart. * a * b * Having a color difference ΔE < 10 in the coordinates, and more preferably from a color number starting with "2" in the RAL color chart according to EN ISO 11664-4. * a * b * The color difference ΔE < 5 is determined according to the coordinate system DIN 5033 (1979).

[0128] In particular, the polyester used in the process according to the present invention is preferably polybutylene terephthalate.

[0129] 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.

[0130] Preferably, in the process 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 fiber are used based on 100 parts by mass of polyester.

[0131] In the process according to the present invention, the glass fibers particularly 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.

[0132] The present invention relates to a manufacturing process for plastic products in the form of laser-transparent, orange, and flame-retardant products or joining partners for further processing by laser transmission welding in the wavelength range of 800 nm to 1200 nm. In laser transmission welding, it is preferable to use an Nd:YAG laser (1064 nm) or a high-performance diode laser (800 to 1000 nm).

[0133] For clarity, it should be noted that the scope of the present invention encompasses all definitions and parameters that are typically referred to in the context of electric mobility components or in the preferred range of any desired combination of processes according to the present invention.

[0134] use The present invention preferably relates to the plastic product: a) at least one type of polyester; 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. The present invention relates to the use of a colorant containing 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 for the manufacture of flame-retardant plastic products, in cases where such a colorant is included.

[0135] In the context of use according to the present invention, 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, and (m is an integer between 1 and 4) It is preferable to use at least one of the following flame retardants.

[0136] Furthermore, in the context of use according to the present invention, a) for every 100 parts by mass of at least one type of polyester; 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.

[0137] In the context of use according to the present invention, preferred polyesters are C2-C 10 Polyalkylene terephthalate or polycarbonate, particularly polybutylene terephthalate.

[0138] In a preferred embodiment, in the context of use according to the present invention, the plastic product also contains, in addition to components a), b), c), and d), similarly used e) glass fibers having an average starting length determined by laser diffraction particle size analysis (laser particle size measurement / laser diffraction) 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.

[0139] 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 fiber are used based on 100 parts by mass of polyester.

[0140] In the context of use according to the present invention, the glass fibers have an average fiber diameter that can be determined by laser diffraction in accordance with ISO 13320, particularly preferably in the range of 7 to 18 μm, and more preferably in the range of 9 to 15 μm.

[0141] Preferably, the present invention relates to L from color numbers starting with "2" in the RAL color chart. * 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 production of plastic products having a coordinate color difference ΔE < 20 and polymer compositions necessary for the production of the same, wherein these colorants comprise a) at least one polyester, b) at least one flame retardant, and c) at least one flame retardant synergistic agent.

[0142] More 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, and polymer compositions necessary for the manufacture of such products, wherein these colorants include a) at least one polyester, and the above components b) at least one flame retardant, c) at least one flame retardant synergist, and e) glass fiber.

[0143] Preferably, in plastic products, 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 are used for laser-transmissive, orange flame-retardant products or bonding partners, more preferably in laser-transmissive welding in the wavelength range of 800 nm to 1200 nm. Preferably, in this context of use, an Nd:YAG laser (1064 nm) or a high-performance diode laser (800 to 1000 nm) is employed.

[0144] The plastic product is preferably an injection-molded plastic product; more preferably a plastic product or an injection-molded plastic product, but laser-transparent and orange flame-retardant product or bonding partner, also referred to as an electric mobility component, which is a component for the electric drive system of an automobile.

[0145] 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.

[0146] The specification and examples are illustrative and not limiting to the present invention, and it will be understood that other embodiments of the spirit and scope of the present invention will be conceivable to those skilled in the art. [Examples]

[0147] To demonstrate the improved properties described in accordance with the present invention, the corresponding polyester 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.

[0148] Starting materials: Component a) Polybutylene terephthalate (Pocan® B 1300, 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', coloring agent, relating to International Publication No. 2020 / 187704A1, namely, 10,10'-oxybis-12H-phthaloperin-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:

[0149] 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 to the mixture, and the mixture was stirred for 30 minutes. Then, 45 g (145 mmol) of 4,4-oxydiphthalic anhydride was introduced, and the reaction mixture was stirred for another 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. Then, 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.

[0150] [Table 2]

[0151] The test results listed in Table 2 show that Examples 1 and 2 of the present invention not only achieved the highest fire resistance classification V-0 but also possessed excellent laser transmittance (+++), and that test specimens containing flame retardants, flame retardant synergens, and colorants both showed no streaking ("+++"), i.e., no browning, after injection molding. The fact that the isomer mixture used as a colorant according to the present invention did not brown during injection molding was demonstrated by the injection-molded articles having an RAL of 2001. In the case of Comparative Examples 1 and 2, which are comparative examples, fire resistance classification V-0 was achieved based on the flame retardant / synergist combination, but the entry is "not determined". This is because no colorants were used that could have caused streaking or browning during injection molding due to temperature during the mixing process or during injection molding. Both the examples and comparative examples of the present invention consistently had an RAL color value of 2001 with ΔE < 10.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] Browning due to injection molding was detected by determining the RAL color of the injection-molded part by comparing it to 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 part was determined by visual matching with the chart.

Claims

1. a) At least one type of polyester; 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 either 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 or 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 either 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.

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

4. a) For every 100 parts by mass of at least one type of polyester: 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 A plastic product according to any one of claims 1 to 3, wherein the above is used.

5. The plastic product according to any one of claims 1 to 4, wherein 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, wherein aluminum trisdiethylphosphinate is used as component b).

7. A plastic product according to any one of claims 3 to 6, wherein a color tone corresponding to color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010, or RAL2011 in the RAL color system is achieved.

8. The plastic product according to any one of claims 1 to 7, further comprising e) at least one filler and / or reinforcing material.

9. The plastic product according to claim 8, wherein the at least one filler and / or reinforcing material is applied in an amount of 1 to 150 parts by mass based on 100 parts by mass of polyester.

10. The plastic product according to claim 8 or 9, wherein 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.

11. The plastic product according to claim 10, wherein 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.

12. A plastic product according to any one of claims 3 to 11, which is a laser-transparent orange flame-retardant product or bonding partner.

13. A plastic product according to claim 12, which is a component for the electric drive system of an automobile.

14. In the manufacturing process of plastic products: a) At least one type of polyester; 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 either 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.

15. L from color numbers starting with "2" in the RAL color chart related to EN ISO 11664-4 ＊ a ＊ b ＊ The process according to claim 14, wherein a color difference ΔE < 20 determined according to DIN 5033 (1979) of coordinates is achieved.

16. a) For every 100 parts by mass of at least one type of polyester 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 at least one coloring agent The process according to claim 14 or 15, wherein the method is used.

17. The aforementioned polyester is C ２ ~C １０ - The process according to claim 16, wherein the material is polyalkylene terephthalate or polycarbonate.

18. Said C ２ ~C １０ - The process according to claim 17, wherein the polyalkylene terephthalate is polybutylene terephthalate.

19. A method for using a colorant comprising 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 polyester; 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 either 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. How to use it when it includes [the specified element].

20. The aforementioned plastic product is L from the color number starting with "2" in the RAL color chart related to EN ISO 11664-4. ＊ a ＊ b ＊ The method according to claim 19, having a color difference ΔE < 20 determined according to the coordinate system DIN 5033 (1979).

21. a) For every 100 parts by mass of at least one type of polyester, 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 method according to claim 19 or 20, wherein the method is used.

22. The aforementioned polyester is C ２ ~C １０ - The method according to claim 21, wherein the material is polyalkylene terephthalate or polycarbonate.

23. Said C ２ ~C １０ - The method according to claim 22, wherein the polyalkylene terephthalate is polybutylene terephthalate.

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