Polyketone molding compositions with improved properties, molded articles made therefrom and

Abstract

The present invention relates to a polyketone molding composition having improved properties, a molded article made therefrom, and a method for manufacturing the same, the flame-retardant polyketone molding composition comprising: (A) from 30 wt% to 73.8 wt% of a semi-crystalline aliphatic polyketone, a copolymer of ethylene and carbon monoxide or a terpolymer of ethylene, carbon monoxide and a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms; and (A1) 0% to 15% by weight of an optional second thermoplastic different from polyketones, consisting of a polyolefin and / or a polyamide; and (B) 20% to 60% by weight of long glass fibers or long carbon fibers; and (C) 0.1% to 2% by weight of an antioxidant; and (D) 0.1% to 2% by weight of a phosphate compound; and (E) from 0% to 3% by weight of an optional colorant; and (F) 6% to 20% by weight of a flame retardant, wherein the weight percentages of components (A) to (F) sum to 100%.

Description

Technical Field

[0001] This invention relates to polyketide molding compositions based on semi-crystalline aliphatic polyketides. In particular, this invention relates to halogen-free, flame-retardant, and long-fiber-reinforced molding compositions based on semi-crystalline aliphatic polyketides. Furthermore, this invention relates to molded articles made from polyketide molding compositions. Additionally, this invention relates to methods for manufacturing polyketide molding compositions.

[0002] The molded composition meets the V0 fire rating according to UL94 and exhibits good mechanical properties.

[0003] These molding compositions are particularly suitable for manufacturing thin-walled molded parts for the electrical and electronic industries, such as housings, housing assemblies, or connectors, as well as housing components for the electric vehicle industry, especially for automotive batteries. Background Technology

[0004] Aliphatic polyketones have been known for many years. Their advantages include nearly constant mechanical properties between 10°C and 100°C, very good hydrolysis resistance, high heat resistance, good abrasion resistance, and good fuel barrier properties.

[0005] On the other hand, although aliphatic polyketones are thermoplastics with consistently good properties, they have the disadvantage of a relatively high melting point, which is close to the temperature at which they undergo chemical degradation (especially intermolecular and intramolecular aldol condensation). That is, when attempting to melt aliphatic polyketones, chemical degradation, particularly intermolecular and intramolecular aldol condensation, may occur. This is problematic in the processing of aliphatic polyketones because, on the one hand, polyketone molding compositions are difficult to process using conventional processing techniques (e.g., in melt form); on the other hand, the properties of such molding compositions may be adversely affected by degradation and crosslinking reactions that occur during processing.

[0006] EP 322959 describes fiber-reinforced polyketone molding compositions, particularly glass fiber-reinforced molding compositions, and methods for producing these molding compositions from polyketone solutions. The aim is to improve the strength and modulus of elasticity of the molding compositions.

[0007] WO 97 / 14743 discloses flame-retardant, glass fiber-reinforced polyketone molding compositions based on aliphatic polyketones. Flame-retardant magnesium hydroxide is preferably included in the molding composition at a concentration of 25% to 40% by weight. If the molding composition does not contain a zinc-containing synergist, a molding composition having 25% by weight magnesium hydroxide and 15% by weight glass fiber achieves a fire rating of V0 with a sample thickness of 1.6 mm.

[0008] KR 2019088230 A describes a method for producing polyketone long fiber granules, and the polyketone long fiber granules produced therefrom comprising polyketone long fibers and a thermoplastic resin. The polyketone long fibers, as a reinforcing material, are impregnated in a thermoplastic resin as a base. The polyketone long fibers can be easily produced in granular form due to their good cutting properties, and are suitable for use as materials for a wide variety of electronic and industrial components due to their excellent mechanical properties.

[0009] KR 2019094827 A describes a method for producing reinforced fiber granules by directly feeding continuous reinforcing fibers in roving form into a twin-screw extruder and mixing them with a matrix containing polyketone resin, followed by granulation of the mixture. The method described in this disclosure enables continuous production in a twin-screw extruder without gelling the polyketone resin. Pultrusion cannot function properly due to gelation; a maximum run time of only two hours is possible.

[0010] US 10047215 B2 describes glass fiber reinforced polyketone having a processing stabilizer and additionally having a fluorine stabilizer and a colorant, wherein the colorant is a black pigment masterbatch comprising carbon black, polyethylene wax, and polyethylene resin. One aspect of this disclosure is providing a polyketone composite resin composition produced by a pultrusion process, and injection molding materials using the same, the pultrusion process comprising impregnating glass fiber filler as long fiber reinforcement with a thermoplastic resin melt, wherein the thermoplastic resin is a polyketone resin composition. The pultrusion process is not described in detail in this disclosure.

[0011] Polyketone possesses excellent mechanical properties, low water absorption, chemical resistance, short cycle time, high elongation at break, good tribological properties with low wear, very high resistance to fuel and oxygen barriers, and high hydrolytic stability. Polyketone does not contain any harmful substances such as heavy metals, formaldehyde, perfluoroalkyl compounds, and polyfluoroalkyl compounds (PFAS), and it is also characterized by a lower carbon footprint compared to other polymers. Given the aforementioned advantages of polyketone, especially aliphatic polyketone, and the processing challenges associated with it, there is a need to develop polyketone-based molding compositions that can be easily processed through injection molding and extrusion processes. Summary of the Invention

[0012] Therefore, the object of the present invention is to provide molding compositions based on semi-crystalline aliphatic polyketones, which are equipped with halogen-free flame retardants, can be easily processed using injection molding and extrusion processes, and exhibit good mechanical properties. In particular, it is generally not possible to efficiently produce long-fiber reinforced rod particles by pultrusion using existing techniques. This is where the present invention comes into play, providing molding compositions whose long-fiber reinforced rod particles can be produced by pultrusion and have good flame-retardant properties. The present invention further develops the prior art because it provides for the first time a long-fiber reinforced polyketone molding composition with good flame-retardant properties that can be easily and efficiently produced by pultrusion.

[0013] For sample thicknesses of 0.35 mm to 3.0 mm, particularly 0.75 mm and 1.5 mm, the molding composition should preferably be V0 according to UL 94 fire rating and have sufficient flowability to enable the production of thin-walled molded parts of good quality.

[0014] According to the present invention, this task is accomplished by the polyketone molding composition described in detail below. The present invention also provides molded articles made from the polyketone molding composition according to the present invention, and provides a series of application examples of the molded articles. Furthermore, the present invention relates to methods for producing molded articles according to the present invention by injection molding, extrusion, or blow molding. Preferred advantageous embodiments are also provided.

[0015] Therefore, the present invention relates to flame-retardant polyketone molding compositions, the long fiber-reinforced particles of which can be efficiently produced by pultrusion molding and have good mechanical properties, comprising or consisting of the following:

[0016] (A) A semi-crystalline aliphatic polyketone, comprising 30% to 73.8% by weight, preferably 30% to 67.8% by weight, particularly preferably 30% to 61.5% by weight, wherein the semi-crystalline aliphatic polyketone is composed of a copolymer of ethylene and carbon monoxide or a terpolymer of ethylene, carbon monoxide and a second olefinically unsaturated hydrocarbon having at least three carbon atoms, and

[0017] (A1) An optional second thermoplastic material different from polyketone, in an amount of 0% to 15% by weight, preferably 0% to 12% by weight, particularly preferably 0% to 10% by weight, the second thermoplastic material being composed of polyolefin, especially polyethylene, and / or polyamide, and

[0018] (B) Long glass fibers or long carbon fibers, in an amount of 20% to 60% by weight, preferably 25% to 55% by weight, particularly preferably 30% to 50% by weight, and

[0019] (C) An antioxidant, in an amount of 0.1% to 2% by weight, preferably 0.1% to 1.5% by weight, particularly preferably 0.2% to 1.0% by weight, and

[0020] (D) A phosphate / ester compound, in an amount of 0.1% to 2% by weight, preferably 0.1% to 1.5% by weight, particularly preferably 0.2% to 1.0% by weight, and

[0021] (E) Optional colorant, in an amount of 0% to 3% by weight, preferably in an amount of 0% to 3% by weight, particularly preferably in an amount of 0.1% to 2.0% by weight, and

[0022] (F) A flame retardant, in an amount of 6% to 20% by weight, preferably 7% to 18% by weight, and particularly preferably 8% to 15% by weight.

[0023] The total weight percentage of components (A) to (F) is 100% by weight, and the molding composition preferably consists only of components (A) to (F).

[0024] The abbreviation for weight% indicates a percentage of weight.

[0025] The flame retardant is preferably a halogen-free flame retardant selected from at least one phosphonic acid, at least one secondary phosphonic acid, metal salts, zinc borate, siloxanes and / or their organic derivatives, and mixtures or combinations thereof, preferably in combination with at least one synergist.

[0026] The concentrations or concentration ranges specified herein and below are based on the total amount of components (A) to (F) in the case of an open formulation (“comprising / including”); or based on the entire molding composition in the case of a closed formulation (“consisting of”). In the latter case, the molding composition consists only of components (A) to (F).

[0027] It should be noted that the phrase “the quantity is…to…” used in the foregoing paragraphs and the remainder of this specification should be understood to include the specified limits (upper and lower limits), that is, the numerical values ​​of the upper and lower limits of the range.

[0028] When referring to the interval from a to b within the meaning of this invention, the endpoints a and b are included. Furthermore, when the interval from a to b is disclosed, it is also considered that all sub-intervals from a1 to b1 are disclosed, provided that a ≤ a1 and b1 ≤ b, and a1 <b1。

[0029] It should also be understood that all sub-intervals of the defined main interval are disclosed herein.

[0030] The molding compositions described herein are particularly suitable for manufacturing battery housings for electric or hybrid vehicles. These housings must possess good mechanical properties and provide sufficient escape time for the occupants of the electric or hybrid vehicle in the event of a fire. This is achieved through the compositions of the invention described below.

[0031] The preferred embodiments of the invention are described in the specification.

[0032] Component (A):

[0033] The matrix of the polyketide molding composition used according to the present invention is based on a semi-crystalline aliphatic polyketide (A), which consists of a copolymer of ethylene and carbon monoxide or a terpolymer of ethylene, carbon monoxide, and a second olefinically unsaturated hydrocarbon having at least three carbon atoms. Based on the total amount of components (A) to (F), the amount of semi-crystalline aliphatic polyketide (A) is from 30% to 73.8% by weight, preferably from 30% to 67.8% by weight, particularly preferably from 30% to 61.5% by weight, for example, 63.2% by weight, and also 48.85% by weight. In this document, the term "second olefinically unsaturated hydrocarbon" is used to distinguish the component in the terpolymer from ethylene (which is also an olefinically unsaturated hydrocarbon). In this regard, the ethylene contained in the terpolymer can also be referred to as a "first olefinically unsaturated hydrocarbon," thereby distinguishing it from the second olefinically unsaturated hydrocarbon.

[0034] Aliphatic polyketides are thermoplastic polymers with a linear alternating structure, where each molecule of unsaturated hydrocarbon essentially corresponds to one carbon monoxide molecule. In particular, suitable unsaturated hydrocarbons are olefins having up to 20 carbon atoms, preferably up to 10 carbon atoms, such as ethylene and other α-olefins, including propylene, 1-butene, isobutene, 1-hexene, 1-octene, and 1-dodecene. Furthermore, alkylene-bonded unsaturated compounds with aryl substituents, such as styrene, p-methylstyrene, p-ethylstyrene, and m-isopropylstyrene, are also suitable as monomers.

[0035] The preferred aliphatic polyketones within the scope of this invention are alternating copolymers of carbon monoxide and ethylene, or terpolymers of carbon monoxide, ethylene, and a second olefinically unsaturated hydrocarbon having at least three carbon atoms, particularly terpolymers containing α-olefins such as propylene or 1-butene. Preferably, the aliphatic polyketone is a terpolymer of carbon monoxide, ethylene, and propylene, or a terpolymer of carbon monoxide, ethylene, and 1-butene.

[0036] In particular, at least one polyketone (A) is a terpolymer of the following general formula.

[0037]

[0038] Wherein Q is a divalent group derived from an olefinic unsaturated hydrocarbon having at least 3 carbon atoms, x and y are the number of repeating units, and the molar ratio y:x is less than or equal to 0.5, preferably less than 0.2, particularly less than or equal to 0.1, and particularly from 0.01 to 0.1. In all cases, the molar ratio y:x is greater than 0. In particular, Q is a divalent unit -CH2-CH(CH3)- derived from propylene.

[0039] In addition, at least one aliphatic semi-crystalline polyketide is characterized by at least one or all of the following properties:

[0040] Polyketone

[0041] a) It is a semi-crystalline aliphatic polyketone, preferably having a melting temperature in the range of 200°C to 240°C, more preferably in the range of 210°C to 230°C, as measured by DSC (differential scanning calorimetry) at a heating rate of 20°C / min according to ISO 11357-13:2023.

[0042] b) The melt viscosity (MFR, melt mass flow rate) determined according to ISO 1133-1:2022 at 240°C with a load of 2.16 kg is in the range of 10 g / 10 min to 200 g / 10 min, particularly in the range of 20 g / 10 min to 200 g / 10 min, and especially preferably in the range of 80 g / 10 min to 200 g / 10 min.

[0043] c) The relative viscosity of a solution of 0.5 g polyketide dissolved in 100 ml m-cresol, measured by a capillary viscometer at 20°C according to ISO 307:2007, is 1.3 to 1.8, preferably 1.4 to 1.7, and / or

[0044] d) The number-average molar mass in hexafluoroisopropanol relative to PMMA (polymethyl methacrylate) standard, determined by GPC (gel permeation chromatography), is in the range of 20,000 g / mol to 100,000 g / mol, particularly in the range of 30,000 g / mol to 72,000 g / mol.

[0045] Aliphatic semi-crystalline polyketone polymers are known in themselves. For example, methods for producing these polyketone polymers are described in US 4,880,903 or US 4,843,144. Therefore, the relevant disclosures of the aforementioned US patents are also included in this application.

[0046] Aliphatic compounds are described as compounds having acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds, particularly aromatic compounds having at least one benzene ring. This follows the IUPAC definition in the IUPAC Gold Book ("Aliphatic compounds" in the IUPAC Compendium of Chemical Terminology, 3rd edition, International Union of Pure and Applied Chemistry, 2006. Online version 3.0.1, 2019). https: / / doi.org / 10.1351 / goldbook.A00217 ).

[0047] If the polyketone has a specific enthalpy of fusion (ΔH) of at least 20 J / g, particularly 20 J / g to 90 J / g, as determined according to ISO 11357-3:2023 (DSC, heating rate 20 °C / min). m If it has a melting point, it is described as a semi-crystalline substance.

[0048] In pultrusion equipment, medium-viscosity polyketides (such as Poketon © M330A from Hyosung Co. Ltd with an MFR of 60 g / 10 min) have been found to be difficult to process. On the other hand, low-viscosity polyketides with an MFR in the range of 80 g / 10 min to 200 g / 10 min (such as Poketon © M230A or Poketon © M130F) are more suitable for use in pultrusion equipment.

[0049] Low-viscosity polyketones (MFRs) with the aforementioned values ​​(80 g / 10 min to 200 g / 10 min) are more suitable for pultrusion than medium-viscosity polyketones (e.g., Poketon© M330A from Hyosung Co. Ltd.) because they enable optimal impregnation of long fibers, especially long glass fibers or long carbon fibers, and significantly improve process stability even over longer production phases. Due to their lower viscosity, polyketones flow more efficiently between fibers, resulting in good long fiber-matrix adhesion. This leads to improved mechanical properties of the final product, such as higher tensile strength and impact resistance. Furthermore, lower viscosity allows for faster processing speeds and reduces the risk of incomplete impregnation or long fiber breakage. High-viscosity or medium-viscosity polyketones require higher temperatures and pressures, which increases energy consumption and the risk of uneven impregnation. Higher viscosity can also cause nozzle clogging on impregnation equipment. The term viscosity is used herein as a synonym for melt viscosity.

[0050] Medium viscosity polyketone is defined herein as polyketone with an MFR in the range of 40 g / 10 min to 80 g / 10 min. High viscosity polyketone is defined herein as polyketone with an MFR in the range of 10 g / 10 min to 40 g / 10 min. Low viscosity polyketone is defined herein as polyketone with an MFR in the range of 80 g / 10 min to 200 g / 10 min.

[0051] Melt viscosity (MFR) is measured here according to ISO 1133-2:2022 at 240°C with a load of 2.16 kg.

[0052] Therefore, polyketones with an MFR in the range of 80 g / 10 min to 200 g / 10 min, i.e., low-viscosity polyketones, are particularly preferred.

[0053] Component (A1):

[0054] The polyketone molding composition according to the invention also optionally includes component (A1), which is a second thermoplastic and different from polyketone (A). The amount of component (A1) is from 0% to 15% by weight, preferably from 0% to 12% by weight, particularly preferably from 0% to 10% by weight, in each case based on the total amount of components (A) to (F). In this document, the term "second thermoplastic" is used to distinguish it from polyketone (which is also a thermoplastic). For this purpose, polyketone may also be referred to as "first thermoplastic" to distinguish it from the second thermoplastic.

[0055] Component (A1) is a second thermoplastic different from polyketone (A), and preferably consists of a polyolefin and an additional or alternative polyamide, i.e., preferably consists of a polyolefin and / or a polyamide. The polyolefin may be polyethylene, polypropylene, polymethylpentene, polyisobutylene and / or polybutene, or mixtures or blends thereof.

[0056] Polyamides can be aliphatic polyamides and / or semi-aromatic polyamides, or blends thereof.

[0057] Examples of aliphatic polyamides are PA 56, PA 66, PA 6, PA 610, PA 612, PA 6 / 12, PA 12, PA 11, PA 1010, PA 1012 and PA 1212.

[0058] Examples of semiaromatic polyamides are PA 4T / 46, PA 4T / 66, PA 4T / 4I, PA 4T / 4I / 46, PA 4T / 46 / 66, PA 4T / 4I / 66, PA 4T / 56, PA 5T / 56, PA 5T / 5I, PA 5T / 66, PA 6T / 6I, PA 6T / 66, PA 6T / 610, PA 6T / 612, PA 6T / 12, PA 6T / 11, PA 6T / 6, PA 6T / 10T, PA 6T / 10I, PA 6T / 106, PA 6T / 1010, PA 6T / 66 / 106, PA 10T / 66, PA 10T / 612, PA 10T / 1010, PA 10T / 1012, PA 10T / 10I, PA10T / 12, PA10T / 11, PA 6T / MACM10, PA 6T / MACM12, PA 6T / MACM18, PA 6T / MACMI, PAMACMT / 6I, PA 6T / PACM6, PA 6T / PACM10, PA 6T / PACM12, PA 6T / PACM18, PA 6T / PACMI, PACMT / 6I, PA MPDT / MPDI, PA MPDT / MPD6, PA 6T / MPDI, PA 6T / MPDT (MPD=2-methylpentanediamine), PA6T / 9T, PA 6T / 12T, PA 6T / 6I / 66, PA 6T / 6I / 6, PA 6T / 6I / 12, PA 6T / 66 / 6, PA 6T / 66 / 12, PA6T / 6I / MACMI, PA 6T / 66 / PACM6.

[0059] In the context of this invention, the term "polyamide" (abbreviated PA) should be understood as a general term; it includes homopolymers and copolymers. The symbols and abbreviations chosen for polyamides and their monomers correspond to those set forth in ISO standard 16396-1 (2015, (D)).

[0060] T is an abbreviation for terephthalic acid (CAS No. 100-21-0). I is an abbreviation for isophthalic acid (CAS No. 121-95-5). MACM is an abbreviation for bis(4-amino-3-methylcyclohexyl)methane (also known as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, CAS No. 6864-37-5). PACM is an abbreviation for bis(4-amino-cyclohexyl)methane (also known as 4,4'-diamino-dicyclohexylmethane, CAS No. 1761-71-3). MPD is an abbreviation for 2-methylpentanediamine.

[0061] The definitions of homopolymer and copolymer are known to those skilled in the art of polymer chemistry.

[0062] When using a mixture or blend of polyolefins and polyamides, the weight ratio of polyolefin to polyamide is preferably 1.0 to 3.0, particularly preferably 1.5 to 2.5. It has been found that components containing polyolefins and polyamides (A1) in such a weight ratio produce good mechanical properties.

[0063] For the purposes of this patent application, polyolefin is a polymer produced by chain polymerization of olefins.

[0064] Component (B):

[0065] The total amount of the polyketone molding composition or components (A) to (F) according to the invention comprises 20% to 60% by weight of long glass fibers or long carbon fibers (B). As component (B), the molding composition according to the invention may preferably comprise 25% to 55% by weight, particularly preferably 30% to 50% by weight of long glass fibers or long carbon fibers or mixtures thereof, such as long glass fibers or long carbon fibers. Based on the total amount of the polyketone molding composition or components (A) to (F), the amount of long glass fibers or long carbon fibers may be 23.5% by weight, or may be 40.0% by weight.

[0066] Carbon fiber can be either carbon fiber or graphite fiber. The differences between carbon fiber and graphite fiber are particularly in structure, carbon content, and manufacturing temperature.

[0067] Long glass fibers and long carbon fibers are collectively referred to as long fibers. Long fibers are also known as continuous fibers.

[0068] Long fibers (also known as continuous fibers) are fibers of similar length to the pellets (typically 10 mm), unlike short fibers. For short fibers, the length is shortened to approximately 0.2 mm to approximately 0.5 mm during extrusion in a twin-screw extruder.

[0069] The preferred component (B) is long glass fiber.

[0070] Long glass fibers are synonymously referred to as continuous glass fibers, and preferably have a diameter of 10 µm to 20 µm, particularly 12 µm to 17 µm.

[0071] Preferably, the long glass fibers or long carbon fibers are coated with a sizing agent and / or an adhesive.

[0072] As component (B), the long glass fibers selected from E-glass fibers, ECR glass fibers, D-glass fibers, L-glass fibers, S-glass fibers and / or R-glass fibers or mixtures thereof are preferred.

[0073] Typically, the fibers of component (B) can have a circular cross-section (circular glass fiber) or a non-circular cross-section (flat glass fiber), thus allowing the use of mixtures of such systems.

[0074] In the case of round fibers, those with a diameter of 10 µm to 20 µm, preferably 12 µm to 17 µm, are preferred.

[0075] In the case of flat fibers, preferred fibers are those with a ratio of vertical cross-sectional axis (ratio of long axis to short axis in cross-section) greater than or equal to 2, particularly in the range of 2.8 to 4.5, and whose shorter cross-sectional axis (short axis) length is greater than or equal to 4µm.

[0076] Preferably, the long glass fibers are surface modified to improve the adhesion between the long glass fibers and polyketone. Surface modification can be performed using amino-functionalized or epoxy-functionalized alkoxysilanes, or with chlorosilanes, pentaerythritol, dipentaerythritol, resorcinol, or mixtures thereof.

[0077] Glass fibers are incorporated into the molding composition in the form of continuous strands (rovings), preferably during pultrusion. To improve compatibility with semi-crystalline aliphatic polyketones, the long glass fibers used may be coated with a sizing agent and / or an adhesive.

[0078] The roving composed of thousands of filaments preferably has a weight of 0.5 kg / km to 2.4 kg / km, more preferably 0.9 kg / km to 1.8 kg / km. The weight of the roving is particularly preferably 1.1 kg / km to 1.5 kg / km. Rovings with a weight greater than 2.4 kg / km have less favorable properties for melt impregnation and pultrusion.

[0079] Preferably, the long glass fibers are derived from long glass fiber rovings, whereby the long glass fiber rovings have the aforementioned weight.

[0080] Suitable long glass fibers are either glass fibers with a circular cross-section (circular glass fibers) or glass fibers with a non-circular cross-section (flat glass fibers).

[0081] The preferred long glass fiber used for component (B) is a glass fiber selected from E-glass fiber, ECR glass fiber, D-glass fiber, L-glass fiber, S-glass fiber and / or R-glass fiber or a mixture thereof.

[0082] E-glass fiber is a special type of glass fiber, commonly used as a reinforcing material in fiber-reinforced plastics. E-glass fiber is composed of a mixture of silica, alumina, calcium oxide, magnesium oxide, and boric acid.

[0083] Unlike the more commonly used E glass fiber, ECR glass fiber is a particularly corrosion-resistant glass that is unaffected by acidic or alkaline environments.

[0084] D-glass fiber is a special type of glass fiber known for its excellent dielectric properties. It is preferred for applications requiring high electrical insulation and low dielectric loss. D-glass fiber contains a higher amount of boron oxide (B2O3) than E-glass fiber.

[0085] L-glass fiber is a special type of glass fiber known for its low density and light weight. The term "L" stands for "low density." Compared to E-glass fiber, L-glass fiber has a modified chemical composition. It typically contains fewer heavy metal oxides (such as aluminum oxide or calcium oxide) and is therefore lighter.

[0086] S-glass fiber is a special type of glass fiber known for its high mechanical strength, stiffness, and thermal stability. It is composed of a special combination of oxides such as silicon dioxide, aluminum oxide, magnesium oxide, and calcium oxide. The higher proportion of aluminum oxide compared to E-glass fiber significantly contributes to its improved mechanical properties.

[0087] R-glass fiber (an abbreviation for Resistant Glass fiber) is a high-strength type of glass fiber known for its mechanical strength, high stiffness, and excellent chemical resistance. R-glass fiber is composed of silicon dioxide, aluminum oxide, magnesium oxide, calcium oxide, sodium oxide, and potassium oxide.

[0088] The glass fibers described above can be used alone or in combination. However, other mixtures of the glass types described above can also be used.

[0089] Long carbon fibers can also be used. In this case, the diameter of the carbon fibers should preferably be between 4 µm and 10 µm. The weight of the carbon fiber roving should preferably be 0.8 kg / km. Based on the weight of the long carbon fibers, the long carbon fibers should preferably contain epoxy resin as a sizing agent at a ratio of 0.5% by weight.

[0090] Component (C):

[0091] Based on the total amount of components (A) to (F), the molding composition according to the invention further comprises 0.1% to 2% by weight of an antioxidant (C). Preferably, the molding composition comprises 0.1% to 1.5% by weight, particularly preferably 0.2% to 1.0% by weight of an antioxidant. Based on the total amount of components (A) to (F), the amount of antioxidant may be, for example, 0.5% by weight, or may be 0.4% by weight.

[0092] Preferably, the antioxidant is a sterically hindered phenol.

[0093] Alternatively, the antioxidant can be an aromatic amine. Other antioxidants that can be used are phosphites or phosphonites, such as tris(2,4-di-tert-butylphenyl) phosphite or bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, or thioethers, such as dilauryl thiodipropionate or distearyl thiodipropionate.

[0094] Other antioxidants that can be used include benzotriazole.

[0095] Antioxidants can also be combinations of sterically hindered phenols and phosphites (mixtures), or combinations of sterically hindered phenols and thioethers (mixtures).

[0096] Stericly hindered pentaerythritol tetra[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] (CAS No.: 6683-19-8) is particularly preferred.

[0097] Other sterically hindered phenols that can be used as antioxidants include ethylene bis(oxyethylene)bis(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate (CAS No.: 36443-68-2), octadecyl-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (CAS No.: 2082-79-3), and 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionylhydrazine (CAS No.: 32687-78-8).

[0098] The sterically hindered phenols mentioned here can be used alone or as a mixture.

[0099] The purpose of antioxidants is to prevent polyketones from undergoing thermal or oxidative degradation during processing, especially during injection molding or extrusion, and at elevated temperatures.

[0100] Component (D):

[0101] Based on the sum of components (A) to (F), the molding composition according to the invention further comprises 0.1 wt% to 2 wt% of a phosphate / ester compound (D). Preferably, the phosphate / ester compound is present in an amount of 0.1 wt% to 1.5 wt%, particularly preferably in an amount of 0.2 wt% to 1.0 wt%, for example, it can be 0.2 wt%, and may also be 0.15 wt%.

[0102] Preferably, the phosphate / ester compound is calcium phosphate, potassium phosphate, magnesium phosphate, sodium phosphate, ammonium phosphate, aluminum phosphate, or a mixture thereof.

[0103] Preferably, the phosphate / ester compound is hydroxyapatite (CAS No.: 12167-74-7). Alternatively or additionally, the phosphate / ester compound may be tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonite (CAS No.: 119345-01-6).

[0104] Phosphate / ester compounds, such as hydroxyapatite, act as stabilizers for polyketide molding compositions.

[0105] Component (E):

[0106] The polyketone molding composition according to the invention also optionally contains a colorant (E) in an amount of 0% to 3% by weight, particularly preferably 0.1% to 2.0% by weight, based on the sum of components (A) to (F) in each case.

[0107] The colorant may be carbon black and / or organic dyes and / or pigments, or mixtures thereof.

[0108] Preferably, the colorant is an orange organic dye and / or an orange pigment.

[0109] Component (F):

[0110] The molding composition according to the invention further comprises 6% to 20% by weight, preferably 7% to 18% by weight, particularly preferably 8% to 15% by weight of flame retardant (F), in each case based on the total amount of components (A) to (F). Based on the total amount of components (A) to (F), the amount of flame retardant may be, for example, 12.6% by weight, or 9.7% by weight.

[0111] Preferably, the entire component (F) is free of halogens.

[0112] The flame retardant is preferably a halogen-free organometallic phosphonate / ester, metal phosphonate / ester, zinc borate and / or siloxane, or a mixture thereof.

[0113] The above-defined amount of flame retardant (F) ensures that the polyketone molding composition meets the UL V0 rating.

[0114] Phosphinates / esters are salts of hypophosphonic acids, such as sodium hypophosphonate, aluminum hypophosphonate, zinc hypophosphonate, and calcium hypophosphonate, and / or their esters.

[0115] The organic phosphonate / ester is preferably aluminum diethylphosphonate.

[0116] Alternatively, the phosphonate / ester can be sodium phosphonate; calcium phosphonate; zinc phosphonate; alkali metal trimethyl phosphonate / ester, such as sodium trimethyl phosphonate; polymeric metal phosphonate / ester; aluminum phosphonate; aluminum triethyl phosphonate; alkali metal phenyl phosphonate / ester, such as sodium phenyl phosphonate; metal diethyl phosphonate / ester, such as aluminum diethyl phosphonate or zinc diethyl phosphonate; metal complex diphenyl phosphonate / ester, such as aluminum diphenyl phosphonate (III) complex; metal dodecyl phosphonate / ester, such as aluminum tri(dodecyl) phosphonate; or metal tetraethyl phosphonate / ester complex, such as aluminum tetraethyl phosphonate (III) complex or aluminum tetraethyl phosphonate or zinc tetraethyl phosphonate (II) complex.

[0117] Suitable flame retardants are available, for example, under the trade name Exolit OP from Clariant (Basel, Switzerland).

[0118] Generally, this preferred embodiment is characterized in that component (F) comprises, and preferably consists of, the following components:

[0119] (F1) 60% to 100% by weight, preferably 70% to 98% by weight, especially 80% to 96% by weight of phosphonates and / or diphosphonates;

[0120] (F2) 0% to 40% by weight, preferably 2% to 30% by weight, particularly 4% to 20% by weight, of synergists, especially nitrogen-containing synergists and / or nitrogen- and phosphorus-containing flame retardants, preferably melamine or condensation products of melamine, and particularly preferably selected from the group consisting of:

[0121] Melem, melam, melon, the reaction product of melamine and polyphosphate, the reaction product of melamine condensation and polyphosphate, or mixtures thereof.

[0122] Component (F2), i.e., synergist, can be metallocene, particularly ferrocene, cobalt dicene, nickel dicene, or titanium dicene.

[0123] Metallocenes are a group of organometallic compounds in which the central metal atom is arranged like a sandwich between two cyclopentadienyl ligands (C5H5). Therefore, metallocenes are called sandwich compounds.

[0124] The weight percentages of components (F1) and (F2) are based on component (F) as a whole and are therefore not based on the total amount of (A) to (F) or on the molded composition.

[0125] Component (F2) is preferably melamine or a condensation product of melamine, such as melatonine, melamine, melamine, or a reaction product of melamine with polyphosphate, a reaction product of a condensation product of melamine with polyphosphate, or a mixture thereof. Melamine polyphosphate is particularly preferred as component (F2). Such flame retardants are known in the art. Reference is made in this regard to DE 103 46 326; the disclosure of which is explicitly included herein. In another embodiment, component (F2) is preferably selected as a synergist in the form of an oxygen-, nitrogen-, or sulfur-containing metal compound. Preferred metals are aluminum, calcium, magnesium, barium, sodium, potassium, and zinc. Suitable compounds are selected from oxides, hydroxides, carbonates, silicates, borates, stannates, alkoxides, carboxylates, and combinations or mixtures of these compounds, such as oxide hydroxides or oxide hydroxide carbonates. Examples include magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, barium carbonate, magnesium hydroxide, aluminum hydroxide, boehmite, pseudoboehmite, dihydrotalcite, hydrocalumite, calcium hydroxide, tin oxide hydrate, zinc hydroxide, zinc borate, zinc sulfide, zinc phosphate, sodium carbonate, calcium carbonate, magnesium carbonate, barium stearate, potassium palmitate, and magnesium behenate.

[0126] According to another preferred embodiment, component (F1) is a phosphonate of general formula (I) and / or a polymer thereof of general formula (II):

[0127]

[0128] in

[0129] R1 and R2 may be the same or different, and are respectively C1-C8 alkyl, linear or branched, saturated, unsaturated or partially unsaturated, and / or aryl; preferably, R1 and R2 may be methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, tert-butyl), pentyl, hexyl, phenyl, etc.

[0130] R3 is a C1-C10 alkylene (linear or branched, saturated, unsaturated or partially unsaturated), C6-C10 arylene, alkylarylene or arylalkylene; preferably, R3 can be methylene, ethylene, propylene, butylene, pentylene, hexylene, phenylene, etc.

[0131] M is a metal from Group 2 or Group 3 of the periodic table, preferably aluminum, barium, calcium, magnesium and / or zinc; and m=2 or 3; n=1 or 3; x=1 or 2. Aluminum and zinc are preferred as metals M.

[0132] Suitable phosphonates for producing the phosphonates according to the invention are, for example, dimethylphosphonic acid, ethylmethylphosphonic acid, diethylphosphonic acid, ethylbutylphosphonic acid, ethylhexylphosphonic acid, methyl-n-propylphosphonic acid, methane-di(methylphosphonic acid), ethane-1,2-di(methylphosphonic acid), hexane-1,6-di(methylphosphonic acid), benzene-1,4-di(methylphosphonic acid), methylphenylphosphonic acid, and diphenylphosphonic acid. Phosphonates can be produced, for example, by reacting a phosphonic acid with a metal carbonate, metal hydroxide, or metal oxide in an aqueous solution, thereby substantially forming a monomeric phosphonate, and, depending on the reaction conditions, polymeric phosphonates can also be formed.

[0133] Therefore, in the case of the polyketone molding composition according to the present invention and the molded articles produced therefrom, it should be emphasized that, in addition to the excellent properties described above, excellent flame retardancy is also achieved. For sample bodies with a thickness of 0.35 mm to 3.0 mm, the molding composition is classified as V0 according to UL rating (UL 94, according to the standards tested by Insurer Laboratories (UL), see www.ulstandards.com).

[0134] The present invention also relates to the use of the above-described molding composition in the production of thermoplastically processable molded articles, and to molded articles obtainable from the composition according to the present invention.

[0135] Examples of such molded parts include: housings or functional components for pumps, gearboxes, valves, water meter throttle valves, cylinders, pistons; headlight housings; reflectors; turn signal adjusters; gears; engine and gearbox bearings; plug connectors; connectors; profiles; films or layers of multilayer films; fibers; electronic components, especially components for portable electronic devices; housings for electronic components; battery housings, especially automotive battery housings; connectors; mobile phone housings; LED housing components; housings or housing parts for personal computers, especially laptop housings; tools; composite materials; fluid transport containers, especially in the automotive field; connectors; fittings for connecting hoses; individual layers in multilayer containers; brake fluid reservoirs; and so on.

[0136] Molded parts can be produced by injection molding, extrusion or blow molding.

[0137] The reinforcing material of the polyketone molding composition described herein can be produced by pultrusion, which represents an improvement over existing technologies.

[0138] Advantageous polyketone molding compositions comprising continuous fibers (long fibers), particularly those according to the invention, can be produced by known methods for producing long fiber-reinforced rod pellets, particularly by a pultrusion process, in which continuous fiber strands (long glass fiber strands, rovings) are fully impregnated with a polymer melt, then cooled and cut. Typically, the polymer components and additives are melted in an extruder and fed directly as a melt into the impregnation unit.

[0139] The long fiber-reinforced rod particles obtained in this way (preferably with a particle length of 3 mm to 25 mm, particularly 4 mm to 12 mm) can be further processed into molded parts using conventional processing methods (e.g., injection molding, compression molding) to form molded parts, thereby achieving particularly good properties of the molded parts when using mild processing methods. In this case, mild primarily means largely avoiding excessive fiber breakage and the associated significant reduction in fiber length. In injection molding, this means that a large-diameter screw should preferably be used.

[0140] Fibers used as continuous fibers (long glass fibers or long carbon fibers, rovings) in pultrusion processes can be treated with a suitable sizing system consisting of a binder and a film-forming agent. Organofunctionalized silanes, such as aminosilanes, epoxysilanes, vinylsilanes, methacryloxysilanes, or methacryloyloxysilanes, can be used as binders. Film-forming agents can include, for example, systems based on polyurethanes, polyesters, polyethers, polyhydroxy ethers, epoxy resins, polyamides, acrylic polymers, or mixtures thereof.

[0141] The polyketone molding composition according to the invention can be produced by known methods for producing continuous fiber-reinforced rod particles, particularly by pultrusion molding, wherein continuous fiber strands are fully impregnated with a polymer melt, then cooled and cut. The continuous fiber-reinforced rod particles obtained in this way (preferably with a particle length of 3 mm to 25 mm, particularly 4 mm to 12 mm) can be further processed into molded parts using conventional processing methods (e.g., injection molding, pressing) to form molded parts, thereby achieving particularly good properties of the molded parts with a mild processing method. In this case, "mild" primarily means largely avoiding excessive fiber breakage and the associated significant reduction in fiber length. In injection molding, this means that a large-diameter screw should be used. Detailed Implementation

[0142] The following describes preferred embodiments of the present invention based on examples of implementation methods. These examples are for illustrative purposes only and should not be construed as limiting.

[0143] Production of polyketone molding compositions:

[0144] Compositions B1 and VB1 are produced by a pultrusion process, in which C, D, F, and optionally E and A1 are mixed and melted in a twin-screw extruder, and then transferred to an impregnation unit and contacted with preheated continuous filament glass fibers (B, long glass fibers). The pultrusion process is as follows: Components A, C, D, F, and optionally E and A1 are fed into the feed zone of a twin-screw extruder with a screw diameter of 40 mm. The components are then mixed with a heating profile of 200°C to 250°C. An extruder permanently connected to the impregnation unit feeds the melt directly into the impregnation unit, impregnating the glass fibers preheated to 180°C to 220°C. The continuous glass fibers (2400 tex rovings in the case of 17 µm fibers) are drawn through the impregnation zone at a speed of 8 m / min to 15 m / min, wherein the heating zone is in the range of 230°C to 270°C. After cooling in water, the strands impregnated in this manner are cut into 10 mm lengths. After granulation and drying at 110°C for 24 hours, the properties of the granules are measured and test samples are produced.

[0145] Manufacturing of molded parts:

[0146] The molded parts were manufactured on an Arburg Allrounder 420C-1000-250 injection molding machine with a rising barrel temperature profile ranging from 200°C to 270°C and an injection pressure ranging from 1000 bar to 1800 bar. The mold temperature was 80°C. The geometry of the molded parts conformed to the specifications of the relevant testing standards.

[0147] Tables 1 and 2 summarize the composition of the molding composition and the properties of the molded parts produced therefrom.

[0148] Use the following materials:

[0149] Polyketone M230A: A low-viscosity aliphatic polyketone made from carbon monoxide, ethylene, and propylene, with a melting point of 220°C; MFR (240°C; 2.16 kg) 150 g / 10 minutes; Hyosung Co. Ltd., South Korea (Poketone© M230A)

[0150] Polyketone M330A: A medium-viscosity aliphatic polyketone made from carbon monoxide, ethylene, and propylene, with a melting point of 220°C; MFR (240°C; 2.16 kg) 60 g / 10 minutes; Hyosung Co. Ltd., South Korea (Poketone© M330A)

[0151] Exolit OP1230: Aluminum diethylphosphinate, Clariant, Switzerland

[0152] Stabilizer: Irganox 1010, a sterically hindered phenolic antioxidant, BASF, Germany

[0153] Sandostab P-EPQ: Tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonite, CAS: 38613-77-3, stabilizer, Clariant, Switzerland

[0154] Fiberglass:

[0155] GF roving Tufrov 4510 / 17µm, E-glass fiber, long glass fiber, 17 µm diameter, 2400 tex roving, Nippon Electric Glass, Japan

[0156] GF Vetrotex 995 EC10-4.5: E-glass fiber, short glass fiber, 4.5 mm in length and 10 μm in diameter, Owens Corning Fiberglass, USA

[0157] GF roving SE 4535 12 1200: ECR glass fiber, long glass fiber, 12 µm diameter, 1200 tex roving, 3B Fibreglass, Belgium

[0158] Tables 1 and 2 summarize the composition of the molding composition according to the invention and the characteristics of the molded articles produced therefrom.

[0159] Comparative Examples 1 and 2 of polyketone molding compositions reinforced with short glass fibers are also shown.

[0160] Table 1: Example B1 and Comparative Example VB1

[0161]

[0162] Table 2: Example B2 and Comparative Example VB2

[0163]

[0164] The following test specimens were measured according to the following standards and in a dry condition. This means that after injection molding and before undergoing testing, the test specimens were stored on silicone in a dry environment at room temperature for at least 48 hours.

[0165] According to DIN EN ISO 307:2007, the relative viscosity (ηrelative) of a solution of 0.5 g of polymer dissolved in 100 ml of m-cresol was determined at 20 °C. Particulate matter was used as the sample.

[0166] Tensile modulus, tensile strength and elongation at break: According to ISO 527 (2019), at 23°C, for ISO tensile bars, standard ISO / CD 3167 (2003), type A1, 170 mm × 20 mm / 10 mm × 4 mm, tensile modulus, tensile strength and elongation at break are determined at a tensile speed of 1 mm / min (tensile modulus) or 5 mm / min (tensile stress, elongation at break).

[0167] Impact strength and Charpy impact strength were measured at 23°C using ISO test bars, standard ISO / CD 3167 (2003), type B1, 80 mm × 10 mm × 4 mm, according to ISO 179 / keU (2020) and ISO 179 / keA (2023).

[0168] MFR (Melt Flow Index or Melt Flow Rate) is determined according to ISO 1133:2:2022 using a capillary rheometer, wherein material (particles) is melted in a heatable cylinder at a temperature of 240°C and pressed through a defined nozzle (capillary) under a pressure generated by a 2.16 kg load. The mass of polymer melt discharged (in grams) is determined as a function of time.

[0169] result:

[0170] Example 1 (Table 1) shows a flame-retardant polyketone molding composition comprising 23.5% by weight of long glass fiber contents (and other components). Comparative Example 1 (Table 1) shows a polyketone molding composition comprising 23.5% by weight of short glass fiber contents (and other components), based on the total weight of the polyketone molding composition in each case.

[0171] Experiments conducted using test specimens of the molding composition of Example 1 and the molding composition of Comparative Example 1 showed that the mechanical properties (e.g., tensile modulus, fracture stress, fracture energy, notched impact strength, flexural modulus) of Example 1 were consistently superior to those of Comparative Example 1. The heat deflection temperature (HDT C) of Example 1 was significantly higher than that of Comparative Example 1.

[0172] Example 2 (Table 2) shows a flame-retardant polyketone molding composition comprising 40.0% by weight of long glass fiber contents (and other components). Comparative Example 2 (Table 2) shows a polyketone molding composition comprising 40.0% by weight of short glass fiber contents (and other components), based on the total weight of the polyketone molding composition in each case.

[0173] Experiments conducted using test specimens of the molding composition of Example 2 and the molding composition of Comparative Example 2 showed that the mechanical properties (e.g., tensile modulus, fracture stress, fracture energy, impact strength at 23°C, notched impact strength) of Example 2 were consistently superior to those of Comparative Example 2. The heat deflection temperature (HDT C) of Example 2 was significantly higher than that of Comparative Example 2.

[0174] The results showed that the mechanical properties of polyketone molding compositions containing long glass fibers, particularly tensile modulus, tensile strength, and notched impact strength, were significantly superior to those of polyketone molding compositions containing short glass fibers. Furthermore, the mechanical properties of polyketone molding compositions containing low-viscosity aliphatic polyketones, particularly tensile modulus, tensile strength, and notched impact strength, were significantly superior to those of polyketone molding compositions containing medium-viscosity aliphatic polyketones.

[0175] It should be noted that the compositions of Examples 1 and 2 given should not be construed as limiting the invention.

Claims

1. A polyketone molding composition comprising or consisting of the following: (A) An aliphatic semi-crystalline polyketone, in an amount of 30% to 73.8% by weight, wherein the aliphatic semi-crystalline polyketone is composed of a terpolymer of ethylene, carbon monoxide, and a second olefinically unsaturated hydrocarbon having at least three carbon atoms, and (A1) An optional second thermoplastic material different from the aliphatic semi-crystalline polyketone, in an amount of 0% to 15% by weight, wherein the second thermoplastic material is composed of polyolefin and / or polyamide, and (B) Long glass fibers or long carbon fibers, in an amount of 20% to 60% by weight, and (C) Antioxidant, in an amount of 0.1% to 2% by weight, and (D) Phosphate / ester compounds, in amounts ranging from 0.1% to 2% by weight, and (E) Optional colorant, in an amount of 0% to 3% by weight, and (F) Flame retardant in an amount of 6% to 20% by weight The total amount of components (A) to (F) is 100 by weight.

2. The polyketone molding composition according to claim 1, characterized in that, The aliphatic semi-crystalline polyketone has a melting temperature of 200°C to 240°C, which is measured by differential scanning calorimetry at a heating rate of 20°C / min according to ISO 11357-1:2023, and / or is characterized in that the melt viscosity of the aliphatic semi-crystalline polyketone is in the range of 10 g / 10 min to 200 g / 10 min, which is determined according to ISO 1133-2:2022 at 240°C with a load of 2.16 kg.

3. The polyketone molding composition according to claim 2, characterized in that, The melt viscosity of the aliphatic semi-crystalline polyketone is in the range of 80 g / 10 min to 200 g / 10 min.

4. The polyketone molding composition according to claim 1, characterized in that, The aliphatic semi-crystalline polyketone has a relative viscosity of 1.3 to 1.8, which is measured according to ISO 307:2007 at 20°C using a capillary viscometer for a solution of 0.5 g of polyketone dissolved in 100 ml of m-cresol, and / or is characterized in that the number-average molecular weight of the aliphatic semi-crystalline polyketone is in the range of 20,000 g / mol to 100,000 g / mol, which is determined by gel permeation chromatography relative to a polymethyl methacrylate standard in hexafluoroisopropanol.

5. The polyketone molding composition according to claim 1, characterized in that, The aliphatic semi-crystalline polyketone is a terpolymer of the following general formula. Where Q is a divalent group derived from an olefinic unsaturated hydrocarbon having at least 3 carbon atoms, x and y are the number of repeating units, and the molar ratio y:x is less than or equal to 0.

5.

6. The polyketone molding composition according to claim 1, characterized in that, The long glass fiber is a continuous glass fiber with a diameter in the range of 10 µm to 20 µm, and / or selected from E-glass fiber, ECR-glass fiber, D-glass fiber, L-glass fiber, S-glass fiber, R-glass fiber, or a mixture thereof.

7. The polyketone molding composition according to claim 1, characterized in that, The long glass fibers are derived from long glass fiber rovings with a weight of 0.5 kg / km to 2.4 kg / km.

8. The polyketone molding composition according to claim 1, characterized in that, The long glass fibers are surface-modified with amino-functionalized or epoxy-functionalized alkoxysilanes, chlorosilanes, pentaerythritol, dipentaerythritol, resorcinol, or mixtures thereof.

9. The polyketone molding composition according to claim 1, characterized in that, The diameter of the long carbon fibers is 4 µm to 10 µm.

10. The polyketone molding composition according to claim 1, characterized in that, The antioxidant is a sterically hindered phenol, an aromatic amine, a phosphite or phosphonite, a benzotriazole, or a mixture thereof.

11. The polyketone molding composition according to claim 10, characterized in that, The sterically hindered phenol is pentaerythritol tetra[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate), octadecyl-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionylhydrazine, or a mixture thereof.

12. The polyketone molding composition according to claim 1, characterized in that, The phosphate / ester compound is calcium phosphate, potassium phosphate, magnesium phosphate, sodium phosphate, ammonium phosphate, aluminum phosphate, or a mixture thereof.

13. The polyketone molding composition according to claim 1, characterized in that, The phosphate / ester compound is hydroxyapatite and / or tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphonate.

14. The polyketone molding composition according to claim 1, characterized in that, The colorant is carbon black, organic dye, pigment, or a mixture thereof.

15. The polyketone molding composition according to claim 1, characterized in that, The flame retardant is a halogen-free organic phosphonate / ester, zinc borate, siloxane, or a mixture thereof.

16. A molded article made from the polyketone molding composition according to any one of claims 1 to 15.

17. The molded article of claim 16, comprising: a housing; a functional component for a pump, gearbox, valve, water meter, throttle valve, cylinder, piston; a headlight housing; a reflector; a turn signal adjuster; a gear; an engine and gearbox bearing; a connector; a profile; a film or layer of a multilayer film; a fiber; an electronic component; a housing for electronic components; a battery housing; a connector; a mobile phone housing; an LED housing component; a housing or housing component for a personal computer; a tool; a composite material; a container for containing fluid; a nozzle; a fitting for connecting a hose; each layer in a multilayer container; or a brake fluid reservoir.

18. A method for producing a molded article according to claim 16 or 17 by injection molding, extrusion or blow molding.

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