Thermally conductive polycarbonate with improved flame retardancy using barium sulfate.

Abstract

The present invention relates to a thermoplastic composition comprising at least one aromatic polycarbonate, talc, at least one anhydride-modified α-olefin polymer, at least one organic flame retardant selected from a fluoropolymer-containing anti-drip agent, a fluorinated sulfonate, an organic phosphate ester, a phosphazene, or a mixture of at least two of the above agents, and barium sulfate. The present invention also relates to a method for producing such a composition and a molded article that can be produced from such a composition. The composition contains barium sulfate in an amount of 3 wt.% or more, based on the total weight of the composition. A preferred amount is 5 wt.% or more.

Description

[Technical field]

[0001] The present invention relates to a thermoplastic composition comprising at least one aromatic polycarbonate, talc, at least one anhydride-modified α-olefin polymer, at least one organic flame retardant selected from fluoropolymer-containing anti-drip agents, fluorinated sulfonates, organic phosphates, phosphazenes, or a mixture of at least two of the aforementioned agents, and barium sulfate. Furthermore, the present invention relates to a method for producing such a composition, and to a molded article that can be produced from this composition. [Background technology]

[0002] Reinforcement of polycarbonate with the filler talc is desirable for many applications due to the thermal conductivity of talc, especially when electrical conductivity is not desired. However, the addition of talc to molten polycarbonate can cause degradation of the polymer chains, which is ultimately reflected in poorer mechanical properties of the resulting polycarbonate molded parts.

[0003] Patent Document 1 discloses a composition obtained by mixing at least components A) to C), in which A) is polycarbonate, B) is unsized talc that has not been coated, and C) has an acid value of at least 30 mgKOH / g and an average molecular weight M of 4000 g / mol to 40000 g / mol. w and wherein the amounts of B) and C) before mixing are adapted to each other such that 0.10 parts by weight to 1.4 parts by weight of component C) are used per 10 parts by weight of component B), and the composition is free of polyesters and graft polymers. According to this document, the inorganic fillers considered include, in particular, titanium dioxide, generally in an amount of 0% to 2.5% by weight relative to the total of the entire composition, or barium sulfate.

[0004] The composition known from WO 02 / 04336 shows improved thermal conductivity due to the use of the filler talc. By using a specific maleic anhydride modified olefin wax in an amount adapted to the amount of talc used, the polycarbonate is stabilized, thus significantly reducing the degradation of the basic polymer, while at the same time achieving advantageous mechanical properties. For example, good Charpy notched impact strength according to ISO 179 / 1eU and good multiaxial impact strength according to DIN EN ISO 6603-2:2002 are achieved. However, the addition of such olefin wax is disadvantageous in terms of further increasing the flame retardancy. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2018 / 037037 Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention is to provide thermally conductive polycarbonate compositions with improved flame retardancy. A particular object of the present invention is to develop compositions such as those according to WO 2005 / 023991 in such a way that they can be used in applications with specific flame retardancy requirements. Such applications can be components of electrical components or housings for electrical components.

[0007] In outline, the requirements may be mentioned that the molding material has a UL94V score of V0 at a wall thickness of 1.5 mm or less, and a UL5V score of 5VA at a wall thickness of 2.0 mm or less. The good heat resistance of the thermoplastic composition known from WO 2005 / 023994 should advantageously not be excessively reduced by the type and amount of flame retardant. For example, a Vicat temperature of 115° C. or more (Vicat B, ISO 306:2014-3, heating rate 50 K / h) can be maintained, which is particularly advantageous for the use of the molding material as a component of an electrical component or as a housing for an electrical component. [Means for solving the problem]

[0008] The above problem is solved according to the invention by a composition according to claim 1. Furthermore, the invention relates to a production method according to claim 11 and to a molding according to claim 13. Advantageous developments are set out in the dependent claims, which can be combined if desired, unless the context indicates otherwise.

[0009] The thermoplastic composition according to the present invention comprises A) at least one aromatic polycarbonate; B) talc; C) an acid value of 30 mg KOH / g or more and an average molecular weight M of 4000 g / mol or more to 40000 g / mol or less w and at least one anhydride-modified α-olefin polymer having the formula: Here, the average molecular weight M w is determined by gel permeation chromatography in orthodichlorobenzene at 150 °C with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025:2005; FR) at least one organic flame retardant selected from fluoropolymer-containing anti-drip agents, fluorinated sulfonates, organic phosphates, phosphazenes, or mixtures of at least two of the aforementioned agents; D) at least one inorganic compound different from talc; Includes.

[0010] Further, the composition contains barium sulfate in an amount of 3% by weight or more based on the total weight of the composition, the composition contains an alkaline earth metal sulfate other than barium sulfate in an amount of 0% to 25% by weight or less based on the total weight of the alkaline earth metal sulfates present in the composition, the composition contains an organic phosphate in an amount of 0% to 7.5% by weight or less based on the total weight of the composition, and the composition contains a fluoropolymer-containing anti-drip agent in an amount of 0.5% by weight or more based on the total weight of the composition. When the composition contains a fluorinated sulfonate in an amount of 0.1% by weight or more based on the total weight of the composition, the content of the fluoropolymer-containing anti-drip agent is 0.7% by weight or more based on the total weight of the composition.

[0011] The present inventors have surprisingly found that above a certain amount, barium sulfate can be considered a flame retardant synergist, and the previously advantageous properties of talc-filled polycarbonate compositions are largely maintained.

[0012] The composition preferably contains at least 4% by weight, more preferably at least 5% by weight, of barium sulfate, in each case relative to the total weight of the composition. A possible upper limit for the barium sulfate content is, for example, at most 20% by weight, or at most 15% by weight, in each case relative to the total weight of the composition.

[0013] Due to its relatively high purity, the barium sulfate used is preferably synthetic barium sulfate obtained from the reaction of barium carbonate with sulfuric acid. The "Branfix" quality is more preferred. The D50 value of the particle size distribution (sedimentation analysis) can be, for example, 7 μm or more and 9 μm or less.

[0014] For reasons of process simplification, it is advantageous if the composition does not contain further alkaline earth metal sulfates other than barium sulfate. If further alkaline earth metal sulfates, such as calcium sulfate, are added, their proportion shall be estimated to be from 0 to 25% by weight (preferably from 0 to 15% by weight, more preferably from 0 to 5% by weight) relative to the total weight of alkaline earth metal sulfates present in the composition.

[0015] The composition contains an organic phosphate ester in an amount of from 0 to 7.5% by weight, preferably from 0 to 5% by weight, based on the total weight of the composition. The phosphate ester can be a flame retardant, such as BDP (bisphenol A bisdiphenyl phosphate and its oligomers), or a stabilizer, such as monohexyl, dihexyl, and trihexyl phosphates, triisooctyl phosphate, and trinonyl phosphate.

[0016] The composition further contains 0.5% by weight or more of a fluoropolymer-containing anti-drip agent based on the total weight of the composition, which can be, for example, PTFE, or preferably a blend of PFTE and SAN polymer. The PTFE content in the SAN polymer is, for example, in the range of 45% to 55% by weight based on the total weight of the anti-drip agent.

[0017] When the composition contains 0.1% by weight or more, preferably 0.2% by weight or more of a fluorinated sulfonate based on the total weight of the composition, the content of the fluoropolymer-containing anti-drip agent is 0.7% by weight or more, preferably 0.8% by weight or more based on the total weight of the composition. One example of such a fluorinated sulfonate is potassium perfluorobutanesulfonate ("C4 salt").

[0018] Ingredient A Component A is at least one aromatic polycarbonate. It is therefore also possible to use mixtures as component A. For the purposes of the present invention, polycarbonates are either homopolycarbonates or copolycarbonates, and polycarbonates can be linear or branched as known. Polycarbonates are produced as known from dihydroxyaryl compounds, carbonic acid derivatives, and optionally chain terminators and branching agents.

[0019] Preferred dihydroxyaryl compounds are selected from at least one of the group consisting of 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethylbisphenol A, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0020] Examples of suitable carbonic acid derivatives are phosgene or diphenyl carbonate. Suitable chain terminators that can be used in the preparation of the polycarbonates used according to the invention are monophenols. Suitable monophenols are, for example, phenol itself, alkylphenols such as cresol, p-tert-butylphenol, cumylphenol, and mixtures thereof. Suitable branching agents are trifunctional or tetrafunctional or higher compounds known in polycarbonate chemistry, in particular compounds having 3 or 4 or more phenolic OH groups.

[0021] Particularly preferred polycarbonates are homopolycarbonates based on bisphenol A, homopolycarbonates based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and copolycarbonates based on the monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, based on bisphenol A and 4,4'-dihydroxybiphenyl (DOD), or based on bisphenol A and 4,4'-dihydroxy-3,3',5,5'-tetra(tert-butyl)biphenyl. In the copolycarbonates, the proportion of comonomers such as DOD can be, for example, 11 mol% to 34 mol%, in particular 26 mol% to 32 mol%.

[0022] Component B Talc in the context of the present invention is preferably a talc, or a mixture of talcs, of essentially the same chemical composition, particle size, porosity, and / or BET surface area.

[0023] Talc is generally a phyllosilicate. It has the general chemical composition Mg 3 [Si 4 O 10 (OH) 2 However, different types of talc contain different impurities and may therefore vary from this general composition.

[0024] The talc or talc mixture used to prepare the composition according to the invention is preferably uncoated. In the context of the present invention, sizing is considered to be the targeted enrichment of molecules at the surface (chemisorbed or physisorbed). Uncoated talc is therefore unsurface-treated talc, meaning that after collecting talc particles with the desired particle size and optionally subjecting them to compression, the talc has preferably not been subjected to any further process steps that modify the surface of the talc in a targeted manner by chemisorption and / or physisorption. However, this does not exclude that impurities, dust or similar particles may unintentionally reach some of the surface during further handling of the talc, as long as the surface of the talc does not lose its properties significantly, especially in terms of pH. However, in the preparation of the composition according to the invention, the talc is sized only by mixing with component C.

[0025] The talc preferably has a pH of 8 to 10, more preferably 8.5 to 9.8, even more preferably 9.0 to 9.7, where the pH is determined according to EN ISO 787-9:1995. It should be noted that EN ISO 787-9:1995 also mentions the option of adding ethanol or other organic solvents to improve the dispersion of the solid being analyzed. According to the present invention, it is preferred to use only distilled water when determining the pH according to EN ISO 787-9:1995.

[0026] Component B) preferably has an iron(II) oxide and / or iron(III) oxide content of 0.2% to 2.5% by weight, more preferably 0.3% to 2.3% by weight, most preferably 0.3% to 2.0% by weight. This content is preferably measured by X-ray fluorescence spectrometry or atomic absorption spectrometry. It has been found that the iron oxide content in the talc influences the degree of polycarbonate degradation. Within the range of iron oxide content specified according to the invention, particularly good results have been achieved with regard to reducing polycarbonate degradation.

[0027] Likewise, it is preferred if component B) has an aluminium oxide content of 0.01% to 0.5% by weight, more preferably 0.05% to 0.48% by weight, most preferably 0.15% to 0.45% by weight.

[0028] Component B) preferably has a median particle size D50 of 0.01 μm to 10 μm, particularly preferably 0.25 μm to 10.00 μm, more preferably 0.5 μm to 10.00 μm, where this particle size D50 is determined by sedimentation analysis. The median D50 is understood by the skilled person to mean the average particle size at which 50% of the particles are smaller than a specified value. The particle size D50 is preferably determined according to ISO 13317-3:2001.

[0029] Component B) is preferably 7.5 m 2 / g~20.0m 2 / g, more preferably 9.0m 2 / g~15.0m 2 / g, most preferably 9.5m 2 / g~14.0m 2 / g BET surface area. The determination of the surface area according to Brunauer, Emmett and Teller by gas adsorption is known per se to the person skilled in the art. The BET surface area is preferably determined according to ISO 4652:2012. This preferred BET surface area is particularly preferably related to the above-mentioned median particle size D50 of talc. In the case of such a combination, it has been found that the component B used according to the invention is optimally matched to the component C used according to the invention. The component C of a certain acid number and molar mass can minimize the decomposition of polycarbonate caused by component B, because, especially under these conditions, the pores of talc are also accessible to wax C.

[0030] It is particularly preferred if the talc has a content of more than 96% by weight, more preferably more than 97% by weight, most preferably more than 98% by weight.

[0031] It is likewise preferred if the talc has a loss on ignition of 5.0% to 7.0% by weight, more preferably 5.2% to 6.5% by weight, most preferably 5.3% to 6.2% by weight at 1050° C. The loss on ignition is preferably determined according to DIN 51081:2002.

[0032] The talc or talc mixture of component B is preferably present in compressed form.

[0033] Component C Component C in the context of the present invention is a component having an acid number of at least 30 mg KOH / g and an average molecular weight M of 4000 g / mol to 40000 g / mol. w (weight average) Component C can also be a mixture of different polymers which together satisfy the characteristics of Component C.

[0034] The anhydride preferred as the modifying unit is at least one unsaturated carboxylic acid anhydride selected from the group consisting of maleic anhydride, phthalic anhydride, fumaric anhydride, and itaconic anhydride. Maleic anhydride is particularly preferred.

[0035] The anhydride modified α-olefin polymer is preferably rubber-free.

[0036] The wax of component C used according to the invention has an acid number of at least 30 mg KOH / g. The acid number is preferably between 30 mg KOH / g and 110 mg KOH / g, more preferably between 40 mg KOH / g and 95 mg KOH / g. The acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025:2005.

[0037] Average molecular weight M of anhydride-modified α-olefin polymer w The molecular weight M is 4000 g / mol to 40000 g / mol, preferably 4000 g / mol to 32000 g / mol, and more preferably 4800 g / mol to 25000 g / mol. wis determined by gel permeation chromatography in orthodichlorobenzene at 150° C. using a polystyrene calibration. Values ​​reported here are preferably the average from duplicate measurements.

[0038] In the case of a smaller molecular weight of 4000 g / mol to 10000 g / mol, the acid number is preferably 30 mgKOH / g to 65 mgKOH / g, more preferably 40 mgKOH / g to 60 mgKOH / g. In the case of an acid number of 30 mgKOH / g to 65 mgKOH / g or 40 mgKOH / g to 60 mgKOH / g specified in each case, the molecular weight is particularly preferably 4500 g / mol to 8000 g / mol, in particular 5000 g / mol to 7000 g / mol.

[0039] In the case of larger molecular weights of 12000 g / mol to 40000 g / mol, the acid number is preferably 30 mgKOH / g to 100 mgKOH / g, in particular 35 mgKOH / g to 95 mgKOH / g. In the case of acid numbers of 30 mgKOH / g to 100 mgKOH / g or 35 mgKOH / g to 95 mgKOH / g specified in each case, the molecular weight is particularly preferably 12000 g / mol to 32000 g / mol, in particular 15000 g / mol to 25000 g / mol, most preferably 17500 g / mol to 23000 g / mol.

[0040] The combination of (minimum) acid number and molar mass of Wax C specified above is particularly suitable for optimizing the multiaxial impact resistance of the moulded articles produced from the compositions according to the invention.

[0041] The amount of component C is in accordance with the amounts specified above per 10 parts by weight of component B. In the compositions according to the invention, the amounts used of B and C are preferably adapted to one another such that 0.10 to 1.4 parts by weight of component C are used per 10 parts by weight of component B. It is preferred to use 0.2 to 1.2 parts by weight, particularly preferably 0.3 to 1.1 parts by weight of component C, very particularly preferably 0.4 to 1.0 parts by weight of component C and most preferably 0.6 to 0.8 parts by weight of component C per 10 parts by weight of component B.

[0042] Ingredients FR The component FR includes organic anti-drip agents and organic compounds that modify the burning behavior. In addition to the above-mentioned anti-drip agents, fluorinated sulfonates, and organic phosphates, the definition of this component also includes phosphazenes.

[0043] Among the cyclic phosphazenes usable according to the present invention, it is preferable to use a cyclic phosphazene having 3 to 5 structural units containing a group P=N in the ring. Among the chain phosphazenes usable according to the present invention, it is preferable to use a chain phosphazene having 3 to 25 structural units containing a group P=N in the molecular chain.

[0044] It is especially preferred to use cyclic phenoxyphosphazene [CAS number 1203646-63-2] or hexaphenoxycyclotriphosphazene [2,2,4,4,6,6-hexahydro-2,2,4,4,6,6-hexaphenoxytriazatriphosphorine CAS number 1184-10-7], for example available as Rabitle™ FP110 from Fushimi Pharmaceutical Co., Ltd. (Kagawa, Japan).

[0045] The composition according to the present invention may further contain conventional additives such as heat stabilizers, release agents, antioxidants, UV absorbers, IR absorbers, antistatic agents, optical brighteners, light scattering agents, and colorants (including white pigments other than titanium dioxide already incorporated as component E).

[0046] In one embodiment, the composition contains at least 3% by weight of an organophosphate ester, based on the total weight of the composition. This content is preferably from 4% to 6% by weight, more preferably from 4.5% to 5% by weight. Examples of phosphate esters are listed above. Particularly preferred in this embodiment is a content of BDP of from 4.5% to 5% by weight.

[0047] In a further embodiment, the composition contains at least 3% by weight of linear and / or cyclic phosphazenes relative to the total weight of the composition. This content is preferably between 4% and 10% by weight, more preferably between 5% and 8% by weight. Examples of phosphazenes are listed above. Particularly preferred in this embodiment is a content of phenoxycyclophosphazenes between 5% and 7.5% by weight.

[0048] In a further embodiment, the composition contains 0% to 1% by weight, preferably 0.1% by weight or less, based on the total weight of the composition, of oligomeric organosiloxanes, and / or 0% to 1% by weight, preferably 0.1% by weight or less, based on the total weight of the composition, of halogen-free organosulfones and / or halogen-free organosulfonate salts, and / or 0% to 1% by weight, preferably 0.1% by weight or less, based on the total weight of the composition, of boron nitride. It is particularly preferred that the above-mentioned substances are not present in the composition. Examples of siloxanes are aromatic tetrasiloxanes, such as octaphenyltetrasiloxane. An example of sulfones and sulfonate salts are the so-called KSS salts, i.e. mixtures of diphenylsulfone, potassium diphenylsulfonesulfonate, and potassium diphenylsulfonedisulfonate.

[0049] In a further embodiment, the composition contains at least one polycarbonate or copolycarbonate comprising units based on bisphenol A. As indicated herein above, particularly preferred polycarbonates are homopolycarbonates based on bisphenol A and copolycarbonates based on the monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane or based on bisphenol A and 4,4′-dihydroxydiphenyl (DOD).

[0050] In further embodiments, the anhydride modified α-olefin polymer C) comprises from ≧90.0 wt % to ≦98.0 wt % α-olefin polymer and from ≧2.0 wt % to ≦10.0 wt % anhydride, where the reported weight percent values ​​are based on the total weight of the anhydride modified α-olefin polymer and total up to 100 wt %. i) 92.0% by weight to 97.5% by weight, particularly preferably 94.0% by weight to 97.0% by weight, of an α-olefin polymer; ii) 2.5% to 8.0% by weight, particularly preferably 3.0% to 6.0% by weight, of an anhydride; It is preferred that the formula (I) includes:

[0051] The olefin portion i) of the α-olefin polymer is preferably The ethylene content is 80.0% by weight to 96.0% by weight, preferably 84.0% by weight to 92.0% by weight, The propylene content is 2.0% by weight to 10.0% by weight, preferably 4.0% by weight to 8.0% by weight, and The octene content is characterized by being 2.0% by weight to 10.0% by weight, preferably 4.0% by weight to 8.0% by weight.

[0052] Likewise, it is preferred if the olefin portion i) of the α-olefin polymer consists exclusively of propylene and / or ethylene.It is further preferred if the olefin portion i) of the α-olefin polymer consists exclusively of propylene.

[0053] In a further embodiment, the talc has a D50 value for the particle size distribution determined by sedimentation analysis (ISO 13317-3:2001) of ≧0.5 μm to ≦10 μm, preferably ≧0.6 μm to ≦2.5 μm.

[0054] In further embodiments, the composition comprises: A) 50% by weight or more and 75% by weight or less of an aromatic polycarbonate; B) 15% by weight or more and 35% by weight or less of talc; C) 0.5% by weight or more and 3% by weight or less, an acid value of 30 mgKOH / g or more, and an average molecular weight M of 4000 g / mol or more and 40000 g / mol or less w an anhydride-modified α-olefin polymer having Here, the average molecular weight M w is determined by gel permeation chromatography in orthodichlorobenzene at 150 °C with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025:2005; FR) a combination of 0.7% to 0.9% by weight of a fluoropolymer-containing anti-drip agent and 0.1% to 0.3% by weight of a fluorinated sulfonate, or a combination of 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 3% to 5% by weight of an organic phosphate, or a combination of 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 3% to 10% by weight of a linear phosphazene or a cyclic phosphazene, D) 3% by weight or more and 10% by weight or less of barium sulfate; E) 0% by weight or more and 3% by weight or less of titanium dioxide; where the weight percentages reported are based on the total weight of the composition and add up to 100 weight percent.

[0055] The composition comprises: A) 52% by weight or more and 70% by weight or less of an aromatic polycarbonate; B) 25% by weight or more and 30% by weight or less of talc; C) 1% by weight or more and 2% by weight or less, an acid value of 30 mgKOH / g or more, and an average molecular weight M of 4000 g / mol or more and 40000 g / mol or less w an anhydride-modified α-olefin polymer having Here, the average molecular weight M wis determined by gel permeation chromatography in orthodichlorobenzene at 150 °C with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025:2005; FR) a combination of 0.7% to 0.9% by weight of a fluoropolymer-containing anti-drip agent and 0.1% to 0.3% by weight of a fluorinated sulfonate, or a combination of 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 4% to 5% by weight of an organic phosphate, or a combination of 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 4% to 8% by weight of a linear phosphazene or a cyclic phosphazene, D) 5% by weight or more and 8% by weight or less of barium sulfate; E) 0% by weight or more and 1.5% by weight or less of titanium dioxide; wherein the weight percentages reported are based on the total weight of the composition and preferably total less than or equal to 100 weight percent.

[0056] In further embodiments, the composition comprises: A) 52% by weight or more and 55% by weight or less of an average molecular weight M of 23,000 g / mol to 25,000 g / mol w , softening temperature of 145°C to 150°C (VST / B 120 according to ISO 306:2014-3), and 18.0 cm at 300°C and a load of 1.2 kg 3 / (10 minutes)~20.0cm 3 an aromatic polycarbonate having a melt volume flow rate (MVR) according to ISO 1133:2012-03 of 1 / (10 min); B) 28% by weight to 30% by weight of talc having a D50 value (sedimentation analysis) for a particle size distribution of 2 μm to 2.5 μm; C) 1% by weight or more and 2% by weight or less, an acid value of 75 mg KOH / g or more and 80 mg KOH / g or less, and an average molecular weight M of 20,000 g / mol or more and 21,000 g / mol or less wan anhydride-modified α-olefin polymer having Here, the average molecular weight M w is determined by gel permeation chromatography in orthodichlorobenzene at 150 °C with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025:2005; FR) 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 5% to 8% by weight of a cyclic phosphazene; D) 7% by weight or more and 8% by weight or less of barium sulfate; E) 0% by weight or more and 1.2% by weight or less of titanium dioxide; where the weight percentages reported are based on the total weight of the composition and add up to 100 weight percent.

[0057] In further embodiments, the composition has the following characteristics: a) Melt viscosity (ISO 11443:2014-04, 300℃, 1000s -1 ) is 100 Pa s or more and 300 Pa s or less (preferably 120 Pa s or more and 270 Pa s or less); b) Charpy impact strength (unnotched, ISO 179 / 1eU, 23°C) of 20 kJ / m 2 or more (preferably 20 kJ / m 2 Above 150kJ / m 2 (below) c) Vicat B softening temperature (ISO 306, 50K / h, 50N) is 115°C or more (preferably 115°C or more and 150°C or less); d) Thermal conductivity (ASTM E 1461, in-plane direction) is 0.68 W / m·K or more (preferably 0.7 W / m·K or more and 1.5 W / m·K or less); e) thermal conductivity (ASTM E 1461, through thickness) of 0.2 W / m·K or more (preferably 0.24 W / m·K or more and 0.4 W / m·K or less); f) UL94V flame test rating (1.5mm wall thickness) is V-0; g) The rating in the UL94-5V flame test (2.0 mm wall thickness) is VA; The present invention has at least two of the above.

[0058] In a preferred variant, the composition has property f) and at least one further property selected from a) to e) and g).

[0059] In a preferred variant, the composition has property g) and at least one further property selected from a) to f).

[0060] A further embodiment of the present invention is a process for producing a composition according to the invention, comprising mixing components A), B), C), FR), and D), wherein the talc B) used is an uncoated talc, and the amounts of B) and C) before mixing are adapted to one another such that 0.10 to 1.4 parts by weight of component C are used per 10 parts by weight of uncoated talc, and wherein mixing of components A), B), FR), and D) comprises mixing components A) and B) at a temperature above the melting temperature of the aromatic polycarbonate A), and adding component C) to the mixture when components A) and B) are both melted.

[0061] In one embodiment, the mixing is carried out in a co-kneader.

[0062] The present invention also provides a molding comprising the thermoplastically processed composition according to the invention.The molding may consist of the composition according to the invention or may further comprise a part region of said composition, for example for multi-component injection molding.The molding according to the invention is notable for the unique combination of properties: electrical insulation, high stiffness, high toughness, especially under multiaxial stress, improved flowability, and specific thermal conductivity combined with high surface quality in thermoplastic processing.

[0063] The moldings made from the compositions according to the invention are in each case thermally conductive and preferably electrically insulating.

[0064] The moldings are also suitable for applications including vehicle parts or interior fittings for automobiles, buses, trucks, mobile homes, rail cars, aircraft, marine vehicles or other vehicles, components for electric vehicles, cover panels in the construction sector, two-dimensional wall elements, partition walls, wall protection bars and edge protection bars, profiles for electrical installation ducts, cable guides or live rail covers.

[0065] In one embodiment, the molding is a battery housing, a two-part cooling body having an electrically conductive layer, or a housing for an electronic device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLES

[0066] The present invention will be more specifically illustrated with reference to the following examples, but is not limited thereto. Unless otherwise specified, all percentages reported in the formulations are weight percent based on the total weight of the formulation. A "V" in the formulation name indicates that the formulation is a comparative example. Talc B1 and Talc B2 used were not coated prior to processing into polycarbonate compositions.

[0067] [Table 1] TIFF0007681515000002.tif28170

[0068] Test Method The melt volume flow rate (MVR) was determined according to ISO 1133:2012-03 using a Zwick 4106 instrument from Zwick Roell at a test temperature of 300° C. and a mass of 1.2 kg. The abbreviation MVR stands for the initial melt volume flow rate (after a preheating time of 4 minutes) and the abbreviation IMVR stands for the melt volume flow rate after 19 minutes.

[0069] The shear viscosity (melt viscosity) at 300° C. was determined according to ISO 11443:2014-04 using a Visco-Robo 45.00 instrument from Goettfert.

[0070] Charpy impact strength was measured according to ISO 179 / 1eU:2010 on single-side injected test bars with dimensions of 80 mm x 10 mm x 4 mm at 23°C.

[0071] The Vicat softening point VST / B50 as a measure of heat resistance was determined according to ISO 306:2013 on test specimens with dimensions 80 mm x 10 mm x 4 mm using a Coesfeld Eco 2920 apparatus from Coesfeld Materialtest with a piston load of 50 N and a heating rate of 50 °C / h.

[0072] 60×60×2mm 3 The thermal conductivity was determined according to ASTM E 1461 (Nano Flash method) on injection molded specimens of dimensions:

[0073] The burning behaviour was measured according to UL94V on bars of dimensions 127 mm x 12.7 mm x "mm reported in the table".

[0074] The UL5V test was carried out on a sheet measuring 150mm x 105mm x 2.0mm.

[0075] Preparation of the composition The production of the molding materials was carried out by melt mixing / melt compounding in a twin-screw extruder / co-kneader at melt temperatures between 260° C. and 310° C. Particularly preferably, the melt mixing was carried out using a co-kneader, limiting the melt temperature to 300° C. or less.

[0076] Component B was added post-melted to components A and C, either pre-melted or dispersed in the melt. The addition of C was carried out simultaneously or immediately after the melting of component A. Components FR, D and E were added at any desired time. The addition of FR and E was preferably carried out simultaneously or immediately after the addition of C. The addition of component D was preferably carried out before or simultaneously with the addition of B. Test specimens were produced in each case by injection molding at melt temperatures of 280°C to 300°C and mold temperatures of 85°C to 95°C.

[0077] result The results obtained from the compositions of the present invention and the comparative examples are given below.

[0078] Comparative Examples V1 to V10 show that the combination of conventional flame retardants FR1 to FR4 in the formulations described in Patent Document 1 results in insufficient flame retardancy: failing both the UL94V test at 1.5 mm to 1.0 mm and the UL94 5V test at 2.0 mm. This is also true when using polycarbonate (A2) with a higher average molecular weight (V2, V4, V6, V8, V10).

[0079] Reducing the amount of B1 to 25% by weight makes it possible to pass the UL94V test at 1.5 mm when 0.8% FR1 and 0.2% FR2 are used (V11), however the 5VA score in UL94 5V at 2.0 mm is not achieved (V11).

[0080] This can only be achieved by adding an appropriate amount of D2 (1, 2, 3, 4), and 2.5% of component D2 is still not enough to achieve a reliable 5VA score (V12). The total amount of filler (component B and component D combined) in Examples 1, 2, and 4 is equal to or exceeds the amount of filler in V1-V10.

[0081] Compared to the addition of D2, the addition of D3 does not improve the UL94 5V test results (V13, V14, V15). The combination of D2 and D3 likewise does not improve the UL94 5V test results (V20, V21).

[0082] Similarly, the addition of component D1 does not positively affect the UL94 5V test results (V16, V17, V18, V19). The combination of D1 and D2 also does not result in an improvement in the UL94 5V test results (V22).

[0083] Examples 2 and 4 show that higher amounts of white pigment E1 in the formulation are tolerable without losing the essential properties of the molding material.

[0084] Copolycarbonates, such as for example the copolycarbonate of bisphenol A and 4,4'-dihydroxybiphenyl (DOD), can be correspondingly flame retarded with the inventive combination of FR1, FR2, and D2 (Example 5).

[0085] When the total amount of filler (component B plus component D) is further increased as in the case of V27, the addition of 0.8% FR1 and 0.2% FR2 is no longer sufficient to achieve a V0 score in the UL94 V test at 1.5 mm and a 5VA score in the UL94 5V test at 2.0 mm.

[0086] In this case, it is preferable to add phosphorus-containing flame retardants such as FR5 and / or FR6 instead of FR2.

[0087] Examples V23, V24 and V29 show that FR1 and FR5 used alone at high concentrations in the absence of component D2 are unable to achieve a 5VA score in the UL94 5V test at 2.0 mm. Furthermore, the addition of more than 7% FR5 significantly reduces the heat resistance of the molding material as measured by the Vicat softening temperature VST / B50 according to ISO 306, so that the molding material is no longer suitable for use temperatures above 115°C (V23, V24 vs. V29).

[0088] A V0 score in the UL94 V test at 1.5 mm and a 5VA score in the UL94 5V test at 2.0 mm is achieved only when the amount of FR5 is reduced to below 7% and component D2 is also added (Example 6).

[0089] An excessive amount of FR5 adversely affects the heat resistance of the molding compound, the Charpy impact test results according to ISO 179 / 1eU, and the UL94 5V test results (V28).

[0090] When the combination of FR1 and FR6 with component D2 is used for flame retardancy, a particularly good combination of properties can be achieved (Examples 7 and 8). The heat resistance (VST / B50 according to ISO 306) in these examples is above 115°C and a V0 score in the UL94V test at 1.5 mm, 1.2 mm and even 1.0 mm, as well as a 5VA score in the UL94 5V test at 2.0 mm, are reliably achieved. Furthermore, the Charpy impact test results according to ISO 179 / 1eU are 20 kJ / m 2 , which represents an exceptional result for a molding material with such a total filler content.

[0091] Example 8 and Example V30 show that the addition of component D2 is necessary to achieve a 5VA score in the UL94 5V test at 2.0 mm.

[0092] [Table 2]

[0093]

Table 3

[0094]

Table 4

[0095]

Table 5

[0096]

Table 6

[0097]

Table 7

[0098]

Table 8

[0099]

Table 9

[0100]

Table 10

[0101]

Table 11

[0102]

Table 12

[0103]

Table 13

[0104]

Table 14

[0105]

Table 15

[0106]

Table 16

Claims

1. A) at least one aromatic polycarbonate; B) talc; C) an acid value of 30 mg KOH / g or more and an average molecular weight M of 4000 g / mol or more to 40000 g / mol or less ｗ At least one anhydride-modified α-olefin polymer having the formula: Here, the average molecular weight M ｗ is determined by gel permeation chromatography in orthodichlorobenzene at 150 ° C. with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025: 2005; FR) at least one organic flame retardant selected from fluoropolymer-containing anti-drip agents, fluorinated sulfonates, organic phosphates, phosphazenes, or a mixture of at least two of the aforementioned agents; D) at least one inorganic compound different from talc; optionally, E) titanium dioxide; and optionally one or more additives selected from the group consisting of heat stabilizers, release agents, antioxidants, UV absorbers, IR absorbers, antistatic agents, optical brighteners and colorants; The colorant includes a white pigment other than titanium dioxide.

1. A thermoplastic composition comprising: The composition contains barium sulfate in an amount of 3% by weight or more, based on the total weight of the composition, and the composition contains an alkaline earth metal sulfate other than barium sulfate in an amount of 0% by weight or more and 25% by weight or less, based on the total weight of the alkaline earth metal sulfates present in the composition; The composition comprises an organophosphate ester in an amount of from 0 to 7.5 wt. %, based on the total weight of the composition; and The composition contains 0.5 wt. % or more of a fluoropolymer-containing anti-drip agent based on the total weight of the composition; wherein when the composition contains 0.1 wt. % or more of a fluorinated sulfonate salt based on the total weight of the composition, the content of the fluoropolymer-containing anti-drip agent is 0.7 wt. % or more based on the total weight of the composition.

2. 2. The composition of claim 1, wherein the composition comprises 3% by weight or more of the organophosphate ester, based on the total weight of the composition.

3. 3. The composition according to claim 1, wherein the composition contains 3% by weight or more of linear and / or cyclic phosphazenes based on the total weight of the composition.

4. The composition comprises: and / or an oligomeric organosiloxane in an amount of from 0 to 1 weight percent, based on the total weight of the composition; 0% to 1% by weight, based on the total weight of the composition, of halogen-free organic sulfones and / or halogen-free organic sulfonate salts, and / or 0% to 1% by weight of boron nitride, based on the total weight of the composition; The composition according to any one of claims 1 to 3, comprising:

5. 5. The composition of any one of claims 1-4, wherein the anhydride modified α-olefin polymer C) comprises from greater than or equal to 90.0 wt % to less than or equal to 98.0 wt % α-olefin polymer and from greater than or equal to 2.0 wt % to less than or equal to 10.0 wt % anhydride, where the reported weight % values ​​are based on the total weight of the anhydride modified α-olefin polymer and add up to 100 wt %.

6. A) 50% by weight or more and 75% by weight or less of an aromatic polycarbonate; B) 15% by weight or more and 35% by weight or less of talc; C) 0.5% by weight to 3% by weight, an acid value of 30 mgKOH / g or more, and an average molecular weight M of 4000 g / mol to 40000 g / mol or less ｗ an anhydride-modified α-olefin polymer having Here, the average molecular weight M ｗ is determined by gel permeation chromatography in orthodichlorobenzene at 150 ° C. with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025: 2005; FR) 0.7% to 0.9% by weight of a fluoropolymer-containing anti-drip agent in combination with 0.1% to 0.3% by weight of a fluorinated sulfonate, or 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent in combination with 3% to 5% by weight of an organic phosphate, or a combination of 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 3% to 10% by weight of a linear or cyclic phosphazene; D) 3% by weight or more and 10% by weight or less of barium sulfate; E) 0% to 3% by weight of titanium dioxide; wherein the reported weight percent values ​​are based on the total weight of the composition and add up to 100 weight percent.

7. A) 52% by weight or more and 55% by weight or less of an average molecular weight M of 23,000 g / mol to 25,000 g / mol ｗ , softening temperature of 145°C to 150°C (VST / B 120 according to ISO 306:2014-3), and 18.0 cm at 300°C and a load of 1.2 kg ３ / (10 minutes) ~20.0cm ３ / (10 min) according to ISO 1133: 2012-03, an aromatic polycarbonate having a melt volume flow rate (MVR); B) 28% by weight to 30% by weight of talc having a D50 value for particle size distribution of 2 μm to 2.5 μm (sedimentation analysis); C) 1% by weight to 2% by weight of an acid value of 75 mg KOH / g to 80 mg KOH / g and an average molecular weight M of 20,000 g / mol to 21,000 g / mol ｗ an anhydride-modified α-olefin polymer having Here, the average molecular weight M ｗ is determined by gel permeation chromatography in orthodichlorobenzene at 150 ° C. with polystyrene calibration, the acid number is determined by potentiometric titration with an alcoholic solution of potassium hydroxide according to DIN ISO 17025: 2005; FR) 0.4% to 0.6% by weight of a fluoropolymer-containing anti-drip agent and 5% to 8% by weight of a cyclic phosphazene; D) 7% to 8% by weight of barium sulfate; E) 0% to 1.2% by weight of titanium dioxide; wherein the weight percentages reported are based on the total weight of the composition and total less than or equal to 100 weight percent; The composition contains at least one polycarbonate or copolycarbonate containing units based on bisphenol A, and The talc has a D50 value for particle size distribution of 0.5 μm to 10 μm as determined by sedimentation analysis. The composition according to any one of claims 1 to 6.

8. A method for making the composition of any one of claims 1 to 7, comprising mixing said component A), said component B), said component C), said component FR), and said component D), The talc B) used is an uncoated talc, Before mixing, the amounts of B) and C) are adapted to one another such that 0.10 to 1.4 parts by weight of component C are used per 10 parts by weight of uncoated talc, wherein said mixing of components A), B), FR), and D) comprises mixing components A) and B) at a temperature above the melting temperature of the aromatic polycarbonate A); and A process comprising adding component C) to the mixture when components A) and B) are both melted.

9. The method according to claim 8, wherein the mixing is carried out in a co-kneader.

10. A molding comprising the thermoplastic processed composition according to any one of claims 1 to 7.

11. 11. The molding according to claim 10, wherein the molding is a battery housing, a two-part cooling body having an electrically conductive layer, or a housing for an electronic device.

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