Polycarbonate composition having high CTI

Abstract

Described is a thermoplastic composition based on aromatic polycarbonate having a high comparative tracking index, good flame retardancy, and high heat distortion temperature. The composition contains a combination of a polyalkyl (meth)acrylate, a phosphorus-containing flame retardant, and a fluorine-containing anti-drip agent.

Description

[Technical field]

[0001] The present invention relates to flame retardant thermoplastic compositions based on polycarbonate having a high comparative tracking index. [Background technology]

[0002] Polycarbonate offers many advantages over other thermoplastic polymers due to its high impact strength, high heat distortion resistance, and certain inherent flame retardancy. Due to this unique property profile, polycarbonate compositions are suitable for a variety of different applications, for example in the field of electrical and electronic components. In particular, good insulating properties and high flame retardancy are essential safety-related basic requirements for materials used in this field. In applications where plastics are in direct contact with conductor paths, high resistance to tracking currents under voltage load is a prerequisite, so that there are no short circuits in the components and therefore no fires.

[0003] Comparative Tracking Index (CTI) generally describes the resistance of plastic materials to environmental influences. The CTI value is a measure of the tendency of plastics to form conductive paths on the surface under voltage and promote the generation of electrical tracking currents under the influence of environmental influences, such as moisture and pollution. The higher the tracking current resistance of a material, i.e. the higher its Comparative Tracking Index (CTI value), the better it is suitable for use in high voltage applications, such as modern electromobility applications. Another advantage of materials with high CTI values ​​is that in electronic components, conductor paths can be placed closer together without risk of short circuits, which in turn allows for reduced component dimensions and therefore more compact designs and weight savings.

[0004] In contrast to other thermoplastic polymers, such as polystyrene, polyesters, etc., polycarbonate has a very low comparative tracking index and a moderate flame retardancy by itself. Due to the high proportion of aromatic structures, polycarbonate has a relatively high tendency to char. The CTI of pure polycarbonate is about 250V or even lower (Non-Patent Document 1). However, for many applications in the electronic / electrical (EE) sector, such as the electromobility sector, for safety reasons, a high CTI is required for the materials used, typically 600V (corresponding to insulating material group PLC 0 according to EN 50124). At the same time, the materials must have a high flame retardancy, i.e. classification V0 according to UL 94V, even in particular at low wall thicknesses.

[0005] Pure polycarbonate typically already has a certain inherent flame retardancy (classification V2 according to UL 94 V), which is insufficient for most applications in the EE sector. In order to achieve the required classification V0 according to UL 94 V, the addition of suitable flame retardants is required. Typically employed in polycarbonates are halogenated sulfonic acid compounds (e.g. Rimar salts (potassium perfluorobutanesulfonate, C4 salts) or KSS salts (potassium diphenylsulfone-3-sulfonate)), or also organophosphate compounds (e.g. bisphenol A bis(diphenylphosphate) (BDP), resorcinol bis(diphenylphosphate) (RDP)), or phosphazenes. The mechanism of action of such flame retardants is based on the formation of a solid charred surface layer that blocks the oxygen supply and thus inhibits the combustion process.

[0006] The effect that forms the basis of a good comparative tracking index is, among other things, a low tendency to form conductive paths on the surface, which is the exact opposite of the "charring" mechanism of action of surfactant flame retardants and therefore poses special challenges in controlling the CTI and flame retardancy. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] F. Acquasanta et al., Polymer Degradation and Stability, 96 (2011), 2098-2103 Summary of the Invention

[0008] The aim was therefore to provide polycarbonate-based compositions which achieve a UL 94 classification V0 at 2 mm, particularly preferably at 1.5 mm (after conditioning for 7 days at 20% relative humidity and 70° C. ambient temperature) and which have a high CTI, preferably specified according to the rapid test method according to IEC 60112:2009, of at least 375 V, preferably at least 400 V, particularly preferably 600 V or more. Due to the field of application and the heat development in EE parts, the compositions should also preferably have a good heat distortion resistance, in particular a Vicat softening temperature, specified according to ISO 306:2014-3, VST method B, of at least 105° C., particularly preferably at least 110° C.±2° C. Furthermore, the CTI should preferably be robust, i.e. a high CTI should be reliably achieved at different working voltages, for example 600 V, but also 300 V or 350 V.

[0009] Surprisingly, it has been found that this property profile is achieved by a special combination of an aromatic polycarbonate in combination with a polyalkyl (meth)acrylate and a phosphorus-containing flame retardant and a fluorine-containing anti-drip agent.

[0010] Accordingly, the present invention provides a thermoplastic composition comprising: A) at least 70% by weight of an aromatic polycarbonate; B) 4% by weight to 25% by weight of a polyalkyl(meth)acrylate; C) 1.5% by weight to 10% by weight of a phosphorus-containing flame retardant; D) 0.3% by weight to 2% by weight of a fluorine-containing drip prevention agent; E) optionally, one or more additional additives, preferably at least one additional additive selected from the group consisting of one or more mold release agents, heat stabilizers, antioxidants, dyes, pigments, UV absorbers, IR absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. the ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is less than 10; A thermoplastic composition is provided.

[0011] It will be understood that all components present in the compositions according to the present invention add up to 100% by weight. When a numerical range has an upper limit indicated by "~X", this includes the stated numerical value and any upward rounding range.

[0012] It is understood that the components used may contain typical impurities, for example impurities resulting from their manufacturing process. It is preferred to use components with the highest possible purity. Moreover, it is understood that such impurities may be present even in the case of closed formulation of the composition.

[0013] The present invention also provides moldings made from the thermoplastic composition according to the invention, i.e. moldings that consist only of the thermoplastic composition according to the invention or that contain areas made of the thermoplastic composition according to the invention. Such moldings are in particular those for which the above-mentioned property profile is particularly attractive, i.e. moldings that are part of components in the EE sector, in particular high-voltage switches, inverters, relays, electronic connectors, electrical connectors, circuit breakers, components for photovoltaic applications, electric motors, heat sinks, chargers and charging plugs for electric vehicles, electrical junction boxes, smart meter housings, miniature circuit breakers, busbars. The components are preferably designed for a working voltage of at least 400V. For this purpose, the materials expediently used preferably have a comparative tracking index of at least 600V, as specified according to the rapid test method according to IEC 60112:2009 as described above.

[0014] The compositions according to the invention do not show any significant tracking current (more than 0.5 A for 2 seconds) even when subjected to at least 50 drops of 0.1% ammonium chloride solution at 375 V, more preferably at 400 V and particularly preferably at 600 V, preferably according to the rapid test method according to IEC 60112:2009 and described in the description section. At the same time, the compositions according to the invention have a flame retardancy according to UL 94 V of V0 at a specimen thickness of 2 mm, still more preferably at least V1 at 1.5 mm and particularly preferably V0, in each case after the specimen has been conditioned for 7 days at 20% relative humidity and 70° C. ambient temperature. In addition to a high CTI and good flame retardancy, the compositions preferably also have good heat distortion resistance, which is expressed in a Vicat softening temperature of at least 105° C., more preferably at least 110° C.±2° C., as specified according to ISO 306:2014-3, VST method B.

[0015] The present invention therefore also provides the use of 4% to 25% by weight, preferably 5% to 20% by weight, of a polyalkyl (meth)acrylate, 1.5% to 10% by weight, preferably 2% to 8% by weight, of a phosphorus-containing flame retardant and 0.3% to 2% by weight of a fluorine-containing anti-drip agent in a thermoplastic composition containing at least 70% by weight of an aromatic polycarbonate, in order to achieve a high CTI of 375V, more preferably 400V, particularly preferably 600V, at a test specimen thickness of 2 mm, and a UL94 classification of V0, more preferably at least V1, particularly preferably V0, at 1.5 mm, in particular after conditioning the test specimen at 20% relative humidity and 70° C. ambient temperature for 7 days, the weight percentage figures being based on the total composition obtained.

[0016] Naturally, the features mentioned as being preferred, particularly preferred etc. for the composition also apply in relation to the uses according to the invention.

[0017] The individual components of the composition according to the invention are described in more detail hereinafter:

[0018] Ingredient A Component A of the composition according to the invention is an aromatic polycarbonate.

[0019] Aromatic polycarbonates in the context of the present invention include not only homopolycarbonates but also copolycarbonates and / or polyestercarbonates. The polycarbonates can be linear or branched in a known manner. Polycarbonate mixtures can also be used according to the present invention.

[0020] The thermoplastic polycarbonates, including thermoplastic aromatic polyester carbonates, preferably have a weight average molecular weight M w is 15000 g / mol to 40000 g / mol, more preferably 34000 g / mol, particularly preferably 17000 g / mol to 33000 g / mol, and particularly preferably 19000 g / mol to 32000 g / mol; wis determined by gel permeation chromatography using dichloromethane as eluent and calibrated against bisphenol A polycarbonate standards, using linear polycarbonate (formed from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, using calibration according to method 2301-0257502-09D (2009 German edition) from Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. The column combination is a crosslinked styrene-divinylbenzene resin. Analytical column diameter: 7.5 mm; length: 300 mm. Column material particle size: 3 μm-20 μm. Solution concentration: 0.2 wt.%. Flow rate: 1.0 ml / min, solution temperature: 30°C. UV and / or RI detection is used.

[0021] The melt volume flow rate (MVR) of the aromatic polycarbonate used is specified according to ISO 1133:2012-03 at a test temperature of 300°C and a load of 1.2 kg, preferably at 5 cm 3 / (10 minutes)~35cm 3 / (10 min), more preferably 6 cm 3 / (10 minutes)~25cm 3 / (10 min), and even more preferably 6 cm 3 / (10 minutes)~21cm 3 / (10 minutes).

[0022] A maximum of 80 mol %, preferably 20 mol % to 50 mol %, of the carbonate groups of the polycarbonate used according to the invention can be replaced by aromatic dicarboxylic acid ester groups. This type of polycarbonate, which has acid radicals derived from aromatic dicarboxylic acids as well as carbonic acid derived acid radicals introduced into the molecular chain, is called aromatic polyester carbonate. For the purposes of the present invention, these are included under the general term "thermoplastic aromatic polycarbonates".

[0023] The details of polycarbonate preparation have been described in numerous patent specifications over the past 40 years or so. In this specification, the following may be mentioned by way of example: Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, D. Freitag, U. Grigo, PR Mueller, H. Nouvertne, BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718, and finally U. Grigo, K. Kirchner and PR Mueller "Polycarbonate" [Polycarbonates] in Becker / Braun, Kunststoff-Handbuch [Plastics Handbook], volume 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester [Polycarbonates, Polyacetals, Polyesters, Cellulose Esters], Carl Hanser Verlag Munich, Vienna 1992, pages 117 to 299.

[0024] Aromatic polycarbonates are prepared, for example, by the interfacial process, by reaction of dihydroxyaryl compounds with carbonyl halides, preferably phosgene, and / or aromatic dicarbonyl dihalides, preferably benzene dicarbonyl dihalides, optionally using chain reaction terminators and optionally using trifunctional or higher branching agents. Also possible is the preparation by reaction of dihydroxyaryl compounds with, for example, diphenyl carbonate, via melt polymerization methods.

[0025] For the preparation of polyester carbonates, a portion of the carbonic acid derivatives is replaced with aromatic dicarboxylic acids or dicarboxylic acid derivatives, specifically aromatic dicarboxylic ester structural units according to the carbonate structural units to be replaced in the aromatic polycarbonate.

[0026] Dihydroxyaryl compounds suitable for the preparation of polycarbonates are of formula (1) HO-Z-OH (1), During the ceremony, Z is an aromatic radical having 6 to 30 carbon atoms, which may have one or more aromatic rings, which may be substituted, and which may have aliphatic or alicyclic radicals or alkylaryl or heteroatoms as bridging elements.

[0027] Suitably, Z in formula (1) is a radical of formula (2): [ka] During the ceremony, R 6 and R 7 are independently H, C1 to C 18 -Alkyl, C1-C 18 -alkoxy, halogen such as Cl or Br, or, in each case, optionally substituted aryl or aralkyl, preferably H or C1-C 12 -alkyl, particularly preferably H or C1-C8-alkyl, especially preferably H or methyl, X is a single bond, -SO2-, -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene or C5-C6-cycloalkylidene, which can be substituted by C1-C6-alkyl, preferably methyl or ethyl, or C6-C 12 -arylene, which may be optionally fused to a further aromatic ring containing a heteroatom.

[0028] X is preferably a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2- or a radical of formula (3). [ka]

[0029] Examples of dihydroxyaryl compounds include: dihydroxybenzene, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)aryls, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, 1,1'-bis(hydroxyphenyl)diisopropylbenzene, and their ring-alkylated and ring-halogenated compounds.

[0030] Dihydroxyaryl compounds suitable for the preparation of polycarbonates include, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, α,α'-bis(hydroxyphenyl)diisopropylbenzene, phthalimidines derived from isatin or phenolphthalein derivatives, and their ring-alkylated, ring-arylated, and ring-halogenated compounds.

[0031] Suitable dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 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, as well as the following dihydroxyaryl compounds (I) to (III): [ka] In the formula, each R' is a C1-C4-alkyl radical, an aralkyl radical or an aryl radical, preferably a methyl radical or a phenyl radical, particularly preferably a methyl radical.

[0032] Particularly preferred dihydroxyaryl compounds are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl, and dimethylbisphenol A, as well as bisphenols of formula (I), formula (II), and formula (III).

[0033] These and other suitable dihydroxyaryl compounds are described, for example, in U.S. Pat. Nos. 2,999,835, 3,148,172, 2,991,273, 3,271,367, 4,982,014 and 2,999,846, in DE-A-1,570,703, DE-A-2,063,050, DE-A-2,036,052, DE-A-2,211,956 and DE-A-3,832,396, in FR-A-1,561,518 and in the research article "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1989, 1991, and 1998, respectively. 1964", as well as in JP-A-1986-62039, JP-A-1986-62040, and JP-A-1986-105550.

[0034] In the case of homopolycarbonates, only one type of dihydroxyaryl compound is used, whereas in the case of copolycarbonates, two or more types of dihydroxyaryl compounds are used.

[0035] Examples of suitable carbonic acid derivatives are phosgene or diphenyl carbonate.

[0036] Suitable chain terminators that can be used in the preparation of the polycarbonates are monophenols. Examples of suitable monophenols include phenol itself, alkylphenols such as cresol, p-tert-butylphenol, cumylphenol, and also mixtures thereof.

[0037] Suitable chain terminators include one or more linear or branched, preferably unsubstituted, C1-C 30 -alkyl radical- or tert-butyl-substituted phenol. Particularly suitable chain terminators are phenol, cumylphenol, and / or p-tert-butylphenol.

[0038] The amount of chain terminator used is preferably 0.1 mol% to 5 mol%, based on the moles of dihydroxyaryl compound used in each case. The chain terminator can be added before, during or after the reaction with the carbonic acid derivative.

[0039] Suitable branching agents are trifunctional or higher compounds known in polycarbonate chemistry, especially those having three or more phenolic OH groups.

[0040] Examples of suitable branching agents include 1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane, and 1,4-bis((4',4''-dihydroxytriphenyl)methyl)benzene, and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

[0041] Whatever branching agent is used, its amount is preferably between 0.05 mol % and 2.00 mol %, based on the moles of dihydroxyaryl compound used in each case.

[0042] The branching agent can either be an initial charge together with the dihydroxyaryl compound and the chain terminator in the aqueous alkaline phase, or it can be added dissolved in an organic solvent prior to the phosgenation. In the case of the transesterification process, the branching agent is used together with the dihydroxyaryl compound.

[0043] Particularly suitable polycarbonates are homopolycarbonates based on bisphenol A, homopolycarbonates based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and copolycarbonates based on the two monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane or based on the two monomers bisphenol A and 4,4'-dihydroxydiphenyl, as well as polycarbonates of formula (I), formula (II), and / or formula (III): [ka] where each R' is C1-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, especially preferably methyl, and in particular homo- or copolycarbonates derived from dihydroxyaryl compounds, in particular from bisphenol A. Especially preferably, the aromatic polycarbonate comprises a bisphenol A-based homopolycarbonate. Very preferably, the aromatic polycarbonate is a bisphenol A-based homopolycarbonate.

[0044] The total proportion of monomer units based on formula (I), formula (II), formula (III), 4,4'-dihydroxydiphenyl and / or bisphenol TMC in the copolycarbonate is preferably 0.1 mol % to 88 mol %, particularly preferably 1 mol % to 86 mol %, especially preferably 5 mol % to 84 mol %, in particular 10 mol % to 82 mol % (based on the sum of the moles of dihydroxyaryl compounds used).

[0045] The relative solution viscosity of the copolycarbonates, as specified according to ISO 1628-4:1999, is preferably in the range of 1.15 to 1.35.

[0046] The dihydroxyaryl compounds used, as well as all other chemicals and auxiliaries added in the synthesis, may be contaminated with contaminants from their own synthesis, handling, and storage, however, it is desirable to use raw materials with the highest possible purity.

[0047] Also suitable are copolycarbonates prepared using diphenols of general formula (4a) [ka] During the ceremony, R 5 is hydrogen or C1-C4-alkyl, C1-C3-alkoxy, preferably hydrogen, methoxy or methyl, R 6 , R 7 , R 8 , and R 9 are each independently C1-C4 alkyl or C6-C 12 -aryl, preferably methyl or phenyl; Y is a single bond, -SO2-, -S-, -CO-, -O-, C1-C6-alkylene, C2-C5-alkylidene, C6-C 12 -arylene, which can optionally be fused to a further aromatic ring containing heteroatoms, or a C5-C6-cycloalkylidene radical, which can be mono- or polysubstituted by C1-C4-alkyl, preferably a single bond, -O-, isopropylidene, or a C5-C6-cycloalkylidene radical, which can be mono- or polysubstituted by C1-C4-alkyl, V is oxygen, C2-C6-alkylene or C3-C6-alkylidene, preferably oxygen or C3-alkylene; p, q, and r are each independently 0 or 1; When q=0, W is a single bond, and when q=1 and r=0, W is oxygen, C2-C6-alkylene, or C3-C6-alkylidene, preferably oxygen or C3-alkylene; when q=1 and r=1, W and V are each independently C2-C6-alkylene or C3-C6-alkylidene, preferably C3-alkylene; Z is C1-C6-alkylene, preferably C2-alkylene; o is the average number of repeating units from 10 to 500, preferably from 10 to 100; m is the average number of repeating units of 1 to 10, preferably 1 to 6, more preferably 1.5 to 5. It is likewise possible to use diphenols in which two or more siloxane blocks of the general formula (4a) are joined together via terephthalic acid and / or isophthalic acid to form ester groups.

[0048] Particularly preferred are (poly)siloxanes of the formula (5) and the formula (6), [ka] in which R1 is hydrogen, C1-C4-alkyl, preferably hydrogen or methyl, particularly preferably hydrogen, each R2 is independently aryl or alkyl, preferably methyl; X is a single bond, -SO2-, -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene, or C6-C 12 -arylene, which can be optionally fused with a further aromatic ring containing a heteroatom; X is preferably a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C 12 -cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, and particularly preferably, X is a single bond, isopropylidene, C5 to C 12 -cycloalkylidene or oxygen, particularly preferably isopropylidene, n is an average number of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50; m is an average number of 1 to 10, preferably 1 to 6, and particularly preferably 1.5 to 5.

[0049] The siloxane blocks may likewise preferably be derived from the following structure: [ka] Preferably or In the formulae (IV), (V), and (VI), a is an average number of 10 to 400, preferably 10 to 100, and particularly preferably 15 to 50.

[0050] It is also preferred that at least two identical or different siloxane blocks of general formula (IV), general formula (V) or general formula (VI) are linked together with one another via terephthalic acid and / or isophthalic acid to form an ester group.

[0051] In formula (4a), p=0, V is C3-alkylene, r=1, Z is C2-alkylene, R 8 and R 9 is methyl, q=1, W is C3-alkylene, m=1, R 5 is hydrogen or C1-C4-alkyl, preferably hydrogen or methyl; R 6 and R 7 is also preferably each independently C1-C4 alkyl, preferably methyl, and o is 10-500.

[0052] Copolycarbonates having monomeric units of formula (4a) and in particular their preparation are also described in WO 2015 / 052106.

[0053] Copolycarbonates having monomeric units of formula (IV) and in particular their preparation are also described in WO 2015 / 052106.

[0054] Examples of aromatic dicarboxylic acids suitable for the preparation of polyester carbonates include orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.

[0055] Among the aromatic dicarboxylic acids, particular preference is given to the use of terephthalic acid and / or isophthalic acid.

[0056] Derivatives of dicarboxylic acids include dicarbonyl dihalides and dialkyl dicarboxylates, especially dicarbonyl dichlorides and dimethyl dicarboxylates.

[0057] The replacement of carbonate groups with aromatic dicarboxylic ester groups is substantially stoichiometric and quantitative, so that the molar ratios of the reactants are also maintained in the final polyestercarbonate. The aromatic dicarboxylic ester groups can be incorporated either randomly or in blocks.

[0058] The composition according to the invention contains at least 70% by weight, preferably at least 70.5% by weight, particularly preferably at least 84% by weight, of aromatic polycarbonate and is therefore based on aromatic polycarbonate.

[0059] Component B Component B is a polyalkyl(meth)acrylate. It will be understood that this may be the only polyalkyl(meth)acrylate or a mixture of various polyalkyl(meth)acrylates. Component B does not include polymers that contain polyalkyl(meth)acrylate as part of the graft polymer. The polyalkyl(meth)acrylate is preferably a linear polymer.

[0060] The polyalkyl(meth)acrylates according to component B preferably have a weight average molecular weight of 80000 g / mol to 300000 g / mol, more preferably 100000 g / mol to 200000 g / mol, as determined by gel permeation chromatography in tetrahydrofuran with PMMA calibration.

[0061] Component B may also be a mixture of two or more polyalkyl (meth)acrylates, one of which may have a low molecular weight. In this case, the weight average molecular weight mentioned is based on the entire polyalkyl (meth)acrylate mixture, which is component B. At least one of the polyalkyl (meth)acrylates may have a low molecular weight and a weight average molecular weight of 1000 g / mol to 70000 g / mol, particularly preferably 5000 g / mol to 60000 g / mol. The low molecular weight polyalkyl (meth)acrylate preferably has a proportion of 2% to 20% by weight, in particular 5% to 10% by weight, based on the total weight of the polyalkyl (meth)acrylates. This makes it possible to improve the processability with polycarbonates. The above-mentioned weight average molecular weight of 80000 g / mol to 300000 g / mol, more preferably 100000 g / mol to 200000 g / mol, is based on all of the polyalkyl (meth)acrylates present in the composition according to the invention.

[0062] The polyalkyl(meth)acrylate is preferably a) 52.0% to 100.0% by weight of repeating alkyl methacrylate units, in particular methyl methacrylate, having 1 to 20, preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4 carbon atoms in the alkyl radical; b) 0% to 40.0% by weight of repeating alkyl acrylate units, in particular methyl acrylate, having 1 to 20, preferably 1 to 12, more preferably 1 to 8, and particularly preferably up to 4 carbon atoms in the alkyl radical; c) 0% to 8.0% by weight of repeating styrene units of general formula (VII); having [ka] In the formula, R 1 ~R 5 are independently hydrogen, halogen, C1-C6-alkyl or C2-C6-alkenyl; R 6 is hydrogen or C1-C6-alkyl, The weight percent amounts of a, b, and c add up to 100% by weight, which is the total weight of the polyalkyl(meth)acrylate.

[0063] Especially preferably, the polyalkyl(meth)acrylate has at least 60.0% by weight, even more preferably at least 75.0% by weight, especially at least 85.0% by weight of repeating methyl methacrylate units.

[0064] Very preferably, the polyalkyl(meth)acrylate comprises 90.0% to 99.0% by weight of methyl methacrylate and 1.0% to 10.0% by weight of methyl acrylate, in each case based on the total weight of the polyalkyl(meth)acrylate.

[0065] The proportion of component B in the composition according to the present invention is 4% by weight to 25% by weight, preferably 5% by weight to 22% by weight, more preferably 5% by weight to 20% by weight, particularly preferably up to 15% by weight, based on the entire composition.

[0066] Component C Component C of the composition according to the invention is a phosphorus-containing flame retardant, which may be a single phosphorus-containing flame retardant or a mixture of different phosphorus-containing flame retardants.

[0067] Suitable phosphorus-containing flame retardants are cyclic phosphazenes, phosphorus compounds of formula (10), and mixtures thereof: [ka] During the ceremony, R 1 , R 2 , R 3 , and R 4 are independently a C1-C8-alkyl radical, which in each case is optionally halogenated, in each case branched or unbranched, and / or a C5-C6-cycloalkyl radical, a C6-C 20 -aryl radical, or C7-C 12- aralkyl radicals, which in each case are optionally substituted by branched or unbranched alkyl and / or halogen, preferably chlorine and / or bromine, n is independently 0 or 1; q is a value between 0 and 30; X is a monocyclic or polycyclic aromatic radical having 6 to 30 carbon atoms, or a straight or branched chain aliphatic radical having 2 to 30 carbon atoms, each of which can be substituted or unsubstituted and bridged or non-bridged.

[0068] Preferably, R 1 , R 2 , R 3 , and R 4 is independently branched or unbranched C1-C4-alkyl, phenyl, naphthyl, or C1-C4-alkyl substituted phenyl. 1 Group, R 2 Group, R 3 Groups and / or R 4 If they are radicals, these in turn can be substituted by halogens and / or alkyl groups, preferably chlorine, bromine and / or branched or unbranched C1-C4-alkyl. Particularly suitable aryl radicals are those corresponding to cresyl, phenyl, xylenyl, propylphenyl or butylphenyl, as well as their brominated and chlorinated derivatives.

[0069] X in formula (10) is preferably derived from a dihydroxyaryl compound.

[0070] X in formula (10) is particularly preferably the following: [ka] or their chlorinated and / or brominated derivatives. X (together with the adjacent oxygen atom) is preferably derived from hydroquinone, bisphenol A or diphenylphenol. It is likewise suitable that X is derived from resorcinol. Particularly preferably, X is derived from bisphenol A. n in formula (10) is preferably equal to 1. q is preferably 0 to 20, particularly preferably 0 to 10, and in the case of mixtures has an average value of 0.8 to 5.0, preferably 1.0 to 3.0, further preferably 1.05 to 2.00, particularly preferably 1.08 to 1.60.

[0071] The phosphorus compound of the general formula (10) is preferably a compound of the formula (11), [ka] During the ceremony, R 1 , R 2 , R 3 , and R 4 are each independently a linear or branched C1-C8 alkyl radical and / or optionally a linear or branched alkyl substituted C5-C6 cycloalkyl radical, C6-C 10 -aryl radical, or C7-C 12 -aralkyl radical, n is independently 0 or 1; q is independently 0, 1, 2, 3, or 4; N is a number between 1 and 30, R 5 and R 6 are independently a linear or branched C1-C4-alkyl radical, preferably a methyl radical, Y is a linear or branched C1-C7 alkylidene, linear or branched C1-C7 alkylene radical, C5-C 12 -Cycloalkylene radical, C5-C 12 - a cycloalkylidene radical, -O-, -S-, -SO-, SO2, or -CO-.

[0072] Phosphorus compounds of formula (10) include, in particular, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, 2-ethyl cresyl diphenyl phosphate, tri(isopropylphenyl) phosphate, resorcinol bridged oligophosphates, and bisphenol A bridged oligophosphates. The use of oligomeric phosphates of formula (10) derived from bisphenol A is particularly preferred.

[0073] Further preference is given to the use of mixtures of the same structure but different chain lengths, in which case the q value specified is the average of the q values, determined by determining the composition (molecular weight distribution) of the mixture of phosphorus compounds by high pressure liquid chromatography (HPLC) in a mixture of acetonitrile and water (50:50) at 40°C and using this to calculate the average value of q.

[0074] Particularly preferably, bisphenol A-based oligophosphates according to formula (12) (bisphenol A bis(diphenyl phosphate)) with q=1 to 20, in particular q=1.0 to 1.2, are present in the composition according to the invention. [ka]

[0075] Phosphorus compounds of this type are known (see, for example, EP-A-0 363 608, EP-A-0 640 655) or can be prepared in an analogous manner by known methods (see, for example, Ullmanns Enzyklopaedie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol. 18, p. 301 ff., 1979; Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], vol. 12 / 1, p. 43; Beilstein vol. 6, p. 177).

[0076] As preferred as the phosphorus compounds according to formula (10), it is also possible to use as component C cyclic phosphazenes according to formula (13), [ka] During the ceremony, R is in each case the same or different, is an amine radical, in each case an optionally halogenated, preferably fluorohalogenated, more preferably monohalogenated, C1-C8-alkyl radical, preferably a methyl, ethyl, propyl or butyl radical, a C1-C8 alkoxy radical, preferably a methoxy, ethoxy, propoxy or butoxy radical, in each case optionally alkyl-substituted, preferably C1-C4-alkyl-substituted and / or halogen-substituted, preferably chlorine- and / or bromine-substituted, C5-C6-cycloalkyl radicals, In each case, optionally alkyl-substituted, preferably C1-C4-alkyl-substituted, and / or halogen-substituted, preferably chlorine, bromine, and / or hydroxy-substituted, C6-C 20 an aryloxy radical, preferably a phenoxy radical, a naphthyloxy radical, In each case, optionally alkyl-substituted, preferably C1-C4-alkyl-substituted, and / or halogen-substituted, preferably chlorine- and / or bromine-substituted, C7-C 12 - an aralkyl radical, preferably a phenyl-C1-C4-alkyl radical, or a halogen radical, preferably chlorine or fluorine, or is the OH radical, k is a natural number of 1 to 10, preferably 1 to 8, particularly preferably 1 to 5, and especially preferably 1.

[0077] Particularly preferably used according to the invention are commercially available phosphazenes, which are typically ring mixtures of different ring sizes.

[0078] Further preference is given to the following, either individually or in mixtures: propoxyphosphazenes, phenoxyphosphazenes, methylphenoxyphosphazenes, aminophosphazenes, fluoroalkylphosphazenes, and also phosphazenes having the following structure: [ka]

[0079] In compounds 13a-13f shown above, k=1, 2, or 3.

[0080] Preferably, the proportion of phosphorus halogen substituted phosphazenes, for example those consisting of incompletely reacted starting materials, is less than 1000 ppm, more preferably less than 500 ppm.

[0081] The phosphazenes can be used alone or in mixtures. The radicals R can always be the same or two or more radicals in the formula can be different. The radicals R of the phosphazenes are preferably identical.

[0082] In one embodiment, only phosphazenes having the same R are used.

[0083] Preferably, the proportion of tetramers (k=2) is 2 mol % to 50 mol %, more preferably 5 mol % to 40 mol %, even more preferably 10 mol % to 30 mol %, and particularly preferably 10 mol % to 22 mol %, based on component B.

[0084] Preferably, the proportion of higher oligomeric phosphazenes (k=3, 4, 5, 6, and 7) is from 0 mol% to 30 mol%, more preferably from 2.5 mol% to 25 mol%, even more preferably from 5 mol% to 20 mol%, and particularly preferably from 6 mol% to 15 mol%, based on component B.

[0085] Preferably, the proportion of oligomers with k≧8 is, based on component B, from 0 mol % to 2.0 mol %, preferably from 0.10 mol % to 1.00 mol %.

[0086] More preferably, the phosphazene of component C satisfies all three above conditions with respect to the proportion of oligomers.

[0087] Particularly preferably, phenoxyphosphazenes (all R=phenoxy, formula 13g) are present as component C, either alone or together with further phosphazenes according to formula (13) as component C, the proportion of oligomers with k=1 (hexaphenoxyphosphazenes) being 50 mol % to 98 mol %, particularly preferably 60% to 72% by weight, based on the amount of phenoxyphosphazene. If phenoxyphosphazenes are used, the proportion of oligomers with k=2 is especially preferably 15% to 22% by weight and those with k≧3 being 10% to 13% by weight. [ka]

[0088] Alternatively, component C particularly preferably comprises a phenoxyphosphazene having, based on component C, a proportion of trimers (k=1) of 70 mol% to 85 mol%, a proportion of tetramers (k=2) of 10 mol% to 20 mol%, a proportion of higher oligomeric phosphazenes (k=3, 4, 5, 6, and 7) of 3 mol% to 8 mol%, and 0.1 mol% to 1 mol% of phosphazene oligomers with k≧8. Such a phenoxyphosphazene is particularly preferred.

[0089] In an alternative preferred embodiment, n is defined as the arithmetic mean of k, where n is in the range of 1.10 to 1.75, preferably 1.15 to 1.50, more preferably 1.20 to 1.45, and especially preferably 1.20 to 1.40 (including the range limits).

number

[0090] Phosphazenes and their preparation are described, for example, in EP-A-728811, DE-A-1961668 and WO-A-97 / 40092.

[0091] The oligomer composition in each blend sample was determined after synthesis as follows: 31 Detection and quantification are possible by P NMR (chemical shifts; trimer δ: 6.5 ppm to 10.0 ppm; tetramer δ: -10 ppm to -13.5 ppm; higher oligomers δ: -16.5 ppm to -25.0 ppm).

[0092] Particularly preferably, component C comprises a bisphenol A-based oligophosphate ester according to formula (12) and / or a cyclic phosphazene according to formula (13), and most preferably component C is a bisphenol A-based oligophosphate ester according to formula (12) and / or a cyclic phosphazene according to formula (13).

[0093] The proportion of phosphorus-containing flame retardant in the composition according to the invention is from 1.5% to 10% by weight, preferably from 2% to less than 8% by weight, particularly preferably up to 6% by weight, especially preferably up to 5% by weight, very particularly preferably up to 4% by weight, based on the total composition. The Vicat temperature decreases significantly with increasing proportion of phosphorus-containing flame retardant.

[0094] Component D The composition according to the invention contains a fluorine-containing anti-drip agent as component D, which may be a mixture of two or more anti-drip agents. The total amount of anti-drip agents (anti-drip agents) is 0.3% to 2% by weight, preferably 0.4% to 1% by weight, particularly preferably 0.5% to 1.0% by weight of at least one anti-drip agent.

[0095] The anti-drip agents used are preferably fluorine-containing polymers, especially polyolefins.

[0096] The fluorinated polyolefins preferentially used as anti-drip agents have a high molecular weight, a glass transition temperature above -30°C, generally above 100°C, and a fluorine content preferably between 65% and 76% by weight, in particular between 70% and 76% by weight. Suitable fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymers, and ethylene / tetrafluoroethylene copolymers. Fluorinated polyolefins are known ("Vinyl and Related Polymers" by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484-494; "Fluoropolymers" by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, volume 13, 1970, pages 623-654; "Modern Plastics Encyclopedia", 1970-1971, volume 47, No. 10 A, October 1970, McGraw-Hill, Inc., New York, pages 134 and 774; "Modern Plastics Encyclopedia", 1975-1976, October 1975, volume 52, No. 10 A, McGraw-Hill, Inc., New York, pages 27, 28 and (See U.S. Pat. Nos. 3,671,487, 3,723,373, and 3,838,092.) These can be prepared by known methods, for example, in an aqueous medium using a free radical forming catalyst (e.g., sodium peroxodisulfate, potassium peroxodisulfate, or ammonium peroxodisulfate, etc.) at a pressure of 7 kg / cm. 2 ~71kg / cm 2 and polymerizing tetrafluoroethylene at a temperature between 0° C. and 200° C., preferably between 20° C. and 100° C. Further details can be obtained, for example, in US Pat. No. 2,393,967.

[0097] Depending on the application, the density of the fluorinated polyolefins is specified according to ISO 1183-1 (2019-09) to be 1.2 g / cm 3 ~2.3g / cm 3 , preferably 2.0 g / cm 3 ~2.3g / cm 3 The average particle size can be between 0.05 μm and 1000 μm as determined by optical microscopy or white light interferometry.

[0098] Suitable tetrafluoroethylene polymer powders are commercially available, for example, from DuPont under the trade name Teflon™.

[0099] Thus, particular preference is given to the use of polytetrafluoroethylene (PTFE), but also to the use of fluorine-containing anti-drip agents in the form of PTFE-containing compositions. When PTFE-containing compositions are used, the minimum amount of PTFE present in the entire composition is preferably at least 0.15% by weight, particularly preferably at least 0.25% by weight. PTFE-containing compositions include Hostaflon™ TF2021 or PTFE blends, such as Blendex™ B449 from Chemtura (approximately 50% by weight of PTFE and approximately 50% by weight of SAN (derived from 80% by weight of styrene and 20% by weight of acrylonitrile)). Particular preference is given to the use of PTFE or PTFE / SAN blends as fluorine-containing anti-drip agents.

[0100] Component E The polycarbonate compositions according to the present invention may contain one or more additional additives different from Component B, Component C, and Component D, which, when present, are collectively referred to as "Component E."

[0101] Other usual additives ("additional additives") are optionally present (0 wt.%), preferably up to 12 wt.%, more preferably up to 5 wt.%, even more preferably up to 3 wt.%, in particular 0.1 wt.% to 3 wt.%, particularly preferably 0.2 wt.% to 1 wt.%, especially preferably 0.5 wt.% to 1.0 wt.%, these weight percentages being based on the total weight of the composition. The group of additional additives does not include any phosphorus-containing flame retardants according to component C. In particular, the group of additional additives does not include any fluorine-containing anti-drip agents, since these have already been described in component D.

[0102] Such further additives are, as typically added to polycarbonates, in particular heat stabilizers, antioxidants, release agents, UV absorbers, IR absorbers, impact modifiers, antistatic agents, flame retardants different from component C, optical brighteners, fillers, light scattering agents, hydrolysis stabilizers, transesterification stabilizers, (organic) dyes, (organic / inorganic) pigments, compatibilizers and / or laser marking additives, in amounts typical of compositions based on polycarbonates. Such additives are described, for example, in EP 0 839 623, WO 96 / 15102, EP 0 500 496 or in "Plastics Additives Handbook", Hans Zweifel, 5th Edition 2000, Hanser Verlag, Munich. Such additives can be added individually or else as mixtures.

[0103] If additional additives are eventually present, more preferably the additional additive is at least one additional additive selected from the group consisting of heat stabilizers, antioxidants, release agents, organic dyes, organic pigments, inorganic pigments.

[0104] Further additives present are particularly preferably at least one heat stabilizer, antioxidant and / or mold release agent.

[0105] It will be understood that such additives may only be added in such amounts if they do not significantly negatively affect the effect of the present invention, which combines high CTI with good flame retardancy, and preferably also do not reduce the Vicat temperature, as determined according to ISO 306:2014-3, VST method B, to below 105°C, more preferably below 110°C ± 2°C.

[0106] Additives which are particularly preferably present are release agents, more preferably release agents based on fatty acid esters, even more preferably release agents based on stearic acid esters, particularly preferably release agents based on pentaerythritol. Particular preference is given to the use of pentaerythritol tetrastearate (PETS) and / or glycerol monostearate (GMS). If one or more release agents are used, their amount is preferably up to 1.0% by weight (inclusive), more preferably 0.01% to 0.7% by weight, particularly preferably 0.2% to 0.60% by weight, in each case based on the total composition.

[0107] An additive which is also particularly preferably present is a heat stabilizer, the amount of which is preferably up to 0.20% by weight, more preferably from 0.01% to 0.15% by weight, even more preferably from 0.01% to 0.1% by weight, and particularly preferably from 0.025% to 0.09% by weight, based on the total composition.

[0108] Suitable heat stabilizers are especially phosphorus-based stabilizers selected from the group of phosphates, phosphites, phosphonites, phosphines, and mixtures thereof.Examples include triphenyl phosphite, alkyl diphenyl phosphite, dialkyl phenyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos® 168), diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite (Do verphos(trademark) S-9228), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-isooctyl peroxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocin, 2,2',2''-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl 2-ethylhexyl (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphiran, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, triphenylphosphine (TPP), trialkylphenylphosphine, bisdiphenylphosphinoethane, or trinaphthylphosphine.These can be used alone or in mixtures, for example Irganox® B900 (a mixture of Irgafos® 168 and Irganox® 1076 (antioxidant) in a ratio of 4:1) or a mixture of Doverphos® S-9228 with Irganox® B900 or Irganox® 1076. Particularly preferably, triphenylphosphine (TPP), Irgafos® 168, or tris(nonylphenyl)phosphite, or mixtures thereof, are used.

[0109] It is also possible to use phenolic antioxidants, such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones.Particular preference is given to using Irganox® 1010 (pentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; CAS: 6683-19-8) and Irganox® 1076 (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), preferably in an amount of 0.01% to 0.5% by weight.

[0110] It is also possible to add sulfonates or alkyl phosphates, such as mono-, di-, and / or trihexyl phosphate, triisooctyl phosphate, and / or trinonyl phosphate, as transesterification inhibitors. The alkyl phosphate used is preferably triisooctyl phosphate (tris-2-ethylhexyl phosphate). It is also possible to use mixtures of various mono-, di-, and / or trialkyl phosphates. Triisooctyl phosphate is preferably used in an amount of 0.003% to 0.05% by weight, more preferably 0.005% to 0.04% by weight, particularly preferably 0.01% to 0.03% by weight, based on the total composition.

[0111] Examples of impact modifiers are: core-shell polymers, such as ABS or MBS; olefin-acrylate copolymers, such as the Elvaloy™ variety from DuPont or the Paraloid™ variety from Dow; silicone acrylate rubbers, such as the Metablen™ variety from Mitsubishi Rayon Co., Ltd. The composition according to the present invention already has an exceptional property profile without additional impact modifiers. Therefore, the composition according to the present invention preferably does not contain impact modifiers.

[0112] Particularly preferably, no fillers are present in the composition according to the invention.

[0113] A preferred composition according to the present invention comprises A) at least 70% by weight of an aromatic polycarbonate; B) 5% to 20% by weight of a polyalkyl(meth)acrylate, in particular polymethyl methacrylate; C) 2% by weight to 10% by weight of a phosphorus-containing flame retardant; D) 0.3% by weight to 2% by weight of a fluorine-containing drip prevention agent; E) 0% to 12% by weight of at least one additional additive selected from the group consisting of one or more release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, ester exchange stabilizers, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. The ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is 5 or less.

[0114] Particularly preferred compositions according to the invention are A) at least 70% by weight of an aromatic polycarbonate; B) 5% to 20% by weight of a polyalkyl(meth)acrylate, in particular polymethyl methacrylate; C) 2% by weight to 8% by weight of a phosphorus-containing flame retardant; D) 0.3% by weight to 2% by weight of a fluorine-containing drip prevention agent; E) 0% to 5% by weight of at least one additional additive selected from the group consisting of one or more release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, ester exchange stabilizers, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. The ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is 5 or less.

[0115] Particularly preferred compositions according to the invention are A) at least 70% by weight of an aromatic polycarbonate, wherein the aromatic polycarbonate present is a bisphenol A based polycarbonate, more preferably the aromatic polycarbonate is a bisphenol A based homopolycarbonate; B) 5% by weight to 20% by weight of a polyalkyl(meth)acrylate; C) 2% by weight to 8% by weight of a phosphorus-containing flame retardant; D) 0.3% by weight to 2% by weight of a fluorine-containing drip prevention agent; E) 0% to 5% by weight of at least one additional additive selected from the group consisting of one or more release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, ester exchange stabilizers, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. The ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is 5 or less.

[0116] In this case, the phosphorus-containing flame retardants present are preferably organic phosphates, in particular those of formula (12): [ka] (In the formula, q=1 to 20, particularly 1.0 to 1.2) Or, Phosphazenes of formula (13g): [ka] where k=1, 2 or 3, including mixtures thereof. It will be understood that this is preferably a mixture of various oligomers of this formula, since mixtures are typically commercially available. Particular preference is given to the use of phosphorus-containing flame retardants of one of formula (12) or formula (13g) as defined above.

[0117] A highly preferred composition is A) at least 70% by weight of an aromatic polycarbonate, where the aromatic polycarbonate is a bisphenol A homopolycarbonate; B) 5% by weight to 20% by weight of a polyalkyl(meth)acrylate; C) 2% by weight to 8% by weight of a phosphorus-containing flame retardant (wherein the phosphorus-containing flame retardant is An organophosphate ester of formula (12): [ka] (In the formula, q=1 to 20, particularly 1.0 to 1.2) and / or A phosphazene of formula (13g), [ka] (wherein k=1, 2 or 3) and mixtures thereof) D) 0.3% by weight to 2% by weight of a fluorine-containing drip prevention agent; E) 0% to 5% by weight of at least one additional additive selected from the group consisting of one or more release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, optical brighteners, hydrolysis stabilizers, transesterification stabilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. The ratio of the amount of polyalkyl(meth)acrylate in % by weight to the amount of phosphorus-containing flame retardant in % by weight is 5 or less, in particular less than 5.

[0118] The polymer composition according to the invention, which contains the components A, B, C, D and, optionally, E in admixture, can be prepared using a powder premix. It is also possible to use a plurality of pellet materials or premixes of pellet materials and powders with the additives according to the invention. It is also possible to use a premix formed from a solution of the component mixture in a suitable solvent, optionally followed by homogenization of the solution and subsequent removal of the solvent. In particular, the additives, designated as component E of the composition according to the invention, can also be introduced by known methods or in the form of a masterbatch. The use of masterbatches is particularly suitable for the introduction of the additives and further components, and masterbatches based on the respective polymer matrix are particularly used.

[0119] The composition according to the invention can be extruded, for example. After extrusion, the extrudate can be cooled and crushed. The premix can also be mixed together in the melt in the plasticizing unit of an injection molding machine. In this case, the melt is directly converted into a molded article in a subsequent step.

[0120] The compositions according to the invention are preferably used to manufacture moldings for components of the EE sector, in particular for high voltage switches, inverters, relays, electronic connectors, electrical connectors, circuit breakers, components for photovoltaic applications, electric motors, heat sinks, chargers and charging plugs for electric vehicles, electrical junction boxes, smart meter housings, miniature circuit breakers, busbars. The invention therefore also provides moldings which are part of the corresponding components. A "part" may be an individual element of a complex product or it may be the whole element.

[0121] Moldings in the sense of the present invention are also insulating layers made of the compositions according to the present invention. Such layers can be provided, for example, on inverters as layers that protect against external influences. For inverters, standard insulating materials have a CTI of 600V. The compositions according to the present invention can also be used as insulating layers for other electrical components, for example transistors. The insulating layer provides a reliable separation, for example, between the transistor and the metal heat sink.

[0122] The components are preferably designed for a working voltage of at least 375 V, more preferably at least 400 V, particularly preferably at least 500 V. However, they can also be designed for a typical European domestic working voltage of 230 V±23 V, although a reduction in the distance of the conductors can be achieved here. The moldings are preferably used such that the moldings themselves have a comparative tracking index, specified as above, of at least 375 V, more preferably at least 400 V, particularly preferably at least 500 V, especially preferably at least 600 V.

[0123] The invention therefore also provides moldings which consist exclusively of the composition according to the invention or which contain areas made of the composition according to the invention, as well as corresponding parts which contain elements or moldings which consist exclusively of the composition according to the invention or which contain areas made exclusively of the composition according to the invention.

[0124] The high comparative tracking index of the polycarbonate composition according to the invention makes it possible to use this polycarbonate material to reduce the distance between two conductors in a component than was previously possible using polycarbonate.

[0125] Accordingly, the present invention also provides an EE component, comprising a first conductor and a second conductor at a first distance d1 and a second distance d2 relative to each other, These electrical conductors are connected via an element made of a thermoplastic composition according to the invention, which is in direct contact with the first electrical conductor and the second electrical conductor, distance d1 is the shortest distance between the first and second electrical conductors along a surface of the element made of the thermoplastic composition; Distance d2 is the shortest distance between the first conductor and the second conductor through air; d2 is selected so as to prevent sparks through the air at each operating voltage; d1 is as follows, at the working voltage U listed below: d1i(0V≦U≦250V):1.8mm~<2.5mm d1ii(250V <U≦500V)=3.6mm~<5.0mm d1iii(500V <U≦1000V)=7.1mm~<10.0mm。 Such small distances are only achievable with materials that have a CTI of at least 400V.

[0126] "Element made of a thermoplastic composition according to the invention" means in this specification that an element is present which consists only of a thermoplastic composition according to the invention, i.e. the composition has not been mixed with additional components.

[0127] Even shorter distances are achievable if the CTI of the material is 600V, for example, in which case d1 is preferably as follows at the recited working voltages: d1i(0V≦U≦250V):1.3mm~<2.5mm, d1ii(250V < U ≤ 500V) = 2.5mm to < 5.0mm, d1iii(500V < U ≤ 1000V) = 5.0mm to < 10.0mm.

[0128] When using a material with a CTI of 600V, d1 is particularly preferably as follows at the listed operating voltages: d1i(0V ≤ U ≤ 250V): 1.3mm to < 1.8mm, d1ii(250V < U ≤ 500V) = 2.5mm to < 3.6mm, d1iii(500V < U ≤ 1000V) = 5.0mm to < 7.1mm. These distances cannot be achieved even when using a material with a CTI of 400V or 450V and require a CTI of 600V.

[0129] It is known that the degree of contamination affects conductivity. The distances d1 and d2 mentioned are useful, for example, in parts that can comply with the IP6K9K protection degree according to ISO 20653:2013-02 due to structural shielding.

[0130] Suitable thermoplastic compositions according to the present invention belong to insulation material group II (400V ≤ CTI < 600V) when classified according to DIN EN 60664-1, and particularly suitable compositions belong to insulation material group I (600V ≤ CTI).

[0131] Various embodiments of the present invention are described below:

[0132] 1. A thermoplastic composition, A) at least 70% by weight of an aromatic polycarbonate, and B) 4% to 25% by weight of a polyalkyl (meth)acrylate, and C) 1.5% to 10% by weight of a phosphorus-containing flame retardant, and D) 0.3% to 2% by weight of a fluorine-containing anti-dripping agent, and E) optionally, one or more additional additives, preferably at least one additional additive selected from the group consisting of one or more mold release agents, heat stabilizers, antioxidants, dyes, pigments, UV absorbers, IR absorbers, impact modifiers, fillers, optical brighteners, hydrolysis stabilizers, ester interchange stabilizers, flame retardants different from component C, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. the ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is less than 10; Thermoplastic composition.

[0133] 2. The thermoplastic composition according to embodiment 1, wherein the ratio of the amount of polyalkyl(meth)acrylate in wt.% to the amount of phosphorus-containing flame retardant in wt.% is 5 or less.

[0134] 3. The thermoplastic composition according to embodiment 1 or 2, wherein the phosphorus-containing flame retardant is an organophosphate ester, a phosphazene, or a mixture thereof.

[0135] 4. The phosphorus-containing flame retardant is an organic phosphate ester of the formula (11), [ka] During the ceremony, R 1 , R 2 , R 3 , and R 4 are each independently a linear or branched C1-C8 alkyl radical and / or an optionally linear or branched alkyl substituted C5-C6 cycloalkyl radical, a C6-C 10 -aryl radical, or C7-C 12 -aralkyl radical, n is independently 0 or 1; q is independently 0, 1, 2, 3, or 4; N is a number between 1 and 30, R 5 and R 6are independently a linear or branched C1-C4-alkyl radical, preferably a methyl radical, Y is a linear or branched C1-C7 alkylidene, linear or branched C1-C7 alkylene radical, C5-C 12 -Cycloalkylene radical, C5-C 12 - a cycloalkylidene radical, -O-, -S-, -SO-, SO2, or -CO-; A thermoplastic composition according to any of the previous embodiments.

[0136] 5. As a phosphorus-containing flame retardant, there is a phosphazene of the formula (13g): [ka] wherein k=1, 2, or 3, including mixtures thereof; A thermoplastic composition according to any of the previous embodiments.

[0137] 6. A thermoplastic composition according to any of the previous embodiments, wherein the composition contains 5% to 20% by weight of a polyalkyl(meth)acrylate.

[0138] 7. A thermoplastic composition according to any of the previous embodiments, wherein the composition contains 0.3 wt.% to 1.0 wt.% of a mold release agent.

[0139] 8. A thermoplastic composition according to any of the previous embodiments, wherein the composition contains a total of 0.02 wt.% to 0.15 wt.% of a heat stabilizer and / or antioxidant.

[0140] 9. The thermoplastic composition according to any of the previous embodiments, wherein the amount of phosphorus-containing flame retardant is from 2% to 8% by weight.

[0141] 10. A thermoplastic composition according to any of the previous embodiments, wherein component B has a weight average molecular weight of 80,000 g / mol to 300,000 g / mol, as determined by gel permeation chromatography in tetrahydrofuran using PMMA calibration.

[0142] 11. A thermoplastic composition according to any of the previous embodiments, wherein component B has a weight average molecular weight of 100,000 g / mol to 200,000 g / mol, as determined by gel permeation chromatography in tetrahydrofuran using PMMA calibration.

[0143] 12. Component B comprises 52.0% to 100.0% by weight of repeating alkyl methacrylate units, in particular methyl methacrylate, having 1 to 20, preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4 carbon atoms in the alkyl radical; b) 0% to 40.0% by weight of repeating alkyl acrylate units, in particular methyl acrylate, having 1 to 20, preferably 1 to 12, more preferably 1 to 8, and particularly preferably up to 4 carbon atoms in the alkyl radical; c) 0% to 8.0% by weight of repeating styrene units of general formula (VII); having [ka] In the formula, R 1 ~R 5 are independently hydrogen, halogen, C1-C6-alkyl or C2-C6-alkenyl; R 6 is hydrogen or C1-C6-alkyl, the weight percent amounts of a, b, and c add up to 100 weight %, which is the total weight of the polyalkyl (meth)acrylate; A thermoplastic composition according to any of the previous embodiments.

[0144] 13. The following: A) at least 70% by weight of an aromatic polycarbonate; B) 5% by weight to 20% by weight of a polyalkyl(meth)acrylate; C) 2% by weight to 8% by weight of a phosphorus-containing flame retardant; D) 0.3% by weight to 2% by weight of a fluorine-containing drip prevention agent; E) 0% to 5% by weight of one or more additional additives selected from the group consisting of mold release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percent figures are based on the total composition. The thermoplastic composition according to any of the previous embodiments, wherein the ratio of the amount of polyalkyl(meth)acrylate in wt% to the amount of phosphorus-containing flame retardant in wt% is 5 or less.

[0145] 14. The polyalkyl(meth)acrylate has a number average molecular weight of 80,000 g / mol to 300,000 g / mol, determined in THF using PMMA calibration; a) 52.0% to 100.0% by weight of repeating methyl methacrylate units; b) 0% to 40.0% by weight of repeating methyl acrylate units; c) 0% to 8.0% by weight of repeating styrene units of general formula (VII); having [ka] In the formula, R 1 ~R 5 are independently hydrogen, halogen, C1-C6-alkyl or C2-C6-alkenyl; R 6 is hydrogen or C1-C6-alkyl, and the weight percent amounts of a, b, and c add up to 100 weight%, where 100 weight% is the total weight of the polyalkyl(meth)acrylate.

[0146] 15. A thermoplastic composition according to any of the previous embodiments, wherein the additional additives are selected from the group consisting of one or more mold release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, optical brighteners, hydrolysis stabilizers, transesterification stabilizers, laser marking additives, and mixtures thereof.

[0147] 16. A molding consisting solely of a thermoplastic composition according to any of the previous embodiments or comprising a region made of a thermoplastic composition according to any of the previous embodiments.

[0148] 17. The molding according to embodiment 16, wherein the molding is part of a high voltage switch, an inverter, a relay, an electronic connector, an electrical connector, a circuit breaker, a photovoltaic power system, an electric motor, a heat sink, an electric vehicle charger, an electrical junction box, a smart meter housing, a miniature circuit breaker, or a busbar.

[0149] 18. The molding according to embodiment 16 or embodiment 17, wherein the molding is part of an EE part designed for a working voltage of at least 375 V.

[0150] 19. The molding according to any of embodiments 16-18, wherein the molding is part of an EE part designed for a working voltage of at least 400 V.

[0151] 20. The molding according to any of embodiments 16-19, wherein the molding is part of an EE part designed for a working voltage of at least 500 V.

[0152] 21. The molding according to any of embodiments 16-20, wherein the molding is part of an EE part designed for a working voltage of at least 600 V.

[0153] twenty two. 1. An EE component comprising a first conductor and a second conductor at a first distance d1 and a second distance d2 relative to each other, These conductors are connected via an element made of a thermoplastic composition according to any one of the first to fifteenth embodiments, the element being in direct contact with the first and second conductors; distance d1 is the shortest distance between the first and second electrical conductors along a surface of the element made of the thermoplastic composition; Distance d2 is the shortest distance between the first conductor and the second conductor through air; d2 is selected so as to prevent sparks through the air at each operating voltage; d1 is the value at the working voltage U listed below: d1i(0V≦U≦250V):1.3mm~<2.5mm d1ii(250V <U≦500V)=2.5mm~<5.0mm d1iii(500V <U≦1000V)=5.0mm~<10.0mm That is, EE parts.

[0154] 23.d1 at the working voltage U listed below: d1i(0V≦U≦250V):1.3mm~<1.8mm, d1ii(250V <U≦500V)=2.5mm~<3.6mm、 d1iii(500V <U≦1000V)=5.0mm~<7.1mm、 The EE part according to embodiment 22.

[0155] 24. An EE part according to any of embodiments 22 and 23, wherein d2 is 1.2 mm or greater.

[0156] 25. An EE part according to any of embodiments 22 to 24, having a degree of protection IP6K9K according to ISO 20653:2013-02.

[0157] 26. An EE component according to any of embodiments 22 to 25, which is designed for a working voltage of at least 400 V, preferably at least 500 V, particularly preferably at least 600 V.

[0158] 27. An EE part according to any of embodiments 22-26, in which the element made of the thermoplastic composition according to any of embodiments 1-15 is a molding according to any of embodiments 16-21.

[0159] 28. Use of a combination of 4% to 25% by weight of a polyalkyl(meth)acrylate, 0.3% to 2% by weight of a fluorine-containing anti-drip agent, and 1.5% to 10% by weight, preferably 2% to 8% by weight of a phosphorus-containing flame retardant in a thermoplastic polycarbonate-based composition to achieve a CTI of 600V at 2mm and a UL94 classification of V0, the weight percentage figures being based on the entire resulting composition.

[0160] 29. The thermoplastic composition according to any of the previous embodiments 1 to 15, the molded product according to any of the previous embodiments 16 to 21, the EE part according to any of the previous embodiments 22 to 27, or the use according to embodiment 28, wherein the aromatic polycarbonate is a bisphenol A-based homopolycarbonate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLES

[0161] 1. Description of raw materials and testing methods a) Raw materials Component A-1: ​​A linear polycarbonate based on bisphenol A, which has a melt volume flow rate of 12 cm 3 / (10 min) (according to ISO 1133:2012-03 at a test temperature of 300° C. and a load of 1.2 kg) and contains 250 ppm (=0.025% by weight, based on the total weight of component A) of triphenylphosphine heat stabilizer as component E-3.

[0162] Component A-2: A linear polycarbonate based on bisphenol A, which has a melt volume flow rate of 6 cm 3 / (10 min) (in accordance with ISO 1133:2012-03 at a test temperature of 300°C and a load of 1.2 kg).

[0163] Component B-1: Glass transition temperature of 117° C., measured according to ISO 11357-1 / -2, a proportion of methyl acrylate of 1% by weight, M determined by gel permeation chromatography in tetrahydrofuran with PMMA calibration w147000 g / mol and available from Roehm GmbH under the trade name Plexiglas™ 8H.

[0164] Component C-1: Organic phosphate ester of formula (12), q=1.0 to 1.2. Bisphenol A bis(diphenyl phosphate), manufactured by ADEKA Corporation.

[0165] Component C-2: Rabitle FP110 phenoxycyclophosphazene, manufactured by Fushimi Pharmaceutical Co., Ltd. (Japan), formula (13g), trimer (k=1) ratio is approximately 68 mol%.

[0166] Component D-1: ADS5000 SAN encapsulated polytetrafluoroethylene (approximately 50% by weight PTFE (a fluorine-containing anti-drip agent) and approximately 50% by weight SAN), manufactured by Chemical Innovation Co., Ltd. Thailand.

[0167] Component E-1: Mold release agent. Pentaerythritol tetrastearate, commercially available as Loxiol VPG 861 from Emery Oleochemicals Group.

[0168] Component E-2: Mixture of heat stabilizers and antioxidants. Irganox® B900 from BASF (a 4:1 weight ratio mixture of Irgafos® 168 (tris(2,4-di-tert-butylphenyl) phosphite) and Irganox® 1076 (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)).

[0169] b) Test method Comparative Tracking Index (CTI): For the purpose of determining the comparative tracking index, the compositions described herein were tested according to the rapid test method according to IEC 60112:2009. For this purpose, a 0.1% ammonium chloride test solution (395 ohm·cm resistivity) was dropped onto the surface of a test specimen with dimensions 60 mm×40 mm×4 mm, between two adjacent electrodes spaced 4 mm apart, with a time interval of 30 seconds. A test voltage was applied between the electrodes and varied over the course of the test. The first test specimen was tested with a starting voltage of 300 V or 350 V. A maximum of 50 drops in total per voltage (one drop every 30 seconds) were dropped as long as no tracking current of more than 0.5 A occurred for 2 seconds or the specimen did not burn. After 50 drops, the voltage was increased by 50 V and a new specimen was tested at this increased voltage according to the procedure described above. This process continued until either 600 V was reached or a tracking current or burning occurred. If one of the above effects occurred already in less than 50 drops, the voltage was reduced by 25V and a new specimen was tested at this reduced voltage. The voltage was reduced until the test completed 50 drops without causing tracking current or burning. Thus, this procedure was used to identify the maximum possible voltage at which the composition could withstand 50 drops of test solution without causing tracking current. Finally, for confirmation, four more specimens were tested with 50 drops each at the maximum voltage specified. This confirmed value was reported as the CTI in the examples. The 100 drop value was not specified because it was a "rapid test method based on" the specified standard.

[0170] PTI (Guaranteed Tracking Index): PTI is tested according to IEC 60112:2009 with the following modifications. For this purpose, a 0.1% ammonium chloride test solution (395 ohm cm resistivity) is dropped onto the surface of a specimen with dimensions 60 mm x 40 mm x 4 mm, between two adjacent electrodes spaced 4 mm apart, with a time interval of 30 seconds. In contrast to the CTI test, in the PTI test a constant test voltage is applied between the electrodes, and a total of five specimens are tested at each voltage. A maximum of 50 drops in total (one drop every 30 seconds) are dropped per specimen, as long as no tracking current of more than 0.5 A occurs for 2 seconds or the specimen does not burn.

[0171] Flame Retardant: The flame retardancy of the polycarbonate compositions was tested at thicknesses of 1.5 mm and 2 mm according to Underwriters Laboratories method UL 94 V. The tested test bars were previously conditioned for 7 days at 20% relative humidity and 70° C. ambient temperature.

[0172] Depending on the behavior of the specimens, they are assigned to various flammability classes, including time to flame extinguish, drip resistance, or whether the material produces flammable drips. Hereinafter, the identified classes will be designated V0, V1, and V2. These are established based on a total of five specimens tested.

[0173] V0: A specimen that, when placed at 180° (perpendicular) with its long axis to the flame, has an average afterflame time of 10 seconds or less after the flame is removed and does not produce any drips of plastic particles that ignite cotton wool placed under the specimen. The total afterflame time with two applications of the flame to each of the five specimens is a maximum of 50 seconds.

[0174] V1: In contrast to V0, the average maximum afterflame time in this case is less than 30 seconds, but again no ignition of dripping particles or cotton wool is permitted. The total afterflame time with two flame applications to each of the five specimens is less than 250 seconds.

[0175] V2: In contrast to V0 and V1, this classification results in the formation of drips of plastic particles which ignite the cotton wool. The individual afterflame times are less than 30 seconds and the total afterflame time of two flame applications to each of the five specimens is less than 250 seconds.

[0176] f.: If the afterflame time exceeds the above, the test does not assign a flame retardant rating.

[0177] Heat Distortion Resistance: The heat distortion resistance of the compositions was determined on test specimens with dimensions 80 mm x 10 mm x 4 mm based on the Vicat softening temperature (Method B, test force 50 N, heating rate 50 K / h) according to ISO 306:2014-3.

[0178] 2. Preparation of Test Specimens The compositions were prepared in a Coperion 25 mm twin screw extruder with a throughput of 20 kg / h. The temperature of the polymer melt in the extruder was 260° C.-280° C. and the average screw speed was 225 rpm.

[0179] Test specimens with dimensions 60mm x 40mm x 4mm were prepared from the molding compound using standard injection molding techniques with a melt temperature of 280°C and a mold temperature of 80°C.

[0180] 3.Results In the table below, "nt." means "not tested" and "f." means "failed." * " means "obtained from UL Yellow Card."

[0181] [Table 1]

[0182] Pure bisphenol A-based polycarbonate without release agent has a CTI (V-1) of 250 V and an inherent flame retardancy V2 measured according to UL94. As shown by the results in Table 1, but also in Table 2, the addition of 5% by weight of polyalkyl (meth)acrylate already significantly improves the comparative tracking index of the polycarbonate, but also significantly worsens the flame retardancy (see V-1 and V-6). Although V-3 and V-4 achieve a result of 600 V in the CTI rapid test, the robustness of these compositions is significantly worse than the compositions with the additional PMMA. This is especially evident in the PTI measurement, which tests a larger number of specimens at a defined voltage (working voltage) and shows weaknesses in terms of voltage range. In this case, the compositions without PMMA tend to fail especially at 300 V and 350 V, but are robust at the higher voltage of 600 V. The comparative PMMA-containing composition (E-14) also exhibits this robustness at low voltages of 300 V and 350 V (see Table 2).

[0183] The addition of mold release agents and heat stabilizers has a negative effect on the Vicat softening temperature and flammability in polycarbonate compositions, and the CTI improves only slightly (see V-2). The flame retardancy of the composition is also not improved by the addition of polyalkyl (meth)acrylates, but rather worsens (V-6), which in this case also results in the need to add additional flame retardant additives. As V-5 shows, the addition of phosphorus-containing flame retardants alone is not enough to achieve V0, and the CTI drops significantly. Only the combination of anti-drip agents with phosphorus-containing flame retardants and polyalkyl (meth)acrylates can finally achieve the desired property profile consisting of high CTI, good flame retardancy, robustness of the CTI, and still a sufficiently high Vicat temperature (see E-7 to E-9). This is also seen with phosphazenes as flame retardants (E-10), in addition to BDP.

[0184] [Table 2]

[0185] Furthermore, higher amounts of polyalkyl(meth)acrylate have a positive effect on the CTI, and with increasing PMMA content the flammability performance deteriorates significantly. With 10 and 20% by weight of polyalkyl(meth)acrylate a CTI of 600V is achieved, but to achieve a V0 classification according to UL 94 V the addition of at least 2% by weight of flame retardant in combination with an anti-drip agent is required (E-12). As E-16 shows, this can also be achieved with phosphazene instead of BDP as flame retardant. The addition of release agents and heat stabilizers (see E-13 and E-15) only negatively affects the results in terms of the Vicat softening temperature, as already mentioned above. From 20% by weight of polyalkyl(meth)acrylate a V0 classification can only be achieved with a relatively high amount of flame retardant (see V-18 vs. V-20 and V-21). Increasing the amount of anti-drip agent when the polyalkyl(meth)acrylate content is high does not provide any further benefit in terms of flame retardancy (V-19). As the results in Tables 1 and 2 show, the ratio of polyalkyl(meth)acrylate to phosphorus-containing flame retardant is preferably at most 5. A smaller ratio, and therefore a higher amount of flame retardant, does not cause problems in terms of CTI, but at the same time the Vicat temperature drops significantly.

Claims

1. 1. A thermoplastic composition comprising: A) at least 70% by weight of an aromatic polycarbonate; B) 4% to 25% by weight of a polyalkyl(meth)acrylate; C) 1.5% to 10% by weight of a phosphorus-containing flame retardant; D) 0.3% to 2% by weight of a fluorine-containing anti-drip agent; E) optionally, at least one additional additive selected from the group consisting of one or more mold release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet light absorbers, infrared light absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, ester interchange stabilizers, compatibilizers, laser marking additives, and mixtures thereof; It consists of: The weight percentages are based on the total composition; the ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is less than 10; Thermoplastic composition.

2. 10. The thermoplastic composition of claim 1, wherein the ratio of the amount of polyalkyl (meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is 5 or less.

3. 3. The thermoplastic composition of claim 1 or 2, wherein the phosphorus-containing flame retardant is an organophosphate ester, a phosphazene, or a mixture thereof.

4. As phosphorus-containing flame retardants, there are organic phosphate esters of formula (11): 【Chemistry 1】 During the ceremony, R １ , R ２ , R ３ , and R ４ are each independently a straight or branched chain C １ ~C ８ - alkyl radicals and / or optionally linear or branched alkyl substituted C ５ ~C ６ -cycloalkyl radical, C ６ ~C １０ -aryl radical, or C ７ ~C １２ - an aralkyl radical, n is independently 0 or 1; q is independently 0, 1, 2, 3, or 4; N is a number from 1 to 30, R ５ and R ６ are independently linear or branched chain C １ ~C ４ is an alkyl radical, preferably a methyl radical, Y is a linear or branched chain C １ ~C ７ -Alkylidene, linear or branched chain C １ ~C ７ - alkylene radical, C ５ ~C １２ -cycloalkylene radical, C ５ ~C １２ -Cycloalkylidene radical, -O-, -S-, -SO-, SO ２ or -CO-; The thermoplastic composition according to any one of claims 1 to 3.

5. As phosphorus-containing flame retardants there are phosphazenes of formula (13g): 【Chemistry 2】 wherein k=1, 2, or 3, including mixtures thereof; The thermoplastic composition according to any one of claims 1 to 4.

6. The thermoplastic composition according to any one of claims 1 to 5, wherein the composition contains from 5% to 20% by weight of polyalkyl(meth)acrylate.

7. The thermoplastic composition according to any one of claims 1 to 6, wherein the composition contains from 0.3 wt% to 1.0 wt% of a mold release agent.

8. The thermoplastic composition according to any one of claims 1 to 7, wherein the composition contains a total of 0.02 to 0.15 wt% of heat stabilizers and / or antioxidants.

9. The thermoplastic composition according to any one of claims 1 to 8, wherein the amount of phosphorus-containing flame retardant is from 2% to 8% by weight.

10. below: A) at least 70% by weight of an aromatic polycarbonate; B) 5% to 20% by weight of a polyalkyl(meth)acrylate; C) 2% to 8% by weight of a phosphorus-containing flame retardant; D) 0.3% to 2% by weight of a fluorine-containing anti-drip agent; E) 0% to 5% by weight of additional additives selected from the group consisting of one or more mold release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet absorbers, infrared absorbers, optical brighteners, hydrolysis stabilizers, laser marking additives, and mixtures thereof; It consists of: The weight percentages are based on the total composition; the ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is less than or equal to 5; The thermoplastic composition according to any one of claims 1 to 9.

11. said polyalkyl(meth)acrylate having a number average molecular weight of 80,000 g / mol to 300,000 g / mol, determined in THF using PMMA calibration; a) 52.0% to 100.0% by weight of repeating methyl methacrylate units; b) 0% to 40.0% by weight of repeating methyl acrylate units; c) 0% to 8.0% by weight of repeating styrene units of general formula (VII); having 【Chemistry 3】 In the formula, R １ ~R ５ are independently hydrogen, halogen, C １ ~C ６ -Alkyl or C ２ ~C ６ -alkenyl, R ６ is hydrogen or C １ ~C ６ -alkyl, and the weight percent amounts of a, b and c add up to 100 weight %, where 100 weight % is the total weight of the polyalkyl (meth)acrylate.

12. below: A) at least 70% by weight of an aromatic polycarbonate; B) 4% to 25% by weight of a polyalkyl(meth)acrylate; C) 1.5% to 10% by weight of a phosphorus-containing flame retardant; D) 0.3% to 2% by weight of a fluorine-containing anti-drip agent; E) optionally, at least one additional additive selected from the group consisting of one or more mold release agents, heat stabilizers, antioxidants, dyes, pigments, ultraviolet light absorbers, infrared light absorbers, impact modifiers, optical brighteners, hydrolysis stabilizers, ester interchange stabilizers, compatibilizers, laser marking additives, and mixtures thereof; A molded article consisting of a thermoplastic composition consisting of only a thermoplastic composition or including a region made of the thermoplastic composition, The weight percentages are based on the total composition; the ratio of the amount of polyalkyl(meth)acrylate in weight percent to the amount of phosphorus-containing flame retardant in weight percent is less than 10; Molded object.

13. 13. The molding according to claim 12, wherein the molding is part of an EE part consisting of the group of high voltage switches, inverters, relays, electronic connectors, electrical connectors, circuit breakers, photovoltaic power systems, electric motors, heat sinks, electric vehicle chargers or charging plugs, electrical junction boxes, smart meter housings, miniature circuit breakers, busbars, the EE part preferably having a degree of protection IP6K9K according to ISO 20653:2013-02.

14. 1. Use of a combination of 4 wt% to 25 wt% of a polyalkyl (meth)acrylate, 0.3 wt% to 2 wt% of a fluorine-containing anti-drip agent, and 1.5 wt% to 10 wt% of a phosphorus-containing flame retardant in a thermoplastic composition containing at least 70 wt% of an aromatic polycarbonate to achieve a CTI of 600V at 2 mm and a UL94 classification of V0, said weight percentage figures being based on the entire resulting composition.

15. a first conductor and a second conductor at a first distance d1 and a second distance d2 from each other; An EE part comprising: They are connected via the thermoplastic composition according to any one of claims 1 to 11, the thermoplastic composition being in direct contact with the first electrical conductor and the second electrical conductor; the distance d1 is the shortest distance between the first electrical conductor and the second electrical conductor along a surface of the thermoplastic composition; the distance d2 is the shortest distance between the first conductor and the second conductor through air, d2 is selected to prevent sparks through the air at each operating voltage; d1 is, at the working voltage U listed below, d1i (0V≦U≦250V): 1.3mm~<2.5mm d1i (250V<U≦500V)=2.5mm~<5.0mm d1iii (500V<U≦1000V)=5.0mm~<10.0mm That is, EE parts.

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