MX2008007699A - Polycarbonate moulding compositions - Google Patents

Abstract

The invention relates to polycarbonate compositions containing sheet silicates which have been modified with organic polymers by means of a solvent-free melt process and also a process for producing them. The resulting moulding compositions have improved thermal stability and a low maximum decomposition rate in the case of fire.

Description

COMPOSITIONS OF POLYCARBONATE MOLDING DESCRIPTION OF THE INVENTION The invention relates to polycarbonate compositions having an improved thermal stability and a low maximum decomposition rate in the case of fire. The compositions of PC / ABS (polycarbonate / acrylonitrile / butadiene / styrene) that have an increased thermal stability are reported by Wang et al. The alkylammonium montmorillonites, which have been distributed preferably in the ABS phase, are used in this document (Wang, S., Hu, Y., Wang, Z., Yong, T., Chen, Z., & Fan, W., Synthesis and Characterization of polycarbonate / ABS / montmorillonite nanocomposites, Polymer Degradation and Stability, 80, No. 1, (2003) 157-61). It is known from Stretz et al. And Yoon et al. That conventional alkylammonium modifiers, such as bait-bis (2-hydroxyethyl) methylammonium fat and impurities contained therein (for example iron ions) decompose the polycarbonate matrix and, for example, increase the rate of heat release (determined by means of cone calorimetry) (Stretz, HA, Koo, JH, Dimas, VM, &Zhang , REF: 193841 Y., Fíame retardant properties of polycarbonate / montmorillonite clay nanocomposite blends, Polymer Preprints, 42, No. 2, (2001) 50; Yoon, PJ, Hunter, DL &Paul, DR, Polycarbonate nanocomposites: Part 2 Degradation and color formation, Polymer, 44, No. 18, (2003) 5341-54). The synergistic effect of alkylammonium montmorillonites for fire resistance properties is known from Wang et al. For ABS molding compositions (Wang, S., Hu, Y., Zong, R., Tang, Y. , Chen, Z., &Fan, W., Preparation and characterization of fíame retardan ABS / montmorillonite nanocomposite, Applied Clay Science, 25, No. 1-2, (2004) 49-55). Wang and colleagues achieve improved fire resistance properties for ABS moldings in combination with antimony oxide and decabromodiphenyl oxide. In the presence of alkylammonium montmorillonite, the rate of heat release (cone calorimeter) was reduced and a longer time was found before ignition, ie the oxygen limit index (LOI) was Higher and combustion properties of the specimens were evaluated with the V-0 classification in the UL94 V test. WO 99/43747 A1 discloses the synergistic effect for the fire resistance properties of the alkylammonium montmorillonites for PC / ABS compositions and teaches that the time to ignition of the PC / ABS compositions is prolonged by the addition of the alkylammonium montmorillonite Clayton HY. A disadvantage of montmorillonites modified with alkylammonium is the involved and expensive modification process for layered silicate. Laminated silicates modified in this way also have an adverse effect on the physical properties of polycarbonate compositions, since the basic modifiers of the lamellar silicate degrade the polymer and thus lead to a reduction in the molecular weight of the polymer and to fogging and discoloration. The process disclosed is carried out with unmodified sheet silicates. US 2005/0137287 Al discloses polycarbonate compositions which comprise sheet silicates and are modified with a block copolymer of 2- (dimethylamino) -styrene / ethyl methacrylate with a quaternary ammonium main group. The resulting polycarbonate molding compositions are transparent and show no discoloration. WO 99/07790 Al and Fischer et al. (Fischer, HR, Gielgens, LH, &Koster, TPM, Nanocomposites from polymers and layered minerals Mat. Res. Soc. Proc, volume 519, 1998, 117-123) give to know nanocomposite materials which comprise block or graft copolymers and a layered silicate, the copolymer carries a structural unit which is compatible with the layered silicate and an additional unit which is compatible with the polymer matrix. The described composite materials are prepared in a first step by mixing the layered silicate with the copolymer at an elevated temperature and in a subsequent step by means of extrusion in the desired polymer matrix. Alternatively, a solvent can also be added. In this way, an improvement in the tensile strength of the modified material is achieved. The PC / ABS compositions and modification processes for the sheet silicates are not described via the aqueous route. The disadvantages of the modification by means of block copolymers are the involved and expensive modification processes and the need for an additional process step for the synthesis of block copolymers. The objective on which the invention is based is to provide polycarbonate molding compositions having a high thermal stability, a low maximum decomposition rate after ignition and a low density of combustion gas. Surprisingly, it has been discovered that by employing sheet silicates which are modified with organic polymers by means of a solvent-free melting process, the thermal stability of the polycarbonate-containing molding compositions is increased and the maximum decomposition rate in the case of fire is reduced. The compositions according to the invention are distinguished because long-chain quaternary ammonium salts are not used as stabilizers and a degradation of the molecular weight of the polycarbonate is avoided, which also results in a high level of mechanical properties of the compositions of molding according to the invention. Therefore, the present invention provides thermoplastic molding compositions or compositions comprising A) an aromatic polycarbonate and / or polyester carbonate, B) optionally an impact modifier, C) optionally a homo- and / or thermoplastic copolymer, D) a laminar compound which is modified with organic polymers by means of a solvent-free melting process and E) optionally a phosphorus compound. The compositions according to the invention preferably comprise A) from 30 to 99.9 parts by weight, preferably from 40 to 90 parts by weight of aromatic polycarbonate and / or polyester carbonate, B) from 0 to 60 parts by weight, preferably 1 to 40 parts by weight, particularly preferably from 2 to 15 parts by weight of a rubber modified graft polymer, C) from 0 to 30 parts by weight, preferably from 0 to 25 parts by weight of homo- and / or copolymer, D) from 0.1 to 40 parts by weight, preferably from 1 to 25 parts by weight, particularly preferably from 2 to 10 parts by weight of a laminar compound which is modified with organic polymers by means of a melting process solvent-free and E) from 0 to 30 parts by weight, preferably from 1 to 20 parts by weight, in particular from 4 to 15 parts by weight of a phosphorus compound. All the parts by weight data in the present application are standardized in such a way that the sum of the parts by weight of the components A + B + C + D + E in the composition is 100. The components of the polycarbonate composition are which are suitable according to the invention are explained by way of example below.

Component A The aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature ( the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396, for the preparation of aromatic polyester carbonates see for example DE-A 3 077 934). The preparation of aromatic polycarbonates is carried out, for example, by the reaction of diphenols with carbonic acid halides, preferably phosgene and / or aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by means of the process of interphase in the phase, optionally using chain terminators, for example monophenols, and optionally using branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols. A preparation via a molten polymerization process is also possible by means of the reaction of diphenols with, for example, diphenyl carbonate. The diphenols for the preparation of aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I wherein A is an individual bond, alkylene of 1 to 5 carbon atoms, alkylidene of 2 to 5 carbon atoms, cycloalkylidene of 5 to 6 carbon atoms, -O-, -SO-, -CO-, -S- , -S02-, arylene of 6 to 12 carbon atoms, in which additional aromatic rings optionally containing heteroatoms or a radical of the formula (II) or (III) can be fused in each case it is alkyl of 1 to 12 carbon atoms, preferably methyl, or halogen, preferably chlorine and / or bromine, is in each case, independently of each other, 0, 1 or 2, is 1 or 0 and R5 and R6 is they can individually select for each X1 and independently indicate hydrogen or alkyl of 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, X1 indicates carbon and m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that in at least one atom X1, R5 and Rd are simultaneously alkyl. Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyl) -alkanes of 1 to 5 carbon atoms, bis- (hydroxyphenyl) -cycloalkanes of 5 to 6 carbon atoms, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulphoxides, bis- (hydroxyphenyl) ketones, bis- (hydroxyphenyl) sulfones, a-bis- (hydroxyphenyl) -diisopropyl-benzenes and brominated derivatives in the nucleus and / or chlorinated in the core of them. Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylsulphone and di- and tetrabrominated or chlorinated derivatives thereof, such as, for example 2, 2- bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3, 5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis- (3, 5-dibromo-4-hydroxyphenyl) -propane. 2, 2-Bis- (4-hydroxyphenyl) -propane (bisphenol-A) is particularly preferred. The diphenols can be used individually or as any desired mixture. Diphenols are known from the literature or can be obtained by means of processes known from the literature. Chain terminators which are suitable for the preparation of thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol and also long-chain alkylphenols, such as 4- [2- (2,4-trimethylpentyl)] -phenol, 4- (1,3-tetramethylbutyl) -phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 atoms of carbon in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol. The amount of chain terminators to be used is generally between 0.5% mol and 10% mol, based on the sum of the moles of the particular diphenols employed. The aromatic, thermoplastic polycarbonates have weight average molecular weights (Mw, measured for example by means of an ultracentrifuge or a scattered light measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably from 24,000 to 32,000 g / mol.

The aromatic, thermoplastic polycarbonates can be branched in a known manner and in particular preferably by the incorporation of 0.05 to 2.0 mol%, based on the sum of the diphenols used, of compounds which are trifunctional or more than trifunctional, for example those who have three and more phenolic groups. Both homopolycarbonates and copolycarbonates are suitable. It is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, based on the total amount of polydiorganosiloxane diphenols having hydroxyaryloxy end groups to be used for the preparation of copolycarbonates according to the invention. invention according to component A. These are known (US Pat. No. 3 419 634) and can be prepared by means of processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxanes is described in DE-A 3 334 782. Preferred polycarbonates are, in addition to the homopolycarbonates of bisphenol A, the copolycarbonates of bisphenol A with up to 15 mol%, based on the sum of the moles of diphenols, of other diphenols mentioned as being preferred or particularly preferred, in particular 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane. The aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Mixtures of diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of 1:20 to 20: 1 are particularly preferred. A carbonic acid halide, preferably phosgene, is further used as a bifunctional acid derivative in the preparation of polyester carbonates. The possible chain terminators for the preparation of aromatic polyester carbonates are, in addition to the aforementioned monophenols, also esters of chlorocarbonic acid thereof as well as the acid chlorides of aromatic monocarboxylic acids, which can be optionally substituted by alkyl groups from 1 to 22 carbon atoms or by halogen atoms, as well as aliphatic monocarboxylic acid chlorides of 2 to 22 carbon atoms. The amount of chain terminators is in each case from 0.1 to 10 mol%, based on the moles of diphenol in the case of phenolic chain terminators and based on the moles of dicarboxylic acid dichloride in the case of terminators of monocarboxylic acid chloride chain.

The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids. The aromatic polyester carbonates can be either linear or branched in a known manner (in this context see DE-A 2 940 024 and DE-A 3 007 934). The branching agents which can be used are, for example, carboxylic acid chlorides which are trifunctional or more than trifunctional, such as trimesic acid trichloride, cyanuric acid trichloride, 3, 3 ', 4, 4-tetrachloride, 4, 4. '-benzophenone-tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or phenols which are trifunctional or more than trifunctional, such as phloroglucinol, 6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4-6-tri- (4 -hydroxyphenyl) -heptane, 1, 3, 5-tri- (4-hydroxyphenyl) -benzene, 1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenyl-methane, 2, 2-bis [4, -bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2, -bis (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) -methane, 2,6-bis- ( 2-hydroxy-5-methyl-benzyl ) -4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2), -dihydroxyphenyl) -propane, tetra- (4- [4-hydroxyphenyl-isopropyl] -phenoxy) -methane and 1, -bis- [4'-dihydroxytriphenyl] -methyl] -benzene, in amounts of 0.01 to 1.0% in mol, based on the diphenols used. The phenolic branching agents can be initially introduced into the reaction vessel with the diphenols and the acid ride branching agents can be introduced together with the acid dirides. The content of carbonate structural units in aromatic polyester carbonates, thermoplastics can be varied as desired. Preferably, the content of carbonate groups is up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. The content of both ester and carbonate of the aromatic polyester carbonates can be present in the polycondensate in the form of blocks or in a random distribution. The relative solution viscosity (? Rei) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.35 (measured in solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene ride at 25 ° C). The aromatic polycarbonates, thermoplastics and polyester carbonates can be used by themselves or in any desired mixture.

Component B Component B comprises one or more graft polymers of Bl from 5 to 95, preferably from 30 to 90% by weight of at least one vinyl monomer in B.2 from 95 to 5, preferably from 70 to 10% by weight of one or more grafting bases having glassy state transmission temperatures of < 10 ° C, preferably < 0 ° C, particularly preferable < -20 ° C. The graft base of B.2 generally has an average particle size (d5o value) of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm. The monomers of B.l are preferably mixtures of Bll from 50 to 99 parts by weight of vinylaromatic and / or vinylaromatic products substituted in the core (such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene) and / or alkyl (C?-C8) esters of acid methacrylics (such as methyl methacrylate and ethyl methacrylate) and Bl2 from 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and / or alkyl esters (Ci-Cß) of acid ( met) acrylic, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide. The preferred monomers of B.l.l. are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate and the preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B.l.l. styrene and B.1.2 acrylonitrile. The graft bases B.2 which are suitable for the graft polymers B are, for example, diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene rubbers and optionally diene and acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate. The preferred grafting bases B.2 are diene rubbers, for example based on butadiene and isoprene or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with additional copolymerizable monomers (for example according to Bll and Bl 2), with the proviso that the transition temperature of the vitreous state of component B.2 is below < 10 ° C, preferably < 0 ° C, particularly preferable < -10 ° C. Pure polybutadiene rubber is particularly preferred. Particularly preferred polymers B are, for example, polymers of ABS (emulsion, volume and suspension ABS), as described, for example, in DE-OS 2 035 390 (= US 3 644 574) or in DE-OS 2 248 242 (= GB 1 409 275) and in Ullmanns, Enzy lopadie der Technischen Chemie, volume 19 (1980), page 280 and the following. The gel content of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene). The graft copolymers B are prepared by means of free radical polymerization, for example by means of emulsion, suspension, solution or bulk polymerization, preferably by means of emulsion or bulk polymerization. Particularly suitable graft rubbers are also ABS polymers which are prepared in the emulsion polymerization process by means of redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to U.S. Patent No. 4 937 285. Since it is known that the graft monomers are not completely grafted on the graft basis during the grafting reaction, according to the invention it is also understood that graft polymers B mean those products which are obtained by means of the (FIG. co) polymerization of the graft monomers in the presence of the graft base and are additionally obtained during the final treatment. Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of alkyl esters of acrylic acid, optionally with up to 40% by weight, based on B.2, of other polymerizable ethylenically unsaturated monomers. Preferred polymerizable acrylic acid esters include alkyl esters of 1 to 8 carbon atoms, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably haloalkyl esters of 1 to 8 carbon atoms, such as chloroethyl acrylate and mixtures of these monomers. For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having from 3 to 8 carbon atoms and unsaturated monohydric alcohols having from 3 to 12 carbon atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate and allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl cyanurate and triallyl; and polyfunctional vinyl compounds, such as di- and trivinylbenzenes; and also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes. The amount of the crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base B.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.2. The "other" ethylenically unsaturated, polymerizable, preferred monomers which may optionally serve for the preparation of the graft base B.2 in addition to the acrylic acid esters are for example acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl ethers -alkyl of 1 to 6 carbon atoms, methyl methacrylate and butadiene. Preferred acrylate rubbers such as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight. Additional suitable graft bases according to B.2 are silicone rubbers having active graft sites, such as described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539. The gel content of the graft base B.2 is determined at 25 ° C in a suitable solvent (M. Hoffmann, H. Krómer, R. Kuhn, Polymeranalytik I und II, Georg Thieme -Verlag, Stuttgart 1977). The average particle size d50 is the upper and lower diameter which in each case constitutes 50% by weight of the particles. It can be determined by means of an ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796). The graft polymers can be used in the composition according to the invention in an amount of 0.5 to 60, preferably 1 to 40 and most preferably 2 to 25 parts by weight. Mixtures of various graft polymers may also be present.

Component C Component C comprises one or more (co) polymers of thermoplastic vinyl C.l and / or polyalkylene terephthalate C.2. Suitable vinyl co-polymers C.sub.1 are polymers of at least one monomer from the group consisting of vinyl aromatics, vinyl cyanides (unsaturated nitriles), alkyl esters (Ci-Cs) of acid (meth) acrylic, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. The (co) polymers of C.1.1 from 50 to 99, preferably from 60 to 80 parts by weight of vinylaromatic products and / or vinylaromatic products substituted in the core, such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene and / or (C?-C8) alkyl esters of methacrylic acid, such as methyl methacrylate and ethyl methacrylate and C.1.2 from 1 to 50, preferably from 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or esters of alkyl (Ci-Ce) of (meth) acrylic acid, such as methyl methacrylate, n-butyl acrylate and p-butyl acrylate and / or unsaturated carboxylic acids, such as maleic acid and / or derivatives, such as anhydrides and imides, of unsaturated carboxylic acids, for example maleic anhydride and n-phenylmaleimide, are particularly suitable. The vinyl C. (co) polymers are resinous, thermoplastic and rubber-free. The copolymer of C.1.1 styrene and C.1.2 acrylonitrile is particularly preferred.

The (co) polymers according to C.l are known and can be prepared by means of free radical polymerization, in particular by means of emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have average molecular weights Mw (weight average, determined by means of light scattering or sedimentation) between 15,000 and 200,000. The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides and aliphatic, cycloaliphatic or araliphatic diols as well as mixtures of these reaction products. The polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 80% by weight, preferably at least 90% by mol , based on the diol component, of ethylene glycol radicals and / or butane-1,4-diol radicals and / or propane-1,3-diol radicals. The preferred polyalkylene terephthalate can contain, in addition to the terephthalic acid radicals, up to 20 mol%, preferably up to 10 mol%, of aromatic or cycloaliphatic dicarboxylic acid radicals having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having from 4 to 12 carbon atoms, such as, for example, italic acid radicals, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid or cyclohexanediacetic Preferred polyalkylene terephthalates can contain, in addition to the ethylene glycol radicals and butane-1,4-diol radicals, up to 20 mol%, preferably up to 10 mol% of other aliphatic diols having from 3 to 12 carbon atoms or diols cycloaliphatics having from 6 to 21 carbon atoms, for example propane-1,3-diol radicals, 2-ethylpropane-1, 3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol , cyclohexane-1,4-dimethanol, 3-ethylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2-ethylhexane-1, 3 -diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di- (β-hydroxyethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane , 2,4-dihydroxy-1,3,3-tetramethyl-cyclobutane, 2,2-bis- (4-β-hydroxyethoxyphenyl) -propane and 2,2-bis- (4-hydroxypropoxyphenyl) -propane (DE -A 2 407 674, 2 407 776 and 2 715 932). The polyalkylene terephthalates can be branched by the incorporation of relatively small amounts of 3- or 4-hydroxy alcohols or 3- or 4-basic carboxylic acids, for example according to DE-A 1 900 270 and US 3 692 744 Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. Polyalkylene terephthalates which have been prepared only from terephthalic acid and reactive derivatives thereof (for example dialkyl esters thereof) and ethylene glycol and / or butane-1, -diol and mixtures of these polyalkylene terephthalates are particularly preferred. The polyalkylene terephthalate mixtures comprise from 1 to 50% by weight, preferably from 1 to 30% by weight of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight of polybutylene terephthalate. The polyalkylene terephthalates used preferably have, in general, a limiting viscosity of 0. 4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 part by weight) at 25 ° C in an Ubbelohde ™ viscometer. The polyalkylene terephthalates can be prepared by known methods (see for example Kunststoff-Handbuch, volume VIII, page 695 and the following, Carl-Hanser-Verlag, Munich 1973). The composition according to the invention may comprise the vinyl (co) polymers or polyalkylene terephthalates in amounts of 0 to 45, preferably 1 to 30 and particularly preferably 2 to 25 parts by weight.

Component D Component D comprises laminar compounds which are modified with organic polymers by means of a solvent-free melting process. The lamellar compounds in the context according to the invention are preferably laminar compounds which are on a nanoscale, ie smaller than 100 nm, in one dimension. This dimension is called the "average thickness" of the laminar composite below. Preferably, those laminar compounds are used which have an average thickness of 0.3 to 10 nm, particularly preferably 0.5 to 10 nm, particularly preferably 0.7 to 2 nm. The layers have a diameter of 5 to 10,000 nm, preferably 10 to 2,000 nm, particularly preferably 10 to 1,000 nm. The cation exchange capacities of unmodified, anionic lamellar compounds are between 10 and 260 meq / 100 g. The counterions (ie, cations) of the unmodified sheet compounds can be calcium, magnesium, potassium, sodium or lithium ions, preferably sodium or lithium ions. These ions may originate from, for example, natural (geological) sources that comprise commercial minerals or may be introduced in a targeted manner by ion exchange, as described by Lagaly (Lagaly, G., Reaktionen der Tonminerale.

In Tonminerale und Tone, Steinkopff Verlag, Darmstadt, 1993). The dimensions of the laminar compounds (ie the diameter or the average thickness of the layers of the laminar composite) can be determined via TEM photographs and XRD measurements. The cation exchange capacity can be determined, for example, by the method of L. P. Meier and G. Kahr (Clays &Clay Minerals, 1999, 47, 3, pages 386-388). The laminar compounds which are used for this are synthetic and laminar compounds of natural origin. Preferably, the laminar compounds of the montmorillonite and hectorite mineral type and the laminar or clay mineral silicates allevardite, amesite, beidellite, fluorohectorite, fluorovermiculite, mica, halloisite, hectorite, iluta, montmorillonite, muscovite, nontronite, paligorskite, saponite, sepiolite, smectite, stevensite, talc and vermiculite, types of synthetic talc and silicates of alkali metal, maghemite, magadiite, kenyaite, makatita, silinaite, grumantite, revdita and hydrated forms thereof and the associated crystalline silicas or other laminar inorganic compounds, such as hydrotalcites, double hydroxides and hetero-polyacids. Silicate-containing laminar compounds are particularly preferably used as lamellar compounds. The silicate-containing laminar compounds which are particularly preferred are those of montmorillonite, as they are contained as the main constituent in the type bentonite and hectorite which has a cation exchange capacity between 10 and 260 meq / 100 g, a thickness average from 0.3 to 10 nm, particularly preferably from 0.5 to 10 nm, particularly preferably from 0.7 to 2 nm and a diameter of the layers from 5 to 10,000 nm, preferably from 10 to 2,000 nm, particularly preferably from 10 to 1,000 nm. According to the invention, the laminar compound is modified with at least one organic polymer by means of a solvent-free melting process. In this process (1) in a first step, the laminar compound is mixed with an organic polymer or a mixture of organic polymers, (2) in a second step, the mixture is heated to a temperature above the melting temperature of the polymer employed or of the polymer mixture employed, preferably with constant mixing, for example by means of an internal kneader or an extruder and (3) optionally in a third step, the mixture of (2) is cooled to room temperature and the laminar compound modified is obtained in the form of a solid.

Alternatively, the heated mixture which results from step (2) can be introduced as such into the polycarbonate composition according to the invention, for example by way of a side extruder. For this modification, the polyalkylene oxides are preferably used as an organic polymer. Preferably, these polyalkylene oxides have a number average molecular weight of from 106 to 20,000 g / mol, particularly preferably from 200 to 10,000 g / mol, it is also possible to use mixtures of several polyalkylene oxides. The polyethylene oxides and polyethylene oxide / propylene oxide copolymers are preferably used as polyalkylene oxides. The linear polyethylene oxides are particularly preferably used, and very particularly preferably the poly (ethylene glycol) monomethyl ether. Optionally, additional suitable oligomers or polymers can also be added further in step (1). The polycarbonate (component A) and / or polymethyl methacrylate (PMMA) is preferably used for this.

Component E Agents for fire resistance containing phosphorus (E) in the context according to the invention are preferably selected from the groups consisting of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonatamines and phosphazenes, it is also possible use mixtures of several components selected from one or more of these groups as agents for fire resistance. Other halogen-free phosphorus compounds which are not specifically mentioned herein may also be employed, by themselves or in any desired combination with other halogen-free phosphorus compounds. The preferred mono- and oligomeric phosphoric and phosphonic acid esters are phosphorus compounds of the general formula (IV) wherein R1, R2, R3 and R4 in each case independently indicate alkyl of 1 to 8 carbon atoms optionally halogenated, in each case optionally cycloalkyl of 5 to 6 carbon atoms, aryl of 6 to 20 carbon atoms or aralkyl from 7 to 12 carbon atoms optionally substituted by alkyl, preferably by alkyl of 1 to 4 carbon atoms and / or halogen, preferably chlorine or bromine, n independently indicates 0 or 1 q indicates 0 to 30 and X indicates a radical mono- or polynuclear aromatic having from 6 to 30 carbon atoms or a linear or branched aliphatic radical having from 2 to 30 carbon atoms, which can be substituted by OH and can contain up to 8 ether bonds. Preferably, R1, R2, R3 and R4 independently represent alkyl of 1 to 4 carbon atoms, phenyl, naphthyl or phenyl-alkyl of 1 to 4 carbon atoms. The aromatic groups R.sub.1, R.sub.2, R.sub.3 and R.sub.4 can be substituted in turn by halogen and / or alkyl groups, preferably chlorine, bromine and / or alkyl of 1 to 4 carbon atoms. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.

X in formula (IV) preferably denotes a mono- or polynuclear aromatic radical having from 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (I). in the formula (IV) can be independently of each other, 0 or 1 and n is preferably 1. q represents values of 0 to 30. If mixtures of several components of the formula (IV) are used, mixtures preferably having values q average in number from 0.3 to 20, particularly preferably from 0.5 to 10, in particular from 0.5 to 6. X represents particularly preferable or chlorinated or brominated derivatives thereof and in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A. The use of oligomeric phosphoric acid esters of the formula (IV) which are derived from bisphenol A is particularly advantageous, since the compositions provided with this phosphorus compound have a particularly high resistance to stress cracking and hydrolysis and a particularly low tendency towards the formation of deposits during processing by means of injection molding. In addition, a particularly high thermal deformation point can be achieved with these agents for fire resistance. The monophosphates (q = 0), oligophosphates (q = 1-30) or mixtures of mono- and oligophosphates can be used as the component E according to the invention. The monophosphorus compounds of the formula (IV) are, in particular, tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, phosphate diphenyl-cresyl, diphenyl-octyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted aryl phosphates, methylphosphonic acid dimethyl ester, methylphosphenic acid diphenyl ester, acid diethyl ester phenylphosphonic, triphenylphosphine oxide or tricresylphosphine oxide. The phosphorus compounds according to component E of formula (IV) are known (see for example EP-A 363 608, EP-A 640 655) or can be prepared by known methods in an analogous manner ( for example Ullmanns Enzyklopádie der technischen Chemie, volume 18, page 301 and those that follow, 1979; Houben-Weyl, Methoden der organischen Chemie, volume 12/1, page 43; Beilstein volume 6, page 177). The average q values can be defined when determining the composition of the phosphate mixture (molecular weight distribution) by means of a suitable method (gas chromatography (GC), high pressure liquid chromatography (CLAP) or gel permeation chromatography). (CPG) and calculate the average values for qa from the same Phosphonatamines are preferably compounds of the formula (V) A3.y-NB'y (V) in which A represents a radical of the formula (Va; : vb i R and R represent independently from each other substituted or unsubstituted alkyl of 1 to 10 carbon atoms or aryl of 6 to 10 carbon atoms substituted or unsubstituted, R13 and R14 independently represent each other alkyl of 1 to 10 carbon atoms substituted or unsubstituted or aryl of 6 to 10 carbon atoms substituted or unsubstituted or R13 and R14 together represent alkylene of 3 to 10 carbon atoms substituted or unsubstituted, and indicates numerical values 0, 1 or 2 and B1 independently represents hydrogen, alkyl of 2 to 8 carbon atoms optionally halogenated or aryl of 6 to 10 carbon atoms substituted or unsubstituted. B1 independently preferably represents hydrogen or ethyl or n- or iso-propyl, which can be substituted by halogen or unsubstituted or aryl of 6 to 10 carbon atoms substituted by alkyl of 1 to 4 carbon atoms and / or halogen , in particular phenyl or naphthyl. Alkyl in R 11, R 12, R 13 and R 14 independently preferably represents methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- or tere-butyl, pentyl or hexyl. Alkyl substituted at R 11, R 12, R 13 and R 14 independently preferably represents alkyl of 1 to 10 carbon atoms substituted by halogen, in particular methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec- or mono- or disubstituted tere-butyl, pentyl or hexyl. Aryl of 6 to 10 carbon atoms in R11, R12, R13 and R 14 independently preferably represents phenyl, naphthyl or binaphthyl, in particular o-phenyl, o-naphthyl, o-binaphthyl, which can be (in general mono-, di- or tri-) substituted by halogen. R13 and R14, together with the oxygen atoms to which they are directly linked and the phosphorus atom, can form a ring structure.

The compounds which are mentioned by way of example and as preferred are: 5, 5, 5 ', 5', 5", 5" -hexamethyltris (1, 3, 2-dioxaphosphorinan-methane) amino-2, 2 ', 2' '-trioxide of the formula (Va-1) P, N-butyl-N- [(5, 5-dimethyl-1,2,3-dioxaphosphorinan-2-yl) methyl] -5,5-dimethyl of the 1,2,3-dioxaphosphorinan- 2-methanamine; P, N- [[5,5-dimethyl-1,2,3-dioxaphosphorin-2-yl) methyl] -5,5-dimethyl-N-phenyl-2,3-dioxaphosphorin-2-dioxide 2-methanamine; 2-N, N-dibutyl-5,5-dimethyl oxide of 1, 3, 2-dioxaphosphorinan-2-methanamine; P, N- [(5, 5-dimethyl-1,2,3-dioxaphosphorinan-2-yl) methyl] -N-ethyl-5,5-dimethyl of the 1,2,3-dioxaphosphorinan- 2-methanimine; P, N-butyl-N- [(5,5-dichloromethyl-1,2,3-dioxaphosphorinan-2-yl) -methyl] -5,5-dichloromethyl ester of the 1, 3, 2-dioxaphosphorinan-2-methanamine; P, N - [(5,5-dichloromethyl-1,2,3-dioxaphosphorin-2-yl) methyl] -5,5-dichloromethyl-N-phenyl-1,2-dioxaphosphorin-2-dioxide 2-methanamine; 2-N, N-di- (4-chlorobutyl) -5,5-dimethyl oxide of 1, 3, 2-dioxaphosphorinan-2-methanamine; P, N- [(5, 5-dimethyl-l, 3,2-dioxaphosphorinan-2-yl) methan] -N- (2-chloroethyl) -5,5-di (chloromethyl) -2-dioxide , 3, 2-dioxaphosphorinan-2-methanimine. The compounds which are further preferred are: The compounds of the formula (Va-2) or (Va-3) wherein R11, R12, R13 and R14 have the meanings mentioned above. The compounds of the formula (Va-2) and (Va-1) are particularly preferred. The preparation of the phosphonatamines is described, for example, in U.S. Patent No. 5,844,028. Phosphazenes are compounds of the formulas (Via) and (VIb) wherein R in each case is identical or different and represents amino, in each case optionally halogenated, preferably halogenated with fluorine, alkyl of 1 to 8 carbon atoms or alkoxy of 1 to 8 carbon atoms, in each case cycloalkyl of 5 to 6 carbon atoms, aryl of 6 to 20 carbon atoms, preferably phenyl or naphthyl, aryloxy of 6 to 20 carbon atoms, preferably phenoxy or naphthyloxy or aralkyl of 7 to 12 carbon atoms, preferably phenyl-alkyl of 1 to 4 carbon atoms optionally substituted by alkyl, preferably by alkyl of 1 to 4 carbon atoms and / or halogen, preferably by chlorine and / or bromine, k represents 0 or a number from 1 to 15, preferably a number from 1 to 10. The examples which can be mentioned They are propoxyphosphazene, phenoxyphosphazene, methylphenofosphazene, aminophosphazene and fluoroalkylphosphazenes. Phenoxyphosphazene is preferred. The phosphazenes can be used by themselves or as a mixture. The radical R can always be identical or 2 or more radicals in the formulas (la) and (Ib) can be different. Phosphazenes and their preparation are described, for example, in EP-A 728 811, DE-A 1 961668 and WO 97/40092. Agents for fire resistance can be used by themselves or in any desired mixture with another or in a mixture with other agents for fire resistance. The phosphorus-containing fire resistance agent can be used in the composition according to the invention in an amount of 0.1 to 30, preferably 1 to 25 and most preferably 2 to 20 parts by weight.

Component F Agents for fire resistance corresponding to component E are frequently used in combination with the so-called anti-sinking agents which reduce the tendency of the material towards burning runoff in the event of fire. The examples which may be mentioned in this document are compounds of the classes of fluorinated polyolefin substances, silicones and aramid fibers. These can also be used in the compositions according to the invention. The fluorinated polyolefins are preferably used as anti-caking agents. The mixture generally comprises the fluorinated polyolefins in an amount of 0.01 to 3, preferably 0.05 to 1.5 parts by weight. Fluorinated polyolefins are known and described, for example, in EP-A 0 640 655. They are marketed under the trade name Teflon ™, for example Tefion 30N ™, from DuPont. The fluorinated polyolefins can be used both in the pure form and in the form of a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of the graft polymers (component B) or with an emulsion of a copolymer, preferably based on styrene / acrylonitrile , the fluorinated polyolefin is mixed as an emulsion with an emulsion of the graft polymer or copolymer and then coagulated. The fluorinated polyolefins can be additionally used as a precompound with the graft polymer (component B) or a copolymer, preferably based on styrene / acrylonitrile. The fluorinated polyolefins are mixed as a powder with a powder or granules of the graft polymer or copolymer and are combined in the melt, generally at temperatures of 200 to 330 ° C, in conventional units, such as internal kneaders, extruders or screws. double spindle. The fluorinated polyolefins can also be used in the form of a basic mixture which is prepared by means of the emulsion polymerization of at least one monoethylenically unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin. The preferred monomeric components are styrene, acrylonitrile and mixtures thereof. After the acid preparation and the subsequent drying, the polymer is used as a free-flowing powder. The coagulates, precompounds or basic mixtures conveniently have fluorinated polyolefin solids contents of 5 to 95% by weight, preferably 7 to 60% by weight.

Component G The composition may further comprise additional conventional, polymeric additives (component G), such as fire resistance agents, lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleic acid building agents, antistatics, stabilizers, fillers and reinforcing substances (for example glass fibers or carbon fibers, mica, kaolin, talcum, CaC0 and glass flakes) as well as coloring matters and pigments.

Preparation of molding compositions and shaped articles The thermoplastic molding compositions according to the invention are prepared by mixing the particular constituents in a known manner and subjecting the mixture to melt blending and melt extrusion at temperatures of 200 °. C at 300 ° C in conventional units, such as internal kneaders, extruders and double screw screws. The mixing of the individual constituents can be carried out in a known manner either successively or simultaneously and in particular either at about 20 ° C (room temperature) or at a higher temperature. In a preferred embodiment (i) in a first step, the laminar compound is modified with organic polymers, preferably with polyalkylene oxides having a number average molecular weight of from 106 to 20,000 g / mol, particularly preferably from 200 to 10,000 g / mol, it is also possible that mixtures of several polyalkylene oxides are used, by means of a solvent-free melting process, (ii) in a second step, the basic mixture of the laminar compound obtained from step (i) is mixed in a known manner with the component (A) and optionally the additional components selected of the group consisting of (B), (C), (E), (F) and (G) and (iii) in a third step, the mixture of step (ii) is subjected to the combination in the molten state and the Melt extrusion at temperatures of 200 ° C to 300 ° C in conventional units, such as internal kneaders, extruders and double screw screws, it is possible that the basic mixture of the laminar compound resulting in the first step (i) is isolated or also be processed directly as a melt, preferably using a secondary extruder, in the molding composition in step (ii). In a particularly preferred embodiment, additional oligomers or polymers selected from the group consisting of polycarbonate (according to component A) and polymethyl methacrylate (PMMA) are used in the first step (i). Due to its high thermal stability and its good mechanical properties, the thermoplastic molding compositions according to the invention are suitable for the production of all types of shaped articles, in particular those which have increased requirements for maximum heat release rates. The molding compositions according to the invention can be used for the production of all types of shaped articles. These can be produced by means of injection molding, extrusion and the blow molding process. Another form of processing is the production of shaped articles by means of the thermoforming of sheets or films produced previously. Therefore, the present invention also provides the use of the molding compositions according to the invention for the production of all types of shaped articles, preferably those mentioned above and the shaped articles of the molding compositions according to the invention. Examples of these shaped articles are films, profiles, all kinds of home components, for example for household accessories, such as juice squeezers, coffee making machines and mixtures; for office machines, such as display units, flat screens, laptops, printers and copiers; sheets, pipes, conduits for electrical installation, windows, doors and additional profiles for the construction sector (interior finishing and exterior uses), as well as electrical and electronic components, such as switches, plugs and sockets and components for vehicles utilities, in particular for the automotive sector. The molding compositions according to the invention can also be used in particular, for example, for the production of the following shaped articles or moldings: components for interior finishes for tread vehicles, ships, aircraft, buses and other vehicles of motor, accommodation of electrical equipment containing small transformers, accommodation for equipment for the processing and transmission of information, accommodation and fittings for medical equipment, massage equipment and accommodation therefor, toy vehicles for children, flat-walled elements, accommodation for safety equipment, thermally insulated transport containers, moldings for sanitary and bathroom fittings, roof grilles for openings and fan housings for garden equipment. The following examples serve to further explain the invention.

Examples Component To branched polycarbonate based on bisphenol A having a relative solution viscosity of 1.34, measured in methylene chloride at 25 ° C and in a concentration of 0.5 g / 100 ml Component A2 Linear polycarbonate based on bisphenol A having a relative solution viscosity of 1.20, measured in methylene chloride at 25 ° C and in a concentration of 0.5 g / 100 ml Component B ABS polymer prepared by means of the emulsion polymerization of 43% by weight, based on the ABS polymer, of a mixture of 27% by weight of acrylonitrile and 73% by weight of styrene in the presence of 57% by weight , based on the ABS polymer, of a cross-linked, particulate polybutadiene rubber (average particle diameter d5o = 0.35 μm).

Component DI Cationically modified lamellar silicate (modified with stearylbenzyldimethyl-ammonium chloride) (Nanofil 9MR, powder, specific gravity approximately 1.8 g / cm3, average particle size 8 μm, primary particle size with complete dispersion approximately 100-500 nm x 1 nm, manufacturer Süd-Chemie AG).

Component D2 Basic mixture of layered silicate / polycarbonate (according to the invention) For the preparation of the layered silicate / polycarbonate basic mixture, the starting substances listed in Table 1 are kneaded at 240 ° C for 5 minutes in a microextruder of 10 ml (DSM), are allowed to leave and are cooled to room temperature.

Table 1 Preparation of laminar silicate / polycarbonate basic mixture Component D2-1 Nanofil 757MR (extremely pure sodium montmopllonite, powder, specific gravity approximately 2.6 g / cm3, average particle size <10 μm, primary particle size with complete dispersion approximately 500 nm x 1 nm, manufacturer Sud- Chemie AG). The dimensions were determined by means of TEM photographs and XRD measurements: average layer thickness of 1 nm and layer diameter of approximately 300 - 1,000 nm.

Component D2-2 Polyethylene glycol monomethyl ether, average molecular weight (number average) Mn = 350) ^ Sigma-Aldrich Chemie) Component D2-3 Polyethylene glycol monomethyl ether (average molecular weight (number average) Mn = 2,000) (Sigma-Aldrich Chemie) Component E Oligophosphate based on bisphenol A Component F Polytetrafluoroethylene powder, CFP 6000 N, Du Pont Component Gl: Pentaerythritol stearate Component G2: Phosphite stabilizer Component G3: Tetraphenylphosphonium phenolate Preparation and testing of the molding compositions according to the invention The starting substances listed in Table 2 are combined in a twin-screw extruder (ZSK-25) (Werner und Pfleiderer) at a rotation speed of 225 rpm and yield of 20 kg / h at a machine temperature of 260 ° C and the compound was granulated. The total batch size is in each case 8 kg. Example 1 represents the comparison without the addition of layered silicate, Example 2 contains a cationically modified layered silicate which can be obtained commercially as a comparison and Example 3 contains the basic layered silicate / polycarbonate mixture described above. The finished granules are processed to the corresponding test specimens in an injection molding machine (melting temperature 260 ° C, mold temperature 80 ° C, front melt velocity 240 m / s) and these are characterized in accordance with ISO standards 1133 (MVR), ISO 5660-1 (cone calorimetry) and ASTM E 662 (combustion gas density) and by means of thermogravimetric analysis (TGA). The determination of the melt volumetric flow rate (MVR value) is carried out in accordance with the ISO 1133 standard (260 ° C, 5 kg). The determination of the cone calorimeter measurement (50 kW / m2 60 mm distance) is carried out in accordance with the ISO 5660-1 standard. The determination of the density of the combustion gas is carried out in accordance with the standard ASTM E 662 (with an ignition flame d = 3 mm). Thermogravimetric analysis (TGA, by its acronym in English) was carried out with TGA / SDTA 851e (Mettler-Toledo). Approximately 10 mg of the samples were weighed and flooded under a mixture of 20% oxygen gas in helium at a flow rate of 80 ml / minute at 25 ° C for 30 minutes and then heated at 800 ° C to a heating speed of 5 K / minute. During the complete measurement, the change in weight was monitored continuously and the masses were recorded in a mass spectrometer. The temperature range for decomposition, which was obtained from the percentage of weight reduction or weight loss rate measured (in% minute "1), is established in Table 2. The starting value corresponds to the start of the decomposition and the final value at the end of the composition.

Table 2 It can be seen from Table 2 that by addition of the layered silicate / polycarbonate basic mixture according to the invention (Example 3), the density of the combustion gas according to ASTM E 662 is decreased, the Maximum heat release rate (heat release, determined by means of cone calorimetry) is reduced and additionally the decomposition temperature (thermogravimetric analysis) is increased, the volumetric flow rate of melted material (MVR value) remains unchanged, inside of the measurement accuracy, compared to the molding composition without filler (Comparison Example 1). In addition, a lower MARHE value is achieved compared to the use of cationically modified sheet silicates (Comparison Example 2) (MARHE = maximum average heat emission speed). The molding composition according to Comparison Example 2 comprising cationically modified layered silicate provides a significantly increased MVR value compared to Comparison Example 1 and Example 3 according to the invention, which indicates an increased weight degradation molecular structure of the polycarbonate matrix.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (17)

1. CLAIMS Having described the invention as above, the claim contained in the following claims is claimed as property: 1. A composition, characterized in that it comprises A) an aromatic polycarbonate and / or polyester carbonate, B) optionally an impact modifier, C) optionally a homo- and / or thermoplastic copolymer, D) a laminar compound which is modified with organic polymers by means of a solvent-free melting process and E) optionally a phosphorus compound.
2. 2. The composition according to claim 1, characterized in that it comprises A) from 30 to 99.9 parts by weight of aromatic polycarbonate and / or polyester carbonate, B) from 0 to 60 parts by weight of a rubber modified graft polymer. , C) from 0 to 30 parts by weight of homo- and / or copolymer, D) from 0.1 to 40 parts by weight of a laminar compound which is modified with organic polymers by means of a solvent-free fusion process and ) from 0 to 30 parts by weight of a phosphorus compound, wherein the sum of the parts by weight of components A, B, C, D and E is standardized to 100.
3. 3. The composition according to claim 1 , characterized in that it comprises laminar compounds having an average thickness of 0.3 to 10 nm.
4. 4. The composition according to claim 3, characterized in that it comprises laminar compounds in which the layers have a diameter of 5 to 10,000 nm.
5. 5. The composition according to any of claims 1 to 4, characterized in that it comprises a laminar compound which is modified with polyalkylene oxide having a number average molecular weight of 106 to 20,000 g / mol by means of a process of Solvent free fusion The composition according to any of claims 1 to 4, characterized in that it comprises a laminar compound which is modified with polyalkylene oxide having a number average molecular weight of 106 to 20,000 g / mol and at least one polymer additional by means of a solvent-free fusion process. The composition according to any of claims 1 to 6, characterized in that a rubber-modified graft polymer of B.l of 65 to 95% by weight, based on B), of a mixture of Bll from 50 to 99% by weight, based on Bl), of at least one monomer selected from the group consisting of vinylaromatic products and vinylaromatic products substituted in the core and B.1.2 from 1 to 50% by weight, based on a Bl), of at least one monomer selected from the group consisting of vinyl cyanides, alkyl (Ci-Cβ) esters of (meth) acrylic acid and unsaturated carboxylic acid derivatives B.2 from 5 to 35% by weight , based on B), of one or more grafting bases having a glass transition temperature of < -10 ° C is used as component B). The composition according to claim 7, characterized in that the monomers B.l.l) are styrene and the monomers B.1.2) are acrylonitrile. 9. The composition according to claim 8, characterized in that the graft base B.2) comprises diene rubber. The composition according to any of the preceding claims, characterized in that it comprises a (co) polymer of Cl of 50 to 99% by weight, based on the (co) polymer, of at least one monomer selected from the group consisting of of vinylaromatic products, vinylaromatic products substituted in the core and esters of (C? -C8) alkyl of (meth) acrylic acid and C.2 of 1 to 50% by weight, based on the copolymer, of at least one selected monomer of the group consisting of vinyl cyanides, alkyl (C? -8) esters of (meth) acrylic acid, unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. 11. A composition according to any of claims 1 to 10, characterized in that for the modification of the laminar compound by means of a solvent-free melting process it comprises: (a) in a first step, the laminar compound is mixed with an organic polymer or a mixture of organic polymers, (b) in a second step, the mixture is heated to a temperature above the melting temperature of the polymer used or of the polymer mixture used. The composition according to any of claims 1 to 11, characterized in that the phosphorus compound according to component E is an oligophosphate. The composition according to any of the preceding claims, characterized in that it comprises additives selected from at least one of the group consisting of agents for fire resistance, anti-drip agents, lubricants and mold release agents, forming agents cores, antistatic, stabilizers, fillers and reinforcing substances and coloring matters and pigments. A process for the preparation of thermoplastic molding compositions from compositions according to any of the preceding claims, characterized in that (i) in a first step, the laminar compound is modified with polyalkylene oxide having an average molecular weight in number from 106 to 20,000 g / mol by means of a solvent-free melting process, (ii) in a second step, the basic mixture of the laminar compound obtained from step (i) is mixed with the component (A) and the optionally additional components selected from the group consisting of (B), (C), (E), (F) and (G) and (iii) in a third step, the mixture of step (ii) is subjected to the combination in melted state and extrusion in the molten state at temperatures of 200 ° C to 300 ° C. 15. The use of the compositions according to claims 1 to 13 for the production of shaped articles. 16. The shaped articles, characterized in that they comprise a composition according to any of claims 1 to 13. 17. A shaped article according to claim 16, characterized in that the shaped article is a part of a motor vehicle, vehicle of tread, aircraft or boat or an accommodation for electrical equipment containing small transformers, accommodation for equipment for the processing and transmission of information, accommodation and cover for medical equipment, massage equipment and accommodation therefor, toy vehicles for children , flat wall elements, housing for safety equipment, thermally insulated transport containers, moldings for sanitary ware and bathroom fixtures, cover grilles for ventilator openings or a housing for garden equipment.