MXPA00005447A - Polycarbonate moulding materials - Google Patents

Abstract

The invention relates to moulding materials containing:A) at least one polycarbonate;B) at least one graft polymer with a base consisting of an elastomer with a glass transition temperature below 10°C;C) at least one copolymerisate containing vinylaromatic monomers;D) at least one filler, and also, optionally, E) at least one flameproofing agent and F) at least one additive. The moulding materials are characterised in that they contain G) at least one low molecular halogen-free acid and also, optionally, H) at least one polyalkylacrylate. The invention also relates to moulded parts, films or fibres, and especially external vehicle body parts produced from the moulding materials.

Description

POLYCARBONATE MOLDING COMPOSITIONS The present invention relates to molding compositions containing A) at least one polycarbonate, B) ~ at least one graft polymer based on an elastomer having a vitreous transition point less than 10 ° C, ) at least one copolymer containing viml aromatic monomers. D) at least one charge, and, if additionally desired E) at least one flame retardant and F) at least one additive and which is characterized in that it contains, as additional components, G) at least one halogen-free acid of low molecular weight and further H) at least one polyalkyl acrylate. In addition, the present invention relates to the use of molding compositions for the preparation of shaped articles, films or fibers and to the shaped articles that are prepared therefrom. Known polycarbonate molding compositions containing graft polymers based on dienes (ABS) or acrylates (ASA) and styrene copolymers are known. It is also known that they can be equipped with various flame retardants. These molding compositions are used primarily for the manufacture of shaped articles, for example, for the automotive industry. Polycarbonate molding compositions based on polycarbonate and functionalized ASA and comprising copolymers of styrene containing oxazoline groups, are described by DE-A1-1, 960,198. They are distinguished by good strength properties and good elongation at break and impact resistance. However, the low temperature damage factor of these molding compositions is unsatisfactory. WO 96/06136 and EP-B 1,391,413 disclose polycarbonate molding compositions that are charged with talc having a dimension ratio of 4 to 40 and 4 to 24 respectively and a particle size of less than 44 and less than 10 μm respectively , for which reason the parts that are prepared there show low tendency to distortion and have good resistance to impact. According to the first named specification, the copolymer that is present in the molding compositions should have a high molecular weight, as high as possible. Disadvantages of the molding compositions are that they do not flow well and are difficult to process. In addition, they have the disadvantage that the impact resistance notched is insufficient for many purposes. EP-A 1,522,397 discloses polycarbonate molding compositions which, when treated with flame, do not deform or form drops of an inflamed substance. They can be obtained by mixing their components with aramid and sulfonate. This has the disadvantage that the toughness of corresponding molding compositions is considerably reduced. DE-AI 4,034,366 discloses polycarbonate molding compositions wherein the anti-drip agent employed is, instead of polytetrafluoroethylene, an alkanesulfonic or carboxylic derivative which is perfluorinated or polyfluorinated. The molding compositions described in said reference show improved tenacities in the penetration test at low temperatures and lower total burn times, but do not meet the current requirements regarding being halogen free, on the one hand and show relatively low resistance to thermal deflection on the other hand. EP-A 1,576,948 proposes that basic impurities that can cause degradation of the polycarbonate and that can be trapped in the recycled ABS molding compositions, are neutralized by adding polymer resins containing acid groups. As examples, poly (meth) acrylic acid or partially saponified poly (meth) acrylates are mentioned. Their molecular weights (weight average Mw) are preferably up to 500,000 g / mol. These molding compositions are not impact resistant or sufficiently tough for many applications. In order to reduce the decomposition of polycarbonate, JP-A 9/137054 proposes that the molding compositions be charged with talcum-neutral. Without. embargo, this requires an additional technical process stage and therefore is elaborate and intense in cost. An object of the present invention is to provide polycarbonate molding compositions that do not have the above disadvantages. In. in particular, the polycarbonate molding compositions should be easy to process into large shaped articles, suitable for use as body parts of external automobiles. Since metal replacement is required in this way, polycarbonate molding compositions that meet a wide range of stringent requirements must be found. This objective is achieved by the molding compositions defined above. Special embodiments are given in the dependent claims and description-Component A The component A present in the molding compositions of the invention comprises a polycarbonate or a mixture of two or more different polycarbonates. Preferred molding compositions of the invention contain from 1 to 97.45% by weight, based on the total weight of the molding compositions, of component A. We particularly prefer molding compositions of the invention containing from 10 to 92.4% by weight with based on the total weight of the molding compositions, of component A. We prefer to use halogen-free polycarbonates as component A. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula wherein Q is a single bond or denotes an alkylene group with 1 to 3 carbon atoms, an alkylidene group with 2 to 3 carbon atoms, a cycloalkylidene group with 3 to 6 carbon atoms, -S- or -S02- and m is an integer from 0 to 2. Preferred diphenols of the formula I are for example hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane and 1,1-bis (4-hydroxyphenyl) cydohexane. Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and also 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. Both hourpolycarbonates and copolycarbonates are suitable for use as component A. In addition to the bisphenol A homopolymer, bisphenol A copolycarbonates are preferred. Convenient polycarbonates may be branched in a known manner, preferably by incorporation from 0.05 to 2.0 mol%, based on the sum of diphenols used, of at least trifunctional compounds, such as those containing three or more OH groups phenolic Particularly suitable polycarbonates have been found to be those having relative viscosities from 1.10 to 1.50, particularly from 1.25 to 1.40. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably 20,000 to 80,000. The diphenols of the general formula I are known per se or can be manufactured by known processes. The preparation of olicarbonates can be carried out, for example, by reacting diphenols with phosgene in the interphase process or with phosgene in the homogeneous phase process (so-called pyridine process), the molecular weight required in each case being reached in a known way by adding an appropriate amount of agents to stop the chain. (For information regarding polycarbonates having polydiorganosiloxane see for example DE-OS 3,334,782.) Suitable chain stop agents are for example phenol, p-tert-butylphenol and also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) ) phenol, according to DE-OS 2,842,005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in an alkyl substituent according to DE-A 3,506,472, such as p-nonylphenyl, 3,5-diols. tert-butylphenol, p-tert-octylphenol, p-dodecyl enol, 2- (3,5-dimethylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol. "Halogen-free polycarbonates" mean for the purposes of the present invention invention, that the polycarbonates are composed of diphenols, free of halogen, halogen-free chain-stopping agents, and optionally halogen-free branching agents, while the content of lower concentrations of saponifiable chlorine ppm, resulting Example of the preparation of polycarbonates with phosgene by the interphase process, shall not be considered as "halogen-containing" for the purposes of the present invention. These polycarbonates having ppm contents of saponifiable chlorine are "halogen-free polycarbonates" for the purposes of the present invention. Component B One or a mixture of two or more different graft copolymers are used as component B in the molding compositions of the invention, preferably in amounts of 1 to 97.45% by weight based on the total weight of the molding composition . Particularly preferred molding compositions of the invention contain from 2 to 50% by weight, based on the total weight of the molding composition, of at least one graft polymer B. In accordance with the invention, the graft polymers B are based on an elastomer having a glass transition point lower than 10 ° C, preferably lower than 0 ° C. For an elastomer we also intend for the purposes of the present invention to understand mixtures of different elastomers. Suitable elastomers are natural rubbers or synthetic rubbers, for example diene rubbers, acrylate rubbers or siloxane rubbers. Of these, acrylate rubbers are preferred. Particularly preferred graft polymers B are composed of: bj.) Of from 40 to 80% by weight, preferably from 50 to 70% by weight of a graft base of a rubber-elastic polymer based on alkyl acrylates having 1 to 20% by weight; at 8 carbon atoms in the alkyl radical and having a vitreous transition point less than 0 ° C b2) of 20 to 60% by weight preferably 30 to 50% by weight of a graft component b2?) of 60 to 95% by weight preferably 70 to 85% by weight of styrene or substituted styrene of the general formula formula II R: CH, wherein R denotes an alkyl radical with 1 to 8 carbon atoms, preferably methyl or ethyl, or hydrogen and R 1 denotes an alkyl radical with 1 to 8 carbon atoms, preferably methyl or ethyl and n has the value 1, 2 or 3, or their mixtures And b22) from 5 to 40% by weight, preferably from 15 to 30% by weight of at least one unsaturated nitrile, preferably acrylonitrile or methacrylonitrile or their mixtures. Particularly preferred polymers for the graft base b2 are polymers whose glass transition temperature is less than -20 ° C. These are, for example, elastomers based on alkyl esters of 1 to 8 carbon atoms of acrylic acid, optionally containing additional comonomers. We prefer bx graft bases composed of: b) from 70 to 99.9% by weight of at least one alkyl acrylate having from 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate , particularly n-butyl acrylate as the only alkyl acrylate. b12) from 0 to 30% by weight of an additional copolymerizable monoethylenically unsaturated monomer such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate or vinylmethyl ester or mixtures thereof. b13) of 0.1 to 5% by weight of a polyfunctional copolymerizable entanglement monomer preferably bifunctional or trifunctional, the percentages by weight are based on the total weight of the graft base. In another preferred embodiment, the grafting base can be composed of 66 to 79% by weight of bu), 20 to 30% by weight of b12) and 1 to 4% by weight of b13), the percentages by weight are based on the total weight of the graft base. Conventional bifunctional or polyfunctional binder monomers b13 are monomers preferably containing two, optionally three or more ethylenic double bonds that are capable of copolymerization and are not conjugated in the 1 to 3 positions. Suitable crosslinking monomers are for example divinylbenzene, diallyl maleate , diallyl fumarate, diallyl phthalate, triallyl cyanurate or triallyl isocyanurate. A particularly advantageous crosslinking monomer has been found to be the tricyclodecenyl alcohol acrylate (cf ^ DE-A 1,260,135). This type of graft base is known per se and it is described in the literature for example in DE-A 3,149,358. Of the graft components b2 those preferred wherein b21 is styrene or -methylstyrene or a mixture thereof and 22 is acrylonitrile methacrylonitrile. The most preferred monomer mixture employed is styrene and acrylonitrile or α-methylstyrene and acrylonitrile. The graft components are obtained by copolymerization of components b21 and b22. The manufacture of the bx graft base of the graft polymers B, composed of the components bu and optionally b12 and b13, are known per se and are described in for example DE-A 2,826,925, DE-A 3,149,358 and DE-A 3,414 , 118.

The preparation of the graft polymers B can be carried out, for example, by the method described in DE-PS 1,260,135. The synthesis of the graft component (covered by graft) of the graft polymers can be carried out in one, two or three stages. In the case of a single stage synthesis of the graft cover, a mixture of the monomers b21 and b22 is polymerized in the desired ratio, by weight, in the range of 95: 5 to 50:50, preferably 90 : 10 to 65:35 in the presence of the bx elastomer in the known way (cf.

DE-OS 2,826,925), preferably in emulsion. In the case of a two-stage synthesis of the graft cover b2, the first stage generally forms from 20 to 70% by weight, preferably 25 to 50% by weight, based on b2. For their preparation, preferably only styrene or substituted styrene or their mixtures (b21) are used. The second stage of the graft cover generally forms from 30 to 80% by weight, particularly from 50 to 75% by weight, based in each case on b2. For its preparation, mixtures of monomers b21 and nitriles b22 are used in a weight ratio of b21 to b22 in general from 90:10 to 60:40, particularly from 80:20 to 70:30. The conditions of the graft polymerization are preferably such that the particle sizes of 50 to 700 nm result (d50 value of the integral mass distribution). Measures to achieve this end are known and described for example in DE-OS 2,826,925. By using the seed latex process it is possible to directly prepare a thick rubber dispersion. In order to make the products as strong as possible, it is often advantageous to use a mixture of at least two graft polymers showing different particle sizes. To achieve this objective, the rubber particles are enlarged in a known manner, for example by agglomeration, in such a way that the latex has a bimodal structure (50 to 180 nm and 200 to 700 nm). In a preferred embodiment, a mixture of two graft polymers having particle sizes (d5Q value of the integral mass distribution) of 50 to 180 nm and 200 to 700 nm respectively, is employed in a weight ratio of 70: 30 to 30:70. The chemical structure of the two graft polymers preferably thereof, although the cover of the thick graft polymer can in particular have a two-stage structure, if desired. Mixtures of components A and B, wherein the latter has a coarse graft polymer, and a finely divided graft polymer, are described for example in DE-OS 3,615,607. Mixtures of components A and B, wherein the latter has a two stage graft cover, are described in EP-A 111,260. In addition to the aforementioned ASA rubbers, rubbers modified with oxazoline groups and described in DE-A 1-19606198 are also suitable. Component B can also be a mixture of the aforementioned graft polymers with one or more different network rubbers. In this case, the contents of the network rubbers based on the total weight of the molding compositions of the invention can be up to 20% by weight, preferably 1 to 15% by weight. We prefer network rubbers based on siloxanes and acrylates or methacrylates. Preferred network rubbers generally contain ßi) from 30 to 95% by weight, preferably from 40 to 90% by weight, of a network serving as a graft base composed of ßxl) of from 10 to 90% by weight, preferably from 20 to 90% by weight. at 80% by weight of at least one polyorganosiloxane and β12) from 10 to 90% by weight preferably from 20 to 80% by weight of a polyalkyl acrylate or a polyalkyl methacrylate or its mixture and β2) from 5 to 70% by weight preferably from 10 to 60% by weight of an injurious component. Preferred polysiloxanes are derived from cyclic organosiloxanes which preferably contain from three to six silicon atoms. Examples of siloxanes with no entities are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, d or d e c a m e t i l c i c l or h e x a s i l a x, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenyl-cyclotetrasiloxane or octaphenyl cyclotetrasiloxane. The polysiloxanes may be composed of an organosiloxane or an amount of different organosiloxanes. In addition, the ßlx polyorganosiloxanes usually contain from 0.1 to 30% by weight based on ßlx of at least one entanglement agent. Trifunctional or tetrafunctional siloxanes, such as trimethoxymethyl silylamine, triethoxyphenylsilane, tetramethoxysilane, tetraethoxyosilane, tetra-n-propoxysilane or tetrabutoxysilane can be used as crosslinking agents. Of these, tetrafunctional silanes are particularly preferred. In addition, the polyorganosiloxanes generally contain from 0 to 10% by weight based on ßu of gradable monomers. The grafting monomers used can, for example, be unsaturated silanes. Preferred graft monomers are methacryloylsilanes. As examples thereof, the following may be mentioned: ß-methacryloyloxyethyldimethoxymethylsilane-methacryloyloxypropylmethoxydimethylsilane-methacryloyloxypropyldimethoxymethylsilane-methacryloyloxypropyltrimethoxysilane-methacryloyloxypropylethoxyidiethyl silane Y-methacryloyloxypropyldiethoxymethylsilane d-methacryloyloxybutyldiethoxymethylisilane. Processes for the preparation of polyorganosiloxanes are described, for example, in U.S. Pat. Nos. 2, 891,920 or 3,294,725. The polyorganosiloxanes are preferably prepared by mixing, in a solvent under shear, a mixture of organosiloxanes, the crosslinking agent and, if desired, grafting monomers, with water in the presence of an emulsifier such as an alkylsulfonic acid or preferably an acid alkylbenzensulfonic. The emulsifier may if desired be a metal salt of alkylsulfonic acid or alkylbenzenesulfonic acid. The polyalkyl acrylates or polyalkyl methacrylates ß12 contain, as monomeric building blocks, generally alkyl acrylates or methacrylates or their mixtures, crosslinking agents and grafting monomers, wherein the crosslinking agents and the gradable monomers in each case can be used alone or together . The content of entanglement agent and grafting monomer as a whole is usually in the range of 0.1 to 20% by weight based on ß12. Examples of suitable alkyl acrylates or alkyl methacrylates are methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate or n-lauryl methacrylate. We particularly prefer to use n-butyl acrylate. The entangling agent for example can be ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or 1,4-butylene glycol dimethacrylate. Allyl methacrylate, triallyl cyanurate or triallyl isocyanurate are examples of suitable grafting monomers. Of these, allyl methacrylate can also act as an entanglement agent. The network is prepared by adding the monomer building blocks of the ß12 component to the polyorganosiloxane ßn, which is neutralized by the addition of an aqueous solution of a base such as sodium hydroxide, potassium hydroxide or calcium hydroxide. This is why the polyorganosiloxane is swollen. Subsequent conventional free radical initiators are added. During the polymerization reaction, a network is formed, where there is mutual penetration of the components ß? X and ß12. Networks can also be linked together by chemical bonds. We very particularly prefer networks in which the polyorganosiloxane has a main structure of dimethyl siloxane and β12 is a polyalkyl acrylate whose main structure is composed of n-butyl acrylate. The gel content of the network is usually greater than 80% (measured by extraction with toluene at 90 ° C for a period of 12 hours). The β2-graft copolymer is usually composed of vinyl monomers. These include styrene, α-methylstyrene, vinyl toluene, acrylates, such as methyl acrylate, ethyl acrylate or n-butyl acrylate, methacrylates such as methyl methacrylate or 2-ethyl methacrylate, nitriles, such as acrylonitrile or methacrylonitrile. The vinyl monomers can be used alone. Alternatively, mixtures of different monomers can be used. In this case, the monomers in general are such as to give a graft component having a glass transition temperature of at least 80 ° C, preferably in the range of 80 ° to 110 ° C (determined by taking a reading of torsion pendulum at a frequency of 1 Hz and a heating rate of 10 ° C / minute). Graft components having a predominant content of methyl methacrylate, preferably graft components containing at least 85% by weight of methyl acrylate, are particularly preferred. Particularly preferred are graft components having a methyl methacrylate content of 95 to 100% by weight. In addition to methyl methacrylate, styrene, n-butyl acrylate or cyclohexyl methacrylate are preferably used. In particular, only methyl methacrylate is used. Component C The molding compositions of the invention contain as component C, preferably from 1 to 97.45% by weight based on the total weight of the molding composition of one or a mixture of two or more different copolymers containing monomers vinylaromatics Preferred are styrene-substituted or styrene-substituted copolymers and unsaturated nitriles. Particularly preferred molding compositions of the invention contain component C in concentrations of 2 to 50% by weight based on - the total weight of the molding compositions. Convenient copolymers are both random copolymers and block copolymers. Examples of suitable copolymers are poly (styrene-co-acrylonitrile) or terpolymers based on styrene acrylonitrile and N-phenylmaleimide or copolymers containing oxazoline group. The copolymers C are more preferably composed of C :) from 60 to 95% by weight, preferably from 65 to 85% by weight, of styrene or substituted styrene of the general formula I or mixtures thereof and C2) of 5 to 40% by weight, preferably 15 to 35% by weight, of at least one unsaturated nitrile, preferably acrylonitrile or methacrylonitrile or mixtures thereof . The C-copolymers are resinous, thermoplastic and rubber-free. Particularly preferred copolymers C are those of styrene and acrylonitrile, of α-methylstyrene and acrylonitrile or of styrene, α-methylstyrene and acrylonitrile. These copolymers are often produced as by-products during the graft polymerization which is carried out for the preparation of component B, particularly when large amounts of monomer are grafted onto small amounts of rubber. The copolymers C are known per se and can be prepared by free radical polymerization, particularly by the use of emulsion, suspension, solution and bulk polymerization methods. They have viscosity numbers in the range of 40 to 160, preferably from 60 to 110 mL / g (measured in a solution with concentration 0.5% by weight in dimethyl formamide at 23 ° C), which corresponds to average molecular weights Mw (average by weight) from 40,000 to 2,000,000. Processes for the preparation of polymers containing oxazoline group are also known per se. Copolymers containing oxazoline group can be prepared for example by causing the reaction of copolymers containing nitrile group with a monoamino alcohol, preferably in the presence of a catalyst such as a zinc salt, or cadmium (cf eg DE-AI -19606198) . Component D An additional component of the molding compositions of the invention comprises a filler or a mixture of two or more fillers. These are usually present in amounts of 0.5 to 25% by weight, particularly 1 to 20% by weight, based on the total weight of the molding compositions. Examples of fibrous fillers are carbon fibers, microfibers or short fibers of potassium titanate, aramid fibers and more preferably glass fibers. When glass fibers are used, these can be coated with a sizing substance and an adhesion promoter to improve their compatibility with the matrix material. In general, the carbon fibers and glass fibers used have a diameter in the range of 6 to 20 μm. The glass fibers may be incorporated either in the form of ground glass fibers or in the form of wicks. In the finished injection molded article, the average length of the glass fibers is preferably in the range of 0.08 to 0.5 mm. Carbon or glass fibers can also be used in the form of fabrics, mats or wicks of glass fibers. Suitable particulate fillers are amorphous silicic acids, carbonates such as magnesium carbonate (chalk), powdered quartz, mica, a wide variety of silicates such as clays, muscovite, biotite, suzoite, tin, talc, chlorite, phlogopite, feldspar , calcium silicates such as wollastonite or alumina silicates such as kaolin, particularly calcined kaolin. In a particularly preferred embodiment, particle loads are used, of which at least 95% by weight, preferably at least 98% by weight of the particles have a diameter (largest dimension), established in the finished product of less than 45% by weight. μm, preferably less than 40 μm, and its so-called dimension ratio is in the range of 1 to 25, preferably in the range of 2 to 20, established in the finished product.

The particle size can be determined, for example by taking electron microscopic photographs of thin sections of the polymer mixture and evaluating at least 25, preferably at least 50 particles of the packaging material. The determination of particle sizes can also be carried out by sedimentation analysis as described in Transactions of ASAE, page 491 (1983). The amount of charge having a diameter less than 40 μm can also be measured by sieve analysis. The proportion of dimensions the ratio of particle size to thickness (larger dimension to smaller dimension). Particularly preferred particulate fillers are talc, kaolin, such as calcined kaolin or wollastonite or mixtures of two or all of these fillers. Of these, talc having a content of at least 95% by weight of particles with a diameter of less than 40 μm and a ratio of dimensions of 1.5 to 25, determined in each case in the particular product, is particularly preferred. The kaolin preferably has a content of at least 95% by weight of particles with a diameter of less than 20 μm and a ratio of dimensions from 1.2 to 20, both established in the finished product. We prefer to use particle loads as the only charges.

Component E Optionally, the molding compositions of the invention may contain a flame retardant or a mixture of two or more different flame retardants. These are generally present in concentrations of 0 to 25% by weight, preferably 1 to 20% by weight, based on the total weight of the molding composition. More preferably, halogen-free flame retardants are employed. Basically all phosphorus flame retardants are particularly convenient. For example, a halogen-free phosphorus compound of the general formula III can be used OR R2 -O O- R1 III OR R4 wherein R.sup.2, R.sup.3 and R.sup.16 A.sub.A are independently modified to denote alkyl groups with 1 to 8 carbon atoms free of halogen or aryl groups with 6 to 20 carbon atoms free of halogen, which may be monosubstituted or disubstituted by alkyl groups with 1 to 4 carbon atoms. Examples of particularly suitable phosphorus compounds of the general formula III are tri (2,6-dimethylphenyl) phosphate, triphenyl phosphate, tricresyl phosphate, di-phenyl-2-ethylcresyl phosphate, diphenylcresyl phosphate and tri (isopropylphenyl) phosphate. In order to achieve a high Vicat temperature of the molding compositions, mixtures of the above-mentioned phosphates for example with triphenylphosphine oxide or tri (2,6-dimethylphenyl) phosphine oxide can also be used, or the phosphine oxides can be used alone. In addition, the phosphates mentioned in DE-A 3,824,356, such as bisphenyl (4-phenylphenyl) phosphate, phenyl-bis (4-phenylphenyl) phosphate, tris (4-phenylphenyl) phosphate, bisphenyl (benzylphenyl) phosphate, phenyl-bis ( benzyl-phenyl) phosphate, tris (benzylphenyl) phosphate, phenyl-bis [(1-phenylethyl) phenyl] phosphate, phenyl-bis [(1-methyl-il-1-phenylethyl) phenyl] phosphate and phenyl-bis [4- ( 1-phenylethyl) -2,6-dimethylphenyl] phosphate is a convenient measure for increasing the Vicat temperature of the molding compositions. In addition, phosphates containing more than one P atom per molecule are suitable for use as component E.

Examples are monomeric or oligomeric phosphorus compounds of the formulas IV, V or VI 11 wherein R5 and R7 independently represent optionally substituted alkyl or aryl; and R 11 independently represent alkyl, aryl or optionally substituted aryloxy or alkoxy; Rs represents alkylene, -S02-, -CO-, -N = N- or - (R12) P (0) -, where R12 represents alkyl, aryl or optionally substituted alkyl aryl and q and t independently denote an average or integral value of 1 to 30. "Optionally substituted" means that the groups may have one to five, preferably one or two substituents, these substituents in the compounds of formulas IV, V and VI are conveniently. cyano, hydroxy or alkyl with 1 to 4 carbon atoms. Preferred alkyl radicals in the compounds of formulas IV, V and VI are alkyl having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, neopentyl, n-hexyl, n-octyl, n-nonyl , n-dodecyl, 2-ethylhexyl or 3, 5, 5-trimethylhexyl. Cyanoethyl is also preferred. Preferred aryl radicals in the compounds of formulas IV, V and VI are phenyl or naphthyl and also monosubstituted or polysubstituted radicals such as tolyl, xylyl, mesityl or cresyl. Preferred alkylaryl radicals in the compounds of formulas IV, V and Vl are alkylaryl with 1 to 20 carbon atoms and especially alkylaryl radicals with 1 to 12 carbon atoms, wherein the alkyl portion and the aryl moiety are as defined above. Preferred alkoxy radicals in the compounds of formulas IV, V and VI are alkoxy radicals having 1 to 20 carbon atoms, wherein the alkyl portion having 1 to 20 carbon atoms is as defined above. Preferred aryloxy radicals in the compounds of formulas IV, V and VI are those in which the alkyl portion is as defined above. Preferred alkylene radicals in the compounds of formulas IV, V and VI are alkylene radicals with 1 to 6 carbon atoms such as methylene, ethylene, n-propylene or n-hexylene. These compounds are preferably synthesized by base catalyzed transesterification or by the reaction of phosphorus oxychloride with phenols catalyzed by magnesium chloride, or aluminum. We prefer to use the commercially available products based on resorcinol diphenyl phosphate and also the commercially available reaction products of bisphenol A and triphenyl phosphate. In this case, one should be aware of the fact that commercially available products are usually mixtures of different oligomers or isomers. In addition, mixtures of phosphates and monophosphides or monophosphine higher oxides can be used in any desired proportions. Phosphates that can be used as component E are also those of formula VII (VII) wherein R 13 denotes hydrogen or alkyl having from 1 to 8 carbon atoms, preferably methyl, and R 1 denotes (VIII) (ix) wherein R1 denotes phenyl, which may be substituted by alkyl with 1 to 4 carbon atoms or by phenyl, benzyl or 2-phenylethyl, and when m is zero, n must be at least 1 and R1 must be a radical of the formula IX, and when n is zero, m is at least 2 and R1 must be a radical of formula VIII, and m is an integer from 0 to 12 and n is an integer from 0 to 5, where the core index of the molecule polyphenol ie the number of benzene rings in compound VII, not counting the radicals R13 to R15 is not greater than 12. Examples of phosphates of formula VII are the novolac phosphates. Convenient novolacs are condensation products of formaldehyde and phenols.

Typical examples of phenols are phenol, o-cresol, m-cresol, p-cresol, and 2, 5-dimethyl, 3, 5-dimethyl, 2, 3, 5-trimethyl, 3, 4, 5-trimethyl, p- tert-butyl, pn-octyl, p-stearyl, p-phenyl, p- (1-phenylethyl), 1-phenylethyl, o-isopropyl, p-isopropyl or m-isopropyl phenols. We prefer to use phenol, o-cresol, p-cresol, p-tert-butylphenol and o-tert-butylphenol and p-octylphenol. Alternatively, a mixture of these phenols can be used. Preferred novolacs used are novolac phenol / formaldehyde, novolac o-cresol / formaldehyde, novolac m-cresol / formaldehyde, novolac p-cresol / formaldehyde, novolac tert-butylphenol / formaldehyde, or novolac or o-octylphenol / formaldehyde. Particularly we prefer to use novolac p-cresol / formaldehyde. (For information on novolacs see Houben-Weyl, Methoden der Organischen Chemie, Vol. XIV / 2, pp. 193-292 and Ullmanns Encyclopaedie der Chemie, 4th edition, Vol 18, pp. 245-257, and for information on phosphates see for example Ullmanns Encyclopaedie der technischen Chemie, Vol. 12/1, p. 299 to 374). Component F The molding compositions of the invention may also contain an additive or mixture of different additives in amounts of 0 to 20% by weight, preferably 1 to 15% by weight based on the total weight of the molding compositions. Suitable components F are additives that are typical for and commonly employed in polycarbonate molding compositions such as dyes, for example pigments, optical brighteners, or fluorescent dyes, antistatic agents, antioxidants such as sterically hindered phenols, particularly tetrakis [methylene (3, 5-di-tert-butyl-4-hydroxyhydroquininamate)] methane or 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, UV stabilizers, adhesion promoters, release agents such as long-chain fatty acid esters or lubricants The UV stabilizers used can conveniently be, for example, phosphites, hypophosphites or phosphonites. Of these, phosphites are preferred wherein the three organic radicals are sterically hindered phenols such as tri (2,4-di-tert-butylphenyl) phosphite. These and other UV stabilizers and antioxidants suitable for use as component F and also processes for their preparation are described in DE-AI 4,419,897. These halogen-free phosphorus compounds F are generally known (cf for example Ullmann, Enzyklopaedie der technischen Chemie, Vol. 18, p. 301-f., 1979, Houben Weyl, Methoden der organischen Chemie, Vol. 12/1, p. 43, p. 136; Beilstein, Vol. 6 p. 177). Component G According to the invention, the molding compositions contain one or a mixture of two or more different low molecular weight halogen-free acids as component G. The content of this component in the molding compositions is generally from 0.05 to 2. % by weight, preferably 0.1 to 1.8% by weight, based on the total weight of the molding compositions. For the purposes of the present invention, "low molecular weight" is taken to refer to polynuclear compounds, for example up to penta-nuclear, particularly mono-molecular compounds. Of courseTypical associated acids are also intended to be understood by the term acid. Acid hydrates are also included. According to the invention, the acids are free of halogen, ie they do not contain halogens in the molecular structure. Acids that have slight halogen-containing impurities, however, are included for the purposes of the invention. Advantageously, acids are used which are only slightly volatile or non-volatile at the processing temperatures, or do not decompose at temperatures up to about 300 ° C.

The acids may contain one, two or more, for example, up to 10 acid groups. Preferably, organic acids are used. Both aromatic and aliphatic acids are suitable. Aliphatic / aromatic acids can also be used. Preferred acids include palmitic acid, stearic acid, benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, sulfonic acids such as p-toluenesulfonic acid, fumaric acid, citric acid, mandelic acid or tartaric acid. Particularly preferred acids used are the citric or p-toluene sulphonic acids or mixtures thereof. For example, the weight ratio of citric acid can be from 1 to 99%, preferably from 10 to 90% and that of p-toluene sulphonic acid in contrast to 99 to 1% and preferably 90 to 10%. Component H According to the invention, the molding compositions contain one or a mixture of two or more different poly (alkyl) acrylate (s). In general, poly (alkyl) acrylates are present in the molding compositions in concentrations of 0 to 10% by weight, preferably 0.5 to 5% by weight based on the total weight of the molding compositions.

Suitable H components are both homopolymers and copolymers such as random copolymers are blocking based on alkyl acrylates or methacrylates or their mixtures. In a preferred embodiment, poly (alkyl) acrylates are used which are compatible with component C. The "compatibility" of two polymer components usually refers to the miscibility of the components or the tendency of one of the polymers to dissolve in the other polymer components (cf B. Vollmert, Grundriss der makromolekularen Chemie, Vol. IV, p. 222 f. , E. Vollmert Verlag 1979). The solubility of two polymers can be determined indirectly, for example by taking the torsion pendulum, DTA or DSC readings, by observing the optical clarity of mixtures thereof or by nuclear magnetic resonance (NMR) relaxation methods. Particularly preferred are copolymers which are composed of at least two different alkyl esters, aromatic or alkyl aromatic esters of acrylic acid or methacrylic acid or mixtures thereof. The esters in general have from 1 to 10, preferably from 1 to 8 carbon atoms in the alkyl radical. The alkyl radical can be linear or branched. Alkyl radicals include methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, tert-butyl, n-pentyl, 2-ethylhexyl or cyclohexyl. Preference is given to methyl methacrylate, cyclohexyl methacrylate, n-butyl acrylate or 2-ethylexyl acrylate. Preferred aromatic esters are ethers having from 6 to 18 carbon atoms, especially phenyl. Particularly preferred are polyalkyl acrylates G containing from 70 to 99% by weight, in particular from 80 to 93% by weight of methyl methacrylate and from 1 to 30% by weight, in particular from 7 to 20% by weight of n-butyl acrylate. H polyalkyl acrylates having a high molecular weight are particularly preferred. They usually have molecular weights (weight average Mw) of at least 1,000,000 g / mol (measured by gel permeation chromatography and tetrahydrofuran against a polystyrene standard). Preferred polyalkyl acrylates G have molecular weights M w of 1,100,000 g / mol or more, for example at least 1,200,000 g / mol. In general, the polyalkyl acrylates G have a glass transition temperature in the range of 40 ° to 125 ° C, preferably 70 ° to 120 ° C (determined) by DSC measurement at a heating rate of 10 k / min, second cycle after heating to 175 ° C and cooling to room temperature).

The poly (alkyl) acrylates are known per se or can be synthesized by methods known per se. For example, they can be prepared by the suspension polymerization process described by H. G. Elias, Makromoleküle, 4th Edition 1981, Hüthig & Wopf Verlag, Basel. The preparation of molding compositions of the invention is carried out by processes known per se involving mixing of the components. It may be advantageous to pre-mix individual components. The network rubbers of component B can be added separately from the other graft polymers. It is also possible to mix the components in solution followed by removal of the solvent. Convenient organic solvents for components A to C and F additives for example are chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene and aromatic hydrocarbons, for example toluene. Evaporation of the solvent mixtures can be carried out for example in evaporative extruders. Mixed for example of the dry components A, B, C, D, G and H and optionally E and / or F can be carried out by all known methods. Preferably, however, the mixing of components A, B, C, D, G, and H and optionally E and / or F is carried out at temperatures of 200 ° to 320 ° C by extrusion, kneading or roller milling of the components together, the components have been previously isolated if necessary from the solution obtained during polymerization or from the aqueous dispersion. The thermoplastic molding compositions of the invention can be processed by known thermoplastic processing methods, i.e. by extrusion, injection molding, calendering, blow molding, compression molding or sintering. The molding compositions of the invention can be used for the preparation of shaped articles, fibers or films. Preferably, shaped articles are made from the molding compositions of the invention. The latter may be of a large or small magnitude and intended for external or internal applications. Preferably, large shaped articles for the construction of vehicles, particularly in the automotive industry, are made from the molding compositions of the invention. In particular, wheel plugs, or external parts of bodies, can be manufactured from the molding compositions of the invention. Specific examples that may be mentioned are fenders, rear doors, hoods, loading areas, covers for loading areas, side walls for loading areas or automotive roofs including removable or collapsible automotive roofs or automotive roof parts. The molding compositions of the invention are distinguished by the fact that they are stable under processing conditions and are easy to process. The formed articles made with them, are dimensionally stable and show improved characteristics at the break at low temperatures, compared to the previous technique. In addition, the molding compositions satisfy strict requirements regarding thermal stability. Examples The average particle size and the particle size distribution were determined from the integral mass distribution. In all cases the average particle sizes were averages by weight of the particle sizes as determined by analytical ultracentrifuge corresponding to the method proposed by W. Scholtan and H. Lange, Kolloid-Z and Z.-Polimere 250 (1972) , p. 782 to 796. Ultracentrifuge readings give the integral mass distribution of the particle size of a sample. From this, the percentage by weight of the particles having a diameter equal to or less than a certain size can be established. The average particle size also referred to as the d50 value of the integral mass distribution is defined as the particle size in which 50% by weight of the particles have a diameter smaller than the diameter corresponding to the d50 value. In this case, 50% by weight of the particles will then have a diameter greater than the value d5Q. To characterize the amplitude of the particle size distribution of the rubber particles, not only the d50 value (average particle size) is used, but also the d10 and d90 values that are provided by the integral mass distribution. The d10 or d90 values of the integral mass distribution are defined as for the d5a value except that they are related to 10% and 90% by weight of the particles respectively. The quotient Q = (d90-d10) / d50 represents a measure of the distribution range of particle sizes. The following components were used: A1) a commercially available polycarbonate based on bisphenol A having a viscosity number of 61.3 mL / g, measured in a solution with a concentration of 0.5% by weight in methylene chloride at 23 ° C. B1) a finely divided graft polymer is prepared from? L) 16 g of butyl acrylate and 0.4 g of tricyclodecenyl acrylate, which were heated to 60 ° C in 150 g of water with the addition of 1 g of sodium salt of a paraffinsulfonic acid with 12 to 18 carbon atoms, 0.3 g of potassium persulfate, 0.3 g of sodium hydrogen carbonate and 0.15 g of sodium pyrophosphate with agitation. Ten minutes after the start of the polymerization reaction, a mixture of 82 g of butyl acrylate and 1.6 g of tricyclodecenyl acrylate was added over a period of 3 hours. After all the monomer has been added, stirring is continued for another hour. The latex of the interlaced butyl acrylate polymer obtained had a solids content of 40% by weight. The average particle size (average weight) is found to be 76 nm and the particle size distribution was narrow (quotient Q = 0.29). Y2) 150 g of polybutyl acrylate latex obtained under? 1), mixed with 40 g of a mixture of styrene and acrylonitrile (weight ratio 75:25) and 60 g of water after the addition of more 0.03 g of Potassium persulfate and 0.05 g of lauroyl peroxide, stirred for a period of 4 hours at 65 ° C. After finishing the graft copolymerization, the polymerization product is precipitated from the dispersion with calcium chloride solution at 95 ° C and washed with water and dried in a hot stream of air. The degree of grafting of the graft copolymer was 35%, the particle size 91 nm. B2) A coarsely divided graft polymer is prepared as follows:? 3) To an initial mixture of 1.5 g of the latex prepared under? L) is added 50 g of water and 0.1 g of potassium persulfate and then over a period of 3 hours, a mixture of 49 g of butyl acrylate and 1 g of tricyclodecenyl acrylate was added as a stream and a solution of 0.5 g of the sodium salt of paraffinsulfadic acid having 12 to 18 carbon atoms in 25 g of water as another current, at 60 ° C. Then polymerization is continued over a period of 2 hours. The latex resulting from the interlaced butyl acrylate polymer had a solids content of 40%. The average particle size (average weight of latex) is found as 430 nm); the particle size distribution was narrow (Q = 0.1). 4) 150 g of latex prepared under? 3) were mixed with 20 g of styrene and 60 g of water, and after the addition of more than 0.03 g of potassium persulfate and 0.05 g of lauroyl peroxide was stirred for a period of time. 3 hour period at 65 ° C. The dispersion obtained during this graft copolymerization was then polymerized with 20 g of a mixture of styrene and acrylonitrile in a weight ratio of 75:25 for a further 4 hours. The reaction product was then precipitated from the dispersion by a solution of calcium chloride at 95 ° C, separated, washed with water and dried in a hot stream of air. The degree of grafting of the graft copolymer was found to be 35%; The average particle size of the latex particles was 510 nm. C1) A copolymer of styrene and acrylonitrile in a weight ratio of 81:19 and having a viscosity number of 72 mL / g (measured in a solution with a concentration of 0.5% by weight in dimethyl formamide a 23 ° C), prepared by continuous solution polymerization according to a process as described for example in Kunststoff-Handbuch, Vieweg-Daumiller, Vol. V (Polystyrol), Carl-Hanser-Verlag, Munich 1969, page 124, lines 12 and following. D ls Talco (IT-Extra sold by Norwegian Tale), characterized in that the average particle size (X50 value) was 4.91 μm and the average particle size of 90% of all the particles (X90 value) was less than 10.82 μm, determined by laser diffraction, the talc is suspended in a suspension cell in a mixture of water and surfactant (VE-Wasser / CV-K8-Tensid 99: 1, sold by CV Chemievertrieb, Hanover) using a magnetic stirrer to a 60 rpm speed. The pH value of the aqueous suspension was 8.5.

D 2) Talc (Microtalc MP 10-52 sold by Pfizer), characterized by an X50 value of 3.6 μm, and an X90 value of less than 8.9 μm, determined in a suspension as described under D1 '. The pH of the aqueous suspension was 8.6. D 3) Talc D11 neutralized with a 0.1 N HCl solution. The pH of the aqueous suspension was 7.3. .1) Triphenyl phosphate (Disflamoll ™ TP sold by Bayer) E¿ Resorcinodiphenyl phosphate (Fyroflex ™ RDP sold by Akzo) .D A high-molecular weight, high molecular weight ester (Loxiol ™ G70S sold by Henkel), characterized by a melt viscosity of 110-150 MPas at 80 ° C. Polytetrafluoroethylene (Teflon dispersion 30N sold by DuPont) G1) Hydrated p-toluenesulfonic acid, purity 98%, melting point 103 ° C. G2) Hydrated citric acid, purity 99%. H1 '- Polymethyl methacrylate, characterized by a molecular weight (Mw weight average) of 1,000,000 g / mol (determined by gel permeation chromatography in tetrahydrofuran against a standard of polymethyl methacrylate) H2) A copolymer of 89% by weight of methyl methacrylate and 11% by weight of n-butyl acrylate, characterized by a molecular weight (average weight Mw) of 1,800,000 g / mol (determined by gel permeation chromatography in tetrahydrofuran against a polystyrene standard). VH3 Polyacrylic acid, characterized by a molecular weight (Mw average in weight) of 2000 g / mol. Preparation of molding compositions. The components listed in the table below were mixed in a twin screw extruder (ZKS 30 sold by Werner und Pfleiderer) at 250 ° to 280 ° C, extruded and cooled and the extrudate was granulated. The dried granules were processed at 250 ° to 280 ° C to standard small rods, specimens and ISO discs (60 x 3 mm) using a mold temperature of 80 ° C. Utilitarian tests. The thermal deviation temperature of the samples is determined by the Vicat softening point.

The Vicat softening point is determined on standard small rods as specified in DIN 53.460, using a force of 49.05 N and a temperature increase of 50 K per hour. The flowability (MVI) of the molding compositions is determined as specified in DIN 53,735 at a temperature of 260 ° C and under a load of 5 kg. The notched impact strength (ak) is determined as specified in ISO 179 leA at room temperature. The percentage elongation at break is determined as specified in ISO 527 at a deformation rate of 50 mm / min at room temperature. The total penetration energies W3 [Nm] (average of five separate readings) were measured using the penetration test specified in DIN 53, 443 at -30 ° C. Both the energy consumption and the deformation distance were determined. The thermal expansion (CTE) was determined as specified in DIN 53,752, process A, in 2 specimens (10 x 10 x 4 cm) per test. The established values are those measured in the longitudinal direction at 25 ° C. Corresponding fire classification are performed in accordance with Ul-94 with reference to the following criteria: The compositions and results of the processing tests are listed in Table 1 and 2 below. Table 1 Table 2

Claims (9)

1. CLAIMS 1. A molding composition comprising: A) at least one polycarbonate, B) at least one graft polymer based on an elastomer having a glass transition temperature less than 10 ° C, C) at least one copolymer which contains vinylaromatic monomers, D) at least one filler and further, if desired, E) at least one flame retardant and F) at least one additive, wherein the molding composition contains G) at least one acid selected from the group comprising acid palmitic acid, stearic acid, benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, p-toluenesulfonic acid, fumaric acid, citric acid, mandelic acid and tartaric acid and also if desired h) at least one polyalkyl acrylic, and component D is at least a particulate filler in which at least 95% by weight of all particles have a diameter (largest dimension) of less than 45 μm and a ratio of dimensions in the range of 2 to 20 ..
2. 2. A c molding composition according to claim 1, characterized in that the component H is a polymethyl methacrylate having a molecular weight (numerical average Mn) of at least 1,000,000 g / mol.
3. 3. A molding composition according to claim 1, characterized in that the component G is citric acid or p-toluenesulfonic acid or its mixture.
4. 4. A molding composition according to any of claims 1 to 3, characterized in that the content of component is 0.05 to 2% by weight, based on the total weight of the molding composition and that of component H) is 0.1 to 10% by weight, based on the total weight of the molding composition
5. 5. A molding composition according to any of claims 1 to 4, characterized in that the B and / or C components are polymers containing groups oxazoline.
6. 6. A method for employing a molding composition according to any of claims 1 to 5 for the manufacture of shaped articles, films or fibers.
7. 7. A method for employing a molding composition according to any of claims 1 to 5, for the manufacture of articles with a large area.
8. 8. A method for employing a molding composition according to any of claims 1 to 5, for the manufacture of vehicular body parts.
9. 9. A shaped article when made from a molding composition according to any of claims 1 to 5