MXPA06008119A - Thermoplastic moulding masses made from styrol copolymers and polyamides - Google Patents

Abstract

The invention relates to thermoplastic moulding masses made from A) a polyamide with amino, or carboxyl end groups, or a mixture of said end groups, B) a mixture of at least two graft copolymers, each containing a rubber as graft base and a graft support made from an unsaturated monomer, differing in the rubber content thereof by at least 5 wt.%, C) a rubber-free copolymer containing, c1) at least 30 wt.%of units derived from a vinylaromatic monomer, based on the total weight of all units which contain C), c2) units derived from a monomer containing a functional group which may react with the end groups of the polyamides A) and c3) units, derived from a monomer containing no functional groups which react with the end groups of the polyamides A) and, optionally in addition, D) a rubber-free matrix polymer, E) a low-molecular weight compound with a dicarboxylic anhydride end group and F) one or a mixture of differing adjuncts.

Description

WO 2005/071013 Al illiril lll l1 !!! l! IIUIUIl! lll! lll Zur Erklarung der Zweibuchstaben-Codes und der anderen Ab-kürzungen wird auf die Erklárungen ("Guidance Notes on Codes and Abbreviations") am Anfang jeder regularen Ausgabe der PCT-Gazette verwiesen.

THERMOPLASTIC MOLDING MASSES PROCESSED FROM STYLE AND POLYAMIDE COPOLYMERS The present invention relates to thermoplastic molding compositions of A) a polyamide having amino or carboxy end groups or a mixture of these end groups, B) a shaped mixture by at least two graft copolymers, each comprising a rubber as the graft base and a graft based on an unsaturated monomer differing by at least 5% by weight from each other in terms of their rubber content, C) a free copolymer of rubber, comprising: cl) at least 30% by weight, based on the total weight of all units present in C), units derived from an aromatic vinyl monomer, c2) units derived from a monomer which comprises a functional group that can react with the end groups of the polyamide A), and c3) units that are derived from a monomer that does not comprise functional groups that react with the end groups of the polyamide A), and also further, if desired, D) a rubber-free matrix polymer, E) a low molecular weight compound comprising a dicarboxylic anhydride group, and F) an additive, or a mixture of several additives The present invention also relates to a process for preparing these molding compositions. The present invention also relates to the use of these molding compositions for the production of molded parts, films, fibers or foams. This invention also relates to molded parts, films, fibers, or foams that can be obtained from these molding compositions. Additional embodiments of the present invention are found in the claims, in the description and in the examples. Without departing from the scope of the present invention it is obviously also possible to use the features that have been mentioned above and the characteristics that will be mentioned below, for the molding compositions of the present invention not only in the specific combination indicated but also in other combinations. Mixtures are known in which polyamide and ABS type plastics are present. It is also known that mixtures of this type can be mixed with polymers having functional groups which can react with the end groups of the polyamide. These polymers act as compatibilizing agents between the polyamide phase and the phase formed by the ABS type plastics. The result is to improve the properties of the blends, and in particular the impact resistances are substantially increased. Mixtures of this type are known, inter alia, from EP-A 202 214, EP-A 402528 and EP-A 784 080. These specifications disclose mixtures each comprising a graft rubber described in greater details through its rubber content, and also, for example, through its gel content, its molecular weight, and its particle size. According to EP-A 784 080, the rubber of the graft copolymer can not contain any group that can react with the end groups of the polyamide. EP-A 220 155 discloses mixtures comprising, in addition to the polyamide, the compatibilizing component and the graft rubber, an acrylate copolymer rubber containing acid for further improvement of the impact resistance. When molded parts composed of plastic are used in apparatuses comprising moving parts that cause vibration, the plastic parts often emit unacceptable noise. In particular, in the vehicle manufacturing sector, there is a particular problem of sound deadening related to the use of plastic parts. Therefore, it is an object of the present invention, starting from the known mixtures and preserving their known good mechanical properties, to find molding compositions having good frictional properties, thus allowing a reduction of noise caused by vibrations, in particular screeching. Accordingly, the molding compositions defined at the beginning were found and furthermore have a better flowability together with a better notch impact strength compared to known mixtures. Component A For the purposes of the present invention, polyamides are long chain, synthetic, homopolymeric or copolymeric polyamides wherein repeating amide groups are a substantive constituent of the polymer backbone. Examples of these polyamides are nylon-6,6 (polycaprolactam), nylon-6,6 (polyhexamethyleneadipamide), nylon-4,6 (polytetramethyleneadipamide), nylon-6,10 (polyhexamethylene sebacamide), nylon-7 (polypentholactam a), nylon -11 (polyundecanolactam), nylon-12 (polidodecanolactam). As is known, these polyamides have the generic name of nylon. In principle there are two processes for the preparation of polyamides. Polymerization starting from dicarboxylic acids and starting from diamine, as in the case of polymerization starting from amino acids, reaction of the amino and carboxy end groups of the initial monomers or initial oligomers between them to form an amide and water group . The water can then be removed from the polymeric material. Polymerization starting from carboxamides reacts with the amino and amide end groups of the initial monomers or initial oligomers together to form an amide and ammonia group. The ammonia is then removed from the polymeric material. Examples of suitable initial monomers or suitable initial oligomers for the preparation of polyamides are: (1) amino acids C2-C20, preferably C3-C? 8, such as for example 6-aminocaproic acid, 11-aminoundecanoic acid, and also dimers, trimers, tetramers, pentamers and hexamers thereof, (2) amino acid amides C2 -C20, for example 6-aminocaproamide, 11-aminoundecanamide, and also dimers, trimers, tetramers, pentamers and hexamers thereof, (3) products of the reaction of: (3a) C2-C2alkylenediamines, preferably C2-C? 2, as for example tetramethylenediamine or preferably hexamethylenediamine, with (3b) a C2-C2o aliphatic dicarboxylic acid, preferably C2-C1, such as for example sebacic acid, decandicarboxylic acid or adipic acid, and dimers, trimers, tetramers, pentamers, and hexamers of these reaction products, (4) reaction products of (3a) with (4b) a C8-C20 aromatic dicarboxylic acid, preferably C8-C? 2 or derivatives thereof, for example chlorides, for example 2-acid, 6- naphthalend boxyl, preferably isophthalic acid or terephthalic acid, and also dimers, trimers, tetramers, pentamers and hexamers of these reaction products, (5) products of the reaction of (3a) with (5b) a C9-C2o arylaliphatic dicarbamoylic acid, preferably C9-C18, or derivatives thereof, for example, chlorides, for example, o-, m- or p-phenylenediacetic acid, and also dimers, trimers, tetramers, pentamers and hexamers of these reaction products, (6) products of the reaction of (6a) aromatic diamines of Ce-C2o, preferably C? -Cio, such as for example m- or p-phenylenediamine, with (3b), and also dimers, trimers, tetramers, pentamers and hexamers of these reaction products, (7) products of the reaction of (7a) arylaliphatic diamines of C-C2o, preferably C8-Ci8, such as for example m- or p-xylylenediamine, with (3b), and also dimers, trimers, tetramers, pentamers and hexamers of these products of the reaction, and (8) monomers or oligomers of an arylaliphatic lactase or preferably C2-C20 aliphatic, preferably C2-C8, such as, for example, enantolactam, undecanolactam, dodecanolactam or caprolactam, and also homopolymers or copolymers or mixtures of these initial monomers or initial oligomers. Preference is given here to the initial monomers or initial oligomers which, during the polymerization, provide the polyamides nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-7, nylon-11, or nylon-12, in particular nylon-6 or nylon-66. A mixture of two or more of these polyamides can also be used as component A). Nylon-6 is very particularly preferably used as polyamide A). In accordance with the present invention, the end groups of the polyamide A) are amino or carboxy end groups, or a mixture thereof. The polyamides A) used herein may comprise polyamides having an excess of amino end groups, or polyamides having an excess of carboxy end groups. The polyamides A) used preferably comprise polyamides having an excess of carboxy end groups. The content of component A) in the molding compositions according to the present invention can vary widely. Preferred molding compositions of the present invention comprise amounts of 5 to 95.05% by weight, in particular from 7.5 to 91.599% by weight, of component A), based on the total weight of the molding composition. Particularly preferred molding compositions comprise from 10 to 89.15% by weight of component A), based on the total weight of the molding composition. Component B According to the present invention, a mixture composed of two or more, for example three to five different graft copolymers is used as component B). The mixture preferably comprises two different graft copolymers. Each of the graft copolymers comprises a rubber as the graft base and a graft. In accordance with the present invention, this should be construed as including the possibility that two or more soft phases (i.e. rubber phases) and two or more hard phases may be present. In accordance with the present invention, the graft copolymers differ from each other at least in rubber content in% by weight, based on the total weight of the graft copolymer and calculated on the basis of the amount of starting material. This difference in content is at least 5% by weight according to the present invention. In one of the preferred embodiments, the difference in rubber content is at least 6% by weight, for example from 6 to 10% by weight. In accordance with the present invention, the rubber content refers to the entire content of the soft phases in each graft copolymer. The graft copolymers can have the same structure in other aspects. However, they can also be based on rubbers of different monomeric composition, or have a different graft. In addition they can have not only a different graft base but also a different graft, for example a different sequence of soft and hard phases, or they can be based on different monomeric units. In principle, suitable rubbers as grafting base are all rubbers whose glass transition temperature is 0 ° C (in accordance with what is determined by DIN 53765) or less. The rubbers can be of very different types. By way of example, silicone rubbers, olefin rubbers, such as, for example, ethylene rubbers, propylene rubbers, ethylene-propylene rubbers, EP (D) M rubbers, block rubbers, such as, for example, rubbers, may be used. styrene-ethylene-butadiene-styrene (SEBS), diene rubbers, acrylate rubbers, ethylene-vinyl acetate rubbers, or ethylene-butyl acrylate rubbers.

Preferred silicone oils comprise, as organic radicals, at least 80 mol% of methyl groups. The end group is generally a diorganylhydroxysiloxy unit, preferably a dimethylhydroxysiloxy unit. Crosslinked silicone oils are particularly preferably used as graft base cl). By way of example, they can be prepared through a first step wherein silane monomers, such as dimethyldichlorosilane, vinylmethyldichlorosilane, or dichlorosilanes having other substituents, react to provide cyclic oligomers. In a further step, crosslinked silicone rubbers can be obtained by ring-opening polymerization of the cyclic oligomers with addition of crosslinking agents, such as for example mercaptopropylmethyldimethoxysilane. The diameter of the silicone rubber particles (average weight d50) is generally 0.09 to 1 μm, preferably 0.09 to 0.4 μm (in accordance with what was determined according to W. Scholtan and H.

Lange, Kolloid-Z. and Z. -Polymere 250 (1972), pages 782-796, through an ultracentrifuge). EP (D) M type rubbers suitable as the graft base are copolymer or terpolymers containing at least one ethylene unit and one propylene unit, and preferably a small number of double bonds, that is, less than 20 double bonds per 1000. carbon atoms. The terpolymers generally comprise at least 30% by weight of units that are derived from ethylene and at least 30% by weight of units that are derived from propylene, based on the total weight of terpolymer. Other units present in the terpolymers generally comprise diolefins having at least five carbon atoms. Processes for their preparation are known per se. The diameters of the rubber particles EP (D) M (average weight d 50) are generally within a range between 0.05 to 10 μm, preferably from 0.1 to 5 μm, in particular from 0.15 to 3 μm (in accordance with the determined as established above through an ultracentrifuge). Acrylate rubber which can be used are in particular polymers formed by alkyl acrylates, which may comprise up to 40% by weight of other copolymerizable monomers, based on the total weight of the acrylate rubber. Preference is given to C? -C8 alkyl esters, for example methyl esters, ethyl esters, butyl esters, n-octyl esters and 2-ethylhexyl esters, or a mixture of the mentioned esters. Crosslinked acrylate rubber is used particularly preferably as a graft base. Processes for their preparation are familiar to the person with knowledge in the field. The diameters of their particles are generally within the range of the diameters mentioned for EP (D) type rubbers. Acrylate rubbers and diene rubbers are preferred as the graft base. However, particular preference is given to the use of diene rubbers as grafting rubbers. As a graft base, very particular preference is given to diene rubbers formed by Bll) of 50 to 100% by weight of at least one diene having conjugated double bonds, and bl2) from 0 to 50% by weight of one or more monoethylenically unsaturated monomers, the weight percentages of bll) and bl2) provide a total of 100. The dienes that can be used and have conjugated double bonds, bll), can in particular comprise butadiene, isoprene, and derivatives thereof substituted with halogen, such as for example chloroprene. Preference is given to butadiene or isoprene, especially butadiene. Examples of other monomers b2) monoethylenically unsaturated which can be present with concomitant reduction of the amounts of monomers bll) in the diene rubber are: vinylaromatic monomers, preferably styrene or styrene derivatives, such as, for example, C est-C8 alkyl substituted styrenes , for example, α-methylstyrene, p-methylstyrene, vinyltoluene; unsaturated nitriles, such as, for example, acrylonitrile or methacrylonitrile; aliphatic esters such as, for example, esters, C 1 -C 4 alkyl of methacrylic acid or acrylic acid, for example, methyl methacrylate, and also the glycidyl esters, glycidyl acrylate and glycidyl methacrylate; N-substituted maleimides, such as N-methyl, N-phenyl, and N-cyclohexylmaleimide; acids, such as, for example, acrylic acid, methacrylic acid; and dicarboxylic acids, such as, for example, maleic acid, fumaric acid, and itaconic acid, and also their anhydrides, such as, for example, maleic anhydride; nitrogen-functional monomers, such as, for example, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinylaniline, acrylamide, and methacrylamide; aromatic and araliphatic esters of (meth) acrylic acid, such as, for example, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, and methacrylate. of 2-phenoxyethyl; unsaturated ethers, such as, for example, vinyl methyl ether or vinyl butyl ether. It is obviously also possible to use a mixture consisting of two or more of these monomers.

Preferred monomers bl2) are styrene, acrylonitrile, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, or butyl acrylate. The preparation of the rubbers is known to persons with experience in the field or can be carried out using methods known to the person skilled in the art. By way of example, the diene rubbers can be prepared through a first step in which they are not produced in the form of particles, examples of methods here are solution polymerization or gas phase polymerization, the polymers are then dispersed in the aqueous phase in a second stage (secondary emulsification). For the preparation of the rubbers, preference is given to the heterogeneous polymerization processes that form particles. This dispersion polymerization can be carried out, by way of example, in a manner known per se, by emulsion polymerization, inverse emulsion polymerization, mini-emulsion polymerization, microemulsion polymerization, or microsuspension polymerization, using a feed process, continuously, or well using a batch process. The rubbers can also be prepared in the presence of fine particle latex which forms an initial charge (known as the "latex seed" polymerization method). By way of example, suitable seed mats consist of polybutadiene or polystyrene. In principle, it is also possible to use the rubbers as the graft base after their preparation. However, before grafting they can be agglomerated first through the agglomeration process to provide larger particles. The agglomeration processes are known to people with experience in the field. Methods known per se of the person skilled in the art can be used for the purpose of undertaking the agglomeration process. For example, physical methods can be used, such as freezing agglomeration processes or pressure agglomeration processes. However, it is also possible to use chemical methods to agglomerate the primary particles. Among the latter, the addition of organic or inorganic acids can be mentioned. The agglomeration is preferably carried out through an agglomeration polymer in the absence or presence of an electrolyte, such as, for example, an inorganic hydroxide. By way of example, agglomeration polymer which may be mentioned are polyethylene oxide polymers or polyvinyl alcohols. Among the suitable agglomeration polymers are copolymers of C 1 -C 2 alkyl acrylates or C 1 -C 2 alkyl methacrylates and of polar comonomers such as acrylamide, methacrylamide, ethacrylamide, n-butylacrylamide, or maleamide. The rubbers preferably have particle sizes (average weight d50) within a range of 100 to 2500 nm. The particle size distribution is preferably almost totally or completely monomodal, or almost bimodal or totally bimodal. The graft copolymers comprise a graft based on an unsaturated monomer, and this means that the graft may also have been prepared from two or more unsaturated monomers. In principle, a very wide variety of unsaturated compounds can be used to graft rubber. Suitable compounds and methods are known per se to the person skilled in the art. Preference is given to a graft comprising B21) of 50 to 100% by weight, preferably 60 to 100% by weight, and particularly preferably 65 to 100% by weight, of a vinylaromatic monomer. B22) from 0 to 50% by weight, preferably from 0 to 40% by weight, and particularly preferably from 0 to 35% by weight, of acrylonitrile or methacrylonitrile or a mixture of these, B23) from 0 to 40% by weight weight, preferably from 0 to 30% by weight, and particularly preferably from 0 to 20% by weight, of one or more other monoethylenically unsaturated monomers, wherein the proportions of components b21) to b23) give a total of 100% in weigh. Vinylaromatic monomers that can be used are vinylaromatic compounds in accordance with that specified in bl2), or a mixture consisting of two or more of these, in particular styrene, or α-methylstyrene. Other monoethylenically unsaturated monomers are, as specified in bl2), the aliphatic, aromatic and araliphatic esters, acids, nitrogen-functional monomers and unsaturated ethers and mixtures of these monomers. However, the graft may also comprise monomers having functional groups, and especially exoxy groups or oxazoline groups may be mentioned among these. To prepare the graft, one or several steps of the process can be used. The monomers here, b21), b22), and b23), can be added individually or in a mixture between them. The proportion of monomers in the mixture can be constant over time or represent a gradient. You can also use combinations of these procedures. By way of example, the polymerized material in the graft base may first be styrene alone, and then a mixture of styrene and acrylonitrile. By way of example, preferred grafts consist of styrene and / or of α-methyl styrene, and of one or more other monomers mentioned in b22) and b23). Preference is given to methyl methacrylate, N-phenylmaleimide, maleic amide, and acrylonitrile, with methyl methacrylate and acrylonitrile being particularly preferred.

Preferred grafts are derived from: b2-l: styrene b2-2: styrene and acrylonitrile, b2-3: α-methylstyrene and acrylonitrile, b2-4: styrene and methyl methacrylate The proportion of styrene or α-methylstyrene, or the The proportion of the total styrene and α-methylstyrene is particularly preferably at least 40% by weight, based on the graft. As mentioned above, other suitable graft copolymers are copolymers with two or more "soft" stages and "hard", especially if the particles are relatively large. Preference is given to the graft copolymers comprising (based on the graft copolymer) b) 30 to 95% by weight, preferably 40 to 90% by weight, and in particular 40 to 85% by weight, based on grafting (ie, rubber), and b2) from 5 to 70% by weight, preferably from 10 to 60% by weight, and in particular from 15 to 60% by weight, of a graft. By way of example of preferred graft copolymers, mention may be made of the copolymers comprising (based on the graft copolymer), bl) from 30 to 95% by weight of a graft base comprising (based on bl)) 100% by weight of butadiene, and b2) from 5 to 70% by weight of a graft comprising (based on b2)) 65 to 85% by weight of styrene and 15 to 35% by weight of acrylonitrile. Other preferred graft copolymers are the copolymers comprising (based on the graft copolymer) bl) from 30 to 95% by weight of a graft base comprising (based on bl)) from 50 to 97% by weight of butadiene and from 3 to 50% by weight of styrene, and b2) from 5 to 70% by weight of a graft comprising (based on b2)) from 65 to 85% by weight of styrene and from 15 to 35% by weight of acrylonitrile. By way of example, among the preferred graft copolymers, there are also those which comprise (based on the graft copolymer)), bl) from 30 to 95% by weight of a graft base comprising n-butyl acrylate and containing a crosslinking agent and b2) from 5 to 70% by weight of a graft comprising (based on graft)) from 65 to 85% by weight of styrene and from 15 to 35% by weight of acrylonitrile. The grafting process is carried out in emulsion. Appropriate process measures are known to people with knowledge in the field. If non-grafted copolymers consisting of the monomers b2) are produced, these amounts, which are generally less than 10% by weight of B), are counted within the weight of component D). The content of component B) in the molding compositions of the present invention can vary widely. Preferred molding compositions of the present invention comprise amounts of from 4 to 50% by weight, in particular from 6 to 45% by weight, of component B), based on the total weight of the molding composition. Particularly preferred molding compositions comprise from 8 to 40% by weight of component B), based on the total weight of the molding composition. Component C) In accordance with the present invention, component C) comprises a rubber-free copolymer. For the purposes of the present invention, this also means that component C) may comprise a mixture of two or more of these copolymers. Structurally, the copolymer C) consists of at least 30% by weight, based on the total weight of all units present in C), of units (cl) which are derived from vinylaromatic monomers. In other aspects, the structure is variable within wide limits and is contemplated especially to render the copolymers C) at least to some extent, preferably substantially, miscible with component B. The nature and amount of the functional groups should be such that a reaction can be carried out with the end groups of the polyamides A). In one of the preferred embodiments, the C-copolymers are based on a vinylaromatic compound (cl) and comprise, as units (c2), dicarboxylic anhydrides (c21) or dicarboxylic imides (c22), or a mixture of c21) and c22), and comprise units (c3) which are derived from other monomers in which the groups present do not react with the end groups of the polyamide, or react only to a small fraction of the speed . In this embodiment, the proportion of the units cl) is preferably from 50 to 85% by weight, in particular from 60 to 80% by weight. The copolymers C) very particularly preferably comprise 65 to 78% by weight of units that are derived from aromatic vinyl compounds. In each case, the weight% data are based on the total weight of cl) to c3). The proportion of the units c21) which are derived from α, β-unsaturated dicarboxylic anhydrides is preferably from 0.3 to 25% by weight. Copolymers C) having substantially less than 0.3% by weight of units c21), for example those having less than 0.1% by weight of these units, in general do not have sufficient reactivity. Those having substantially more than 25% by weight generally become difficult to process due to their excessively high crosslinking activity. The copolymers C) preferably comprise from 0.5 to 15% by weight, in particular from 0.7 to 10% by weight, very particularly preferably from 0.8 to 5% by weight, of c21), for example from 1 to 3% by weight from c21). The weight% data are based here in each case on the total weight of units cl) to c3). Instead of the units c21) or, as preferred, in addition to them, the copolymers C) can comprise units c22) which are derived from cyclic dicarboxylic imides in particular, α, β-unsaturated. They are generally present from 0 to 49.7% by weight in copolymers C). Preferred copolymers C) comprise from 0 to 39.5% by weight of c22), in particular from 0 to 34.2% by weight, the weight% data are based in each case on the total weight of units cl) to c3) . If the copolymers do not comprise c22), the copolymers C) may further comprise from 14.7 to 40% by weight, preferably from 19.5 to 35% by weight, in particular from 21.3 to 33% by weight, based on the total weight of the units cl) to c3), of units c3) that are derived from other compounds capable of polymerization by free radicals. Particular aromatic vinyl compounds that can be used are styrene and styrene derivatives. Suitable styrene derivatives include α-methylstyrene and styrene derivatives substituted on the aromatic ring, for example vinyltoluene, tert-butylstyrene, or chlorostyrene. It is obviously also possible to use a mixture of different vinyl compounds. aromatic. It is very particularly preferable to use styrene. Among the preferred α, β-unsaturated dicarboxylic anhydrides are cyclic compounds, especially those having 2 to 20 carbon atoms. The double bond can be either exocyclic or endocyclic. Among these compounds, particular preference is given to maleic anhydride, methylmaleic anhydride, or itaconic anhydride. It is also possible to use a mixture of several dicarboxylic anhydrides. It is very particularly preferable to use maleic anhydride alone. The c22) a, β-unsaturated dicarboxylic imides correspond generally to the aforementioned dicarboxylic anhydrides. The substituent on the nitrogen is generally a C 1 - C 2 - alkyl radical, C 4 - C 2 - cycloalkyl, C 1 -C 6 - o - aryl - C 6 - Ci 8 - alkyl or a C 6 - C 18 aryl radical. The alkyl radicals can be either linear or branched and can have interruption through one or several oxygen atoms, there being no direct bond of the oxygen atoms with the nitrogen atoms or another oxygen atom. Among these alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-decyl, and n-dodecyl. The cycloalkyl radicals can be either unsubstituted or substituted. Examples of suitable substituents are alkyl groups such as methyl or ethyl. Examples that may be mentioned of cycloalkyl radicals are cyclobutyl, cyclopentyl, cyclohexyl, and p-methylcyclohexyl. The alkyl group of the alkylaryl radicals may be either linear or branched, and the alkylaryl radicals may also have substituents. Examples of these substituents are alkyl groups, such as, for example, methyl or ethyl, or halogen atoms, such as, for example, chlorine or bromine. Examples of alkylaryl radicals that can be used are benzyl, ethylphenyl, or p-chlorobenzyl. The aryl radicals may also be substituted or unsubstituted, examples of suitable substituents being alkyl groups, such as for example methyl or ethyl, or halogen atoms, such as for example chlorine or bromine. Among the preferred aryl radicals are phenyl and naphthyl. Very particularly preferred radicals are cyclohexyl or phenyl. By way of example of units c3), mention may be made here of acrylic acid and acrylic acid derivatives, such as, for example, methacrylic acid, alkyl acrylates, such as, for example, ethyl acrylate, methyl methacrylate, ethyl methacrylate, or cyclohexyl methacrylate. , or unsaturated nitrates, such as acrylonitrile, methacrylonitrile. Mixtures of these monomers can also be used. It is very particularly preferable to use acrylonitrile alone. By way of example of preferred copolymers C), those having the following composition can be mentioned: Copolymers comprising cl) from 50 to 85% by weight, preferably from 60 to 81% by weight, of styrene, c2) from 0.5 to 10% by weight, preferably 1 to 5% by weight, of maleic anhydride, and c3) of 14.5 to 40% by weight, preferably 18 to 35% by weight, of acrylonitrile, wherein the proportions of cl) to c3 ) give a total of 100% by weight. The copolymers C) for this embodiment preferably comprise the units cl) to c3) with random distribution. The molar masses M (weight-average) of the copolymers C) are generally within a range between 30,000 to 500,000 g / mol, preferably between 50,000 to 250,000 g / mol, in particular between 70,000 to 200,000 g / mol, in accordance with that determined by GPC using tetrahydrofuran (THF) as eluent and calibration with polystyrene. The copolymers C) for this embodiment can, by way of example, be prepared by free radical polymerization of the corresponding monomers. This reaction can be carried out either in suspension or in emulsion, or in solution or in bulk, the latter mode being preferred. The free radical reaction can generally be initiated using the usual methods, for example, light, or preferably employing free radical initiators, such as peroxides, for example benzoyl peroxide. It is also possible to carry out a thermally initiated polymerization. Another method for preparing the copolymers C) for this embodiment is to first react the components cl), c21), and, if appropriate, c3) between them in a free radical reaction, and then convert some of the anhydride groups present in the product of the reaction in imide groups, using appropriate primary amines or ammonia, thus producing the c22 units). This reaction is usually carried out in the presence of a tertiary amine as catalyzing at temperatures between 80 and 350 ° C. In another preferred embodiment, the copolymers C) comprises, in place of units c21) and c22) or a mixture thereof, units (c23) which are derived from an unsaturated monomer comprising an epoxy group. The units c23) can also be based on a mixture of two or more different monomers of this type. The monomers may have one epoxy group, or two or more epoxy groups. It is particularly preferable to use glycidyl methacrylate alone. Among the preferred copolymers C) for this embodiment are: Copolymers comprising cl) of 65 to 85% by weight, preferably 70 to 80% by weight, of styrene, c23) of 0.5 to 10% by weight, preferably 1 to 5% by weight, of glycidyl methacrylate, and c3) from 14.5 to 34.5% by weight, preferably from 19 to 29% by weight, of acrylonitrile, wherein the proportions of cl) to c3) give a total of 100% by weight. The copolymers C) for this embodiment can be prepared, for example, by suspension polymerization in polyvinyl alcohol in the presence of a peroxide initiator. The copolymers C) for this embodiment generally have molar masses (weight-average Mw) within a range of 50,000 to 1,000,000 g / mol, preferably 70,000 to 500,000 g / mol, as determined by GPC using THF as eluent, against a polystyrene standard. The amount of component C) generally used in the molding compositions according to the present invention is from 0.95 to 25% by weight, preferably from 1.4 to 20% by weight, in particular from 1.8 to 15% by weight, based on the total weight of the molding composition. Component D In accordance with the present invention, component D is a rubber-free matrix polymer, a term which also includes mixtures consisting of two or more different matrix polymers. The selection of the molecular structure of the matrix polymer is preferably such that the matrix polymer is compatible with the graft. The monomers b2) therefore preferably correspond to the monomers of the matrix polymer. However, the matrix polymers preferably do not comprise functional groups that can react with the end groups of the polyamides. By way of example, amorphous polymers are suitable as a matrix polymer. The material here may be, for example, SAN (styrene-acrylonitrile), AMSAN (α-methylstyrene-acrylonitrile), styrene-maleimide-maleic anhydride.

(SNPMIMA), polymers of styrene-maleic acid (anhydride) -acrylonitrile, or SMSA (styrene-maleic anhydride). Component D therefore preferably comprises a copolymer consisting of di) from 60 to 100% by weight, preferably from 65 to 80% by weight, of units of a vinylaromatic monomer, preferably of styrene, of a substituted styrene, or of a (meth) acrylic ester, or a mixture thereof, in particular styrene or α-methyl styrene, or a mixture thereof. d2) from 0 to 40% by weight, preferably from 20 to 35% by weight, of units of an ethylenically unsaturated monomer, preferably of acrylonitrile or of a methacrylonitrile or of methyl methacrylate, in particular of acrylonitrile. In one embodiment of the present invention, the matrix polymer herein consists of 60 to 99% by weight vinylaromatic monomer and 1 to 40% by weight of at least one of the other monomers indicated. In one embodiment of the invention, a copolymer of styrene and / or α-methylstyrene with acrylonitrile is used as the matrix polymer. The content of acrylonitrile in these copolymers is from 0 to 40% by weight, preferably from 18 to 35% by weight, based on the total weight of the matrix polymer. The molar masses (average weight Mw) are generally within the range of 50,000 to 500,000 g / mol, preferably in the range of 70,000 to 450,000 g / mol. The matrix polymers are known per se or can be prepared by methods known to the person skilled in the art. The content of component D) in the thermoplastic molding compositions is generally from 0 to 50% by weight, preferably from 1 to 45% by weight, in particular from 1 to 40% by weight, based on the total weight of the composition of molding. Component E) A low molecular weight compound having only one dicarboxylic anhydride group can be used concomitantly as an additional component. However, it is also possible to use two or more of these compounds as component E). These compounds may comprise, in addition to the dicarboxylic anhydride group, other functional groups which can react with the end groups of the polyamides. Examples of suitable -compounds E) are C 1 -C 0 alkyldicarboxylic anhydrides, such as, for example, succinic anhydride, glutaric anhydride, adipic anhydride. It is also possible to use cycloaliphatic dicarboxylic anhydrides, such as, for example, 1,2-cyclohexanedicarboxylic anhydride. It is also possible to use dicarboxylic anhydrides which are ethylenically unsaturated or aromatic compounds, for example, maleic anhydride, phthalic anhydride, or trimellitic anhydride. The content of component E) is generally from 0 to 3% by weight, preferably from 0.001 to 2% by weight, based on the total weight of components A to F. Component F) The molding compositions can comprise additives. Their content is generally from 0 to 60% by weight, preferably from 0 to 50% by weight, based on the total weight of components A to F. Examples of fillers that can be used are particulate mineral fillers. Suitable substances among these particulate mineral fillers are amorphous silicas, carbonates, such as magnesium carbonate (gis), quartz powder, mica, a very wide range of silicates, such as clays, muscovite, biotite, suzoite, tin maquette, talc, chloride, phlogophyte, fedelspate, calcium silicates, such as volastonite, or kaolin, particularly calcined kaolin. In a particularly preferred embodiment, particulate fillers are used of which at least 95% by weight, preferably at least 98% by weight of the particles have a diameter (largest dimension), as determined in the finished product, lower at 45 μm, preferably below 40 μm, and for which what is known as the aspect ratio is preferably within a range of 1 to 25, especially within a range of 2 to 20, as determined in the finished product, that is, generally in an injection molded product. An example of a method for determining this particle diameter records electron micrographs of thin sections of the polymer mixture and uses at least 25, preferably at least 50, filler particles for evaluation. The particle diameters can also be determined by sedimentation analysis, in accordance with that indicated in Transactions [Transactions] of ASAE, page 491 (1983). The proportion of fillers by weight that is less than 40 μm can also be measured through sieve analysis. The aspect ratio is the ratio between the particle diameter and the thickness (the relationship between the largest dimension and the smallest dimension). Particularly preferred particulate fillers comprise talc, kaolin, such as calcined kaolin, or volastonite, or a mixture of two or all of these fillers. Among these, particular preference is given to talc with a proportion of at least 95% by weight of particles whose diameter is less than 40 μm and whose aspect ratio is from 1.5 to 25, in each case in accordance with that determined in the product. finished. The kaolin preferably has a proportion of at least 95% by weight of particles whose diameter is less than 20 μm and whose aspect ratio is 1.2 to 20, in accordance with what is determined in each case in the finished product. These fillers can be used in amounts of 0 to 40% by weight, preferably up to 30% by weight, based on the total weight of A to F. The component F) used can also comprise fibrous fillers such as carbon fibers, fibers of potassium titanate, aramid fibers, or preferably glass fibers, at least 50% by weight of the fibrous fillers (glass fiber) have a length greater than 50 μm. The fibers (glass) used can preferably have a diameter of up to 25 μm, particularly preferably from 5 to 13 μm. It is preferable that at least 70% by weight of the glass fibers have a length greater than 60 μm. In the finished molded product, the average length of the glass fibers is particularly preferably 0.08 to 0.5 mm. The length of the glass fibers refers to a finished molded product, for example a product obtained by injection molding. The glass fibers added to the molding compositions can be either strands of continuous filaments (twisted) or they may have been previously converted to the appropriate length. The amounts used of these fibers, based on the total weight of A to F, are generally from 0 to 60% by weight, preferably up to 50% by weight. Pyro-retarding agents containing phosphorus can be used as component F). Examples are tris (2, g-dimethylphenyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcresyl phosphate, diphenyl cresyl phosphate, tris (isopropylphenyl) phosphate, and also diphenyl 4-phenyl phosphate, phenyl bis (4-phenylphenyl) phosphate , tris (4-phenylphenyl) phosphate, diphenyl benzylphenyl phosphate, phenyl bis (benzylphenyl) phosphate, tris (benzylphenyl) phosphate, phenyl bis (l-phenylethylphenyl) phosphate, phenyl bis (1-methyl-1-phenylethylphenyl) phosphate, and phenyl bis [4- (1-phenethyl) -2,6-dimethylphenyl] phosphate. They can also be used in a mixture with triphenylphosphine oxide and tris (2,6-dimethylphenyl) phosphine oxide. Other preferred pyro-retardant agents are resorcinol diphosphate and higher oligomers thereof, hydroquinone diphosphate and higher oligomers thereof. The generally used amounts of the pyro-retarding agents are from 0 to 20% by weight, preferably from 0 to 17.5% by weight. If present, the amounts present are preferably 0.4 to 10% by weight. In each case, the amounts given are based on the total weight of A to F. Examples of other additives that may be mentioned are processing aids, stabilizers, and oxidation retardants, agents to counteract the decomposition by heat and decomposition by light ultraviolet, lubricants and mold release agents, dyes and pigments, and also plasticizers. The proportion of these is generally from 0 to 45% by weight, preferably from 0 to 20% by weight, in particular from 0% by weight, and if 0.2 to 10% by weight are present, based on the total weight of the product. A to F. The generally present amounts of pigments and dyes are from 0 to 4% by weight, preferably from 0 to 3.5% by weight, and in particular from 0% by weight, and if present, from 0.5 to 3% by weight. weight, based on the total weight of A to F. The pigments for the coloring of thermoplastic agents are well known. A first preferred group of pigments that may be mentioned is the group of white pigments such as for example zinc oxide, zinc sulphide, white lead (2PbC03 * Pb (OH) 2), lithopones, antimony white, and titanium dioxide. Of the two most commonly found crystalline forms (rutile and anatase) of titanium dioxide, it is in particular the rutile form which is used for the white coloration of the molding compositions according to the present invention. Black pigments which can be used in accordance with the present invention are iron oxide black (Fe304), spinel black (Cu (Cr, Fe) 20), manganese black (a mixture of manganese dioxide, silicon oxide, and iron oxide, cobalt black, and antimony black, and also particularly preferably carbon black, which is used primarily in the form of furnace black or gas black) .

To establish particular color tones, inorganic color pigments can obviously be used according to the present invention. It may also be advantageous to use the pigments and, respectively, mentioned dyes in a mixture, for example, carbon black with copper phthalocyanines, since the dispersion of the color in the thermoplastic becomes generally simpler. Examples of oxidation retarding agents and thermal stabilizers that can be added to the thermoplastic compositions of the present invention are metal halides of group I of the periodic table, for example, sodium halides, lithium halides, if appropriate in combination with cuprous halides such as for example with chlorides, bromides, or iodides. Halides, in particular copper halides, may also contain electron-rich p-ligands. As an example of these copper complexes, there can be mentioned copper halide complexes with, for example, triphenyl phosphine. Zinc fluoride and zinc chloride can also be used. Other compounds which can be used are sterically hindered phenols, hydroquinones, substituted members of this group, secondary aromatic amines, HALS, if appropriate in combination with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations up to 2. % by weight, based on the total weight of A to F. Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones which are usually used in amounts of up to 2% by weight based on the total weight of A F. Lubricants and mold release agents which are generally used in amounts of up to 1% by weight based on the total weight of A to F are stearic acids, stearyl alcohol, alkyl stearates and stearamides, and pentaerythritol esters with long chain fatty acids. It is also possible to use calcium stearate, zinc stearate, or aluminum stearate, or dialkyl ketones, such as, for example, distearyl ketone. Other lubricants and mold release agents that may be used are copolymers of ethylene oxide-propylene oxide. It has been found that the addition of stearates or silicone oils in amounts of 0.3 to 1.5% by weight, based on the total weight of the molding compositions, can greatly reduce the formation of flow lines during processing. The molded objects formed by the molding compositions in which these additives are present are also especially resistant to scratches. The amounts of the stearates or silicone oil preferably added for this purpose are within a range of 0.3 to 1.3% by weight, in particular 0.1 to 1% by weight, based on the total weight of the molding compositions. It can be used here, for example, of the stearic acid salts mentioned above. It is also possible to use a mixture consisting of two or more different salts of stearic acid. The silicone oils used are preferably those derived from linear polysiloxanes. Linear polydimethylsiloxanes are particularly preferred. Particularly preferred silicone oils include oils whose viscosity is within a range of 20 to 100,000 mPas (dynamic viscosity at 25 ° C), preferably 100 to 60,000 mPas. It is also possible to use a mixture consisting of two or more different silicone oils. Mixtures consisting of a stearate, or a mixture of different stearates, with a silicone oil, or a mixture of different silicone oils, can also be used. By way of example, a mixture consisting of calcium stearate with polydimethylsiloxane can be used. However, it is preferable to use either a stearate or a silicone oil alone. Calcium stearate is used as particularly preferred stearate and polydimethylsiloxane is used as a particularly preferred silicone oil. It has been found particularly helpful to use calcium stearate alone.

There is a very wide range of methods for introducing the stearate or the silicone oil or its mixtures into the molding compositions. By way of example, they can be fed separately or in a mixture. By way of example, it is possible here to add these additives together with the other components or after addition of some of the other components, and mix them with them. However, it is possible to delay the addition of these additives, by way of example, until the molding compositions have formed into pellets, and then apply them to the surface of the pellets. The thermoplastic molding compositions in accordance with the present invention can be prepared through processes known per se, by mixing component A) with components B) and C), and also, if present with components D) to F). All the components here can be mixed together. However, it can also be advantageous to pre-mix individual components. It is also possible, although less preferred, to mix the components in solution with removal of the solvents. In accordance with one embodiment of the present invention, it is preferable to pre-mix the component C) and a portion of the component A) in the form of their pellets and then melt them together and react them to provide a graft copolymer P). This process can use the mixture of different copolymers C), or only a copolymer C). In principle, a very wide range of methods can be used to mix the pellets together, for example manually, with turbine mixer, fluid mixer, Róhnrad mixer. It is particularly preferred to mix the pellets together at room temperature by means of a turbine mixer and within a period of 1 to 5 minutes. The melt assembly used may comprise, for example, Maxwell mixers, Banbury mixers, kneaders, Buss co-kneaders, Farrell kneaders, or single screw, two screw, or multiple screw extruders, for example a ring extruder or an extruder. of planetary gears. In the case of the use of the twin screw extruders, those that are co-rotating screws or those that are counter-rotating screws can be used, particularly the extruders with interlocking co-rotating screws being preferred. The preferably used co-rotating twin screw extruders generally have at least one feed section equipped with forward feed screw elements, at least one homogenization section equipped with kneading and transporting back elements, and with at least one Mixing section with forward transport elements, transport backwards, and kneading. It is also possible to use specific mixing elements such as, for example, toothed mixing elements, melt mixing elements or turbine-type mixing elements. The extruders preferably comprise a feed section, a homogenization section, and a mixing section. Preferred extruders preferably also have 1, 2 or more devolatilization sections. These follow particularly preferably the (last) mixing section. The devolatilization sections can be operated at atmospheric pressure, superatmospheric pressure, or vacuum. It is preferable that the devolatilization sections are operated at atmospheric or vacuum pressure. It is particularly preferable that the devolatilization sections are operated under a vacuum of 10 to 900 mbar, preferably 20 to 800 mbar, in particular 30 to 600 mbar. After the devolatilization section (s), the preferred extruders generally have an introduction section and a pelletizing unit. The latter • can be, for example, a pellet former made from strands, a pellet former submerged in water, or a die-face pelletizer cooled with water, with strand pellet formers and pellet formers submerged in water being preferred. The introduction section can obviously be an injection molding unit. The temperature during the preparation of the graft copolymers P) by the melting process is generally within a range of 200 to 350 ° C, preferably within the range of 220 to 340 ° C. If the entire amount of component C) reacts with a portion of component A) to provide the graft copolymers P), the amount of component A) may vary within a wide range. The portion used of A) must, however, be considered in such a way that first an adequate amount of graft copolymer B) is formed and secondly such that there is not a large excess of polyamide along the graft copolymer P). The graft copolymers P) may comprise from 5 to 95% by weight, preferably from 10 to 90% by weight, of copolymer C) and from 5 to 95% by weight, preferably from 10 to 90% by weight of polyamide A) . The amount of polyamide is determined particularly preferably in such a way that the molar ratio between the functional groups of component C) and the end groups of the polyamide is between 0.8: 1 and 1.3: 1, preferably 0.9: 1 to 1.3: 1. The resulting graft copolymers P) can be mixed with the remainder of component A), and also with the other components, if present. Any of the known methods can be used to mix the components, which may be dry as for example. The mixing is preferably carried out at temperatures of 200 to 320 ° C by extrusion, kneading, or roller milling of the components together, the components having been isolated in advance, if appropriate, from the solution obtained during the polymerization or from the aqueous dispersion. The thermoplastic molding compositions of the present invention can be processed through processes known for the processing of thermoplastics, for example, by extrusion, injection molding, calendering, blow molding, or sintering. The molding compositions according to the present invention can be used to produce films, fibers, molded objects, or foams. They can also be processed, particularly preferably, for the production of parts for vehicle interiors. In one of the preferred embodiments, the thermoplastic molding compositions of the present invention can serve as a substrate material whose surface has been totally or partially metallized. Examples The viscosity index of the polyamides was determined according to DIN 53 727 in solutions at 0.5% by weight in 96% by weight sulfuric acid at a temperature of 23 ° C. The viscosity index of the terpolymer and styrene-acrylonitrile copolymer (SAN) was determined in dimethylformamide at 25 ° C in 0.5% by weight solutions. The particle size of the grafted rubber is the average weight dso, determined as. Scholtan and H. Lange, Kolloid-Z. und Z. -Polymere 250 (1972), pages 782-796, through an analytical ultracentrifuge. The heat resistance of the samples was determined through the Vicat softening point. The Vicat softening point was determined according to 53 460, in small standard samples, using a force of 49.05 N and a temperature rise of 50 K per hour. The notch impact resistance (ak) of the products was determined in ISO samples for ISO 179 leA. The flow capacity (melt volume index, MVI) was determined according to ISO 1133 at 240 ° C with a load of 5 kg. The melt viscosity was determined in a capillary rheometer at a temperature of 290 ° C and at a cutting speed of 55hz. To characterize the processing stability, the melt viscosity was determined after 4 and 24 minutes of residence time in the capillary rheometer under these conditions. The table offers the change during the residence time, based on the measured value at 4 minutes. The friction properties were determined according to ISO 8925, 199E (E), in sheets of the respective molding composition. The variable (? CF) used, which correlates with the tendency of the plastic parts to grind, was the difference in friction coefficients in what is known as the "grip / slip" region. Component Ai Polyamide A2? used comprised a nylon-6, obtained from e-caprolactam, with a viscosity index of 150 ml / g. Component A2 Polyamide A2? used comprised a nylon-6, obtained from e-caprolactam, with a viscosity index of 125 ml / g. Bi Component Graft rubber with 62% by weight of polybutadiene in the core and 38% by weight of a shell of a graft composed of 75% by weight of styrene and 25% by weight of acrylonitrile.

Particle size: approximately 400 nm. Component B Graft rubber with 70% by weight of polybutadiene in the core and 30% by weight of a shell of a graft composed of 75% by weight of styrene and 25% by weight of acrylonitrile.

Particle size: approximately 370 nm. Component B3 Graft rubber with 85% by weight of polybutadiene in the core and 15% by weight of a shell of a graft composed of 75% by weight of styrene and 25% by weight of acrylonitrile.

Particle size: approximately 390 nm. Component B4 Graft rubber with 66% by weight of polybutadiene in the core and 34% by weight of a shell of a graft composed of 75% by weight of styrene and 25% by weight of acrylonitrile.

Particle size: approximately 375 nm. Component Ci Styrene-acrylonitrile-maleic anhydride terpolymer whose composition was 74 / 23.5 / 2.5 (% by weight), viscosity index: 80 ml / g. Component Di styrene-acrylonitrile copolymer with 75% by weight of styrene and 25% by weight of acrylonitrile and with a viscosity index of 80 ml / g. Component Ei Phthalic anhydride Preparation of the molding compositions The components were mixed in a two-screw extruder at a melting temperature of 240 to 260 ° C. The melt was passed through a water bath and formed into pellets. The results of the tests are presented in Table 1. Table 1

Claims (11)

1. CLAIMS 1. A thermoplastic molding composition consisting of A) a polyamide having amino or carboxy end groups or a mixture of these end groups, B) a mixture formed by at least two graft copolymers, each comprising a rubber like graft base and a graft based on an unsaturated monomer, where these differ from each other by at least 5% by weight in terms of their rubber content, C) a rubber-free copolymer, comprising cl) at least 30% by weight weight, based on the total weight of all units present in C), of units deriving from an aromatic vinyl monomer, c2) units that are derived from a monomer comprising a functional group that can react with the groups of end of the polyamide A), and c3) units that are derived from a monomer that does not comprise functional groups that react with the end groups of the polyamide A), and also further, if desired, D) a free matrix polymer rubber , E) a low molecular weight compound comprising a dicarboxylic anhydride group, and F) an additive or a mixture of various additives.
2. 2. The thermoplastic molding composition according to claim 1, wherein each of the graft copolymers is an ABS.
3. 3. The thermoplastic molding composition according to claims 1 to 2, wherein component A) is nylon-6.
4. 4. The thermoplastic molding composition according to claims 1 to 3, wherein component C) is a terpolymer comprised of styrene, maleic anhydride, and acrylonitrile.
5. 5. The thermoplastic molding composition according to claims 1 to 4, wherein the component F) comprises a stearate or a silicone oil or a mixture thereof.
6. 6. A process for preparing thermoplastic molding compositions according to claims 1 to 5, comprising, in a first step, the preparation of a graft copolymer P) from a portion of component A) and starting from the amount of component B), and, in a second step, mixing the graft copolymers P) with the other components and with the remainder of component A).
7. 7. The use of the thermoplastic molding compositions according to claims 1 to 5, or prepared according to claim 6, for the production of molded parts, films, fibers or foams.
8. 8. The use according to claim 7, for the production of molded parts, films or fibers with improved friction properties.
9. 9. A molded product, film, fiber or foam, which can be obtained using thermoplastic molding compositions according to claims 1 to 5, or prepared according to claim 6.
10. 10. A molded product according to claim 9, Wich value ? CF is less than 0.05, measured according to ISO 8925, 199E (E).
11. 11. Parts for interiors of motor vehicles, which can be obtained using molded products, films, fibers or foams according to claim 9. SUMMARY OF THE INVENTION Thermoplastic molding compositions composed of A) a polyamide having amino or carboxy end groups or a mixture of these end groups, B) a mixture formed by at least two graft copolymers, each comprising a rubber like graft base and a graft based on an unsaturated monomer, where these differ from each other by at least 5% by weight in terms of their rubber content, C) a rubber-free copolymer, comprising cl) at least 30% by weight weight, based on the total weight of all units present in C), of units deriving from an aromatic vinyl monomer, c2) units that are derived from a monomer comprising a functional group that can react with the groups of end of the polyamide A), and c3) units that are derived from a monomer that does not comprise functional groups that react with the end groups of the polyamide A), and also further, if desired, D) a polymer of rubber-free matrix, E) a low molecular weight compound comprising a dicarboxylic anhydride group, and an additive or a mixture of various additives,