MXPA01007934A - Flame-proofed molding materials - Google Patents

Abstract

The invention relates to thermoplastic molding materials which contain A) 10 to 98.9 wt.-%of a thermoplastic polymer, B) 1 to 30 wt.-%of a flame-retardant combination consisting of, based on 100 wt.-%of B), b1) 20 to 99 wt.-%of a halogen-containing flame retardant, b2) 1 to 80 wt.-%of an antimonoxide, C) 0.1 to 5 wt.-%of a stabilizer which is not component b2) or D), D) 0 to 70 wt.-%of further additives. The invention is further characterized in that the total of the weight percentages of components A) to D) is 100%.

Description

FLAMED PROOF MOLDING MATERIALS The invention relates to thermoplastic molding compositions, comprising A) from 10 to 98.9% by weight of a thermoplastic polymer, B) from 1 to 30% by weight of a flame retardant combination made from, based on 100 % by weight of B), bi) from 20 to 99% by weight of a flame retardant containing halogen, and b2) from 1 to 80% by weight of an antimony oxide, C) from 0.1 to 5% by weight weight of a stabilizer different from components b2) and D), D) from 0 to 70% by weight of other additives, where the sum of the percentages by weight of components A) to D) is 100%. The invention further relates to the use of novel molding compositions for producing fibers, films or moldings, and also to resulting molding of any type. EP-A 410 301 and EP-A 736 571, for example, describe halogen-containing flame retardant polyamides and polyesters, which for the most part utilize antimony oxides as a synergist.

Applications in particular in the electrical industry require flame retardancy and relatively high long service temperatures. In heat aging, polycondensates in particular, such as polyamides and polyesters, exhibit brown coloration and undesirable molecular weight degradation. Discoloration, although not molecular weight degradation, can be suppressed to some extent by antioxidants. Metal salts are known as, for example, red phosphorus stabilizers as a flame retardant (see DE-A 27 54 491). These hydrolytic cleavages suppressed from red phosphorus in particular in polymers which can absorb water. It is an object of the present invention to provide flame retardant halogen-containing molding compositions which are more stable to molecular weight degradation during processing and are more stable at high long term service temperatures. It has been found that this object is achieved by means of the molding compositions defined in the beginning. Preferred embodiments are given in the sub-claims. The novel molding compositions comprise, as component A), from 10 to 98.9% by weight, preferably from 20 to 97% by weight and in particular from 30 to 80% by weight, of a thermoplastic polymer different from B) and D). The advantageous effect is in principle apparent in novel molding compositions with any type of thermoplastic. A list of suitable thermoplastics is found, for example, in Kunststoff-Taschenbuch (ed. Saechtling), 1989 edition, which also give reference sources. The processes for preparing thermoplastics of this type are known per se by the skilled person. Some preferred types of plastic are described in a bit more detail in the following: 1. Polycarbonates and polyesters The use is generally made of polyesters based on aromatic dicarboxylic acids and on an aliphatic or aromatic dihydroxy compound. A first group of preferred polyesters is that of polyalkylene terephthalates having from 2 to 10 carbon atoms in the alcohol moiety. Polyalkylene terephthalates of this type are known per se and are described in the literature. Its main chain contains an aromatic ring which is derived from the aromatic dicarboxylic acid. The aromatic ring may also have substitution, for example by halogen, such as chlorine or bromine, or by a C? -C4 alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl . These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, or their esters or other ester forming derivatives, with aliphatic dihydroxy compounds in a manner known per se. Examples of preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and mixtures of these. Up to 30 mol%, but more preferably not more than 10 mol%, of the aromatic dicarboxylic acids may have been replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanediol acids and cyclodextricarboxylic acids. Among the aliphatic dihydroxy compounds, it is preferably given to diols having from 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1, 4-hexanediol, 1,4-cyclohexanediol, 1-cyclohexanedimethylanol and neopentyl glycol, and mixtures thereof. Particularly preferred polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having from 2 to 6 carbon atoms. Among these, the particular preference is given to polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and mixtures thereof. Other preferred polyesters are PET and / or PBT, comprising up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as other monomer units. The viscosity number of the polyesters (A) is generally from 50 to 220, preferably from 80 to 160 (measured at a resistance of 0.5% weight solution in a mixture of phenol / orthodichlorobenzene (weight ratio 1: 1) to 25 ° C in accordance with ISO 1628. Particular preference is given to polyesters whose carboxyl end group content is up to 100 mval / kg polyester, preferably up to 50 mval / kg polyester, and in particular up to 40 mval / kg polyester. Polyesters of this type can be prepared, for example, by the process of DE-A 44 01 055. The content of the carboxyl terminal group is usually determined by titration methods. (for example potentiometry). Particularly preferred molding compositions comprise, as component A), a polyester mixture that differs from PBT, for example polyethylene terephthalate (PET). The proportion of, for example, polyethylene terephthalate is preferably up to 50% by weight in the mixture, in particular from 10 to 30% by weight, based on 100% by weight of A). It is also advantageous to use recycled PET materials (also known as PET waste) in a mixture with polyalkylene terephthalates, such as PBT. For the purposes of this invention, recycled materials are generally: 1) those known as post-industrial recycled materials: these are production wastes that arise during polycondensation or during processing, for example burrs, from injection molding, starting material from injection molding or extrusion or edged edge to emerge from sheets or extruded films. 2) post-consumer recycled materials: these are plastic items which are collected and treated after use by the final consumer. Blow-molded PET bottles for mineral water, soft drinks and juices are easily the predominant items in terms of quantity. Both types of recycled material can be used either as a grinding material or in the form granules. In the latter case, the raw recycled materials are isolated and purified and then melted and pelletized using an extruder. This usually facilitates the handling and promotes the fluid-free properties, and also measures by additional stages in processing. Recycled or used materials can either be pelletized or in the form of re-proofing. The edge length should not be greater than 6 mm, preferably less than 5 mm. Because polyesters undergo hydrolytic splitting during processing (due to moisture signals) it is advisable to pre-dry the recycled materials. The residual moisture after drying is preferably from 0.01 to 0.7%, in particular from 0.2 to 0.6%. Another class is that of the fully aromatic polyesters which are derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds. Suitable aromatic dicarboxylic acids are the aforementioned compounds for polyalkylene terephthalates. The mixtures preferably used are composed of from 5 to 100 mol% isophthalic acid and from 0 to 95 mol% terephthalic acid, in particular from about 50 to about 80% terephthalic acid and from 20 to about 50% isophthalic acid . The aromatic dihydroxy compounds preferably have the formula where Z is alkylene or cycloalkylene having up to 8 carbon atoms, arylene having up to 12 carbon atoms, carbonyl, sulfonyl, oxygen or sulfur or a chemical bond, and m is from 0 to 2. The phenylene groups of the compounds I can also having substitution by Ci-Cß alkyl or alkoxy, and fluoro, chloro or bromo. Examples of the main compounds for these compounds are: dihydroxydiphenyl, di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide , a, a1-di (hydroxyphenyl) dialkylbenzene, di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene, resorcinol, and hydroquinone and also derivatives alkylated in the ring or halogenated in the ring thereof. Among these, preference is given to 4,4'-dihydroxydiphenyl, 2,4-di ('-hydroxyphenyl) -2-methylbutane a, a'-di (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-di ( 3 '-methyl-4' -hydroxyphenyl) propane and 2, 2-di (3'-chloro-4 '-hydroxyphenyl) propane, and also in particular to 2,2-di (4'-hydroxyphenyl) propane 2, 2 -di (3 A 5-dichlorodihydroxyphenyl) propane, 1,1-di (4'-hydroxyphenyl) cyclohexane, 3,4 '-dihydroxybenzophenone, 4, 4' -dihydroxydiphenylsulfone, and 2, 2-di (3 ', 5' -dimethyl-4 '-hydroxyphenyl) propane or mixtures thereof. This is, of course, also possible to use mixtures of polyalkylene terephthalates and fully aromatic polyesters. These generally comprise from 20 to 98% by weight of the polyalkylene terephthalates and from 2 to 80% by weight of the complete aromatic polyester. For the purposes of the present invention, the polyesters include polycarbonates, which are obtainable by aromatic dihydroxy polymerization compounds, in particular 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) or its derivatives, with phosgene, for example. The corresponding products are known per se and are described in the literature, and many of these are also commercially available. The amount used of the polycarbonates is up to 90% by weight, preferably up to 50% by weight, in particular from 10 to 30% by weight, based on 100% by weight of component A). It is, of course, also possible to use polyester block copolymers, such as copolyester ethers. Products of this type are known per se and are described in the literature, for example in US-A 3 651 014. The corresponding products are also commercially available, for example Hytrel® (DuPont). 2. Vinylromatics Polymers The molecular weight of these polymers which are known per se and commercially available, is generally from 1500 to 2,000,000, preferably from 70,000 to 1,000,000. Simply as examples, mention may be made herein of vinylaromatic polymers made from styrene, chlorostyrene, α-methylstyrene and p-methylstyrene; Comonomers, such as (meth) acrylonitrile or (meth) acrylates, can be subordinate participants in the structure with preferably not more than 20% by weight, in particular not more than 8% by weight. Particularly preferred vinylaromatic polymers are impact modified polystyrene and polystyrene. Mixtures of these polymers can, of course, also be used. The preparation is preferably by the process described in EP-A-302 485. The preferred ASA polymers are soft or rubber phase compounds made of graft polymer composed of: Ai from 50 to 90% by weight of a graft base n-based from 95 to 99.9% by weight of an alkyl acrylate of C2-C? o and Ai2 from 0.1 to 5% by weight of a bifunctional monomer having two non-conjugated olefinic double bonds and A2 from 10 to 50% by weight of a graft composed of A2? 20 to 50% by weight of styrene or substituted styrenes of the formula I or mixtures of these and A22 of 10 to 80% by weight of acrylonitrile, methacrylonitrile, acrylates or methacrylates, or mixtures thereof, mixed with a hard matrix based in an A3) SAN copolymer composed of: A3? from 50 to 90% by weight, preferably from 55 to 90% by weight and in particular 65 to 85% by weight, styrene and / or substituted styrenes of formula I and A32 from 10 to 50% by weight, preferably from 10 to 45% by weight and in particular from 15 to 45% by weight 35% by weight, of acrylonitrile and / or methacrylonitrile. Component i) is an elastomer which has a glass transition temperature below -20 ° C, in particular below -30 ° C. The main monomers An) used to prepare the elastomer are acrylates having from 2 to 10 carbon atoms, in particular from 4 to 8 carbon atoms. Particularly preferred monomers are tert-butyl, isobutyl and n-butyl acrylate, and also 2-ethylhexyl acrylate, and the last two named are particularly preferred. In addition to these acrylates, the use is made from 0.1 to 5% by weight, in particular from 1 to 4% by weight, based on the total weight of An + Ai2, of a polyfunctional monomer having at least two olefinic double bonds not conjugated Among these, preference is given to the use of bifunctional compounds, that is to say those that have two non-conjugated double bonds. Examples of these are divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate, and particularly preferred is given to the last two mentioned. The processes for preparing the graft base i are known per se and are described, for example, in DE-B 1 260 135. The corresponding products are also commercially available. The preparation by emulsion polymerization has proved particularly advantageous in some cases. The precise polymerization conditions, in particular the type, the feed ratio and the amount of emulsifier, are preferably selected in such a manner to give an acrylate latex with at least some degree of crosslinking and an average particle size (weight- average D50) of about 200 to 700 nm, in particular 250 to 600 nm. The latex preferably has a narrow particle size distribution, that is, the quotient d5o is preferably less than 0.5, in particular less than 0.35. The proportion of the graft base Ai in the Ai + A2 polymer of the graft is 50 to 90% by weight, preferably 55 to 85% by weight and in particular 60 to 80% by weight, based on the total weight of the graft Ai. Ai + A2. The graft on the graft base Ai is a graft shell A2 prepared by copolymerization. A2i from 20 to 90% by weight, preferably from 30 to 90% by weight and in particular from 30 to 80% by weight, of styrene or substituted styrenes of the formula where R is alkyl having from 1 to 8 carbon atoms, or they are hydrogen or halogen, and R1 is alkyl having from 1 to 8 carbon atoms, or is halogen, and n is 0, 1, 2 or 3, and A22 from 10 to 80% by weight, preferably from 10 to 70% by weight and in particular from 20 to 70% by weight, of acrylonitrile, methacrylonitrile, acrylates or methacrylates, or mixtures thereof. Examples of substituted styrenes are α-methylstyrene, p-methylstyrene, p-chlorostyrene and p-chloro-α-methylstyrene, among which preferably styrene and α-methylstyrene are given. Preferred acrylates and methacrylates are those whose homopolymers or copolymers with other monomers of component A22) have vitreous transition temperatures above 20 ° C; however, in principle the use can also be made of other acrylates, preferably in amounts which result in glass transition temperatures Tg of above 20 ° C per total A2 component. Particular preference is given to (meth) acrylates with Ci-Cs alcohols and to esters containing epoxy groups, such as glycidyl acrylate or glycidyl methacrylate. Particularly preferred examples are methyl methacrylate, tert-butyl methacrylate, glycidyl methacrylate and n-butyl acrylate. It is preferable to avoid also using a high proportion of the last mentioned compound since it forms polymers with a very low Tg. The graft shell A2) can be prepared in one or more, for example two or three, stages, its total arrangement remaining therefore unaffected. The graft shell is preferably prepared in emulsion, as described, for example, in DE-C 12 60 135, DE-A 32 27 555, DE-A 31 49 357 and DE-A 34 14 118. Depending on the selected conditions , the graft copolymerization gives a certain proportion of styrene-free copolymers and / or substituted styrene derivatives and (meth) acrylonitrile and / or (meth) acrylates. The graft copolymer Ax + A2 generally has an average particle size of 100 to 1000 nm, in particular of 200 to 700 nm (weight average dso) • The conditions for the preparation of the Di elastomer) and for grafting are therefore preferably selected in such a way as to give particle sizes in their range. Measurements for these purposes are known and described, for example, in DE-C 1 260 135 and DE-A 28 26 925, and also in Journal of Applied Polymer Science, Vol. 9 (1965), pp. 2929-2938. The size of the particle of the elastomer latex can be elongated, for example, by agglomeration. For the purposes of this invention the free, non-grafted homo- and copolymers produced in the graft copolymerization prepare the A2) component as part of the graft polymer (A? + A2).

Some preferred graft polymers are given in the following: 1: 60% by weight of base Ax of graft composed of An 98% by weight of n-butyl acrylate and A? 2 2% by weight of dihydrodicyclopentadienyl acrylate, and % by weight of shell A2 of composite graft of A2? 75% by weight of styrene and A22 25% by weight of acrylonitrile 2: graft base as in 1 with 5% by weight of a first graft shell composed of styrene and 35% by weight of a second graft composed of A2? 75% by weight of styrene and A22 25% by weight of acrylonitrile 3: Graft base as in 1 with 13% by weight of a first graft composed of styrene and 27% by weight of a second graft composed of styrene and acrylonitrile in one 3: 1 weight ratio. The present products as component A3) can, for example, be prepared by the process described in DE-B 10 01 001 and DE-B 10 03 436. Copolymers of this type are also commercially available. The weight average molecular weight determined by light scattering is preferably 50,000 to 500,000, in particular 100,000 to 250, 000 The weight ratio of (Ai + A2): A3 is from 1: 2.5 to 2.5: 1, preferably from 1: 2 to 2: 1 and in particular from 1: 1.5 to 1.5: 1. The SAN polymers suitable as component A) have been described in the above (see A3? And A32). The viscosity number of SAN polymers, measured in DIN 53 727 as 0.5% tenacity of 0.5% by weight of solution in dimethylformamide at 23 ° C is generally 40 to 100 ml / g, preferably 50 to 80 ml / g . The ABS polymers used as polymer A) in the novel polymer blends have two or more phases having the same structure as described above by the ASA polymers. Instead of the acrylate rubber Ax) of the graft base in the ASA polymer the use is usually made of conjugated dienes, preferably giving the following arrangement for the A4 graft base: A4? from 70 to 100% by weight of a conjugated diene and A42 from 0 to 30% by weight of a bifunctional monomer having two non-conjugated olefinic double bonds. The A2 graft and the hard matrix of the A3 copolymer) SAN remains without change in the provision. Products of this type are commercially available. The preparation processes are known to the skilled person, and no additional detail needs to be given here.

The weight ratio of (A4 + A): A3 is from 3: 1 to 1: 3, preferably from 2: 1 to 1: 2. Particularly preferred arrangements of novel molding compositions comprise, as component A), a mixture of: Ai) from 10 to 90% by weight of a polybutylene terephthalate A2) from 0 to 40% by weight of a polyethylene terephthalate and A3) from 1 to 40% by weight of an ASA or ABS polymer or mixtures of these. Products of this type are available under the brand name Ultradur® S (previously Ultrablend® S) from BASF Aktiengesellschaft. Other preferred provisions for the component A) comprise Ai) from 10 to 90% by weight of a polycarbonate A2) from 0 to 40% by weight of a polyester, preferably polybutylene terephthalate and A3) from 1 to 40% by weight of an ASA or ABS polymer or mixtures of these. Products of this type are available under the Terblend® brand from BASF AG. 3. Polyamides The polyamides of the novel molding compositions generally have a viscosity number of 90 to 350 ml / g, preferably 110 to 240 ml / g, determined at ISO 307 in resistance to 0.5% by weight of the solution in 96 % strength by weight of sulfuric acid at 25 ° C. Preference is given to semicrystalline or amorphous resins with molecular weights (weight-average) of at least 5000, as described, for example, in U.S. Patent Nos. 2 071 250, 2 071 251, 2 130 523, 2 130 948, 2 241 322, 2 312 966, 2 512 606 and 3 393 210. Examples of these are polyamides which are derived from lactams having members of 7 to 13 rings, such as polycaprolactam, polycaprylactam and polylaurolactam, and also polyamides obtained reacting dicarboxylic acids with diamines. The dicarboxylic acids that can be used are alkanedicarboxylic acids having from 6 to 12 carbon atoms, in particular from 6 to 10 carbon atoms, and aromatic dicarboxylic acids. Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic acid and / or isophthalic acid are few acids that can be mentioned here. Particularly suitable diamines are alkanediamines having from 6 to 12 carbon atoms, in particular from 6 to 8 carbon atoms, or also m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, 2, 2-di (4-aminophenyl) propane or 2,2- di (4-aminocyclohexyl) propane. Preferred polyamides are polyhexamethylenediamide, polyhexamethylene sebacamide and polycaprolactam, and also nylon 6 / 6,6, in particular with a proportion of 5 to 95% by weight of caprolactam units. In addition, mention may also be made of polyamides obtained, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperatures (nylon-4.6). The preparation process for the polyamides of this structure is described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524. Other suitable polyamides are obtained by the copolymerization of two or more of the monomers aforementioned. Mixtures of more than one polyamide are also suitable, and the mixing ratio can be as desired. Other copolyamides which have proved particularly advantageous are the partially aromatic copolyamides, such as nylon-6/6, T and nylon-6, 6/6, which have a triamine content of less than 0.5% by weight, preferably less than 0.3 % by weight (see EP-A 299 444). Preferred partially aromatic copolyamides with the triamine content can be prepared by the processes described in EP-A 129 195 and 129 196. 4. Polyphenylene Ethers Suitable polyphenylene ethers generally have a molecular weight (weight-average) of from 10,000 to 80,000, preferably from 20,000 to 60,000 and in particular from 40,000 to 55,000. The molecular weight distribution is generally determined using gel permeation chromatography (GPC) For this, the PPE specimens are dissolved in THF under pressure at 110 ° C using THF as eluent, 0.16 ml of a 0.25% strength solution is injected at room temperature in suitable separation columns. A UV detector is usually used. The separation columns are usefully calibrated with PPE specimens of known molecular weight distribution. This corresponds to a reduced specific viscosity of 0.2 to 0.9 dl / g, preferably of 0.35 to 0.8 dl / g and in particular of 0.45 to 0.6 dl / g, measured in a resistance to 0.5% by weight of chloroform solution at 25 °. C. The unmodified polyphenylene ethers ax) are known per se and are preferably prepared by oxidative coupling of o-disubstituted phenols. Examples of substituents are halogen, such as chlorine or bromine, and alkyl having 1 to 4 carbon atoms, preferably without a tertiary hydrogen at the a position, for example methyl, ethyl, propyl or butyl. The alkyl radicals may in turn have substitution by the halogen, such as chlorine or bromine, or by a hydroxyl group. Other examples of possible substituents are alkoxy, preferably having up to 4 carbon atoms, or phenyl, which may be unsubstituted or substituted by halogen and / or alkyl. Copolymers of different phenols are also suitable, for example copolymers of 2,6-dimethylphenol and 2, 3,6-trimethylphenol. This is, of course, also possible to use mixtures of different polyphenylene ethers. The polyphenylene ethers used as component ai) may, if desired, have defects arising from their production as described, for example, by White et al. in Macromolecules 23, (1990) 1318-1329. Preference is given to the use of polyphenylene ethers which are compatible with vinylaromatic polymers, ie they are completely or very substantially soluble in these polymers (see, A. Noshay, Block Copolymers, pp. 8-10, Academic Press, 1977 and O. Olabisi, Polymer-polymer Miscibility, 1979, pp. 117-189). Examples of polyphenylene ethers are poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl-1-phenylene) ether, poly (2,6-dimethoxy) ether. 1, 4-phenylene), poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1, 4-phenylene) ether, poly (2-ethyl) ether -6-stearyloxy-1,4-phenylene), poly (2,6-dichloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,6-dibenzyl-1, 4-phenylene), poly (2-ethoxy-1, 4-phenylene) ether, poly (2-chloro-1,4-phenylene) ether, poly (2-ether) , 5-dibromo-l, 4-phenylene).

Preference is given to the use of polyphenylene ethers whose substituents are alkyl having from 1 to 4 carbon atoms, for example; poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene ether) ), poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2,6-dipropyl-1, 4-phenylene) ether and poly (2-ethyl-β-propyl) ether 1, 4-phenylene). Other suitable polymers are graft copolymers composed of polyphenylene ether and vinylaromatic polymers, such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene. Modified or functionalized polyphenylene ethers are known per se, for example from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 116 and EP-A-254 048 and are preferred for use in blends with PA or polyester.

An unmodified polyphenylene ether ai) is usually modified by the incorporation of at least one carbonyl group, carboxylic acid group, acid anhydride group, acid amide group, acid imide group, carboxylic ester group, carboxylate group, amino group, hydroxyl group , epoxy group, oxazoline group, urethane group, urea group, lactam group or halobenzyl group, to ensure sufficient compatibility, for example with the polyamide. The modification is generally carried out by reacting an unmodified polyphenylene ether ax) with a modifier containing at least one of the aforementioned groups and at least one double C-C or triple C-C bond, in solution (WO-A 86/2086), in aqueous dispersion, in a gas-phase process (EP-A-25 200) or in the melt, if desired in the presence of suitable vinylaromatic polymers or impact modifiers, and free radical initiators may be present. Examples of suitable modifiers (a3) are maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, anhydrides and imides thereof, fumaric acid, the mono- and diesters of these acids, for example alkanols (a3?) Of Ci and C2-C8, the mono- or diamides of these acids, such as N-phenylmaleimide (monomers a32), and maleic hydrazide. Other examples are N-vinylpyrrolidone and (meth) acryloylcaprolactam (a33).

Component A) in the compositions of novel molding preferably is a polyphenylene ether modified obtainable by reacting i) from 70 to 99.95% by weight, preferably 76.5 to 99.94% by weight of a polyphenylene ether unmodified, a2) from 0 to 25 % by weight, preferably from 0 to 20% by weight, of a vinylaromatic polymer, a3) from 0.05 to 5% by weight, preferably from 0.05 to 2.5% by weight of at least one compound selected from the class consisting of, a3?) a beta-unsaturated dicarbonyl compound, a32) a monomer containing amide groups and having a polymerizable double bond, and a33) a monomer containing lactam groups and having a polymerizable double bond, and a4) from 0 to 5% by weight, preferably from 0.01 to 0.09% by weight, of a free radical initiator, where the percentages by weight are based on the sum of ax) to a4), in appropriate mixing and kneading assembly, such as double screw extruders, from 0.5 to 15 minutes at 240 to 375 ° C. The vinylaromatic polymer a2) should preferably be compatible with the polyphenylene ether used, as described in 2.

Examples of preferred vinylaromatic polymers compatible with the polyphenylene ethers can be found in the monograph mentioned above by Olabisi, p. 224-230 and 245. a4) free radical initiators which may be mentioned are: peroxide 2, 4-dichlorobenzoyl, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, decanoyl peroxide, propionyl peroxide, peroxide benzoyl, 2-tertbutyl etilperoxihexoato, dietilperoxiacetato tertbutyl, tertbutyl peroxyisobutyrate, 1,1-di-tertbutyl? eroxi-3, 3, 5-trimethylcyclohexane, tert-butylperoxy carbonate isopropyl, tert- butylperoxy-3, 3, 5-trimetilhexoato, tert-butyl peracetate, tert -butyl perbenzoate, 4, 4-di-tert-butyl butilperoxivalerato, 2,2-di-tert-butylperoxybutane peroxide, cumyl peroxide, tert-butyl cumyl, 1,3-di (tert-butylperoxyisopropyl) benzene and tert-butyl peroxide. Mention may also be made of organic hydroperoxides, such as diisopropylbenzene monohydroperoxide hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-menthyl hydroperoxide, pinane highly branched alkanes of the structure R4 Ri I i R5 CC R2 R6 R3 wherein R1 to R6 are alkyl having from 1 to 8 carbon atoms, alkoxy having from 1 to 8 carbon atoms, aryl, such as phenyl or naphthyl, or 5- or 6-membered heterocyclics with an electron system p and nitrogen, oxygen or sulfur as heteroatoms. The substituents of R1 to R6 can in turn have substitution by functional groups, such as carboxyl groups, carboxyl derivative groups, hydroxyl groups, amino groups, thiol groups or epoxy groups. Examples of these compounds are 2, 3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and 2,2,3,3-tetraphenylbutane. Particularly preferred polyphenylene ethers A) in the novel molding compositions are obtained by modifying with maleic acid, maleic anhydride and fumaric acid. The polyphenylene ethers of this type preferably have an acid number of 1.8 to 3.2, in particular 2.0 to 3.0. The acid number is a measure of the degree of modification of the polyphenylene ether, and is generally determined by titration with bases under inert gas conditions.

The acid number generally corresponds to the amount of base in mg which is required (according to DIN 53 402) to neutralize 1 g of polyphenylene ether A) which has been modified in acid in this manner. Other suitable polymers are polyolefins, such as homo- or copolymers of polyethylene or polypropylene. The novel molding compositions comprise, as component B), from 1 to 30% by weight, preferably from 2 to 25% by weight and in particular from 5 to 20% by weight, of a flame retardant combination made of, bi ) from 20 to 99% by weight, preferably from 50 to 85% by weight, of a halogen-containing flame retardant, and b2) from 1 to 80% by weight, preferably from 15 to 50% by weight, of an antimony oxide. The preferred b2 oxides) are antimony trioxide and antimony pentoxide. To improve dispersion, oxide b2) can be incorporated into polymer A) in a master batch (concentrate). The polymers used in the concentrate can be, for example, the same as those of component A) or different from the particular component A) used. Preference is given to concentrates of b2) in polyolefins, preferably polyethylene. Suitable flame retardants bi) are preferably brominated compounds, such as brominated oligocarbonates (BC 52 or BC 58 from Great Lakes), brominated diphenyl ethers, polypentabromobenzyl acrylate (eg FR 1025 from Dead Sea Bromine (DSB)), trimethylphenylin brominated (FR 1808 of DSB), oligomeric reaction products of tetrabromobisphenol A with epoxides (for example FR 2300 and FR 2400 of DSB), tetrabromobisphenol A and hexabromocyclododecane. Preferred brominated oligoestirines used as flame retardants have an average degree of polymerization (average number) of 3 to 90, preferably 5 to 60, as measured by vapor-pressure osmometry in toluene. Cyclic oligomers are also suitable. In a preferred embodiment of the invention the brominated oligomeric styrenes to be used have the following formula I, wherein R is hydrogen or an aliphatic radical, in particular alkyl, for example CH2 or C2H5, and n is the number of building blocks recurrent in the chain. R 'can be either H or bromine, or otherwise a fragment of a conventional free radical generator. n can be from 1 to 88, preferably from 3 to 58. The brominated oligoestirenes contain from 40 to 80% by weight, preferably from 55 to 70% by weight, of bromine. Preference is given to a product which is predominantly composed of polydibromostyrene. The substances can be fused without decomposition and are, for example, soluble tetrahydrofuran. They can be prepared either by ring-bromination of if desired aliphatically hydrogenated styrene oligomers, as obtained, for example, by thermal polymerization of styrene (as in DT-A 25 37 385) or by free-radical oligomerization of brominated styrenes adequate. The flame retardant can also be prepared by ionic oligomerization of styrene followed by bromination. The amount of brominated oligoestirene required to give flame retardant polyamides depends on the bromine content. The bromine content in the novel molding compositions is from 2 to 20% by weight, preferably from 5 to 12% by weight.

The brominated polystyrenes according to the invention are usually obtained by the process described in EP-A 47 549: - Cl Cl (II) (III) The brominated polystyrenes obtainable by this process and commercially available are tribrominated products predominantly of substituted ring. n '(see III) is generally from 125 to 1500, correspondingly to a molecular weight of 42,500 to 235,000, preferably from 130,000 to 135,000. The bromine content (based on the ring-substituted bromine content) is generally at least 55% by weight, preferably at least 60% by weight and in particular 65% by weight. Commercially available powdery products in form generally have a vitreous transition temperature of 160 to 200 ° C and are, for example, obtainable as HP 7010 from Albemarle or Pyrocheck® PB 68 from Ferro Corporation. Mixtures of brominated oligoestirines with brominated polystyrenes can they can also be used in novel molding compositions and the mixing ratio can be as desired. Bi-flame retardants containing chlorine are also available and are preferably available in Dechlorane® plus from Oxychem. The novel molding compositions comprise amounts from 0.1 to 5% by weight, preferably from 0.5 to 4% by weight and in particular from 0.7 to 3% by weight, or also very particularly from 0.7 to 2% by weight, of a stabilizer C, preferably at least one metal compound containing oxygen- or sulfur- or nitrogen. Particular preference is given to oxygen- or sulfur-containing compounds of zinc or alkaline earth metals, or mixtures thereof. A first group of preferred metal compounds to be mentioned is hydrotalcite, ZnO, leaving oxide, iron oxide, aluminum oxide, TiO2, CaO, SnO and MgO, Mg (OH) 2 and mixtures thereof, preferably ZnO. Suitable metal borates are those of the alkaline earth metals, for example Ba, Ca and Mg borates, and are preferably given in anhydrous zinc borate or zinc borate of the formula 2 ZnO • 3 B203 • H20 where x is 3.3 to 3.7. Examples of metal sulphides which can be used are ZnS and SnS, preferably ZnS. The alkaline earth metal carbonates are also suitable as component C), preferably BaC03 and MgC03 and in particular CaCO3. Among the nitrogen-containing compounds - those particularly suitable are nitrides, such as TiN, boron nitrides, magnesium nitrides and zinc nitrides. Suitable phosphates which should be mentioned are in particular zinc phosphate and calcium phosphate. This is, of course, also possible to use mixtures, and the mixing ratio may also be desired. The novel molding compositions may comprise, as component D), from 0 to 70% by weight, in particular up to 50% by weight, of other additives. Component D) in the novel molding compositions can comprise from 0 to 5% by weight, in particular from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight and very particularly preferably from 0.1 to 2% by weight, of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having from 10 to 40 carbon atoms, preferably from 16 to 22 carbon atoms, with saturated aliphatic alcohols or amines having from 2 to 40 carbon atoms , preferably from 2 to 6 carbon atoms.

The carboxylic acids can be monos- or dibasic. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecandioic acid, behenic acid and, particularly preferred stearic acid, capric acid and montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms ). The aliphatic alcohols can be mono- to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol and pentaerythritol. Glycerol and pentaerythritol are preferred. Aliphatic amines can be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine and di (6-aminohexyl) amine. Ethylenediamine and hexamethylenediamine are particularly preferred. Correspondingly, the preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate and glycerol monobehenate and pentaerythritol tetrastearate. It is also possible to use mixtures of different esters or combinations of esters with amides. The mixing ratio can be as desired. Examples of other additives D) are amounts of up to 40% by weight, preferably up to 30% by weight, of elastomeric polymers (also often finished impact modifiers, elastomers or rubbers). They are very generally copolymers which have been preferably constructed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylates and / or methacrylates having from 1 to 18 carbon atoms in the alcohol component. Polymers of this type have been described, for example in Houben-Weyl, Methoden der organischen Chemie, Vol., 14/1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pages 392-406, and in the monograph by CB Bucknall, Toughened Plastics "(Applied Science Publishers, London, 1977) Some preferred types of such elastomers are described in the following: Preferred types of such elastomers are those known as ethylene-propylene rubber (EPM) and ethylene-propylene-diene (EPDM) EPM rubbers generally have virtually non-residual double bonds while EPDM rubbers can have from 1 to 20 double bonds per 100 carbon atoms The examples which can be mentioned of the diene monomers for EPDM rubbers are dienes conjugates such as isoprene and butadiene, non-conjugated dienes having from 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1, 5- hexadiene and 1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-iso propenyl-5-norbornene, and tricyclodienes, such as 3-methyl-tricyclo [5.2.1. O2.6] -3,8-decadiene, or mixtures thereof. The preference is given to 1,5-hexadiene, 5-ethylidene norbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50% by weight, in particular 1 to 8% by weight, based on the total weight of the rubber. The EPM and EPDM rubbers may preferably also have been grafted with reactive carboxylic acids with derivatives thereof. Examples of these are acrylic acid, methacrylic acid and derivatives thereof, for example glycidyl (meth) acrylate, and also maleic anhydride. Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or with the esters of these acids are another group of preferred rubbers. The rubbers may also include dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, for example esters and anhydrides, and / or monomers containing epoxy groups. These monomers contain dicarboxylic acid derivatives or contain epoxy groups are preferably incorporated in the rubber by adding to the monomer mixture the monomers containing carboxylic acid groups and / or epoxy groups and have the formula I, II, III or IV RC (COOR2 ) = C (COOR3) R4 (I) R1 ^. R4 C C. (II) CO CO / \ CHR7 = CH (CH2) m- (CHR6) g CH CHR5 (III) CH2 = CR9 COO- (CH2) p-CH CHRβ (IV) \ / where R1 to R9 are hydrogen or alkyl having 1 to 6 carbon atoms, and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5. R1 to R9 are preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

Preferred compounds of formula I, II and IV are maleic acid, maleic anhydride and (meth) acrylates containing epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols, such as terry acrylate. butyl. Although the latter do not have free carboxyl groups their approximate behavior to that of free acids and are so-called monomers with latent carboxyl groups. The copolymers are advantageously composed of from 50 to 98% by weight of ethylene, from 0.1 to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing anhydride groups, the remaining amount being (meth) acrylates . Particular preference is given to copolymers made from 50 to 98% by weight, in particular from 55 to 95% by weight, of ethylene, from 0.1 to 40% by weight, in particular from 0.3 to 20% by weight, of acrylate of glycidyl and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and from 1 to 45% by weight, in particular from 10 to 40% by weight, of n-butyl acrylate and / or 2-ethylhexyl acrylate . Another preferred (meth) acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters. In addition to these, the comonomers that can be used are vinyl esters and vinyl ethers. The ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization at elevated pressure and elevated temperature. The appropriate processes are well known. Preferred elastomers also include polymers of the emulsion whose preparation is described, for example, by Blackley in the monograph "Emulsion Polymeriation". The emulsifiers and catalysts that can be used are known per se. In principle it is possible to use homogenously structured elastomers or those with a shell construction. The shell structure is determined by the sequence of addition of the individual monomers. The morphology of the polymers is also affected by this sequence of addition. The monomers which can be mentioned herein, merely as examples, by the preparation of the rubber fraction of the elastomers are acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, and corresponding methacrylates, and butadiene and isoprene, and also mixtures of these. These monomers can be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ethers and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate. The soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers can be the core, the outer shell or an intermediate shell (in the case of elastomers whose structure has more than two shells). The elastomers have more than one shell that can also have more than one shell made from a rubber phase. If one or more of the hard components (with glass transition temperatures above 20 ° C) are involved, in addition to the rubber phase, in the structure of the elastomer, these are generally prepared by polymerization, as main monomers, styrene, acrylonitrile , methacrylonitrile, α-methylstyrene, p-methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or methyl methacrylate. Besides these, it is also possible to use relatively small proportions of other comonomers. It has been advantageously tested in some cases the use of emulsion polymers which have reactive groups on their surface. Examples of groups of this type are epoxy, carboxyl, latent carboxyl, amino and amide groups, and also functional groups which can be introduced by concomitant use of monomers of the formula R 10 Rll CH 2 = C X N C R 2 wherein: R10 is hydrogen or C? -C alkyl, R11 is hydrogen or C? -C8 alkyl or aryl, in particular phenyl, R12 is hydrogen, C1-C10 alkyl, C6? C2 aryl or -OR13 . R 13 is C 1 -C 8 alkyl or C 6 -C 2 aryl, if desired with substitution by groups containing 0- or N-, X is a chemical or alkylene bond of Ci-Cio or arylene of Ce-C? 2, or 0 II -c -YY is OZ or NH-Z, and Z is Ci-Cio alkylene or CG ~ CI2 arylene. The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups to the surface. Other examples which may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates, such as (N-tert-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ethyl acrylate. The particles of the rubber phase can also be crosslinked. Examples of the crosslinked monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP A 50 265. It is also possible to use the monomers known as graft-binding monomers, ie monomers having two or more polymerizable double bonds that react at different ratios during polymerization. Preference is given to using compounds of this type in which at least one reactive group polymerizes in about the same ratio as the other monomers, while the other reactive group (or reactive groups) for example, significantly polymerizes more slowly. The different polymerization ratios give rise to a certain proportion of unsaturated double bonds in the rubber. If another phase is then grafted onto a rubber of this type, at least some of the double bonds present in the rubber reactor with the graft monomers from chemical bonds, ie the grafted phase has at least some degree Linkage through chemical bonds in the graft base. Examples of graft-binding monomers of this type are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids, for example allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, and the corresponding monoalyl compounds of these dicarboxylic acids. In addition to this there is a wide variety of other suitable graft-binding monomers. For further details reference may be made herein, for example in US-A 4 148 846. The proportion of these crosslinked monomers in the impact modification polymer is generally up to 5% by weight, preferably not more than 3% by weight, based on in the impact modifier polymer. Instead of graft polymers whose structure has more than one shell it is also possible to use homogeneous, ie simple shell elastomers made of 1,3-butadiene, isoprene and n-butyl acrylate or copolymers thereof. These products, too, can be prepared by the concomitant use of crosslinked monomers or monomers having reactive groups. Examples of preferred emulsion polymers are copolymers of n-butyl acrylate- (meth) acrylic acid, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl methacrylate copolymers, graft polymers with an inner core made of n-butyl acrylate or butadiene-based acrylate and with an outer shell made of the aforementioned copolymers, and ethylene copolymers with comonomers with reactive delivery groups. The described elastomers can also be prepared by another conventional process, for example by suspension polymerization. Preference is also given to silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290. This is, of course, also possible for use of mixtures of the types of rubber listed in the above. The fibrous or particulate fillers which can be mentioned are carbon fibers, vitreous fibers, vitreous beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, coal, quartz powder, mica, barium sulfate and feldspar, used in quantities of up to 50% by weight, in particular from 1 to 40% by weight, particularly from 20 to 35% by weight. Preferred fiber fillers which may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, and particularly preferably are given to vitreous fibers in the form of glass E. These can be used as fiber yarns of glass or in the commercially available forms of crushed glass.

The fiber fillers may have been pre-cast on the surface with a silane compound for improved compatibility with the thermoplastic. Suitable silane compounds have the formula: (X ~ (CH2) n) k-Si- (0-CmH2m +?) 4_k where: n is an integer from 2 to 10, preferably 3 or 4, m is an integer from 1 to 5, preferably 1 or 2, and k is an integer from 1 to 3, preferably 1. The -. Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes containing a glycidyl group as substituent X. The silane compounds are generally used for the surface coating in amounts of 0.05 to 5% by weight, preferably of 0.5 to 1.5% by weight and in particular from 0.8 to 1% by weight (based on D). The acicular mineral fillers are also suitable.

For the purposes of the present invention, acicular mineral fillers are mineral fillers with strongly developed acicular. An example is acicular calcium silicate. The ore preferably has a L / D ratio (length to diameter) from 8: 1 to 35: 1, preferably from 8: 1 to 11: 1. The mineral filler may, if desired, have been pretreated with the aforementioned silane compounds, but pretreatment is not essential. Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk. The novel thermoplastic molding compositions may comprise, as component D), conventional processing aids, such as stabilizers, oxidation inhibitors, agents for preventing decomposition by heat or ultraviolet light, lubricants, molding release agents, dyes, such as dyes and pigments, nucleating agents, plasticizers, etc., which differ from components B) and C). UV stabilizers which can be mentioned and are usually used in amounts of up to 2% by weight based on the molding composition, are various substituted resorcinols, salicylates, benzotriazoles and benzophenones. The colorants that can be added are inorganic pigments, such as ultramarine blue, iron oxide, carbon black, and also organic pigments, such as organics, such as phthalocyanines, quinacridones and perylenes, and also dyes, such as nigrosine and anthraquinones. The nucleating agents that can be used are sodium phenyl phosphinate, alumina, silica, and preferably talc. Other lubricants and molding release agents which are usually used in amounts of up to 1% by weight are preferably long-chain fatty acids (for example stearic acid or behenic acid), salts thereof (eg calcium stearate or sodium stearate). zinc) or montan waxes (mixtures of straight chain saturated carboxylic acids having chain lengths from 28 to 32 carbon atoms), and also low molecular weight polyethylene waxes and low molecular weight polypropylene faces. Examples of plasticizers that may be mentioned are dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalates, hydrocarbon oils and N- (n-butyl) benzenesulfonamide. The novel molding compositions can also comprise from 0 to 2% by weight of ethylene polymers containing fluorine. These are ethylene polymers with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight. Examples of these are copolymers of polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene and tetrafluoroethylene copolymers with relatively low proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are described, for example, by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484-494 and by Wall in "Fluoropolymers" (Wiley Interscience, 1972). These fluorine-containing ethylene polymers have homogenous distribution in the molding compositions and preferably have a particle size d50 (average number) in the range of 0.05 to 10 μm, in particular 0.1 to 5 μm. These small particle sizes can particularly preferably be achieved by the use of aqueous dispersions of fluorine-containing ethylene polymers and the incorporation of these in a polyester melt. The novel thermoplastic molding compositions can be prepared by methods known per se, by mixing the starting components in conventional mixing apparatuses, such as screw extruders, Brabender mixers or Banbury mixers, and then extruding them. The extrudate can be cooled and frred. This is also possible for pre-mixed individual components and then aids the remaining starting materials individually and / or otherwise in a mixture. The mixing temperatures are generally from 230 to 290 ° C. In a preferred method, components B) to D), and also, if desired, conventional additives E), can be mixed with a prepolymer of polyester, composites and pellets. The resulting pellets are then condensed at the desired viscosity in the solid phase under an inert gas, continuously or discontinuously, at a temperature below the melting point of component A). The novel thermoplastic molding compositions have good long thermal stability in use at elevated temperatures, and have good flame retardancy. They are processed with very small changes in the polymer shade (discoloration). The molding compositions also have good molecular weight stability during processing. They are suitable for producing fibers, films and moldings, in particular for applications in the electrical and electronic sectors. Particular applications are lamp parts, such as lamp sockets and lamp holders, plug and multipoint connectors, coil formers, capacitor or connector liners, and circuit breakers, relay housings and reflectors.

Examples Component Al: polybutylene terephthalate with a viscosity number of 125 ml / g and a carboxyl terminal group content of 25 mval / kg. The VZ was measured at a resistance of 0.5% by the weight solution of a 1: 1 mixture of phenol / o-dichlorobenzene at 25 ° C to ISO 1628. Component bi: brominated oligocarbonate (BC 52 from Great Lakes) Component b2: antimony trioxide (as a 90% polyethylene concentrate) Component C / l: zinc oxide Component C / 2: calcium carbonate Component D / l: vitreous fibers of average thickness μm (epoxysized size) Component D / 2: polytetrafluoroethylene (Teflon) In Examples 1 and Cl components A), bi) and b2) and only D / l and D / 2 are mixed in an extruder at 250 ° C, homogenized , pelletized and dried. The pellets are then mixed in an amateur at 250 ° C and 60 rpm in examples 1, 2 and Cl a mixture is taken after 10, 20 and 30 minutes and recorded at 160 ° C (in air). The viscosity number of the samples is taken at respective intervals and mature, and also from the immature samples, were measured at ISO 1628.

In the case of Examples 2, 3 and C2 the samples are taken after 5, 10 and 20 min. The arrangements of the molding compositions and the results of the test are found in the table.

Table (l in

Claims (5)

1. CLAIMS 1. A thermoplastic molding composition comprising A) from 10 to 98.9% by weight of a thermoplastic polymer, B) from 1 to 30% by weight of a flame retardant combination made from, based on 100% by weight of B), bi) from 20 to 99% by weight of a halogen containing flame retardant, and b2) from 1 to 80% by weight of an antimony oxide, C) from 0.1 to 5% by weight of a stabilizer made from a compound containing oxygen- or nitrogen- or sulfur- zinc, or made from mixtures thereof, D) from 0 to 70% by weight of other additives, where the sum of the percentages by weight of the components A) to D) is 100%.
2. 2. The thermoplastic molding composition as claimed in claim 1, wherein the thermoplastic polymer has been selected from the class consisting of polyamides, polyesters, vinylaromatic polymers, ASA polymers, ABS polymers, SAN polymers and mixtures of these .
3. 3. The thermoplastic molding composition as claimed in claim 1 or 2, wherein component A) is composed of polybutylene terephthalate which may comprise, based on 100% by weight of A), from 0 to 50% by weight of different polyesters from polybutylene terephthalate.
4. 4. The thermoplastic molding composition as claimed in any of claims 1 to 3, wherein b2) is composed of antimony trioxide or antimony pentoxide or mixtures thereof. 5. The thermoplastic molding composition as claimed in any of claims 1 to 4, comprising, a component C), ZnO, ZnS, zinc borate, Zn3N2,. Zn3 (P04) 2 or mixtures of these. 6. The use of the thermoplastic molding compositions as claimed in any of claims 1 to 5 to produce fibers, films or moldings. 7. The molding obtainable from the thermoplastic molding compositions as claimed in any of claims 1 to
5. 5.