MXPA99010761A - Flame-resistant polycarbonate moulding materials which are dimensionally stable at high temperatures and have high flow line strength - Google Patents

Abstract

The invention relates to flame-resistant thermoplastic moulding materials containing A) 70 to 98 parts by weight of an aromatic polycarbonate, B) 0.5 to 20 parts by weight of a graft polymer, C) 0.5 to 5 parts by weight of a mixture of C.1) 10 to 90 weight percent, in relation to C, of a monophosphoric compound of formula (I) and C.2) 90 to 10 weight percent, in relation to C, of a phosphorus compound of the formula (II), and D) 0.05 to 5 parts by weight of a fluorinated polyolefin having a mean particle diameter ofbetween 0.05 and 1000&mgr;m, a density of 1.2 to 2.3 g/m3 and a fluorine content of between 65 and 76 weight percent.

Description

POLYCARBONATE MOLDING MASSES REPELLENT TO THE FLAME, WITH HIGH DIMENSIONAL STABILITY IN HOT, WITH HIGH RESISTANCE TO WELDING BY FLUENCY. FIELD OF THE INVENTION The present invention relates to flame retardant molding compositions of polycarbonates and graft polymers, which are flame retardant by means of an effective combination of additives constituted by a monomeric phosphorus compound and by a compound of the oligomeric phosphorus. The molding compositions according to the invention are characterized by high hot dimensional stability, very high creep resistance and excellent flame repellency. Description of the prior art EP-A 0 174 493 (US-P 4 983 658) describes halogenated, flame-protected polymer mixtures, consisting of aromatic polycarbonate, styrene-containing graft copolymer, monophosphates and by a formulation special polytetrafluoroethylene. These mixtures are sufficient in the behavior to the fire and in regard to the level of mechanical values, of course there can be shortcomings in terms of the resistance to welding by creep as well as thermal stability. In US Pat. No. 5,030,675, masses of REF .: 31850 thermoplastic molding, flame repellents, constituted by aromatic polycarbonate, ABS polymer, polyalkylene terephthalate as well as monophosphates and fluorinated polyolefins as flame protection additives. Compared with the good resistance to stress fracture and the good resistance to creep welding, the drawbacks are the lack of notch resilience and insufficient thermal stability under high thermal stresses, such as during the process, for example. So of transformation. Another disadvantage must be considered in this case in the fact that, in order to obtain an effective protection against the flame, relatively high quantities of flame protection agent are required, which greatly reduce the dimensional resistance in the flame. Diphosphates are known as flame-protective additives. JA 59 202 240 describes the production of a product of this type from phosphorus oxychloride, diphenols such as hydroquinone or bisphenol A and monophenols such as phenol or cresol. These diphosphates can be used as flame retardants in polyamide or polycarbonate. EP-A 0 363 608 (= US-P 5 204 394) describes polymer mixtures consisting of aromatic polycarbonate, copolymer containing styrene and graft copolymer as well as oligomeric phosphates, in the form of flame retardant additives. These mixtures certainly exhibit good flame repellency and reduced formation of deposits in the molds, but nevertheless they do not have the high resistance to creep welding required for many applications nor the protective effect against the flame. As the molecular weight of the oligomeric phosphates increases, the activity in terms of flame protection decreases. EP-A 0 640 655 describes molding compositions consisting of polycarbonate, styrene copolymer, ABS graft polymers and a combination of mono-phosphates and oligomeric phosphates as flame retardants. Also in this case, the low resistance to fluence welding caused by the styrene copolymers should be mentioned as a drawback. According to DE-A 195 47 013 the molding compositions consisting of polycarbonates, graft polymer and oligomeric phosphates, as flameproofing agents, have excellent flame repellency. Monophosphates are not contained in the molding compositions according to the invention. EP-A 0 731 140 describes polymer mixtures consisting of carbonate, m graft polymer and a combination formed by monophosphates and oligomeric phosphates, by way of protective agents against the flame. These mixtures have good flame repellency and good thermal stability. However, it is a disadvantage that, in order to obtain an effective flame protection agent (V-0 at 1.6 mm thickness according to UL 94 V), at least five parts by weight of phosphorus compound are required, which has negative effects on hot dimensional stability. DETAILED DESCRIPTION OF THE INVENTION Surprisingly it has been found at the time that molding compositions, free from halogen, consisting of polycarbonate, graft polymer and by a combination of flame-protective additives formed by a monomeric phosphorus compound and by a compound of phosphorus present a very good combination of properties formed by a high dimensional stability in hot, a good mechanical level (resilience with notch, resistance to welding by creep) and excellent flame repellency. The subject of the invention are thermoplastic, flame-retardant molding compositions containing A) from 70 to 98 parts by weight, preferably from 75 to 98 parts by weight, particularly preferably from 80 to 98 parts by weight of a aromatic polycarbonate, B) from 0.5 to 20 parts by weight, preferably from 1 to 20 parts by weight, particularly preferably from 2 to 12 parts by weight of a graft polymer, C) from 0.5 to 5 parts by weight, preferably from 0.5 to 4 parts by weight, particularly preferably from 0.5 to 3 parts by weight of a mixture formed by Cl) to 90 parts by weight, preferably 12 to 50, in particular up to 40, very particularly preferably 15 to 40% by weight (based on the total amount of C) of a monomeric phosphorus compound of the form (I) OR R1- (O) -P ?? - (O) -R2 (|), (?) M R3 wherein R1, R2 and R3, independently of one another, mean alkyl of 1 to 8 carbon atoms, aryl of 6 to 20 carbon atoms or aralkyl of 7 to 12 carbon atoms, m means 0 or 1 and n means 0 or 1 and C.2) 90 to 10% by weight, preferably 88 to 50, especially 86 to 60, very particularly preferably 85 to 60% by weight, (based on the total amount of C) of a phosphorus compound of the formula (II), (II) wherein R4, R5, R6, R7, independently of one another, mean alkyl having 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 12 carbon atoms, carbon, 1 independently of each other, mean 0 or 1, N means 1 to 5 and X means an aromatic or polynuclear moiety with 6 to 30 carbon atoms, D) of 0.05 to 5 parts by weight, preferably 0.1 up to 2 parts by weight, more preferably from 0.1 to 1 part by weight of a fluorinated polyolefin with an average particle diameter of 0.05 to 1,000 μm, a density of 1.2 to 2.3 g / cm3 and a fluorine content of 65 to 76% by weight.

Component A. The aromatic polycarbonates, thermoplastics, suitable according to the invention, according to component A are those based on diphenols of the formula (III), wherein A means a single bond, alkylene having 1 to 5 carbon atoms, alkylidene with 2 to 5 carbon atoms, cycloalkylidene with 5 to 6 carbon atoms -S- or -S02 ~, B independently of one another, means alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 carbon atoms, aralkyl with 7 to 12 carbon atoms, q means 0, 1 or 2 and p means 1 or 0, or alkyl-substituted dihydroxyphenylcycloalkanes of the formula (IV) , wherein QQR and r, independently from each other, mean hydrogen, alkyl having 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, aryl with 6 to 10 carbon atoms, preferably phenyl, and aralkyl with 7 a 12 carbon atoms, preferably phenyl-C 1 -C 4 -alkyl, especially benzyl, m means an integer of 4, 5, 6 or 7, preferably 4 or 5, R 10 and R 11, which can be chosen individually for each Z, means, independently of each other, hydrogen or alkyl having 1 to 6 carbon atoms, and Z means carbon, with the proviso that at least one of the atoms of Z, R ° and R1 simultaneously mean alkyl. Suitable diphenols of the formula (III) are, for example, hydroquinone, resorcin, 4,4'-dihydroxydiphenol, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (-hydroxyphenyl) ) -2-methylbutane, 1, 1-bis- (4-hydroxyphenyl) -cciohexane. Preferred diphenols of the formula (III) are 2,2-bis- (4-hydroxyphenyl) -propane, 2,2- and 1,1-bis- (4-hydroxyphenyl) -cciohexane. Preferred diphenols of the formula (IV) are 1,1-bis- (-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the 1,1-bis- (4-hydroxyphenyl) -2,4,4-trimethyl-cyclopentane. The polycarbonates suitable according to the invention are both hsmopolycarbonates and also copolycarbonates. The component A can also be a mixture of the above-defined thermoplastic polycarbonates. The polycarbonates can be prepared in a known manner from diphenols with phosgene according to the process of the boundary surface between the phases or with phosgene according to the homogeneous phase process, the so-called pyridine process, the molecular weight being adjustable, in a known manner , by means of a corresponding quantity of known chain switches. Suitable chain terminators are, for example, phenol, p-tert. -butylphenol or also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) -phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenol with a total of 8 to 20 carbon atoms in the alkyl substituents according to German patent application P 3 506472.2, such as 3, 5-di-tert. -butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol. The number of chain switches is, in general, between 0.5 and 10% in moles, based on the sum of the diphenols used, respectively, of the formulas (III) and / or (IV). The polycarbonates A, suitable according to the invention, have average molecular weights (Mw, measured for example by ultracentrifugation or by measurement of light scattering) of 10,000 to 200,000, preferably 20,000 to 80,000. The polycarbonates A, suitable according to the invention, can be branched in a known manner and specifically, preferably, by the incorporation of 0.05 to 2 mol%, based on the sum of the diphenols used, of trifunctional compounds or with a functionality greater than 3, for example those with three or more than three phenolic groups. Preferred polycarbonates are, in addition to the bisphenol-A homopolycarbonate, the polycarbonates of bisphenol A with up to 60 mol%, based on the sum of the diphenols, of 1, 1-bis- (4-hydroxyphenyl) -3 , 3, 5-trimethylcyclohexane. The polycarbonates A can be partially or completely replaced by aromatic polyester carbonates. In another embodiment, the aromatic polycarbonate A can be replaced by a mixture of two or more polycarbonates A.l and A.2 with the same or different structure, having different relative solution viscosities. Preferably the polycarbonates have the same structure. With regard to the mixture of the polycarbonates Al and A.2, the proportion by weight of Al is from 5 to 95, preferably from 25 to 75% by weight, especially from 10 to 35% by weight, and the proportion by weight of A.2 is 95 to 5, preferably 75 to 25% by weight, especially 35 to 10% by weight. The mixture of the polycarbonates A.l and A.2 is characterized in that the relative solution viscosity of A.l is 1.18 to 1.24, because the relative solution viscosity of A.2 is 1.24 to 1.34. Preferably the difference between the relative viscosities in solution of A.l and A.2 is greater than or equal to 0.06 especially greater than or equal to 0.09, ie relative viscosity in solution (A.2) - relative viscosity in solution (A.l) >; 0.06, especially > 0.09. The relative viscosity in solution is measured in CH2Cl2 as solvent at 25 ° C at a concentration of 0.5 g / 100 ml. One of the two components of the polycarbonate A.l or A.2 in the mixture can be a recycled polycarbonate. By recycled polycarbonate those products that have already undergone a transformation cycle and of. and that they have been released from impurities adhering by means of special processing procedures in such a way that they are suitable for further use. Component B The graft polymers B comprise, for example, graft polymers with rubber-elastic properties, which can essentially be obtained from at least two of the following monomers: chloroprene, butadiene-1,3, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and esters of (meth) acrylic acid having 1 to 18 carbon atoms in the alcohol component; ie polymers, such as those described for example in "Methoden der Organischen Chemie" (Houben-Weyl), volume 14/1, Georg Thieme-Verlag. Stuttgart 1961, page 393-406 and in C.B. Bucknall, "Toughened Plastics", Appl. Science Publishers, London 1977. Preferred B polymers are partially crosslinked and have gel contents above 20% by weight, preferably above 40% by weight, especially above 60% by weight. Preferred graft polymers B comprise graft polymers consisting of: Bl) 5 to 95, preferably 30 to 80 parts by weight, of a mixture formed by Bll) to 95 parts by weight of styrene, α-methylstyrene, methylsubstituted styrene in the nucleus, alkyl methacrylate with 1 to 8 carbon atoms, especially methyl methacrylate, alkyl acrylate with 1 to 8 carbon atoms, especially methyl acrylate or mixtures of these compounds and Bl2) 5 to 50 parts by weight , of acrylonitrile, methacrylonitrile, alkyl methacrylates with 1 to 8 carbon atoms, especially methyl methacrylate, alkyl acrylates with 1 to 8 carbon atoms, especially methyl acrylate, maleic anhydride, maleinimides N-alkyl or N -phenylsubstances with 1 to 4 carbon atoms or mixtures of these compounds on B.2) 5 to 95, preferably 20 to 70 parts by weight of polymer with a glass transition temperature below -10 ° C . Preferred graft polymers B are, for example, polybutadiene grafted with styrene and / or with acrylonitrile and / or with alkyl esters of (meth) acrylic acids, butadiene / styrene copolymers and acrylate rubbers; that is to say copolymers of the type described in DE-OS 1 694 173 (= US-PS 3 564 077); polybutadienes grafted with alkyl esters of acrylic acid or methacrylic acid, vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes, butadiene / styrene or butadiene / acrylonitrile copolymers, polyisobutenes or polyisoprenes, such as those described for example in DE-OS 2 348 377 (= US-PS 3 919 353). Especially preferred graft polymers B are graft polymers, which can be obtained by grafting reaction from I. 10 to 70, preferably 15 to 50, especially 20 to 40% by weight, based on the graft product, of at least one ester of (meth) acrylic acid or 10 to 70, preferably 15 to 50, especially 20 to 40% by weight of a mixture formed by 10 to 50, preferably 20 to 35% by weight, based on the mixture, of acrylonitrile or esters of (meth) acrylic acid and 50 to 90, preferably 65 to 80% by weight, based on the mixture, of styrene on II. 30 to 90, preferably 50 to 85, in particular 60 to 80% by weight, based on the graft product, of a butadiene polymer with at least 50% by weight, based on II, of butadiene esters as the graft base. , the gel proportion of the graft base II being preferably at least 70% by weight (measured in toluene), the degree of graft G of 0, 15 to 0.55 and the average diameter of the particles d ^ g of the graft polymer B from 0.05 to 2, preferably from 0.1 to 0.6 μm. The esters of (meth) acrylic acid I are esters of acrylic acid or methacrylic acid and monovalent alcohols with 1 to 18 carbon atoms. Particular preference is given to methyl, ethyl and propyl methacrylate. The graft base II may contain, in addition to the butadiene residues, 50% by weight, based on II, of residues of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, esters of acrylic acid or methacrylic acid with 1 to 4 carbon atoms in the alcohol component (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and / or vinyl ethers. The preferred graft base II is constituted by pure polybutadiene.

Since in the grafting reaction of the graft monomers, as is known, total grafting on the grafting base is not carried out, graft polymers B according to the invention will be understood as those products which are obtained by polymerization of the graft monomers in accordance with the invention. presence of the graft base. The degree of grafting G refers to the weight ratio between grafted graft monomers and graft base and is dimensionless. The average particle size d50 is the diameter above and below which it finds 50% by weight of the particles respectively. This can be determined by means of ultracentrifugation measurements (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-796). Especially preferred graft polymers B are, for example, also graft polymers constituted by (a) 20 to 90% by weight, based on B, of acrylate rubber with a glass transition temperature below -20 ° C. as the graft base and (b) 10 to 80% by weight, based on B, of at least one polymerizable, ethylenically unsaturated monomer, of which the homo or copolymers formed in the absence of a) have a transition temperature vitreous located above 25 ° C, as a graft monomer.

The acrylate rubbers (a) of the polymers B are preferably polymers formed by alkyl esters of acrylic acid, optionally with up to 40% by weight, based on (a), of other polymerizable, ethylenically unsaturated monomers. Preferred polymerizable acrylic esters include alkyl esters with 1 to 8 carbon atoms, for example methyl, ethyl, n-butyl, n-octyl and 2-ethylhexyl esters and mixtures of these monomers. For the crosslinking, monomers with more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and monovalent unsaturated alcohols with 3 to 12 carbon atoms or unsaturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as , for example, ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as for example trivinyl cyanurate and triallyl; vinyl-polyfunctional compounds, such as di- and tri-inylbenzenes; as well as triallyl phosphate and diethyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds, which have at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers consisting of diallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, trialkylohexahydro-s-triazine, triallylbenzenes. The amount of the crosslinking monomers is preferably from 0.02 to 5, in particular from 0.05 to 1% by weight, based on the graft base (a). In the case of cyclic crosslinking monomers with at least three ethylenically unsaturated groups it is advantageous to limit the amount to a value situated below 1% by weight of the graft base (a). Preferred "other" polymerizable monomers, ethylenically unsaturated, which can be used, in addition to the esters of acrylic acid, for the preparation of the graft base (a), are, for example, acrylonitrile, styrene, methylstyrene, acrylamide, vinyl alkyl ethers with 1 to 6 carbon atoms, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base (a) are emulsion polymers having a gel content of at least 60% by weight. Other suitable grafting bases are silicone rubbers with active spots for grafting, such as those described in published patent applications, not examined DE 37 04 657, DE 37 04 655, DE 36 31 5140 and DE 36 31 539 The gel content of the graft base (a) is determined at 25 ° C in dimethylformamide (M. Hoffmann, H. Krómer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977). The aqueous dispersions of graft polymer B to be used for the preferred embodiment of the co-precipitation with the tetrafluoroethylene polymer D have, in general, solids contents of 25 to 60, preferably 30 to 45% by weight . Component C. The polymer mixtures according to the invention contain as flame protection agents a mixture consisting of a monomer phosphorus compound C.l and a phosphorus compound C.2. Component C.l represents a phosphorus compound according to formula (I), In the formula R, R and R are, independently of each other, alkyl having 1 to 8 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, aryl having 6 to 20 carbon atoms, preferably phenyl or naphthyl or aralkyl having 7 to 20 carbon atoms. to 12 carbon atoms, preferably phenyl-alkyl with 1 to 4 carbon atoms, m means 0 or 1 and n means 0 or 1. The phosphorus compounds suitable according to the invention according to the Cl component are generally known (cf. example Ullmanns Enzyklopadie der technischen Chemie, volume 18, page 301 et seq 1979, Houben-Weyl, Methoden der Organischen Chemie, volume 12/1, page 43, Beilstein, volume 6, page 177). Preferred substituents R and R3 include methyl, butyl, octyl, phenyl, cresyl, cumyl and naphthyl. Particular preference is given to methyl, ethyl, butyl, optionally substituted phenyl by methyl or ethyl. Preferred Cl phosphorus compounds (form-mule (I)) include, for example, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-cresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tricalphosphate, (isopropylphenyl), dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl phenylphospho- nate, triphenylphosphine oxide and tri-cresylphosphine oxide. Component C.2 represents a phosphorus compound of the formula (II), O O II II - (O), - -p- -O-X- -p- - (O) G -R '(ll) R_j N In the formula R, R, R, R, independently of one another, are alkyl of 1 to 8 carbon atoms, preferably alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 12 carbon atoms, phenyl, naphthyl, benzyl are preferred. The aromatic groups R 4, R 5, R 6 and R 7 may be substituted, for their part, with alkyl groups. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl. In the formula (II), X means a mono or polynuclear aromatic residue with 6 to 30 carbon atoms.

This is derived from diphenols such as for example bisfe-npl A, resorcin, hydroquinone or from the diphenols described above in formula (III). In the formula (II), 1 can be, independently of each other, 0 or 1, preferably n means 1. The values of N can be comprised between 1 and 5, preferably between 1 and 2. As components C.2 according to the invention mixtures of various phosphates can also be used. In this case N has an average value between 1 and 5, preferably between 1 and 2. The polymer mixtures according to the invention contain as flame protection agents, a mixture consisting of C.l and C.2. The quantitative proportions between C.l and C.2 will be chosen in this case in such a way that a synergistic effect is achieved. The mixture is generally composed of 10 to 90% by weight of C.l and 90 to 10% by weight of C.2 (referred to C respectively). Especially favorable properties conditions occur in the preferred range of 10 to 50, especially 14 to 40, very particularly preferably 15 to 40% by weight of Cl and 88 to 50, preferably 86 to 60, very particularly preferred of 85 to 60% by weight of C.2. Component D. Fluorinated polyolefins D are of high molecular weight and have glass transition temperatures located above -30 ° C, generally above 100 ° C, contained in fluorine, preferably from 65 to 76, especially from 70 up to 76% by weight, average diameter of the d5Q particles from 0.05 to 1,000, preferably from 0.08 to 20 μm. In general, fluorinated polyolefins D have a density of 1.2 to 2.3 g / cm3. Preferred fluorinated polyolefins D are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoro propylene copolymers and ethylene / tetrafluoroethylene copolymers. The fluorinated polyolefins are known (see "Vinyl and Related Polymers" by Schildknecht, John Wiley & amp;; Sons, Inc., New York, 1962, pages 484-494; "Fluorpoly ers" by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, pages 623-654; "Modern Plastics Encyclopedia", 1970-1971, volume 47, No. 10 A. October 1970, c Graw-Hill, Inc. New York, pages 134 and 774; "Modern Plastics Encycloedia" 1975-1976, October 1975, Volume 52, No. 10A, Mc Graw-Hill, Inc., New York, pages 27, 28 and 472 and US-PS 3 671 487, 3 723 373 and 3 838 092). These can be prepared according to known processes, for example by polymerization of tetrafluoroethylene in aqueous medium with a free radical-forming catalyst, for example sodium, potassium or ammonium peroxydisulfate, at pressures of 7 to 71 kg / cm 2 and at temperatures of 0 to 200 ° C, preferably at temperatures of 20 to 100 ° C. (For more details see for example the US patent US 2 393 967). According to the application form, the density of these materials can be between 1.2 and 2.3 g / cm 3, the average particle size between 0.05 and 1,000 μm. The preferred fluorinated polyolefins D according to the invention are tetrafluoroethylene polymers and have average particle diameters of 0.5 to 20 μm, preferably 0.08 to 10 μm, and a density of 1.2 to 1.9 g / cm3 and they are preferably used in the form of a coagulated mixture of emulsions of polymers of tetrafluoroethylene D with emulsions of the graft polymer B. In order to obtain a coagulated mixture formed by B and D, an aqueous emulsion (latex) of a graft polymer B with a mean diameter of the latex particles of 0.05 to 2 μm, especially 0.1 to 0.6 μm, with a finely divided emulsion of a tetrafluoroethylene polymer D in water with a diameter medium of the particles from 0.05 to 20 μm, especially from 0.08 to 10 μm; Suitable tetrafluoroethylene polymer emulsions usually have solids contents of from 30 to 70% by weight, in particular from 50 to 60% by weight. The emulsions of graft polymers B) have solids contents of from 25 to 50% by weight, preferably from 30 to 45% by weight. The quantitative data in the description of component B encompass the proportion of the graft polymer for the coagulated mixture formed by graft polymer and fluorinated polyolefins. In the emulsion mixture, the weight ratio between the graft polymer B and the tetrafluoroethylene polymer D with a value of 95: 5 to 60:40 is presented. The emulsion mixture is then coagulated in a known manner, for example by spray drying, freeze-drying or coagulation by means of the addition of inorganic or organic salts or acids or bases or organic solvents, miscible with water, such as alcohols. , ketones, preferably at temperatures of 20 to 150 ° C, especially 50 to 100 ° C. If necessary, it can be dried at 50 to 200 ° C, preferably at 70 to 100 ° C.

Suitable tetrafluoroethylene polymer emulsions are commercially available products and are offered, for example, by the DuPont Company as Teflon 30 N. The suitable fluorinated polyolefins D, which are used in powder form, are polymers of tetrafluoroethylene with an average diameter. of particles from 100 to 1,000 μm and densities from 2.0 g / cm to 2.3 g / cm3. Suitable powders of tetrafluoroethylene polymer are commercially available products and are offered, for example, by the firm DuPont under the trade name Teflon. The molding compositions according to the invention can contain customary additives such as lubricants and release agents, nucleating agents, antistatics, stabilizers, fillers and reinforcing products as well as dyes and pigments. The molded or reinforced molding compositions can contain up to 60, preferably 10 to 40% by weight, based on the reinforced or reinforced molding compositions, fillers and / or reinforcing materials. Preferred reinforcing materials are glass fibers. The preferred fillers, which may also act as reinforcing agents, are glass beads, mica, silicates, quartz, talc, titanium dioxide, Wollastonite. The molding compositions according to the invention consist of components A to D and, if appropriate, other known additives such as stabilizers, co-molars, pigments, lubricants and release agents, fillers and reinforcing agents, nucleating agents as well as antistatic agents are prepared by mixing the corresponding components in a known manner and by forming melt-melt or melt extrusion mixtures at temperatures of 200 ° C to 330 ° C in conventional devices such as internal kneaders, extruders or double spindles. tree . The object of the present invention is therefore also a process for obtaining thermoplastic molding compositions, consisting of components A to D as well as optionally stabilizers, dyes, pigments, purifiers and release agents, fillers and reinforcement products, nucleating agents as well as antistats, characterized in that mother mixtures are formed by melting or melt extruded components A to D as well as optionally stabilizers, dyes, pigments, lubricants, fillers and reinforcing agents, lubricants and demolding agents, nucleating and / or antistatic agents, once the mixture is verified, at temperatures of 200 to 330 ° C in conventional devices, the D components being preferably used in the form of a coagulated mixture with the B components. of the individual components can be carried out in known manner both successively and simultaneously and concretely both at 20 ° C approximately (room temperature) as well as at higher temperature. The molding compositions of the present invention can be used for the production of moldings of any type. Especially molded bodies can be manufactured by injection molding. Examples of moldable bodies that can be manufactured are: parts for housings of any type, for example for household appliances, such as juice squeezers, coffee machines, mixers, for office machines, such as monitors or printers or cover plates for the sector of civil construction and parts for the automobile sector. They are also used in the field of electrical engineering, since they have very good electrical properties. The molding compositions are particularly suitable for the production of thin-walled moldings (for example housing parts for the data processing technique), and particularly high requirements are required in terms of notched resilience, resistance to deformation, etc. welding by creep and flame repellency of the synthetic materials used. Another form of transformation is the manufacture of molded bodies by means of blow molds or by embossing from previously manufactured plates or sheets. Examples Component A.l Polycarbonate based on bisphenol A, with a relative solution viscosity of 1.26 to 1.28 measured in methylene chloride at 25 ° C and a concentration of 0.5 g / 100 ml. Component A.2 Polycarbonate based on bisphenol A, with a relative solution viscosity of 1.195 to 1.205 measured in methylene chloride at 25 ° C and a concentration of 0.5 g / 100 ml. Component A.3 Polycarbonate based on bisphenol A, with a relative solution viscosity of 1.305 to 1.315 measured in methylene chloride at 25 ° C and a concentration of 0.5 g / 100 ml. Component A.4 Polycarbonate based on bisphenol A, with a relative solution viscosity of 1.235 to 1.245 measured in methylene chloride at 25 ° C and a concentration of 0.5 g / 100 ml. Component B Graft polymer of 40 parts by weight of styrene and acrylonitrile in the proportion of 73:27 on 60 parts by weight of cross-linked polybutadiene rubber in the form of particles (average diameter of the particles d5Q = 0.3 μm) prepared by polymerization in emulsion.

Component C. ® C.l) Triphenyl Phosphate (Disflamoll TP from Bayer AG). C.2) m-Phenylene-bis (di-phenyl-phosphate) (Fyroflex RDP from the Akzo Company). Component D. ® Tetrafluoroethylene polymer (Teflon from DuPont) in the form of a coagulated mixture of a graft polymer emulsion B in water and a tetrafluoroethylene polymer emulsion in water. The weight ratio between graft polymer B) and tetrafluoroethylene polymer D in the mixture is 90% by weight with respect to 10% by weight. The tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the average diameter of the particles is between 0.05 and 0.5 μm. The SAN-graft polymer emulsion has a solids content of 34% by weight and an average diameter of the latex particles of 0.3 μm. Obtaining the coagulated mixture. The emulsion of the tetrafluoroethylene polymer ® (Teflon 30 N of the DuPont) with the emulsion of graft polymer B and stabilized with 1.8% by weight, based on the solid matter of the polymer, of phenolic antioxidants. The mixture is coagulated at 85 to 95 ° C with an aqueous solution of MgSO4 (bitter salt) and acetic acid at pH 4 to 5, filtered and washed until the practical absence of electro-lithos, then released from the main quantity of water by centrifugation and then dried at 100 ° C to give a powder. This powder can then be converted into a masterbatch with the other components in the described devices. Fabrication and testing of the molding compositions according to the invention. The mixture of components A to D is carried out in an internal 3-liter kneader. The temperature of the dough is 220-240 ° C. They are manufactured from the molding compound in an injection molding machine, rods with dimensions of 80 x 10 x 4 mm2 (transformation temperature 260 ° C), on which both the measurement of the notched resilience at room temperature (according to the ISO 180 1A method) as well as the measure of the hot dimensional stability according to Vicat B according to DIN 53 460. For the determination of the anne creep weld strength the Tenacity to the shock according to DIN 53 453 in the joining seam of specimens injected on both sides (transformation temperature: 260 ° C) with dimensions of 170 x 10 x 4 mm. The behavior to the fire of the test pieces was measured according to UL-Subj. 94 V in rods with the dimensions of 127 x 12.7 x 1.6 mm manufactured in an injection molding machine at 260 ° C. The UL 94 V test was carried out in the following manner: Substance samples are molded to give variolines with dimensions of 127 x 12.7 x 1.6 mm. The rods are mounted vertically in such a way that the bottom side of the specimens is 305 mm above a strip of bandage fabric. Each test rod is turned on individually by means of two successive firing processes of 10 seconds duration, the combustion properties are observed after each ignition process and then the sample is evaluated. For the ignition of the samples a Bunsen burner with a blue flame with a height of 10 mm (3.8 inches) of natural gas is used with a thermal unit of 3.73 x 10 hJ / m3 (1000 BUT per cubic foot) . The UL 94 V-0 classification covers the properties of the materials described below, which have been tested according to the UL 94 V protocol. The molding materials in this class do not contain samples that burn for more than 10 seconds after each application of the test flame; do not present a total flame time greater than 50 seconds during the two applications of the flame in each test group; they do not contain samples that burn completely to the upper end of the clamp that holds the sample; they do not present samples that ignite the cotton placed below the sample due to droplets or particles in combustion, nor do they contain samples that are incandescent for more than 30 seconds after the test flame has been removed. Other UL 94 classifications designate samples that are less flame repellent or that can self-extinguish in a smaller proportion because they produce droplets or particles in combustion. These classifications are designated with UL 94 V-l and V-2. N.B. means "not exceeded" and is the classification of the samples that have a subsequent burn time of > . 30 s. In the following tables 1 and 2 a summary of the properties of the molding compositions according to the invention has been indicated: H Cp or cn cp Table 1. Composition and properties of the molding compositions.

I OJ I Vgl: Comparative.

H1 O Cp or Cp Table 2. Composition and properties of molding compositions.

I? ? i Vgl: Comparative.

The molding compositions according to the invention show a very advantageous combination of properties formed by high hot dimensional stability, good mechanical properties such as notch resilience and resistance to creep welding and excellent flame retardancy (V-0 a 1.6 mm according to UL-94 V). An addition of styrene copolymers leads to a lower drop in the hot dimensional stability and notch resilience and to a drastic drop in the yield strength. An increase in the amount of the flameproofing agents is expressed in a strong drop of the hot dimensional stability. If a monophosphate alone is used, ie an oligophosphate, the flame protection does not reach the high level of the examples according to the invention. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present detailed description of the invention.

Claims (12)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. - Thermoplastic molding masses, flame retardants containing A) from 70 to 98 parts by weight of an aromatic polycarbonate, B) from 0.5 to 20 parts by weight of an injurious polymer, C) from 0.5 to 5 parts by weight of a mixture formed by C. l) 10 to 90% by weight, based on C, of a monomeric phosphorus compound of the formula (I), characterized because; R1, R and R3, independently of each other, mean alkyl with 1 to 8 carbon atoms, aryl with 6 to 20 carbon atoms or aralkyl with 7 to 12 carbon atoms, m means 0 or 1, and ri means 0 or 1 and C.2) 90 to 10% by weight, based on C, of a phosphorus compound of the formula (II) O O II II "(O), - P- rO-X- -P- - < o) r (ll) I (O). (9) R5 L? JN wherein R- R- Rc R, independently they mean alkyl with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 12 carbon atoms, 1 independently of each other, mean 0 or 1, N means from 1 to 5 and X means a mono or polynuclear aromatic radical with 6 to 30 carbon atoms and D) from 0.05 to 5 parts by weight of a fluorinated polyolefin with an average particle diameter of 0, 05 to 1,000 μm, a density of 1.2 to 2.3 g / cm3 and a fluorine content of 65 to 76% by weight 2.- Molding masses according to claim 1, fish acptLenai from 75 to 98 ports in weight of aromatic polycarbonate A. 3.- Molding masses according to claim 1, charcoal perca ccptiapa pipoiipoxs graft B exAracicR par cqx > -limerization of 5 to 95 parts by weight of a mixture formed by fifty to 95 parts by weight of styrene-α-methylstyrene, alkylsubstituted styrene in the nucleus, alkyl methacrylate with 1 to 8 carbon atoms, alkyl acrylate with 1 to 8 carbon atoms or mixtures of these compounds and 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, alkyl methacrylate with 1 to 8 carbon atoms, alkyl acrylate with 1 to 8 carbon atoms, maleic anhydride, maleinimide N-alkylsubstituted with 1 to 4 carbon atoms or N -phenyl-substituted or mixtures of these compounds on 5 to 95 parts by weight of rubber with a vitreous transition temperature situated below -10 ° C. 4. Molding masses according to claim 3, characterized perqué scptiaiai cato letters, diax letters > , acrylate, silicone rubbers or ethylene-propylene-no-diene rubbers. 5. Molding masses according to claim 1, characterized perqué < xptLata? crppcnaite C in an active synergistic pHi-te amount formed by a monomer phosphorus compound C.l and an oligomeric compound of phosphorus C.2. 6 - Molding masses according to claim 1, characterized per septLenen crpo empeñarte C see mixture formed per 12 to 50% by weight of C. l and by 50 to 88% by weight of C. 2 . 7 - Molding masses according to claim 1, CdtccUS raised perqué contiena! cone oaipensite C.1 trifaiyl phosphate. 8 - Molding masses according to claim 1, per ccptii = riai choir empéñente C.2 a feefeto? or, in which R 4, R, R ° and R 7 are phenyl groups and X is a phenylene group. 9. - Molding compositions according to claim 8, characterized in that X denotes a bisphenylisopropylidene group. 10 - Molding masses according to claim 1, characterized in that in which component D is used in the form of a mixture coagulated with component B. 11. - Thermoplastic molding compositions, trowel repellents, according to claim 1, cararterizadas acptL = n = n additives chosen from the group consisting of stabilizers, colorantes, pigments, lubricants and demolding agents, fillers and reinforcing agents, nucleating agents and anti-static. 12 - Use of the molding compositions according to claim 1, for the production of moldings.