MXPA00001444A - Flame resistant abs polycarbonate mouldable materials - Google Patents

Abstract

<0°C and mean particle size distribution (value d50) of 0.20 to 0.35 mm;C) o to 45 parts by weight of a vinyl thermoplastic copolymer;D) 0.5 to 20 parts by weight of a phosphorus compound;E) 0.05 to 5 parts by weight of a fluorinated polyolefin.

Description

Flame Resistant Polycarbonate-ABS Molding Masses Description of the invention: The present invention relates to ABS polycarbonate molding compositions endowed with flame resistance based on phosphorus compounds, which exhibit an excellent level of mechanical properties , especially a significantly improved breaking strength and elongation tension as well as an outstanding E-traction module.

EP-A-0 363 608 discloses mixtures of aromatic polycarbonate polymers, copolymer containing styrene or graft copolymer as well as oligomeric phosphates as flame retardant additives. For certain purposes of use, the level of properties of these mixtures is often not sufficient.

EP-A-0 704 488 describes aromatic polycarbonate molding compositions, copolymerized compositions containing styrene and graft polymers with a special grafting base in certain quantities. These molding compositions show a very good impact resistance in a notched specimen and can be provided, if necessary, with phosphorus compounds to make them resistant to flame. To obtain REF .: 32762 molding parts with a high elasticity load is not always sufficient level of mechanical properties.

Therefore, the problem that the present invention must solve is to provide polycarbonate-ABS molding compositions that exhibit excellent breaking strength and an excellent tensile modulus E.

It has now been found that flame-resistant PC / ABS molding compositions containing phosphorus compounds of component D (see below) and graft polymerization from a graft base of a given particle size can be process to form molding parts with a very good level of mechanical properties especially also under a high elasticity load.

The subject of the present invention are therefore thermoplastic flame-resistant molding compositions containing: A. from 40 to 99, preferably from 60 to 98.5 parts by weight of aromatic polycarbonate or polyester carbonate B. of 0.5 to 60, preferably from 1 to 40, especially from 2 to 25 parts by weight of B-graft polymer from 5 to 95%, preferably from 30 to 80% by weight of one or more vinyl monomers on B.2 from 95 to 5%, with preference of 20 to 70% in weight of one or more grafting bases with a vitreous transition temperature < 0 ° C, preferably < -20 ° C and a medium particle size (d5o value) of 0.20 to 0.35 μm, preferably 0.25 to 0.30 μm. C. from 0 to 45, preferably from 0 to 30, particularly preferably from 2 to 25 parts by weight of thermoplastic vinyl (co) polymerized D. from 0.5 to 20 parts by weight, preferably from 1 to 18 parts by weight, particularly preferably from 2 to 15 parts by weight of at least one monomeric phosphorus compound and at least one oligomeric phosphorus compound of general formula (I) (OR in which: R1, R2, R3 and R4 each independently represent C1 to C8 alkyl, optionally halogenated, C5 to C6 cycloalkyl, C to C20 aryl or C to C12 aralkyl, each optionally substituted with alkyl, preferably alkyl Ci to C, and / or halogen, preferably chlorine, bromine, n represents, independently of each other, 0 or 1 N represents, from 0 to 30 and X represents an aromatic residue of one or several nuclei with 6 to 30 carbon atoms, E from 0.05 to 5 parts by weight, preferably from 0.1 to 1 parts by weight, particularly preferably from 0.1 to 0.5 parts by weight of fluorinated polyolefin, giving 100 the sum of all parts by weight A + B + C + D + E Especially preferred are molding compositions in which the weight ratio of components B: C is between 2: 1 and 1: 4, preferably between 1: 1 and 1: 3.

In the molding compositions according to the invention, the component D preferably appears as a mixture of 10 to 90% by weight, preferably 12 to 40% by weight, of at least one monophosphorus compound of formula (I) and from 10 to 90% by weight, preferably from 60 to 88% by weight, based in each case on the total amount of the phosphorus compounds, of at least one oligomeric phosphorus compound of formula (I), the mixture showing an average N of from 0.3 to 20, preferably from 0.5 to 10, particularly preferably from 0.5 to 6.

Component A Aromatic polycarbonates and / or aromatic polyester carbonates of Component A suitable according to the invention are known from the literature or can be obtained according to processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates" "(Chemistry and Physics of Polycarbonates), Interscience Publishers, 1964 as well as DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 10396; for obtaining polyester carbonates, p. and. DE-OS 3 077 934). The preparation of aromatic polycarbonates is carried out, for example, by the reaction of diphenols with carbonic acid halides, preferably phosgene and / or dihalogenides of aromatic dicarboxylic acids, preferably dihalides of benzenedicarboxylic acids according to the process of the interface, optionally using, for example, chain terminators, such as for example monophenols, and optionally using branching agents trifunctional or more than trifunctional, for example triphenols or tetraphenols.

The diphenols for the preparation of aromatic polycarbonates and / or polyester carbonates are preferably those of formula (II) wherein A represents a single bond, C1-C5 alkylene, C2-Cs alkylidene, C5-C? cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, arylene C6-C? 2, which may be condensed with other aromatic rings containing, if appropriate, heteroatoms, or a radical of formula (III) or (IV) B represents in each case hydrogen, C1-C12 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine x represents in each case and independently of each other 0, 1 or 2, p represents 1 or 0, and R5 and R6 are individually selectable for each X1, independently of one another hydrogen or C? -C6 alkyl, preferably hydrogen, methyl or ethyl, X1 represents carbon and m represents an integer from 4 to 7, preferably 4 or 5, with the reservation that in at least one atom X1, R5 and R6 are at the same time alkyl.

Preferred diphenols are hydroquinone, resorcin, dihydroxydiphenols, bis (hydroxyphenyl) alkane- (C? -C5), bis- (hydroxyphenyl) cycloalkane- (C5-C6), bis- (hydroxyphenyl) -ethers, bis- (hydroxyphenyl) - sulfoxides, bis- (hydroxyphenyl) -ketones, bis- (hydroxyphenyl) -sulphones and a, bis (hydroxyphenyl) -di- 'isopropyl-benzenes as well as their brominated derivatives in the nucleus and / or chlorinated in the nucleus.

Particularly preferred diphenols are 4,4 '-dihydroxy-diphenyl, bisphenol-A, 2,4-bis- (4-hydroxyphenyl) -2-methyl-butane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, , l-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 4,4'-dihydroxy-diphenyl-sulfide, 4, '-dihydroxy-diphenyl-sulfone as well as their di- and tetra- derivatives brominated or chlorinated, as for example 2, 2'-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane or 2, 2-bis- (3, 5) dibromo-4-hydroxyphenyl) -propane.

Particular preference is given to 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A).

The diphenols can be used individually or as mixtures at will.

Diphenols are known from the literature or can be obtained according to methods known from the literature.

For the preparation of the thermoplastic aromatic polycarbonates, suitable chain terminators are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but so are long-chain alkylphenols, such as 4- ( 1,3-tetramethylbutyl) -phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3, 5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol. The amount to use of chain breaker is generally between 0.5% in moles and 10% in moles with respect to the sum of moles of the diphenols used in each case.

Thermoplastic aromatic polycarbonates have weight average molecular weights (Mw, measured by means of an ultracentrifuge or light scattering measurement, for example) of 10,000 to 200,000, preferably 20,000 to 80. 000 The thermoplastic aromatic polycarbonates can be branched in a known manner, and preferably with the incorporation of 0.05 to 2.0 mole% based on the sum of the diphenols used, in trifunctional or more than trifunctional compounds, for example those having three or more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. For the preparation of copolycarbonates according to the invention and according to component A), it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight (based on the total amount of diphenols) to be used) of polydiorganosiloxanes with hydroxyaryloxy end groups. These are known (see, for example, US Pat. No. 3 419 634) or can be obtained according to methods known from the literature. The preparation of copolycarbonates containing polydiorganosiloxanes is described, for example, in DE-OS 3 334 782.

Preferred polycarbonates are, in addition to the bisphenol-A homopolycarbonates, the bisphenol-A copolycarbonates with up to 15 mol%, based on the sum of the moles of diphenols, of other diphenols other than those mentioned as preferred or especially preferred diphenols, in particular , 2-bis- (3, 5-dibromo-4-hydroxyphenyl) -propane.

Dihalogenides of aromatic dicarboxylic acids for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

Mixtures of the diacid dichloride of isophthalic acid and terephthalic acid in a ratio of 1:20 to 20: 1 are especially preferred.

In the case of the preparation of polyester carbonates, a haiogenide of carbonic acid, preferably phosgene, as a bifunctional acid derivative will also be used together with them.

For the production of aromatic polyester carbonates chain interrupters in addition to the aforementioned monophenols, their chlorocarboxylic acid esters as well as the acid chlorides of aromatic monocarboxylic acids, which, if appropriate, can be substituted with C?-C22 alkyl groups or with halogen atoms, are contemplated , as well as chlorides of C2-C22 aliphatic monocarboxylic acids.

The amount of chain switches is in each case from 0.1 to 10% by mole, referred in the case of phenolic chain terminators to the moles of diphenols, and in the case of the chain-link chain onocarboxylic acid to the moles of dicarboxylic acid dichloride. The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates can be both linear and branched in a known manner (see also DE-OS 2 940 024 and DE-OS 3 007 934).

As the branching agent, for example, 3- or polyfunctional carboxylic acid chlorides, such as trimesinic trichloride, cyanuric acid trichloride, 3, 3'-4,4'-benzophenone-3-tetrachloride, can be used. tetracarboxylic acid, 1, 4, 5, 8-naphthalene-tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.1 to 10% by moles (based on the amount of dicarboxylic acid dichloride used) or phenols 3- or polyfunctional such as phloroglucin, 4,6-dimethyl-2,4,6- tri- (4-hydroxyphenyl) -heptene-2,4,4-dimethyl-2,4,6- tri- (4-hydroxyphenyl) -heptane, 1, 3, 5-tri- (4-hydroxyphenyl) -benzene, 1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenyl-methane, 2, 2-bis [ 4,4'-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2, -bis (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) -methane, 2,6-bis- (2-hydroxy-5-methyl-benzyl) -4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2, 4- dihydroxyphenyl) -propane, tetra- (4- [-hydroxyphenyl-isopropyl] -phenoxy) -methane, 1, -bis- [4,4'-dihydroxy-tri-phenyl) -methyl] -benzene, in amounts of 0, 01 to 1.0 mol% based on the diphenols used. The phenolic branching agents are. they can be applied with the diphenols and the acid chloride branching agents together with the acid dichlorides.

In the thermoplastic aromatic polyester carbonates a proportion of units of the carbonate structure can be varied at will. Preferably, the proportion of carbonate groups is up to 100% by mol, in particular up to 80% by mol, with particular preference up to 50% by mol, based on the sum of the ester groups and groups carbonate. Both the ester and carbonate moieties of the aromatic polyester carbonates can be present in block form or statistically distributed in the polycondensate.

The relative solution viscosity (? R _?) Of the polyester carbonates is in the range of 1.18 to 1.4, preferably from 1.22 to 1.3 (measured in solutions of 0.5 g of polyester carbonate in 100 ml of methylene chloride solution at 250 ° C) The thermoplastic aromatic polycarbonates and polyester carbonates can be used alone or mixed together at will.

Make-up B Component B comprises one or more graft copolymers of Bl from 5 to 95%, preferably from 30 to 80%, by weight of one or more vinyl monomers on B.2 from 5 to 95%, with preference of 20 to 70%, by weight of one or more grafting bases with glass transition temperatures < 0 ° C, preferably < -20 ° C, and with a mean particle size (dso value) of 0.20 to 0.35 μm. The monomers B.l are preferably mixtures of: Bl.l of 50 to 99 parts by weight of vinyl aromatic compounds and / or vinyl-substituted aromatic compounds in the core (such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or alkyl (C? -C4) esters of methacrylic acid (such as methyl methacrylate, ethyl methacrylate) and B1.2 of 1 to 50 parts by weight of vinylcyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or alkyl (C? ~ C8) esters of (meta) acrylic acid (such as, for example, methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (eg anhydride) of maleic acid and N-phenyl-maleimide).

The preferred Bl.l monomers are chosen from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, the preferred B1.2 monomers are chosen from at least one of the monomers acrylonitrile, maleic anhydride and methacrylate of methyl.

Especially preferred monomers are Bl.l styrene and B1.2 acrylonitrile.

The graft bases B.2 suitable for graft polymers B are, for example, diene rubbers, EP (D) M rubbers, therefore those based on ethylene / propylene and, where appropriate, rubbers of diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate.

Preferred grafting bases B.2 are diene rubbers (for example with the base of butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymerized diene rubbers or of their mixtures with other copolymerizable monomers (for example according to Bl.ly B1.2) with the proviso that the glass transition temperature of components B.2 is below 0 ° C.

Especially preferred is pure polybutadiene rubber.

Especially preferred polymers B are, for example, ABS polymers (ABS of emulsions, masses and suspensions) as described, for example, in DE-OS 2 035 390 (= US-PS 3 644 574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ullman, Enzyklopádie der Technischen Chemie, volume 19 (1980), page 280 et seq. The gel proportion of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene) and the average particle size dso of the graft base B .2 is from 0.20 to 0.35 μm, preferably 0.25 to 0.30 μm.

The graft copolymers B are obtained by means of radical polymerization, for example by means of emulsion, suspension, solution or bulk polymerization, preferably by means of emulsion polymerization.

Particularly suitable grafting rubbers are the ABS polymers obtained by means of a redox initiation with an initiation system consisting of an organic hydroperoxide and ascorbic acid according to the document.

US-P 4 937 285.

Suitable acrylate rubbers of B.2 of polymerized B are preferably polymerized from esters of acrylic acid, optionally with up to 40% by weight, based on B.2 of other polymerizable ethylenically unsaturated monomers. Preferred polymerizable acrylic acid esters include C?-C8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters, haloalkyl esters, preferably halogenalkyl esters Ci-Cs, as chloroethyl acrylate as well as mixtures of these monomers.

For the crosslinking, monomers with more than one polymerizable double bond can be copolymerized. Examples Preferred crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and monofunctional unsaturated alcohols with 3 to 12 carbon atoms or polyols saturated with 2 to 4 OH groups and 2 to 20 carbon atoms, for example ethylene glycol dimethacrylate, allyl methacrylate, polyunsaturated heterocyclic compounds, such as trivinyl- and triallylcyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes, but also triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds showing at least 3 unsaturated ethylenic groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallylisocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The amount of the crosslinking monomers is preferably from 0.02 to 5, in particular from 0.05 to 2% by weight, based on the graft base B.2.

In the case of cyclic crosslinking monomers with at least 3 unsaturated ethylenic groups it is advantageous to limit the amount below 1% by weight of base graft B.2.

"Other preferred polymerizable ethylenically unsaturated monomers which, together with the esters of acrylic acid, can be used, if appropriate, for the preparation of graft bases B.2 are acrylonitrile, styrene, α-methylstyrene, acrylamide, alkyl ether (Ci) -C6) vinyl, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft bases B.2 are emulsion polymers which have a gel content of at least 60% by weight.

Other suitable B.2 grafting bases are silicone rubbers with active sites for grafting, such as those described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE -OS 3 631 539.

The gel content of the graft base B.2 is determined at 25 ° C in a suitable solvent (M. Hoffmann, H. Krómer, R. Kuhn, Polimeranalyti I und II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size dso is the diameter above and below which 50% of the particles are respectively found. It can be determined by means of ultracentrifugation measurements (Scholtan, H. Lange, Kolloid, Z. ünd Z. Polymere 250 (1972), 782-1796).

As in the grafting reaction, the graft monomers, in a known manner, do not necessarily graft completely onto the graft base, it is understood according to the invention that the term graft polymers B also includes the products obtained by means of (co) polymerization of the graft monomers in the presence of the graft bases and appearing during processing. Component C Component C comprises one or more (co) thermoplastic vinyl polymer.

Suitable as (C) -C polymerized are those polymerized with at least one monomer from the group of vinylaromatics, vinylcyanides (unsaturated nitriles), (C 1 -C 8) ester of (meth) acrylic acid, unsaturated carboxylic acids as well as derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co) polymerizations of: Cl from 50 to 99, preferably from 60 to 80 parts by weight, of vinylaromatics and / or vinylaromatics substituted in the core, such as, for example, styrene, α-methylstyrene, methylstyrene, p-chlorostyrene and / or alkyl (C 4 -C 4) ester of methacrylic acid such as, for example, methacrylate methyl, ethyl methacrylate, and C.2 from 1 to 50, preferably from 20 to 40 parts by weight of vinylcyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or (C? -C8) ester of (meta) acrylic acid (as for example methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic acid and N-phenyl-maleimide).

The (co) polymerized C are resinous, thermoplastic and do not contain rubber.

Especially preferred is the copolymer of C.l. styrene and C.2 acrylonitrile. The (co) polymerizations corresponding to component C are known and can be obtained by means of radical polymerization, in particular by means of emulsion, suspension, solution or bulk polymerization. The (C) polymerized corresponding to component C preferably have molecular weights M w (weight average calculated by means of light scattering or sedimentation) of between 15,000 and 200,000.

The (co) polymerizations corresponding to component C they frequently appear in the graft polymerization of component B as byproducts, especially when large amounts of B.l monomers are grafted onto small amounts of B.2 rubber. The amounts to be used also in the case of C according to the invention do not include these by-products of the B-graft polymerization.

However, for certain application purposes, component C must be present in the molding compositions according to the invention.

If component C is present in the molding compositions, the weight ratio of components B: C should be between 2: 1 and 1: 4, preferably between 1: 1 and 1: 2, in order to reach the level of mechanical values desired for certain application purposes. Component D Component D is a mixture of at least one monomeric phosphorus compound and at least one oligomeric compound of formula (I) (OR In the formula R1, R2, R3 and R4 have the meanings indicated above. Preferably R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are, independently of each other, C.sub.1 -C.sub.4 alkyl, phenyl, naphthyl or phenylalkyl C.sub.x -C.sub.4. The aromatic groups R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may in turn be substituted by halogen and / or alkyl groups, preferably chlorine, bromine and / or C? -C alkyl. Especially preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl as well as the corresponding brominated and chlorinated derivatives thereof. X in the formula (I) means an aromatic residue of one or several nuclei with 6 to 30 carbon atoms. This is derived from the diphenols of formula (II). Preferred diphenols are diphenylphenol, bisphenol A, resorcin or hydroquinone or their chlorinated or brominated derivatives. n in formula (I) can be, independently of each other, 0 or 1, preferably n is equal to l.

N represents values from 0 to 30, preferably a mean value from 0.3 to 20, particularly preferably from 0.5 to 10, especially from 0.5 to 6.

As component D according to the invention, mixtures preferably of 10 to 90% by weight are preferably used from 12 to 40% by weight, of at least one monomeric phosphorus compound of formula (I) and at least one oligomeric phosphorus compound or a mixture of oligomeric phosphorus compounds in amounts of 10 to 90% by weight weight, preferably from 60 to 88% by weight, based on the total amount of phosphorus compounds.

Monomeric phosphorus compounds of formula (I) are in particular tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-cresyl phosphate. , diphenyloctyl phosphate, diphenyl-2-ethyl-cresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted arylphosphates, methylphosphonic acid dimethyl ester, diphenyl methylphosphonic acid ester, phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide.

The mixtures of monomeric and oligomeric phosphorus compounds of formula (I) have on average N values of from 0.3 to 20, preferably from 0.5 to 10, in particular from 0.5 to 6.

The phosphorus compounds of component D are known (cf. EP-A-363 608, EP-A 640 655) or can be obtained according to known methods in an analogous manner (for example üllmanns Enzyklopadie der tecnischen Chemie, volume 18, page 301 et seq 1979, Houben-Weyl, Methoden der organischen Chemie, volume 12/1, page 43, Beilstein volume 6, page 177). 5 Component E The fluorinated polyolefins E are of high molecular weight and have glass transition temperatures higher than -30 ° C, normally above 100 ° C, contained in fluorine, preferably from 65 to 76%, especially from 70 to 76% by weight, average particle diameter d50 from 0.05 to 1,000, preferably from 0.08 to 20 μm. In general, the fluorinated polyolefins E) have a density of 1.2 to 2.3 g / cm3. Preferred fluorinated polyolefins E) are polytetrafluoroethylene, polyvinylidene fluoride, copolymerized tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene. The fluorinated polyolefins are known (see "Vinyl and Related Polymers" by Schildknecht, John Wiley &Sons, Inc. New York, 1962, pp. 20484-494, "Fluoropolymers" by Wall, Wiley-Interscience, John Wiley and Sons, Inc. New York, Volume 13, 1970, pp. 623-654, "Modern Plastic Encyclopedia," 1970-1971, Volume 47, No. 10 A, Oct. 1970, Me Graw-Hill, Inc., New York, p. 134 and 774, "Modern Plastic Encyclopedia," 1975-1976, volume 52, No. 10 A, October 25, 1975 Me Graw-Hill, Inc., New York, pp. 27, 28 and 472 and the US- PS 3 671 487, 3 723 373 and 3 838 092) They can be obtained by known processes, for example, by polymerization of tetrafluoroethylene in aqueous medium with a catalyst that forms free radicals, for example sodium, potassium or ammonium peroxydisulfate at pressures of (7 to 71) * 9.81 Pa and at temperatures of 0 to 200 ° C, preferably at temperatures of 20 to 100 ° C (for more precise details see U.S. Patent 2 393 967). Depending on the form of use, the density of these materials can be between (1,2 and 2,3) * 103 Kg / m3, and the average particle size between 0.5 and 1,000 μm.

Preferred fluorinated polyolefins E) according to the invention are polymerized tetrafluoroethylene with an average particle diameter of 0.05 to 20 μm, preferably 0.08 to 10 μm, and a density of (1.2 to 1.9) * 103 Kg / m 3 and are preferably used in the form of a coagulated mixture of tetrafluoroethylene polymer emulsions E) with emulsions of graft polymers B).

Epoxy fluorinated polyolefins E) are suitable and can be used in the form of powder tetrafluoroethylene polymers with an average particle diameter of 100 to 1000 μm and densities of 2.0 * 103 Kg / m3 to 2.3 * 103 Kg / m3.

To obtain a coagulated mixture from B) and E) an aqueous emulsion (latex) of a graft polymer B) is first mixed with a fine particle emulsion of a tetraethylene polymerized E); The emulsions of suitable tetrafluoroethylene polymers usually have solids concentrations of 30 to 70% by weight, in particular 50 to 60% by weight, preferably 30 to 35% by weight.

The indication of amounts in the description of components B) may include the fraction of the graft polymer for the coagulated mixture from graft polymer and fluorinated polyolefins.

In the emulsion mixture the equilibrium ratio of graft polymer B to polymerized tetrafluoroethylene E is between 95: 5 and 60:40. The emulsion mixture is then coagulated in a known manner, for example by means of spray drying, lyophilization or coagulation by means of the addition of salts, acids, inorganic or organic bases, or organic solvents miscible with water, such as alcohols, ketones, preferably at temperatures of 20 to 150 ° C, in particular 50 to 100 ° C. If necessary, it can be dried at 50 to 200 ° C, preferably 70 to 100 ° C.

Suitable emulsions of polymers of tetrafluoroethylene are commercially available products and are offered, for example, by DuPont, such as Teflon1"" 30 N.

The molding compositions according to the invention can contain at least one of the usual additives, such as glidants and demolding agents, nucleating agents, anti-static agents, stabilizers as well as dyes and pigments.

Furthermore, the molding compositions according to the invention can contain, in addition, inorganic powder of very fine particles in an amount of up to 50 parts by weight, preferably up to 20, in particular from 0.5 to 10 parts by weight.

The inorganic compounds of very fine particles are composed of compounds of one or more metals of the main groups 1 to 5 or of the 1 to 8 secondary groups of the periodic system, preferably of the main groups 2 to 5 and from the 4th to the 8th secondary groups, with special preference preferably from the main groups 3 ° to 5 ° and from the 4 ° to 8 ° secondary groups with at least one element selected from the group of oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen, and silicon.

Preferred compounds are for example oxides, hydroxides, hydrated oxides, sulfates, sulphites, sulphides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.

Preferred inorganic compounds of very fine particles are, for example, TiN, Ti02, Sn02, WC, ZnO, Al203, Al (OH), Zr02, Sb203, SiO2, iron oxides, Na2SO4, BaSO4, vanadium oxides, zinc borate, silicates. such as Al silicate, Mg silicate, mono-, di-, three-dimensional silicates, mixtures and doped compounds are equally usable. Otherwise, these nanoscale particles can be modified on their surface with organic molecules to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be achieved.

The average particle diameters are less than or equal to 200 nm, preferably less than or equal to 150 nm, in particular from 1 to 100 nm. Particle size and particle diameter always mean the mean particle diameter d50 calculated by means of ultracentrifuge measurements according to W. Scholtan et al. Kolloid-Z. Und Z .. Polymere 250 (1972), pages 782 to 796.

The inorganic compounds can be presented as powders, pastes, sols, dispersions or suspensions. By precipitation, powders can be obtained from dispersions, sols or suspensions.

The powders can be incorporated into thermoplastic plastics according to customary methods, for example by means of direct kneading or extrusion of the components of the molding compound and the inorganic powders of very fine particle. Preferred procedures are obtaining a master batch, e.g. and. in flame-retardant additives, other additives, monomers, solvents, in component A or coprecipitation of dispersions of graft rubbers with dispersions, suspensions, pastes or sols of inorganic materials of very fine particles.

The molding compositions according to the invention can contain up to 35% by weight, based on the total molding composition, of another fireproofing agent, which optionally acts synergistically. Mention may be made, by way of example, of other flame retardants, organic halogenated compounds such as decabromo-bis-phenyl ether, tetrabromo-bis-phenol, inorganic halogenated compounds such as ammonium bromide, nitrogen-containing compounds such as melamine, melamine-formaldehyde resins, inorganic hydroxide compounds such as hydroxides of Mg, Al, inorganic compounds such as antimony oxide, metaborate of barium, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate and tin oxide, as well as siloxane compounds. The molding compositions according to the invention containing components A) to E) and optionally other additives known as stabilizers, dyes, pigments, slip and release agents, nucleating agents as well as antistatics, are obtained by mixing the corresponding components and integrating them in the molten state and extruding them in the molten state in a known manner at temperatures of 200 ° C to 300 ° C in the groups of usual equipment such as internal mixers, extruders and double shaft spindle machines, the components E) being used, preferably in the form of the aforementioned coagulated mixture.

The mixing of the individual components can be carried out in a known manner both successively and simultaneously, and in particular both at about 20 ° C (room temperature) and also at a higher temperature.

The thermoplastic molding compositions according to the invention are suitable due to their excellent resistance to flame, their very good processing property and their very good mechanical properties, especially their outstanding. rigidity, for the manufacture of molding parts of any type, especially those with high requirements of resistance to breakage.

The molding compositions of the present invention can be used for the production of molding parts of any type. In particular, molding parts can be produced by means of injection molding. Examples of fabricable molding parts are: housing parts of any kind, e.g. and. for household appliances such as juice squeezers, coffee machines, mixers, for office equipment, or cover plates for the construction sector, and parts for the automotive vehicle sector. They are also applicable in the field of electrical engineering because they have very good electrical properties.

Another way of processing is the manufacture of molding parts by means of deep drawing from plates or sheets manufactured in advance. Another object of the present invention is therefore also the use of the molding compositions according to the invention for the production of molding parts of any type, preferably those mentioned above, as well as the molding parts from the masses of molding according to the invention.

Examples Component A Linear polycarbonate based on Bisphenol A with a relative solution viscosity of 1.252, measured in CH2Cl2 as a solvent at 25 ° C and a concentration of 0.5 g / 100 ml Component B Graft polymerized 45 parts by weight of a copolymerized from styrene and acrylonitrile in the ratio of 72:28 to 55 parts by weight crosslinked polybutadiene rubber in particulate form (average particle diameter d50 = 0.28 μm ), obtained by means of emulsion polymerization.

Component C Copolymerized styrene / acrylonitrile with a weight ratio of styrene / acrylonitrile of 78:28 and a limit viscosity of 0.55 dl / g (measured in dimethyl formamide at 20 ° C) Component D .1 Mixture of m-phenylene-bis- (di-phenyl-phosphate) (Fyrolflex RDP of the Akzo signature) and triphenyl phosphate (TPP) in the weight ratio 3: 1.

Component D .2 Triphenyl phosphate (TPP) as a comparison Component E Polymerization of tetrafluoroethylene as a coagulated mixture from a SAN graft polymerization emulsion of component B mentioned above, in water and a water emulsion of tetrafluoroethylene polymer. The weight ratio of graft polymer B to the tetrafluoroethylene polymerized E in the mixture is 90% by weight to 10% by weight. The tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the average particle diameter is between 0.05 and 0.5 μm. The graft polymer emulsion of SAN has a solids content of 34% by weight and a mean latex particle diameter of d50 = 0.28 μm.

E Manufacturing The emulsion of the tetrafluoroethylene polymer (Teflon 30 N from DuPont) is mixed with the emulsion of graft polymer B of SAN and stabilized with 1.8% by weight based on the polymer solid fraction of phenolic antioxidants. Between 85 and 95 ° C the mixture is coagulated with an aqueous solution of MgS04 (Epsom salt) and acetic acid at a pH of 4 to 5, filtered and washed until a practical disappearance of the electrolyte, then the greater is eliminated part of the water by means of centrifugation and thereafter dried at 100 ° C to form a powder. This powder can then be formulated with the rest of the components in the described equipment groups.

Production and analysis of the molding compositions according to the invention The mixing of the components is done in an internal mixer of 3-1. The molding parts are manufactured in an injection molding machine of the Arburg 270 E type at 260 ° C.

The determination of the resistance to heat deformation according to Vicat B is carried out according to DIN 53 460 (ISO 306) in bars measuring 80 x 10 x 4 mm3. The determination of the traction module E is carried out according to DIN 53 457 / ISO 527. _3 The determination of the elongation tension according to ISO 527 The determination of the breaking strength (tensile test) is carried out according to ISO 527 / DIN 53455 Table 1 Composition and properties of polycarbonate-ABS molding materials It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (1)

CLAIMS Having described the invention as above, property is claimed as < _onter_ido in the following claims:

1. Flame resistant thermoplastic molding masses, characterized by contain; A. from 40 to 99 parts by weight of thermoplastic polycarbonate or polyester carbonate B. from 0.5 to 60 parts by weight of B-graft polymer from 5 to 95% by weight of one or more vinyl monomers on B. 2 from 95 to 5% by weight of one or more graft bases with a vitreous transition temperature < 0 ° C and a medium particle size (d50 value) of 0.20 to 0.35 μm, C. of 0 to 45 parts by weight of thermoplastic vinyl copolymer, D. of 0.5 to 20 parts by weight of at least one monomeric phosphorus compound and at least one oligomeric phosphorus compound of formula (I) (I) wherein: R1, R2, R3 and R4 each independently represent Ci to C8 alkyl, optionally halogenated, C5 to C6 cycloalkyl, aryl C? to C2o or C7 to C12 aralkyl, each optionally substituted with halogen and / or alkyl, n represents, independently of each other, 0 or 1 N represents 0 to 30 and X represents an aromatic residue of one or more nuclei with 6 to 30 carbon atoms, and E from 0.05 to 5 parts by weight of fluorinated polyolefin, . Molding masses according to claim 1, characterized in that they contain from 1 to 40 parts by weight of component B and of 0 to 30, parts by weight of component C Molding masses according to one of claims 1 and 2, characterized in that the average particle size d50 of component B is from 0.25 to 0.30 μm . Molding compositions according to one of the preceding claims, characterized in that the weight ratio of the components B: C is between 2: 1 to 1: 4. Molding masses according to one of the claims p_B_a_er? _es, _a ___ ± __ ± za_as perqué cptptén? N 10 to vxi 90? - in weight ce at least one monophosphate compound of the formula (I) and from 90 to 10% by weight (in each case based on the total amount of the phosphorus compounds) of at least one oligomeric phosphorus compound of the formula (I) . Molding masses according to one of the preceding claims, characterized in that in formula (I) N shows xin average value of 0.3 to 20. Molding compositions according to one of the preceding claims, characterized in that they contain, as a monomeric phosphorus compound of the formula (I) tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethyl-cresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted aryl phosphates, methylphosphonic acid dimethyl ester, diphenyl ester of the methylphosphonic acid, phenylphosphonic acid diethyl ester, triphenylphosphine oxide and / or tricresylphosphin oxide. Molding masses according to one of the preceding claims. c__3-? E_ ± __cl_e perqué run up to xxi 355- in weight ü? ferdcb to the total of the molding mass, of at least one fireproofing agent different from component D. Molding masses according to one of the preceding claims, characterized in that they contain from 1 to 18 parts by weight of component D. Molding masses according to one of the preceding claims, characterized in that the graft base B.2 is a diene rubber, acrylate rubber, silicone rubber or ethylene-propylene-diene rubber. Molding masses according to one of the claims p_x__e___tbes, rar. -.! »-! garfas p rqué cr_ntien_n an irxaigdtñco sarpuesto of very fine particles of the main groups 1 to 5 or of Io to 8 or secondary groups of the periodic system, with at least one element selected from the group of oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon. Molding masses according to one of the claims p_ea_ó__t_es, O-C-t; They are made from a group of stabilizers, pigments, release agents, flow aids and / or antistats. Use of the molding compositions according to one of the preceding claims for the production of molding parts. Molding pieces made from the molding compositions according to one of the preceding claims.