MXPA00012154A - Flame resistant polycarbonate/abs plastic molding materials - Google Patents

Abstract

The invention relates to polycarbonate/ABS plastic molding materials containing phosphazenes and inorganic nanoparticles which exhibit an excellent flame protection and very good mechanical properties.

Description

POLYCARBONATE / ABS GRINDING MOLDING MASSES.

FIELD OF THE INVENTION The present invention relates to polycarbonate / ABS molding compositions, which contain phosphazenes and inorganic nanoparticles, which have excellent flame protection and very good mechanical properties.

BACKGROUND OF THE INVENTION DE-A-196 16 968 discloses polymerizable derivatives of phosphazene, suitable for their preparation and their use as hardenable binders for varnishes, coatings, fillers, masses for plastering, glues, castings or sheets. WO 97/40092 describes flame-protected molding compositions consisting of thermoplastic polymers and unsubstituted phosphazenes of the PNn.xH? -y type. EP-A-728 811 describes a thermoplastic mixture consisting of aromatic polycarbonate, graft copolymer, copolymer and phosphazenes, "which has good properties REF .: 125351 protective against flame, resistance to shock and dimensional stability to heat. There is disclosed neither in WO 97/400 92 nor in EP-A-728 811 a combination consisting of phosphazenes and special graft polymers.

DETAILED DESCRIPTION OF THE INVENTION The task of the present invention consists of the provision of polycarbonate / ABS molding compounds with excellent flame resistance, high dimensional stability to heat and excellent mechanical properties, such as impact resistance with notch. , bond strength by welding and resistance to break under tension. This combination of properties is especially required in the case of applications in the field of data system technology, such as, for example, for monitor housings, printers or copiers, etc. It has now been found that PC / ABS molding compositions containing phosphazenes in combination with inorganic nanoparticles have the desired properties.

The subject of the invention are, therefore, thermoplastic molding compositions containing polycarbonate and / or polyester carbonate, graft polymer, phosphazenes and inorganic powder with a mean particle diameter of less than or equal to 200 nm, which may contain other polymers , for example (co) thermoplastic vinyl polymers and / or polyalkylene terephthalates and, if appropriate, other additives. The subject of the invention are preferably thermoplastic molding compositions containing A) from 40 to 99, preferably from 60 to 98.5 parts by weight of aromatic polycarbonate and / or of polyester tercarbonate, B of 0.5 to 60, preferably 1 up to 40, especially from 2 to 25 parts by weight of graft polymer, B.1 from 5 to 95, preferably from 30 to 80% by weight of one or more vinyl monomers and B.2) of 95 is enough 5, preferably 20 to 70% by weight of one or more grafting bases with a vitreous transition temperature < 10 ° C, preferably < 0 ° C, so especially preferred < -20 ° C, C) from 0 to 45, preferably from 0 to 30, particularly preferably from 2 to 25 parts by weight of at least one thermoplastic polymer, selected from the group of the vinyl (co) polymers and polyalkylene terephthalates , D) from 0.1 to 50, preferably from 2 to 35, particularly preferably from 5 to 25 parts by weight of at least one component, chosen from the group of phosphazenes of the formulas where R are respectively the same or different and mean alkyl amino with 1 to 8 carbon atoms respectively halogenated, preferably halogenated with fluorine, or means alkoxy with 1 to 8 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, respectively substituted optionally by alkyl, preferably by alkyl having 1 to 4 carbon atoms, and / or by halogen, preferably chlorine and / or bromine, aryl with 6 to 20 carbon atoms, preferably phenoxy or naphthyloxy, or aralkyl with 7 to 12 carbon atoms, preferably phenylalkyl with 1 to 4 carbon atoms, k means 0 or a number from 1 to 15, preferably means a number from 1 to 10, E) from 0.5 to 40, preferably from 1 to 25, in particular preferably from 2 to 15 parts by weight finely divided inorganic powder with a mean particle diameter less than or equal to 200 nm, and F) from 0 to 5 parts by weight, preferably from 0. 15 to 1 part by weight, in a way especially preferred from 0.1 to 0.5 parts by weight of a fluorinated polyolefin.

Component A. The aromatic polycarbonates and / or the aromatic polyester carbonates, suitable according to the invention, according to component A, are known from the literature or can be prepared according to processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell , "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 3 832 396, for the preparation of aromatic polyester carbonates, for example DE-OS 3 077 934). The preparation of the aromatic polycarbonates is carried out, for example, by reaction of diphenols with carbonyl halides, preferably phosgene and / or aromatic dicarbonyl dihalides, preferably benzodicarbonyl dihalides, according to the surface-to-phase interface, optionally with use of switches chains, for example monophenols and, if appropriate, using trifunctional branching agents or having a functionality greater than 3, for example triphenols or tetraphenols. The diphenols for the preparation of the aromatic polycarbonates and / or the aromatic polyester carbonates are preferably those of the formula (I) wherein A means a single bond, alkylene with 1 to 5 carbon atoms, alkylidene with 2 to 5 carbon atoms, cycloalkylidene with 5 to 6 carbon atoms, -0-, -SO-, -CO-, -S -, -S02-, arylene with 6 to 12 carbon atoms, on which other aromatic rings containing, if appropriate, heteroatoms, or a radical may be condensed of the formula (II) or (III) B respectively represent alkyl having 1 to 12 carbon atoms, preferably methyl, halogen, preferably chlorine and / or bromine. X mean respectively, independently of each other, 0, 1 or 2, p mean 1 or 0, and R5 and R6 for each X1 can be chosen individually, independently of one another, hydrogen or alkyl having 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, X 1 means carbon and m means an integer from 4 to 7, preferably 4 or 5, with the proviso that at least an atom X1, R5 and R6 simultaneously represent alkyl. Preferred diphenols are hydroquinone, resorcin, dihydroxydi phenols, bis- (hydroxyphenyl) -alkanes with 1 to 5 carbon atoms, bis (hydroxy-phenyl-1) -cycloalkanes with 5 to 6 carbon atoms, bis- (hydroxy-phenyl) -ethers , bis- (hydroxyphenyl) -sulphoxides, bis- (hydroxy phenyl) -ketones, bis- (hydroxy phenyl) -sulfones and a, -bis- (hydroxy phenyl) -di-isopropyl-benzenes as well as their brominated derivatives in the core and / or gold in the core. Especially preferred diphenols are 4, '-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxy phenyl) -2-methylbutane, 1,1-bis- (4-hydroxy phenyl) -cciohexane, 1,1-bis- (4- hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'- dihydroxydi phenylsul furo, 4,4'-dihydroxydiphenyl-sulfone, and also di- and tetrabrominated or chlorinated derivatives thereof, such as, for example, 2,2-bis (3-chloro-4-hydroxy phenyl) -propane, 2,2-bis- ( 3, 5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-di-romo-4-hydroxy-phenyl) -propane. 2, 2-bis- (4-hydroxyphenyl) -propane (bisphenol-A) is particularly preferred. The diphenols can be used individually or as arbitrary mixtures. Diphenols are known from the literature or can be obtained according to methods known from the literature. Chain switches suitable for the preparation of the aromatic, thermoplastic polycarbonates are, for example, phenol, p-chlorophenol, p-tert. butyl phenol or 2, 4,6-tribromophenol, as well as long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) -phenol, according to DE-OS 2 842 005 or monoalkylphenol or dialkyl phenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3-, 5-di-tert. -butylphenol, p-iso-octyl phenol, p-tert. -octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3,5- dimethylheptyl) -phenol. The amount of chain switches to be used is generally between 0.5% by mole and 10% by mole based on the sum in moles of the diphenols used in each case. The aromatic polycarbonates, thermoplastics, have weight-average molecular weights (Mw, measured for example by ultracentrifugation or by measurement of light scattering) of from 10,000 to 200,000, preferably from 20,000 to 800,000. The aromatic, thermoplastic polycarbonates can be branched from known manner and specifically in a preferred manner by incorporating 0.05 to 2.0% in moles, 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 phenolic groups. Both homopolycarbonates and copolycarbonates are suitable. For the preparation of the copolycarbonates according to the invention 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 employees) of polydiorganosiloxanes with terminal hydroxy-aryloxy groups. These are known (see for example US Pat. No. 3 419 634) or can be prepared according to methods known from the literature. The preparation of the copolycarbonates containing polydiorganosiloxane is described, for example, in DE-OS 3 334 782. Preferred polycarbonates are, in addition to the homopolycarbonates of bisphenol-A, the copolycarbonates of bisphenol-A with up to 15 mol%, referred to to. the sum in moles of diphenols, of other diphenols mentioned as preferred or cited, especially preferred, especially 2-2-bis (3, 5-dibromo-4-hydroxy phenyl) -propane. The aromatic dicarbonyl dihalogenides for the preparation of the aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenylether-, 4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1:20 and 20: 1 are particularly preferred.

In addition, a halogenide of carbonic acid, preferably phosgene, is used concomitantly as a bifunctional acid derivative in the preparation of polyester carbonates. As chain breakers for the preparation of the aromatic polyester carbonates, in addition to the aforementioned monophenols, also their chlorocarbonic acid esters as well as the acyl chlorides of aromatic monocarboxylic acids, which may be substituted by alkyl groups, may be used. with 1 to 22 carbon atoms or halogen atoms, as well as chlorides of aliphatic monocarboxylic acids with 2 to 22 carbon atoms. The amount in chain switches amounts, respectively, from 0.1 to 10% in moles, referred in the case of the phenolic chain switches to the moles of diphenols and in the case of the chain blockers of monocarboxylic acid chlorides to the moles of the dicarboxylic acid dichlorides. The aromatic polyester carbonates can also contain 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 branching agents, for example, trifunctional carboxylic acid chlorides or with a functionality greater than 3, such as trimesinic trichloride, cyanuric acid trichloride, 3-, 3-4,4'-benzophenone tetracarboxylic acid tetrachloride, can be used. 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0% in moles, (based on the chlorides of the dicarboxylic acids used) or trifunctional phenols or with a functionality greater than 3, such as fluoroglucin, 4,6 (dimet i 1-2, 4,6-tri (4-hydroxyphenyl) -hepten-2,4,4,4-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane , 1, 3, 5-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1, 1, 1-1 ri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phene-n-methane, 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra - (4-hydroxy phenyl) -methane, 2,6- bis- (2-hydroxy-5-methyl-benzyl.) 4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2, -dihydroxyphenyl) -propane, tetra- (4- [4-hydroxyphenyl- isopropyl] phenoxy) -methane, 1,4-bis [4,4'-dihydroxytriphenyl) -methyl] -benzene, in amounts of 0.01 to 1.0 mol% based on the diphenols used. The phenolic branched agents can be arranged with the diphenols, the branched chain-bonding agents can be incorporated together with the acyl dichlorides. In aromatic polyester carbonates, thermoplastics, the proportion in carbonate structural units can vary arbitrarily. Preferably, the proportion of carbonate groups is up to 100 mol%, especially up to 80 mol%, more preferably up to 50 mol%, based on the sum of the ester groups and the carbonate groups. Both the ester ratio and the carbonate content of the aromatic polyester carbonates can be present in the polycondensate either in block form or statistically distributed. The relative solution viscosity (? Rel) of the aromatic polycarbonates and of the polyestercarbonate 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 polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C). Aromatic polycarbonates, thermoplastics and polyester carbonates can be used alone or in arbitrary mixtures with one another.

Component B. Component B comprises one or more graft polymers Bl from 5 to 95, preferably from 30 to 80% by weight, at least one vinyl monomer on B.2 from 95 to 5, preferably from 70 to 20% by weight. weight of one or several grafting bases, with vitrea transition temperatures < 10 ° C, preferably < 0 ° C, particularly preferably < -20 ° C. The graft base B.2 has, in general, an average particle size (d50 value) of 0.05 to 5 μm, preferably 0.10 to 0.50 μm, particularly preferably 0.20 to 0.40 μm.

The monomers Bl are preferably mixtures consisting of Bll of 50 to 99 parts by weight of vinyllacoates and / or vinylaro ro-substituted substitutes (such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or alkyl esters (with 1 to 8 carbon atoms) of methacrylic acid (such as for example methyl methacrylate, ethyl methacrylate), and Bl2 of 1 to 50 parts by weight of vinyl anurans (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or alkyl (1 to 8 carbon atoms) esters of (meth) 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 for example maleic acid anhydride and N-phenyl-maleimide). Preferred monomers B.l.l are selected from at least one of the monomers consisting of styrene, α-methylstyrene and methyl methacrylate, the preferred monomers B.l.2 are chosen from at least one of the monomers consisting of acrylonitrile, maleic acid anhydride and methyl methacrylate. Particularly preferred monomers are B.l.l. styrene and B.l.2 acrylonitrile. The preferred grafting bases B.2, suitable for the graft polymers B, are for example diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, diene, rubbers. acrylate, silicone, chloroprene and ethylene / vinyl acetate. Preferred B.2 grafting bases are diene rubbers (for example based on butadiene, isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to Bll and Bl 2) with the proviso that the vitreous transition temperature of component B.2 is below < 10 ° C preferably < 0 ° C, particularly preferably < -10 ° C. Especially preferred is pure polybutadiene rubber. Particularly preferred polymers B are, for example, ABS polymers (ABS in emulsion, in bulk and in suspension), such as those 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 Ullmann, Enzykiopádie der Technischen Chemie, volume 19 (1980) pages 280 et seq. The gel content of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene). The graft polymers B are prepared by radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization. Particularly suitable graft rubbers are also ABS polymers, which are prepared by initiation by Redox with an initiator system constituted by organic hydroperoxide - and by ascorbic acid according to US Pat. No. 4,937,285. Since in the grafting reaction the monomers of graft do not have to be grafted unconditionally, as is known, completely on the basis of grafting, graft polymers B according to the invention will also be understood as those products which are obtained by means of. { co) polymerization of the graft polymers in the presence of the graft base and 'which are formed concomitantly during the elaboration. Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers consisting of alkyl 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 alkyl esters with 1 to 8 carbon atoms, for example methyl, ethyl, butyl, n-octyl and 2-ethyl esters; halogenoalkyl esters, preferably halogenalkyl esters with 1 to 8 carbon atoms, such as chloroethyl acrylate, as well as 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 saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as example ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as for example trivinyl cyanurate and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; as well as triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers consisting of triallyl cyanurate, triallyl isocyanurate, triacrylohexahydro-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 ethylenically unsaturated groups, it is advantageous if the amount is limited to a value below 1% by weight of the graft base B.2. The "other" preferred polymerizable, ethylenically unsaturated monomers, which they can also serve, in addition to the esters of acrylic acid, for the preparation of the graft base B.2, they are, for example, alkyl nitrile, styrene, α-methylstyrene, acrylamide, vinylalkyl ethers with 1 to 6 carbon atoms, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base B.2 are emulsion polymers, which have a gel content of at least 60% by weight. Other suitable graft bases according to B.2 are silicone rubbers with spots with graft activity, 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. Khmer, R. Kuhn, Polymeranalytik I and II, Georg Thi eme-Verlag, Stuttgart 1977). The average particle size d50 is the diameter above and below which 50% by weight of the particles are present respectively. This can be determined with the aid of an ultracentrifuged measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1872), 782-1796).

Component C. Component C comprises one or more thermoplastic (co) vinyl polymers C.l and polyalkylene terephthalates C.2. Suitable (co) polymers Cl are polymers of at least one monomer from the group consisting of vinylaromatics, vinylcyanides (unsaturated nitriles), alkyl (1 to 8 carbon atoms) esters of (meth) acrylic acid, unsaturated carboxylic acids and derivatives , (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co) polymers consisting of Cll of from 50 to 99, preferably from 60 to 80, parts by weight of vinylaromatins and / or vinylaromatos substituted in the nucleus such as for example styrene, α-methylstyrene, p-methyl tyrosine, p-chloroestene and / or alkyl (1 to 4 carbon atoms) of methacrylic acid, such as, for example, methyl methacrylate, ethyl methacrylate) and C.1.2. from 1 to 50, preferably from 20 to 40, parts by weight of vinylcyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or alkyl (1 to 8 carbon) esters of (meth) acrylic acid (such as for example methyl methacrylate, butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (such such as maleic acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic acid anhydride and N-phenyl-maleimide). The (co) polymers C.l are resinous, thermoplastic and rubber-free. So . The copolymer is particularly preferably composed of C.1.1 styrene and C.1.2 acrylonitrile. The (co) polymers according to C.l are known and can be prepared by radical polymerization, especially by emulsion, suspension, solution or bulk polymerization. The (co) polymers according to component Cl preferably have molecular weights Mw (weight average, determined by light scattering or by sedimentation) between 15,000 and 200,000. The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or Their derivatives reagents, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols as well as mixtures of these reaction products. The preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid components of terephthalic acid moieties and at least 80% by weight, preferably at least 90% by mole , based on the diol components of ethylene glycol residues and / or butanediol-1, 4 residues. Preferred polyalkylene terephthalates can contain, in addition to residues of terephthalic acid, up to 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or of aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or of aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as, for example, phthalic acid, isophthalic acid, naphthalene-2, dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, acid Adipic acid, sebacic acid, azelaic acid, cyclohexane-diacetic acid. Preferred polyalkylene terephthalates can contain, in addition to ethylene glycol or butanediol-1,4 residues, up to 20% by mole, preferably up to 10% by mole, of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 12 carbon atoms. to 21 carbon atoms, for example residues of propanediol-1, 3, of 2-ethylpropanediol-1,3, of neopentyl glycol, of pentanediol-1,5, of hexanediol-1,6, of cyclohexanedimethanol-1,4, of 3-ethylpentanediol -2,4, of 2-methylpentanediol-2,4,4-2,2,4-trimethylpentanediol-1,3, of 2-ethyhexanediol-1,3, of 2,2-diethylpropanediol-1,3-hexanediol -2, 5, of 1,4-di- (ß-hydroxyethoxy) -benzene, of 2, 2-bis- (4-hydroxycyclohexyl) -propane, of 2,4-dihydroxy- 1, 1, 3, 3- tetramethyl-cyclobutane, of 2, 2-bis- (4-β-hydroxyethoxyphenyl) -propane and of 2, 2-bis- (4-hydroxy-propoxyphenyl) -propane (DE-OS 2 407 674, 2 407 776, 2 715 932). The polyalkylene terephthalates can be branched by incorporating relatively small amounts of tri or trihydric alcohols. tetravalent or tri or tetrabasic carboxylic acids, for example according to DE-OS 1 900 270 and US Pat. No. 3,692,744. Preferred examples of branching agents are trimesinic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol Especially preferred are polyalkylene terephtalates which have been prepared only from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or butanediol-1,4, and mixtures of these polyalkylene terephthalates. The mixtures of the polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutyl enterate phthalate.

The polyalkylene terephthalates which are preferably used have, in general, a limit viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in the viscometer of Ubbelohde The polyalkylene terephthalates can be prepared according to known methods (see for example Kunststoff-Handbuch, Volume VIII, page 695 et seq., Carl-Hanser-Verlag, München 1973). Component D. The phosphazenes according to component D, which are used according to the present invention, are linear phosphazenes according to formula (la) and cyclic phosphazenes according to formula (Ib) where R and k have the meaning indicated above. By way of example, they may be cited; propoxyphosphazene, phenoxy phosphazene, methylphenoxyphosphazene, aminophosphazene and fluorouralkyl phosphazene. Phenoxy phosphazene is preferred. The phosphazenes can be used alone or in the form of mixtures. The rest R can always be the same or 2 or several residues of the formulas (la) and (Ib) can be different. Phosphazenes and their preparation have been described, for example, in EP-A-728 811, DE-A-1 961 668 and WO 97/40092.

Component E Component E encompasses a finely divided inorganic powder. The finely divided inorganic powder E which is used according to the invention is preferably composed of at least one polar compound of one or more metals of the main groups 1 ° to 5 ° or of the secondary groups 1 ° to 8 ° of the periodic system of the elements, preferably of the main groups 2 ° to 5 ° or of the secondary groups 4 ° to 8 °, particularly preferably of the main groups 3 ° to 5 ° or of the secondary groups 4 ° to 8 ° with at least one element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or 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. Preferably the finely divided inorganic powder is constituted by oxide, phosphates, hydroxides, preferably by Ti02, Si02, Sn02, ZnO, ZnS, boehmite, Zr02, A1203, aluminum phosphates, iron oxide, in addition TiN, WC, AIO (OH) , Sb203, iron oxides, NaS04, vanadium oxides, zinc borate, silicates such as Al silicates, Mg silicates, mono, di, three-dimensional silicates. It is also possible to use mixtures and gifted compounds. In addition, these nanoparticles can be surface modified with molecules organic to achieve better compatibility with polymers. In this way, hydrophobic or hydrophilic surfaces can be obtained. Especially preferred are hydrated aluminum oxides, for example boehmite or TiO ?. The average diameter of the particles of the nanoparticles is less than or equal to 200 nm, preferably less than or equal to 150 nm, especially 1 to 100 nm. The size of the particles and the diameter of the particles always means the average diameter of the particles dso, determined with the help of measurements by ultracentri leakage according to W. Scholtan et al., Kolloid-Z. and Z. Polymere 250 (1972), pages 782-796. The inorganic powder is incorporated in the thermoplastic molding compositions in amounts of 0.5 to 40, preferably 1 to 25, particularly preferably 2 to 15% by weight, based on the thermoplastic material. The inorganic compounds can be in the form of powder, pastes, sols, dispersions or suspensions. Dusts can also be obtained from dispersions, sols or suspensions by precipitation. The powders can be incorporated into the thermoplastic molding compositions by customary methods, for example by direct kneading or extrusion of the molding compositions and finely divided inorganic powders. The preferred processes consist in the preparation of a masterbatch, for example in flame-retardant additives and at least one component of the molding compositions according to the invention in monomers or in solvents, or the coprecipitation of a thermoplastic component and the powders. finely divided inorganics, for example by co-precipitation of an aqueous emulsion and finely divided organic powders, if appropriate in the form of dispersions, suspensions, pastes or sols of finely divided organic materials.

Component F. The fluorinated polyolefins F are of high molecular weight and have glass transition temperatures above -30 ° C, generally above 100 ° C, contained in fluorine, preferably from 65 to 76, especially from '70 up to 76% in weight, mean diameter of the d5o particles from 0.05 to 1000, preferably from 0.08 to 20 μm. In general, fluorinated polyolefins F have a density of 1.2 to 2.3 g / cm3. Preferred fluorinated polyolefins F are polytetrafluoroethane, polyvinylidene fluoride, tetrafluoroethylenehexafluoropropylene- and ethylene / tetrafluoroethylene copolymers. The fluorinated polyolefins are known (see the publications "Vinyl and Related Polymers" by Schildknecht, John Wiley &Sons, Inc., New York, 1962, pages 484-494; "Fluorpolymers" by Wall, Wiley-Interscience, John Wiley & amp; Sons, Inc., New York, Volume 13, 1970, pages 623-654, "Modern Plastics Encyclopedia", 1970-1971, volume 47, No. 10 A, October 1970; Me Graw-Hill, Inc., New York , pages 134 and 774; "Modern Plastic Encyclopedia", 1975-1976, October 1975, volume 52, No. 10 A. Me 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 catalyst which forms free radicals, for example sodium, potassium or ammonium peroxydisulfate, pressures of 7 to 71 kg / cm2 and at temperatures of 100 to 200 ° C, preferably at temperatures of 20 to 100 ° C. (For more details, see US Pat. No. 2 393 967). Depending on the application form, the density of these materials can be between 1.2 and 2.3 g / cm3, the average particle size between 0.5 and 1000 μm. The preferred fluorinated polyolefins F according to the invention are tet rafluroethylene polymers 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 g / cm 3 and are preferably used in the form of of a coagulated mixture of emulsions of polymers of tetrafluoroethylene F with emulsions of graft polymers B. Suitable fluorinated polyolefins F, used in the form of powder, are polymers of tet rafluoroethylene with an average particle diameter of 100 to 1000 μm and densities of 2.0 g / cm3 up to 2.3 g / cm3. In order to obtain a coagulated mixture consisting of B and F, a aqueous emulsion (latex) of a graft polymer B with a finely divided emulsion of a tetrafluoroethylene polymer F; Suitable tetrafluoroethylene polymer emulsions usually have a solids content of 30 to 70% by weight, in particular 50 to 60% by weight, preferably 30 to 35% by weight. The quantitative indication of the description of component B may include the proportion of the graft polymer for the coagulated mixture constituted by graft polymer and fluorinated polyolefin. In the emulsion mixture the equilibrium ratio between the graft polymer B and the tetrafluoroethylene polymer F is from 95: 5 to 60:40. The emulsion mixture is then coagulated in a known manner, for example by 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, especially 50 to 100 ° C. If necessary, it can be dried at 50 to 200 ° C, preferably at 70 ° C. up to 100UC. Suitable emulsions of tetrafluoroethylene polymer are commercially available products and are offered, for example, by the DuPont Company as Teflon® 30N. The molding compositions according to the invention can contain at least one of the usual additives, such as lubricants, mold release agents, nucleating agents, antistatics, stabilizers as well as dyes and pigments. The molding compositions according to the invention can contain up to 35% by weight, based on the molding compound as a whole, of another flameproofing agent, which optionally acts synergistically. For example, other flame retardants, organic phosphorus compounds, such as those described, for example, in EP-A 363 608, EP-A 345 522 and EP-A 640 655, will be cited. halogenated organic compounds such as decabromobisphenyl ether, tet rabromobisphenol, halogenated inorganic compounds such as ammonium bromide, nitrogen compounds, such as melamine, melamine formaldehyde resins, inorganic hydroxy compounds such as Mg hydroxide, Al, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate talc, silicate, silicon dioxide and tin oxide as well as siloxane compounds. The molding compositions according to the invention containing the components A to F and, if appropriate, other known additives such as stabilizers, dyes, pigments, lubricants and release agents, nucleating agents as well as antistatics, are prepared by mixing, in a known manner, of the corresponding components. and formation of melt blends and melt extrusion at temperatures of 200 ° C to 300 ° C in conventional devices such as internal kneaders, extruders and double-shaft spindles, the component F being preferably used in the form of the aforementioned coagulated mixture . The mixing of the individual components can be carried out in known manner both successively and simultaneously, and specifically at about 20 ° C (room temperature) as well as at a higher temperature. The thermoplastic molding compositions according to the invention are suitable, owing to their excellent flame resistance and their dimensional stability to heat, as well as their good properties such as welding strength and ESC behavior (resistance to stress fracture). , for the manufacture of molded bodies of any type, especially those with high demands with respect to breaking strength. The molding compositions of the present invention can be used for the production of moldings of any type. In particular, moldings can be produced by injection molding. Examples of molded bodies that can be manufactured are: parts for housings of any type, for example for household appliances such as juicing apparatus, coffee machines, blenders, for office machines such as monitors, printers, copiers, or plates coverage for the construction sector and parts for the automotive sector. They can also be used in the electronics sector, since they have very good electrical properties. Furthermore, the molding compositions according to the invention can be used, for example, for the production of molded bodies or of the following molded parts: internal component parts for rail vehicles, hubcaps, housings for electrical equipment containing small transformers, housings for devices for the distribution and transmission of information, covers and coating for medicinal purposes, massage devices and housings for them, toys for children, flat elements for walls, housings for safety devices, rear bumpers, thermally insulated transport containers, device for the maintenance or care of small animals, molded parts for sanitary and bathroom equipment, cover grilles for ventilation openings, molded parts for garden and tool sheds, housings for garden equipment. Another form of the elaboration consists of the manufacture of molded bodies by means of drawing deep from plates or sheets manufactured previously. Another object of the present invention is therefore the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, as well as the moldings formed by the molding compositions according to the invention. Examples Component A. Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1252, measured in CH2C12 as solvent at 25 ° C and at a concentration of 0.5 g / 100 ml.

Component B. Graft polymer consisting of 40 parts by weight of a copolymer consisting 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 dso = 0.28 μm), prepared by emulsion polymerization.

Component C.

Styrene / acrylonitrile copolymer with a weight ratio of styrene / acrylonitrile of 72:28 and a limit viscosity of 0.55 dl / g (measured in dimethylformamide at 20 ° C). Component D. Phenoxyphosphazene of the formula Commercial product: P-3800, Firm Nippon Soda Co. , Ltd. Japan.

Component E Pural®200, an aluminum oxide hydroxide (from Condea, Hamburg, Germany), average particle size approximately 50 nm.

Component F. Tetrafluoroethylene polymer as a coagulated mixture constituted by a SAN graft polymer emulsion according to component B mentioned above in water and a polymer emulsion of tetrafluoroethylene in water. The weight ratio between graft polymer B and tetrafluoroethylene polymer F in the mixture is 90% by weight with respect to 10% by weight. The tetrafluoroethylene polymer emulsion. it has a solids content of 60% by weight, the average diameter of the particles is between 0.05 and 0.5 μm. The graft polymer emulsion SAN has a solids content of 34% by weight and an average diameter of the latex particles of d5o = 0.28 μm.

Obtaining F The emulsion of the tetrafluoroethylene polymer (Teflon 30 N of the DuPont Firm) is mixed with the emulsion of the graft polymer SAN B and stabilized with 1.8% by weight, based on the solid matter of the polymer, of phenolic antioxidant. The mixture is coagulated at 85 to 95 ° C with an aqueous solution of MgSO (bitter salt) and acetic acid at pH 4 to 5, filtered and washed until practically absence of electrolytes, then released by centrifugation of the main quantity of water and then dried at 100 ° C to give a powder. This powder can then be transformed into masterbatch with the other components in the described devices.

Obtaining and testing the molding compositions according to the invention.

The mixing of the components is carried out in an internal 3-liter kneader. The molded bodies are manufactured in an injection casting machine of the Arburg 270 E type at 260 ° C. The determination of the dimensional stability to heat according to Vicat B is carried out according to DIN 53 460 (ISO 306) in rods with dimensions of 80 x 10 x 4 mm. The determination of the impact strength with ak notch is carried out according to ISO 180/1 A. The resistance of the welding line is determined by measuring the impact resistance DIN 53 453 in the welding line of test specimens injection molded from both sides (process temperature 262 ° C) of dimensions 170 x 10 x 4 m. The combustion behavior of the samples was measured according to UL-Subj. 94 V in rods with dimensions of 127 x 12.7 x 1.6 mm, prepared in an extruder machine at 260 ° C.

The UL 94V test is carried out in the following manner: The test substances are shaped as rods with dimensions of 127 x 12.7 x 1.6 mm. The rods are mounted vertically in such a way that the underside of the specimen is at a distance of 305 mm above a strip of bandage fabric. Each test rod is turned on individually by means of two successive ignition processes of 10 seconds in duration, the properties to the combustion are observed after each ignition process and then they are evaluated the samples. For the ignition of the samples a Bunsen burner with a blue flame with a height of 100 mm (3.8 inches) of natural gas is used with a thermal unit of 3.73 x 104 kJ / m3 (1000 BTU per cubic foot). The UL 94 V-0 classification covers the properties of the materials described below, which are tested according to the UL 94 V protocol. Molding compositions of this type do not contain specimens that burn more than 10 seconds after each flame action. of testing; do not show a total flame formation time greater than 50 seconds in the case of the second flame action in each test group; do not contain show that they burn completely until the clamp fixed on the upper end of the sample; they do not present samples that cause the ignition of the cotton located below the sample due to droplets or particles ignited; nor do they contain samples that remain incandescent more than 30 seconds after the withdrawal of the test flame. Other UL 94 classifications designate samples that are less resistant to flame or less self-extinguishing, since they give off drops or particles lit. These classifications are designated with UL 94 V-l and V-2. N.B. means "not suitable" and is the classification of the samples that have a final combustion time > 30 seconds . The stress fracture behavior (ESC behavior) was tested on rods with dimensions of 80 x 10 x 4 mm, processing temperature 260 ° C. A mixture consisting of 60% by volume of toluene and 40% by volume of isopropanol was used as the test medium. The specimens were subjected to a previous dilation by means of a template in arc of circle (previous dilation in percentage) and were stored at room temperature in the test medium. The stress fracture behavior was evaluated by the formation of cracks or rupture as a function of the previous dilation in the test medium. In the following Table 1 a summary of the properties of the molding compositions according to the invention has been given: By using the combination of phosphazene and finely divided inorganic powder, molding compositions are obtained with greater dimensional stability to heat, which are characterized by very good mechanical properties such as notch impact resistance, low fracture strength Tension and bond strength by welding. Surprisingly, the good flame protection of the molding compositions according to the invention is achieved with clearly reduced amounts of phosphazene.

Table: Molding masses and their properties.

It is noted that in relation to this date, the best method known to the applicant, to carry out the said invention, is that which is clear from the present description of the invention. Having described the invention as above, it is claimed as property what is contained in the following:

Claims (21)

R E I V I N D I C A C I O N S

1. Thermoplastic molding compositions, characterized in that they contain polycarbonate and / or polyester-carbonate, graft polymer, phosphazenes and inorganic powder with an average particle diameter less than or equal to 200 nm.

2. Thermoplastic molding compositions according to claim 1, characterized in that they contain A) from 40 to 99 parts by weight of aromatic polycarbonate and / or polyestercarbonate, B) from 0.5 to 60 parts by weight of inert polymer, Bl) of 5 to 95% by weight of one or more vinyl monomers on B.2 of 95 to 5% by weight of one or more grafting bases with a vitreous transition temperature < 10 ° C, C) from 0 to 45 parts by weight of at least one thermoplastic polymer, chosen from the group of vinyl (co) polymers and polyalkylene terephthalates, D) from 0.1 to 50 parts by weight of at least one component, chosen from the group of phosphazenes of the formulas wherein R are respectively the same or different and mean amino, alkyl with 1 to 8 carbon atoms or alkoxy with 1 to 8 carbon atoms, respectively halogenated, optionally, cycloalkyl with 5 to 6 carbon atoms, aryl with 6 to 20 carbon atoms, aryloxy with 6 to 20 carbon atoms or aralkyl with 7 to 12 carbon atoms respectively optionally substituted by alkyl and / or by halogen, k means 0 or a number from 1 to 15, E: from 0.5 to 40 parts by weight finely divided inorganic powder with a mean particle diameter less than or equal to 200 nm , and F) from 0 to 5 parts by weight of a fluorinated polyolefin.

3. Molding compositions according to claims 1 and 2, characterized in that they contain from 60 to 98.5 parts by weight of A, from 1 to 40 parts by weight of B, from 0 to 30 parts by weight of C, from 1 to 18 parts by weight of D, from 1 to 25 parts by weight of E, from 0.15 to 1 part by weight of F.

4. Molding compositions according to claims 1 to 3, characterized in that they contain from 2 to 25 parts by weight of C.

Moldings according to claims 1 to 4, characterized in that they contain from 5 to 25 parts by weight of D.

6. Molding masses according to the preceding claims, characterized in that the vinyl monomers B.l are mixtures constituted by B.l.l. from 50 to 99 parts by weight of vinylaromatos and / or of vinylaromatos substituted in the nucleus and / or of esters alquilicos (with 1 to 8 carbon atoms) of methacrylic acid, and B.l.2. from 1 to 50 parts by weight of vinylcyanides AND / or alkyl esters with (1 to 8 carbon atoms) of (meth) acrylic acid and / or unsaturated derivatives of carboxylic acids.

7. Molding masses according to the preceding claims, characterized in that the base for grafting is chosen at least between a rubber of the group of diene rubbers, EP (D) M, acrylate, polyurethane, silicone, chloroprene and of ethylene / vinyl acetate.

8. Molding masses according to the preceding claims, characterized in that component D is selected from the group consisting of propoxy phosphazenes, phenoxyphosphazenes, methylphenoxyphosphazenes, aminophosphenes and fluoroalkylphosphazenes.

9. Molding masses according to the preceding claims, characterized in that the component E is chosen from at least one polar compound of one or several metals of the main groups 1 to 5 or of the secondary groups 1 to 8 of the periodic system of the elements with at least an element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.

10. Molding masses according to claim 9, characterized in that the component E is chosen from at least one polar compound of one or more metals of the main groups 2 to 5 or of the secondary groups 4 to 8 with at least one element selected from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.

Moldings according to claim 10, characterized in that the component E is chosen from at least one polar compound of one or more metals of the main groups 3 to 5 or of the secondary groups 4 to 8 of the periodic system of the elements with at least one element chosen from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.

12. Molding compositions according to the preceding claims, characterized in that the component E is selected from at least one oxide, hydroxide, hydrous oxide, sulphate, sulfite, sulfide, carbonate, carbide, nitrate, nitrite, nitride, borate, silicate, phosphate, hydride, phosphite and phosphonate.

13. Molding masses according to the preceding claims, characterized in that the component E is chosen from oxides, phosphates and hydroxides.

14. Molding compositions according to the preceding claims, characterized in that E is selected from Ti02, Si02, Sn02, Sn02, ZnO, ZnS, boehmite, Zr02, A1203, aluminum phosphate, iron oxides, TiN, WC, AIO (OH) , Sb203, iron oxides, Na2SO4, vanadium oxides, zinc borate, silicates such as Al silicates, Mg silicates, mono-, di-, three-dimensional silicates, their mixtures and compounds.

15. Molding masses according to the preceding claims, characterized in that E is chosen from the hydrated aluminum oxides, Ti02 and mixtures thereof.

16. Molding compositions according to the preceding claims, characterized in that they contain at least one additive selected from the group of lubricants and release agents, nucleating agents, antistatics, stabilizers, dyes and pigments.

17. Molding masses according to the preceding claims, characterized in that they contain other flameproofing agents, which are different from the component D.

18. Process against obtaining the molding compositions according to claim 1, characterized in that the components A are mixed. to E and, if necessary, other additives and they are transformed into master blends by fusion.

19. Use of the molding compositions according to claim 1, for the production of moldings.

20. Molded bodies, manufactured from the molding compositions according to claims 1 to 17.

21. Housing parts according to claim 20.