MXPA00003043A - Polycarbonate-abs moulding materials - Google Patents

Abstract

The invention relates to thermoplastic moulding materials containing 1 to 99 parts by weight of an aromatic polycarbonate or polestercarbonate, 1 to 99 parts by weight of at least one grafted polymerizate produced by solvent polymerization, containing 20 to 50 weight percent rubber in relation to the grafted polymer and with an average rubber phase particle diameter of 80 to 600 nm, and optionally, additives, flameproofing agents and/or reinforcing agents.

Description

POLYCARBONATE-ABS MOLDING MASSES. Field of the invention. The present invention relates to polycarbonate-ABS molding compositions, which have an excellent level of mechanical properties, especially excellent stress cracking behavior, high notch tenacity and high resistance to the flow line. DESCRIPTION OF THE PRIOR ART Polycarbonate-ABS molding compositions have been known for a long time (for example EP-A 363 608, EP-A 345 522, EP-A 640 655). A special field of application of these molding compositions after the production of moldings with very good resilience. In order to achieve or also to achieve specific properties of the rubber with these molding compositions, graft rubbers especially manufactured by emulsion polymerization are preferably used. In order to obtain the molded articles with high impact and elasticity demands, the level of indexes of the known molding compositions or of the molded articles produced therefrom is not always sufficient. An increase in the proportion of these graft rubbers, manufactured by emulsion polymerization, often leads to molding compositions with significant properties disadvantages (hot deformation resistance, modulus E). DETAILED DESCRIPTION OF THE INVENTION The task of the present invention is therefore to provide polycarbonate-ABS molding compositions having excellent mechanical properties such as outstanding resilience, excellent resistance to the flow line, high modulus E as well as a high resistance to cracking under tension. It has now surprisingly been found that, by employing REF. : 32985 ABS special polymers are obtained polycarbonate-ABS molding compounds, which can be transformed into molded bodies with a very good mechanical properties level, especially with an excellent notch resilience, a high resistance to the flow line, a high E module and excellent long-term stability. The object of the present invention are therefore thermoplastic molding compositions containing A. from 1 to 99, preferably from 15 to 80, particularly preferably from 30 to 70, parts by weight of an aromatic polycarbonate or a polyester carbonate, and B. from 1 to 99, preferably from 15 to 80, particularly preferably from 30 to 70, parts by weight, of at least one graft polymer produced by solution polymerization with a rubber content of 20 to 50, preferably 22 5 to 45 and particularly preferably 25 to 40% by weight, based on the graft polymer, and with an average particle diameter of the rubber phase of 80 to 600 nm, preferably 150 to 400 nm and particularly preferably from 200 to 350 nm, the sum of all the components of the molding compositions according to the invention being 100 parts by weight. 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 methods 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, DOS 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 the aromatic polyester carbonates, for example DE-i OS 3 007 934). The preparation of the aromatic polycarbonates is carried out, for example, by reacting diphenols with carbonyl halides, preferably phosgene and / or aromatic dicarbonyl dihalides, preferably benzenedicarbonyl halides, by the process of the boundary surface between phases, if appropriate. using chain switches, for example monophenols and, if appropriate, using trifunctional branching agents or having a functionality greater than 3, for example triphenols or tetraphenols. Aromatic polycarbonates, suitable according to the invention, are especially those based on diphenols of the formula (I), wherein A means a single bond, alkylene with 1 to 5 carbon atoms, alkylidene with 3 to 5 carbon atoms, cycloalkylidene with 5 to 6 carbon atoms, -S-, - SO -, -O-, -CO - or arylene with 6 to 12 carbon atoms, which may be condensed, if appropriate, with other aromatic rings containing heteroatoms, B, independently of one another, meaning halogen, alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 atoms carbon, preferably chlorine, bromine, phenyl, aralkyl with 7 to 12 carbon atoms, for example benzyl, x independently of each other mean respectively 0, 1 or 2, and p means 1 or 0, or dihydroxyphenylcycloalkanesalkylsubstituted of the formula (II), wherein R1 and R2, independently of one another, mean hydrogen, halogen, preferably chlorine or bromine, alkyl having 1 to 8 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, for example methyl, ethyl, cycloalkyl with 5 to 6 carbon atoms, aryl with 6 to 10 carbon atoms, preferably phenyl, or aralkyl with 7 to 12 carbon atoms, preferably phenyl-alkyl with 1 to 4 carbon atoms, especially benzyl, m means an integer of 4 to 7, preferably 4 or 5, R3 and R4, which can be chosen individually for each Z, stand independently from each other, hydrogen or alkyl having 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, and Z means carbon, with the proviso that at least one of the atoms Z, R3 and R4 simultaneously represent alkyl, preferably methyl. Preferred diphenols are hydroquinone, resorcin, dihydroxy-diphenyl, bis- (hydroxyphenyl) -alkanes with 1 to 5 carbon atoms, bis- (hydroxyphenyl) -cycloalkanes with 5 to 6 carbon atoms, bis- (hydroxyphenyl) -ethers, bis- (hydroxyphenyl) -sulphoxides, bis- (hydroxyphenyl) -ketones, bis- (hydroxyphenyl) -sulfones, a- bis- (hydroxyphenyl) -diisopropyl-benzene and their brominated derivatives in the nucleus and / or chlorinated in the core. Particularly preferred diphenols are diphenylphenol, bisphenol-A, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (4- hi-droxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxyphenylsulfide, 4,4'-dihydroxydi-phenyl-sulfone as well as its di- and tetrabrominated and chlorinated derivatives such 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. Particularly preferred is 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A).

The diphenols can be used individually or also in the form of arbitrary mixtures. Diphenols are known from the literature or can be obtained according to methods known from the literature. Suitable chain terminators for the preparation of the aromatic, thermoplastic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 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 the 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 be used of the chain switches is generally between 0.5% in moles and 10% in moles, based on the sum in moles of the diphenols used respectively. The aromatic polycarbonates, thermoplastics, have weight-average molecular weights (Mw, measured for example by ultracentrifugation or by measurement of the diffractivity of light) of 10,000 to 200,000, preferably 20,000 to 80,000. The aromatic polycarbonates, thermoplastics, can be branched in a known manner and, specifically, preferably by the incorporation of 0.05 to 2.0 mole%, based on the sum of the diphenols used, of compounds with a functionality greater than or equal to three, for example those with three or more than three phenolic groups. Both homopolycarbonates and copolycarbonates are suitable. For the preparation of the copolycarbonates according to the invention as 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 to be used of diphenols, of polyhydroorganosiloxanes with hydroxy-aryloxy end groups. These are known (see for example also 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%, based on the sum in moles of the diphenols, of other diphenols mentioned as being preferred or especially preferred, in particular 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane. The aromatic dicarbonyl dihalogenides for the preparation of the aromatic polyester carbonates are preferably the diacyl dichlorides of isophthalic acid, terephthalic acid, diphenylether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio of 1: 20 to 20: 1 are particularly preferred. In the preparation of the polyester carbonates, a carbonyl halide, preferably phosgene, is also used as a bifunctional derivative. of acid.

As chaining switches for the preparation of the aromatic polyester carbonates, in addition to the aforementioned monophenols, their chlorocarbonic acid esters as well as the acyl chlorides of aromatic monocarboxylic acids, which optionally can be substituted by alkyl groups with 1 to 22 carbon atoms or halogen atoms, as well as aliphatic monocarbonyl chlorides with 2 to 22 carbon atoms. The amount of the chain switches is respectively from 0.1 to 10 mol%, referred in the case of phenolic chain terminators to the moles of diphenols, and in the case of the monocarbonyl chloride chain terminators to the moles of dicarbonyl dichlorides. 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). Branching agents which can be used are, for example, functional carbonyl chlorides or with a functionality greater than 3, such as trimesyl trichloride, cyanuric acid trichloride, 3,3'4,4'-benzophenone tetracarboxylic acid tetrachloride. , 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in quantities of 0.01 to 1 mol%, based on the dicarbonyl dichlorides used) or trifunctional phenols or with a higher functionality than 3, 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, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenyl-methane, 2,2-bis [ 4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxy-phenyl-isopropyl) -phenol, tetra (4-hydroxyphenyl) -methane, 2,6-bis (2- hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, tetra- (4- [4-hi] droxyphenyl-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 branching agents can be present with the diphenols, the acyl chloride branching agents can be incorporated together with the acyl dichlorides. The proportion in carbonate structural units may vary arbitrarily in aromatic, thermoplastic polyester carbonates. Preferably, the proportion of the 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. The part of the esters as well as the part of the carbonates can be present in the aromatic polycarbonates in the form of blocks or statistically distributed in the polycondensate. The relative viscosity (? Rel) of the aromatic polyester carbonates is in the range from 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 solution of methylene chloride at 25 ° C). Aromatic polycarbonates, thermoplastics and polyester carbonates can be used alone or in arbitrary mixtures with each other. Component B. As component B, graft polymers of the ABS type are used, which are obtained by solution polymerization. Preferably, the graft polymer according to component B is radically polymerized from Bl 90 to 20 parts by weight of monoalkenyl aromatics, B.2 0 to 50 parts by weight of ethylenically unsaturated nitriles, B.3 0 to 30 parts by weight of other copolymerizable compounds, in the presence of 15 to 50 parts by weight, per 100 parts by weight of monomers Bl to B.3, of a butadiene polymer free of gel, soluble or butadiene / styrene copolymer and in the presence of 50 to 200 parts by weight of a solvent, per 100 parts by weight of the monomers Bl to B.3, the solvent being an alcohol, ketone, ether, ester, nitrile (Ll) aliphatic (with 1 to 8 carbon atoms) or cycloaliphatic (with 5 to 6 atoms) carbon) or a mixture of (Ll) with an aliphatic, cycloaliphatic or aromatic hydrocarbon (L2) in the weight ratio L1: L2 from 100: 0 to 30:70 and the polymerization is conducted to a polymer content of the group of the mixture of 30 to 70% by weight under mixed and optionally further dosed regulators and initiators in such a way that the graft polymer contains from 20 to 50% by weight of butadiene polymer. Preferably the total rubber content of the graft polymer is 22.5 to 45, particularly preferably from 25 to 40% by weight, and very particularly preferably from 10 to 20% by weight. The preparation of component B is carried out by solution polymerization using at least one solvent, chosen from alcohols, ketones, ethers, esters, aliphatic (1 to 8 carbon atoms) or cycloaliphatic nitriles with 5 to 6 atoms of carbon or a mixture of at least one of the mentioned solvents with an aliphatic or cycloaliphatic hydrocarbon having 4 to 10 carbon atoms and / or an aromatic hydrocarbon under special framework conditions. Preferably the polymer content of the mixture in this case is from 30 to 60% by weight, especially from 35 to 50% by weight, the total content in solvent is from 25 to 60% by weight and the rest up to 100% by weight. monomers without converting.

In the preferred preparation of component B, it is possible to quickly carry out an inversion of the phases with sufficient conversions, when the solvents or solvent mixtures formed by the group (Ll) and, if applicable, the group (L2) in the proportions are used. in weight indicated from 1: 0 to 3: 7, despite the high rubber contents, in such a way that a finely dispersed phase formed by graft rubber is formed. The production of component B can be carried out discontinuously, semicontinuously and continuously. In the continuous embodiment, the solution of the monomers and of the rubber in the solvents can advantageously be polymerized in a continuously charged tank reactor, mixed and stirred with a conversion of the stationary monomers, which occurs after the inversion of the phases , in the first stage greater than 10% by weight, based on the sum of the monomers and the radical-initiated polymerization can be continued at least in another step up to a conversion of the monomers, with respect to the sum of the monomers , from 30 to 70% by weight under mixed in one or several tanks with stirring, which are made to work continuously, in cascade or in a reactor with piston flow, with mixing action, and / or in a combination of both types of reactors, residual monomers and solvents are removed according to traditional techniques (for example in evaporators with heat exchange, evaporators by decompression, evap continuous speakers, thin film or thin film evaporators, screw evaporators), and recycled to the process. It may also be advantageous to carry out the polymerization in continuous in three steps, the first step being carried out with a conversion of the stationary monomers of less than 10% by weight, which occurs before the inversion of the phases and the other steps are carried out with the conversions described above. The polymerization in batch or semicontinuous can be carried out in one or several stirred tanks, connected in series, full or partially filled, with prior arrangement or mixing of the monomers, rubber and solvent and polymerization until the conversion of the monomers indicated from 30 to 70% by weight. In order to improve the mixing and comminution of the fed rubber, the polymer syrup can be pumped both when working continuously and when working discontinuously, in closed circuit by means of mixing and shearing organs. Such "loop operations" constitute the state of the art and can be of help in adjusting the size of rubber particles. However, the provision of shear organs between two separate reactors to avoid remixing is advantageous, leading to an enlargement of the particle size distribution. The average residence time is from 1 to 10 hours. The polymerization is advantageously carried out at 60 to 120 ° C, preferably at the boiling point of the solvent / polymer mixture. It is advantageous to carry out the polymerization at normal pressure. However, it is also possible to carry out the polymerization at a slight overpressure of up to 6 bar. The viscosities of the agitated or transported media move in the range of 150 Pa.s at most. The graft polymer can be isolated in a known manner by precipitation in solvents, by distillation by stripping with water and / or water vapor or by concentration by evaporation until melting of the polymer for example in decompression evaporators, continuous evaporators, evaporators of coiled tubes, thin film evaporators, certain thin film evaporators , falling film evaporators, screw evaporators. The solvent and the residual monomers can also be removed in stirred polyphase evaporators with kneading and scraping devices. The concomitant use of propellants and entrainers, for example water vapor, is possible in this case and, despite the high amounts of solvents, even without the use of such entraining agents, a very low residual monomer content can be achieved with simple methods of concentration by evaporation.

The solvents of group (Ll) are alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol, isoamyl alcohol, isooctanol, cyclohexanol, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl, -diethyl, -dipropyl, -diisopropyl ether. esters such as ethyl acetate, propyl acetate, butyl acetate or nitriles such as acetonitrile, propionitrile, butyronitrile. Preference is given to using methyl ethyl ketone and acetone. The solvents of the group (L2) are aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, or their iso-derivatives, cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, alkylcyclopentane, alkylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylenes , ethylbenzene. Preference is given to using toluene and ethylbenzene. Mixtures formed by acetone and ethylbenzene as well as acetone and toluene are especially preferred. It is also possible to use only solvents from group (Ll). Methyl ethyl ketone is then preferred. For adjusting the molecular weights, customary molecular weight regulators such as mercaptans and defines can be used, for example tert-dodecyl mercaptan, n-dodecyl mercaptene, cyclohexane, terpine, a-methylstyrene dimer and the like in amounts of 0.05 to 1.0. % by weight, based on the monomers to be copolymerized.

Suitable initiators for radical polymerization are peroxides with grafting activity, which are broken down into radicals such as peroxycarbonates, peroxydicarbonates, diacylperoxides, perketals or dialkylperoxy and / or azo compounds or mixtures thereof. Examples are azodiisobutyryltrinyl, alkyl azoisobutyrates, pervillate, peroctoate, tere-butyl perbenzoate. These initiators are used in amounts of 0.01 to 1% by weight, based on the monomers B.l to B.3. During the polymerization or as a step prior to processing, customary additives such as colorants, antioxidants, lubricants, stabilizers, which are known to those skilled in the art can be added. Suitable rubbers for the preparation of component B are preferably gel-free, soluble butadiene polymers, such as, for example, polybutadienes, as well as styrene-butadiene copolymers in statistical and / or block form, with a high proportion in 1, 2- vinyl from 2 to 40%, preferably from 8 to 25%, based on double bonds, with molecular weights of 50,000 to 500,000, including branched and crashed polymers with gel contents below 1,000 ppm. The monoalkenyl aromatic compounds B.sub.1 are preferably styrene, α-methylstyrene, substituted alkylstyrenes in the nucleus, cycloatyrenes substituted in the nucleus. As ethylenically unsaturated nitriles B.2, acrylonitrile or methacrylonitrile is preferably used. The copolymerizable compounds B.3 are, for example, acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, tere-butyl (meth) acrylate, esters of fumaric acid, itaconic acid, malein-derivatives such as maleic acid anhydride, maleic acid esters, N-substituted maleinimides such as N-cyclohexyl- or N-phenyl-maleinimide, N-alkyl-phenyl-maleinimides, acrylic acid, methacrylic acid, fumaric acid, itaconic acid or their amides. The ABS polymers B, which are suitable according to the invention, have a rubber content of 20 to 50% by weight, preferably 22.5 to 45% by weight, and particularly preferably 25 to 40% by weight, The average diameter of the particles is from 80 to 660 nm, preferably from 150 to 400 nm and more preferably from 250 to 350 nm. In addition, the graft polymer B preferably has a degree of grafting of 0., 2 to 1 (see M. Hoffmann, H. Krómer, R. Kuhn in "Polymeranalytik I", Georg Thieme Verlag Stuttgart 1977) and a gel content of 30 to 50% by weight (measured in methyl ethyl ketone). In addition to the component B according to the invention, customary ABS polymers can also be used (see, for example, EP-A 345 522 or 640 6555). The molding composition may contain, in addition to the components A and B according to the invention, other components which will be described in an exemplary manner below. The quantitative data refer respectively to the whole of the molding mass. As other thermoplastics, vinyl (co) polymers (component C.l) and / or polyalkylene terephthalates (component C.2) can be used in an amount of up to 30% by weight, preferably up to 20% by weight, respectively. The sum of all the components is added up to 100%. Component C.l). The vinyl copolymers, employable according to the invention, according to (component C.l) are resinous, thermoplastic and rubber-free. They are those constituted by at least one monomer of the styrene series, α-methylstyrene, styrene substituted by alkyl in the nucleus, alkyl alkyls with 1 to 8 carbon atoms, alkyl methacrylates with 8 carbon atoms, component Cll) with at least one monomer of the series consisting of acrylonitrile, methacrylonitrile, alkyl methacrylates with 1 to 8 carbon atoms, alkyl acrylates with 1 to 8 carbon atoms, maleic anhydride and / or N-substituted maleinimide (component Cl2). The alkyl acrylates with 1 to 8 carbon atoms or the alkyl methacrylates with 1 to 8 carbon atoms are esters of acrylic acid or of methacrylic acid and monovalent alcohols with 1 to 8 carbon atoms. Methyl, ethyl and propyl methacrylates are particularly preferred. Methyl methacrylate will be mentioned as a particularly preferred methacrylic ester. Thermoplastic copolymers with a composition according to the component C.l) can be formed as byproducts during graft polymerization for the preparation of component B), especially when large amounts of monomers are grafted onto small amounts of rubber. The amounts used according to the invention of copolymer C.l) do not include these secondary products of graft polymerization. The thermoplastic copolymers C.l) contain from 50 to 95% by weight, preferably from 60 to 90% by weight of component C.l.l) and from 5 to 50% by weight, preferably from 10 to 40% by weight of component C.l.2). Particularly preferred copolymers Cl) are those formed by styrene, with acrylonitrile and, if appropriate, with methyl methacrylate, by a-methylstyrene with acrylonitrile and, if appropriate, with methyl methacrylate, or by styrene and α-methylstyrene with acrylonitrile, and given case, with methacrylate. The styrene-acrylonitrile copolymers according to component C.l) are known and can be obtained by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The copolymers according to component C.l) preferably have molecular weights (weight average, determined by light diffraction or by sedimentation) of between 15,000 and 200,000. Particularly preferred copolymers Cl) according to the invention are also copolymers formed statistically by styrene, maleic anhydride and / or N-substituted maleinimide, which can be obtained by continuous bulk or solution polymerization with incomplete conversions from the corresponding monomers. The proportion of both components of the styrene-maleic acid anhydride copolymers formed in a statistical manner, suitable according to the invention, can vary within wide limits. The preferred anhydride content of maleic acid is between 5 and 25% by weight. The molecular weights (number average n) of the styrene / maleic acid anhydride copolymers statistically constituted, suitable according to the invention, according to component C.l) can vary within wide limits. It is especially preferred in the range of 60,000 to 200,000. For these products, a limit viscosity of 0.3 to 0.9 dl / g is preferred. (measured in dimethylformamide at 25 ° C). Instead of styrene the vinyl copolymers C.l) may also contain substituted core styrenes such as vinyltoluenes, 2,4-dimethylstyrene and other substituted halogen-free styrenes such as α-methylstyrene. Component C.2). The polyalkylene terephthalates of component C.2) are reaction products of aromatic dicarboxylic acids or reactive derivatives, such as methyl esters or anhydrides, and aliphatic, cycloaliphatic or aromatic diols and mixtures of these reaction products. Preferred polyalkylene terephthalates contain at least 80% by weightpreferably at least 90% by weight, based on the dicarboxylic components, of terephthalic acid residues and at least 80% by weight, preferably at least 90% by weight, based on the diol-components, of ethylene glycol residues and / or butanediol-1,4. Preferred polyalkylene terephthalates can contain, in addition to residues of terephthalic acid, up to 20% by mole, preferably up to 10% by mole, of residues of other 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-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, acid azelaic, of cyclohexane-diacetic acid. Preferred polyalkylene terephthalates can contain, in addition to the ethylene glycol or butanediol-1,4 moieties, 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 21 carbon atoms, for example residues of propanediol-1,3, 2-ethylpropanpdiol-1, 3, neopentyl glycol, pentane-diol-1,5, hexane-diol-1,6, cyclohexane-dimethanol-1, 4, 3-ethylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-l, 3, 2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1, 3, hexa- nodiol-2,5, 1, 4-di- (β-hydroxy-ethoxy) -benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy- 1,1, 3,3- tetra-methyl-cyclobutane, 2,2-bis- (4-β-hydroxyethoxy-phenyl) -propa-no and 2,2-bis- (4-hydroxypropoxyphenyl) -? ropano (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 tetravalent alcohols or tri or tetrabasic carboxylic acids, for example according to DE-OS 1 900 270 and US-PS 3 692 744. Examples of preferred branching agents are trimesilic acid , trimellitic acid, trimethylolethane and -propane and pentaerythritol. Especially preferred are polyalkylene terephthalates which have been prepared solely 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 polyalkylene terephthalate mixtures 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 polybutylene terephthalate . The polyalkylene terephthalates, which are preferably used, generally have 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). weight) at 25 ° C in the Ubbelohde viscometer. The polyalkylene terephthalates can be prepared according to known methods (see for example Kunststoff-Handbuch, volume HIV, page 695 et seq., Carl-Hanser-Verlag, München 1973). The molding compositions according to the invention can also contain the usual additives such as lubricants and mold release agents, nucleating agents, antistatics, stabilizers, dyes, pigments, flame retardants and / or reinforcing materials. Preferably the molding compositions according to the invention contain as flame retardants at least one organic compound of the phosphorus of the formula (IH) In the formula R5, R6, R7, R8 mean, independently of each other, 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. carbon halides, respectively, where appropriate, with aryl having 6 to 10 carbon atoms or aralkyl having 7 to 12 carbon atoms being preferred. The aromatic groups R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may be substituted, for their part, by halogens, preferably by chlorine or bromine, and / or by alkyl groups, preferably alkyl having 1 to 4 carbon atoms, especially methyl, ethyl. . Particularly preferred aryl radicals are cresyl, phenyl, silyl, propylphenyl or butylphenyl, and the corresponding brominated and chlorinated derivatives. In the formula (III) X means a mono or polynuclear aromatic radical with 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (I). Bisphenol A, resorcinol, hydroquinone, biphenyl or their chlorinated or brominated derivatives are particularly preferred. In the formula (IH), n can be, independently of each other, 0 or 1, preferably n is equal to 1. N takes values from 0 to 30, preferably takes values from 0.3 to 20, particularly preferably 0 , From 5 to 10, in particular from 0.5 to 6. The phosphorus compounds, which are covered by the formula (III), are both monophosphorus compounds and also oligomeric phosphorus compounds. Likewise, mixtures of the monophosphorus compounds and the oligomeric phosphorus compounds are encompassed by the formula (III). In particular, monophosphate compounds of the formula (IH) are organic monophosphates such as tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromoporopyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl phenylphosphonate, triphenylphosphine oxide or tricresylphosphine oxide.

Mixtures of oligomeric phosphorus compounds of the formula (III), preferably oligomeric phosphates of the formula (IH), with N values of from 0.5 to 10, in particular from 0.5 to 6, or mixtures formed will be especially preferred as flame retardants. by monophosphorus compounds and oligomeric phosphorus compounds of the formula (IH). In the mixture, the monomeric and oligomeric compounds of the phosphorus of the formula (III) are preferably chosen in such a way that a synergistic effect is achieved. The mixture is generally composed of 10 to 90% by weight of oligomeric phosphorus compounds and 90 to 10% by weight of monophosphorus compounds, preferably monophosphorus compounds of the formula (H [). Preferably, the monophosphorus compounds will be mixed in the range of 12 to 50, in particular 14 to 40, very particularly preferably 15 to 40% by weight with the complementary amount of oligomeric phosphorus compounds. Said phosphorus compounds are preferably used together with fluorinated polyolefins as a combination of flame retardants in amounts of 0.05 to 5 parts by weight. The fluorinated polyolefins, which are used, are of high molecular weight and have glass transition temperatures above -30 ° C, as a rule above 100 ° C, fluorine contents of 65 to 76, especially 70 to 76 % by weight, average diameter of the d50 particles from 0.05 to 1,000, preferably from 0.08 to 20 μm. In general, the fluorinated polyolefins have a density of 1.2 to 2.3 g / cm3. Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene, copolymers of hexafluoroethylene and ethylene / tetrafluoroethylene. Fluorinated polyolefins are known (see Vinyl and Related Polymers "by Schildknecht, John Wiley & amp;; Sons, Inc. New York 1962, pages 484-494; "Fluorpolymers" by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, page 623-654, "Modern Plastics Encyclopedia", 1970-1971, volume 46, 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, Me Graw-Hill, Inc., New York, pages 27, 28 and 472 and US-PS 3 67.1 487, 3 723 373 and 3 838 092). They can also 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 / cm2 and at a temperature 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). Depending on the form of application, the density of these materials can be between 1.2 and 2.3 g / cm3, the average particle size between 0.05 and 1000 μm. Particularly preferred fluorinated polyolefins according to the invention are tetrafluoroethylene polymers with a mean particle diameter of 0.05 to 20 μm, preferably 0.08 to 10 μm, and a density of 1.2 to 1.9 g / cm3 . Suitable fluorinated polyolefins, which can be used in powder form, are tetrafluoroethylene polymers with an average particle diameter of 100 to 1,000 μm, and densities of 2.0 g / cm 3 to 2.3 g / cm 3. Suitable emulsions of tetrafluoroethylene polymer are commercially available products which are marketed, for example, by DuPont as Teflon® 30 N. They can be used in the form of a coagulated mixture of emulsions of the tetrafluoroethylene polymer with emulsions of the graft polymer. To obtain a coagulated mixture, an aqueous emulsion (latex) of a graft polymer is first mixed with a finely divided emulsion of a tetrafluoroethylene polymer; suitable emulsions of tetrafluoroethylene polymer usually have solids contents of 30 to 70% by weight, especially 50 to 60% by weight, preferably 30 to 35% by weight. In the emulsion the equilibrium ratio of graft polymer to the tetrafluoroethylene polymer is presented in 95: 5 to 60:40. The emulsion mixture is then coagulated in a known manner, for example by spray drying, drying by lyophilization, or coagulation by 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. The molding compositions according to the invention can also contain inorganic reinforcing materials. Inorganic reinforcing materials which may be used are glass fibers, optionally cut or ground, glass beads, glass beads, platelet reinforcing materials, such as kaolin, talc, mica, biotite, carbon fibers or mixtures thereof. . Preferably, cut or ground glass fibers, preferably with a length of 1 to 10 mm and smaller than 20 μm in an amount of up to 40 parts by weight, are preferably used as reinforcing materials; preferred are surface treated glass fibers. The molding compositions according to the invention can also contain finely divided inorganic powders 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 finely divided inorganic compounds are composed of compounds of one or more metals from the first to fifth major groups or from the first to eighth secondary groups of the Periodic Element System. preferably from the second to fifth major groups and from the fourth to eighth secondary groups, particularly preferably from the third to fifth major groups and from the fourth to eighth secondary groups with at least one element selected from the group consisting of oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen and silicon. Preferred compounds are, for example, oxides, hydroxides, oxides containing water, sulfates, sulphites, sulphides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates. Preferred finely divided inorganic compounds are, for example, TiN, TiO2, SnO2, WC, ZnO, Al2O3, AIO (OH), ZrO2, Sb2O3, SiO2, iron oxides, NaSO4, BaSO4, vanadium oxides, zinc borate, Silicates such as Al silicates, Mg silicates, mono, di, three-dimensional silicates, mixtures and compounds are equally employable. Furthermore, these particles, at the nanoscale, can be surface modified with organic molecules to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be generated. The average diameter of the particles is less than or equal to 200 nm, preferably less than or equal to 150 nm, especially from 1 to 100 nm. The size of the particles and the diameter of the particles always mean the average diameter of the d50 particles, determined by ultracentrifugation according to W. Scholtan et al. Kolloid-Z. and Z. Polymere 250 (1972), page 782 to 896.

The inorganic compounds may be in the form of powder, pastes, sols, dispersions or suspensions. Dusts can be obtained by precipitation from the dispersions, sols or suspensions. The powders can be incorporated into the thermoplastic synthetic materials according to customary methods, for example by kneading or direct extrusion of the components of the molding compositions and finely divided inorganic powders. The preferred processes represent the manufacture of a masterbatch, for example 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 finely divided inorganic materials. The molding compositions according to the invention may contain, in addition to the flameproofing agents specified, from 0.01 to 10% by weight, based on the composition of the molding composition, of another flameproofing agent, which acts in the case given in a synergistic way. For example, other halogen-containing organic compounds such as decabromobisphenyl ether, tetrabromobisphenol, halogenated inorganic compounds such as ammonium bromide, nitrogen-containing compounds, such as melamine, melamine-formaldehyde resins, inorganic hydroxy-compounds, such as hydroxide, may be mentioned as other flame retardants. of Mg, of Al, inorganic compounds such as antimony oxides, barium metaborate, hydroxyantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate and tin as well as siloxane compounds. The molding compositions according to the invention consisting of the individual components and, where appropriate, additives are prepared by mixing the corresponding components in a known manner and by melt-kneading or melt extrusion at temperatures of 200 ° C to 300 ° C. in conventional devices such as internal kneaders, extruders and double-shaft spindles, in the case of the addition of organic reinforcing materials, the technology of the masterbatch is especially suitable. 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 at a higher temperature.

The molding compositions of the present invention can be used for the production of moldings by injection molding. Examples of workable molded bodies are: housing parts of any type, for example for household appliances such as juicers, coffee machines, mixers, for office machines, or cover plate for the construction sector and others for the automobile sector. They are also used for the electrical engineering sector because they have very good electrical properties. Another form of manufacturing consists of the manufacture of molded bodies by means of drawing from previously manufactured plates or sheets. The thermoplastic molding compositions according to the invention are suitable, owing to their very good conversion property and very good mechanical properties, especially their outstanding combination of properties formed by notched resilience and high modulus, for the production of moldings of any type. type, especially those with high requirements related to breaking strength. The fields of application are in the field of data processing technology, such as, for example, housing parts for monitors, printers and copiers. In this case, these are molded bodies that are configured in a complicated manner with relatively thin wall thicknesses. Another object of the present invention is therefore also the use of the molding compositions according to the invention, for the manufacture of molded bodies of any type, preferably those previously mentioned, as well as the molded bodies constituted 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. The graft polymer B is prepared in the following manner: A solution prepared at 40 ° to 50 ° C under a nitrogen of 72 is placed in a 100 liter reactor with an anchor stirrer (80 revolutions per minute). parts by weight of a rubber (poly-cis-butadiene-co-block styrene, 11% styrene, solution viscosity 27.5 mPa-s, 5% solution in styrene) in 275 parts by weight of styrene, 120 parts by weight of acrylonitrile and 229 parts by weight of 2-butanone. together with 0.95 parts by weight of tert-dodecyl mercaptan, 0.15 parts by weight of 2,5-di-tert.-butylphenol and 7.6 parts by weight of paraffin oil. After heating to 75 ° C, a solution of 0.57 parts by weight of tere-butyl perpivalate (60% by mixture of hydrocarbons) and 0.16 parts by weight of tere-butyl peroctoate in 18 parts by weight is added. weight of 2-butanone and continue stirring for approximately 45 minutes until the phase inversion ends (recognizable by the fall of the moment of rotation). It is then polymerized until the final conversion by subsequent metering of 0.19 parts by weight of tert-dodecyl mercaptan (dissolved in 37 parts by weight of 2-butanone) and with an increase in temperature (1.5 h to 84 ° C, 1 hour at 87 ° C, 4.5 hours at 90 ° C), after which 2 parts by weight of p-2,5-di-tert-butylphenol-octyl propionate are added as stabilizers (Irganox 1076, Ciba -Geigy) (dissolved in 11 parts by weight of 2-butanone).The solids content of the polymerization syrup at the end of the reaction is 39% by weight. The solution is then concentrated by evaporation in a ZSK laboratory evaporation screw at 250 ° C final temperature and granulated. The granulate contains 27% by weight of rubber, the gel content (measured in acetone) is 33% by weight, the average particle size of the rubber phase (average value by weight) is approximately 250 nm.

Component C. Styrene / acrylonitrile copolymer with a styrene / acrylonitrile ratio of 72:28 and a limit viscosity of 0.55 dl / g (measured in dimethylformamide at 20 ° C). Emulsion graft polymer (Comparative). Graft polymer of 45 parts by weight of a copolymer of styrene and acrylonitrile in the proportion of 72:28 on 55 parts by weight of cross-linked polybutadiene rubber in the form of particles (average particle diameter d 50 = 0.4 μm), prepared by emulsion polymerization. Triphenyl phosphate (Disflamoll TP from Bayer, Leverkusen, Germany). Anti-drip agent. Tetrafluoroethylene polymers as a coagulated mixture of a graft polymer-SAN emulsion according to the aforementioned component in water and an emulsion of tetrafluoroethylene polymer in water. The weight ratio between graft polymer and tetrafluoroethylene polymer in the mixture is 90 parts by weight over 10 parts 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 graft polymer emulsion-SAN has a solids content of 34% by weight and a mean diameter of the latex particles of d50 = 0.28 μm. Manufacturing. The emulsion of the tetrafluoroethylene polymer (Teflon 30 N of the DuPont Fa) is mixed with the emulsion of the graft polymer and stabilized with 1.8% by weight, based on the solid matter of the polymer, of phenolic antioxidants. The mixtures are 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 mixed with other components in the described devices. Release agent. Pentaerythritol tetrastearate. Fabrication and testing of the molding compositions according to the invention. The mixing of all the components of the molding compositions is carried out in an internal 3 liter mixer. The moldings are manufactured in a machine decorated by injection of the Arburg 270 E type at 260 ° C. The determination of the notched resilience is carried out according to the ISO 180 1A method on test pieces with dimensions of 80 x 10 4 mm3 at room temperature. The determination of an is carried out according to the method DIN 53 453. The determination of the hot dimensional stability according to Vicat B s is carried out according to DIN 53 460 in test pieces with dimensions of 80 x 10 x 4 mm. The determination of the traction module E is carried out according to ISO 527 / DIN 53 457. The stress cracking behavior (ESC behavior) is tested on specimens with dimensions of 80 x 10 x 4 mm. A mixture of 60% by volume of toluene and 40% by volume of isopropanol is used as the test medium. The specimens are subjected to a previous expansion by means of a circular arc strip (previous dilation in percentage) and stored at room temperature in the test medium. The cracking behavior under tension is evaluated by means of breaking according to the previous expansion in the test medium with an exposure time of 5 minutes. The bending modulus E is verified according to the method DIN 53 457-B3 in test pieces with dimensions of 80 x 10 x 4 mm3.

Table 1: Composition and properties of polycarbonate graft molding compositions. 0 0 * Absence of breakage after 10 minutes. The molding compositions according to the invention have, despite a low rubber content, high notch resilience, high modulus E and improved resistance to stress cracking. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (8)

1. CLAIMS Efefc? Dest rito the invention of the chorus a-beoede, is claimed as p p ?? to what is added in the follow-up & reivirrrir r rnps: 1.- Thermoplastic molding masses because crptiena A. from 1 to 99 parts by weight of aromatic or polyestercarbonate polycarbonate
2. B. from 1 to 99 parts by weight of at least one graft polymer prepared by solution polymerization with a rubber content of 20 to 50% by weight, based on the graft polymer, and with an average particle diameter of the rubber phase from 80 to 600 nm. 2.- Molding masses according to claim 1, eaLacUa zrrlris patque the graft polymer B ae pLlirrrrrr from Bl 90 to 20 parts by weight of monoalkenyl aromatics, B.2 0 to 50 parts by weight of ethylenically unsaturated nitriles , B.3 0 to 30 parts by weight of other copolymerizable compounds, in the presence of 15 to 50 parts by weight, per 100 parts by weight of monomers Bl to B.3, of a soluble, gel-free butadiene polymer or of butadiene / styrene copolymer and in the presence of 50 to 200 parts by weight of a solvent, per 100 parts by weight of monomers Bl to B.3, by means of radicals, up to a polymer content of the whole of the mixture of 30 to 70% by weight under mixed and optionally further dosed regulator and initiator, the solvent being an alcohol, ketone, ether, ester, nitrile (Ll), aliphatic (with 1 to 8 carbon atoms) or cycloaliphatic (with 5 to 6 carbon atoms no) or a mixture of (Ll) with an aliphatic, cycloaliphatic or aromatic hydrocarbon (L2) in a weight ratio L1: L2 from 100: 0 to 30:70 and the polymerization is conducted to a polymer content of the whole of the mixture of 30 to 70% by weight, under mixed and optionally further metered, of regulator and initiator in such a way that the graft polymer contains 20 to 50% by weight of butadiene polymer.
3. 3.- Molding masses according to the rejvirrlicpr? Rt__s anta-aders, charactrensis because the component B is prepared by polymerization in solution using at least one solvent chosen from alcohol, ketone, ether, ester, nitrile with 1 to 8 aliphatic or cycloaliphatic carbon atoms or a mixture of at least one of the solvents mentioned with a hydrocarbon with 4 to 10 carbon atoms aliphatic or cycloaliphatic and / or aromatic hydrocarbon.
4. 4. Molding masses according to claim 1, wherein the graft polymer B présenla your caitenido in rubber from 22.5 to 45 and ui diameter GGBCÜO of the pg- i inflasts of the phase d = rubber of 150 to 400 rm.
5. 5. Molding masses according to claims 1 to 4, because they contain caiponone ** at least between one of the components of polyurethane ABS, vinyl (co) polymers, polyalkyltereilalates, phosphorus compounds, fluorinated polyolefins, inorganic reinforcing materials. .
6. 6. Molding masses according to claims 1 to 5, characterized in that adsorptive crxirienai between at least one of the characters of Jcs.dyb_t.Les litrificsnlas and release agents, nucleating agents, antistatics, stabilizers, dyes, pigments, protective agents against the call.
7. 7.- molding masses according to one of the preceding claims, characterized in that a trait of the prosthesis is inserted into the trance. wherein R5, R6, R7, R8, independently of each other, 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 carbon, halogenated respectively if appropriate, X means a mono or polynuclear aromatic residue with 6 to 30 carbon atoms, n means 0 or 1 and N means values of 0 to 30. 8. Molding masses according to one of the preceding claims , t • - »± 4 A» -ri? -G1-H park contain a fine compound divided from the first to the first fifth of the groups p_.iii.3X > a cctawo S9ajdari.ns of the Beri? djpo System of the Elements with at least one element chosen from the group consisting of oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon. 9. Use of the molding compositions according to one of the preceding claims, for the production of moldings. 10. Molded bodies manufactured from the molding compositions according to claims 1 to
8. 8. POLYCARBONATE-A MOLDING MASSES SUMMARY OF THE INVENTION Thermoplastic molding compositions containing from 1 to 99 parts by weight of an aromatic polycarbonate or polyester carbonate and from 1 to 99 parts by weight of at least one graft polymer manufactured by polymerization in solution with a rubber content of 20 to 50% by weight, based on the graft polymer, and with an average particle diameter of the rubber phase of 80 to 600 nm and optionally additives, anti-caking agents the flame and / or reinforcing agents.