DE10224616A1 - Polycarbonate or polyester carbonate composition, useful for the production of molded articles having modified impact resistance, contains at least one oxalate compound - Google Patents

Abstract

The invention relates to polycarbonate and/or polyester carbonate compositions containing at least one oxalate compound selected from the group consisting of metal oxalates, metal hydroxy oxalates, oxalic acid esters and metal salts of oxalic acid esters in quantities of between 0.1 and 5 parts by weight, (in relation to 100 parts by weight of the total composition). Said compositions exhibit an advantageous combination of joint seam stability in moulded parts and stress cracking stability under the influence of chemicals, in addition to a high level of thermal stability, excellent processing behaviour and flame-retardant properties.

Description

The invention relates to impact modified polycarbonate compositions good processing behavior and advantageous combination of Impact strength, stress crack resistance under the influence of chemicals, Heat resistance and weld line strength, as well as moldings available from it. The invention relates in particular to flame-retardant, impact-modified polycarbonate Compositions with the properties mentioned. The invention further relates to the use of oxalate compounds for flame retardant finishing of impact modified polycarbonate compositions.

Flame-retardant, impact-modified polycarbonate compositions are known. In addition to halogen-containing substances, flame retardants are also used especially phosphorus-containing compounds, on an industrial scale in particular aromatic phosphoric acid esters are used. such Compositions are described, for example, in EP-A 0 363 608 and EP-A 0 640 655.

Such flame retardant finish with phosphoric acid esters Impact-modified polycarbonate compositions can contain silicate materials such as talc (see, for example, JP-A 11199768, WO 00/46298, EP-A 1 026 205) to improve the Flame retardant properties can be added. You can also do the same Purpose added nanoscale inorganic powders such as basic aluminum oxides (see e.g. US-A 5 849 827). The compositions thus obtained are characterized by insufficient weld line strength.

The use of mineral flame retardants such as aluminum trihydroxide, Magnesium dihydroxide or antimony trioxide in polymers is summarized e.g. B. in M. Weber, "Mineral Flame Retardants", Industrial Minerals, February 2000, pages 19 to 27. Such flame retardants come in polycarbonate and whose blends are usually not used. The most common mineral flame retardant aluminum trihydroxide has a comparatively low Decomposition temperature of about 200 ° C and is therefore like for polymers Polycarbonate and polycarbonate blends at a processing temperature> 200 ° C are manufactured or processed, unsuitable. For polymers with Processing temperatures> 200 ° C is therefore often used magnesium dihydroxide, which is a Has decomposition temperature of about 340 ° C. Has magnesium dihydroxide however, the disadvantage that it is much more expensive than aluminum trihydroxide and in Polycarbonate and its blends due to its basic character Polymer degradation leads.

In J. Stinson, W. Horn, "Flame Retardant Performance of a Modified Aluminum Trihydroxides With Increased Thermal Stability ", Journal of Vinyl & Additives Technology, June 1995, Vol. 1, No. 2, pp. 94-97 is an oxalate-modified aluminum hydroxide with a decomposition temperature> 330 ° C and its use as a flame retardant described in various polymer compositions. The described oxalate-modified aluminum hydroxide showed concentrations of 50 to 60% various polymers such as high-density polyethylene (HDPE), polyvinyl chloride (PVC), polypropylene (PP), polyethylene terephthalate (PET) etc. a good one Flame retardancy assessed in the UL-94 V test. Only led in polycarbonate (PC) the addition of oxalate modified aluminum hydroxide to the desired one Improvement of flame retardancy according to UL-94 V.

From US-A 5 075 472 is also the production and characterization of Aluminum hydroxide-lithium oxalate compounds known. In the scripture noted that such compounds could be useful, polymers flame retardant equip.

WO 01/58999 describes polymer blends containing a phosphorus compound and Oxalate salts, the oxalate salts in an amount of up to 30 parts by weight be added. In the examples are polycarbonate / ABS compositions described, which contain 10 parts by weight of aluminum oxalate.

It has been found that oxaxal compounds in amounts according to the present Invention the impact properties of the test specimens not or hardly negatively influence, however, the positive effects on the weld line strength and the ESC Behavior (stress crack behavior under the influence of chemicals) occur. in the With regard to a particularly balanced property profile from impact resistance, Weld line strength and ESC behavior is the most preferred concentration range Oxalate compound 0.3 to 3.0 wt .-%, based on the total composition.

The molding compounds have a particular thickness with thin walls (1.2 mm) excellent flame retardancy according to UL-94 V and an excellent Processability, d. H. in particular a good melt flowability.

This task is solved by an impact modified Polycarbonate composition containing at least one oxalate compound selected from the group consisting of metal oxalates, basic metal oxalates (metal hydroxy oxalates), Oxalic acid esters and metal salts of oxalic acid esters, in amounts from 0.1 to 5 Parts by weight (based on 100 parts by weight of total composition).

Characteristic of the impact modified according to the invention Compositions is that they contain at least one oxalate compound. invention Oxalate compounds are, for example, metal oxalates, basic metal oxalates, all metal salts of oxalic acid and esters of oxalic acid and metal salts such esters. The metal salts of oxalic acid and oxalic acid esters can be Single, double, mixed and complex salts with one or more of the same or different, ionic, covalently or complexly bound metals act. The metal oxalates, basic metal oxalates and Metal salts of oxalic acid esters can contain any metal. Especially metals of the first, second and third main groups of the Periodic Table. Aluminum, magnesium and / or are very particularly suitable Lithium salts and mixed forms of these salts. Such metal oxalates and basic Metal oxalates are generally known and in the literature, for example in "Ullmanns Encyclopedia of Technical Chemistry ", 4th ed., Vol. 17, Verlag Chemie, Weinheim, 1979, p. 480 ff.

Metal oxalate compounds which can preferably be used according to the invention are described below under component D.

According to a preferred embodiment of the invention, a Impact-modified polycarbonate composition provided in addition to the Metal oxalate compound as a flame retardant containing phosphorus, such as an oligophosphate contains further flame retardants. By combining the two Flame retardant is a particularly good property profile Obtained polycarbonate composition.

The impact-modified polycarbonate compositions according to the invention, can in addition to the previously described metal oxalate compounds thermoplastic polymers, especially polyester carbonates, polyesters, Contain graft polymers and vinyl (co) polymers. These components and others in components that can be used in these compositions according to the invention explained below as an example.

Component A

The composition according to the invention contains polycarbonate and / or Polyester carbonate, preferably aromatic polycarbonate and / or polyester carbonate. Aromatic polycarbonates and / or aromatic suitable according to the invention Polyester carbonates according to component A are known from the literature or according to processes known from the literature, such as phase interface or melt polymerization processes producible (for the production of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and the DE-AS 14 95 626, DE-A 22 32 877, DE-A 27 03 376, DE-A 27 14 544, DE-A 30 00 610, DE-A 38 32 396; for the production of aromatic polyester carbonates, e.g. B. DE-A 30 77 934).

The production of aromatic polycarbonates takes place e.g. B. by implementing Diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably Benzene dicarboxylic acid dihalides, by the interfacial process, optionally using of chain terminators, for example monophenols and optionally under Use of trifunctional or more than trifunctional branches, for example triphenols or tetraphenols.

Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)


in which
A is a single bond, C ₁ to C ₅ alkylene, C ₂ to C ₅ alkylidene, C ₅ to C ₆ cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₂ -, C ₆ to C ₁₂ aryls, to which further aromatic rings optionally containing heteroatoms can be condensed,
or a radical of the formula (II) or (III)


B in each case C ₁ to C ₁₂ alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
x each independently of the other 0, 1 or 2,
p are 1 or 0, and
R ⁵ and R ^{6 can be} selected individually for each X ¹ , independently of one another hydrogen or C ₁ to C ₆ alkyl, preferably hydrogen, methyl or ethyl,
X ¹ carbon and
m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X ¹ , R ⁵ and R ^{6 are} simultaneously alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C ₁ -C ₅ alkanes, bis (hydroxyphenyl) -C ₅ -C ₆ cycloalkanes, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and α, α-bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4- Bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and its di- and tetrabrominated or chlorinated Derivatives such as 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. 2,2-Bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.

The diphenols can be used individually or as any mixtures. The diphenols are known from the literature or by processes known from the literature available.

Suitable for the production of thermoplastic, aromatic polycarbonates Chain terminators are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 28 42 005 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 of Chain terminators to be used are generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.

The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M _w , measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 15,000 to 80,000.

The thermoplastic, aromatic polycarbonates can in a known manner be branched, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, on trifunctional or more than tri-functional compounds, for example those with three and more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. to Production of copolycarbonates according to component A according to the invention can also be 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount Diphenols to be used, polydiorganosiloxanes with hydroxyaryloxy end groups be used. These are known (US 3,419,634) and according to the literature Process can be produced. The production of polydiorganosiloxane-containing copolycarbonates is described in DE-A 33 34 782.

In addition to the bisphenol A homopolycarbonates, preferred polycarbonates are Copolycarbonates of bisphenol-A with up to 15 mol%, based on the Molar sums of diphenols, other than those mentioned as preferred or particularly preferred Diphenols, especially 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Aromatic dicarboxylic acid dihalides for the production of aromatic Polyester carbonates are preferably the diacid dichlorides of isophthalic acid, Terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

Mixtures of the diacid dichlorides of isophthalic acid and of terephthalic acid in a ratio between 1:20 and 20: 1.

In the production of polyester carbonates, an additional Carbonic acid halide, preferably phosgene, is used as a bifunctional acid derivative.

In addition to the monophenols already mentioned, the chain terminators for the preparation of the aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by C ₁ to C ₂₂ alkyl groups or by halogen atoms, and aliphatic C ₂ to C ₂₂ monocarboxylic acid chlorides into consideration.

The amount of chain terminators is 0.1 to 10 mol%, based on the case the phenolic chain terminator on mol diphenol and in the case of Monocarboxylic acid chloride chain terminator on moles of dicarboxylic acid dichloride.

The aromatic polyester carbonates can also be aromatic Hydroxycarboxylic acids included.

The aromatic polyester carbonates can be linear as well as known Be branched (see DE-A 29 40 024 and DE-A 30 07 934).

Trifunctional or multifunctional, for example, can be used as branching agents Carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarbonate acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on Dicarboxylic acid dichlorides used) or trifunctional or multifunctional phenols, such as Phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-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) phenylmethane, 2,2-bis [4,4-bis (4- hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, Tetra (4-hydroxyphenyl) methane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, Tetra- (4- [4-hydroxyphenyl-isopropyl] -phenoxy) -methane, 1,4-bis [4,4'-dihydroxytriphenyl) methyl] benzene, used in amounts of 0.01 to 1.0 mol% based on the diphenols used become. Phenolic branching agents can be introduced with the diphenols, Acid chloride branching agents can be used together with the acid dichlorides be entered.

In the thermoplastic, aromatic polyester carbonates, the proportion of Vary carbonate structural units as desired. The proportion is preferably Carbonate groups up to 100 mol%, in particular up to 80 mol%, particularly preferred up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and carbonate content of the aromatic polyester carbonates can be in the form of blocks or statistically distributed in the polycondensate.

The relative solution viscosity (Urel) of the aromatic polycarbonates and Polyester carbonates are in the range 1.18 to 1.4, preferably 1.20 to 1.32 (measured on Solutions of 0.5 g polycarbonate or polyester carbonate in 100 ml methylene chloride Solution at 25 ° C).

The thermoplastic, aromatic polycarbonates and polyester carbonates can used alone or in any mixture.

Component A can in the compositions according to the invention in a Amount of preferably 20 to 95 parts by weight, particularly preferably 30 to 90 parts by weight and most preferably 40 to 80 parts by weight, be included.

Component B

As an impact modifier B, the composition according to the invention can preferably be one or more graft polymers of
B.1 5 to 95, preferably 20 to 90 wt .-%, of at least one vinyl monomer
B.2 95 to 5, preferably 80 to 10% by weight of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C
contain.

The graft base B.2 generally has an average particle size (d ₅₀ value) of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm.

Monomers B.1 are preferably mixtures of
B.1.1 50 to 99 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) alkyl esters (such as methyl methacrylate , Ethyl methacrylate) and
B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide).

Preferred monomers B.1.1 are selected from at least one of the monomers Styrene, α-methylstyrene and methyl methacrylate are preferred monomers B.1.2 selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.

Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.

Examples of graft bases B.2 suitable for the graft polymers B are Diene rubbers, EP (D) M rubbers, i.e. those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / Vi acetate rubbers. Likewise, composites from various of the above are Rubbers are suitable as a graft base.

Preferred graft bases B.2 are diene rubbers (e.g. based on butadiene, Isoprene) or mixtures of diene rubbers or copolymers of Diene rubbers or their mixtures with other copolymerizable monomers (e.g. according to B.1.1 and B.1.2), with the proviso that the glass transition temperature of the Component B.2 below <10 ° C, preferably <0 ° C, particularly preferred <-10 ° C.

Pure polybutadiene rubber is particularly preferred.

Particularly preferred polymers B are z. B. ABS polymers (emulsion, Mass and suspension ABS), such as z. B. in DE-A 20 35 390 (= US-PS 3 644 574) or in DE-A 22 48 242 (= GB-PS 1 409 275) or in Ullmanns, Encyclopedia of Technical Chemistry, Vol. 19 (1980), p. 280 ff. The The gel fraction of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).

The graft copolymers B are by radical polymerization, for. B. by Emulsion, suspension, solution or bulk polymerization, preferably by Emulsion or bulk polymerization.

Particularly suitable graft rubbers are also ABS polymers that pass through Redox initiation with an initiator system made of organic hydroperoxide and Ascorbic acid can be prepared according to US Pat. No. 4,937,285.

As is known, in the grafting reaction the grafting monomers are not necessarily are completely grafted onto the graft base, are according to the invention under Graft polymers B also understood such products as (Co) polymerization of the graft monomers in the presence of the graft base and incurred during processing.

Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers made from acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C ₁ to C ₈ alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C ₁ -C ₈ alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.

Monomers with more than one polymerizable can be used for crosslinking Double bond can be copolymerized. Preferred examples of crosslinking monomers are Esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH Groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also Triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, Ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three have ethylenically unsaturated groups.

Cyclic monomers are particularly preferred crosslinking monomers Triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The The amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 up to 2% by weight, based on the graft base B.2.

For cyclic crosslinking monomers with at least three ethylenic unsaturated groups, it is advantageous to reduce the amount to less than 1% by weight of the graft base B.2 limit.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base B.2 are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C ₁ - C ₆ alkyl ethers, 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 include silicone rubbers graft-active sites, as described in DE-A 37 04 657, DE-A 37 04 655, DE-A 36 31 540 and DE-A 36 31 539 can be described.

The gel content of the graft base B.2 is at 25 ° C in a suitable Solvent determined (M. Hoffmann, H. Krömer, R. Kuhn, polymer analysis I and II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d ₅₀ is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).

Component B can in the compositions according to the invention in a Amount of preferably 1 to 40 parts by weight, particularly preferably 2 to 30 parts by weight and most preferably 3 to 25 parts by weight his.

Component C

The composition according to the invention can be a further component C or several thermoplastic vinyl (co) polymers C.1 and / or Contain polyalkylene terephthalates C.2.

Suitable vinyl (co) polymers C.1 are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C ₁ to C ₈ ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. (Co) polymers of are particularly suitable
C.1.1 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics such as, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) - Alkyl esters such as methyl methacrylate, ethyl methacrylate), and
C.1.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert .-Butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide).

The (co) polymers C.1 are resinous, thermoplastic and rubber-free.

The copolymer of C.1.1 styrene and C.1.2 acrylonitrile is particularly preferred. The (co) polymers according to C.1 are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have average molecular weights M _w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.

The polyalkylene terephthalates of component C.2 are reaction products aromatic dicarboxylic acids or their reactive derivatives, such as Dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic Diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90 wt .-%, based on the dicarboxylic acid component Terephthalic acid residues and at least 80 wt .-%, preferably at least 90 mol%, based on the diol component ethylene glycol and / or 1,4-butanediol radicals.

The preferred polyalkylene terephthalates can besides terephthalic acid residues to 20 mol%, preferably up to 10 mol%, residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic Contain dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, Isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.

The preferred polyalkylene terephthalates can in addition to ethylene glycol or 1,4-butanediol residues up to 20 mol%, preferably up to 10 mol%, other aliphatic Diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms included, e.g. B. residues of 1,3-propanediol, 2-1,3-propanediol, neopentylglycol, Pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2,4, 2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2- 1,3-diethyl propanediol, 2,5-hexanediol, 1,4-di (β-hydroxyethoxy) benzene, 2,2-bis (4- hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (4-β-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-A 24 07 674, 24 07 776, 27 15 932).

The polyalkylene terephthalates can be tri-or by incorporation of relatively small amounts tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. B. according DE-A 19 00 270 and US-PS 3,692,744 can be branched. Examples more preferred Branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and Pentaerythritol.

Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred and their reactive derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures thereof Polyalkylene.

Preferred mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.

The preferred polyalkylene terephthalates generally have an intrinsic 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 an Ubbelohde viscometer.

The polyalkylene terephthalates can be prepared by known methods (e.g. Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Munich 1973).

Component C can in the compositions according to the invention in a Amount of preferably 0 to 30 parts by weight, particularly preferably up to 25 parts by weight, and most preferably up to 20 parts by weight, based on the mass of the composition.

Component D

Any preferred metal oxalates and / or come as preferred oxalate compounds D. any basic metal oxalates can be used.

The preparation and properties of such compounds are known to the person skilled in the art known and described for example in US-A 5 075 472.

A metal oxalate compound of the general formula is preferred

M ¹ _{x (1)} M ² _{x (2)} . , , M ⁿ _{x (n)} (OH) _a (C ₂ O ₄ ) _b

used, where n is a running index and M ¹ , M ² to M ⁿ for the same or different metals of the same or different valence, the variable b for any number> 0 and the variables a and x (1) to x (n) for any number 0, whereby at least one of the variables x (1) to x (n) has a value> 0.

M ¹ to M ⁿ are preferably selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, Al, Ga, In and Tl. In particular, M ¹ to M ⁿ selected from the group consisting of Al, Mg and Li. M ¹ to M ^{n are} preferably Al ³⁺ and / or Mg ²⁺ ions.

The ratio 2b / (a + 2b) is preferably an arbitrary number from 0.1 to 1, especially any number from 0.2 to 0.5.

The metal oxalate compound is preferably a compound of the aforementioned formula with M ¹ = Al, x (1) = 1, x (2) to x (n) = 0, a = 2 and b = 0.5.

Metal oxalate compounds which can be used according to the invention are, for example, the aluminum hydroxide-lithium oxalate compounds of the general formula described in US Pat. No. 5,075,472

[Al ₂ (OH) ₆ ] X - [Li ₂ C ₂ O ₄ ],

where X is any number from 0.1 to 1. In particular, the substances mentioned in the exemplary embodiments of this publication are suitable for use in the composition according to the invention. With regard to the production and properties of the aluminum hydroxide-lithium oxalate compounds, reference is expressly made to US Pat. No. 5,075,472, the content of which is incorporated into the present application.

The metal oxalate compound preferably has a particle size of 0.05 to 50 µm, in particular 0.1 to 20 µm, particularly preferably 0.2 to 10 µm.

The oxalate compound, in particular the metal oxalate or the metal hydroxyoxalate, is also preferably a compound that is dynamic in the nitrogen stream of 50 ml / min with a heating rate of 10 K / min thermogravimetric analysis at a temperature of 300 ° C less than 5% by weight Mass loss shows.

According to a further preferred embodiment of the invention, the Oxalate compound, especially the metal oxalate or metal hydroxy oxalate, a Connection that occurs under the above conditions in the temperature interval of 300 ° C decomposes to 600 ° C with the release of at least 30 wt .-%, preferably of at least 40% by weight of the net mass of gases, in particular non-combustible Gases.

Oxalate compounds which can be used according to the invention are, for example Magnesium oxalate and oxalate-modified aluminum hydroxide (basic aluminum oxalate).

The metal oxalate compound is in the composition in an amount of 0.1 to 5 parts by weight, preferably from 0.1 to 4 parts by weight, particularly preferably from 0.3 to 3 parts by weight, most preferably 0.3 to 2 parts by weight, maximum preferably contain from 0.5 to 2 parts by weight.

Component E

The compositions may contain other flame retardants. exemplary are halogen compounds, in particular based on Chlorine and bromine and compounds containing phosphorus are mentioned. Are suitable also silicon-based compounds such as silicones or (alumino) silicates.

The compositions preferably contain phosphorus-containing flame retardants from the groups of the mono- and oligomeric phosphoric and phosphonic acid esters, Phosphonatamines and phosphazenes, including mixtures of several Components selected from one or different of these groups as Flame retardants can be used. Others not specifically mentioned here Phosphorus compounds can be used alone or in any combination with others Flame retardants are used.

Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IV)


wherein
R ¹ , R ² , R ³ and R ⁴ , independently of one another in each case optionally halogenated C ₁ to C ₈ alkyl, each optionally substituted by alkyl, preferably C ₁ to C ₄ alkyl, and / or halogen, preferably chlorine, bromine C ₅ to C ₆ cycloalkyl, C ₆ to C ₂₀ aryl or C ₇ to C ₁₂ aralkyl,
n independently of one another, 0 or 1
q 0 to 30 and
X is a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms, or a linear or branched aliphatic radical having 2 to 30 carbon atoms, which can be OH-substituted and can contain up to 8 ether bonds.

R ¹ , R ² , R ³ and R ⁴ are preferably independently of one another C ₁ to C ₄ alkyl, phenyl, naphthyl or phenyl-C ₁ -C ₄ alkyl. The aromatic groups R ¹ , R ² , R ³ and R ⁴ can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C ₁ to C ₄ alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.

X in the formula (IV) preferably denotes a mononuclear or polynuclear aromatic radical having 6 to 30 C atoms. This is preferably derived from diphenols of the formula (I).
n in the formula (IV), independently of one another, can be 0 or 1, preferably n is 1.
q stands for values from 0 to 30. When mixtures of different components of the formula (N) are used, mixtures with number-average q values of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6, most preferably 0.9 to 1.3 are used.
X particularly preferably stands for


or their chlorinated or brominated derivatives, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A.

Particularly preferred compounds containing phosphorus are compounds of the formula (IVa)


in which
R ¹ , R ² , R ³ , R ⁴ and n have the meaning given for the formula (IV),
m independently of one another 0, 1, 2, 3 or 4, preferably 0, 1 or 2,
R ⁵ and R ⁶ independently of one another are C ₁ to C ₄ alkyl, preferably methyl or ethyl and
q is 0.9 to 2, preferably 0.9 to 3 and particularly preferably 1 to 2.

As component C according to the invention, monophosphates (q = O), Oligophosphates (q = 1-30) or mixtures of mono- and oligophosphates can be used.

Monophosphorus compounds of the formula (IV) are in particular tributyl phosphate, Tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, triphenyl phosphate, Tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, Diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted Aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphate, Phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide.

The phosphorus compounds according to component C. Formula (IV) are known (cf. z. B. EP-A 0 363 608, EP-A 0 640 655) or can be in accordance with known methods in an analogous manner (e.g. Ullmann's encyclopedia of industrial chemistry, Vol. 18, pp. 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12 / l, P. 43; Beilstein Vol. 6, p. 177).

The mean q values can be determined by using a suitable method (Gas Chromatography (GC), High Pressure Liquid Chromatography (HPLC), Gel Permeation Chromatography (GPC)) the composition of the phosphate mixture (Molecular weight distribution) is determined and from this the mean values for q be calculated.

Phosphonatamines are preferably compounds of the formula (V)

A _3-y -NB ¹ _y (V)

in which
A for a residue of the formula (Va)


stands,
R ¹¹ and R ¹² independently of one another represent unsubstituted or substituted C ₁ to C ₁₀ alkyl or unsubstituted or substituted C ₆ to C ₁₀ aryl,
R ¹³ and R ¹⁴ independently of one another represent unsubstituted or substituted C ₁ to C ₁₀ alkyl or unsubstituted or substituted C ₆ to C ₁₀ aryl or
R ¹³ and R ¹⁴ together represent unsubstituted or substituted C ₃ to C ₁₀ alkylene,
y are the numerical values 0, 1 or 2 and
B ¹ independently represents hydrogen, optionally halogenated C ₂ to C ₈ alkyl, unsubstituted or substituted C ₆ to C ₁₀ aryl.
B ¹ preferably independently represents hydrogen, represents ethyl, n- or iso-propyl, which may be substituted by halogen, unsubstituted or C ₆ to C ₁₀ aryl, in particular phenyl or substituted by C ₁ to C ₄ alkyl and / or halogen naphthyl.

Alkyl in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently preferably represents methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl.

Substituted alkyl in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently preferably represents C ₁ to C ₁₀ alkyl substituted by halogen, in particular mono- or di-substituted methyl, ethyl, n-propyl, iso-propyl, n- , iso-, sec- or tert-butyl, pentyl or hexyl.

C ₆ to C ₁₀ aryl in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently independently preferably represent phenyl, naphthyl or binaphthyl, in particular o-phenyl, o-naphthyl, o-binaphthyl, which is substituted by halogen (generally a , two or three times) can be substituted.

R ¹³ and R ¹⁴ together with the oxygen atoms to which they are directly attached and the phosphorus atom can form a ring structure.

The following are mentioned by way of example and preferably: 5,5,5 ', 5', 5 ", 5" -hexamethyltris (1,3,2-dioxaphosphorinane-methane) amino-2,2 ', 2 "-trioxide of the formula (Va 1)


(Trial product XPM 1000 from Solutia Inc., St. Louis, USA) 1,3,2-dioxaphosphorinan-2-methanamine, N-butyl-N [(5,5-dimethyl-1,3,2-dioxaphosphorinan-2 -yl) methyl] -5,5-dimethyl-, P, 2-dioxide; 1,3,2-dioxaphosphorinane-2-methanamine, N - [[5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl) methyl] -5,5-dimethyl-N-phenyl-, P, 2-dioxide; 1,3,2-dioxaphosphorinan-2-methanamine, N, N-dibutyl-5,5-dimethyl-, 2-oxide, 1,3,2-dioxaphosphorinan-2-methanimine, N - [(5,5-dimethyl -1,3,2-dioxaphosphorinan-2-yl) methyl] -N-ethyl-5,5-dimethyl-, P, 2-dioxide, 1,3,2-dioxaphosphorinan-2-methanamine, N-butyl- N - [(5,5-dichloromethyl-1,3,2-dioxaphosphorinan-2-yl) methyl] -5,5-di-chloromethyl-, P, 2-dioxide, 1,3,2-dioxaphosphorinan-2 -methanamine, N - [(5,5-di-chloromethyl-1,3,2-dioxoaphosphorinan-2-yl) methyl] -5,5-di-chloromethyl-N-phenyl-, P, 2-dioxide; 1,3,2-dioxaphosphorinane-2-methanamine, N, N-di- (4-chlorobutyl) -5,5-dimethyl-2-oxide; 1,3,2-dioxaphosphorinan-2-methanimine, N - [(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl) methane] -N- (2-chloroethyl) -5,5-di (chloromethyl) -, P2 dioxide.

Also preferred are:
Compounds of formula (Va-2) or (Va-3)




wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 have} the meanings given above.

Compounds of the formulas (Va-2) and (Va-1) are particularly preferred.

The preparation of the phosphonate amines is described, for example, in US Pat. No. 5,844,028 described.

Phosphazenes are compounds of the formulas (VIa) and (VIb)


wherein
R is in each case identical or different and for amino, in each case optionally halogenated, preferably halogenated with C ₁ to C ₈ alkyl, or C ₁ to C ₈ alkoxy, in each case optionally with alkyl, preferably C ₁ to C ₄ alkyl, and / or halogen, preferably chlorine and / or bromine, substituted C ₅ to C ₆ cycloalkyl, C ₆ to C ₂₀ aryl, preferably phenyl or naphthyl, C ₆ to C ₂₀ aryloxy, preferably phenoxy, naphthyloxy, or C ₇ to C. ₁₂ - aralkyl, preferably phenyl-C ₁ -C ₄ -alkyl,
k represents 0 or a number from 1 to 15, preferably a number from 1 to 10.

Examples include propoxyphosphazen, phenoxyphosphazen, Methylphenoxyphosphazen, Aminophosphazen and fluoroalkylphosphazenes called. Especially phenoxyphosphazene is preferred.

The phosphazenes can be used alone or as a mixture. The rest R can always be the same or can have 2 or more radicals in the formulas (Ia) and (Ib) to be different.

Phosphazenes and their preparation are described, for example, in EP-A 0 728 811, DE-A 19 61 668 and WO 97/40092.

The flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants.

Component E can in the composition according to the invention in a Amount of preferably 0.5 to 30 parts by weight, particularly preferably 1 to 25 parts by weight Parts, and most preferably 2 to 20 parts by weight.

Component F

The flame retardant (s) used according to the invention can be used in Combination with so-called anti-dripping agents can be used, which the Reduce the tendency of the material to drip in the event of fire. exemplary here are compounds of the substance classes of fluorinated polyolefins, the Silicones and aramid fibers called. These can also in the invention Compositions are used. Fluorinated polyolefins are preferred used as an anti-dripping agent.

Fluorinated polyolefins are known and for example in EP-A 0 640 655 described. They are marketed by DuPont under the Teflon® 30N brand.

The fluorinated polyolefins can be either in pure form or in the form of a coagulated mixture of emulsions of fluorinated polyolefins with emulsions the graft polymer (component B) or with an emulsion of a Copolymers, preferably based on styrene / acrylonitrile, which fluorinated polyolefin as an emulsion with an emulsion of the graft polymer or Copolymer is mixed and then coagulated.

The fluorinated polyolefins can also be used as a precompound with the Graft polymer (component B) or a copolymer, preferably on Styrene / acrylonitrile base. The fluorinated polyolefins are powdered with a powder or granules of the graft polymer or copolymer are mixed and in the melt generally at temperatures of 200 to 330 ° C in usual units such as internal kneaders, extruders or twin-shaft screws compounded.

The fluorinated polyolefins can also be used in the form of a masterbatch be by monoethylene by emulsion polymerization unsaturated monomer in the presence of an aqueous dispersion of the fluorinated Polyolefins is produced. Preferred monomer components are styrene, Acrylonitrile and mixtures thereof. The polymer is after acidic precipitation and subsequent drying used as a free-flowing powder.

The coagulates, pre-compounds or masterbatches usually have Solids contents of fluorinated polyolefin from 5 to 95% by weight, preferably 7 to 70% by weight.

For example, fluorinated polyolefins can be used in the compositions in amounts from 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, and particularly preferably 0.1 to 0.5 parts by weight may be included.

G Other additives

The compositions according to the invention can also contain at least one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, antistatic agents, stabilizers, for example those based on phosphite, fillers and reinforcing materials such as glass or carbon fibers, talc, wollastonite, mica, kaolin, CaCO ₃ and glass scales as well as dyes and pigments.

The compositions according to the invention can furthermore have very fine particles contain inorganic powders, as described, for example, in US Pat. No. 5,849,827 are.

All parts by weight in this document are standardized so that the sum of the Parts by weight of all components in the composition are 100.

The compositions of the invention are prepared by the each constituent mixed in a known manner and at temperatures of 200 ° C to 300 ° C in common units such as internal kneaders, extruders and Twin-shaft screws melt-compounded and melt-extruded.

The mixing of the individual components can both in a known manner successively and simultaneously, both at about 20 ° C. (Room temperature) as well as at a higher temperature.

The compositions according to the invention can be used to produce Shaped bodies of any kind can be used. These can be done by injection molding, extrusion and Blow molding process can be produced. Another form of processing is Production of molded articles by deep drawing from previously produced plates or Films.

Examples of such moldings are foils, profiles, housing parts of any kind, for. B. for Household appliances such as juicers, coffee machines, mixers; for office machines like Notebooks, telecommunications equipment, monitors, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the Construction sector (interior and exterior applications) as well as electrical and electronic parts like switches, plugs and sockets.

In particular, the compositions according to the invention can also be used, for example, for the production of the following moldings or moldings:
Interior components for rail vehicles, ships, airplanes, buses and other motor vehicles, exterior body parts in the motor vehicle sector, housings for electrical devices containing small transformers, housings for devices for information processing and transmission, housings and casings for medical devices, massagers and housings therefor toy vehicles for children, planar Wall elements, housings for safety devices, heat-insulated transport containers, devices for keeping or supplying small animals, molded parts for sanitary and bathroom equipment, cover grilles for ventilation openings, molded parts for garden and tool sheds, housings for garden tools, garden and camping items.

The invention further relates to the use of oxalate compounds, in particular those selected from the group consisting of metal oxalates, basic Metal oxalates (metal hydroxy oxalates), oxalic acid esters and metal salts of Oxalic acid esters for the flame-retardant finishing of impact-modified polycarbonate and / or polyester carbonate compositions.

• a) eine Reduktion der Nachbrennzeiten in normgerechten Flammwidrigkeitstests wie beispielsweise solchen nach UL 94V oder UL 945V und/oder
• b) eine Reduktion der Neigung zum Abtropfen brennenden Materials und/oder
• c) eine Reduktion der Neigung zur Lochbildung in flächigen Prüfkörpern unter Einwirkung externer Zündquellen und/oder
• d) eine Verringerung der Flammenausbreitungsgeschwindigkeit im Brandfall und/oder
• e) eine Reduktion der Wärmefreisetzung im Brandfall und/oder
• f) eine Reduktion der Rauchdichte im Brandfall.

Flame-retardant equipment in the sense of this invention means in particular:

• a) a reduction in the afterburning times in standardized flame retardancy tests such as those according to UL 94V or UL 945V and / or
• b) a reduction in the tendency to drip burning material and / or
• c) a reduction in the tendency to form holes in flat test specimens under the influence of external ignition sources and / or
• d) a reduction in the rate of flame spread in the event of fire and / or
• e) a reduction in the release of heat in the event of fire and / or
• f) a reduction in smoke density in the event of a fire.

The following examples serve to further explain the invention.

Examples A. Preparation and characterization of the oxalate compounds I. Magnesium oxalate

Magnesium oxalate was produced by reacting an aqueous dispersion of magnesium hydroxide VI (e.g. Magnifin® H10 from Martinswerk GmbH, Bergheim, Germany) with a stoichiometrically equivalent amount of one 8.2% aqueous oxalic acid solution. After adding the oxalic acid solution to the aqueous Mg (OH) 2 dispersion was stirred for 24 hours at room temperature, the Solid subsequently filtered off and at 50 ° C. in vacuo to constant mass dried. Magnesium oxalate hydrate VII was obtained.

Magnesium oxalate dihydrate VIII is a commercial product from Dr. Paul Lohmann GmbH, Emmerthal, Germany.

By calcining the magnesium oxalate hydrate VII at 250 ° C for 4 hours in The magnesium oxalate I was obtained in a forced air oven Magnesium oxalate from the Prepare magnesium oxalate dihydrate VIII.

II. Oxalate modified aluminum hydroxide

A product commercially available from Alcoa Industrial Chemicals, Bauxite, USA, under the name "BAO 10", was used (II). Table 1 Properties of the oxalate compounds

B. Preparation and testing of polymer compositions

According to the information in Table 2, polycarbonate compositions 1 to 3 (according to the invention) and V1 to V3 (comparison) produced, to test specimens processed and checked.

The individual components were compounded on a ZSK-25 at 240 ° C. The Test specimens were placed on an Arburg 270 E injection molding machine at 240 ° manufactured.

Component A

Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.24, measured in CH ₂ Cl ₂ as a solvent at 25 ° C and a concentration of 0.5 g / 100 ml.

Component B

Graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d ₅₀ = 0.3 μm), produced by emulsion polymerization.

Component C

Styrene / acrylonitrile copolymer with a styrene / acrylonitrile weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).

Component D.1

Basic aluminum oxalate BAO10 from ALCOA Industrial Chemicals, Bauxite, USA.

Component D.2

Talk: Naintsch® A3 (Naintsch Mineralwerke GmbH, Graz, Austria)

Component E

Bisphenol A based oligophosphate of the formula

Component F

Tetrafluoroethylene polymer as a coagulated mixture of a SAN graft polymer emulsion according to component B mentioned above in water and a tetrafluoroethylene polymer emulsion in water. The weight ratio of graft polymer B to tetrafluoroethylene polymer E in the mixture is 90% by weight to 10% by weight. The tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the average particle diameter is between 0.05 and 0.5 μm. The SAN graft polymer emulsion has a solids content of 34% by weight and an average latex particle diameter of d ₅₀ = 0.3 μm.

The emulsion of the tetrafluoroethylene polymer (Teflon® 30 N) is mixed with the emulsion of the SAN graft polymer B and stabilized with 1.8% by weight, based on polymer solids, of phenolic antioxidants. At 85 to 95 ° C the mixture is coagulated with an aqueous solution of MgSO ₄ (Epsom salt) and acetic acid at pH 4 to 5, filtered and washed until practically free of electrolytes, then freed from the main amount of water by centrifugation and then at 100 ° C dried to a powder.

Component G1

Pentaerythritol tetrastearate (PETS) as a mold release agent

Component G2

phosphite

Testing the compositions according to the invention

The weld line strength was determined in accordance with ISO 179 / 1eU by a Impact strength determination at the weld line of double-molded Test specimens measuring 80 mm × 10 mm × 4 mm.

The melt viscosity was determined at 260 ° C. and a shear rate of 1,000 s ^{-1 in} accordance with DIN 54811.

The heat resistance according to Vicat B 120 was determined in accordance with DIN 53 460 (ISO 306) on rods measuring 80 mm × 10 mm × 4 mm.

The stress crack behavior (ESC behavior) was measured on bars of dimension 80 mm × 10 mm × 4 mm examined. A mixture of was used as the test medium 60 vol .-% toluene and 40 vol.% Isopropanol used. The test specimens were pre-stretched using a circular arc template (εx = pre-stretching in percent) and at Room temperature stored in the test medium. The stress crack behavior was over the cracking or breaking depending on the pre-stretch in the Test medium assessed.

The impact strength (a _k ) is determined in accordance with ISO 180 / 1A at 23 ° C. The test rods are hosed down at 240 ° C.

The fire behavior of the samples was determined according to UL 94V on rods with a thickness of 1.2 mm measured.

A summary of the properties of the compositions according to the invention or molded articles obtained therefrom is shown in Table 2. Table 2 Composition and properties of the polymer compositions

The results show that Example 1 according to the invention containing 0.5% by weight oxalate compound, in comparison to comparative example V1 without oxalate Add a significantly better ESC behavior, a significantly improved Total afterburn time in the UL 94 V test at 1.2 mm wall thickness, better weld line strength with comparable good processing properties (melt viscosity) and Has heat resistance (Vicat B 120).

Comparative examples V2 and V3 differ from the invention Example 2 by using talc as an FR synergist instead of the oxalate compound contain. The examples according to the invention show comparable behavior regarding flame retardancy, ESC behavior, heat resistance and Flowability, but they have a significantly better weld line strength.

A comparison of Example 2 with Comparative Example 1 shows that by adding 2% by weight of the oxalate compound according to the invention not only the afterburn time in the UL 94 V test, but also reduces the tendency of the molding compounds to drip this fire test can be prevented (rating V-0 instead of V-2) and at the same time with unchanged good heat resistance and flowability of the Melt an improved ESC behavior and an improved weld line strength is realized.

Comparing Examples 1 and 2 according to the invention with Comparative Example 3 it follows that the amounts of oxalate according to the invention (0.5 and 2.0 parts by weight) Impact properties of the test specimens not or hardly influenced negatively the positive effects on the weld line strength and that ESC behavior can already be observed.

C. Flame retardant finish with oxalate compounds impact modified polycarbonate compositions Example 3 / Comparative Example 5

Example 3 illustrates the use of oxalate compounds for flame-retardant finishing of impact-modified polycarbonate compositions, which represents another aspect of the invention.

80 parts by weight of the commercially available PC / ABS blend Bayblend® T 85 (Bayer AG, Leverkusen, Germany) were with 20 parts by weight of magnesium oxalate Substance I in Table 1 melt-compounded in a 50 g internal kneader at 220 ° C., the cooled molding compound is granulated and then at 200 ° C. to form a press plate (10 cm × 10 cm) with a thickness of 2 mm. One on the same served as a comparison Pressed plate made in this way from the Bayblend® T 85 (comparative example 5). The Melt volume index (MVR at 260 ° C / 5 kg) was in the oxalate containing Compound (Example 3, according to the invention) at 12.6 ml / 10 min compared to 20.5 ml / 10 min at Bayblend T 85 (comparative example 5), from which it can be seen that the PC / ABS blend survived the compounding without decomposition. In the Thermogravimetric analysis shows the oxalate-containing composition at 280 ° C a mass loss of about 1 wt .-%, which is about the decomposition of the Oxalate compound I corresponds to its proportion in the molding composition. From this it follows that at the usual processing temperatures of PC / ABS molding compounds Polymers in the oxalate-containing compositions show no signs of decomposition demonstrate.

The press plates were clamped horizontally and from below for 100 seconds with a Flamed according to the UL 94 V test standard flame.

The Bayblend T 85 panel (Comparative Example 5) was initially one surface charring. It finally came during the Flame formation for hole formation. The plate burned up after the external flame was removed to completely destroy the test specimen.

The plate made of the composition containing oxalate (Example 3) occurred superficial foaming and charring, but not pitting. The flame went out without pitting the plate 45 seconds after the external one Ignition source was withdrawn.

Claims (27)

1. Impact-modified polycarbonate and / or Polyester carbonate composition containing at least one oxalate compound selected from the Group consisting of metal oxalates, metal hydroxyoxalates, Oxalic acid esters and metal salts of oxalic acid esters in amounts of 0.5 to 5 Parts by weight (based on 100 parts by weight of the total composition). 2. The composition of claim 1, wherein the oxalate compound is a compound of the general formula

M ¹ _{x (1)} M ² _{x (2)} . , , M ⁿ _{x (n)} (OH) _a (C ₂ O ₄ ) _b

is where n represents a running index and M ¹ , M ² to M ⁿ for the same or different metals of the same or different valence, the variable b for any number> 0 and the variables a and x (1) to x (n) for any number 0, whereby at least one of the variables x (I) to x (n) has a value> 0. 3. The composition of claim 2, wherein M ¹ to M ^{n are} selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, B, Al, Ga, In and Tl. 4. The composition of claim 2, wherein M ¹ to M ^{n are} selected from the group consisting of Al, Mg and Li. 5. A composition according to any one of claims 2 to 4, wherein the ratio 2b / (a + 2b) is any number from 0.1 to 1. 6. A composition according to any one of claims 2 to 4, wherein the ratio 2b / (a + 2b) is any number from 0.2 to 0.5. 7. The composition of claim 2, wherein x (1) = 1, x (2) to x (n) = 0, M ¹ = Al, a = 2 and b = 0.5. 8. The composition according to any one of the preceding claims, wherein the Oxalate compound is contained in an amount of 0.1 to 4 parts by weight, where the sum of the parts by weight of the components in the Composition 100 results. 9. The composition of claim 8, wherein the oxalate compound in one Amount of 0.3 to 3 parts by weight is included. 10. Composition according to one of the preceding claims, containing Polycarbonate in an amount of 20 to 95 parts by weight. 11. The composition according to any one of the preceding claims, containing as Impact modifier at least a graft polymer from 5 to 95 wt .-% of a vinyl monomer to 95 to 5 wt .-% at least one Graft base with a glass transition temperature less than about 10 ° C. 12. The composition of claim 11, wherein the graft polymer such based on diene, EP (D) M, acrylate, silicone or corresponding composite rubbers. 13. The composition according to any one of claims 11 or 12, wherein the Graft polymer is contained in an amount of 1 to 40 parts by weight. 14. Composition according to one of the preceding claims, containing as further component at least one thermoplastic vinyl (co) polymer and / or polyalkylene terephthalate. 15. The composition of claim 14, wherein the thermoplastic vinyl (co) - Polymer and / or polyalkylene terephthalate in an amount of up to 30 parts by weight is included. 16. The composition according to any one of the preceding claims, wherein as another component contains a halogen-free flame retardant. 17. The composition according to claim 16 containing compounds of the formula (IV),


wherein
R ¹ , R ² , R ³ and R ⁴ , independently of one another in each case optionally halogenated C ₁ to C ₈ alkyl, in each case optionally substituted by alkyl and / or halogen C ₅ to C ₆ cycloalkyl, C ₆ to C ₂₀ aryl or C ₇ to C ₁₂ aralkyl,
n independently of one another, 0 or 1
q 0 to 30 and
X is a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms, or a linear or branched aliphatic radical having 2 to 30 carbon atoms, which can be OH-substituted and can contain up to 8 ether bonds. 18. Composition according to claim 17, comprising compounds of the formula (IVa)


in which
R ¹ , R ² , R ³ , R ⁴ and n have the meaning given for the formula (N),
m independently of one another 0, 1, 2, 3 or 4,
R ⁵ and R ^{6 are} independently C ₁ to C ₄ alkyl and
q means 0.9 to 2. 19. The composition of claim 17 or 18, wherein the flame retardant is contained in an amount of 0.5 to 30 parts by weight. 20. The composition according to any one of the preceding claims, wherein as further component fluorinated polyolefin is included. 21. The composition of claim 20, wherein fluorinated polyolefin in one Amount of 0.05 to 5 parts by weight is included. 22. The composition according to any one of the preceding claims, wherein as further component at least one polymer additive selected from sliding and mold release agents, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials as well as dyes and pigments. 23. A method for producing a composition according to one of the Claims 1 to 22, wherein the individual components are mixed together and at temperatures of 200 to 300 ° C in conventional units such as Internal kneaders, extruders and twin-screw extruders melt-compounded become. 24. Use of a composition according to one of claims 1 to 23 for Manufacture of molded articles. 25. Shaped body containing a composition according to one of claims 1 until 22. 26. Shaped body according to claim 25, wherein the shaped body is part of a Motor vehicle, rail vehicle, aircraft or watercraft Housing for a household appliance, an office machine or a Device containing a small transformer, an electrical or electronic part or a plate, a profile or a flat element for a building interior or - outdoor application is. 27. Use of metal oxalate in polycarbonate-containing Compositions to improve weld line strength.