WO2011009877A1

WO2011009877A1 - Flameproofed polyamide molding compounds

Info

Publication number: WO2011009877A1
Application number: PCT/EP2010/060522
Authority: WO
Inventors: Dietrich Scherzer; Matthias Scheibitz; Klaus Uske; Philippe Desbois
Original assignee: Basf Se
Priority date: 2009-07-24
Filing date: 2010-07-21
Publication date: 2011-01-27

Abstract

The invention relates to thermoplastic molding compounds comprising A) 10 to 98.5% by weight of a thermoplastic polyamide, B) 0.5 to 40% by weight of a flameproofing compound comprising phosphorus, C) 1 to 80% by weight of natural fibers, mineral fibers being excepted, D) 0 to 50% by weight of further additives, the sum of the percentages by weight of A) through D) being 100%.

Description

Flame-retardant Polyamide Molding Compositions The invention relates to thermoplastic molding compositions containing

A) 10 to 98.5% by weight of a thermoplastic polyamide,

B) 0.5 to 40% by weight of a phosphorus-containing flame retardant compound,

C) 1 to 80 wt .-% natural fibers, with mineral fibers are excluded, D) 0 to 50 wt .-% of other additives, wherein the sum of the weight percent A) to D) gives 100%.

Furthermore, the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings of any kind, as well as the moldings obtainable in this case.

Thermoplastic polyamides such as PA6 and PA66 are often used in the form of glass fiber reinforced molding materials as construction materials for components that are exposed to elevated temperatures during their life.

Many applications in the E / E sector require flame retardancy, including phosphorus compounds. The use of red phosphorus as a flame retardant is known, for example, from DE-A 39 05 038, DE-A 41 00 740 and DE-A 1 96 48 503, this being usually combined with reinforcing materials, in particular glass fibers, for the necessary mechanical properties. However, glass fibers show the so-called wick effect, i. the fire class deteriorates considerably by the addition of fibers.

A compensation by adding increased amounts of flame retardants usually leads to an influence on the mechanical properties in a negative way and to an increase in the production costs of such molding compositions. Object of the present invention was therefore to provide flame-retardant polyamides which contain renewable raw materials in combination with P-containing flame retardants, which have good flame retardancy, low production costs and good mechanics and should be ecologically better tolerated.

Accordingly, the molding compositions defined above were found. Preferred embodiments are given in the dependent claims. As component A), the molding compositions according to the invention contain 10 to 98.5, preferably 20 to 94 and in particular 20 to 90 wt .-% of at least one polyamide. The polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 1 10 to 240 ml / g, determined in a 0.5% strength solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307th

Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000, e.g. U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred.

Examples of these are polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.

As dicarboxylic acids alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used. Here only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid are mentioned as acids.

Suitable diamines are in particular alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms and m-xylylenediamine, di (4-aminophenyl) methane, di (4-amino-cyclohexyl) methane, 2,2-di (4 -aminophenyl) -propane, 2,2-di (4-aminocyclohexyl) propane or 1, 5-diamino-2-methyl-pentane.

Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also copolyamides 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.

Further suitable polyamides are obtainable from ω-aminoalkyl nitriles such as, for example, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP 922065 described.

In addition, polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide 4,6). Production processes for polyamides of this structure are described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524. Furthermore, polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary. Particular preference is given to mixtures of polyamide 66 with other polyamides, in particular copolyamides 6/66.

Furthermore, such partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).

The production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.

The following non-exhaustive list contains the mentioned, as well as other polyamides A) in the context of the invention and the monomers contained.

AB-polymers:

PA 4 pyrrolidone

PA 6 ε-caprolactam

PA 7 ethanolactam

PA 8 capryllactam

PA 9 9-aminopelargonic acid

PA 1 1 1 1-aminoundecanoic acid

PA 12 laurolactam

AA / BB-polymers

PA 46 tetramethylenediamine, adipic acid

PA 66 hexamethylenediamine, adipic acid

PA 69 hexamethylenediamine, azelaic acid

PA 610 hexamethylenediamine, sebacic acid

PA 612 hexamethylenediamine, decanedicarboxylic acid

PA 613 hexamethylenediamine, undecanedicarboxylic acid

PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid

PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid

PA 6T hexamethylenediamine, terephthalic acid

PA MXD6 m-xylylenediamine, adipic acid

AA / BB-polymers

PA 6I hexamethylenediamine, isophthalic acid

PA 6-3-T trimethylhexamethylenediamine, terephthalic acid

PA 6 / 6T (see PA 6 and PA 6T)

PA 6/66 (see PA 6 and PA 66) PA 6/12 (see PA 6 and PA 12)

PA 66/6/610 (see PA 66, PA 6 and PA 610)

PA 6I / 6T (see PA 6I and PA 6T)

PA PACM 12 diaminodicyclohexylmethane, laurolactam

PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane

PA 12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid

PA 12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid

PA PDA-T phenylenediamine, terephthalic acid

As component B), the thermoplastic molding compositions contain 0.5 to 40, preferably 1 to 30 and in particular 1 to 10 wt .-% of a phosphorus-containing

Flame retardant.

The phosphorus-containing compounds of component B) are organic and inorganic phosphorus-containing compounds in which the phosphorus has the valence state -3 to +5. The term "level of oxidation" should be understood as meaning the term "oxidation state" as used in the textbook of inorganic chemistry by A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, 57th to 70th edition), pages 166 to 177, is reproduced. Phosphorus compounds of valence levels -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphine oxide (-1), elemental phosphorus (+0), hypophosphorous acid (+1), phosphorous acid (+3), Hypodiphosphoric acid (+4) and phosphoric acid (+5).

From the large number of phosphorus-containing compounds, only a few examples are mentioned.

Examples of phosphine-type phosphorus compounds having the valence state -3 are aromatic phosphines such as triphenylphosphine, tritolylphosphine, trinonylphosphine, trinaphthylphosphine and trisnonylphenylphosphine, and the like. Particularly suitable is triphenylphosphine.

Examples of phosphorus compounds of the diphosphine class which have the valence state -2 are tetraphenyldiphosphine, tetranaphthyldiphosphine and the like. Particularly suitable is tetranaphthyldiphosphine.

Phosphorus compounds of valence state -1 are derived from the phosphine oxide. Suitable phosphine oxides of the general formula R ¹

where R ¹ , R ² and R ³ denote identical or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.

Examples of phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisynylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) - phosphine oxide, benzyl bis (cyclohexyl) phosphine oxide, benzyl bisphenyl phosphine oxide, phenyl bis (n-hexyl) phosphine oxide. Also preferred are oxidized reaction products of phosphine with aldehydes, especially from t-butylphosphine with glyoxal. Particular preference is given to using triphenylphosphine oxide, tricyclohexlyphosphine oxide, tris (n-octyl) phosphine oxide and tris (cyanoethyl) phosphine oxide. Also suitable is triphenylphosphine sulfide and its derivatives of phosphine oxides as described above.

Phosphorus compounds of the "oxidation state" +1 are e.g. Hypophosphites of purely organic nature, e.g. organic hypophosphites, such as cellulose hypophosphite esters, esters of hypophosphorous acids with diols, e.g. of 1, 10-dodecyldiol. Also substituted phosphinic acids and their anhydrides, e.g. Diphenylphosphinic can be used. Also suitable are diphenylphosphinic acid, di-p-tolylphosphinic acid, di-cresylphosphinic anhydride, but there are also compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic) - ester u.a. in question. Further suitable are aryl (alkyl) phosphinic acid amides, e.g. Diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, e.g. p-Tolylsulfonamidodiphenylphosphinsäure. Hydroquinone and ethylene glycol bis (diphenylphosphinic) esters and the bis-diphenylphosphinate of hydroquinone are preferably used.

Phosphorus compounds of the oxidation state +3 are derived from the phosphorous acid. Cyclic phosphonates which are derived from pentaerythritol, neopentyl glycol or pyrocatechol, for example, are suitable

where R is a Ci to C4 alkyl radical, preferably methyl, x = 0 or 1 (ammonium gard ^® P 45 from Albright & Wilson).

Further, +3 valence phosphorous is in triaryl (alkyl) phosphites, e.g.

Triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite or phenyldidecyl phosphite and the like. contain. But there are also diphosphites, such. Propylene glycol-1, 2-bis (diphosphite) or cyclic phosphites derived from pentaerythritol, neopentyl glycol or catechol, in question.

Particularly preferred are methyl neopentyl glycol phosphonate and phosphite and dimethyl pentaerythritol diphosphonate and phosphite. As phosphorus compounds of the oxidation state +4, especially hypodiphosphates, such as. Tetraphenyl hypodiphosphate or Bisneopentylhypodiphosphat into consideration.

Suitable phosphorus compounds of the oxidation state +5 are, in particular, alkyl- and aryl-substituted phosphates. Examples are phenylbisdodecylphosphate, phenylethylhydrogenphosphate, phenylbis (3,5,5-trimethylhexyl) phosphate, ethyldiphenylphosphate, 2-ethylhexyldi (tolyl) phosphate, diphenylhydrogenphosphate, bis (2-ethylhexyl) -p-tolylphosphate, tritolylphosphate, bis (2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, p-tolylbis (2,5,5-trimethylhexyl) phosphate or 2-ethylhexyldiphenyl phosphate. Particularly suitable are phosphorus compounds in which each radical is an aryloxy radical. Especially suitable is triphenyl phosphate and resorcinol bis (diphenyl phosphate) and its nucleus-substituted derivatives of the general formula (RDP):

in which the substituents have the following meanings: R ⁴ -R ^{7 is} an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical which may be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl, R ^{8 is} a dihydric phenol radical, preferably

and n an average value between 0.1 to 100, preferably 0.5 to 50, in particular 0.8 to 10 and very particularly 1 to 5.

The commercially available products under the trademark RDP Fyroflex ^® or Fyrol ^® -RDP (Akzo) and CR-S 733 (Daihachi) are due to the manufacturing process, mixtures of about 85% RDP (n = 1) of about 2, 5% triphenyl phosphate and about 12.5% oligomeric portions in which the degree of oligomerization is usually less than 10. Furthermore, cyclic phosphates can also be used. Particularly suitable here is diphenylpentaerythritol diphosphate and phenylneopentyl phosphate.

In addition to the above-mentioned low molecular weight phosphorus compounds are still oligomeric and polymeric phosphorus compounds in question.

Such polymeric, halogen-free organic phosphorus compounds containing phosphorus in the polymer chain are formed, for example, in the preparation of pentacyclic, unsaturated phosphine dihalides, as described, for example, in DE-A 20 36 173. The molecular weight measured by vapor pressure osmometry in dimethylformamide, the Polyphospholinoxide should be in the range of 500 to 7000, preferably in the range of 700 to 2000.

The phosphorus here has the oxidation state -1. Further, inorganic coordination polymers of aryl (alkyl) phosphinic acids such as e.g. Poly-ß-sodium (l) -methylphenylphosphinat be used. Their preparation is given in DE-A 31 40 520. The phosphorus has the oxidation number +1.

Furthermore, such halogen-free polymeric phosphorus compounds by the reaction of a phosphonic acid chloride, such as phenyl, methyl, propyl, styryl and Vinylphosphonsäuredichlorid with bifunctional phenols, such as hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbiphenol-A arise.

Further halogen-free polymeric phosphorus compounds which may be present in the molding compositions according to the invention are prepared by reaction of phosphorus oxide trichloride or phosphoric ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and compounds carrying other hydroxyl groups (see Houben-Weyl- Müller, Thieme-Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)). Furthermore, polymeric phosphonates can be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (cf., DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (cf., US Patent 4,403,075). In question is also the inorganic poly (ammonium phosphate). It can also oligomeric pentaerythritol phosphites, phosphates and phosphonates in accordance with EP-B 8 486, are used as mobile Antiblaze ^® 19 (registered trademark of Mobil Oil).

Preferred components B) are phosphinic acid salts of the formula

1 O

R ¹ \ ll

> -O M

R ^{2 /}

m

and / or diphosphinic acid salts of the formula

where the substituents have the following meaning: R ¹ , R ^{2 is} hydrogen, C 1 - to C ₆ -alkyl which optionally contains a hydroxyl group, preferably C 1 to C ₄ -alkyl, linear or branched, for example methyl, ethyl, n-propyl, iso Propyl, n-butyl, tert -butyl, n -pentyl; phenyl; wherein preferably at least one radical R ¹ or R ² , in particular R ¹ and R ^{2 is} hydrogen; R ³ d- to Cio-alkylene, linear or branched, for example methylene, ethylene, n-

Propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-

dodecene;

Arylene, eg phenylene, naphthylene; Alkylarylene, for example methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene;

Arylalkylene, e.g. Phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene;

M is an alkaline earth, alkali metal, Al, Zn, Fe, boron; m is an integer of 1 to 3; n is an integer of 1 and 3 and x is 1 or 2.

Particular preference is given to compounds of the formula I in which R ¹ and R ^{2 are} hydrogen, where M is preferably Ca, Zn or Al and calcium phosphinate is very particularly preferred as the compound.

Such products are commercially available, for example, as calcium phosphinate. Suitable salts of the formula I or II in which only one radical R ¹ or R ^{2 is} hydrogen are, for example, salts of phenylphosphinic acid, their Na and / or Ca salts being preferred.

Further preferred salts have a hydroxyl-containing alkyl radical R ¹ and / or R ² . These are obtainable, for example, by hydroxymethylation. Preferred compounds are Ca, Zn and Al salts.

The mean particle size (d.sub.50 value) of component B) is preferably less than 10 .mu.m, preferably less than 7 .mu.m and in particular less than 5 .mu.m.

As a rule, a dso value is understood to mean the particle size value at which 50% of the particles have a smaller particle size and 50% have a larger particle size. The dio value is preferably less than 4 μm, in particular 3 μm and very particularly preferably less than 2 μm.

Preferred dgo values are less than 40 μm and in particular less than 30 μm and very particularly preferably less than 20 μm. The particle sizes are generally determined by laser diffraction, at injector pressures greater than 2 bar, preferably greater than 2.5 bar and a gas velocity greater than 100 m / s, preferably greater than 140 m / s. Further preferred are phosphorus compounds of the general formula:

in which the substituents have the following meanings:

R ¹ to R ²⁰ independently of one another hydrogen, a linear or branched alkyl group up to 6 C atoms an average value of 0.5 to 50 and

X is a single bond, C = O, S, SO ₂ , C (CH ₂ ) ₂

Preferred compounds B2) are those in which R ¹ to R ²⁰ independently of one another are hydrogen and / or a methyl radical. In the event that R ¹ to R ²⁰ independently of one another are methyl, those compounds are preferred in which the radicals R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ , R ²⁰ in ortho Position to the oxygen of the phosphate group represent at least one methyl radical. Preference is furthermore given to compounds B2) in which one methyl group is present per aromatic ring, preferably in the ortho position, and the other radicals are hydrogen.

Particularly preferred substituents are SO ₂ and S, and most preferably C (CH ₂ ) ₂ for X in the above formula. n is preferably 0.5 to 5, in particular 0.7 to 2 and in particular "1" as an average value.

The indication of n as an average value results from the preparation of the compounds listed above, so that the degree of oligomerization is usually less than 10 and small amounts (usually <5 wt .-%) of triphenyl phosphate are included, this being different from batch to batch. Compounds B2) are commercially available as CR-741 from Daihachi. Particularly preferred component B) is elemental phosphorus (valence state 0). In question come red and black phosphorus, with red phosphorus is preferred.

Preferred flame retardant (B) is elemental red phosphorus, which can be used in untreated form.

However, particularly suitable are preparations in which the phosphorus is superficial with low molecular weight liquid substances such as silicone oil, paraffin oil or esters of phthalic acid or adipic acid or with polymeric or oligomeric compounds, e.g. coated with phenolic resins or aminoplasts.

A so-called superficial phlegmatization based on polyester polyurethanes or polyurethanes can be found, for example, in DE-A 39 05 038.

Further suitable phlegmatizers are mineral oils, paraffin oils, chloroparaffins, esters of trimellitic acid, preferably of alcohols having from 5 to 10 carbon atoms, such as trioctyl trimellitate, and aromatic phosphate compounds such as, for example, tricresyl phosphate.

Particular preference is given to using esters of phthalic acid as phlegmatizing agents which are obtainable from phthalic acid and alcohols having 6 to 13 carbon atoms. Particularly preferred are dioctyl phthalates, with di-2-ethyl-hexyl phthalate being particularly preferred.

Particular preference is given to coatings which comprise a combination of 0.01 to 2, preferably 0.1 to 1, 5 and in particular 0.4 to 1, 0 wt .-% of a phlegmatizing agent and 2 to 15, preferably 3 to 10 and in particular 4 to 8 wt .-% of a mineral filler.

The percentages by weight of the mineral filler and the Phlegmatisie- agent and the red phosphorus give each 100 wt .-%.

The average particle size (dso) of the phosphor particles distributed in the molding compositions is usually in the range up to 2 mm, preferably from 0.0001 to 0.5 mm. As mineral fillers are preferably calcium or magnesium silicates suitable, with wollastonite and talc are preferred. The average particle size (dso) is usually from 1 to 500 μm.

Such compositions and methods of preparation of component B) can be found in DE-A 1 96 48 503.

In addition, concentrates of phlegmatized phosphorus are e.g. in a polyamide or polyolefin or an elastomer which may have phosphorus contents of up to 60% by weight. Further suitable compounds (often also referred to as salts or adducts) are melamine phosphate prim., Phosphate sec. And pyrophosphate sec, ammonium polyphosphate and polymeric melamine phosphate (CAS No. 56386-64-2).

Particularly preferred melamine is available under the brand Melapur ^® from BASF SE. Preferred phosphorus content is 10-15, in particular 12-14%, the water content is preferably below 0.3% and the specific gravity at 1.83 to 1.86 g / cm ³ .

As component C), the molding compositions according to the invention contain from 1 to 80, preferably from 5 to 50, and in particular from 10 to 35,% by weight of natural fibers, mineral fibers being excluded.

DIN 60001-1: 2001-05 defines natural fibers as "natural, linear structures that can be processed textile. They can be derived from plant parts or the hair coat of animals or can be obtained from the cocoons of silk moths. "All natural fibers described in this standard are listed with the international abbreviation (see table).

Preference is given to vegetable fibers such as seed fibers (example: cotton), fruit fiber fibers (example: kapok), bast fibers (flax, hemp, jute etc.) or hard fibers (sisal, coconut). In animal fibers, a distinction is made between wool, fine and coarse animal hair and silk. Length and cross-section of natural fibers result from natural growth; by the processing one obtains shorter fiber pieces, which according to DIN 6001-02 [1] also received own designations: Flock, Linters, Kämmlinge (when combing resulting short natural fibers), Bour (r) ette and Schappe (with silk), tow and Flake bast (mechanically and / or chemically divided bast fibers).

Table: Overview of the different natural fiber groups with corresponding shorthands according to DIN 6001-01 [2]

Preferred are plant fibers, which are plant-derived or plant-derived fibers. All plant fibers consist of the polysaccharide cellulose as a basic building block. In addition, polyoses (hemicellulose), pectins and lignin are found in varying amounts.

Especially preferred are cellulose fibers. According to Römpp's Chemie Lexikon Online Version 3.4, April 2007, this is a collective name for textile fibers made of natural, regenerated and derivatized cellulose, such as cellulose esters. For cellulose fibers of natural cellulose, a distinction is made between seed fibers (cotton, kapok) and bast fibers [e.g. Linen (see flax), ramie, hemp, jute]. Regenerate cellulose (copper silk, cellophane, viscose fibers) is produced by dissolution and reprecipitation of cellulose and spun to the thread via nozzles.

Plant and cellulose fibers should also be understood to mean wood fibers or particles of wood. Wood fibers and suitable wood particles are produced from wood chips by thermal-mechanical processing. Preference is given to wood fibers made of softwood, in particular spruce wood. Suitable wood fibers and wood particles are prepared, for example, under the trade name Lignocel ^® from the company J. Meier Save & Sons.

By nitration and acylation reactions, derivatized cellulose fibers [e.g. Acetate silk, so-called artificial silk]. The derivatized cellulose fibers are used for example in car tires, so-called tire cord. In the molding compositions according to the invention the fibers are used in chopped form. The mean fiber length is preferably 0.5 to 30 mm, in particular 1 to 5 mm.

As component D), the molding compositions of the invention may contain up to 50, preferably up to 30 wt .-% of other additives.

Fibrous or particulate fillers D) which may be mentioned are carbon fibers, glass fibers, glass spheres, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, in amounts of from 1 to 30% by weight, in particular 5 to 20, preferably 10 to 20 wt .-% are used.

Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms. The fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.

Suitable silane compounds are those of the general formula

(X- (CH 2) n) k -si- (OC _m H 2 _m + i) 4-k in which the substituents have the following meanings:

X is NH ₂ -, CH ₂ -CH-, HO-,

\ /

°

n is an integer from 2 to 10, preferably 3 to 4

m is an integer from 1 to 5, preferably 1 to 2

k is an integer from 1 to 3, preferably 1 Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.

The silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1.0, and in particular 0.05 to 0.5 wt .-% (based on E)) for surface coating.

Also suitable are acicular mineral fillers. In the context of the invention, the term "needle-shaped mineral fillers" is understood to mean a mineral filler with a pronounced, needle-like character. An example is acicular wollastonite. Preferably, the mineral has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler may optionally be pretreated with the aforementioned silane compounds; however, pretreatment is not essential.

As further fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called as well as platelet or needle-shaped nanofillers preferably in amounts between 0.1 and 10%. Boehmite, bentonite, montmorillonite, vermicullite, hectorite and laponite are preferably used for this purpose. In order to obtain a good compatibility of the platelet-shaped nanofillers with the organic binder, the platelet-shaped nanofillers according to the prior art are organically modified. The addition of the platelet- or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical strength. As further component D), the molding compositions according to the invention may contain 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.

Preference is given to Al, alkali metal, alkaline earth metal salts or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably having 12 to 44 carbon atoms.

The metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.

Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate.

It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.

The carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).

The aliphatic alcohols can be 1 - to 4-valent. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.

The aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Correspondingly, preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

It is also possible to use mixtures of different esters or amides or esters with amides in combination, the mixing ratio being arbitrary.

As further component D), the molding compositions of the invention 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a Cu stabilizer, preferably a Cu (l) halide, in particular in admixture with an alkali metal halide, preferably KJ, in particular in the ratio 1: 4, or of a sterically hindered phenol or mixtures thereof. Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. These are contained in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide. The advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide. This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution. A typical concentrate consists for example of 79 to 95 wt .-% polyamide and 21 to 5 wt .-% of a mixture of copper iodide or bromide and potassium iodide. The concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 1 1, 5, preferably between 1 and 5.

Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular polyamide 6 and polyamide 6.6.

In principle, all compounds having a phenolic structure which have at least one sterically demanding group on the phenolic ring are suitable as sterically hindered phenols D).

Preferably, e.g. Compounds of the formula

into consideration, in which mean:

R ¹ and R ^{2 are} an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R ¹ and R ^{2 may be the} same or different and R ^{3 is} an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.

Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).

Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.

Particularly preferred compounds of this class are compounds of the formula

where R ⁴ , R ⁵ , R ⁷ and R ⁸ independently of one another are C 1 -C ⁸ -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding group) and R ^{6 is} a bivalent aliphatic radical having 1 to 10 C atoms means that may also have CO bonds in the main chain.

Preferred compounds corresponding to this formula are

(Irganox ^® 245 of the BASF SE

(Irganox ^® 259 from BASF SE)

By way of example, the following may be mentioned by way of example as sterically hindered phenols:

2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate ], Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2, 6,7-Trioxa-i-phosphabicyclo-p ^^ locM-yl-methyl-S ^ -di-tert-butyl ^ -hydroxyhydro-cinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl-3 , 5-distearyl-thiotriazylamine, 2- (2'-

Hydroxy-3'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1, 3,5-trimethyl-2, 4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -benzene, 4,4'-methylenebis (2,6-di-tert-butylphenol), 3,5 -Di-tert-butyl-4-hydroxybenzyl-dimethylamine. Have been found to be particularly effective and therefore preferably used are 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1, 6-hexanediol bis (3,5-di-tert-butyl) butyl-4-hydroxyphenyl) propionate (Irganox ^® 259), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and N, N'-hexamethylene-bis- 3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox ^® 1098), and Irganox ^® 245 from Ciba Geigy, which is particularly well suited described above.

The antioxidants D), which can be used individually or as mixtures, are present in an amount of from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight, in particular 0.1 to 1 wt .-%, based on the total weight of the molding compositions A) to D).

In some cases, sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time.

As further component D), the molding compositions according to the invention may contain 0.05 to 5, preferably 0.1 to 2 and in particular 0.25 to 1 wt .-% of a nigrosine.

Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, gas-soluble) used in wool dyeing and printing, in black dyeing of silks, for dyeing of leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscopy dyes.

The nigrosine is technically obtained by heating nitrobenzene, aniline and aniline with anhydrous metal. Iron and FeCb (name of Latin niger = black).

Component D) can be used as free base or else as salt (for example hydrochloride).

Further details on nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".

Other customary additives D) are, for example, in amounts of up to 25, preferably up to 20 wt .-% rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers). In general, these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic esters with 1 to 18 C Atoms in the alcohol component.

Such polymers are e.g. in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph of CB. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

In the following some preferred types of such elastomers are presented.

Preferred types of such elastomers are the so-called ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

As diene monomers for EPDM rubbers, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1, 5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes, and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preference is given to hexa-1, 5-diene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber. EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.

Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers may also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture R ¹ C (COOR ² ) = C (COOR ³ ) R ⁴ (I)

R ¹ _V R ^Λ

C --------- Z C

I I (H)

OC. ^ CO

O

CHR ⁷ = CH (CH ₂ ) _m O (CHR ⁶ ) _g CH CHR ⁵ C ")

CH ₂ = CR ⁹ COO (CH ₂ ) _p CH-CHR ⁸ (IV) °

wherein R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 0 to 5.

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is O or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether. Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.

Advantageously, the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to

20 wt .-% of epoxy-containing monomers and / or methacrylic acid and / or acid-anhydride-containing monomers and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of

50 to 98, in particular 55 to 95 wt .-% ethylene,

0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and 1 to 45, in particular 5 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate. Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.

In addition, vinyl esters and vinyl ethers can also be used as comonomers. The ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known. Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se.

Basically, homogeneously constructed elastomers or those with a shell structure can be used. The shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.

By way of example, as monomers for the preparation of the rubber portion of the elastomers, acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called. These monomers may be reacted with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.

The soft or rubbery phase (having a glass transition temperature lower than ⁰ ° C.) of the elastomers may be the core, the outer shell, or a middle shell (for elastomers having more than two shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.

In addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 2O ⁰ C) on the structure of the elastomer, so these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, Acrylsäureestern and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers. In addition, smaller proportions of other comonomers can also be used here. In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula

wherein the substituents may have the following meaning: R ^{10 is} hydrogen or a C 1 to C 4 alkyl group,

R ^{11 is} hydrogen, a C 1 - to C 5 -alkyl group or an aryl group, in particular phenyl,

R ^{12 is} hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or -OR ¹³

R ^{13 is} a C 1 - to C 5 -alkyl or C 6 - to C 12 -aryl group which may optionally be substituted by O- or N-containing groups,

X is a chemical bond, a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group

O

- C- Y

Y O-Z or NH-Z and

Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group. The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.

Further examples which may be mentioned are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-) Diethylamino) ethyl acrylate. Furthermore, the particles of the rubber phase can also be crosslinked. Examples of monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.

Furthermore, so-called graft-linking monomers can also be used, i. Monomers having two or more polymerizable double bonds, which react at different rates in the polymerization. Preferably, those compounds are used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerized much slower (polymerize). The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie. the grafted phase is at least partially linked via chemical bonds to the graft base.

Examples of such graft-crosslinking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a variety of other suitable graft-linking monomers; for further details, reference is made here, for example, to US Pat. No. 4,148,846.

In general, the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.

In the following, some preferred emulsion polymers are listed. First, graft polymers having a core and at least one outer shell, which have the following structure:

Instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1, 3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by co-use of crosslinking monomers or monomers having reactive groups.

Examples of preferred emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.

Silicone rubbers, as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred. Of course, it is also possible to use mixtures of the rubber types listed above.

As component D) thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc.

Examples of oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites and amines (eg TAD), hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight called on the weight of the thermoplastic molding compositions. As UV stabilizers, which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned. It is possible to add inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.

The nucleating agents used may be sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc.

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed. The mixing temperatures are generally from 230 to 320 ^° C. According to a further preferred procedure, the components B) to C) and optionally D) can be mixed with a prepolymer, formulated and granulated. The resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.

Also preferred is the preparation by means of so-called. Pultrusionverfahren.

The thermoplastic molding compositions of the invention are characterized by a good flame retardancy and good mechanics. In addition, lower levels of flame retardant are needed to achieve fire class V-O.

These are suitable for the production of fibers, films and moldings of any kind. The following are some examples: Cylinder head covers, motorcycle covers, intake pipes, intercooler caps, connectors, gears, fan wheels, cooling water boxes.

In the E / E area, such polyamides can be used to produce plugs, plug parts, plug connectors, wiring harness components, circuit carriers, circuit carrier components, three-dimensionally injection-molded circuit carriers, electrical connection elements, mechatronic components. Inside the car, there is use for dashboards, steering column switches, seat parts, headrests, center consoles, gear components and door modules, in the car exterior for door handles, exterior mirror components, windscreen wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds (In particular intake manifold), windscreen wipers and body exterior parts possible.

For the kitchen and household sector, the use of flow-improved polyamides for the production of components for kitchen appliances, such. Fryers, irons, buttons, and garden leisure applications, e. Components for irrigation systems or garden tools and door handles possible.

Examples The following components were used:

Component A / 1

Polyamide 6 (polycaprolactam) having a viscosity number VZ of 148 ml / g, measured as 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307. (It was Ultramid ^® B3K BASF SE used).

Component A / 2

Polyamide 66 with a VZ of 150 ml / g according to ISO 307

(It was used Ultramid ^® A27E BASF SE).

Component A / 3

PA 6.10 with a VZ of 150 ml / g according to ISO 307.

(It was Ultramid ^® S3K BASF SE balance used). Component B

Red phosphorus (phlegmatized with dioctyl phthalate) Manufacturer: Clariant

(as a 50% batch in PA 6, values in parentheses).

Component C / 1

Kenaf (average fiber length 2 mm) Supplier: H. Hiendl GmbH

Component C / 2

Acetylated cellulose fiber (Cordenka), average fiber length 4 mm. Component D

Glass fibers. The molding compositions were prepared on a ZSK 30 at a throughput of 10 kg / h and about 260 ⁰ C flat temperature profile.

The following measurements were carried out:

Determination of flame retardance class according to UL 94 on 1, 6 mm thick bars.

The composition of the molding compositions and the results of the measurements are shown in the table.

Claims

claims

1. Thermoplastic molding compositions comprising A) from 10 to 98.5% by weight of a thermoplastic polyamide,

B) 0.5 to 40% by weight of a phosphorus-containing flame retardant compound,

C) 1 to 80% by weight of natural fibers, excluding mineral fibers,

D) 0 to 50 wt .-% of other additives, wherein the sum of the weight percent A) to D) gives 100%

2. Thermoplastic molding compositions according to claim 1 comprising A) 20 to 94 wt .-%

B) 1 to 30% by weight

C) 5 to 50% by weight

D) 0 to 30% by weight

3. Thermoplastic molding compositions according to claims 1 or 2, containing as component C) vegetable fibers.

4. Thermoplastic molding compositions according to claims 1 to 3, containing as component C) cellulose fibers.

5. Thermoplastic molding compositions according to claims 1 to 4, containing as component C) wood fibers.

6. Thermoplastic molding compositions according to claims 1 to 5, containing as component B) at least one triarylphosphine, a phosphate, a phosphite, a

Salt of phosphoric acid, a phosphoric acid ester or its salts, a phosphine, a phosphinate, a phosphinic acid salt, red phosphorus or mixtures thereof.

7. Thermoplastic molding compositions according to claims 1 to 6, wherein component B) is made up of superficially pretreated red phosphorus.

8. Use of the thermoplastic molding compositions according to claims 1 to 7 for the production of fibers, films and moldings of any kind.

9. fibers, films and moldings obtainable from the thermoplastic molding compositions according to claims 1 to 7.