WO2012013564A1 - Flameproofed molding compounds - Google Patents

Abstract

The invention relates to thermoplastic molding compounds, containing: A) 10 to 98 wt % of a thermoplastic polymer, B) 0.5 to 40 wt % of a phosphorus-containing flameproofing compound, C) 0.5 to 35 wt % of iron sulfide, and D) 0 to 70 wt % of further additives, wherein the sum of the weight percentages of components A) to D) is 100%.

Description

 Flame-retardant molding compounds

Description The invention relates to thermoplastic molding compositions containing

A) 10 to 98% by weight of a thermoplastic polymer,

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

 C) 0.5 to 35% by weight of iron sulfide

D) 0 to 70% by weight of further additives,

 where the sum of the weight percent of components A) to D) is 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 lifetime.

Many applications in the E / E sector require flame retardancy, including phosphorus compounds.

The use of red phosphorus as a conventional 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. The replacement of halogen-containing compounds is desirable from an ecological point of view.

For PVC, a flame retardant combination of metal hydroxides and iron sulfide (pyrite) is known s. JP-A 54/1 14558. However, the content of metal hydroxides adversely affects the mechanics of the molding compositions in the given amounts.

It is an object of the present invention to provide flame-retardant thermoplastics which are intended to be halogen-free and to have the required flameproofing and mechanical properties for most applications.

Accordingly, the molding compositions defined above were found. Preferred embodiments can be found in the subclaims. Surprisingly, the combination of phosphorus-containing flame retardants with iron sulfide leads to a UL 94 classification of VO and a better LOI value and to higher phosphorus stability. Basically, the advantageous effect in the molding compositions according to the invention in thermoplastics of any kind. An enumeration of suitable thermoplastics can be found for example in the plastic paperback (Hrsg. Saechtling), edition 1989, where sources are also called. Processes for the production of such thermoplastics are known per se to the person skilled in the art.

Preferred thermoplastics are selected from the group of polyamides, polyesters, polycarbonates, vinylaromatic polymers, ASA, ABS, SAN polymers, POM, PPE, polyarylene ether sulfones, polyamides, polyesters and polycarbonates being preferred. As component (A), the molding compositions according to the invention contain 10 to 98, preferably 20 to 97 and in particular 30 to 95 wt .-% of at least one thermoplastic polymer, preferably polyester / polycarbonates.

In general, polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.

A first group of preferred polyesters are polyalkylene terephthalates, in particular those having 2 to 10 carbon atoms in the alcohol part. Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, e.g. by halogen such as chlorine and bromine or by C 1 -C 4 -alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

These polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se. Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.

Of the aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4- Cyclohexanediol, 1, 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.

Particularly preferred polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, in particular, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred. Also preferred are PET and / or PBT, which contain up to 1 wt .-%, preferably up to 0.75 wt .-% 1, 6-hexanediol and / or 2-methyl-1, 5-pentanediol as further monomer units.

The viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (wt. 1) at 25 ° C. in accordance with ISO 1628. Particular preference is given to polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg of polyesters Method of DE-A 44 01 055. The carboxyl end group content is usually determined by titration method (eg potentiometry).

Particularly preferred molding compositions contain as component A) a mixture of polyesters which are different from PBT, such as polyethylene terephthalate (PET). The proportion e.g. of the polyethylene terephthalate is preferably in the mixture up to 50, in particular 10 to 35 wt .-%, based on

100% by weight of A).

Furthermore, it is advantageous to use PET recyclates (also termed scrap PET), optionally mixed with polyalkylene terephthalates such as PBT. Recyclates are generally understood as:

1) so-called Post Industrial Recyclate: these are production waste in polycondensation or in processing, e.g. Sprues in injection molding processing, starting goods in injection molding or extrusion

 or edge portions of extruded sheets or foils.

2) Post Consumer Recyclate: These are plastic items that are collected and processed after use by the end user. By far the most dominant items in volume terms are blow-molded PET bottles for mineral water, soft drinks and juices. Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.

Both granulated and as regrind present recyclates can be used, the maximum edge length should be 10 mm, preferably less than 8 mm.

Due to the hydrolytic cleavage of polyesters during processing (due to traces of moisture) it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably <0.2%, in particular <0.05%.

Another group to be mentioned are fully aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to mixtures of 5 to

 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures of these two acids used.

The aromatic dihydroxy compounds preferably have the general formula

 in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m is the value 0 to 2 has. The compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds his example

dihydroxydiphenyl,

 Di (hydroxyphenyl) alkane,

 Di (hydroxyphenyl) cycloalkane,

 Di (hydroxyphenyl) sulfide,

 Di (hydroxyphenyl) ether,

 ketone di- (hydroxyphenyl),

 di- (hydroxyphenyl) sulfoxide,

a, a'-di- (hydroxyphenyl) -dialkylbenzol, Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene

Resorcinol and

 Hydroquinone and their nuclear alkylated or ring-halogenated derivatives called. Of these will be

4,4'-dihydroxydiphenyl,

2,4-di- (4'-hydroxyphenyl) -2-methylbutane

a, a'-di- (4-hydroxyphenyl) -p-diisopropylbenzene,

2,2-di- (3'-methyl-4'-hydroxyphenyl) propane and

2,2-di- (3'-chloro-4'-hydroxyphenyl) propane, and in particular 2,2-di- (4'-hydroxyphenyl) propane

 2,2-di- (3 ', 5-dichlordihydroxyphenyl) propane,

 1,1-di- (4'-hydroxyphenyl) cyclohexane,

 3,4'-dihydroxybenzophenone,

 4,4'-dihydroxydiphenylsulfone and

2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof are preferred.

Of course, it is also possible to use mixtures of polyalkylene terephthalates and fully aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and from 2 to 80% by weight of the wholly aromatic polyester.

Of course, polyester block copolymers such as copolyetheresters may also be used. Such products are known per se and are known in the literature, e.g. in the

US Pat. No. 3,651,014. Also in the trade, corresponding products are available, e.g. Hytrel® (DuPont).

As a polyester to be understood according to the invention also halogen-free polycarbonates. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula

wherein Q is a single bond, a d- to Ce-alkylene, a C2 to C3 alkylidene, a C3 to C6 cycloalkylidene group, a CQ to Ci2-arylene group and -O-, -S- or -SO 2 - and m is an integer from 0 to 2.

The diphenols may also have substituents on the phenylene radicals, such as C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy.

Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1 bis (4-hydroxyphenyl) -cyclohexane. Particular preference is given to 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane and also 1,1-bis- (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane.

Both homopolycarbonates and copolycarbonates are suitable as component A, in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred. The suitable polycarbonates may be branched in a known manner, preferably by the incorporation of 0.05 to 2.0 mol -%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic OH groups. Particularly suitable polycarbonates have proven, the relative viscosities n _re i from 1, 10 to 1, 50, in particular from 1, 25 to 1, 40 have. This corresponds to average molecular weights M w (weight average) of from 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol. The diphenols of the general formula are known per se or can be prepared by known processes.

The polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators. (With respect polydiorganosiloxanhaltigen polycarbonates see, for example, DE-OS 33 34 782). Suitable chain terminators include phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenol, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- ( 3,5-dimethylheptyl) -phenol.

Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are selected from halogen-free diphenols, halogen-free chain terminators and optionally halogenated genfrei-free branching, wherein the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the production of polycarbonates with phosgene by the interfacial process, is not to be regarded as halogen-containing in the context of the invention. Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.

As further suitable components A) may be mentioned amorphous polyester carbonates, wherein phosgene against aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units, was replaced in the preparation. For further details, reference is made at this point to EP-A 71 1 810.

Further suitable copolycarbonates with cycloalkyl radicals as monomer units are described in EP-A 365 916. Furthermore, bisphenol A can be replaced by bisphenol TMC. Such polycarbonates are available under the trademark APEC HT® from Bayer.

As preferred component A), the molding compositions according to the invention contain 10 to 98, preferably 20 to 97 and in particular 30 to 95 wt .-% of at least one polyamide.

The polyamides of the molding compositions according to the invention generally have a viscosity number of from 90 to 350, preferably from 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. ISO 307. Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000, such as 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 include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.

Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids. Here only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be 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 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. In addition, polyamides may also be mentioned which, for example, by condensation of 1, 4-

Diaminobutane with adipic acid are available at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 described. 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 / B B 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

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 61 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 2 to 20 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" is understood to mean 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 phosphorus compounds of the phosphine class which have the valence state -3 are aromatic phosphines, such as triphenylphosphine, tritolylphosphine, trinonylphosphine, Trinaphthylphosphine and trisnonylphenylphosphine, among others. Triphenylphosphine is particularly suitable.

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

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

wherein R ¹ , R ² and R ^{3 are the} same or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.

Examples of phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisnonylphenylphosphine 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, for example, hypophosphites of purely organic nature, for example organic hypophosphites, such as cellulose hypophosphite esters, esters of hypophosphorous acids with diols, for example of 1,10-dodecyldiol. Also substituted phosphinic acids and their anhydrides, such as diphenylphosphinic, can be used. Also suitable are diphenylphosphinic acid, di-p-tolylphosphinic acid, di-cresylphosphinic anhydride, but also compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic acid) esters, inter alia, are suitable. Also suitable are aryl (alkyl) phosphinic acid amides, such as, for example, diphenylphosphinic acid dimethylamide and sulfonamicodaryl (alkyl) phosphinic acid derivatives, for example p-tolylsulfonamidodiphenylphosphinic acid. 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 derived from pentaerythritol, neopentyl glycol or pyrocatechol, for example, are suitable

where R is a C1 to _C4 alkyl radical, preferably a methyl radical, x = 0 or 1 (Amgard ^® 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 phenyldi- dide 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 oxidation state +4 are mainly hypodiphosphates, such. 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-

Ethylhexyl di (tolyl) phosphate, diphenyl hydrogen phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis (2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate , p-tolyl-bis (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 with

 Alkyl groups having 1 to 4 carbon atoms, preferably methyl, may be substituted,

R ^{8 is} a divalent phenol radical, preferred

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 abovementioned low molecular weight phosphorus compounds, oligomeric and polymeric phosphorus compounds are also suitable.

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 Polyphospholino- xide 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 vinylphosphonyl acid dichloride with bifunctional phenols, such as hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbiphenol-A arise.

Other halogen-free polymeric phosphorus compounds which may be present in the molding compositions according to the invention are obtained by reaction of phosphorus oxychloride or

Phosphorsäureesterdichloriden with a mixture of mono-, bi- and trifunctional phenols and other hydroxyl-bearing compounds produced (see Houben-Weyl-Muller, Thieme-Verlag Stuttgart, Organic Phosphorus Part II (1963)). Furthermore, polymeric phosphonates can be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (see DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (compare US Pat. No. 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

 and / or diphosphinic acid salts of the formula

O O

^■ PRP M.

 R R where the substituents have the following meanings:

R ¹ , R ^{2 are} identical or different, hydrogen, Ci-Cö-alkyl, linear or branched and / or

 aryl;

R ³ Ci-Cio-alkylene, linear or branched, C _ß -Cio-arylene, alkylarylene or arylalkylene;

M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;

m 1 to 4; n 1 to 4; x is 1 to 4.

Preferably, R ¹ , R ² of component B are the same or different and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl. Preferably, R ³ of component B is methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; Methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; Phenyl-methylene, phenyl-ethylene, phenyl-propylene or phenyl-butylene.

R ¹ , R ² is particularly preferably methyl, ethyl and M = Al.

Also preferred are melamine polyphosphate salts of a 1,3,5-triazine compound whose number n of the average degree of condensation is between 20 and 200 and the 1,3,5-triazine content of 1, 1 to 2.0 mol of a 1, 3,5-triazine compound, selected from the group consisting of melamine, melam, meiern, melon, ammeiin, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine and diaminophenyltriazine, per mole of phosphorus atom. Preferably, the n value of such salts is generally between 40 and 150, and the ratio of a 1,3,5-triazine compound per mole of phosphorus atom is preferably between 1.2 and 1.8. Furthermore, the pH of a 10% by weight aqueous slurry of salts prepared according to EP1095030B1 will generally be more than 4.5 and preferably at least 5.0. The pH is usually determined by adding 25 g of the salt and 225 g of clean water of 25 ° C to a 300 ml beaker, stirring the resulting aqueous slurry for 30 minutes and then measuring the pH. The o.g. n value, the number-average degree of condensation, can be determined by 31 P solid NMR. From J.R. van Wazer, C.F. Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc, 78, 5715, 1956, it is known that the number of adjacent phosphate groups indicates a unique chemical shift that allows for a clear distinction between orthophosphates, pyrophosphates and polyphosphates. In EP1095030B1 is also a process for the preparation of the desired polyphosphate salt of a 1, 3,5-triazine compound having an n value of 20 to 200 and their 1, 3,5-triazine content 1, 1 to 2.0 mol of a 1, 3,5-triazine compound is described. This process involves the conversion of a 1,3,5-triazine compound with orthophosphoric acid into its orthophosphate salt, followed by dehydration and heat treatment to convert the orthophosphate salt to a polyphosphate of the 1,3,5-triazine compound. This heat treatment is preferably carried out at a temperature of at least 300 ° C, and preferably at least 310 ° C. In addition to orthophosphates of 1,3,5-triazine compounds, other 1,3,5-triazine phosphates may also be used, including, for example, a mixture of orthophosphates and pyrophosphates.

Further preferred are phosphorus compounds of the general formula:

in which the substituents have the following meanings: R ¹ to R ²⁰ are independently hydrogen, a linear or branched alkyl group up to 6 carbon atoms, n has an average value of 0.5 to 50 and X is a single bond, C = 0, S, S0 ₂ , C (CH ₃ ) ₂

Preferred compounds B) 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 further given to compounds B) 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 ₃ ) 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 B) 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 superficially mixed 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 5 to 10 carbon atoms, such as trioctyltri mel itate and aromatic phosphate compounds such as tricresyl phosphate.

Particularly preferred esters of phthalic acid are used as phlegmatizers, 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. Particularly preferred are 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 phlegmatizer 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 phlegmatizer and the red phosphorus each give 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 μιη.

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 suitable, for example, in a polyamide or polyolefin or an elastomer, which can have phosphorus contents of up to 60% by weight. As component C), the molding compositions of the invention contain 0.5 to 35, preferably 1 to 20 and in particular 1 to 10 wt.% Of an iron sulfide.

Preferred iron sulfide is FeS 2, which is the Fe (II) salt of the S2 ^{2 "} ion.

In nature, this is formed from FeS and sulfur compounds in organic matter or sulfate with the help of microorganisms.

As a mineral FeS2 occurs in two modifications, as pyrite or marcasite, both also referred to as iron gravel.

Synthetically, FeS2 is available by reacting FeC with H2S at red-hot or by heating Fe (II) sulfide with elemental sulfur. Commercially FeS2 is available as a black powder, which preferably has an S content (elemental sulfur) of greater than 35%, in particular 45%.

The sulfur content is determined as follows:

 The sample is weighed into a tin capsule and burnt in helium stream at about 1000 ° C with added oxygen. The resulting combustion gases are converted into defined species with the aid of appropriate catalysts and detected by WLD.

Sulfur: quantification as SO2 by means of thermal conductivity detection (WLD).

Weighing range: 1 - 5 mg, accurate to 0.001 mg

 Bestimmungsgren; w (C) 0.01 g / 100 g

 Measuring accuracy: ± 0.001 g / 100 g

 Device eg: elementary analyzer Euro EA, company Eurovector

 Literature: F. Ehrenberger "Quantitative Organic Elemental Analysis." The preferred particle size is dgo <1000 μιη, especially dgo <100 μιη, the dso is preferably <50 μιη (determined according to ISO 13320-1).

As component D), the molding compositions of the invention may contain up to 70, preferably up to 50 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 30, preferably 10 to 30 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 (O-C _m H ₂ m ₊ 1) 4-k in which the substituents have the following meanings:

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 an L / D (length: diameter ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1) The mineral filler may optionally be pretreated with the silane compounds mentioned above, the pretreatment however, is not essential.

As further fillers are kaolin, caicinated kaolin, wollastonite, talc and chalk called and additionally 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 nano fillers to nanocomposites according to the invention leads to a further increase in mechanical strength.

As further component D), the molding compositions of 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 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are correspondingly 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 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} identical 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, for example, in DE-A 27 02 661

(US-A 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 oo ^r7

CH ₂ - CH ₂ - COROC-CH-CH ₂

wherein R ⁴ , R ⁵ , R ⁷ and R ⁸ independently represent d-Ce-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 carbon atoms means that may also have CO bonds in the main chain.

Preferred compounds corresponding to this formula are

(Irganox ^® 245 from BASF SE)

(Irganox ^® 259 from BASF SE)

By way of example, a total of sterically hindered phenols may be mentioned: 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-hydroxybenzyl phosphonate, 2,6,7-trioxa-1-phosphabicyclo [2.2.2] oct-4-ylmethyl-3,5-di-tert-butyl-4-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 be used 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 1, 6-hexanediol bis (3,5-di-tert. -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 in an amount of 0.05 to 3 wt .-%, preferably from 0.1 to 1, 5 wt .-%, 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 as meaning a group of black or gray induline-related phenazine dyes (azine dyes) in various forms (water-soluble, fat-soluble, gas-soluble) which are useful in wool dyeing and printing, in the art

Black dyeing of silks, for dyeing leather, shoe creams, varnishes, plastics, baked enamels, inks and the like, and find use as microscopy dyes.

The nigrosine is technically obtained by heating nitrobenzene, aniline and aniline with anhydrous metal. Iron and FeC (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 acid esters having 1 to 18 carbon atoms in the alcohol component. Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by 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, Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (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 still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. 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

 \ /

 C C

OC CO

Ό

CH,: CR COO - ( ^CH ₂ ) _P CH-CHR ^! (IV)

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

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is 0 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 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 monomers containing acid anhydride groups and the remaining amount of

(Meth) acrylsäureestern.

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 whose preparation is described, for example, in Blackley in the monograph "Emulsion Polymerization". The usable emulsifiers and catalysts are known per se.

In principle, homogeneously constructed elastomers or else 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.

As representatives for the preparation of the rubber part 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 rubber phase (with a glass transition temperature below 0 ° C) of the elastomers may be the core, the outer shell or a middle shell (at

Elastomers with more than two-shell construction); in multi-shelled

Elastomers may also consist of several shells of a rubber phase. If, in addition to the rubber phase, one or more hard components (having glass transition temperatures of more than 20 ° C.) are involved in the construction of the elastomer, these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic esters and methacrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers. In addition, smaller amounts 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 e.g. Epoxy, carbo xyl, latent carboxyl, amino or amide groups and functional groups, which by Mit- use of monomers of the general formula

can be introduced where the substituents may have the following meanings:

R 10 is hydrogen or a C 1 to C 4 alkyl group, R ^{11 is} hydrogen, a C 1 to C 6 alkyl group or an aryl group, in particular phenyl,

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

R ^{13 is} a C 1 to C 12 alkyl or C 2 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 or

 O

- C- Y Y O-Z or NH-Z and

Z is a C 1 -C 10 -alkylene or C 2 -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, it is also possible to use so-called graft-linking monomers, ie monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preference is given to using those compounds 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), for example, polymerizes (polymerizes) much more slowly. 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 graft monomers to form chemical bonds, ie, the grafted phase is at least partially linked via chemical bonds with 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, it is also possible to use homogeneous, ie single-shell, elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers. These products can also be prepared by concomitant 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 on butadiene base and an outer shell of the aforementioned copolymers and copolymers of ethylene with comonomers providing 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, mixtures of the rubber types listed above can be used.

As component D), the thermoplastic molding compositions according to 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, etc.

Examples of antioxidants 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 up to 1 wt .-%, based on the Called 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, Benzotriazo- le 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.

As nucleating agents, sodium phenylphosphinate, alumina, silica and preferably talc may be used. PTFE, zinc salts (zinc borate, Zn oxide), silica salts (silicon dioxides), for example, can be used as flame retardant synergists.

The thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which the starting components are mixed 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. Individual components can also be premixed and then the rest of the output Substances are added individually and / or also mixed. The mixing temperatures are usually 230 to 320.

According to a further preferred procedure, the components B) to C) and, if appropriate, 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 required to achieve fire class V-0. In addition, the LOI value and P stability are improved.

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 a use for dashboards, steering column switches, seat parts, headrests, center consoles, transmission 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. Deep fryers, irons, buttons, as well as applications in the garden leisure area, e.g. Components for irrigation systems or garden tools and door handles possible.

Examples

The following components were used: Component A

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

(It was Ultramid ^® A24 from BASF SE used). Component B / 1

 Red phosphorus (phlegmatized with dioctyl phthalate)

(as a 50% batch in PA 6)

Component B / 2

Red phosphorus as a 40% masterbatch in PA 6

Component B / 3

Aluminum diethylphosphinate (Exolit OP1230 ^® from Clariant) component B / 4

Melamine polyphosphate (Melapur ^® 200 from BASF SE)

Component C

 FeS2 dgo <60 μιη, dso <25 μιη

 S-content: 50%, determined according to method p. 17 of the description

Component D1

Glass fibers component D2

 Antioxidants: Irganox® 1098 from BASF SE and ZnO (1: 2)

Component D3

 Lubricants: Ca-Stearate, Zn-Stearate, Stearyl Stearate (5: 0.5: 1)

Component D4

 Copolymer of ethylene / n-butyl acrylate / acrylic acid / maleic anhydride

The molding compositions were prepared on a ZSK 25 at a throughput of 10 kg / h and about 290 ° C flat temperature profile.

The following measurements were carried out:

Determination of flame retardancy according to UL 94 on 0.8 mm thick bars.

The limiting oxygen index (LOI) values were determined according to ISO 4589-2. The composition of the molding compositions and the results of the measurements are shown in the table.

 V = for comparison

Claims

claims

Thermoplastic molding compositions containing

A) 10 to 98 wt.% Of a thermoplastic polymer

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

C) 0.5 to 35% by weight of iron sulfide,

 D) 0 to 70% by weight of further additives,

where the sum of the weight percent of components A) to D) is 100%.

Thermoplastic molding compositions according to claim 1, containing as component C)

FeS ₂ .

Thermoplastic molding compositions according to claims 1 or 2, containing as component D) 1 to 50 wt.% Of a fibrous or particulate filler.

Thermoplastic molding compositions according to claims 1 to 3, in which component C) has a sulfur content, based on elemental sulfur, of at least 35%.

Thermoplastic molding compositions according to claims 1 to 4, in which the component

 C) has a dgo value (particle size primary) <1000 μιη.

Thermoplastic molding compositions according to claims 1 to 5, in which the component

B) of red phosphorus, melamine polyphosphate or phosphinic acid salts of the formula

 (I) or / and diphosphinic acid salts of the formula (II) or their polymers is constructed.

(I)

(II) in which R ^1, R ^{2 are} identical or different are hydrogen, Ci-C _ß alkyl, linear or branched and / or aryl;

R ³ Ci-Cio-alkylene, linear or branched, C _ß -Cio-arylene, -alkylarylene

 or -arylalkylene;

 M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;

m 1 to 4; n 1 to 4; x is 1 to 4.

Use of the thermoplastic molding compositions according to claims 1 to 6 for the production of fibers, films and moldings of any kind.

Fibers, films and moldings obtainable from the thermoplastic molding compositions according to claims 1 to 6.