WO2000066658A1 - Thermoplastic moulding materials - Google Patents

Abstract

The invention relates to thermoplastic moulding materials containing A) between 10 and 99 % by weight of at least one thermoplastic polymer, B) between 1 and 50 % by weight of a mixture consisting of b1) at least one phosphorous compound and b2) at least one stabiliser compound of the general formulas (I) to (IV). In formula (I), R?1 and R2¿ represent, independently of one another, a hydrogen radical, a C¿1? to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, or a C7 to C13 alkylaryl radical, a, b independently of one another, have the values 1 to 5, c, d independently of one another, have the values 0 to 10. In formula (II), R?3¿ represents a hydrogen radical, a C¿1? to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, a C7 to C13 alkylaryl radical, e has the value 1 to 4, f has the value 1 to 100. In formula (III), R?4 and R13¿ independently of one another, represent NCO or NHCOOR', whereby R' represents an alkyl polyetherglycol or an alcohol containing between 1 and 20 C-atoms, R?5, R6, R7, R8, R9, R10, R11, R12¿ independently of one another, represent a hydrogen radical, a C¿1? to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, a C7 to C13 alkylaryl radical, g indicates 0 to 5, h indicates 1 to 100. In formula (IV) R?14, R15, R16¿ independently of one another, represent a hydrogen radical or a radical (a), whereby R17 represents a hydrogen radical, a C¿1? to C10 alkyl radical, a C6 to C12 aryl radical, a C7 to C13 aralkyl radical, a C7 to C13 alkylaryl radical, or (CH2)1-N=C=O, whereby 1 indicates 1 to 20, i indicates 2 to 8, j indicates 1 to i-k, k indicates 0 to i-j, whereby j + k ≤ i, or at least two of these groups. Said thermoplastic moulding materials also contain C) between 0 and 40 % by weight of a flame-retardant which is different from b1); and D) between 0 and 70 % by weight of additives. The weight percentages of components A) to D) always correspond to 100 %.

Description

Thermoplastic molding compounds

description

The invention relates to thermoplastic molding compositions containing

A) 10 to 99% by weight of at least one thermoplastic polymer

B) 1 to 50% by weight of a mixture of

bi) at least one phosphorus compound and

b) at least one stabilizer compound of the general formulas I to IV

in which

R ¹ , R ² independently of one another are hydrogen, Ci to Cio alkyl, C ₆ to Cχ ₂ aryl, C ₇ to Cχ ₃ aralkyl,

C ₇ to C ₁₃ alkylaryl radical,

a, b independently of one another 1 to 5,

c, d independently of one another 0 to 10;

in which

R3 is a hydrogen, Ci to Cio-alkyl, Cζ - to Cι ₂ aryl, C ₇ - to C ₁₃ aralkyl, C ₇ - to Cι ₃ alkylaryl radical,

1 to 4,

1 to 100;

in which

R ⁴ , R ⁱ³ independently of one another are NCO or NHCOOR ', where R' is an alkylpolyether glycol or an alcohol having 1 to 20 C atoms,

R ⁵ , R ⁵ , R ⁷ , R ^β , R9, RIO, Rll, Rl2 independently of one another a hydrogen, Ci to

Cio-alkyl, C ₆ - to Cι ₂ -aryl, C ₇ - to C _i3 aralkyl -, C - to C ₁₃ alkylaryl radical,

0 to 5

1 to 100;

in which

R ¹⁴ , R ¹⁵ , R independently of one another a hydrogen ^residue or

where R ^{17 is} a hydrogen, Ci to Cio alkyl, C ₈ to Ci ₂ aryl, C ₇ to C ₃ aralkyl, C ₇ to C ₁₃ alkylaryl radical,

or

(CH ₂ ) ι-N = C = 0, where 1 is 1 to 20, i 2 to 8,

j 1 to i - k,

k 0 to i-j, where j + k <i, or at least two of them

mean.

C) 0 to 40% by weight of a flame retardant, different as bi)

D) 0 to 70% by weight of further additives, the weight percentages of components A) to D) always giving 100%.

Furthermore, the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings, and to the moldings obtainable here.

There is increasing market interest for halogen-free flame-retardant thermoplastics, especially polyester. Essential requirements for the flame retardant are: light color, sufficient temperature stability for incorporation into thermoplastics, as well as its effectiveness in reinforced and unreinforced polymer (so-called wicking effect on glass fibers).

In addition to the halogen-containing systems, four halogen-free FR systems are used in principle in thermoplastics:

Inorganic flame retardants, which have to be used in large quantities in order to be effective.

Nitrogen-containing FR systems, such as melamine cyanurate, which have a limited effectiveness in thermoplastics e.g. Polyamide shows. In reinforced polyamide, it is only effective in combination with shortened glass fibers. Melamine cyanurate alone is not effective in polyesters.

Phosphorus-containing FR systems that are generally not particularly effective in polyesters.

FR / phosphorus-containing FR systems, such as ammonium polyphosphates or melamine phosphates, which do not have sufficient thermal stability for thermoplastics that are processed at temperatures above 200 ° C. JP-A 03/281 652 discloses polyalkylene terephthalates which contain melamine cyanurate and glass fibers, and a phosphorus-containing flame retardant. These molding compositions contain derivatives of phosphoric acid, such as phosphoric acid esters (valence level +5), which tend to "bloom" when subjected to thermal stress.

These disadvantages are also evident for the combination of melamine cyanurate (MC) with resorcinol bis - (diphenyl phosphate), which is known from JP-A 05/070 671. Furthermore, these molding compositions show high phenol values and insufficient mechanical properties during processing.

JP-A 09/157 503 discloses polyester molding compositions with MC, phosphorus compounds and lubricants which contain less than 10% reinforcing agents. Flame retardant and mechanical properties of such molding compositions are in need of improvement as well as migration and phenol formation during processing.

From EP-A 699 708 and BE-A 875 530 phosphinic acid salts are known as flame retardants for polyester.

WO 97/05705 discloses combinations of MC with phosphorus-containing compounds and lubricants for polyesters.

From EP-A 628 541 and WO-A 96/17011 carbodiimides are known as hydrolysis stabilizers for thermoplastics.

Particularly in the case of electronic components in the case of phosphorus-containing flame-retardant thermoplastics, the stability at high long-term use temperatures (against dry heat) is still in need of improvement. At the same time, such flame retardants show an increased tendency to corrode when they come into contact with metal parts, so that both blooming or fission products of the flame retardants lead to short circuits in such components.

The present invention was therefore based on the object of providing halogen-free, flame-retardant thermoplastics which show improved stability at high long-term use temperatures and reduce the degradation of the polymer matrix in a dry, warm environment. At the same time, blooming and the tendency of the flame retardants to corrode should be minimized. Accordingly, the molding compositions defined at the outset were found. Preferred embodiments can be found in the subclaims. As component A), the molding compositions according to the invention contain 10 to 99, preferably 20 to 95 and in particular 30 to 80% by weight of a thermoplastic polymer.

Basically, the advantageous effect of the molding compositions according to the invention can be seen in thermoplastics of all kinds. A list of suitable thermoplastics can be found, for example, in the plastic pocket book (ed. Saechtling), edition 1989, where sources of supply are also mentioned. Processes for the production of such thermoplastics are known per se to the person skilled in the art. Some preferred types of plastic are explained in more detail below.

1. Polycarbonate and polyester

Generally, polyesters based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.

A first group of preferred polyesters are polyalkylene terephthalates with 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid. The aromatic ring can also be substituted, e.g. by halogen such as chlorine and bromine or by -CC alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

These polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.

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 can be replaced.

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

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

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 (weight ratio 1: 1 at 25 ° C) according to ISO 1628.

Particularly preferred are 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 polyester. Such polyesters can be produced, for example, by the process of DE-A 44 01 055. The carboxyl end group content is usually determined by titration methods (e.g. potentiometry).

Particularly preferred molding compositions contain as component A) a mixture of polyethylene terephthalate (PET) and polyalkylene terephthalates with 3 to 10 carbon atoms in the alcohol part, in particular polybutylene terephthalate (PBT). The proportion of polyethylene terephthalate in the mixture is preferably up to 50, in particular 10 to 30% by weight, based on 100% by weight of A).

Such molding compositions according to the invention show very good flame retardant properties and better mechanical properties.

It is also advantageous to use PET recyclates (also called scrap PET) in a mixture with polyalkylene terephthalates such as PBT.

Recyclates are generally understood to mean:

1) So-called post industrial recyclate: this is about

Production waste in the case of polycondensation or in processing, for example sprues in injection molding processing, start-up goods in injection molding processing or extrusion, or edge sections of extruded sheets or foils. 2) Post consumer recyclate: these are plastic items that are collected and processed by the end consumer after use. The most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the pipe cyclates are melted and granulated in an extruder after separation and cleaning. This usually facilitates handling, free-flowing properties and meterability for further processing steps.

Recycled materials 15 which are both granulated and in the form of regrind can be used, the maximum edge length being 6 mm, preferably less than 5 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 0.01 to 0.7, in particular 0.2 to 0.6%.

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

Aromatic dicarboxylic acids which are suitable are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% isophthalic acid and 0 to 30 95 mol% terephthalic acid, in particular mixtures of approximately 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids, are used.

The aromatic dihydroxy compounds preferably have the general formula

in which Z represents an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom 5 or a chemical bond and in which the Has value 0 to 2. The compounds I can also on the phenylene groups C ₁ -C ₆ alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents.

As the stem of these compounds, for example

Dihydroxydiphenyl,

Di - (hydroxyphenyl) alkane,

Di - (hydroxyphenyl) cycloalkane,

Di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether,

Di- (hydroxyphenyl) ketone, di - (hydroxyphenyl) sulfoxide, α, α '-di (hydroxyphenyl) dialkylbenzene,

Di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene resorcinol and

Hydroquinone and their nuclear alkylated or nuclear halogenated

Called derivatives.

Of these will be

4,4'-dihydroxydiphenyl,

2, 4 -Di- (4'-hydroxyphenyl) -2 -methylbutane α, α '-Di- (4-hydroxyphenyl) -p-diisopropylbenzene,

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

as well as in particular

2,2-di - (4'-hydroxyphenyl) propane 2,2-di (3 ', 5-dichlorodihydroxyphenyl) ropane, 1,1-di- (4' -hydroxyphenyl) cyc1ohexane, 3,4'-dihydroxybenzophenone, 4 , 4 '-Dihydroxydiphenylsulfone and 2,2 -Di (3', 5 '-dimethyl-4' -hydroxyphenyl) propane

or their mixtures are preferred,

Of course, mixtures of polyalkylene terephthalates and fully aromatic polyesters can also be used. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.

Polyesters for the purposes of the present invention are also to be understood as meaning polycarbonates which can be obtained by polymerizing aromatic dihydroxy compounds, in particular bis - (4-hydroxyphenyl) 2, 2-propane (bisphenol A) or its derivatives, for example with phosgene. Corresponding products are known and described in the literature and for the most part also available commercially. The amount of the polycarbonates is up to 90% by weight, preferably up to 50% by weight, in particular 10 to 30% by weight, based on 100% by weight of component (A).

Of course, polyester block copolymers such as copolyether esters can also be used. Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also available on the market, eg Hytrel ^® (DuPont).

2. Vinyl aromatic polymers

The molecular weight of these known and commercially available polymers is generally in the range from 1,500 to 2,000,000, preferably in the range from 70,000 to 1,000,000.

Vinyl aromatic polymers made from styrene, chlorostyrene, α-methylstyrene and p-methylstyrene are only representative here; In minor proportions (preferably not more than 20, in particular not more than 8% by weight), comonomers such as (meth) acrylonitrile or (meth) acrylic acid esters can also be involved in the structure. Particularly preferred vinyl aromatic polymers are polystyrene and impact modified polystyrene. It is understood that mixtures of these polymers can also be used.

The production is preferably carried out according to the method described in EP-A-302 485.

Preferred ASA polymers are made up of a soft or rubber phase made of a graft polymer of:

Ai 50 to 90 wt .-% of a graft base based on

At 95 to 99.9 wt .-% of a C ₂ alkyl acrylate and ₀ -Cι

A ₂ 0.1 to 5 wt .-% of a difunctional monomer with two olefinic, non-conjugated double bonds, and

A ₂ 10 to 50 wt .-% of a graft

A ₂ ι 20 to 50 wt .-% styrene or substituted styrenes of the general formula I or mixtures thereof, and

A ₂₂ 10 to 80 wt .-% acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or their

Mixtures, in a mixture with a hard matrix based on a SAN copolymer A ₃ ) from:

₃₁ 50 to 90, preferably 55 to 90 and in particular 65 to 85% by weight of styrene and / or substituted styrenes of the general formula I and

A ₃ 10 to 50, preferably 10 to 45 and in particular 15 to 35% by weight of acrylonitrile and / or methacrylonitrile.

Component Ai) is an elastomer which has a glass transition temperature of below -20, in particular below -30 ° C.

The main monomers used for the production of the elastomer are an) esters of acrylic acid with 2 to 10 C atoms, in particular 4 to 8 C atoms. Particularly preferred monomers here are tert.-, iso- and n-butyl acrylate and 2-ethylhexyl acrylate, of which the latter two are particularly preferred.

In addition to these esters of acrylic acid, 0.1 to 5, in particular 1 to 4,% by weight, based on the total weight of An + A _{12, of} a polyfunctional monomer having at least two olefinic, non-conjugated double bonds are used. Of these, difunctional compounds, ie with two non-conjugated double bonds, are preferably used. Examples include divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate and dihydrodicyclopentadienyl acrylate, the latter two being particularly preferred.

Methods for producing the graft base Ai are known per se and e.g. described in DE-B 1 260 135. Corresponding products are also commercially available.

In some cases, production by emulsion polymerization has proven to be particularly advantageous.

The precise polymerization conditions, in particular the type, dosage and amount of the emulsifier, are preferably selected so that the latex of the acrylic acid ester, which is at least partially crosslinked, has an average particle size (weight average ds ₀ ) in the range from about 200 to 700, in particular from 250 to 600 nm. The latex preferably has a narrow particle size distribution, ie the quotient d ₉ o - dio

Q =

^ 50

is preferably less than 0.5, in particular less than 0.35.

The proportion of the graft base Ai in the graft polymer Aι + A ₂ is 50 to 90, preferably 55 to 85 and in particular 60 to 80% by weight, based on the total weight of Aι + A ₂ .

A graft A _{2 is} grafted onto the graft base Ai, which is obtained by copolymerization of

A ₂ ι 20 to 90, preferably 30 to 90 and in particular 30 to 80 wt .-% styrene or substituted styrenes of the general formula _2nd

wherein R represents alkyl radicals with 1 to 8 C atoms, hydrogen atoms or halogen atoms and R ^{1 represents} alkyl radicals with 1 to 8 C atoms or halogen atoms and n has the value 0, 1, 2 or 3, and

A ₂₂ 10 to 80, preferably 10 to 70 and in particular 20 to

70% by weight of acrylonitrile, methacrylonitrile, acrylic acid esters or methacrylic acid esters or mixtures thereof is available.

Examples of substituted styrenes are α-methylstyrene, p-methylstyrene, p-chlorostyrene and p-chloro-α-methylstyrene, of which styrene and α-methylstyrene are preferred.

Preferred acrylic or methacrylic acid esters are those whose homopolymers or copolymers with the other monomers of component A ₂ ) have glass transition temperatures of more than 20 ° C .; in principle, however, other acrylic acid esters can also be used, preferably in amounts such that overall a glass transition temperature T _{g of} above 20 ° C. results for component A.

Esters of acrylic or methacrylic acid with Ci-Cg alcohols and esters containing epoxy groups, such as glycidyl acrylate or glycidyl methacrylate, are particularly preferred. Methyl methacrylate, t-butyl methacrylate, Called glycidyl methacrylate and n-butyl acrylate, the latter being preferably used in a not too high proportion due to its property of forming polymers with a very low T _g .

The graft A ₂ ) can be produced in one or more, for example two or three, process steps, the gross composition remains unaffected.

Preferably the graft is made in emulsion as e.g. is described in DE-PS 12 60 135, DE-OS 32 27 555, DE-OS 31 49 357 and DE-OS 34 14 118.

Depending on the conditions selected, a certain proportion of free copolymers of styrene or substituted styrene derivatives and (meth) acrylonitrile or (meth) acrylic acid esters are formed in the graft polymerization.

The graft copolymer Ai + A ₂ generally has an average particle size of 100 to 1,000 nm, in particular from 200 to 700 nm, (mean weight average). The conditions in the preparation of the elastomer Di) and in the grafting are therefore preferably chosen so that particle sizes result in this range. Measures for this are known and are described, for example, in DE-PS 1 260 135 and DE-OS 28 26 925 as well as in Journal of Applied Polymer Science, Vol. 9 (1965), pp. 2929 to 2938. The particle enlargement of the latex of the elastomer can be accomplished, for example, by means of agglomeration.

In the context of this invention, the graft polymer (Aι + A) also includes the free, non-grafted homopolymers and copolymers formed in the graft copolymerization for the preparation of component A).

Some preferred graft polymers are listed below:

1: 60 wt .-% pork base Ai from An 98 wt .-% n-butyl acrylate and

A ₁₂ 2% by weight dihydrodicyclopentadienyl acrylate and 40% by weight graft shell A ₂ made from Aι 75% by weight styrene and A ₂₂ 25% by weight acrylonitrile

2: graft base as in 1 with 5% by weight of a first graft shell made of styrene and

35 wt .-% of a second graft from Aι 75 wt .-% styrene and A ₂₂ 25% by weight acrylonitrile

3: Graft base as in 1 with 13% by weight of a first grafting stage made of styrene and 27% by weight of a second grafting stage made of styrene and acrylonitrile in a weight ratio of 3: 1

The products contained as component A ₃ ) can be produced, for example, by the process described in DE-AS 10 01 001 and DE-AS 10 03 436. Such copolymers are also commercially available. The weight average molecular weight determined by light scattering is preferably in the range from 50,000 to 500,000, in particular from 100,000 to 250,000.

The weight ratio of (Ai + A ₂ ): A ₃ is in the range from 1: 2.5 to 2.5: 1, preferably from 1: 2 to 2: 1 and in particular from 1: 1.5 to 1.5: 1.

Suitable SAN polymers as component A) are described above (see A ₃₁ and A ₃₂ ).

The viscosity number of the SAN polymers, measured according to DIN 53 727 as a 0.5% strength by weight solution in dimethylformamide at 23 ° C., is generally in the range from 40 to 100, preferably 50 to 80 ml / g.

ABS polymers as polymer (A) in the multiphase polymer mixtures according to the invention have the same structure as described above for ASA polymers. Instead of the acrylate rubber Ai) of the graft base in the ASA polymer, conjugated dienes are usually used, so that the following composition preferably results for the graft base A:

Aι 70 to 100 wt .-% of a conjugated diene and A ₄ 0 to 30 wt .-% of a difunctional monomer with two olefinic non-conjugated double bonds

The composition of graft pads A ₂ and the hard matrix of SAN copolymer A ₃ ) remain unchanged. Such products are commercially available. The production processes are known to the person skilled in the art, so that further information on this is unnecessary.

The weight ratio of (A ₄ + A ₂ ): A ₃ is in the range from 3: 1 to 1: 3, preferably from 2: 1 to 1: 2. Particularly preferred compositions of the molding compositions according to the invention contain as component A) a mixture of:

Ai) 10 to 90% by weight of a polybutylene terephthalate A ₂ ) 0 to 40% by weight of a polyethylene terephthalate

A ₃ ) 1 to 40% by weight of an ASA or ABS polymer or their

Mixtures

Such products are available under the trademark Ultradur ^® S (formerly Ultrablend ^® S) from BASF Aktiengesellschaft.

Contain further preferred compositions of component A)

Ai) 10 to 90% by weight of a polycarbonate A) 0 to 40% by weight of a polyester, preferably

Polybutylene terephthalate, A ₃ ) 1 to 40% by weight of an ASA or ABS polymer or their

Mixtures.

Such products are available under the trademark Terblend ^® from BASF AG.

3. Polyamides

The polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. in accordance with ISO 307.

Semi-crystalline or amorphous resins with a molecular weight (weight average) 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 include polyamides which are derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurinlactam, and polyamides which are obtained by reacting dicarboxylic acids with diamines.

Alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned here as acids. Particularly suitable diamines are alkane diamines having 6 to 12, in particular 6 to 8, carbon atoms and m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) ) propane or 2,2-di- (4-aminocyclohexyl) propane.

Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam as well as copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactarn units.

Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-, 6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.

Polyamides obtainable by copolymerizing two or more of the aforementioned monomers or mixtures of two or more polyamides are also suitable, the mixing ratio being arbitrary.

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

The preferred partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196.

4. Polyphenylene ether

Suitable polyphenylene ethers generally have a molecular weight (weight average) in the range from 10,000 to 80,000, preferably from 20,000 to 60,000 and in particular from 40,000 to 55,000.

The molecular weight distribution is generally determined by means of gel permeation chromatography (GPC). For this purpose, PPE samples are dissolved in THF under pressure at 110 ° C. At room temperature, 0.16 ml of a 0.25% solution is injected onto suitable separation columns using THF as the eluent. The detection is generally carried out with a UN detector. The separation columns are expediently calibrated with PPE samples of known molecular weight distribution. This corresponds to a reduced specific viscosity η _red of 0.2 to 0.9 dl / g, preferably 0.35 to 0.8 and in particular 0.45 to 0.6, measured in a 0.5% by weight solution in chloroform at 25 ° C.

The unmodified polyphenylene ethers ai) are known per se and are preferably prepared by oxidative coupling of phenols disubstituted in the o-position.

Examples of substituents are halogen atoms such as chlorine or chromium and alkyl radicals with 1 to 4 carbon atoms, which preferably do not have an α-position tertiary hydrogen atom, e.g. To name methyl, ethyl, propyl or butyl radicals. The alkyl radicals can in turn be substituted by halogen atoms such as chlorine or bromine or by a hydroxyl group. Further examples of possible substituents are alkoxy radicals, preferably with up to 4 carbon atoms or phenyl radicals optionally substituted by halogen atoms and / or alkyl groups. Copolymers of various phenols such as e.g. Copolymers of 2, 6-dimethylphenol and 2, 3, 6 -trimethylphenol. Mixtures of different polyphenylene ethers can of course also be used.

The polyphenylene ethers used as component ai) may contain process-related defects, which are described, for example, by White et al. , Macromolecules 23, 1318-1329 (1990).

Preferably those polyphenylene ethers are used which are compatible with vinyl aromatic polymers, i.e. are wholly or largely soluble in these polymers (cf. A. Noshay, Block Copolymers, pp. 8 to 10, Academic Press, 1977 and 0. Olabisi, Polymer-Polymer Miscibility, 1979, pp. 117 to 189).

Examples of polyphenylene ethers are poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1), 4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether, poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl -6-stea- ryloxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1,4-phenylene) ether, poly (2,4- dibenzyl-1,4-phenylene) ether, poly (2-ethoxy-1,4-phenylene) ether, poly (2-chloro-1,4-phenylene) ether, poly (2,5-dibromo-1, 4-phenylene) ether. Polyphenylene ethers in which the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1,4-phenylene (ether, poly (2,6-diethyl-1,4-phenylene), are preferably used. ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, Poly (2, 6-dipropyl-1,4-phenylene) ether and poly (2-ethyl -6-propyl-1,4-phenylene) ether.

Graft copolymers of polyphenylene ether and vinyl-aromatic polymers such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene are also suitable.

Functionalized or modified polyphenylene ethers are known per se, e.g. from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 116 and EP-A-254 048 and are preferably used for mixtures with PA or polyester.

Usually an unmodified polyphenylene ether ai) is obtained by incorporating at least one carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, Lactam or halobenzyl group modified so that a sufficient compatibility, for example is guaranteed with the polyamide.

The modification is generally carried out by reacting an unmodified polyphenylene ether ai) with a modifier which contains at least one of the above-mentioned groups and at least one CC double or CC triple bond in solution (WO-A 86/2086) aqueous dispersion, carried out in a gas phase process (EP-A-25 200) or in the melt, if appropriate in the presence of suitable vinyl aromatic polymers or impact modifiers, it being possible for free radical initiators to be present.

Suitable modifiers (a ₃ ) are, for example, maleic acid, methyl maleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, for example Ci- and C- to Cs-alkanols (a ₃ ι), the mono - Or diamides of these acids such as N-phenylmaleinimide (monomers a ₃₂ ), maleic hydrazide. N-vinylpyrrolidone and (meth) acryloylcaprolactam (a ₃₃ ) may also be mentioned, for example.

A modified polyphenylene ether is preferably used as component A) in the molding compositions according to the invention, which can be obtained by reacting

ai) 70 to 99.95, preferably 76.5 to 99.94% by weight of an unmodified polyphenylene ether,

a ₂ ) 0 to 25, preferably 0 to 20% by weight of a vinylaromatic polymer, a ₃ ) 0.05 to 5, preferably 0.05 to 2.5% by weight of at least one compound from the group formed from

a ₃ i) an α, β-unsaturated dicarbonyl compound,

a ₃ ) a monomer containing amide groups with a polymerizable double bond and

a ₃₃ ) a monomer containing lactam groups with a polymerizable double bond,

a) 0 to 5, preferably 0.01 to 0.09% by weight of a radical initiator,

the percentages by weight based on the sum of a) to a) being obtainable in the course of 0.5 to 15 minutes at 240 to 375 ° C. in suitable mixing and kneading units such as twin-screw extruders.

The vinyl aromatic polymer a) should preferably be compatible with the polyphenylene ether used, as described under 2 above.

Examples of preferred vinyl aromatic polymers compatible with polyphenylene ethers can be found in the aforementioned monograph by Olabisi, pp. 224 to 230 and 245.

The following are mentioned as radical starters a):

Di- (2,4-dichlorobenzoyl) peroxide, tert. -Butyl peroxide, di- (3, 5, 5-trimethylhexanol) peroxide, dilauroyl peroxide, didecanoyl peroxide, dipropionyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexoate, tert. -Butylperoxydiethylacetat, tert. - Butyl peroxyisobutyrate, 1, 1 -di-tert. -butylperoxy-3, 3, 5-trimethyl-cyclohexane, tert. -Butylperoxyisopropyl carbonate, tert. -Butylperoxy-3, 3, 5-trimethylhexoate, tert. -Butyl peracetate, tert. -Butylper- benzoate, 4, 4 -Di -tert. -butylperoxyvalerian acid butyl ester, 2, 2-di- tert. -butylperoxybutane, dicumyl peroxide, tert. -Butylcumyl- peroxide, 1, 3 -Di- (tert-butylperoxyisopropyl) benzene and di-tert-butyl peroxide. Organic hydroperoxides such as diisopropylbenzene monohydroperoxide, cumene hydroperoxide, tert are also mentioned. - Butyl hydroperoxide, p-methyl hydroperoxide and pinane hyperperoxide as well as highly branched alkanes of the general structure R ⁴ R ^l

R5 C C R2

R ⁶ R ³ , where R ¹ to R ^{6 are} alkyl groups with 1 to 8 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles with a π-electron system and nitrogen Represent oxygen or sulfur as heteroatoms. The substituents R ¹ to R ⁶ can in turn contain functional groups as substituents, such as carboxyl, carboxyl derivative, hydroxyl, amino, thiol or epoxy groups. Examples are 2,3-dimethyl-2,3-diphenylbutane, 3, 4 -dimethyl-3, 4 -diphenylhexane and 2, 2, 3, 3-tetraphenylbutane.

Particularly preferred polyphenylene ethers A) in the molding compositions according to the invention are obtained by modification with maleic acid, maleic anhydride and fumaric acid. Such polyphenylene ethers preferably have an acid number from 1.8 to 3.2, in particular from 2.0 to 3.0.

The acid number is a measure of the degree of modification of the polyphenylene ether and is generally determined by titration with bases under inert gas conditions.

The acid number generally corresponds to the amount of base in mg which is required to neutralize 1 g of an acid-modified polyphenylene ether B) (according to DIN 53 402).

5. Thermoplastic polyurethanes

Other suitable thermoplastics include thermoplastic polyurethanes (TPU), as described, for example, in EP-A 115 846 and EP-A 115 847 and EP-A 117 664.

Suitable TPUs can be produced, for example, by reacting

a) organic, preferably aromatic diisocyanates,

Polyhydroxyl compounds with molecular weights from 500 to 8000 and c) chain extenders with molecular weights of 60 to 400 in the presence of optionally

d) catalysts,

e) auxiliaries and / or additives.

For the starting materials (a) to (c), catalysts (d), auxiliaries and additives (e) that can be used for this, we would like to do the following:

a) Suitable organic diisocyanates (a) are, for example, aliphatic, cycloaliphatic and preferably aromatic diisocyanates. The following may be mentioned as examples: aliphatic diisocyanates such as hexamethylene diisocyanate, cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2, 4- and -2,6- cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate as well as the corresponding isomer mixtures and preferably aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate. Mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and / or 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanato-diphenylethane (1, 2) and 1, 5-naphthylene diisocyanate. Hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthylene diisocyanate, diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of greater than 96% by weight and in particular are preferably used 4,4'-diphenylmethane diisocyanate.

b) Polyetherols and polyesterols are preferably suitable as higher molecular weight polyhydroxyl compounds (b) with molecular weights of 500 to 8000. However, hydroxyl-containing polymers, for example polyacetals, such as polyoxymethylenes and, above all, water-insoluble formals, for example polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular those made from diphenyl carbonate and 1, 6-hexanediol, produced by transesterification, with the above-mentioned molecular weights are also suitable. The polyhydroxyl compounds must be at least predominantly linear, ie they have a difunctional structure in the sense of the isocyanate reaction. The polyhydroxyl compounds mentioned can be used as individual components or in the form of mixtures. Suitable polyetherols can be prepared by reacting one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen atoms bonded. Examples of alkylene oxides are: ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide. Ethylene oxide and mixtures of propylene oxide-1, 2 and ethylene oxide are preferably used. The alkylene oxides can be used individually, alternately in succession or as a mixture. Examples of suitable starter molecules are: water, amino alcohols, such as N-alkyl-diethanolamines, for example N-methyl-diethanolamine, and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. If appropriate, mixtures of starter molecules can also be used. Suitable polyetherols are also those containing hydroxyl groups

Polymerization products of tetrahydrofuran (polyoxytetra methylene glycols).

Polyetherols of propylene oxide-1,2 and ethylene oxide are preferably used in which more than 50%, preferably 60 to 80% of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block; e.g. in particular polyoxetetramethylene glycols.

Such polyetherols can be obtained by e.g. first polymerized to the starter molecule the 1,2-propylene oxide and then the ethylene oxide or first copolymerized all of the 1,2-propylene oxide in a mixture with part of the ethylene oxide and then polymerized the rest of the ethylene oxide or gradually a part of the ethylene oxide, then that all propylene oxide-1, 2 and then the rest of the ethylene oxide, polymerized onto the starter molecule.

The essentially linear polyetherols have molecular weights of 500 to 8000, preferably 600 to 6000 and in particular 800 to 3500. They can be used both individually and in the form of mixtures with one another.

Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example in the form of a succinic, glutaric and adipic acid mixture. Mixtures of aromatic and aliphatic dicarboxylic acids can also be used. For the preparation of the polyesterols it may be advantageous to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters with 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid chlorides instead of the dicarboxylic acids. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10, 2-decanediol, 2-dimethylpropanediol-1,3, propanediol-1,3 and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols can be used alone or, if appropriate, in mixtures with one another.

Also suitable are esters of carbonic acid with the diols mentioned, in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexanediol, condensation products of ω-hydroxycarboxylic acids, for example ω-hydroxycaproic acid, and preferably polymerization products of Lactones, for example optionally substituted ω-caprolactones.

Dialkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene radical, such as, for. B. Ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-butanediol-1,4-polyadipates, 1,6-hexanediol-neopentyl glycol polyadipates, polycaprolactones and in particular

1,6-hexanediol-1,4-butanediol polyadipate.

The polyesterols have molecular weights from 500 to 6000, preferably from 800 to 3500.

Suitable chain extenders (c) with molecular weights of 60 to 400, preferably 60 to 300, are preferably aliphatic diols with 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, such as e.g. Ethanediol, hexanediol-1, 6, diethylene glycol, dipropylene glycol and in particular butanediol-1, 4 into consideration. However, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, such as e.g. Terephthalic acid bis-ethylene glycol or butanediol-1,4, hydroxyalkylene ether of hydroquinone, e.g. 1,4-di- (β-hydroxyethyl) hydroquinone,

(cyclo) aliphatic diamines, such as, for example, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, Isophorone-diamine, ethylenediamine, 1,2-, 1,3-propylene-diamine, N-methyl-propylenediamine-1,3, N, N'-dimethyl-ethylenediamine and aromatic diamines such as 2,4- and 2, 6-tolylene-diamine, 3, 5-diethyl-2, 4- and -2, 6-toluylene-diamine and primary site-ho-di-, tri- and / or tetraalkyl-substituted 4, 4'-diamino-diphenylmethane.

To set the hardness and melting point of the TPU, the structural components (b) and (c) can be varied in relatively wide molar ratios. Molar ratios of polyhydroxyl compounds (b) to chain extenders (c) from 1: 1 to 1:12, in particular from 1: 1.8 to 1: 6.4, have proven successful, the hardness and melting point of the TPU increasing with the content of Diols increases.

To produce the TPU, the structural components (a), (b) and (c) are reacted in the presence of optionally catalysts (d), auxiliaries and / or additives (e) in amounts such that the equivalence ratio of NCO groups of Diisocyanates (a) to the sum of the hydroxyl groups or hydroxyl and amino groups of components (b) and (c) 1: 0.85 to 1.20, preferably 1: 0.95 to 1: 1.05 and in particular 1: 0, Is 98 to 1.02.

d) Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c) are the tertiary amines known and customary in the prior art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds such as e.g. Iron (III) acetyl acetonate, tin compounds, e.g. Tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like. The catalysts are usually used in amounts of 0.001 to 0.1 part per 100 parts of polyhydroxy compound (b).

In addition to catalysts, auxiliary components and / or additives (e) can also be incorporated into the structural components (a) to (c). Examples include lubricants, inhibitors, stabilizers against hydrolysis, light, heat or discoloration, dyes, pigments, inorganic and / or organic fillers and plasticizers. rather, as well as additives for the production of foamed TPU moldings.

More detailed information on the auxiliary and additive substances mentioned above can be found in the specialist literature, for example the monograph by J.H. Saunders and K.C. Frisch "High Polymers", Volume XVI, Polyurethane, Part 1 and 2, published by Interscience Publishers 1962 and 1964 or DE-OS 29 01 774.

As component B), the molding compositions according to the invention contain 1 to 50, preferably 5 to 30 and in particular 5 to 20% by weight of a mixture of

bi) at least one phosphorus compound and

b ₂ ) at least one stabilizer compound of the general formulas I to IV

in which

R ¹ , R ² independently of one another are a hydrogen, Ci to Cio alkyl, C ₆ to C ₂ aryl, C ₇ to C13 aralkyl, C ₇ to C13 alkylaryl radical,

a, b independently of one another 1 to 5,

independently 0 to 10;

in which

R ^{3 is} a hydrogen f -, Ci - to Cio alkyl, Cς to Ci ₂ aryl, C ₇ to C _i3 aralkyl, C ₇ to C ₁₃ alkyl aryl radical,

1 to 4 , 1 to 100;

in which

R ⁴ , R ¹³ independently of one another are NCO or NHCOOR ', where R' is an alkyl polyether glycol or an alcohol having 1 to 20 C atoms,

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² independently of one another are hydrogen, C - to Cio-alkyl, C ₆ - to Cι ₂ -aryl-, C ₇ - to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl,

g 0 to 5

h 1 to 100;

in which

Rl, R15, R16 independently of one another a hydrogen residue or

wherein R ^{17 is} a hydrogen, Ci- to Cio-alkyl, Cζ - to Cι ₂ aryl, C ₇ - to C ₁₃ aralkyl radical, C ₇ - to C _i3 alkylaryl radical,

2 to 8, j 1 to ik

k 0 to i, where j + k i

or at least two of them,

or

(CH ₂ ) ι-N = C = 0, where 1 is 1 to 20, dissolved

mean.

According to the invention, R ¹ and R ² each independently of one another preferably represent Ci to Cio, particularly preferably Ci to C - and moreover preferably C ₃ alkyl. Of these, a 2 -propyl radical is particularly preferred.

The variables a and b each independently mean preferably 1, 2, 3 or 4 and particularly preferably 2. In the event that a and b each represent 2, the corresponding radicals R ¹ and R ^{2 are} each adjacent to the carbons to the carbon that the NCN group joins on the benzene ring.

In addition to the C ₆ - to Cι aryl radicals according to the invention are C _ß - to Cio-aryl and preferably Cε- to Cs aryl group is particularly preferred. Of the aforementioned aryl groups, phenyl and naphthyl groups are particularly preferred. Preferred aralkyl radicals with preferably 7 to 14 carbon atoms are toluene, xylyl, tert. -Butyl-phenyl and di -tert. -butyl-phenyl. Benzyl is preferred as the alkylaryl radical having preferably 7 to 14 carbon atoms.

According to the invention, the variables c and d independently of one another are preferably 0, 1, 2, 3, 4 or 5 and particularly preferably 0, 1 or 2. Furthermore, it is preferred if c and d are each 0.

The remarks on radicals R ¹ and R ² apply to the preferred meaning of radical R ³ according to the invention.

The variable e preferably denotes 1, 2 or 3 and particularly preferably 3. In the event that the variable e denotes 3, it is preferred that the radicals R ^{3 are} each bonded to the carbon atoms of the benzene ring which are adjacent to them to which nitrogen is bound. The integer variable f preferably has the values in the range from 1 to 50 and particularly preferably in the range from 1 to 20.

R 'is preferably derived from a Ci to Cio and particularly preferably C ₂ to C ₅ alcohol. Among these alcohols are again ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert. -Butanol, n-pentanol and isopentanol are preferred, with ethanol being particularly preferred.

When R 'is an alkyl polyether glycol, Ci to Cio-alkyl polyether glycols are preferred and Ci to C5 alkyl polyether glycols are particularly preferred. Among these, methyl, ethyl, propyl, isopropyl polyether glycols are preferred and methyl polyether glycol is particularly preferred.

For the preferred meanings of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , the explanations given for R ¹ and R ² apply, with the difference that instead of the 2-propyl radical, one is used here Methyl radical is particularly preferred.

The variable g preferably has the values 0, 1, 2, 3 and particularly preferably 0. The variable h preferably has the values

1, 2, 3, 4, 5, 6, 7, 9 or 10 and particularly preferably the values

2, 3, 4, 5, 6.

It is preferred that the radicals R ¹⁴ , R ¹⁵ and R ¹⁶ are not a hydrogen atom.

The same applies to R ¹⁷ to R ⁵ to R ¹² . The variable i is preferably 3, 4 or 5 and particularly preferably 5, so that a cyclohexyl ring forms with the carbon via which the cyclic radical is bonded to the nitrogen of the heterocycle. It is further preferred that the variable i is 1.

In the event that a cyclohexyl ring is formed, the variable k is preferably 4. In this case, it is again preferred that in each case 2 out of 4 R ¹⁷ radicals are bonded to a carbon of the cyclohexyl ring and to the rest, likewise 2 radicals R ¹⁷ bearing carbon, are spaced by an intermediate carbon.

A preferred embodiment of the molding compositions according to the invention contains 0.01 to 50% by weight, preferably 1 to 20% by weight, in particular 0.05 to 2% by weight, based on 100% of component B), of at least one stabilizer compound b ₂ ) and 99.99 to 50% by weight, preferably 99 to 80 and in particular 99.95 to 98% by weight, of at least one phosphorus compound bi).

Phosphorus compounds preferred according to the invention have 6 to 120, preferably 6 to 80 and particularly preferably 8 to 40 carbon atoms.

All phosphorus compounds known to the person skilled in the art are possible. Among these, particular preference is given to the organic phosphorus compounds which are used on an industrial scale or in which there is little storage stability or a high tendency to corrode, or both. Among these organic phosphorus compounds, those with the general formula (V) are particularly preferred. R ¹⁸ (0) _m

R ¹⁹ (0) _n _p = _X (V)

R ²⁰ (0) _o ^

in which

R ¹⁸ , R ¹⁹ , R ²⁰ independently of one another are an alkyl, alkylaryl, arylalkyl or cycloalkyl radical having 7 to 40 carbon atoms,

X is a sulfur or oxygen atom,

m, n, o are independently 0 or 1.

In one embodiment of the phosphorus compound having the general formula V, it is preferred that two of the variables m, n and o are 0 and one is 1.

Examples of phosphine oxides as phosphorus compounds 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, benzylbis (cyclohexyl) phosphine oxide, benzylbisphenylphosphine oxide, phenylbis - (n-hexyl) phosphine oxide. Oxidized reaction products of phosphine with aldehydes, in particular of t-butylphosphine with glyoxal, are also preferred. Triphenylphosphine oxide, tricyclohexylphosphine oxide and tris (n-octyl) phosphine oxide are particularly preferably used. Also suitable as a phosphorus compound is triphenylphosphine sulfide and its derivatives of the phosphine oxides and triphenylphosphate as described above.

Phosphorus compounds of valence level ± 0 is the elementary phosphorus. Red and black phosphorus are possible. Red phosphorus is preferred.

Phosphorus compounds of the "oxidation level" +1 are e.g. Hypophosphites. Examples are organic hypophosphites, such as

Cellulose hypophosphite esters, esters of hypophosphorous acids with diols, e.g. of 1, 10-dodecyldiol. Substituted phosphinic acids and their anhydrides, e.g. Diphenylphosphinic acid can be used. Also suitable are dipotolylphosphinic acid, dicresylphosphinic anhydride. However, there are also compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic acid) esters and others. in question. Aryl (alkyl) phosphinamides, such as e.g. Diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, such as e.g. p-Tolylsulfonamidodiphenylphosphinic acid. Hydroquinone and ethylene glycol bis (diphenylphosphinic acid) esters and the bisdiphenyl phosphinate of hydroquinone are preferably used.

Preferred phosphorus compounds are in particular phosphinic acid salts of the formulas (VI) and / or diphosphinic acid salts of the formula (VII) or their polymers or mixtures thereof

where the substituents have the following meaning:

R ¹ , R ^{2 are} hydrogen, χ -Ce alkyl, preferably C ₁ -C ₄ alkyl, linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n- Pentyl; preferably at least one radical R ¹ or R ² , in particular R ¹ and R ² , is hydrogen, R ³ -CC-alkylene, linear or branched, for example methylene, ethylene, n-propylene, isopropylene, n-butylene, tert. -Butylene, n-pentylene, n-octylene, n-dodecylene; Arylene, for example phenylene, naphthylene; Alkylarylene, for example methylphenylene, ethylphenylene, tert.-

Butyl phenylene, methyl naphthylene, ethyl naphthylene, tert-butyl naphthylene;

Aralkylene, e.g. Pheny1-methylene, phenylethylene, phenylpropylene, phenylbutylene;

M is an alkaline earth metal, alkali metal, Al, Zn, Fe, boron, Ti, Zr;

m is an integer from 1 to 3;

n is an integer from 1 to 3;

x 1 or 2.

Compounds in which R ¹ and R ^{2 are} hydrogen are particularly preferred, where M is preferably Al or Zn and calcium phosphate is very particularly preferred.

Such products are commercially available e.g. available as calcium hypophosphite.

Suitable salts of the formula (VI) or (VII) in which only one radical

R ¹ or R ^{2 is} hydrogen, are sodium benzene phosphinate

(Na [HC ₆ H ₅ PO ₂ ]) and calcium benzene phosphinate and Zn ((CH ₃ ) ₂ PO ₂ ) _2>

Zn ((C ₂ H ₅ ) CH ₃ P0 ₂ ) ₂ and AI [(C ₂ H ₅ ) (CH ₃ ) P0 ₂ ] ₃ .

Methods for the production are from EP-A 699 708 and

BE-A 875 530 known.

Phosphorus compounds of oxidation level +3 are derived from the phosphorous acid. Cyclic phosphonates derived from pentaerythritol, neopentyl glycol or catechol are suitable, as in general formula VIII

where R "is a C 1 -C ₄ -alkyl radical, preferably a methyl radical, P = 0 or 1 (Amgard® P45 from Albright & Wilson). Furthermore, phosphorus of valence level +3 in triaryl (alkyl) phosphites, such as triphenylphosphite, tris (4 -decylphenyl) phosphite, tris (2, 4 -ditert. Butylphenyl) phosphite, tris-nonylphenylphosphite (for example Irgaphos®) TNPP from Ciba Geigy AG) or Phenyldidecylphosph.it included. However, diphosphites, such as, for example, propylene glycol-1,2-bis (diphosphite) or cyclic phosphites, which are derived from pentaerythritol, neopentyl glycol or pyrocatechol, are also suitable.

The phosphorus compounds are particularly preferred

Oxidation level +3 methyl neopentyl glycol phosphonate and phosphite and dimethylpentaerythritol diphosphonate and phosphite.

Hypodiphosphates, such as e.g. Tetraphenyl hypodiphosphate or bisneopentyl hypodiphosphate.

Alkyl and aryl-substituted phosphates are particularly suitable as phosphorus compounds of oxidation level +5. Examples are phenylbisdodecylphosphate, phenylethyl hydrogen phosphate, phenyl bis (3,5,5-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (tolyl) phosphate, diphenyl hydrogen phosphate, bis (2-ethylhexyl) -p-tolyl phosphate, tritolyl phosphate -ethyl-hexy1) -phenyl phosphate, di (nony1) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) -p-tolyl phosphate, p-tolyl bis (2, 5, 5-trimethylhexyl) phosphate or 2-ethylhexyldiphenyl phosphate. Phosphorus compounds in which each radical is an aryloxy radical are particularly suitable. Triphenyl phosphate and resorcinol bis - (diphenyl phosphate) (RDP) and its core-substituted derivatives of the general formula IX are very particularly suitable

OR ²² OR ²³

R21 ₀ p. -R. ² 5 ⁵ PI -OR ²⁴ (IX)

0

in which

R ²¹ to R ^{24 are} an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical, which can be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl,

R ^{25 is} a divalent phenol radical, preferred

with Y -CH ₂ -, C = 0, S, S0 ₂ , -C (CH ₃ ) ₂ -, preferably -C (CH ₃ ) ₂ -

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

The phosphorus compound of the general formula X is particularly preferred

With

R ² ^, R 7, _R 28 _R 29 independently of one another hydrogen atom, Ci to C ₆ alkyl,

Z as the previously defined residue Y

r, s, t, u independently of one another 1, 2, 3, 4 or 5, 1 and the para position of the corresponding radical to the phosphorus being preferred.

The commercially available RDP products under the trademarks Fyroflex®-RDP (Akzo Nobel) and CR 733 -S (Daihachi) are due to the manufacturing process mixtures of approx. 85% RDP with approx. 2.5% triphenyl phosphate and approx. 12.5% oligomeric proportions in which the degree of oligomerization is usually less than 10. Cyclic phosphates can also be used as phosphorus compounds. Diphenylpentaerythritol diphosphate and phenylneopentyl phosphate are particularly suitable.

In addition to the low molecular weight phosphorus compounds listed above, oligomeric and polymeric phosphorus compounds are also suitable.

Such polymeric, preferably halogen-free, organic phosphorus compounds with phosphorus in the polymer chain arise, for example, in the production of pentacyclic, unsaturated phosphorine dihalides, as described, for example, in DE-A 2036173. The molecular weight measured by vapor pressure osmometry in dimethylformamide, the polyphospholine oxides should be in the range from 500 to 7,000, preferably in the range from 700 to 2,000. The phosphorus has the oxidation state -1.

Furthermore, inorganic coordination polymers of aryl (alkyl) phosphinic acids such as e.g. Poly-b-sodium (I) methylphenylphosphinate can be used as phosphorus compounds. Their manufacture is specified in DE-A 3140520. The phosphorus has an oxidation number of +1.

Furthermore, such, preferably halogen-free, polymeric phosphorus compounds can be obtained by the reaction of a phosphonic acid chloride, such as e.g. Phenyl, methyl, propyl, styryl and vinyl phosphonic acid dichloride with bifunctional phenols, such as e.g. Hydroquinone, resorcinol, 2, 3, 5-trimethylhydroquinone, bisphenol-, tetramethylbisphenol-A arise.

Further, preferably halogen-free, polymeric phosphorus compounds which may be present in the molding compositions according to the invention are prepared by reacting phosphorus oxide trichloride or phosphoric acid ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and other hydroxyl-bearing compounds (cf. Houben-Weyl -Müller, Thieme- Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)). Polymeric phosphonates can also be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (cf. DE-A 2925208) or by reactions of phosphonic acid esters with diamines or diamines or hydrazides (cf. US Pat. No. 4403075). However, the inorganic poly (ammonium phosphate) can also be used. It is also possible to use oligomeric pentaerythritol phosphites, phosphates and phosphonates according to EP-B 8486, for example Mobil Antiblazeä 19 (registered trademark of Mobil Oil) as phosphorus compounds.

Furthermore, a component B) according to the invention is preferred which over a period of 1 to 100, preferably 2 to 50 and particularly preferably 10 to 30 days from the time when the phosphorus compound is brought into contact with the stabilizer compound by a maximum of 20, preferably a maximum of 15 and particularly preferably at most 5% deviates from the acid number at the time of contact.

The phosphorus compound and the stabilizer compound and, if appropriate, other auxiliaries and additives which are usually to be added to them can be brought into contact with one another by all processes which are generally known to the person skilled in the art. However, mixing in tanks with moving mixers or mixing the composition, which is moved, for example, through a downpipe, using a static mixer has proven successful.

The composition of component B according to the invention is preferably used to increase the storage stability or to reduce the tendency to metal corrosion of phosphorus compounds.

The storage stability is usually determined via the deviation of the acid number over the storage period of the corresponding composition.

As storage stability it is preferred that the acid number deviates from the acid number at the beginning of the aforementioned period over a period of 5 days, preferably 2 weeks and particularly preferably one month by at most 10, preferably at most 5 and particularly preferably at most 1%.

The strength of the tendency to metal corrosion results from the comparison of the before corrosion of a corresponding connection with or without a stabilizer connection under otherwise identical conditions over a same period of time.

Particularly preferred stabilizer compounds contain at least one of the following compounds represented by their structural formulas: Stabaxol® 1 (Rhein Chemie GmbH) Stabaxol® p (Rhein Chemie GmbH)

Elastostab® (Elastogran GmbH)

n from 1 to 100

with R = NHCOOR ', R' = methyl polyether glycol, R '= ethanol

R = NCO or reaction product

Carbodiimide free isocyanurates:

Vestanat® 1890/100 (Hüls AG)

Basonat® H / 100 (BASF AG)

As component C), the thermoplastic molding compositions according to the invention can contain 0 to 40, preferably 1 to 30, preferably 1 to 20, and in particular 5 to 15% by weight of a flame retardant, different from bi). Preferred flame retardants are for the combination with b ₂ ), in particular nitrogen compounds.

The melamine cyanurate which is preferably suitable according to the invention (component C) is a reaction product of preferably equimolar amounts of melamine (formula XI) and cyanuric acid or isocyanuric acid (formulas XIa and Xlb)

NH ₂

N ;; ^C -N (XI)

N ^• c-

H ₂ N NH ₂

OH 0

N ^ ^C _^ N HN ^ ^C ^ NH

HO ^N OH O ^N 0

H

(XIa) (Xlb)

Enolform keto form

You get it e.g. by reacting aqueous solutions of the starting compounds at 90 to 100 ° C. The commercially available product is a white powder with an average grain size dso of 1.5-7 µm.

Other suitable compounds (often referred to as salts or adducts) are melamine borate, oxalate and phosphate prim. , -phosphate sec. and -pyrophosphate sec., neopentylglycol boric acid melamine and polymeric melamine phosphate (CAS No. 56386-64-2).

Suitable guanidine salts are CAS number

G-carbonate 593-85-1

G-cyanurate prim. 70285-19-7

G-phosphate prim. 5423-22-3 G-phosphate sec. 5423-23-4

G-sulfate prim. 646-34-4

G sulfate sec. 594-14-9

Pentaerythritol boric acid guanidine N.A.

Neopentylglycolboric acid guanidine N.A. Urea phosphate green 4861-19-2

Urea cyanurate 57517-11-0

Ammeiin 645-92-1

Ammelid 645-93-2

Meiern 1502-47-2 Melon 32518-77-7

Among compounds within the meaning of the present invention, both e.g. Benzoguanamine itself and its adducts or salts as well as the nitrogen-substituted derivatives and its adducts or salts are to be understood.

Also suitable are ammonium (NH ₄ P0 _{3) n} with n about 200 to 1000 preferably 600 to 800, and tris (hydroxyethyl) isocyanate cyanurate (THEIC) of the formula XII

HOH ₄ C ₂ WN C2H4OH (XII) o ^N

C ₂ H ₄ OH

or its reaction products with aromatic carboxylic acids Ar (COOH) _m , which may optionally be in a mixture with one another, where Ar is a mono-, dinuclear or trinuclear aromatic six-ring system and m is 2, 3 or 4.

Suitable carboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, 1, 3, 5-benzenetricarboxylic acid,

1, 2, 4-benzenetricarboxylic acid, pyromellitic acid, mellophanoic acid, prehnitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acids and anthracenecarboxylic acids. The preparation is carried out by reacting the tris (hydroxyethyl) isocyanurate with the acids, their alkyl esters or their halides in accordance with the processes of EP-A 584 567.

Such reaction products are a mixture of monomeric and oligomeric esters, which can also be crosslinked. The degree of oligomerization is usually 2 to about 100, preferably 2 to 20. Mixtures of THEIC and / or its reaction products with phosphorus-containing nitrogen compounds, in particular (NH ₄ PO ₃ ) _n or melamine pyrophosphate or polymeric melamine phosphate, are preferably used. The mixing ratio, for example of (NH ₄ P0 ₃ ) _n to THEIC, is preferably 90 to 50 to 10 to 50, in particular 80 to 50 to 50 to 20% by weight, based on the mixture of such components B).

Benzoguanamine compounds of the formula XIII are also suitable

in which R, R 'is straight-chain or branched alkyl radicals having 1 to 10 carbon atoms, preferably hydrogen, and in particular their adducts with phosphoric acid, boric acid and / or pyrophosphoric acid.

Allantoin compounds of the formula XIV are also preferred

where R, R 'have the meaning given in formula XIII and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid and glycolurils of the formula XV or its salts with the above. Acids

R R

RR in which R has the meaning given in formula XIII.

Suitable products are commercially available or in accordance with DE-A 196 14 424.

The cyanguanidine (formula XVI) which can be used according to the invention is obtained e.g. by reacting lime nitrogen (calcium cyanamide) with carbonic acid, the resulting cyana dimerizing at pH 9 to 10 to cyanguanidine.

CaNCN + H ₂ 0 C0 ₂ ► H ₂ N-CN + CaC0 ₃

HN _^ pH 9-10 2 H ₂ N - CN

The commercially available product is a white powder with a melting point of 209 ° C to 211 ° C.

The molding compositions according to the invention can contain 0 to 70, in particular up to 50% by weight of further additives as component D).

As component D), the molding compositions according to the invention can contain 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2% by weight of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids with 10 to 40, preferably 16 to 22, C. Contain atoms with aliphatic saturated alcohols or amines with 2 to 40, preferably 2 to 6 carbon atoms.

The carboxylic acids can be 1- or 2-valent. Examples include his pelargonic acid, palmitic acid, lauric acid, margaric acid, didecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 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 include stearylamine, ethylene diamine, propylene diamine, hexamethylene diamine, di (6-aminohexyl) amine, with ethylene diamine and hexamethylene diamine being particularly preferred. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.

Mixtures of different esters or amides or esters with amides can also be used in combination, the mixing ratio being arbitrary.

Customary additives D) are, for example, in amounts of up to 40, preferably up to 30,% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers), which are different from component A).

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 ester with 1 to 18 carbon 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 by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

Some preferred types of such elastomers are presented below.

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

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

Examples of diene monomers for EPDM rubbers are 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, He- xa-l, 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene 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-methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadiene or their mixtures called. Hexa-1,5-diene, 5-ethylidene norbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.

EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as 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 can 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 adding monomers of general formulas I or II or III or IV containing dicarboxylic acid or epoxy groups to the monomer mixture

RlC (COOR ² ) = C (COOR ³ ) R ⁴ (I)

R ¹ - _ R ⁴

(II)

CO CO

10 o

/ \

CHR ⁷ = CH (CH ₂ ) _m - 0 (CHR ⁶ ) _g CH CHR5 (III)

15

CH ₂ = CR ⁹ COO (CH ₂ ) _P CH CHR ⁸ (IV)

\ /

20 wherein R ¹ to R ^{9 represent} 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 are} preferably hydrogen, where m is 25 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 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 that of the free acids and 35 are therefore referred to as monomers with latent carboxyl groups.

The copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / 40 or monomers containing methacrylic acid and / or acid anhydride groups and the remaining amount of (meth) acrylic acid esters.

Copolymers are particularly preferred

45 50 to 98, in particular 55 to 95% by weight of ethylene, 0.1 to 40, in particular 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and

1 to 45, in particular 10 to 40% by weight of 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 processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.

Preferred elastomers are also emulsion polymers, the production of which e.g. is described in Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts that can be used are known per se.

In principle, homogeneous elastomers can be used or they can be used with a shell structure. 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.

Representative here are as monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof. These monomers can be combined 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 can be copolymerized.

The soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two layers). in the case of multi-layer elastomers, several shells can also consist of a rubber phase.

If, in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C.) are involved in the construction of the elastomer, these are generally replaced by Polymerization of styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers. In addition, smaller proportions of further 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, carboxyl, latent carboxyl, amino or amide groups as well as functional groups by the use of monomers of the general formula

_R ιo _R n II

CH2 = CXNCR ¹²

can be introduced

where the substituents can have the following meanings:

Rio hydrogen or a Ci to C ₄ alkyl group,

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

R ¹² is hydrogen, a Cι ~ to Cio-alkyl, C ₆ - to Cι group ₂ -aryl or -OR ¹³

R ^{13 is} a C 1 -C 6 -alkyl or C 1 -C ₂ aryl group, which may optionally be substituted with 0 or N-containing groups,

X is a chemical bond, a C ~ to C ~ ~ alkylene or C - Ci ₂ ~ arylene group or

0 C Y

Y 0-Z or NH-Z and

Z is a Ci to Cio alkylene or ξ to Cι ₂ arylene group. The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.

Further examples include 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) called ethyl acrylate.

The particles of the rubber phase can also be crosslinked. Monomers acting as crosslinkers are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.

So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization. Compounds are preferably 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. polymerizes much slower (polymerize). The different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. 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, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.

Examples of such graft-crosslinking monomers are monomers containing allyl groups, 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. There are also a large number of other suitable graft-crosslinking monomers; for further details, reference is made to, for example, 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. Some preferred emulsion polymers are listed below. First of all, graft polymers with a core and at least one outer shell have the following structure:

Instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of buta-l, 3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be prepared by using crosslinking monomers or monomers with 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 with an inner core of n-butyl acrylate or based on a butadiene and an outer shell from the above mentioned copolymers and copolymers of ethylene with comonomers which provide reactive groups.

The elastomers described can also be produced by other customary processes, for example 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 also preferred.

Of course, mixtures of the rubber types listed above can also be used.

Fibrous or particulate fillers are carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in quantities of up to 50% by weight. %, in particular 1 to 40%, in particular 20 to 35% by weight, are used.

Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.

The fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.

Suitable silane compounds are those of the general formula

(X- (CH ₂ ) _n ) _k -Si- (0-C _m H _{2m +} ι) ₄ - _k

in which the substituents have the following meaning:

NH ₂ -, CH -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 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on D) for surface coating. Acicular mineral fillers are also suitable.

For the purposes of the invention, acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character. An example is needle-shaped wollastonite. The mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler can optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.

Kaolin, calcined kaolin, wollastonite, talc and chalk may be mentioned as further fillers.

As component D), the thermoplastic molding compositions according to the invention can contain customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.

Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called.

As UV stabilizers, generally in amounts up to

2 wt .-%, based on the molding composition, are used, various substituted resorcinols, salicylates, benzotriazoles and benzophenones.

Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants.

Sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc can be used as nucleating agents.

Further lubricants and mold release agents, which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain , saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes.

Examples of plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.

The molding compositions according to the invention can also contain 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.

Examples of these are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are e.g. by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in "Fluorpolymers" (Wiley Interscience, 1972).

These fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size dso (number average) in the range from 0.05 to 10 μm, in particular from 0.1 to 5 μm. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.

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 the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and the remaining starting materials added individually and / or likewise mixed. The mixing temperatures are usually 230 to 290 ° C.

According to a preferred procedure, components B) to D) can be mixed, made up and granulated with a polyester prepolymer or polyamide prepolymer. The granules obtained are then condensed in the solid phase under inert gas continuously or batchwise at a temperature below the melting point of component A) to the desired viscosity. The thermoplastic molding compositions according to the invention are notable for good mechanical properties and good flame retardant properties. Processing is largely carried out without changing the polymer matrix and the mold coating and metal corrosion tendency are greatly reduced. In particular, moldings of this type show improved stability against dry heat or heat. They are suitable for the production of fibers, foils and moldings, in particular for applications in the electrical and electronics sector. These applications include, in particular, lamp parts such as lamp sockets and holders, plugs and connector strips, coil formers, housings for capacitors or contactors, as well as fuse switches, relay housings and reflectors.

Examples

Component A / l polybutylene terephthalate with a viscosity number (VZ) of 130 ml / g (Ultradur®B 4520 from BASF AG), VZ measured in 0.5% solution of phenol / o-dichlorobenzene (1: 1 mixture) 25 ° C according to ISO 1628

Component A / 2: polyethylene terephthalate with a VN of 97 ml / g

Component bi) resorcinol -bis - (diphenylphosphate) (CR 733 -S from Daihachi)

Component b ₂ i) Stabaxol® 1 (Rhein Chemie GmbH)

Component b ₂₂ ) Stabaxol® p (Rhein Chemie GmbH)

Component b ₂₃ ) Elastostab® (Elastogran GmbH)

n from 1 to 100 with R = NHCOOR ', R' = methyl polyether glycol,

Component b ₂ ) Elastostab® (Elastogran GmbH)

n from 1 to 100

R = NCO

Component b ₂ s) Basonat® H / 100 (BASF AG)

) ₆ NCO

N ^{^} ^ 0 I (CH ₂ ) ₆ NCO

Component b ₂₆ ) Vestanat® 1890/100 (Hüls AG)

52

Component b ₂₇ ) Elastostab® (Elastogran GmbH)

n from 1 to 100 with R = NHCOOR ', R' = ethanol

Component C): melamine cyanurate

Component D / 2 1: 1 mixture of Irgafos® 168 and pentaerithritol - tyl - tetrakis - (3 - (3, 5-di - tert.-butyl - -hydroxyphenyl) propionate (Irganox® 1010) (Ciba Speziali tätchemie AG)

Irgafos® 168

Components A) to D) were mixed in a twin-screw extruder at 250 to 260 ° C. and extruded in a water bath. After granulation and drying, test specimens were injected and tested on an injection molding machine.

The test of the stability at elevated operating temperatures was carried out as follows: molded parts (small plates 60x60x2 mm, approx. 11 g) were injected. One molded part each was weighed on the analytical balance and heated to the specified temperature in an aluminum pan in a convection oven.

After the respective storage time (0/10/20 days at 130 ° C), the impact strength a _{k was determined in} accordance with ISO 75 leU on the samples cooled under vacuum.

Granules were also stored under the above conditions (0/10/20 days at 130 ° C) and the VZ was determined in accordance with ISO 1628.

Assessment of discoloration after 30 days at 130 ° C visually by comparison with the starting material

- - = clear brown coloring = slight brown coloring + = slight discoloration (just tolerable) ++ = almost the same color as the starting material

Cu corrosion: storage of a copper plate in direct contact with granulate and visual assessment of the formation of deposits.

strong: clearly black light: isolated dark spots on the copper plate.

The composition of the molding compounds and the results of the measurements can be found in the table.

ng = not measured V - for comparison

Claims

claims

1. Containing thermoplastic molding compositions

A) 10 to 99% by weight of at least one thermoplastic polymer

B) 1 to 50% by weight of a mixture of

bi) at least one phosphorus compound and

b ₂ ) at least one stabilizer compound of the general formulas I to IV

in which

R ¹ , R ² independently of one another are a hydrogen, Ci to Cio alkyl, C ₆ to C ₂ aryl, C ₇ to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl radical,

a, b independently of one another 1 to 5,

c, d independently of one another 0 to 10;

in which

R ^{3 is} a hydrogen, Ci - to Cio-alkyl, C _ß - to Cι ₂ aryl, C ₇ - to C ₁₃ aralkyl, C ₇ - to C ₁₃ alkylaryl radical, 1 to 4,

1 to 100;

in which

R ⁴ , R ¹³ independently of one another are NCO or NHCOOR ', where R' is an alkylpolyether glycol or an alcohol having 1 to 20 C atoms,

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² independently of one another are a hydrogen, Ci- to Cio-alkyl, Cς to Cι ₂ aryl, C ₇ - to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl,

0 to 5

1 to 100;

in which

Rl ⁴ , R15, R16 independently of one another a hydrogen residue or

wherein R ^{17 is} a hydrogen, Ci to Cio alkyl, Cξ to Cι ₂ aryl, C ₇ to C ₁₃ aralkyl, C ₇ to C ₁₃ alkylaryl radical, or

(CH ₂ ) ι-N = C = 0, where 1 is 1 to 20,

l 2 to 8,

j 1 to l-k,

k 0 to ι-j, where j + k <i, or at least two of them

mean,

C) 0 to 40% by weight of a flame retardant, different from b _x )

D) 0 to 70% by weight of further additives, the weight percentages of components A) to D) always giving 100%.

2. Thermoplastic molding compositions according to claim 1, containing based on 100% B)

b _x ) 50 to 99.99% by weight

b ₂ ) 0.01 to 50% by weight

3. Thermoplastic molding compositions according to claims 1 or 2, in which component A) is selected from the group of polyesters, polyamides, polyphenylene ethers, vinyl aromatic polymers, thermoplastic polyurethanes or mixtures thereof.

4. Thermoplastic molding compositions according to claims 1 to 3, containing as component A) at least one polyalkylene terephthalate having 3 to 10 carbon atoms in the alcohol part, which, based on 100 wt.% A), up to 50 wt. - May contain polyethylene terephthalate.

5. Thermoplastic molding compositions according to claims 1 to 4, wherein the phosphor compound bi) has the general formula V. 58

in which

Rl8, R19, _R 20 independently of one another are an alkyl, alkylaryl, arylalkyl or cycloalkyl radical with 7 to

40 carbon atoms,

X is a sulfur or oxygen atom,

m, n, o independently of one another 0 or 1

mean.

6. Thermoplastic molding compositions according to claims 1 to 5, wherein the phosphorus compound is selected from the group triphenylphosphine oxide, triphenylphosphine sulfide, triphenylphosphate, resorcinol bis (diphenylphosphate) or triphenylphosphine or mixtures thereof.

7. Thermoplastic molding compositions according to claims 1 to 6, containing a nitrogen compound as a further flame retardant C).

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

9. Moldings obtainable from the thermoplastic molding compositions according to claims 1 to 7.