CA2076843A1

CA2076843A1 - High impact flameproofed polyphenylene ether-polyamide molding materials

Info

Publication number: CA2076843A1
Application number: CA002076843A
Authority: CA
Inventors: Klaus Muehlbach; Peter Steiert; Wilfried Vogel; Armin Kurps
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1991-09-05
Filing date: 1992-08-25
Publication date: 1993-03-06
Also published as: EP0530693A1; JPH05222286A; DE4129500A1; US5260359A

Abstract

O.Z. 0050/42646 Abstract of the Disclosure: Flameproofed thermoplastic molding materials comprises A) from 5 to 93.5% by weight of a thermoplastic poly-amide, B) from 5 to 85% by weight of a polyphenylene other, of which up to 40% by weight, based on B), may be replaced by an aromatic vinyl polymer, C) from 0.5 to 20% by weight of red or black phos-phorus, D) from 1 to 20% by weight of a block copolymer which has a Shore A hardness > 80 and has been formed from a conjugated diene and an aromatic vinyl compound, E) from 0 to 15% by weight of an impact modifying polymer other than D), F) from 0 to 45% by weight of a fibrous or particulate filler or a mixture of a fibrous with a particulate filler, G) from 0 to 20% by weight of customary additives in effective amounts, the percentages A) to G) adding up to 100%.

Description

r ~ ~ 8 l ~
O.~. 0050/42646 Hi~h Lmpact flameproofed polyphenylene ether-polyamide moldinq materials The present invention relates to flameproofed thermoplastic molding materials comprising A) from 5 to 93.5% by weight of a thermoplastic poly-amide, B) from 5 to 85% by weight of a polyphenylene ether, of which up to 40~ by weight, based on B), may be replaced by an aromatic vinyl polymer, C) from 0.5 to 20~ by weight of red or black phos-phorus, D) from 1 to 20% by weight of a block copolymer which has a Shore A hardness > 80 and has been formed from a con~ugated diene and an aromatic vinyl compound, E) from 0 to 15% by weight of an impact modiEying polymer other than D), F) from 0 to 45~ by weight of a fibrous or particulate filler or a mixture of a fibrous with a particulate filler, G) from 0 to 20% by weight of customary additives, the percentayes A) to G) adding up to 100~.
The present invention also rPlates to the use of these molding materials for producing shaped articles and to the shaped articles obtainable therefrom.
DE-~ 38 31 992 and US 4 242 254 disclose poly-phenylene ether-polyamide molding materials comprising a mixture of halogen-containing flameproofing agents/ red phosphorus and stabilizers. However, halogon-containing compounds are disadvantageous from an environmental point of view, since the burning of such plastics gives rise to highly toxic organic products.
Phosphorus-containin~ compounds are used a~
flameproofing agents for PPE-PA blends are known from EP-A 129 825. The effectiveness of thase compounds is insufficient, so that very large amounts need to be used thereof for UL 94 compliance.

- 2 - O.Z. 0050/42646 ~ Since compounds such as triphenyl phosphate can also be used as plasticizers, the addition of large quantities leads to a deterioration in the mechanical properties, for example the toughness and heat resis-tance, of such molding materials~
The addition of red phosphorus is known from EP-A 384 232, JP-A 63/089567 and JP-A 63/048356. However, the toughness properties of these molding materials are in need of improvement.
More particularly, utility for some purposes is also crucially dependent on the fracture characteristics of damaged articles. Not just a high flame resistance rating is required but also a ~ery large plastic deforma-tion before fracture (ductile fracture).
It is an object of the present invention to make available thermoplastic PPE-PA molding materials which with the addition of a very small amount of flameproofing agent po~sess not only good flame resistance properties but also very good toughness properties.
We have found that thi~ object is achieved by the thermoplastic molding material~ defined in the opening paragraph. Preferred materials of this kind and a use thereof are revealed in subclaims.
As component A) the molding materials according to the prQsent invention contain from 5 to 93~5, prefe-rably from 30 to 71, in particular from 35 to 65, ~ by weight of a thermopla~tic polyamide.
Th~ polyamides used as component A) are known per se and include the partly crystalline and amorphous resins having weight average molecular weights of at least 5000 which are usually referred to as nylons. Such polyamides are described for example in US Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,~41,322, 2,312,966, 2,5t2,606 and 3,393,210.
The polyamides can be prepared for P~ample hy condensation of equimolar amount~ of a saturated or aromatic dicarboxylic acid of from 4 to 12 carbon atoms ~ ~ 7 ~ 3 - 3 - ~.Z. 0~50t42646 with a.saturated or aromatic diamine o 14 carbon atoms or by condensation of ~-aminocarboxylic acids or poly-merization of lactams.
Examples of polyamides are polyhexamethylene-adipamide (nylon 66), polyhexamethyleneazelamide (nylon69)l polyhexamethylenesebacamide (nylon 610), polyhexa-methylenedodecanediamide (nylon 612), the polyamides obtained by ring opening of lactams such as polycapro-lactam (nylon 6) and polylaurolactam, and also poly-ll-aminoundecanoic acid and a polyamide of di(p-amino-cyclohexyl)methane and dodecanedioic acid.
It is also possible to carry out the present invention using polyamides prepared by copolycondensation of two or more of the abovementioned polymers or com-ponents thereof, for example copolymers of adipic acid,isophthalic acid or terephthalic acid and hexamethylene-diamine (nylon 66/6T) or copolymers of caprolactam, terephthalic acid and hexamethylenediamine (nylon 6/6T).
Such partly aromatic copolyamides contain from 4Q to 90%
by weight of units derived from terephthalic acid and hexamethylenediamine. A small proportion of the tereph-thalic acid, preferably not more than 2Q% by weight of the total aromatic dicarboxylic acid used, may be replaced by isophthalic acid or other aromatic dicar-boxylic acids, preferably those in which ths carboxylgroups are para-disposed.
As well as units derived from terephthalic acid and hexamethylenediamine, the partly aromatic copolya-mides contain units derived from ~-caprolactam and/or units derived from adipic acid and haxamethylen~diamine.
The proportion of units derived from ~-caprolactam is up to 50~ by weight, preferably from 20 to 50~ by weight, in particular from 25 to 40~ by weight, while the proportion of units derived from adipic a~id and hexamethylenediamine is up to 60% by weight, prefer-ably from 30 to 60~ by weight, in particular from 35 to 55% by weight.

'? 1' 4 - O. 2 . 0050/42646 - The copolyamides may contain not only units of ~-caprolactam but also units of adipic ~cid and hexa-methylenediamine; in this case it has to be ensured that th~ proportion of units which are free of aromatic groups is not less than 10~ by weight, preferably not less than 20~ by weight. In this case, the ratio of units derived from ~-caprolactam on the one hand and from adipic acid and hexamethylenediamine on the other is not subject to any particular restriction.
Of particular advantage for many purposes are polyamides containing from 50 to 80, in particular from 60 to 75, ~ by weight of units derived from terephthalic acid and hexamethylenediamine and from 20 to 50, prefer-ably from 25 to 40, % by weight of units derived from ~-caprolactam.
Of particular advantage for ternary copolyamides are compositions of from 50 to 70~ by weight of units derived from terephthalic acid and hexamethylenediamine and from 10 to 20~ by weight of units derived from adipic acid and hexam~thylenediamine and also from 20 to 30~ by weight of units derived from isophthalic acid and hexa-methylenediamine.
The partly aromatic copolyamides may be prepared for example by the process described in EP~A-129 195 and ? 129 196.
Preference is given to linear polyamides having a melting point above 200~C.
Preferred polyamides are polyhexamethyleneadip-amide, pol~hexamethylenesebacamide and polycaprolactam and also nylon 6/6T and nylon 66/6T. The polyamides have in general a relative viscosity of from 2.0 to 5, deter mined on a 1~ by weight solution in 96% sulfuric acid at 23C, which corresponds to a molecular weight of from about 15,000 to 45,000. Polyamides having a relative viscosity of from 2.4 to 3.5~ in particular from 2.5 to 3.4, are used with preference.
It is also possible to use polyamides which are h ~ 3 _ 5 _ O.Z. 0050/42646 obtainable for example by condensation of 1,4-diamino-butane with adipic acid at el~vated temperature (nylon-4,6). Methods for preparing polyamides of this structure are described for example in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
It is also possible to use mixtures of different polyamides.
As component B) the molding materials according to the present invention contain from 5 to 85, preferably from 25 to 65, in part,icular from 30 to 65, % by weight of a polyphenylene ether.
The polyphenylene ethers generally have a weight average molecular weight within the range from 10, noo to 80,000, preferably from 20,000 to 60,00Q, in particular from 40,000 to 55,000.
This corresponds to a reduced specific viscosity ~r~d Of from 0.2 to 0.9 dl/g, preferably of from 0.35 to 0.8, in particular from 0.45 to 0.6, measured in a 0.5 by weight solution in chloroform at 25C.
The unmodified polyphenylene ethers bl) are known per se and are preerably prepared by oxidative coupling of ortho-disubstituted phenols.
Examples of substituents are halogen atoms such as chlorine or bromine and alkyl radicals of from 1 to 4 carbon atoms which preferably have no a-disposed ~ertiary hydrogen atom, e.~. methyl, ethyl, propyl or butyl. The alkyl radicals may in turn be substituted by halogen atoms such as chlorine or bromine or by hydroxyl. Further examples of po~sible substituents are alkoxy radicals, preferably of up to 4 carbon atoms, or unsubstituted or halogen and~or alkyl-substituted phenyl radicals. It is similarly possible to use copol~mers of various phenols, for example copolymers of 2,6-dimethylphenol and 2,3,6-trLmet~ylphenol. It is o~ course also possible ~o use mixtures of various polyphenylene ethers.
The polyphenylene ethers used as component bl) may contain process-induced flaws as described for ~ ~ 7 .~
- 6 - 0.2. 0050/42646 example by White et al.l Macromolecules 23 (1990), 1318-29.
Preference i~ given to using those polyphenylene ethers which are compatible with, i.e. wholly or sub~tan-tially soluble in, aromatic vinyl polymers (cf.A. Noshay, Block Copol~mers, pages 8 to 10, ~cademic Press, 1977, and O. Olabisi, Polymer-Polymer Miscibility, 1979, page~ 117 to 189).
Examples of polyphenyl~ne ethers are poly(2,6-di-lauryl-1,4-phenylene ether), poly(~t6-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-stearyloxy-1,4-phenylene ether), poly~2,6-dichloro-1,4-phenylene ether), poly(2~me~hyl-6-phenyl-1,4-phenylene ether), poly(2,6-dibenzyl-1,4-phenylene ether), polyl2-ethoxy-1,4-phenylene ether), poly-(2-chloro-1,4-phenylene ether), poly(2,5-dibromo-1,4-phenylene ether). Preference i~ given to using polyphenylene ethers wh~re the substituents are alkyl radicals of from 1 to 4 carbon atoms, such as poly-(2,6-dimethyl-1,4-phenylene ether)/ poly(2,6-diethyl-1,4-phenyleneether),poly~2-methyl-6-ethyl-1,4-phenylene ether)/ poly(2-methyl-6-propyl-l/4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether) and poly(2-ethyl-6-propyl-1,4-phenylene ether).
It i~ further pos~ible to use graft copolymers formed from polyphenylene ethers and aromatic vinyl monomers such as styrene, -methylstyrene, vinyltoluene and chlorostyrene.
Functionalized or modified polyphenylene ethers are known per se, for example from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 116 and EP-A-254 048.
Customarily, an unmodified polyphenylene ether b1) is modified by incorporation of t least one car-bonyl, carboxyl, anhydride, ~mide, Lmide, carbo~ylic - 7 - O.Z. 0050/~2646 ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl group to ensure adequate compatibility with the polyamide (component A).
The modification is in general carried out by reacting an unmodified polyphenylene ether bl) with a modifier which contains at least one of the abovemen-tioned groups and at least one C-C double or C-C txiple bond, in solution (WO-A 86/2086), in aqueous dispersion, in a gas phase process (~P-A-25 200) or in the melt in the presence or absence of suitable aromatic vinyl polymers or tougheners with or without free radical initiators.
Suitable modifiers (b3) are for example maleic acid, methylmaleic acid, itaconic acid, tetrahydro-phthalic acid, anhydrides and imides thereof, fumaricacid, the mono- and diesters of these acids, for example with Cl- and C2- to C~-alkanols (b31), the mono- and diamides of these acids such as N-phenylmaleimide (monomer b32), maleohydrazide. It is also possible to use for example N-vinylpyrrolidone and (meth)acryloyl-caprolactam ~b33).
Another group of modifiers includes for ex~mple the acid chloride of trimellitic anhydride, 4-acetoxy-carbonyl-1,2-phthalic anhydride, pyromellitic anhydride, chloroethanoylsuccinaldehyde, chloroformylsuccinaldehyda, citric acid and hydroxysuccinic acid.
Proference is given to u~ing as component B) in the molding material~ according to the present invention a modified polyphenylene ether which is obtainabl~ by 30 reacting b~) from 70 to 99.95, preferably from 76.5 to 99.94, %
by weight of an unmodified polyphenylPne ether~
b2) from 0 to 40~ preferably from 0 to 20, ~ by weight o a~ aromatic vinyl polymer, b33 from 0.05 to 10, preferably form Q.05 to 5/ ~ by weight of at lea~t one compound of ~he group con-sisting of - 8 - O.Z. 0050/42646 b3~) an a,~-unsaturated dicarbonyl compound, b32) an amido-containing monomer having a polymerizable double bond, and b33) a lactamo-containing monomer having a polymerizable double bond, b4) from 0 to 5, preferably from 0.01 to 0.09, % by weight of a free radical initiator, the weight percentages being based on the sum total of bI) to b4), in the course of 0.5 to 15 minutes at from 240 to 375C in suitable mixing and kneading apparatus such as twin-screw extruders.
The aromatic vinyl polymer b2) should preferably be compatible with the polyphenylene ether used.
The molecular weight of these polymers, ~hich are known per se, i~ in general within the range from 1500 to 2,000,000, preferably within the range from 70,000 to 1, 000, 000 .
Examples of preferred aromatic vinyl polymPrs which are compatible with polyphenylene ethers may be found in the abovementioned monograph by Olabisi, pages 224 to 230 and 245. ~Ierely representative examples are aromatic vinyl polymers resulting from styrène, chloro-styrene, a-methylstyrene and p-methylstyrene; minor amounts ~pre~erably not more than ~0, in particular not more than 8, % by weight) can also be present of comono-mers ~uch a~ (meth)acrylonitrile or (meth)acrylic ester~.
Particularly preferred aromatic vinyl polymers are poly~tyrene and high impact polystyrene. I~ i~ of cour3e also pos~ible to use mixtures of these polymers. The preparation is preferably effected by the process described in EP-A-302 485.
Examples of free radical initiators b4) are:
dit2,4-dichlorobenzoyl) peroxide, tert-butyl peroxide, di(3,5,5-trimethylhexanol) peroxide, dilauroyl peroxide, didecanoyl peroxide, dipropionyl peroxide, diben20yl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyi~obutyra~e, _ g - o.z. 0050~42646 1,1-di-tert-butyl peroxy-3,3,5-trimethylcyclohexane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-3,3,5-trimethylhexanoate, tert-butyl peracetate, tert-butyl perbenzoate, butyl 4,4-di-tert-butyl peroxy-valerate, 2,2-di-tert-butylperoxybutane, dicumyl peroxide, tert-butyl cumyl peroxide, 1,3-di(tert-butyl-peroxyisopropyl)benzene, and di-tert-butyl peroxide. It is also possible to use organic hydroperoxides such as diisopropylbenzene monohydroperoxide, cumene hydro-peroxide, tert-butyl hydroperoxide, p-menthyl hydro-peroxide and pinane hydroperoxide and also highly branch-ed alkanes of the general structure R4 ~1 R6 ~3 ~

where R1 to R6 are alkyl groups of from l to 8 carbon atoms, alkoxy groups of 1 to 8 carbon atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles having a ~-electron system and nitrogen, oxygen or sulfur as hetero atoms. The substituents R1 to R6 may each 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-diphenyl-butane, 3,4-dimethyl-3,4-diphenylhexane and 2,2,3,3-tetraphenylbutane.
Particularly preferred polyphenylene ethars B) for the molding materials according to the present invention are obtained by modification with maleic acid, maleic anhydride and fumaric acid. Such polyphenylene ether~ preferably have an acid number of from 1.8 to 3.2, in particular from 2.0 to 3Ø
The acid number is a measure of the degree of modification of the polyphenylene ether and is in general determined by titration with bases under inert ga9 conditions.
The acid number corresponds in general to the ~J~ 3 - 10 - O.Z. 0050/42646 amount of base in mg which is required for neutralizing 1 g of a thus acid-modified polyphenylene ether B) (according to DIN 53 402).
The molding materials according to ths present invention contain as component C) from 1 to 20% by weight, preferably from 1 to 10, in particular Erom 1 to 6, % by weight of red or black phosphorus.
The preferred flameproofing agent (C) is elemen-tal red phosphorus, which can be used in untreated form.
However, of particular suitability are prepara-tions in which the phosphorus has been coated at the surface with low molecular weight liquid substances such as silicone oil, paraffin oil or esters of phthalic acid or adipic acid or with polymeric or oligemeric compounds, eg. with phenolic or amino resins and polyurethanes.
It is also possible to use masterbatches of red phosphorus, for example in a polyamide or elastomer.
Particularly suitable masterbatch pol~ners are polyolefin homopolymers and copolymers. However, the proportion of masterbatch polymer in the molding material according to the invention should not be more than 3~% by weight, based on the weight of components (A) to (D).
The median paxticle size (d50) of the phosphorus particles dispersed in the molding materials is pre-ferably within the range from 0.0001 to 0.5 mm, in particular from 0.001 to 0.2 mm.
As component D) the thermoplastic molding materials accordins ~o the present invention contain from 1 to 20, preferably from 3 to 18, in particular from 4 to 12, % by weight of a block copolymer of a con~ugated dien and an aromatic vinyl compound and which has a Shore A hardness > 80, preferably > 82, in particular >
85.
The Shore A hardness is measured as laid down in DIN 53 505. In general, the hardness of ~he elastomer is taken to mean the measured value of the resistance of an elastomer to the pe~etration into a molding article of an ~ ,3ll'~
- 11 - O.Z. 0050/42646 implement of defined shape and ~ize under a defined forco at 23C. Accordingly, the results obtained as measured values are integers along a relative scale ranging from O = very soft surface to 100 = very hard surface.
S Block copolymers having up to six, preferably up to four, identical or different blocks, which may be linked linearly or else radially, have been found to be particularly suitable.
Preference is given to block rubbers in which at least one block, pref~rably two blocks, is composed of aromatic vinyl monomers such as styrene, a-methylstyrene, vinyltoluene, vinylnaphthalene or isopropenylnaphthalene.
Polystyrene is particularly preferred ~s aromatic vinyl block, in particular as end block.
These preferred block copolymers customarily also contain an elastomeric block which is characterized by a glass transition temperature of less than -30C~ This block is derived for example from con;ugated dienes such as butadiene, isoprene, 1,3-pentadiene or 2,3-dimethyl-butadiene.
The transitions between the individual blocks can be not only sharp but also tapered.
The rubbers which increase the toughness of polyphenylene ethers are preferably linear block copolymers of the general structure A-B, A-B-A' or A-B-A'-B', whare A and A' are each an aromatic vinyl block, preferably polystyrene, and B and B' are each an elastomeric block, which is preferably composed of butadiene and/or isoprene.
Such block copolymers are commercially available (Tufprene- from Asahi Chem. Ind. JP).
The styrene content of the block copolymers C) is in general from 35 to 48, preferably from 38 to 45, ~ by weight, based on the total amount of CompQnent C~.
In addition to the essential components A) to D) the molding materials according ~o the present invention may contain from O to 15, preferably from 3 to 15, in ~ O~3 3 - 12 - O.~. 0050/~2646 particular from 5 to 15, % by weight of an impact modifiPd polymer E) which is different from D).
It is possible to use customary impact modifiers E) which are suitable for polyamides (component A), and rubbers E) which customarily sexv~ to impact modify polyphenylene ethers B) but are different from C).
Examples of rubbers which increase the toughness of polyphenylene ethers are:
polyoctenylenes, graft rubbers having a cross-linked, elastomeric core, derived for example from butadiene, isoprene or alkyl acrylates, and a grafted sheath of polystyrene, also copolymers of ethylene and acrylates or methacrylates and also ethylene-propylene (EP) and ethylene-propylene-diene monomer (EPDM) rubbers, also styrene-grafted EP and EPDM rubbers.
It is also possible to use block copolymers having up to six, preferably up to four, identical or different blocks, which may be linked linearly or else radially, provided that they are different from D), ie.
have a Shore A hardness of up to 80.
It is likewise possible ~o use mixture~ o~ block copolymers of different structures, for example mixtures of two- and three block copolymers or of hydrogenated and unhydrogenated block copolymers.
Such impact modifying polymers are known per se and described in the literature, for example US-A 4,085,163, US-A 4,041,103, US-A 3,149,182, US-A 3,231,635 and US-A 3,462,1S2.
Preference is given to molding materials which contain no further block copolymer~.
Appropriate products are also available commer-cially, for example a polyoctylene under the designation Vestenamer~ from Huls AG and a multiplicity of suitable block copolymer~ containing at least one aromatic vinyl and one elastomeric block. Examples are the Carifle~-TR
range (shell)~ the Kraton~-G range (Shell), the Finaprene range (Fina) and the Europrene~ SOL-T~ range .

- 13 - o.z. 0050/42646 (Enichem).
Rubbers which increase the toughness of poly-amides generally have two essential features: an elas-tomeric portion which has a glass transition temperature of less than -10C, preferably of less than -30C, and at least one functional group capable of reacting with the polyamide. Suitable functional groups are for example carboxylic acid, carboxylic anhydride, carboxylic ester, carboxamide, carboximide, amino, hydroxyl, epoxy, urethane and oxazoline groups.
Examples of rubbers which increase the toughness of polyamides are:
EP and EPDM rubbers which have been grafted with the abovementioned functional groups. Suitable grafting reagents are for example maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacry-late. These monomexs can be grafted onto the polymer in the melt or in solution in the presence or absence of a free radical initiator such as cumene hydroperoxide.
Further examples are copolymers of a-olefins. The a-olefins are customarily monomers of from 2 to 8 carbon atoms, preferably ethylene and propylene. Suitable comonomers are alkyl acrylates or alkyl methacrylates derived from alcohols of from 1 to 8 carbon atoms, preferably from ethanol, butanol or ethylhexanol, and also reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (meth)acrylate and vinyl ester~, in particular vinyl àcetato. It is also possiblQ to use mixtures of different comonomers. Of particular suitability are copolymers of ethylene with ethyl or butyl acrylate and acrylic acid and/or maleic anhydride.
The copolymers can be prepared in a high pressure process at a pressure of from 400 ~o 4500 bar or by grafting the comonomers onto the poly-a-olefin. The proportion of a-olefin in the copolymer is in general within the range from 99.95 to 55% by weight.

- 14 - O.Z. 0050~ 3 ~ 3 A further group of suitable elastomers are coreshell graft rubbers. These are graft rubbers which are prepared in emulsion and consist of at least one hard and one soft part. The hard part customarily comprises a polymer having a glass transition temperature of at least 25C and the soft part a polymer having a glass transi-tion temperature of not more than 0C. These products have a structure with a core and at least one shell, due to the order of addition of the monomars. The soft parts are in general derived from butadiene, isoprene, alkyl acrylates or alkyl methacrylates with or without further comonomers. Suitable comonomers for this purpose are for example styrene, acrylonitrile and crosslinking or grafting monomers having more than one polymerizable double bond such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso)cyanurate. The hard parts are in general derived rom styrene, a-methyl-styrene and copolymers thereof~ the preferred comonomers here being acrylonitrile, methacrylonitrile and methyl methacrylate.
Preferred core-shell graft rubbers contain a sot core and a hard shell or a hard core, a first, soft shell and at least one further, hard shell. ~he incorporation of functional groups such as carbonyl, carboxyl, an-hydride, amide, imide, carboxylic ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups is preferably effected here by the addition of ~ui~able functionalized monomers in the course of the polymerization of the last shell. Suitable functionalized monomer~ are for example maleic acid, maleic anhydride, mono- and diesters of maleic acid, tert-butyl (meth)acry late, ac~ylic acid, glycidyl (meth)acrylate and vinyl-oxazoline. The proportion of monomer~ having functional groups is in general from 0.1 to 25~ by weight, prefer-ably from 0.25 to 15% by weight, based on the total weight of the core-shell graft rubber. The weight ratio of soft to hard is in general from 1:9 to 9:1, preferably A~
- lS - o . z . 0050/42646 from 3:7 to 8:2.
Rubbers of this type, which increase the toughness of polyamides, are known per se and described for example in EP-A 208,187.
A further group of suita~le impact modifiers E) are thermoplastic polyester elastomers. For the purposes of the present invention polyester elastomers here are segm~nted copolyether-esters which contain long-chain segments, in general derived from poly(alkylene) ether glycols, and short-chain segments~ derived from low molecular weight diols and dicarboxylic acids. Products of this type are known per se and described in the literature, for example in US-A 3,651,014. Corresponding products are also commercially available under the designation~ Hytrel~ (Du Pont), Arnitel~ (Akzo) and Pelprene~ (Toyobo Co. Ltd.).
It is of course also possible to use mixtures of various rubbers.
As component F) the molding materials according to the present invention may contain from 0 to 45, preferably from 10 to 40, ~ by weight of fibrous or particulate fillers or mixtures thereof. Examples of fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass rovings, glass balls and also wollastonite.
Preferred fibrous reinforcing materials (com-ponent F) are carbon fibers, potassium titanate whiskers, aramid fibers and particularly preferably glass fibers.
If glass fibers are used, their compatibility with the thermoplastic polyamide (A) or the modified polyphenylene ether (B) may be improved by treating them with a size and an adhesion promoter. In general, the carbon and glass fibers used have a diameter within the range from 6 to 20 ~m.
These gla~s fibers may be incorporated not only in the form of chopped fiber but also in the foxm of continuous rovings. In the ready-produced injec~ion ~7~ 3 - 1~ - O.Z. 0050/42646 moldin~, the average length of the glass fibers i5 preferably within the range from 0.08 to 0.5 mm.
Suitable particulate fillers (component F) are amorphous silica, asbestos, magnesium carbonate (chalk), pulverulent quartz, mica, talc, feldspar and in par-ticular calcium silicates such as wollastonite and kaolin (in particular calcined kaolin).
Preferred combinations of fillers are for example 20~ by weight of glass fiber with 15% by weight of wollastonite and 15% by weight of glass fiber with 15~ by weight of wollastonite.
As well as the essential components A) to D) and the optional components E) and F) the molding materials according to the present invention may contain customary additives and processing aids G). The proportion thereof is in general up to 20, preferably up to 10, ~ by weight, based on the total weight of components A to E.
Customary additives are for example antioxidants, thermal stabilizers, W stabilizers, lubricants, demolding agents, dyes, pigments and plasticizers.
Oxidation retarders and heat stabilizers which can be added to the thermoplastic materials of the present invention are for example halidas o metals of group I of the periodic table, for example sodium, potassium or lithium halides, with or without copper(I~
halides, for example chlorides, bromides or iadides It i~ also possible to use zinc 1uoride and zinc chloride.
Other possibilities are sterically hindered phenols, hydroquinones, substituted representatives of this group and mixtures of these compounds, preferably in concentrations up to 1~ by weight, based on the weight of the mixture.
Examples of W stabilizers are various substi-tuted resorcinols, salicylAtes, benzotriazoles and benzophenones, which in general are used in amounts up ~o 2~ by weight.
Materials for enhancing the shielding from 2~7~4~
- 17 - O.~. OOS0/42646 electromagnetic waves such as metal flakes, powders, fibers and conductive polymers can also be used.
Lubricants and demolding agents, which in ~eneral are added to the thermoplastic material in amounts up to 1~ by weight, are stearic acid, stearyl alcohol, alkyl stearates, N-alkylstearamides and also esters of pentaerythritol with long-chain fatty acids.
Furthermore, it i~ advantageous to reduce the water imbibition of the polyamide by adding monophenolic compound~ such as 2- or 4-t-butylphenol or dihydroxy-biphenyls and derivatives thereof in amounts of up to 8%
by weight.
Additives also include stabilizers which prevent the decomposition of red phosphorus in the presence of moisture and atmospheric oxygen. Examples are compounds of cadmium, zinc, aluminum, silver, iron, copper, an-timony, tin, magnesium, manganese, vanadium, boron and titanium. Particularly suitable compounds are for example oxides of said metals and also carbonates or oxycar-bonates, hydroxides and also salts of organic or inorga-nic acids such as acetates or phosphates or hydrogen-phosphates and sulfates.
The thenmoplastic molding materials according to the present invention are advantageously obtained by mixing the individual components at ~rom ~70 to 350~C in customary mixing apparatus, such as kneaders, Banbury mixers and single-screw extruders, but preferably using a twin-screw extruder. To obtain as homo~eneous a molding material as possible, thorough mixing is crucial. The order of addition of components can be varied, so that two or even three components may be premixed, but it is also possible to mix all the components together.
It is to be noted that the preparation of the molding materials may be accompanied by a reaction between the components A) to D), in particular between A) and B~, so that the end product no longer represents a pure mixture of these components.

2 ~ 3 - 18 - O.Z. 0050/42646 The molding materials according to the present invention are notable for excellent flame resistance properties but in particular for very high toughness.
They are suitable in paxticular for producing shaped articles by injection or extrusion molding, in particular for thermally stressed components in the automotive sector. In the latter sector it is of par-ticular advantage that the components produced from the molding materials according to the present invention retain toughness even at low temperatures.
EXAMPLES

Component A
Polyhexamethyleneadipamide having a K value of 70; measured in a 1% by weight solution in 96~ by weight sulfuric acid at 25C. This K value corresponds to a relative viscosity of 2.5 or a viscosity number of 133 ml/g.

Component B/l A modified polyphenylene ether of 90% by weight of poly(2,6-dimethyl-1,4-phenylene ether) (~r~d = 0.58, measured in a 0.5~ by weight solution in chloroform at 25C), 9~ by weight of polystyrene (melt flow index NFI at 200C under a load of 5 kg: 24 g~min), 1~ by weight of fumaric acid wa~ prepared hy mixing the components at 2gO-310C in a twin-scre-~ extruder with subsequent devolatilization. The melt was passed through a water bath, granulated and dried.

Component B/2 A modified polyphenylene ether of 88~ by weight of poly~2,6-dimethyl-1,4-phenyl~ne ether) ( ~r~ = 0.63, measured in a 1~ by weight solution in chloroform at 25C~, 6~
- l9 - O.Z. 0050/42646 10~ by weight of polystyrene (melt flow index MFI at 200C under a load of 5 kg: 24 g/min), 2% by weight of maleic anhydride was prepared by mixing the components at 290-310C in a twin-screw extruder with subsequent devolatilization. The melt was passed through a water bath, granul ted and dried.

Component C/l Red phosphorus of median particle size (d~o) of from lO to 30 ~m.
The phosphorus was phle~matized with polyurethane (Astacin~ Finish PUD, BASF Aktiengesellschaft). To this end 500 ml of aqueous-alkaline suspension of phosphorus containing 250 g of red phosphorus (particle size 0.001-0.4 mm) was heated to 60C and ad~usted to pH 8 with 5% sulfuric acid.
Then 6.5 g of Astacin~ Finish PUD (~0~ aqueous, anionic polyester~polyurethane dispersion prepared as described in DE-C3-26 45 779) were stirred in. The suspension was then stirred at 60C for 1 hour and thereafter filtered. The filter resi~ue was washed with water and then dried in nitrogen at 100C. The poly-urethane content was 1% by weight.

Component C/2 Red phosphorus of median particle size (d50~ of 45 ~m (Exolit~ 385, Hoechst). The phosphorus contained 0.5% by weight of dioctyl phthalate as coating agent.

Component Dtl Four-block rubber (S-B-S'-B') having a styrene content of 42%, a butadiene content of 58~ and a Shore A
hardness of 87 (Tufprene~ A from Asahi Chem) Component D/2~) Three-block rubber (S-B-S') having a styrene - 20 - O.Z. 0050/42646 content of 29%, a butadi~ne content of 71~ and a Shore ~ 7~ 3 hardness of 70 (Cariflex3 TR 1102 from Shell) Component D/3*) Three-block rubber (S-EB-S') having a styrene content of 29%, a hydrogenated butadiene content of 71%
and a Shore A hardness of 75 (Karaton~ G 1650 fxom Shell) Component D/4*) Two-block rubber (S-EP) ha~ing a styrene content of 37%, a hydrogenated isoprene content of ~3% and a Shore A hardness of 72 (Kraton~ G 1701 from Shell) Component G) Zinc oxide Preparation of molding materials The components were mixed in a twin-scrPw extru-der at a barrel temperature of ~90C and extruded into a water bath. Component ~ was only added at the melt stage.
After granulation and drying, specimens were injection molded for testing.
The following measurements were carried out:
Izod notched impact strength (ak) [kJ/m~] ISO 180/4A
Penetration energy (W8) ~Mm] DIN 53 443 Flammability test UL-94 The flammability test was carried out as the Underwriters' Laboratories vertical burning test for classif~ing materials ~4 V-0, 94 V-1 or 94 V-2.
A flameproofed thermoplastic is classed UL 94 V-0 if it meet~ the following criteria: in a set of 5 speci-mens me~suring 127 x 12.7 x 3.2 mm there shall not be any specimens which burn with flaming combustion (flame height 19 mm) after each of ~wo 10 sPcond applications of the test flame. The total flaming combustion ~Lme for the lQ flame applications for each set of S samples mus~ no~
exceed 50 s. There must not be any spacLmens which drip 2~76~
- 21 - O.Z. 0050~42646 flaming particles, which burn up to the holding clamp or whoss glowing combustion persists beyond 30 s. For classification as UL 94 V-l the combustion times must not exceed 30 s and the total flaming combustion time for the 10 flame applications for each set of 5 specimens must not exceed 250 s.
Glowing combu~tion must never persis-t beyond 60 s. The other criteria are identical with those men-tioned above. A material is classed as UL 94 V-2 if, while meeting the other criteria of UL 94 V-l, it does have specimens that drip flaming particles.
The compositions of the molding materials and the results of the measurements are revealed in the Table.

- 22 - ~.Z. 0050/~ 3 .

_ ' ,3~77 d' CO ~
_ ~ C~

~3 , t~
~ , _. C~
.~ ooo o ~ ~
,~
~o ~S S S~
oooooo N N ~ ~ ~ O
N ~i ~ ~ ~ 0 ~ . ~
.~ m m ài à~ m ai .~ ~ 5~n o o o o _~ o ~D_l ~ ~ ~
~ ~ U~ D .~
~ r ~ ~
~ __ '~ ~ ~
'~JH H ~

- 23 - O.Z. 0050/ ~ g~ 3 . The novel combination of block copolymer and pho~phorus in the molding materials achieves a V-O
classification coupled with good toughness. This is unexpected in that the block copolymer with the highest Shore A hardness gives the tougher moldings coupled with good flame resistant properties when combined with red phosphorus. When hydrogenated block copolymers (see Examples II and III) and low levels of phosphorus are used, classification under UL 94 is not possible.

Claims

1. A flameproofed thermoplastic molding material comprising A) from 5 to 93.5% by weight of a thermoplastic poly-amide, B) from 5 to 85% by weight of a polyphenylene ether, of which up to 40% by weight, based on B), may be replaced by an aromatic vinyl polymer, C) from 0.5 to 20% by weight of red or black phosp-horus, D) from 1 to 20% by weight of a block copolymer which has a Shore A hardness > 80 and has been formed from a conjugated diene and an aromatic vinyl compound, E) from 0 to 15% by weight of an impact modifying polymer other than D), F) from 0 to 45% by weight of a fibrous or particulate filler or a mixture of a fibrous with a particulate filler, G) from 0 to 20% by weight of customary additives in effective amounts, the percentages A) to G) adding up to 100%.

2. A flameproofed thermoplastic molding material as claimed in claim 1, comprising A) from 30 to 71% by weight, B) from 25 to 65% by weight, C) from 1 to 10% by weight, D) from 3 to 18% by weight.

3. A flameproofed thermoplastic molding material as claimed in claim 1, wherein the block copolymer D) is composed of at least two blocks of an aromatic vinyl polymer and at least one block of a conjugated diene polymer.

4. A flameproofed thermoplastic molding material as claimed in claim 1, wherein the block copolymer D) has the general formula A-B-A'-B', where A and A' are each an aromatic vinyl block and B and B' are each an elastomeric - 25 - O.Z. 0050/42646 block of a conjugated diene.

5. A flameproofed thermoplastic molding material as claimed in claim 1, wherein the polyphenylene ether B) has been prepared from b1) from 70 to 99.95% by weight of a polyphenylene ether, b2) from 0 to 40% by weight of an aromatic vinyl poly-mer, b3) from 0.05 to 5% by weight of at least one compound which contains at least one double or triple bond and at least one functional group selected from the group consisting of the carboxamides, epoxides, oxazolines and urethanes.

6. Flameproofed thermoplastic molding material as claimed in claim 5, wherein component b3) is maleic acid, maleic anhydride or fumaric acid.

7. A shaped article produced from a molding material as claimed in claim 1.