CA2687362A1 - Impact strength modified polycarbonate compositions - Google Patents

Abstract

The present invention relates to compositions comprising: A) 10 - 99 weight percent aromatic polycarbonate and/or aromatic polyester carbonate, B) 1 - 35 weight percent rubberized graft copolymer of B.1 5 to 95 of at least one vinyl monomer and B.2 95 to 5 of one or more graft foundations having a glass transition temperature of < 10° C, C) 0 - 40 weight percent vinyl(co)polymer and/or polyalkylene terephthalate, excepting a copolymer made of .alpha.-methyl-styrene and acrylnitrile, D) 0 - 50 weight percent phosphorous flame retardant, relative to the sum of components A+B+C, E) 0 - 50 weight percent of additives, relative to the sum of components A+B+C, characterized in that component B can be obtained by reacting component B.1 and the graft foundation B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is used, said compositions being characterized by a high resistance to hydrolysis. The invention further relates to the use of polycarbonate compositions for producing molds and molded parts.

Description

BMS 06 1 150-WO-Nat.

IMPACT STRENGTH MODIFIED POLYCARBONATE COMPOSITIONS
The present invention relates to polycarbonate compositions comprising, as an impact modifier, specific rubber-containing graft polymers prepared by the emulsion polymerization process, these compositions being distinguished by a high stability to hydrolysis and by a high stability during processing, and simultaneously having good mechanical properties. This invention likewise relates to the use of the polycarbonate compositions for the production of shaped articles and the shaped articles themselves.

Polycarbonate compositions comprising graft polymers as impact modifiers can have a varying stability to hydrolysis and exposure to heat, depending on the purity and additive content of the impact modifier, e.g. ABS
(acrylonitrile/butadiene/
styrene terpolymer). Thus, B. S. Patty, L. Novak and H. Phan (in "Thermal and hydrolytic stability of polycarbonate/acrylonitrile-butadiene-styrene based blends", Society of Automotive Engineers, [Special Publication] SP (2005), SP-1960 (Advances in Plastic Components, Processes and Technologies), 145-151) describe polycarbonate compositions which have a significantly better stability to hydrolysis and heat stability for bulk ABS as the modifier than in the case of emulsion ABS as the modifier. In this context, the different properties of the polycarbonate/bulk ABS
compositions compared with polycarbonate/emulsion ABS compositions is attributed to the fact that the preparation process for emulsion ABS requires a higher number of various chemicals as auxiliary substances compared with bulk ABS, such as e.g. emulsifiers, flow inlprovers, stabilizers, salts etc., these chemicals also including those which can lead to destruction of the polycarbonate.

Certain polycarbonate compositions comprising emulsion graft polymers as an impact modifier have some industT-ial advantages over polycarbonate compositions comprising bulk ABS. e.g. in respect of the nature of the surface (gloss), so that for some uses it is advantageous to employ emulsion graft polymers. If a higli stability to hydrolysis and heat stability are requiT-ed. high reduii-ements must be imposed on the emulsion graft polymers employed, such as e.g. in respect of the purity thereof, the working up process during the preparation thereof and the omission of certain auxiliary substances during the preparation thereof.

For example, EP-A 0 900 827 discloses impact-modified polycarbonate compositions of improved heat stability comprising emulsion graft polymers which are substantially free from components which degrade the polycarbonate. In order to obtain an emulsion graft polymer substantially free from components which degrade the polycarbonate, such components must be dispensed with completely in every process stage in the emulsion process, or the emulsion graft polymers prepared must be freed from these components by an appropriate working up process, e.g.
by washing after coagulation of the graft emulsion.

WO-A 99/01489 discloses emulsion graft polymers of the ABS type which are prepared by means of the most diverse emulsifiers. Sulfosuccinates, inter alia, are mentioned as possible emulsifiers for the preparation thereof.

The patent application US 2006/0106163 teaches that certain thermoplastic compositions with good stability to weathering and scratch resistance which comprise fine- and coarse-particled ASA graft polymers and further specific resins, inter alia maleic anhydride-modified SAN resins, can be prepared. In addition to the usual long-chain sulfate- and sulfonate-based metal salts, specific metal salts of sulfosuccinic acid derivatives can also be employed inter alia for the preparation of the acrylate rubber bases which are required as the elastic crosslinked core for the ASA graft polymers. For carrying out the grafting step for the preparation of ASA
emulsion polymers, alkali metal salts of fatty acids or resin acids are used as emulsifiers.

DE 697 34 663 T2 describes impact-modified compositions which comprise a vinyl graft polymer as the impact modifier, which can be prepared via the process of emulsion polymerization and preferably in the presence of at least one emulsifier which can be polymerized via free-radical polymerization, i.e. contains double bonds, to which further non-polymerizable emulsifiers can optionally be added.
The hydrophilic-lipophilic structure of the polymerizable emulsifiers can include all known classes of emulsifier, i.e. nonionic, cationic and anionic emulsifiers.
The non-polymerizable emulsifiers optionally added can be all the conventional emulsifiers suitable for emulsion polymerization, inter alia resin acid salts (rosinates), fatty acid salts, alkyl sulfate salts, sulfonates and inter alia also dialkyl-succinic acid salts.

The patent specification EP-A 0390 081 describes impact-modified polyester and polycarbonate compositions with improved impact strength which comprise specific MBS impact modifiers obtainable via the emulsion polymerization path. For the preparation of these MBS impact modifiers, conventional emulsifiers for emulsion polymerization, such as fatty acid salts, alkyl sulfates, alkylbenzenesulfonates, alkyl phosphates and inter alia dialkyl sulfosuccinate salts and the usual nonionic emulsifiers, are employed in the grafting step of the emulsion polymerization.

JP-A 08067789 describes odour-free and heat-stable thermoplastic compositions which comprise styrene-based emulsion polymers. Cationic, anionic and nonionic emulsifiers can be employed for the preparation of these styrene-based emulsion polymers. Anionic emulsifiers which are employed are e.g. fatty acid salts, alkyl sulfates, alkylsulfonates and inter alia sulfosuccinates.

DE 698 27 302 T2 discloses resin compositions with increased impact strength, which can be achieved by addition of hollow particulate rubber-like graft polymers.
The hollow rubber particles are prepared via specific process methods, e.g. by initial swelling with organic solvents, a subsequent grafting reaction in emulsion and removal of all the volatile constituents after the grafting. Known emulsifiers, such as e.g. fatty acid and resin acid metal salts, alkyl- and arylsulfonates, inter alia sodium dioctyl sulfosuccinate, are used for the grafting reaction in the preparation of hollow rubber-like graft polymers. Compositions which comprise a-methylstyrene/acrylonitrile copolymer, polycarbonate and a graft polymer of non-hollow rubber grafted particles with a shell of styrene and acrylonitrile, sodium dioctyl sulfosuccinate being employed as an emulsifier in the grafting stage for the preparation of the graft polymer, are disclosed as comparison examples The object of the present invention is to provide polycarbonate moulding compositions comprising at least one emulsion graft polymer as an impact modifier, which are distinguished by a high resistance to hydrolysis and by a high stability during processing with simultaneously good mechanical properties.

A further object of the invention is to provide flameproofed polycarbonate moulding compositions comprising at least one emulsion graft polymer as an impact modifier, which are distinguished by a high resistance to hydrolysis, a high stability during processing, an improved notched impact strength (ak), an improved weld strength (anF) and simultaneously by an improved elongation at tear.

It has been found, surprisingly, that compositions comprising A) 10 - 99 parts by wt., preferably 40 - 95 parts by wt., particularly preferably 50 - 73 parts by wt. of aromatic polycarbonate and/or aromatic polyester carbonate, B) 1- 35 parts by wt., preferably 4 - 30 parts by wt., particularly preferably 20 parts by wt. of rubber-modified graft polymer of B. I 5 to 95, preferably 30 to 90 wt.% of at least one vinyl monomer on B.2 95 to 5, preferably 70 to 10 wt.% of one or more graft bases having a glass transition temperature of < 10 C, preferably < 0 C, particularly preferably < -20 C, C) 0 - 40 parts by wt., preferably 1- 30 parts by wt., particularly preferably 25 parts by wt. of vinyl (co)polymer and/or polyalkylene terephthalate, excluding a copolymer of a-methylstyrene and acrylonitrile, D) 0 - 50 parts by wt., preferably 1- 40 parts by wt., particularly preferably 30 parts by wt., in each case based on the sum of components A+B+C, of phosphorus-containing flameproofing agent, E) 0 - 50 parts by wt., preferably 0.5 - 25 parts by wt., in each case based on the sum of components A+B+C, of additives, characterized in that component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is employed EWG
I
R9 - C - Y - [Mz+] 1 /z (I) I
w wherein EWG is an electron-withdrawing group, such as e.g. a carbonyl, a carboxyl, a nitrile, a nitro or a sulfone group, preferably a nitrile group, carbonyl group -C(=O)Rg or carboxyl group -C02R8, particularly preferably a carboxyl groups -C02R8, wherein R8 in each case denotes H, alkyl, cycloalkyl, (aryl)alkyl or alkyl(aryl) having 1 to 30 carbon atoms, preferably methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, (methyl)hexyl, octyl, (ethyl)hexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, phenyl, benzyl, phenyl substituted by C, to C30-alkyl (such as e.g.
methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, (tridecyl)phenyl) or in each case C2 to Cloo ethoxylated fatty alcohol radicals having 3 to 130 carbon atoms, C3 to C99 propoxylated fatty alcohol radicals having 4 to 129 carbon atoms, C2 to Cloo ethoxylated (alkyl)phenol radicals having 3 to 130 carbon atoms, C3 to C99 propoxylated (alkyl)phenol radicals having 4 to 129 carbon atoms, particularly preferably propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, especially preferably hexyl, cyclohexyl, heptyl, n-octyl and 2-ethylhexyl, W is a group chosen from C, to C30-alkyl, Cl- to C30-cycloalkyl, C6- to C30-aryl, CI -to C30-(aryl)alkyl, Cl- to C30-(alkyl)aryl, Cl- to C30-alkoxy, CI- to C30-aryloxy, C2 to Cloo ethoxylated alkoxy or aryloxy group according to the formula RO-(CH2-CH2-O)a , where a = I to 50 and R= Cl- to C30-alkyl or Cl- to C30-aryl, wherein all the groups mentioned can also be substituted, e.g.
by one or more electron-withdrawing groups according to the above definition for EWG, R9 denotes H or a C, to C30-alkyl, C, to C30-aryl, C, to C30-(alkyl)aryl, which in each case can also be substituted, preferably denotes H, C, to C30-alkyl, C, to C30-(aryl)alkyl or C, to C30-(alkyl)aryl, particularly preferably H, Y- is an anionic group, preferably chosen from borate (-O-BO(OR9)-), boronate (-BO(OR9)-), nitrate (-O-NO2-), nitro (-N02-), sulfate (-O-S03-), sulfonate (-S03-), phosphate (-O-P(OR9)O2-), phosphonate (-P(OR9)O2-), particularly preferably chosen from sulfate or sulfonate, especially preferably a sulfonate group -S03-, wherein R9 in each case has the meaning explained above, z represents the number 1 or 2, and z is preferably 1, MZ+ is chosen, for z = 1, from the group consisting of alkali metals (such as e.g. Li+, Na+> K+> Rb+> Cs+)> ammonium cation, alkylammonium cation (NH4-nR9n+
, wherein n can be 1 to 4), phosphonium cation and alkylphosphonium cation (PH4_õR9õ+, wherein n can be I to 4), wherein R9 in each case has the meaning explained above, or, for z = 2, is chosen from the series consisting ~+ 2+
of the alkaline earth metals (such as e.g. Mg , Ca , Sr2+, Ba~+), Mz +

preferably represents M+ (i.e. z = 1) and is chosen from the group consisting of Li+, Na+, K+, ammonium cation, alkylammonium cation, phosphonium cation and alkylphosphonium cation, and M+ is particularly preferably Na+ or , K

all the parts by weight stated in the present Application being standardized such that the sum of the parts by weight of all the components A+B+C in the composition is 100, have the desired profile of properties.

It has been found, surprisingly, that in the preparation of the graft polymer B by means of emulsion polymerization, no particular purification is required, e.g.
by washing the coagulated graft polymer with one to up to 100 times the amount of water, since surprisingly, in spite of the emulsifier remaining in the resulting graft polymer, the resulting impact-modified polycarbonate compositions have a high resistance to hydrolysis.

Component A

Aromatic polycarbonates and/or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396; for the preparation of aromatic polyester carbonates e.g. DE-A 3 077 934).

The preparation of aromatic polycarbonates is carried out e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols, and optionally using branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols. A preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is also possible.

Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (II) (B)X (B)X OH
-A--'~ (II), HO
P
wherein A is a single bond, C, to C5-alkylene, C2 to C5-alkylidene, C5 to C6-cycloalkylidene, -0-, -SO-, -CO-, -s-, -SOZ-, C6 to C12-arylene, on to which further aromatic rings optionally containing hetero atoms can be fused, or a radical of the formula (III) or (IV) _C1 X1 )m (III) R 5 \ R 6 ~ H3 iH3 CH3 i - (~') B in each case is C, to C12-alkyl, preferably methyl, halogen, preferably chlorine and/or bromine, x in each case independently of one another, is 0, 1 or 2, p is 1 or 0 and R5 and R6 can be chosen individually for each Xl and independently of one another denote hydrogen or C, to C6-alkyl, preferably hydrogen, methyl or ethyl, X~ denotes carbon and m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom Xl R5 and R6 are simultaneously alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C1 -C5-alkanes, bis-(hydroxyphenyl)-C5-C6-cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones and a,a-bis-(hydroxyphenyl)-diisopropyl-benzenes and nucleus-brominated and/or nucleus-chlorinated derivatives thereof.

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and di- and tetrabrominated or chlorinated derivatives thereof, such as, for example, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. 2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred.

The diphenols can be employed individually or as any desired mixtures. The diphenols are known from the literature or obtainable by processes known from the literature.

Chain terminators which are suitable for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, and also long-chain alkylphenols, such as [2-(2,4,4-trimethylpentyl)] -phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain terminators to be employed is in general between 0.5 mol% and 10 mol%, based on the sum of the moles of the particular diphenols employed.

The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (MW, measured e.g. by GPC, ultracentrifuge or scattered light measurement) of from 10,000 to 200,000 g/mol, preferably 15,000 to 80,000 g/mol, particularly preferably 24,000 to 32,000 g/mol.

The thermoplastic, aromatic polycarbonates can be branched in a known manner, and in particular preferably by incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, for example those having three and more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. It is also possible for 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of diphenols to be employed, of polydiorganosiloxanes having hydroxyaryloxy end groups to be employed for the preparation of copolycarbonates according to the invention according to component A. These are known (US 3 419 634) and can be prepared by processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxanes is described in DE-A 3 334 782.

Preferred polycarbonates are, in addition to the bisphenol A
homopolycarbonates, the copolycarbonates of bisphenol A with up to 15 mol%, based on the sum of the moles of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.

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

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

A carbonic acid halide, preferably phosgene, is additionally co-used as a bifunctional acid derivative in the preparation of polyester carbonates.

Possible chain terminators for the preparation of the aromatic polyester carbonates are, in addition to the monophenols already mentioned, also chlorocarbonic acid esters thereof as well as the acid chlorides of aromatic monocarboxylic acids, which can optionally be substituted by C, to C22-alkyl groups or by halogen atoms, as well as aliphatic C2 to C22-monocarboxylic acid chlorides.

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

The aromatic polyester carbonates can also contain incorporated aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates can be either linear or branched in a known manner (in this context see DE-A 2 940 024 and DE-A 3 007 934).

Branching agents which can be used are, for example, carboxylic acid chlorides which are trifunctional or more than trifunctional, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3',4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of from 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides employed), or phenols which are trifunctional or more than trifunctional, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl] -propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis-(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4- [4-hydroxyphenyl-i sopropyl] -phenoxy) -methane and 1,4-bis-[4,4'-dihydroxytriphenyl)-methyl] -benzene, in amounts of from 0.01 to 1.0 mol%, based on the diphenols employed. Phenolic branching agents can be initially introduced into the reaction vessel with the diphenols, and acid chloride branching agents can be introduced together with the acid dichlorides.

The content of carbonate structural units in the thermoplastic, aromatic polyester carbonates can be varied as desired. Preferably, the content of carbonate groups is up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the polycondensate in the form of blocks or in random distribution.

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

The thermoplastic, aromatic polycarbonates and polyester carbonates can be employed by themselves or in any desired mixture.
Component B
Component B comprises one or more graft polymers of B.1 5 to 95, preferably 30 to 90 wt. % of at least one vinyl monomer on B.2 95 to 5, preferably 70 to 10 wt. % of one or more graft bases having a glass transition temperature of < 10 C, preferably < 0 C, particularly preferably < -20 C.

characterized in that the reaction of component B.1 with the graft base B.2 is carried out by means of emulsion polymerization ("grafting reaction"), an emulsifier according to formula (I) being employed.

The graft base B.2 in general has an average particle size (d50 value) of from 0.05 to m, preferably 0.1 to 5 m, particularly preferably 0.2 to 0.8 m.

Monomers B.1 are preferably mixtures of B.l.l 50 to 99 parts by wt. of vinylaromatics and/or nucleus-substituted 10 vinylaromatics (such as styrene and p-chlorostyrene) and/or (meth)acrylic acid (Ci-Cg)-alkyl esters (such as methyl methacrylate and ethyl methacrylate) and B. 1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and/or (meth)acrylic acid (CI-Cg)-alkyl esters, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate, and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.

Preferred monomers B.1.1 are chosen from at least one of the monomers styrene and methyl methacrylate, and preferred monomers B. 1.2 are chosen from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
Particularly preferred monomers are B.1.1 styrene and B. 1.2 acrylonitrile.

Graft bases B.2 which are suitable for the graft polymers B are, for example, diene rubbers, EP(D)M rubbers, that is to say those based on ethylene/propylene and optionally diene, and acrylate, polyurethane, silicone, chloroprene and ethylene/vinyl acetate rubbers.

Preferred graft bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (e.g. according to B.1.1 and B.
1.2), with the proviso that the glass transition temperature of component B.2 is below < 10 C, preferably < 0 C, particularly preferably < -10 C. Pure polybutadiene rubber is particularly preferred.

The gel content of the graft base B.2 is at least 30 wt.%, preferably at least 40 wt.%
(measured in toluene at 25 C).

The graft base B.2 is prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization.
Since as is known the grafting monomers are not necessarily grafted completely on to the graft base during the grafting reaction, according to the invention graft polymers B are also understood as meaning those products which are obtained by (co)polymerization of the grafting monomers in the presence of the graft base and are additionally obtained during working up.

Emulsion graft polymers which have a core-shell structure are preferably employed.
Suitable acrylate rubbers according to B.2 of the polymers B are, preferably, polymers of acrylic acid alkyl esters, optionally with up to 40 wt.%, based on B.2, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C, to C8-alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-Cl-Cg-alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.
For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or saturated polyols having 2 to 4 OH

groups and 2 to 20 C atoms, such as ethylene glycol di(meth)acrylate, trimethyloipropane tri(meth)acrylate and allyl (meth)acrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; and polyfunctional vinyl compounds, such as di- and trivinylbenzenes; and also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl (meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and trivinylbenzenes. The crosslinking monomers can be employed individually, but also in mixtures. The amount of the crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt.%, based on the graft base B.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1 wt.% of the graft base B.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which can optionally serve for the preparation of the graft base B.2 in addition to the acrylic acid esters are e.g. acrylonitrile, styrene, a-methylstyrene, (meth)acrylamides, vinyl Cl-C6-alkyl ethers, methyl methacrylate and butadiene. Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 40 wt.% (measured in toluene at 25 C).

Further suitable graft bases according to B.2 are silicone rubbers having grafting-active sites, such as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS

631 540 and DE-OS 3 631 539.

The gel content of the graft base B.2 is determined at 25 C in a suitable solvent (M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d50 is the diameter above and below which in each case 50 wt.% of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 796).

It is known from the prior art that the graft base B.2 can be prepared by the process of emulsion polymerization. In this context, the polymerization is conventionally carried out at 20 C to 100 C, preferably at 30 C to 80 C. As a rule, conventional anionic emulsifiers are used, for example alkali metal salts of alkyl- or alkylarylsulfonic acids, alkyl-sulfates, fatty alcohol sulfonates, salts of higher carboxylic acids having 10 to 30 carbon atoms, sulfosuccinates, ether-sulfonates or resin soaps. The alkali metal salts, in particular the Na and K salts, of alkylsulfonates, sulfosuccinates, fatty acids or carboxylic acids having 10 to carbon atoms are conventionally used.

The choice of emulsifier for the preparation of the rubber base in the present invention depends on criteria known to the person skilled in the art, such as e.g. the shear stability of the latex and the nature of the latex particles, particle size, particle size distribution, viscosity, residual monomer content and gel content, and in contrast to the teaching of EP-A 0 900 827 therefore does not depend on the exclusion of components which degrade the polycarbonate. According to the present invention e.g. alkali metal salts of resin acids, alkali metal salts of higher fatty acids having 10 to 30 carbon atoms, alkali metal salts of specific dicarboxylic acids (as described e.g. in DE 3 639 904 Al), alkali metal salts of alkyl- or aryl-sulfates or -sulfonates or alkali metal salts of sulfosuccinates are used.
Emulsifier mixtures and combinations of ionic and nonionic emulsifiers can also be employed in the manner known to the person skilled in the art.

As a rule, 0.1 to 10 wt.%, preferably 0.2 to 5 wt.%, particularly preferably 0.3 to 2.5 wt.% of emulsifier, based on the sum of the monomers employed for the preparation of the rubber base, is employed.

For the preparation of the emulsion graft polymer B employed for the polycarbonate compositions according to the invention, the choice of the emulsifier is decisive in the grafting reaction. It has been found, surprisingly, that not all conventional emulsifiers such as are described e.g. in WO 99/01489 Al for the preparation of graft polymers for particularly light-coloured ABS moulding compositions can be used in the grafting reaction. To achieve the object according to the invention, only the anionic emulsifiers according to formula (I) are suitable in the grafting reaction.
In a preferred embodiment for the preparation of component B of the polycarbonate compositions according to the invention, an anionic emulsifier of the formula (V) EWG

R9 - C - Y - [MZ+] 1 /z (V) F

EWG
wherein R9 and Y- have the meaning explained above, EWG independently of one another have the meaning explained above, F represents an alkylidene group -CR10R'' -, wherein R10 and R11 independently of one another in each case represent H, an alkyl, cycloalkyl, (aryl)alkyl, (alkyl)aryl, alkoxy or aryloxy group having 1 to 30 carbon atoms, preferably H, methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and particularly preferably R10 =
R" = H, is employed in the grafting reaction.

In a particularly preferred embodiment for the preparation of component B of the polycarbonate compositions according to the invention, an anionic emulsifier of the formula (VI) R

O O
O

R O ~O
S' /~ "O-M+
O
(VI) wherein R12 and R13 independently of one another in each case denote H, alkyl, cycloalkyl, (aryl)alkyl or alkyl(aryl) having I to 30 carbon atoms, preferably methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, (methyl)hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, phenyl, benzyl, phenyl substituted by C, to C30-alkyl (such as e.g. methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, (tridecyl)phenyl), C2 to Cioo ethoxylated fatty alcohol radicals having 1 to 130 carbon atoms, C3 to C99 propoxylated fatty alcohol radicals having 4 to 129 carbon atoms, C2 to Cloo ethoxylated (alkyl)phenol radicals having 3 to 130 carbon atoms, C3 to C99 propoxylated (alkyl)phenol radicals having 4 to 129 carbon atoms, particularly preferably propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, especially preferably hexyl, cyclohexyl, heptyl, n-octyl and 2-ethylhexyl, and M+ is chosen from the series consisting of the alkali metals (such as e.g.
Li+, Na+, K+, Rb+, Cs+), preferably Na+ or K+.

is employed in the grafting reaction.

Some of these emulsifiers are known and commercially obtainable, such as e.g.
Aerosol OT, Aerosol TR, Aerosol A196 (Aerosol types from Cytec Industries Inc.), Empimin OT, Empimin OP (Empimin types from Hunstman), Geropon CYA 75, Geropon SDS, Geropon SS 0 75, Geropon WS 25 I(Geropon types from Rhodia), Triton GR (from Dow Chemical) and Lutensit A BO (from BASF).
These emulsifiers can be employed either individually or also as mixtures with one another, as well as in combination with other nonionic emulsifiers known to the person skilled in the art, for the purpose of better stabilization of the dispersion.

In a very preferred embodiment for the preparation of component B of the polycarbonate compositions according to the invention, sulfosuccinic acid dicyclohexyl diester is employed as the emulsifier in the grafting reaction.

The emulsifiers for the grafting reaction in the preparation of component B of the compositions according to the invention are employed in amounts of from 0.1 to 5 wt.%, preferably from 0.1 to 3 wt.%, particularly preferably from 0.1 to 1,5 wt.%, based on the monomers used in the preparation of the graft polymer.

Preferably, water is used for the preparation of the graft polymer dispersion in an amount such that the finished dispersion has a solids content of from 20 to 50 wt.%.
All agents which form free radicals and which dissociate at the reaction temperature chosen, that is to say both those which dissociate solely by means of heat and those which do so in the presence of a redox system, are suitable for initiating the polymerization reaction. These are, for example, peroxides, preferably peroxosulfates (for example sodium peroxodisulfate or potassium peroxodisulfate).
However, redox systems, in particular those based on hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide, can also be employed.

As a rule, the polymerization initiators are employed in an amount of from 0.05 to 1 wt.%, based on the grafted-on monomers (B.1).

The agents which form free radicals and also the emulsifiers and optionally the molecular weight regulators explained in the next paragraph are added to the reaction batch, for example, discontinuously as the total amount at the start of the reaction, or, divided into several portions, in portions at the start and at one or more later points in time, or are added continuously during a particular time interval.
Continuous addition can also take place along a gradient, which can be e.g.
ascending or descending, linear or exponential, or also stepwise (stepped function).
Molecular weight regulators, such as e.g. ethylhexyl thioglycollate, n- or t-dodecylmercaptan and/or other mercaptans, terpinols and/or dimeric a-methylstyrene and/or other compounds suitable for regulating the molecular weight, can furthermore be co-used.

The molecular weight regulators are added to the reaction batch discontinuously or continuously, as has been described above for the agents which form free radicals and the emulsifiers.

If molecular weight regulators are used in the polymerization, they can be added in the manner described above during the preparation of the graft base B.2 or during the preparation of the grafted-on substance B.1 or both during the preparation of the graft base B.2 and of the grafted-on substance B.1.

The dispersion of the emulsion graft polymer B is worked up in a process known to the person skilled in the art, without particular requirements regarding the purity of the worked-up graft polymer being imposed thereon: for example, the graft polymer B is first precipitated out of the dispersion, for example by addition of salt solutions (such as calcium chloride, magnesium sulfate, alum) or acids (such as acetic acid, hydrochloric acid or sulfuric acid) having a precipitating action, or also be freezing (freeze-coagulation) or by a precipitation by means of high shear forces (so-called shear precipitation), the high shear forces being generated, for example, by rotor/stator systems or by forcing the dispersion through a narrow gap. The resulting aqueous phase is separated off in a conventional manner, for example by sieving, filtering, decanting or centrifuging. After the dispersion water has been separated off, the water-moist graft polymer, which conventionally has a residual water content of up to 60 wt.%, is obtained.

In this context, no or only partial separation of the auxiliary substances, such as e.g.
emulsifiers, salts and buffer substances, is achieved, so that a considerable portion of up to 100 % of the auxiliary substances (i.e. emulsifiers and other auxiliary substances) remains in the graft polymer and consequently in the end product.

As an alternative to precipitation, spray drying, in which the dispersion is converted, without being coagulated beforehand, into fine drops distributed in air or an inert gas and is then dried to a powder in the stream of air or inert gas, can be used.
All the auxiliary substances then remain in the end product to the extent of 100 %.

Component C
Component C comprises one or more thermoplastic vinyl (co)polymers C.1 and/or polyalkylene terephthalates C.2.

Suitable vinyl (co)polymers C.l are polymers of at least one monomer from the group consisting of vinylaromatics, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid (CI-Cg)-alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. (Co)polymers of C.1.1 50 to 99, preferably 60 to 80 parts by wt. of vinylaromatics and/or nucleus-substituted vinylaromatics, such as styrene and p-chlorostyrene, and/or (meth)acrylic acid (CI-Cg)-alkyl esters, such as methyl methacrylate and ethyl methacrylate, and C.1.2 1 to 50, preferably 20 to 40 parts by wt. of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile, and/or (meth)acrylic acid (Ci-C8)-alkyl esters, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate, and/or unsaturated carboxylic acids, such as maleic acid, and/or derivatives, such as anhydrides and imides, of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide, are particularly suitable.

The vinyl (co)polymers C.l are resinous, thermoplastic and rubber-free. The copolymer of C.1.1 styrene and C. 1.2 acrylonitrile is particularly preferred.

The (co)polymers according to C.1 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co)polymers preferably have average molecular weights Mw (weight-average, determined by light scattering or sedimentation) of between 15,000 and 200,000.

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

Preferred polyalkylene terephthalates contain at least 80 wt. %, preferably at least 90 wt. %, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 80 wt. %, preferably at least 90 mol %, based on the diol component, of ethylene glycol radicals and/or butane-1,4-diol radicals.

Preferred polyalkylene terephthalate can contain, in addition to terephthalic acid radicals, up to 20 mol %, preferably up to 10 mol % of radicals of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as e.g. radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid or cyclohexanediacetic acid.

Preferred polyalkylene terephthalates can contain, in addition to ethylene glycol radicals and butane-1,4-diol radicals, up to 20 mol %, preferably up to 10 mol % of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C
atoms, e.g. radicals of propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, 3-ethylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di-((3-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(4-(3-hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-A 2 407 674, 2 407 776 and 2 715 932).

The polyalkylene terephthalates can be branched by incorporation of relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US 3 692 744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
Polyalkylene terephthalates which have been prepared solely from terephthalic acid and reactive derivatives thereof (e.g. dialkyl esters thereof) and ethylene glycol and/or butane-l,4-diol, and mixtures of these polyalkylene terephthalates are particularly preferred.
Mixtures of polyalkylene terephthalates comprise I to 50 wt. %, preferably 1 to wt. % of polyethylene terephthalate and 50 to 99 wt. %, preferably 70 to 99 wt. %
of polybutylene terephthalate.

The polyalkylene terephthalates preferably used in general have a limiting viscosity of from 0.4 to 1.5 dl/g, preferably 0.5 to 1.2 dl/g, measured in phenol/
o-dichlorobenzene (1:1 part by weight) at 25 C in an Ubbelohde viscometer.

The polyalkylene terephthalates can be prepared by known methods (see e.g.
Kunststoff-Handbuch, vol. VIII, p. 695 et seq., Carl-Hanser-Verlag, Munich 1973).
Component D
Phosphorus-containing flameproofing agents (D) in the context according to the invention are preferably chosen from the groups consisting of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonatamines and phosphazenes, it also being possible to employ mixtures of several components chosen from one or various of these groups as flameproofing agents. Other halogen-free phosphorus compounds which are not mentioned here specifically can also be employed, by themselves or in any desired combination with other halogen-free phosphorus compounds.

Preferred mono- and oligomeric phosphoric and phosphonic acid esters are phosphorus compounds of the general formula (VII) R-(O)-P O-X-O-P (O)-R
(o)n I I (vIII) (0), R R3 q wherein R', R2, R3 and R4 independently of one another denote C, to C8-alkyl-, C5 to cycloalkyl, C6 to C20-aryl or C7 to C12-aralkyl, which can in each case be optionally substituted by alkyl, preferably C, to C4-alkyl, and/or halogen, preferably chlorine or bromine, n independently of one another, denotes 0 or 1, and preferably n = 1, q denotes 0 to 30 and X denotes a mono- or polynuclear aromatic radical having 6 to 30 C atoms or a linear or branched aliphatic radical having 2 to 30 C atoms, which can be OH-substituted and can contain up to 8 ether bonds.

Preferably, R1, R2, R3 and R4 independently of one another represent C, to C4-alkyl, phenyl, naphthyl or phenyl-CI -C4-alkyl. The aromatic groups Rl, R2, R3 and R4 can in their turn be substituted by halogen and/or alkyl groups, preferably chlorine, bromine and/or C, to C4-alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
X in the formula (VII) preferably denotes a mono- or polynuclear aromatic radical having 6 to 30 C atoms. This is preferably derived from diphenols of the formula (II);
n in the formula (VII) can be, independently of one another, 0 or 1, and n is preferably 1;
q represents values of from 0 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6, very particularly preferably 1.0 to 1.6;
X particularly preferably represents CH /

\ - -or chlorinated or brominated derivatives thereof, and in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A.

Mixture of various phosphates can also be employed as component D according to the invention.

Phosphorus compounds of the formula (VII) are, in particular, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethylcresyl phosphate, tri-(isopropylphenyl) phosphate, resorcinol-bridged diphosphate and bisphenol A-bridged diphosphate. The use of oligomeric phosphoric acid esters of the formula (VII) which are derived from bisphenol A is particularly preferred.

The phosphorus compounds according to component D are known (cf. e.g. EP-A
363 608, EP-A 0 640 655) or can be prepared by known methods in an analogous manner (e.g. Ullmanns Enzyklopadie der technischen Chemie, vol. 18, p. 301 et seq.
1979; Houben-Weyl, Methoden der organischen Chemie, vol. 12/1, p. 43;
Beilstein vol. 6, p. 177).

The mean q values can be determined by determining the composition of the phosphate mixture (molecular weight distribution) by means of a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC) or gel permeation chromatography (GPC)), and calculating the mean values for q therefrom.

Phosphonatamines and phosphazenes such as are described in WO 00/00541 and WO 01/18105 can furthermore be employed as flameproofing agents.
The flameproofing agents can be employed by themselves or in any desired mixture with one another or in a mixture with other flameproofing agents.

Component E
The composition can comprise further commercially available additives, such as flameproofing synergists, various rubber-modified graft polymers which differ from component B, antidripping agents (for example compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibres), lubricants and mould release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatics (for example conductive carbon blacks, carbon fibres, carbon nanotubes and organic antistatics, such as polyalkylene ethers, alkylsulfonates or polyamide-containing polymers), acids, fillers and reinforcing substances (for example glass fibres or carbon fibres, mica, kaolin, talc, CaCO3 and glass flakes) as wells as dyestuffs and pigments.

The acids according to component E are preferably chosen from at least one of the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids and hydroxy-functionalized dicarboxylic acids. Citric acid, oxalic acid, terephthalic acid or mixtures of the compounds mentioned are preferred in particular.

The graft polymers which differ from component B are prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, an emulsifier which differs from formula (I) being employed in the case of emulsion polymerization. Graft polymers which differ from component B and are prepared by solution or bulk polymerization are preferred.

Production of the moulding compositions and shaped articles The thermoplastic moulding compositions according to the invention are prepared by mixing the particular constituents in a known manner and subjecting the mixture to melt compounding and melt extrusion in conventional units, such as internal kneaders, extruders and twin-screw extruders, at temperatures of from 200 C
to 300 C.

The mixing of the individual constituents can be carried out in a known manner both successively and simultaneously, and in particular both at about 20 C (room temperature) and at a higher temperature.

The invention likewise provides processes for the preparation of the moulding compositions and the use of the moulding compositions for the production of shaped articles and the mouldings themselves.

The moulding compositions according to the invention can be used for the production of all types of shaped articles. These can be produced by injection moulding, extrusion and blow moulding processes. A further form of processing is the production of shaped articles by thermoforming from sheets or films produced beforehand.
Examples of such shaped articles are films, profiles, all types of housing components, e.g. for domestic appliances, such as televisions, juice presses, coffee machines, mixers; for office machines, such as monitors, flat screens, notebooks, printers, copiers; sheets, pipes electrical installation conduits, windows, doors and further profiles for the building sector (internal and external uses), as well as electrical and electronic parts, such as switches, plugs and plug sockets, as well as body and interior components for utility vehicles, in particular for the automobile sector.

In particular, the moulding compositions according to the invention can also be used, for example, for the production of the following shaped articles or mouldings:
interior finishing components for track vehicles, ships, aircraft, busses and other motor vehicles, housing of electrical equipment containing small transformers, housings for equipment for processing and transmission of information, housings and linings of medical equipment, massage equipment and housings therefore, toy vehicles for children, flat wall elements, housings for safety devices and for televisions, thermally insulated transportation containers, mouldings for sanitary and bath fittings, cover gratings for ventilator openings and housings for garden equipment.
The following examples serve to further illustrate the invention.

Examples Component A
A. 1: Linear polycarbonate based on bisphenol A with a weight-average molecular weight ( M,,,) of 27,500 g/mol (determined by GPC in CHzCIz at 25 C).
A.2: Linear polycarbonate based on bisphenol A with a weight-average molecular weight (M ) of 28,500 g/mol (determined by GPC in CH2C12 at 25 C).
Component B
Emulsion graft polymers of type B with a polybutadiene rubber base The particulate crosslinked rubber base employed for the preparation of component B (emulsion graft polymer) was prepared by free-radical emulsion polymerization of butadiene in the presence of the sodium salt of a specific TCD emulsifier such as is described in DE 3913509A1 (Example 1). The polybutadiene bases obtained in this way have an average particle size d50 = 350 nm and were employed in the further reaction step in the form of polymer latices (procedure in each case in accordance with general instructions (I) or (II)).

All the parts by weight stated in the following examples for graft polymers are standardized such that in each graft polymer mentioned in the following the sum of the parts by weight (parts by wt.) of the graft base (polybutadiene) and of the parts by wt. of the graft monomers (styrene and acrylonitrile) gives 100 parts by wt. The amounts of water, emulsifiers, initiators and other auxiliary substances relate to this sum of the parts by wt. of the graft base and of the graft monomers (= 100 parts by wt.).

General instructions (I): Preparation of graft polymers B(1.1a) to B(1.2c):
60 parts by wt. of polybutadiene (in the form of a latex, which was prepared using the compound TCD emulsifier as an emulsifier, solids content 25 wt.%, average particle diameter d50 = 350 nm) and 0 - 2 parts by wt. of the particular emulsifier employed are heated to 65 C under nitrogen and 0.5 parts by wt. of potassium peroxodisulfate (dissolved in 20 parts by wt. of water) and 0.3 part by wt. of sodium hydroxide (dissolved in 20 parts by wt. of water) are added.
Thereafter, a mixture of 30 parts by wt. of styrene and 10 parts by wt. of acrylonitrile is metered in over a period of 4 hours, the grafting reaction taking pace. After an after-reaction time, the latex is coagulated in a magnesium sulfate/acetic acid solution filtered off and, if appropriate, washed, and the resulting powder is dried in vacuo at 70 C.
General instructions (II): Preparation of graft polymers B(2.1a) to B(2.2e):
60 parts by wt. of polybutadiene (in the form of a latex, which was prepared using the compound TCD emulsifier as an emulsifier, solids content 25 wt.%, average particle diameter d50 = 350 nm) and 0 - 2 parts by wt. of the particular emulsifier employed are heated to 65 C under nitrogen and 0.4 part by wt. of tert-butyl hydroperoxide (dissolved in 20 parts by wt. of water) and 0.5 part by wt. of sodium ascorbate (dissolved in 20 parts by wt. of water) are metered in over a period of 4 hours. In parallel with this, a mixture of 30 parts by wt. of styrene and 10 parts by wt. of acrylonitrile are metered in over a period of 4 hours, the grafting reaction taking pace. After an after-reaction time, the latex is coagulated in a magnesium sulfate/acetic acid solution, filtered off and, if appropriate (see below), washed, and the resulting powder is dried in vacuo at 70 C.
Graft polymer B(1.1a): Preparation in accordance with general instructions (I) Emulsifier: 1.5 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196, Cytec Industries).
Working up of the coagulate: The coagulate obtained after the precipitation is only filtered off (approx. 20 1 of filtrate solution) and is not washed.

Graft polymer B(1.lb): Preparation in accordance with general instructions (I) Emulsifier: 1.5 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed once with a large amount of distilled water (i.e.
approx. 20 1 per 1 kg of polymer).

Graft polymer B(1.1c): Preparation in accordance with general instructions (1) Emulsifier: 1.5 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 801itres per 1 kg of polymer)).

Graft polymer B(1.1d): Preparation in accordance with general instructions (I) Emulsifier: 0.5 part by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and is not washed.

Graft polymer B(1.1e) (comparison): Preparation in accordance with general instructions (I) Emulsifier: No emulsifier employed in the grafting stage Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 80 litres per 1 kg of polymer)).

Graft polymer B(1.2a) (comparison): Preparation in accordance with general instructions (I) Emulsifier: 0.5 part by wt. of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 80 litres per 1 kg of polymer)).

Graft polymer B(1.2b) (comparison): Preparation in accordance with general instructions (I) Emulsifier: 1.0 part by wt. of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 80 litres per 1 kg of polymer)).

Graft polymer B(1.2c) (comparison): Preparation in accordance with general instructions (I) Emulsifier: 1.5 parts by wt. of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 801itres per 1 kg of polymer)). 20 Graft polymer B(2.1a): Preparation in accordance with general instructions (II) Emulsifier: 2 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196) Working up of the coagulate: The coagulate obtained after the precipitation is only filtered off (approx. 20 1 of filtrate solution) and is not washed.
Graft polymer B(2.1b): Preparation in accordance with general instructions (II) Emulsifier: 2 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed once with a large amount of distilled water (i.e.
approx.
20 litres per 1 kg of polymer).

Graft polymer B(2.1c): Preparation in accordance with general instructions (II) Emulsifier: 2 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 80 litres per 1 kg of polymer)).

Graft polymer B(2.1d): Preparation in accordance with general instructions (II) Emulsifier: 1.5 parts of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A 196) Working up of the coagulate: The coagulate obtained after the precipitation is only filtered off (approx. 20 1 of filtrate solution) and is not washed.

Graft polymer B(2.1e): Preparation in accordance with general instructions (II) Emulsifier: 1.0 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196) Working up of the coagulate: The coagulate obtained after the precipitation is only filtered off (approx. 20 1 of filtrate solution) and is not washed.

Graft polymer B(2.1f): Preparation in accordance with general instructions (II) Emulsifier: 0.5 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A 196) Working up of the coagulate: The coagulate obtained after the precipitation is only filtered off (approx. 20 1 of filtrate solution) and is not washed.

Graft polymer B(2.2a) (comparison): Preparation in accordance with general instructions (II) Emulsifier: 2 parts of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is only filtered off (approx. 20 1 of filtrate solution) and is not washed.

Graft polymer B(2.2b) (comparison): Preparation in accordance with general instructions (I1) Emulsifier: 2 parts of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed once with a large amount of distilled water (approx.
20 1 per I kg of polymer).

Graft polymer B(2.2c) (comparison): Preparation in accordance with general instructions (II) Emulsifier: 2 parts of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 801itres per 1 kg of polymer)).

Graft polymer B(2.2d) (comparison): Preparation in accordance with general instructions (II) Emulsifier: 0.5 part of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 80 litres per 1 kg of polymer)).

Graft polymer B(2.2e) (comparison): Preparation in accordance with general instructions (II) Emulsifier: 1.0 part of sodium dodecylsulfate (Aldrich) Working up of the coagulate: The coagulate obtained after the precipitation is filtered off and washed thoroughly (i.e. 4 times suspended in distilled water, subsequently filtered off and washed with a large amount of distilled water (in total approx. 80 litres per 1 kg of polymer)).

Emulsion graft polymers according to component B based on a poly-(n-butyl acrylate) rubber base:

For the preparation of the particulate crosslinked rubber base of poly(n-butyl acrylate) rubber, a seed latex was first prepared by polymerization of 10 parts by wt.
of n-butyl acrylate in the presence of 83 parts by wt. of deionized water, 0.2 part by wt. of sodium dodecylsulfate and 0.18 part by wt. of potassium peroxodisulfate (K2S208), dissolved in 7.0 parts by wt. of water, at 80 C over 3 h. An acrylate latex with a solids content of 10.0 % and a weight-average particles size of d50 =
50 nm was obtained.

10.0 parts by wt. of the seed latex prepared (1.0 part by wt., based on the solid polymer) were initially introduced into the reaction vessel together with 145 parts by wt. of water, 6.85 parts by wt. of n-butyl acrylate monomer and 0.3 part by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol A196) dissolved in water beforehand, and the mixture was heated to 65 C. When 65 C was reached, 0.25 part by wt. of potassium peroxodisulfate, dissolved in 12,5 parts by wt.
of water, were added in the course of 5 minutes and thereafter meterings of monomer solution comprising 90 parts by wt. of n-butyl acrylate, 0.45 part by wt. of trimethylol triacrylate and 2.70 parts by wt. of allyl methacrylate, and a solution comprising 1.20 parts by wt. of Aerosol A196, 0.20 part by wt. of potassium peroxodisulfate and 24.0 parts by wt. of water were started in the course of over 5 h.
After the end of the meterings the temperature was brought to 70 C and a solution of 0.05 part by wt. of potassium peroxodisulfate dissolved in 2.34 parts by wt. of water was added over one hour. Thereafter, the mixture was stirred for a further hour at 70 C. A bimodal acrylate rubber base was obtained as a 35 % strengtli dispersion (- 100 % conversion) with a weight-average particle size of d50 =
450 nm.

For the preparation of the graft polymers, 180 parts by wt. of poly(n-butyl acrylate) latex (solids content 34 %) were initially introduced into a flask with 17 parts by wt.
of water and 0.06 part by wt. of the particular emulsifier, dissolved in 1,14 parts by wt. of water, and the mixture was heated to 65 C under nitrogen. 0.4 part by wt. of tert-butyl hydroperoxide, 0.54 part by wt. of emulsifier (both components dissolved in 20 parts by wt. of water) and 0.5 part by wt. of sodium ascorbate (dissolved in 20 parts by wt. of water) were metered in over a period of 7 hours. In parallel with this, a mixture of 30 parts by wt. of styrene and 10 parts by wt. of acrylonitrile was metered in over a period of 4 hours, during which the grafting reaction took place. After an after-reaction time of 2 hours, a conversion of 99 %
was reached. The latex was coagulated with a magnesium sulfate solution, filtered and dried in vacuo at 70 C.

Graft polymer B(2.3a):
Emulsifier: 1.5 parts by wt. of the sodium salt of sulfosuccinic acid dicyclohexyl diester Working up of the graft polymer dispersion: The polymer dispersion was precipitated with magnesium sulfate and the coagulate obtained after the precipitation was only filtered off (approx. 20 1 of filtrate) and was not washed.

Component C
C.1:
Copolymer of 75 wt.% styrene and 25 wt.% acrylonitrile with a weight-average molecular weight M,,, of 130 kg/mol (determined by GPC), prepared by the bulk polymerization process.

C.2 (comparison):
Copolymer of 70 wt.% a-methylstyrene and 30 wt.% acrylonitrile with a weight-average molecular weight M, of 90 kg/mol (determined by GPC), prepared by the bulk polymerization process.
Component D.1 Bisphenol A diphenyl diphosphate, Reofos BAPP, Greate Lakes Component E
E.1 Pentaerythritol tetrastearate as a lubricant/mould release agent E.2 Phosphite stabilizer, Irganox B 900, Ciba Speciality Chemicals E.3 Citric acid (anhydrous), DSM
E.4 Poly(perfluoroethylene) PTFE, Polyflon FA-500, Daikin E.5 Boehmite, Pural 20, Sasol E.6 Bulk ABS from Nippon A&L, obtainable under the trade name "Santac AT
08"

Preparation and testin$! of the mouldinIZ compositions The compositions listed in Tables 1 to 4 are prepared in a 1.5 1 internal kneader.
Table 1: PC/ABS composition without flameproofing agent Component Parts by wt.

A.1 58 C.1 24 E.1 0.75 E.2 0.12 E.3 0.1 Table 2: PC/ABS composition with flameproofing agent Component Parts by wt.

A.2 70.5 B 4.0 D.1 13.0 E.1 0.3 E.2 0.1 E.4 0.5 E.5 0.8 E.6 10.8 Table 3: Further PC/ABS composition with flameproofing agent Component Parts by wt.
A.1 77.3 C.1 3.5 B 7.7 D.1 9.8 E.1 0.4 E.2 0.1 E.4 0.4 E.5 0.8 Table 4: PC/ASA composition Component Parts by wt.
A.1 58 E.1 0.75 E.2 0.12 E.3 0.1 The change in the MVR measured in accordance with ISO 1133 at 260 C with a stamp load of 5 kg after storage of the granules at 95 C and 100 % relative atmospheric humidity for 7 days serves as a measure of the resistance to hydrolysis of the compositions prepared in this way. In this context, the increase in the MVR
value compared with the starting MVR value, DMVR (hydr.), is evaluated (calculated as a percentage here). To take into account variations in temperature during storage, a control samples was co-used for each storage batch, the MVR
value of which varied by 50 ml/10 min after storage and was then standardized to exactly 50. The resulting standardization factor was also used on all the MVR
measurement values of a measurement series. The change in the MVR, based on the standardized values, is called DMVR (hydr.; corr.).

The change in the MVR measured in accordance with ISO 1133 at 260 C with a stamp load of 5 kg after a dwell time of the melt of 15 minutes with exclusion of air at a temperature of 300 C for non-flameproofed PC/ABS compositions and after a dwell time of the melt of 30 minutes with exclusion of air at a temperature of serves as a measure of the stability during processing (the degradation of the polycarbonate under intensified processing conditions) of the compositions prepared in this way.
The determination of the notched impact strength ak is carried out in accordance with ISO 180/1 For determination of the weld strength aNF, the impact strength is measured in accordance with ISO 179/IU at the flow line of test specimens injection moulded from both sides of dimensions 80 mm x 10 mm x 4 mm.

The elongation at tear is determined in the tensile test in accordance with ISO 527.

The results of the storage in a damp climate (stability to hydrolysis) and at (stability during processing) are summarized in Table 5 (the PC/ABS
compositions according to Table 1, i.e. without flameproofing agent) were employed).

These results show that the object of providing polycarbonate compositions according to the invention with an improved resistance to hydrolysis was achieved by using specific emulsifiers corresponding to the formulae I, V and VI in the grafting stage B. l(preparation of component B(a)):

Compositions 1 to 3 and 8 to 10 according to the invention show a slight increase in the MVR value after storage in a controlled climate of 37-50 % (DMVR (hydr.;
corr.), and in particular regardless of whether the graft polymer was washed thoroughly or was not washed at all. This result is also surprising in particular because the resistance to hydrolysis of composition 4 (comparison example), which comprises an ABS which was prepared without an emulsifier at the grafting stage, has a DMVR (hydr.; corr.) of 49 %. This means that the compositions comprising the graft polymers according to the invention have at least as good a resistance to hydrolysis as the composition which comprises a graft polymer which was prepared without any emulsifier.

The compositions of Comparison Examples 5 to 7 and 13 to 15, which comprise an ABS prepared with sodium dodecylsulfate, i.e. an emulsifier described in the prior art (e.g. EP-A 0 900 827), show that at best DMVR (hydr.; corr.) values of from 56 to 85 % can be achieved after storage in a controlled climate if the graft polymer was washed thoroughly, i.e. no longer contains emulsifier. These resistances to hydrolysis are significantly poorer than those of the polycarbonate compositions according to the invention.

If a thorough working up of the graft polymer with the emulsifiers described in the prior art is omitted (compositions of Comparison Examples I 1 and 12), a dramatic degradation of the polycarbonate takes place, which is to be concluded from the DMVR (hydr.; corr.) values of from 140 to 206 %.

Compositions 1 to 3 and also 8 to 10 according to the invention moreover show a good stability during processing, which is to be seen from DMVR (proc.) values of from 37 to 69 % (storage of the melt at 300 C, 15 min).

In the case of the flameproofed PC/ABS compositions of Table 6 (the PC/ABS
compositions according to Table 2 were employed), it is likewise found that the object on which this invention is based is achieved by using specific emulsifiers corresponding to the formulae I, V and VI in the grafting stage B.l (preparation of component B(a)). Thus, compositions 17 to 21 according to the invention from Table 6 show only a moderate increase in the MVR value of from 64 to 92 %, compared with the comparison from the prior art (composition 16), and moreover have advantages in the notched impact strength (ak), weld strength (aõF) and the elongation at tear.

In the case of the flameproofed PC/ABS compositions of Table 7 (the PC/ABS
compositions according to Table 3 were employed), it is likewise found that compositions 23-25 according to the invention have advantages over composition in respect of the resistance to hydrolysis, stability during processing, notched impact strength, weld strength and elongation at tear.

The PC/ASA compositions of Table 8 show an analogous behaviour: The compositions according to the invention have both a good resistance to hydrolysis and a good processing stability, as long as no polymer containing alpha-methylstyrene is employed as component C (cf. prior art DE 698 27 302 T2). In the case of composition 27, which indeed has a good resistance to hydrolysis but contains as component C SAN containing a-methylstyrene, the processing stability is significantly reduced compared with composition 26 according to the invention.

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Claims (10)

1. Compositions comprising A) 10 - 99 parts by wt. of aromatic polycarbonate and/or aromatic polyester carbonate, B) 1- 35 parts by wt. of rubber-modified graft polymer of B.1 5 to 95 wt.% of at least one vinyl monomer on B.2 95 to 5 wt.% of one or more graft bases having a glass transition temperature of < 10 °C, C) 0 - 40 parts by wt. of vinyl (co)polymer and/or polyalkylene terephthalate, excluding a copolymer of .alpha.-methylstyrene and acrylonitrile, D) 0 - 50 parts by wt., based on the sum of components A+B+C, of phosphorus-containing flameproofing agent, E) 0 - 50 parts by wt., based on the sum of components A+B+C, of additives, characterized in that component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is employed in which EWG is an a carbonyl, a carboxyl, a nitrile, a nitro or a sulfone group, W is a group chosen from C1 to C30-alkyl, C1- to C30-cycloalkyl, C1- to C30-aryl, C1- to C30-(aryl)alkyl, C1- to C30-(alkyl)aryl, C1- to C30-alkoxy, C1- to C30-aryloxy, C2 to C100 ethoxylated alkoxy or aryloxy group according to the formula RO-(CH2-CH2-O)a-, where a = 1 to 50 and R= C1- to C30-alkyl or C1- to C30-aryl, wherein all the groups mentioned can also be substituted, e.g. by one or more electron-withdrawing groups according to the above definition for EWG, R9 denotes H or a C1 to C30-alkyl, C1 to C30-aryl or C1 to C30-(alkyl)aryl, which in each case can also be substituted, Y- is chosen from the group consisting of borate (-O-BO(OR9)-), boronate (-BO(OR9)-), nitrate (-O-NO2-), nitro (-NO2-), sulfate (-O-SO3-), sulfonate (-SO3-), phosphate (-O-P(OR9)O2-) and phosphonate (-P(OR9)O2-), z represents the number 1 or 2, and M z+ is chosen, for z= 1, from the group consisting of Li+, Na+, K+, Rb+, Cs+, ammonium cation, alkylammonium cation (NH4-n R9n+, wherein n can be 1 to 4), phosphonium cation and alkylphosphonium cation (PH4-n R9n+, wherein n can be 1 to 4), or, for z = 2, is chosen from the group consisting of Mg2+, Ca 2+, Sr2+ and Ba2+.

2. Composition according to claim 1, characterized in that component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (V) is employed wherein R9, Y- have the meaning explained in claim 1, EWG independently of one another have the meaning defined in claim 1, F represents an alkylidene group -CR10R11 -, wherein R10 and R11 independently of one another in each case are H, an alkyl, cycloalkyl, (aryl)alkyl, (alkyl)aryl, alkoxy or aryloxy group having 1 to 30 carbon atoms.

3. Composition according to claim 1, characterized in that component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (VI) is employed wherein R12 and R13 independently of one another in each case denote H, alkyl, cycloalkyl, (aryl)alkyl or alkyl(aryl) having 1 to 30 carbon atoms and M+ is chosen from the series of the group consisting of Li+, Na+, K+, Rb+, Cs+.

4. Composition according to claim 1, characterized in that component B is obtainable by reaction of component B.1 with the graft base B.2 by means of emulsion polymerization, wherein sulfosuccinic acid dicyclohexyl diester is employed as an emulsifier.

5. Composition according to one of claims 1 to 4, characterized in that the emulsifiers for the grafting reaction in the preparation of component B are employed in amounts of from 0.1 to 5 wt.%.

6. Compositions according to one of claims 1 to 5, comprising as component D
compounds according to formula (VII) wherein R1, R2, R3 and R4 independently of one another denote C1 to C8-alkyl, C5 to C6-cycloalkyl, C6 to C20-aryl or C7 to C12-aralkyl, which can in each case be substituted by alkyl and/or halogen, n independently of one another, denotes 0 or 1, q denotes 0 to 30 and X denotes a mono- or polynuclear aromatic radical having 6 to 30 C
atoms or a linear or branched aliphatic radical having 2 to 30 C
atoms, which can be OH-substituted and can contain up to 8 ether bonds.

7. Compositions according to one of claims 1 to 6, wherein the additives according to component E are chosen from at least one of the group consisting of flameproofing synergists, rubber-modified graft polymers which differ from component B, antidripping agents, lubricants and mould release agents, nucleating agents, stabilizers, antistatics, acids, fillers and reinforcing substances, dyestuffs and pigments.

8. Use of the compositions according to one of claims 1 to 7 for the production of shaped articles.

9. Shaped article comprising a composition according to one of claims 1 to 7.

10. Shaped article according to claim 9, characterized in that the shaped article is an interior finishing component for track vehicles, ships, aircraft, busses and other motor vehicles, a housing of electrical equipment containing small transformers, a housing for equipment for processing and transmission of information, a housing or a lining of medical equipment or of massage equipment, a toy vehicle for children, a flat wall element, a housing for safety devices or for televisions, a thermally insulated transportation container, a moulding for sanitary and bath fittings, a cover grating for ventilator openings or a housing for garden equipment.