EP2148902A2

EP2148902A2 - Impact strength modified polycarbonate compositions

Info

Publication number: EP2148902A2
Application number: EP08758407A
Authority: EP
Inventors: Andreas Seidel; Evgueni Avtomonov; Eckhard Wenz; Thomas Eckel; Herbert Eichenauer
Original assignee: Bayer MaterialScience AG
Current assignee: Covestro Deutschland AG
Priority date: 2007-05-16
Filing date: 2008-05-08
Publication date: 2010-02-03
Also published as: JP2010526922A; KR20100016530A; DE102008015124A1; CN101679736A; MX2009011440A; WO2008138534A3; BRPI0811878A2; CA2687362A1; RU2009146338A; WO2008138534A2

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 a-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

Impact modified polycarbonate compositions

The present invention relates to polycarbonate compositions containing special, produced by the process of emulsion polymerization rubbery graft polymers as impact modifier, these compositions are characterized by high hydrolytic stability and high processing stability, and at the same time have good mechanical properties. This invention also relates to the use of the polycarbonate compositions for the production of moldings and the moldings themselves.

Polycarbonate compositions containing graft polymers as impact modifiers may vary depending on the purity and additive nature of the toughening modifier, e.g. ABS (acrylonitrile-butadiene-styrene terpolymer), have different stability to hydrolysis and thermal stress. Thus, by BS Patty, L. Novak and H, Phan (in "Thermal and hydrolytic stability of polycarbonates / acrylonitrile-butadiene styrene based blends", Society of Automotive Engineers, [Special Publication] SP (2005), SP-1960 ( Advances in Plastic Components, Processes and Technologies), 145-151) describes polycarbonate compositions which have a significantly better hydrolytic stability and thermal stability for bulk ABS as a modifier than in the case of emulsion ABS as a modifier. The difference in behavior of the polycarbonate / bulk ABS compositions over polycarbonate / emulsion ABS compositions is attributed to the fact that the production process of emulsion ABS requires a higher number of different chemicals as auxiliaries than bulk ABS, e.g. Emulsifiers, flow improvers, stabilizers, salts, etc., which include those chemicals that can lead to decomposition of the polycarbonate.

Certain polycarbonate compositions containing emulsion graft polymers as impact modifiers have some technical advantages over polycarbonate compositions containing bulk ABS, e.g. in terms of surface finish (gloss level), so that it is advantageous for some applications to use emulsion graft polymers. If a high hydrolysis stability and thermal stability are required, high demands must be placed on the emulsion graft polymers used, such as, for example, in terms of their purity, the work-up procedure in their preparation and a waiver of certain aids in their preparation.

For example, EP-A 0 900 827 discloses impact-modified polycarbonate compositions with improved thermostability comprising emulsion graft polymers, which are described in US Pat Substantially free of components that degrade the polycarbonate. In order to obtain an emulsion graft polymer essentially free of components which degrade the polycarbonate, it is necessary to completely dispense with such components in the emulsion process in each process stage or to free the emulsion graft polymers prepared from these components by a corresponding work-up procedure, for example by washing the coagulation of the graft emulsion.

WO-A 99/01489 discloses emulsion graft polymers of the ABS type which are prepared by means of a wide variety of emulsifiers. Among others, sulfosuccinates are mentioned as possible emulsifiers for their preparation.

The patent application US 2006/0106163 teaches that certain thermoplastic compositions with good weathering stability and scratch resistance can be prepared, the fine and coarse ASA graft polymers and other specific resins, i.a. Maleic anhydride-modified SAN resins. For the preparation of the acrylate rubber bases needed for the ASA graft polymers as an elastic, crosslinked core, i.a. In addition to common long-chain sulfate and sulfonate-based metal salts, special metal salts of sulfosuccinic acid derivatives are used. For the execution of 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 in which a vinyl graft polymer is included as an impact modifier which is prepared by the emulsion polymerization process and preferably in the presence of at least one free-radical polymerizable, i. double bond-containing emulsifier to which, if appropriate, other non-polymerizable emulsifiers can be added, can be produced. The hydrophilic-lipophilic structure of the polymerizable emulsifiers may include all known emulsifier classes, i. nonionic, cationic and anionic emulsifiers. The optionally added non-polymerizable emulsifiers may be any of the usual emulsifiers suitable for emulsion polymerization, i.a. Rosin acid salts (rosinates), fatty acid salts, alkyl sulfate salts, sulfonates, and the like. also Dialkylbernsteinsulfonsäuresalze.

In the patent EP-A 0390 081 are impact-modified polyester and

Polycarbonate compositions with improved impact resistance containing special MBS impact modifiers obtainable by the emulsion polymerization route. For the production of these MBS impact modifiers in the grafting step of Emulsion polymerization for emulsion polymerization conventional emulsifiers, such as fatty acid salts, alkyl sulfates, Alkylnezosulfonate, alkyl phosphates and other dialkylsulfosuccinate salts and common nonionic emulsifiers.

In JP-A 08067789 odorless and thermally stable thermoplastic compositions are described which contain styrene-based emulsion polymers. For the preparation of these styrene-based emulsion polymers cationic, anionic and nonionic emulsifiers can be used. As anionic emulsifiers, e.g. Fatty acid salts, alkyl sulfates, alkyl sulfonates, and the like. Sulfosuccinate used.

DE 698 27 302 T2 discloses resin compositions with increased impact strength, which can be achieved by adding hollow particulate rubbery graft polymers. The hollow rubber particles are prepared by special processing methods, e.g. produced by swelling with organic solvents, subsequent grafting reaction in emulsion and removal of all volatiles after grafting. For the grafting reaction in the preparation of hollow rubbery graft polymers, known emulsifiers, e.g. Fatty acid and resin acid metal salts, alkyl and aryl sulfonates, and the like. Sodium dioctyl sulfosuccinate used. As comparative examples, compositions are disclosed which comprise α-methystyrene-acrylonitrile copolymer, polycarbonate and a graft polymer of non-hollow rubber grafting particles with a shell of styrene and acrylonitrile, sodium dioctylsulfosuccinate being used as emulsifier in the grafting step to prepare the graft polymer.

The object of the present invention is to provide polycarbonate molding compositions containing at least one emulsion graft polymer as an impact modifier, which are distinguished by a high resistance to hydrolysis and by a high processing stability with simultaneously good mechanical properties.

A further object of the invention is to provide flame-retardant polycarbonate molding compositions comprising at least one emulsion graft polymer as an impact modifier, which is distinguished by high resistance to hydrolysis, high processing stability, improved impact strength (ak), improved weld line strength (anF) and at the same time by an improved impact strength Distinguish elongation at break.

It has surprisingly been found that compositions containing A) 10 to 99 parts by weight, preferably 40 to 95 parts by weight, particularly preferably 50 to 73 parts by weight of aromatic polycarbonate and / or aromatic polyester carbonate,

B) 1 to 35 parts by weight, preferably 4 to 30 parts by weight, more preferably 12 to 20 parts by weight of rubber-modified graft polymer of B.l 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 <10 ⁰ C, preferably <0 ⁰ C, particularly preferably <-20 ⁰ C,

C) 0-40 parts by weight, preferably 1-30 parts by weight, more preferably 15-25 parts by weight of vinyl (co) polymer and / or polyalkylene terephthalate, where a copolymer of α-

Methystyrene and acrylonitrile excepted,

D) 0-50 parts by weight, preferably 1-40 parts by weight, more preferably 2-30 parts by weight, in each case based on the sum of the components A + B + C, phosphorus-containing flame retardant, E) 0-50 Parts by weight, preferably 0.5-25 parts by weight, in each case based on the sum of the components A + B + C, additives,

characterized in that component B is obtainable by reaction of the component B.l with the graft base B.2 by means of emulsion polymerization, wherein an emulsifier according to formula (I) is used,

EEC

R ⁹ - C - Y - [M ^{z +} ] _{1 / Z} (I) I

W where

EWG is an electron-withdrawing group, such as a carbonyl, a carboxyl, a nitrile, a nitro or a sulfone group, preferably a nitrile, carbonyl group -C (= O) R ⁸ or carboxyl group -CO ₂ R ⁸ , especially preferably a carboxyl group -CO ₂ R ⁸ , wherein

R ⁸ are each 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 with C 1 to C ₃₀ alkyl

(such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl, dodecyl, (tridecyl) phenyl) or in each case C ₂ to C ₁₀₀ ethoxylated fatty alcohol radicals having 3 to 130 carbon atoms, C ₃ to C ₉₉ propoxylated fatty alcohol radicals having 4 to 129 carbon atoms, C ₂ to C ₁₀₀ ethoxylated (alkyl ) phenol radicals having 3 to 130 carbon atoms, C ₃ to C ₉₉ 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, particularly preferably hexyl, cyclohexyl, heptyl, n-octyl and 2-ethylhexyl,

W is a group selected from Cp to C ₃ -alkyl, d- to C ₃ -cycloalkyl, C ₆ - to C ₃ o-aryl, Ci - C ₃ o- (aryl) alkyl, Ci to _C3 o- (alkyl) aryl, Ci - to C ₃₀ alkoxy, C, - to C ₃ o-aryloxy, C ₂ to Cioo ethoxylated alkoxy or aryloxy group according to the formula RO- (CH ₂ -CH ₂ -O) ₃ - with a = 1 to 50 and R = C] - to C ₃ o-alkyl or Ci- to C ₃₀ -aryl, all of which groups may also be substituted, for example by one or more electron-withdrawing groups as defined above for EWG .

R ^{9 is} H or a Q to C ₃₀ -alkyl, C ₁ to C ₃₀ -aryl, C ₁ to C ₃ o- (alkyl) aryl, which may in each case also be substituted, preferably H, C 1 to C ₃₀ -alkyl, C 1 to C C ₃₀ - (aryl) alkyl, C 1 to C ₃₀ - (alkyl) aryl, particularly preferably H,

Y ^"is an anionic group, preferably selected from borate (-O-BO (OR ⁹ ) ^' ), boronate

(-BO (OR ⁹ ) ^' ), nitrate (-O-NO ₂ ^" ), nitro (-NO ₂ O ₁ sulfate (-O-SO ₃ ^" ), sulfonate (-SO ₃ ^" ),

Phosphate (-OP (OR ⁹ ) O ₂ ), phosphonate (-P (OR ⁹ ) O ₂ ^" ), particularly preferably selected from

Sulfate or sulfonate, particularly preferably a sulfonate group -SO ₃ ^" , where in each case R ^{9 has} the meaning explained above,

z is the number 1 or 2, preferably z is 1,

M ^{2+ is} selected for z = 1 from the group consisting of alkali metals (such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ), ammonium cation, alkylammonium cation (NH _4-11 RV, where n = 1 can be up to 4), phosphonium cation and alkylphosphonium cation (PH ₄ _n R ⁹ _n ⁺ , where n = 1 to 4), where in each case R ^{9 has} the meaning explained above, or for z = 2 is selected from the series of Alkaline earth metals (such as Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ ), preferably M ^{2+ is} M ⁺ (ie z = 1) and is selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Ammonium cation, alkylammonium cation), phosphonium cation and

Alkylphosphonium cation, more preferably M ⁺ Na ⁺ or K ⁺ , wherein all parts by weight in the present application are normalized such that the sum of the parts by weight of all components A + B + C in the composition 100 give the desired property profile.

Surprisingly, it has been found that in the preparation of the graft polymer B by means of emulsion polymerization no special purification is required, e.g. by washing the coagulated graft polymer with up to 100 times the amount of water, since, surprisingly, despite the whereabouts of the emulsifier in the resulting graft polymer, the resulting impact-modified polycarbonate compositions have 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 example, see 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, DE-A 3 832 396, for the preparation of aromatic polyester carbonates, eg DE-A 3 077 934) ,

The preparation of aromatic polycarbonates z. Example by reacting diphenols with carbonic acid halides, preferably phosgene and / or aromatic dicarboxylic, preferably Benzoldicarbonsäuredihalogeniden, by the interfacial process, optionally using Kettenabbrechem, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols. Likewise, preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is possible.

Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (H)

(H), in which

A is a single bond, C ₁ to C ₅ -alkylene, C ₂ to C ₅ -alkylidene, C ₅ to C ₆ -cycloalkylidene,

O, -SO-, -CO-, -S-, -SO ₂ -, C _fi to C ₁₂ -arylene, to the further aromatic optionally

Heteroatom-containing rings may be condensed, or a radical of the formula (DT) or (IV)

B are each C ₁ to C _{) 2-} alkyl, preferably methyl, halogen, preferably chlorine and / or

Each bromine x is independently 0, 1 or 2, p is 1 or 0, and

R ⁵ and R ^{6 are} individually selectable for each X ¹ independently of one another hydrogen or C to C -

Alkyl, preferably hydrogen, methyl or ethyl, X ¹ carbon and m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X ¹ , R ⁵ and R ^{6 are} simultaneously alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis- (hydroxyphenyl) - C ^ C _j -alkanes, bis- (hydroxyphenyl) _-C5 _-C6 -cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl ) -sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) -sulfones and α, α-bis (hydroxyphenyl) -diisopropyl-benzenes and their nuclear-brominated and / or nuclear-chlorinated derivatives.

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'-dihydroxydiphenylsulfido, 4,4-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as 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. Particularly preferred is 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A). The diphenols can be used individually or as any mixtures. The diphenols are known from the literature or obtainable by literature methods.

Chain terminators suitable for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenols or dialkylphenols with total

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 used is generally between 0.5 mol%, and 10 mol%, based on the molar sum of the particular used

Diphenols.

The thermoplastic, aromatic polycarbonates have weight average molecular weight (M _w , measured, for example, by GPC, ultracentrifuge or scattered light measurement) of 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 may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those containing three and more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. For the preparation of inventive copolycarbonates according to component A, it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, based on the total amount of diphenols to be used, of hydroxyaryloxy endblocked polydiorganosiloxanes. These are known (US 3 419 634) and can be prepared by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates 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 molar amounts of diphenols, of other than preferred or particularly preferred diphenols, 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 ¹ - dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

Particularly preferred are mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in the ratio between 1:20 and 20: 1.

In the production of polyester carbonates, a carbonyl halide, preferably phosgene, is additionally used as the bifunctional acid derivative.

As chain terminators for the preparation of the aromatic polyester, in addition to the aforementioned monophenols still their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids which may optionally be substituted by Ci to C ₂₂ alkyl groups or by halogen atoms, and aliphatic C ₂ to C ₂₂ -Monocarbonsäurechloride in consideration.

The amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators. The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates can be branched both linearly and in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).

Examples of suitable branching agents are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1-.S _j δ-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0, 01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or polyfunctional phenols, such as phloroglucinol, 4 ₎ 6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,6-dimethyl-2,4,6-tris (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-hydroxy-phenyl) -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-isopropyl] -phenoxy) -methane, 1,4-bis [4,4'-dihydroxytri-phenyl) -methyl] -benzene , in Meng from 0.01 to 1.0 mol% based on diphenols used. Phenolic branching agents can interact with the diphenols submitted, acid chloride branching agents can be registered together with the acid dichlorides.

In the thermoplastic, aromatic polyester carbonates, the proportion of carbonate structural units can vary as desired. The proportion of carbonate groups is preferably 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 portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.

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

The thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone 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

B.2 95 to 5, preferably 70 to 10 wt .-% of one or more graft bases having a glass transition temperature <10 ⁰ C, preferably <0 ⁰ C, particularly preferably <- 20 ⁰ C, characterized, the reaction of the component Bl with the graft B.2 by means of emulsion polymerization ("grafting reaction"), wherein an emulsifier according to formula (I) is used.

The graft base B.2 has, in general, an average particle size (d ₅ o-value) of 0.05 to 10 microns, preferably 0.1 to 5 microns, more preferably 0.2 to 0.8 microns.

Monomers B.l are preferably mixtures of

B.1.1 50 to 99 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics (such as styrene, p-chlorostyrene) and / or (meth) acrylic acid (C 1 -C ₈ ) -alkyl esters, (such as methyl methacrylate, 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 (C 1 -C ₈ ) -alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.

Preferred monomers B.1.1 are selected from at least one of the monomers styrene and methyl methacrylate, preferred monomers B.1.2 are selected 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.

Examples of suitable graft bases B.2 for the graft polymers B are diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.

Preferred grafting 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 other copolymerizable monomers (for example according to B.1.1 and B.1.2), with the proviso that the glass transition temperature of Component B.2 below <10 ⁰ C, preferably <0 ⁰ C, particularly preferably <-10 ⁰ C. Especially preferred is pure polybutadiene rubber.

The gel content of the graft base B.2 is at least 30% by weight, preferably at least

40% by weight (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, in the grafting reaction, the grafting monomers are not necessarily grafted completely onto the grafting base, according to the invention grafted polymers B are also those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during workup.

Preference is given to using emulsion graft polymers which have a core-shell structure. Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of alkyl acrylates, optionally with up to 40 wt .-%, based on B.2 other polymerizable, ethylenically unsaturated monomers. The preferred polymerisable acrylic acid esters include C 1 to C 6 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-Ci-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, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but 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 having at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexa-hydro-s-triazine, trivinylbenzenes. The crosslinking monomers can be used individually, but also in mixtures. The amount of crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft B.2. For 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 B.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft base B.2 are, for example, acrylonitrile, styrene, α-methylstyrene, (meth) acrylamides, vinyl-C ₁ -C ₆ -alkyl ethers, methyl methacrylate , 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 ⁰ C).

Further suitable graft bases according to B.2 are silicone rubbers with graft-active sites, as described in DE-OS 3,704,657, DE-OS 3,704,655, DE-OS 3 631 540 and DE-OS 3 631 539. The gel content of graft base B.2 is determined at 25 ⁰ C in a suitable solvent (M. Hoffmann, H. Kromer, R. Kuhn, polymer analysis I and π, Georg Thieme-V succumbed, Stuttgart 1977).

The average particle size d ₅ o is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid.Z. and Z. Polymere 250 (1972), 782-796).

It is known from the prior art that the graft base B.2 can be prepared by the emulsion polymerization process. Usually polymerized at

20 ⁰ C to 100 ⁰ C, preferably at 30 ⁰ C to 80 ⁰ C. In general, conventional anionic

Emulsifiers, 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 rosin soaps. Usually one takes the alkali metal salts, in particular the Na and K salts, of alkyl sulfonates, sulfosuccinates, fatty acids or

Carboxylic acids with 10 to 30 carbon atoms.

The choice of emulsifier for the preparation of the rubber base in the present invention depends on the criteria known to those skilled in the art, e.g. the latex shear stability and the nature of the latex particles, particle size, particle size distribution, viscosity, residual monomer content, gel content and thus, in contrast to the teaching of EP-A 0 900 827, do not depend on the exclusion of components which decompose the polycarbonate. According to the present invention, e.g. Alkali metal salts of rosin acids, alkali metal salts of higher fatty acids having 10 to 30 carbon atoms, alkali metal salts of specific dicarboxylic acids (such as described in DE 3 639 904 A1), alkali metal salts of alkyl or aryl sulfates or sulfosuccinates or alkali metal salts. Emulsifier mixtures and combinations of ionic and nonionic emulsifiers may also be used in the manner known to those skilled in the art. In general, 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-%, particularly preferably 0.3 to 2.5 wt .-% emulsifier based on the sum of those used for the preparation of the rubber base Monomers used.

For the preparation of the emulsion graft polymer B used for the polycarbonate compositions according to the invention, the choice of emulsifier is crucial in the grafting reaction. It has surprisingly been found that not all conventional emulsifiers can be used in the grafting reaction, as described, for example, in WO 99/01489 A1 in US Pat Production of graft polymers for particularly light ABS molding compositions are described. In order 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 the component B of the polycarbonate compositions according to the invention, an anionic emulsifier of the formula (V) is used in the grafting reaction,

EEC I

R ⁹ - C - Y - [M ^{Z +} ] _{I / Z} (V)

EEC

in which

R ⁹ and Y ^'have the abovementioned meaning, EWG independently of one another have the meaning explained above, F represents an alkylidene group -CR ¹⁰ R ¹ ' -, wherein

R ¹⁰ and R ¹¹ are each independently H, 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, more preferably R ¹⁰ = R ¹ '= H.

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

in which

R ¹² and R ¹³ are each independently H, alkyl, cycloalkyl, (aryl) alkyl or alkyl (aryl) of 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, with Ci to C ₃ o-alkyl-substituted phenyl (such as methyl, ethyl , Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,

(Tridecyl) phenyl), C ₂ to Qoo ethoxylated fatty alcohol radicals having 1 to 130 carbon atoms, C ₃ to C ₉₉ propoxylated fatty alcohol radicals having 4 to 129 carbon atoms, C ₂ to C ₁₀₀ ethoxylated (alkyl) phenol radicals having 3 to 130 carbon atoms, C ₃ to C ₉ 9 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, particularly preferably hexyl, cyclohexyl, heptyl, n-octyl and 2-ethylhexyl, and

M ⁺ is selected from the group of alkali metals (such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ), preferably Na ⁺ or K ⁺ .

Some of these emulsifiers are known and commercially available, such as Aerosol OT ^®, ^® TR aerosol, aerosol Al ^® 96 (Aerosol types from. Cytec Industries Inc.), Empimin OT ^®, Empimin ^® OP (Empimin grades from. Hunstman), Geropon ^® CYA 75, Geropon ^® SDS, Geropon ^® SS O 75, Geropon ^® WS 25 I (Geropon grades from. Rhodia), Triton ^® GR (Fa. Dow Chemical), Lutensit ^® A BO ( Fa. BASF).

These emulsifiers can be used both individually, but also as mixtures with one another, as well as in combination with other non-ionic emulsifiers known to the skilled person for the purpose of better stabilization of the dispersion. In a most preferred embodiment for the preparation of component B of the polycarbonate compositions according to the invention, sulfosuccinic acid dicyclohexyl diester is used as the emulsifier in the grafting reaction.

The emulsifiers for the graft reaction in the preparation of the component B of the compositions according to the invention are in the amounts of 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 used.

The amount of water used to prepare the graft polymer dispersion is preferably such that the finished dispersion has a solids content of from 20 to 50% by weight.

To start the polymerization reaction, all radical formers are suitable which decompose at the chosen reaction temperature, ie both those which thermally decompose alone, as well as those which do so in the presence of a redox system. For example, it is peroxides, preferred

Peroxosulfates (such as sodium or potassium peroxodisulfate). However, it is also possible to use redox systems, in particular those based on hydroperoxides such as cumene hydroperoxide or tertiary

Butyl hydroperoxide used.

In general, the polymerization initiators in an amount of 0.05 to 1 wt .-%, based on the grafting monomers (B.1) used.

The radical formers and also the emulsifiers and, if appropriate, the molecular weight regulators explained in the next paragraph are added in portions to the reaction mixture, for example batchwise as total amount at the beginning of the reaction or divided into several portions

Begin and added at one or more later times, or added continuously during a certain time interval. The continuous addition can also be done along a

Gradients occur, the z. B. ascending or descending, linear or exponential, or even stepwise (step function) can be.

Furthermore, molecular weight regulators such. As ethylhexyl thioglycolate, n- or t-dodecyl mercaptan and / or other mercaptans, terpinols and / or dimeric α-methyl styrene and / or other suitable compounds for controlling the molecular weight, concomitantly used. The molecular weight regulators are added to the reaction mixture batchwise or continuously, as described above for the free-radical formers and emulsifiers.

If molecular weight regulators are used in the polymerization, they can be added in the preparation of the graft base B.2 or in the preparation of the graft B.l or both in the preparation of graft B.2 and graft B.l in the manner described above.

The workup of the dispersion of the emulsion Pfropφolymerisats B takes place in a method known in the art, without any special requirements on the purity of the reclaimed graft polymer are made: the graft polymer B is, for example, initially precipitated from the dispersion, for example by adding precipitating acting

Saline solutions (such as calcium chloride, magnesium sulfate, alum) or acids (such as acetic acid,

Hydrochloric acid or sulfuric acid) or else by freezing (freeze coagulation) or 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 in a conventional manner, for example by sieving, filtering, decanting or centrifuging. To

Separation of the dispersion water, the water-moist graft polymer is obtained, which usually has a residual water content of up to 60 wt .-%.

There is no or only partial separation of the excipients, e.g. Emulsifiers, salts, buffering agents, so that a substantial portion of up to 100% of the excipients (i.e., emulsifiers and other adjuvants) remain in the graft polymer and thus in the final product.

As an alternative to precipitation, spray-drying may be used in which the dispersion, without first being coagulated, is converted into fine droplets distributed in the air or inert gas and subsequently dried to powder in air or inert gas countercurrent. All excipients then remain 100% in the final product.

Component C

Component C comprises one or more thermoplastic vinyl (co) polymers C1 and / or polyalkylene terephthalates C.2.

Suitable as Vmyl (co) polymers Cl polymers of at least one monomer the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C] -Cg) - alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable are (co) polymers of

C.1.1 50 to 99, preferably 60 to 80 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics such as styrene, p-chlorostyrene) and / or (meth) acrylic acid (C 1 -C ₈ ) -alkyl esters, such as methyl methacrylate, ethyl methacrylate) , and C.1.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as

Acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C 1 -C ₈ ) -alkyl esters, such as

Methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids such as maleic acid, and / or derivatives such as anhydrides and imides, unsaturated

Carboxylic acids, for example maleic anhydride and N-phenylmaleimide).

The vinyl (co) polymers Cl are resinous, thermoplastic and rubber-free. Particularly preferred is the copolymer of C.1.1 styrene and Cl .2 acrylonitrile.

The (co) polymers according to Cl 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 and mixtures of these reaction products.

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

In addition to terephthalic acid residues, the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as radicals of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid. In addition to ethylene glycol or 1,4-butanediol radicals, the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms. Contain radicals, for example radicals of propanediol 1, 3, 2-ethylpropanediol 1, 3, neopentyl glycol, pentanediol 1, 5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2, 4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3,3,2-diethylpropanediol-1,3-hexanediol-2,5,1,4 Di (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4 -β-hydroxyethoxy-phenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane (DE-A

2 407 674, 2 407 776, 2 715 932).

The polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US-PS

3 692 744, to be branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Particularly preferred are polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.

Mixtures of polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate.

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

The polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VHI, page 695 ff, Carl Hanser Verlag, Munich 1973).

Component D

Phosphorus-containing flame retardants (D) in the sense of the invention are preferably selected from the groups of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonateamines and phosphazenes, whereby mixtures of several components selected from one or more of these groups can be used as flame retardants. Others too Non-specifically mentioned halogen-free phosphorus compounds can be used alone or in any combination with other halogen-free phosphorus compounds.

Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (VII)

wherein

R ¹ , R ² , R ³ and R ⁴ are each independently C _j to Cg-alkyl, C5 to Cg-cycloalkyl, Cg to C20-aryl or C7 to C ^ -aralkyl, each with alkyl, preferably C _j to C4 -Alkyl, and / or halogen, preferably chlorine, bromine may be substituted, n are independently O or 1, preferably n = 1, q is O to 30 and

X is a mononuclear or polynuclear aromatic radical having 6 to 30 C atoms or a linear or branched aliphatic radical having 2 to 30 C atoms, which may be OH-substituted and may contain up to 8 ether bonds.

R *, R ^, R ^ and R ⁴ are preferably independently C \ to C4 alkyl, phenyl, naphthyl or phenyl-C _j -C alkyl. The aromatic groups R ¹ , R 1, R ³ and R ⁴ may in turn be substituted by halogen and / or alkyl groups, preferably chlorine, bromine and / or C _] to C ⁴ -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) is preferably a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (II); n in the formula (VII) may independently be 0 or 1, preferably n is i; q is from 0 to 30, preferably from 0.3 to 20, particularly preferably from 0.5 to 10, in particular from 0.5 to 6, very particularly preferably from 1.0 to 1.6; X is particularly preferred for

or their chlorinated or brominated derivatives, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol; X is particularly preferably derived from bisphenol A.

As component D according to the invention it is also possible to use mixtures of different phosphates.

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

The phosphorus compounds according to component D are known (cf., for example, EP-A 0 363 608, EP-A 0 640 655) or can be prepared by known methods in an analogous manner (eg Ullmanns Enzyklopadie der technischen Chemie, Vol ff. 1979; Houben-Weyl, Methods of Organic Chemistry, 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) using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and from this the mean values for q are calculated.

Furthermore, phosphonatamines and phosphazenes, as described in WO 00/00541 and WO 01/18105, can be used as flame retardants.

The flame retardants can be used alone or in any mixture with each other or in mixture with other flame retardants. Component E

The composition may contain further commercially available additives such as flame retardant synergists, rubber-modified graft polymers other than component B, antidripping agents (for example compounds of the substance classes of the fluorinated polyolefins, of the silicones as well

Aramid fibers), lubricants and mold release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatic agents (for example carbon blacks, carbon fibers, carbon nanotubes and also organic antistatics such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers),

Acids, fillers and reinforcing materials (for example glass or carbon fibers, mica, kaolin, talc, CaCO ₃ and glass flakes) as well as dyes and pigments.

The acids according to component E are preferably selected from at least one of the group of the aliphatic dicarboxylic acids, the aromatic dicarboxylic acids and the hydroxy-functionalized dicarboxylic acids. Particular preference is given to citric acid, oxalic acid, terephthalic acid or mixtures of the compounds mentioned.

The graft polymers other than component B are prepared by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, wherein, in the case of emulsion polymerization, an emulsifier other than formula (I) is used. Preference is given to component B different graft polymers which are prepared by solution or bulk polymerization.

Preparation of the molding compositions and molded articles The thermoplastic molding compositions of the invention are prepared by mixing the particular constituents in a known manner and poundiert schmelzcom- in conventional units such as internal kneaders, extruders and twin-screw at temperatures of 200 ⁰ C to 300 ⁰ C and melt.

The mixing of the individual constituents may take place in known manner, either successively or simultaneously, and either at about 2O ⁰ C (room temperature) or at a higher temperature.

The invention also provides processes for the preparation of the molding compositions and the use of the molding compositions for the production of moldings and the moldings themselves. The molding compositions of the invention can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films.

Examples of such moldings are films, profiles, housing parts of any kind, e.g. for household appliances such as televisions, juicers, coffee machines, blenders; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets, as well as body and interior components for commercial vehicles, in particular for the automotive sector.

In particular, the molding compositions according to the invention can also be used, for example, for the production of the following moldings or moldings: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, housings of electrical appliances containing small transformers, housings for information processing and transmission equipment, housings and panels for medical applications Apparatus, massagers and housings therefor, toy vehicles for children, flat wall elements, housing for safety devices and for televisions, heat-insulated transport containers, fittings for plumbing and bathroom equipment, grille for ventilation openings and housings for garden tools.

The following examples serve to further illustrate the invention.

Examples Component A

A.l: linear polycarbonate based on bisphenol A with a weight average

Molecular weight M _w of 27500 g / mol (determined by GPC in CH ₂ Cl ₂ at 25 ° C).

A.2: Linear polycarbonate based on bisphenol A having a weight-average molecular weight M _w of 28500 g / mol (determined by GPC in CH ₂ Cl ₂ at 25 ° C.).

Component B Type B emulsion graft polymers with polybutadiene rubber base

The particulate crosslinked rubber base used for the preparation of component B (emulsion graft polymer) was prepared by free-radical emulsion polymerization of butadiene in the presence of sodium salt of a specific TCD emulsifier as described in DE 3913509A1 (Example 1). The polybutadiene bases thus obtained have an average particle size d.sub.50 = 350 nm and were used in the form of polymer latexes in the further reaction step (carried out in each case according to general instructions (I) or (II)).

All parts by weight in the examples below of graft polymers are normalized such that the sum of the parts by weight (parts by weight) of the graft base (polybutadiene) and the parts by weight of the graft monomers (styrene and acrylonitrile) of each graft polymer indicated below is 100 wt. Parts results. The amounts of water, emulsifiers, initiators and other auxiliaries are based on this sum of the parts by weight of the grafting base and the grafting monomers (= 100 parts by weight).

General Procedure (I): Preparation of the graft polymers B (I.1a) to B (1.2c): 60 parts by weight of polybutadiene (in the form of a latex prepared using the compound TCD emulsifier as emulsifier, solids content 25 wt .-%, average particle diameter dso = 350 nm) and 0 - 2 parts by weight of the emulsifier used in each case are heated to 65 ⁰ C under nitrogen and with 0.5 parts by weight of potassium peroxodisulfate (dissolved in 20 parts by weight of water ) and 0.3 parts by weight of sodium hydroxide (dissolved in 20 parts by weight of water) were added. Thereafter, a mixture of 30 parts by weight of styrene and 10 parts by weight of acrylonitrile is added within 4 hours, wherein the grafting reaction takes place. After a post-reaction time, the latex is coagulated in a magnesium sulfate / acetic acid solution, filtered off, optionally washed and the resulting powder dried at 70 ^° C. in vacuo. General procedure (II): Preparation of the graft polymers B (2.1a) to B (2.2e):

60 parts by weight 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 d _S o = 350 nm) and 0-2 parts by weight of each used emulsifier are heated to 65 ⁰ C under nitrogen. 0.4 part by weight of tert-butyl hydroperoxide (dissolved in 20 parts by weight of water) and 0.5 part by weight of sodium ascorbate (dissolved in 20 parts by weight of water) are added within 4 hours. In parallel, a mixture of 30 parts by weight of styrene and 10 parts by weight of acrylonitrile is added within 4 hours, wherein the grafting reaction takes place. After a post-reaction time, the latex is coagulated in a magnesium sulfate / acetic acid solution, filtered, optionally washed (see below) and the resulting powder dried at 70 ^° C. in vacuo.

Graft Polymer B (I.1a): Preparation According to General Procedure (I)

Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic dicyclohexyl diester (Aerosol Al 96, from Cytec Industries).

Coagulant work-up: the coagulum obtained after the precipitation is filtered off only (about 20 L filtrate solution) and not washed.

Graft polymer B (I-Ib): Preparation according to general procedure (I) Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulation work-up: the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water ( ie about 20 L per 1 kg of polymer).

Graft Polymer B (I, Ic): Preparation according to general procedure (I) Emulsifier: 1.5 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulate work-up: the coagulum obtained after the precipitation is filtered off and carefully (ie 4 times in distilled water) Slurried water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).

Graft polymer B (I-Id): Preparation according to general instructions (I) Emulsifier: 0.5 part by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulant work-up: The coagulum obtained after the precipitation is filtered off and not washed. Graft polymer B (Ie) (comparative): Preparation according to general procedure (I) Emulsifier: no emulsifier used in the grafting step

Coagulant work-up: the coagulum obtained after the precipitation is filtered off and carefully slurried (i.e., slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer).

Graft Polymer B (1.2a) (Comparison): Preparation According to General Procedure (I) Emulsifier: 0.5 part by Weight Sodium Dodecyl Sulfate (Aldrich)

Graft polymer B (1.2b) (comparative): Preparation according to general procedure (I) Emulsifier: 1.0 part by weight Sodium dodecyl sulfate (Aldrich) Coagulant work-up: The coagulum obtained after the precipitation is filtered off and carefully (ie 4 times in distilled water) Slurried water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).

Graft Polymer B (1.2c) (Comparison): Preparation According to General Procedure (I) Emulsifier: 1.5 parts by weight of sodium dodecylsulfate (Aldrich)

Graft Polymer B (2.1a): Preparation According to General Procedure (IT)

Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester (aerosol

Al 96)

Graft polymer B (2.1b): Preparation according to the general procedure (ET) Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulate work-up: the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water (ie approx. 20 liters per 1 kg of polymer). Graft polymer B (2.1c): Preparation according to general procedure (E) Emulsifier: 2 parts by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Coagulate work-up: the coagulum obtained after the precipitation is filtered off and carefully (ie slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).

Graft polymer B (2.1d): Preparation according to general procedure (II) Emulsifier: 1.5 parts of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol Al 96) Coagulant work-up: the coagulum obtained after the precipitation is filtered off only (about 20 l filtrate solution) and not washed.

Graft Polymer B (2.1e): Preparation According to General Procedure (D) Emulsifier: 1.0 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol Al 96)

Graft polymer B (2.1f): Preparation according to the general procedure (H) Emulsifier: 0.5 part of the sodium salt of sulfosuccinic acid dicyclohexyl diester (Aerosol Al 96)

Graft Polymer B (2.2a) (Comparison): Preparation according to General Method (II) Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)

Graft Polymer B (2.2b) (Comparison): Preparation according to General Method (II) Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich)

Coagulant processing: the coagulum obtained after the precipitation is filtered off and washed once with a large amount of distilled water (about 20 L per 1 kg of polymer).

Graft Polymer B (2.2c) (Comparison): Preparation according to general instructions (JT) Emulsifier: 2 parts sodium dodecyl sulfate (Aldrich) Coagulant workup: the coagulum obtained after the precipitation is filtered off and carefully (ie, slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (in total about 80 liters per 1 kg of polymer)).

Graft Polymer B (2.2d) (Comparison): Preparation According to General Method (II)

Emulsifier: 0.5 part sodium dodecyl sulfate (Aldrich)

Coagulum workup: the coagulum obtained after the precipitation is filtered off and carefully (i.e.

Slurried 4 times in distilled water, then filtered off and washed with a large amount of distilled water (a total of about 80 liters per 1 kg of polymer)).

Graft Polymer B (2.2e) (Comparison): Preparation According to General Method (II)

Emulsifier: 1.0 TIe sodium dodecyl sulfate (Aldrich)

Emulsion graft polymers according to component B based on 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 polymerizing 10% by weight of n-butyl acrylate in the presence of 83 parts by weight of deionized water, 0.2 part by weight Sodium dodecyl sulfate and 0.18 parts by weight potassium peroxodisulfate (K ₂ SaOg) dissolved in 7.0 parts by weight of water for 3 h at 80 ⁰ C. An acrylate latex having a solids content of 10.0% and a weight-average particle size of d50 = 50 nm was obtained.

10.0 parts by weight of the prepared seed latex (1.0 part by weight based on solid polymer) were together with 145 parts by weight of water, 6.85 parts by weight of n-butyl acrylate monomer and 0.3 parts by weight of the previously dissolved in water sodium salt of sulfosuccinic acid Dicyclohexyldiester (Aerosol Al 96) submitted xmd heated to 65 ° C. After reaching 65 ° C were 0.25 parts by weight. Potassium peroxodisulfate dissolved in 12.5 parts by weight. Add water within 5 minutes and then the dosages of monomer solution consisting of 90 parts by weight of n-butyl acrylate, 0.45 parts by weight of trimethyloltriacrylate and 2.70 parts by weight. Allyl methacrylate, as well as a solution consisting of 1, 20 Gew.Tle d of aerosol Al 96, 0.20 parts by weight of potassium peroxodisulfate and 24.0 parts by weight of water) within 5h started. After the end of the doses, the temperature was brought to 70 ⁰ C and then a solution of 0.05 parts by weight of potassium peroxodisulfate, dissolved in 2.34 parts by weight of water, added over one hour. Thereafter, it was stirred at 70 ⁰ C for an additional hour. you obtained a bimodal acrylate rubber base as a 35% dispersion (~ 100% conversion) with a weight average particle size d50 = 450 nm.

For the preparation of the graft polymers, 180 parts by weight of poly (n-butyl acrylate) latex (solids content 34%) were mixed with 17 parts by weight of water, 0.06 parts by weight of respective emulsifier, dissolved in 1.14 wt . -It water, placed in a flask and heated to 65 ⁰ C under nitrogen. 0.4 part by weight of tert-butyl hydroperoxide, 0.54 part by weight of emulsifier (both components dissolved in 20 parts by weight of water), and 0.5 part by weight of sodium ascorbate (dissolved in 20 parts by weight of water) are added within 7 hours. In parallel, a mixture of 30 parts by weight of styrene and 10 parts by weight of acrylonitrile is added within 4 hours, wherein the grafting reaction takes place. After a reaction time of 2 hours, a conversion of 99% is achieved. The latex is coagulated with a magnesium sulfate solution, filtered and dried at 70 ⁰ C in a vacuum.

Graft polymer B (2.3a):

Emulsifier: 1.5% by weight of the sodium salt of sulfosuccinic acid dicyclohexyl diester Work-up of the graft polymer dispersion: The polymer dispersion was precipitated with magnesium sulfate and the coagulum obtained after the precipitation was filtered off (about 2 × filtrate) and not washed.

Component C

Cl:

Copolymer of 75% by weight of styrene and 25% by weight of acrylonitrile having a weight-average molecular weight M _w of 130 kg / mol (determined by GPC), prepared by the bulk polymerization process.

C.2 (comparative): copolymer of 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile having a weight-average molecular weight M _w of 90 kg / mol (determined by GPC), prepared by the bulk polymerization process.

Component Dl Bisphenol-A-diphenyl diphosphate, Reofos BAPP, Greate Lakes Component E

E.1: Pentaerythritol tetrastearate as lubricant / release agent

E.2 phosphite stabilizer, Irganox ^® B 900, Ciba Specialty Chemicals E.3 citric Fa. (Anhydrous), Fa. DSM

E.4 Poly (perfluoroethylene) PTFE, Polyflon FA-500, Fa. Daikin

E.5 Boehmite, Pural 200, Fa. Sasol

E.6 bulk ABS Fa. Nippon A & L, available under the trade name "Santac ^® AT 08".

Production and testing of molding compounds

In a 1.5 L internal kneader, the compositions listed in Tables 1 to 3 are prepared.

Table 1: PC / ABS composition without flame retardant

Table 2: PC / ABS composition with flame retardant

Table 3: further PC / ABS composition with flame retardant

Table 4: PC / ASA composition

As a measure of the resistance to hydrolysis of the compositions thus prepared is the change in MVR measured according to ISO 1 133 at 260 ⁰ C with a 5 kg punch load at a 7-day storage of the granules at 95 ° C and 100% relative humidity. The increase in the MVR value is evaluated (calculated as a percentage here) with respect to the initial MVR value DMVR (hydr.). In order to account for variations in temperature during storage, a control sample was used with each storage, the MVR value of which fluctuated after storage by 50 ml / 10 min and then normalized to exactly 50. The resulting normalization factor was also applied to all MVR measured values of a series of measurements. The normalized value MVR change is referred to as DMVR (hydr., Corr.).

As a measure of the processing stability (degradation of the polycarbonate at stringent processing conditions) of the compositions thus prepared is used the change in the MVR measured according to ISO 1133 at 260 ⁰ C with a plunger load of 5 kg at a 15-minute residence time of the melt under the exclusion of air at a temperature of 300 ⁰ C for non-flame-retardant PC / ABS compositions and a 30-minute residence time of the melt with exclusion of air at a temperature of 300 ° C. The determination of the notched impact strength a ^ is carried out in accordance with ISO 180/1 A.

To determine the weld line strength, the impact resistance at the weld line of specimens injection molded on both sides and measuring 80 mm × 10 mm × 4 mm was measured in accordance with ISO 179/1 U.

The elongation at break is determined in the tensile test according to ISO 527.

In Table 5 (were used, the PC / ABS compositions according to Table 1, ie without flame retardants) results of storage in humid climates (hydrolytic stability) and at 300 ⁰ C (processing stability) are summarized.

These results show that the use of specific emulsifiers corresponding to formulas I, V and VI in the grafting step B.l (preparation of component B (a)) has solved the problem of providing polycarbonate compositions according to the invention having improved hydrolysis resistance:

The inventive compositions 1 to 3 and 8 to 10 show a slight increase in the MVR value after climate storage of 37-50% (DMVR (hydr., Corr.)), Regardless of whether the graft polymer was thoroughly washed or not washed at all This result is surprising in particular because the hydrolysis resistance of Composition 4 (Comparative Example), which contains an ABS prepared emulsifier-free on the grafting step, has a DMVR (hydr.corresponding) of 49% means that the compositions containing the graft polymers according to the invention have at least as good resistance to hydrolysis as the composition comprising a graft polymer prepared without any emulsifier.

The compositions of Comparative Examples 5 to 7 and 13 to 15, which contain an ABS prepared with sodium dodecyl sulfate, ie, an emulsifier described in the prior art (eg EP-A-0 900 827), show that at best DMVR (hydr. corr.) values of 56 to 85% after climate storage can be achieved if the graft polymer has been thoroughly washed, ie no emulsifier is left. These hydrolysis resistances are significantly worse than those of the polycarbonate compositions according to the invention. Omission of a careful workup of the graft polymers with the emulsifiers described in the prior art (compositions of Comparative Examples 11 and 12) results in a dramatic degradation of the polycarbonate, which results from the DMVR (hydr. Corr.) Values of 140 to 206% is closing.

Moreover, the compositions according to the invention 1 to 3 and 8 to 10 show a good processing stability, which from DMVR (proc.) - values of 37-69% visible (melt storage at 300 ⁰ C, 15 min).

In the flame retardant PC / ABS compositions of Table 6 (employing the PC / ABS compositions shown in Table 2), it is also found that the object underlying this invention is achieved by the use of specific emulsifiers corresponding to Formulas I, V and VI in the grafting step B1 (preparation of component B (a)) is dissolved. Thus, compositions 17 to 21 according to the invention from Table 5 show only a moderate increase in the MVR value of 64 to 92% compared to the comparison from the prior art (composition 16) and furthermore have advantages in the notched impact strength (a 1, Bindenahtfestigkeit (a ^) and the elongation at break.

In the flame retardant PC / ABS compositions of Table 7 (employing the PC / ABS compositions shown in Table 3), it is also found that Compositions 23-25 have advantages over Composition 22 in terms of resistance to hydrolysis, processing stability, notched impact strength, Bindenahtfestigkeit and elongation at break have.

The PC / ASA compositions of Table 8 show an analogous behavior: the compositions of the invention have both a good resistance to hydrolysis and a good processing stability, provided that no alpha-methylstyrene-containing polymer is used as component C (cf state of the art DE 698 27 302 T2). In the case of composition 27, which has good resistance to hydrolysis but contains α-methystyrene-containing SAN as component C, the processing stability relative to composition 26 according to the invention is markedly reduced.

Table 6 Properties of the flame retardant PC / ABS composition of Table 2

5 Table 7 Properties of the further flame-retardant PC / ABS composition of Table 3 Ul

Table 8 Characteristics of the PC / ASA compositions of Table 4

Claims

claims

1. Containing compositions

A) 10 to 99 parts by weight of aromatic polycarbonate and / or aromatic polyester-carbonate,

B) 1 to 35 parts by weight of rubber-modified Pfiropfpolymerisat of B.l 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 <10 ⁰ C, C) 0 -. 40 parts by weight of vinyl (co) polymer and / or polyalkylene terephthalate, wherein a copolymer of α-methystyrene and acrylonitrile -excluded,

D) 0-50 parts by weight, based on the sum of the components A + B + C, phosphorus-containing flame retardant,

E) 0-50 parts by weight, based on the sum of the components A + B + C, additives,

EEC

I

R ⁹ - C - Y - [M ²⁺ ] _{1 / z} (I)

I W at the

EWG is a carbonyl, a carboxyl, a nitrile, a nitro or a sulfone group, W is a group selected from Cp to C ₃ o-alkyl, Ci to C ₃₀ cycloalkyl, Q to C ₃₀ - aryl , C ₁ - to C ₃ o- (aryl) alkyl, C ₁ - to C ₃₀ - (alkyl) aryl, C _r - to C ₃₀ -alkoxy, C _r - to C ₃₀ -alkyl, C ₂ - to C ₀₀ -oxyoxylated alkoxy or aryloxy group according to the

Formula RO- (CH ₂ -CH ₂ -O) ₃ - a = 1 to 50 and R = C, - to C ₃₀ -alkyl or C ₁ - to C ₃₀ - aryl, wherein all said groups may also be substituted, eg by one or more electron-withdrawing groups as defined above for the EEC,

R ⁹ is H or a C ₁ to C ₃₀ alkyl, Ci to C _3o aryl, C] -C ₃₀ - (alkyl) aryl, which may also be substituted, Y ^'is selected from the group consisting of borate (-O-BO (OR ⁹ ) ^' ), boronate (-BO (OR ⁹ ) ^" ), nitrate (-O-NO ₂ ^" ), nitro (-NO ₂ ^" ), sulphate (-O-SO ₃ ^' ), sulphonate (-SO ₃ ^' ), phosphate (-OP (OR ⁹ ) O ₂ ^" ) and phosphonate (-P (OR ⁹ ) O ₂ ) .

z is the number 1 or 2, and

M ^{z + is} selected for z = 1 from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ,

Ammonium cation, alkylammonium cation (NH _4, _n R ⁹ _n ⁺ , where n = 1 to 4), phosphonium cation and alkylphosphonium cation (PH _4, _n R ⁹ _n ⁺ , where n = 1 to 4), or for z = 2 is selected from the group consisting of Mg ²⁺ , Ca ²⁺ ,

Sr ²⁺ and Ba ²⁺ .

2. Composition according to claim 1, characterized in that component B is obtainable by reaction of the component B.l with the graft base B.2 by means of

Emulsion polymerization, wherein an emulsifier according to formula (V) is used,

EEC

R ⁹ - C - Y - [M ²⁺ ] _{1 / z} (V)

EEC

in which

R ⁹ , Y ^"have the meaning explained in claim 1

EEC independently have the meaning as defined in claim 1, F an alkylidene group -CR ¹⁰ R ¹¹ -, where R ¹⁰ and R ¹¹ are each independently H, 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 the component B.l with the graft base B.2 by means of

Emulsion polymerization, wherein an emulsifier according to formula (VI) is used,

in which

R ¹² and R ¹³ are each independently H, alkyl, cycloalkyl, (aryl) alkyl or

Alkyl (aryl) having 1 to 30 carbon atoms, and

M ^{+ is} selected from the group consisting of the group. Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ .

4. The composition according to claim 1, characterized in that component B is obtainable by reaction of the component B.l with the graft B.2 by means of emulsion polymerization, being used as an emulsifier sulfosuccinic Dicyclohexyldiester,

5. The composition according to any one of claims 1 to 4, characterized in that the emulsifiers for the graft reaction in the preparation of component B in the amounts of 0.1 to 5 wt.% Are used.

6. Compositions according to one of claims 1 to 5, containing as component D compounds of formula (VII),

(Vπ) embedded image in which

Rl, R ^, R ^ and R ^ independently of each other C _j to Cg alkyl, C5 to mean Cg-cycloalkyl, Cg to C20 "aryl or C7 to C ^ aralkyl, which may each be substituted by alkyl and / or halogen . n are independently 0 or 1, q is 0 to 30 and

X is 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 may be OH-substituted and may contain up to 8 ether bonds.

7. Compositions according to one of claims 1 to 6, wherein the additives according to component E are selected from at least one of the group consisting of flame retardant synergists, different from component B rubber-modified

Graft polymers, antidripping agents, lubricants and mold release agents, nucleating agents, stabilizers, antistatic agents, acids, fillers and reinforcing agents, dyes and pigments:

8. Use of the compositions according to any one of claims 1 to 7 for the production of moldings.

9. Shaped body containing a composition according to any one of claims 1 to 7.

10. Shaped body according to claim 9, characterized in that the molded body an interior fitting for rail vehicles, ships, aircraft, buses and others

Automobiles, a housing of electrical appliances containing small transformers, a housing for information processing and transmission equipment, a housing or paneling of medical equipment or massagers, a toy vehicle for children, a flat wall element, a housing for safety devices or for television sets, a heat-insulated Transport container, a molding for sanitary and

Bathing equipment, a grille for ventilation openings or a housing for garden tools is.