EP1037945A1

EP1037945A1 - Polycarbonate moulding materials

Info

Publication number: EP1037945A1
Application number: EP98958246A
Authority: EP
Inventors: Martin Weber; Thomas Fritzsche; Manfred Knoll; Xaver Hopfenspirger
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1997-12-03
Filing date: 1998-11-20
Publication date: 2000-09-27
Also published as: JP2001525439A; US6423767B1; AU1435799A; WO1999028386A1; DE19753541A1

Abstract

The invention relates to moulding materials containing: A) at least one polycarbonate; B) at least one graft polymer with a base consisting of an elastomer with a glass transition temperature below 10 °C; C) at least one copolymerisate containing vinylaromatic monomers; D) at least one filler; E) at least one low molecular halogen-free acid and also, optionally; F) at least one polyacrylate; G) at least one flameproofing agent and H) at least one additive. The moulding materials are characterised in that they contain I) at least one aromatic or partially aromatic polyester or mixtures thereof. The invention also relates to moulded parts, films or fibres, and especially external vehicle body parts produced from the moulding materials.

Description

Polycarbonate molding compounds

description

The present invention relates to molding compositions which

A) at least one polycarbonate,

B) at least one graft copolymer based on an elastomer with a glass transition temperature of below 10 ° C.,

C) at least one copolymer containing vinyl aromatic monomers,

D) at least one filler,

E) at least one low molecular weight halogen-free acid

as well as if desired

F) at least one polyalkyl acrylate and

G) at least one flame retardant and

H) at least one additive,

contain and which are characterized in that they

I) at least one aromatic or partially aromatic polyester or mixtures thereof

included as a further component. In addition, the present invention relates to the use of the molding compositions for the production of moldings, films or fibers and to the moldings obtainable from the molding compositions.

Filler-containing polycarbonate molding compositions which contain graft copolymers based on dienes (ABS) or acrylates (ASA) and styrene copolymers are known. It is also known that they can be equipped with various flame retardants. Such molding compounds are primarily used in the production of molded parts, for example for the automotive sector.

From DE-Al-40 34 336, polycarbonate molding compositions were known in which per- or polyfluorinated alkanesulfonic acid or carboxylic acid derivatives were used instead of polytetrafluoroethylene as anti-dripping agents were used. The molding compositions described there have increased toughness in the puncture test at low temperatures and lower overall burning times, but on the one hand they do not meet today's requirements with regard to freedom from halogen and on the other hand they have relatively low heat resistance.

Filler-containing molding compositions based on polycarbonate, which have styrene copolymers containing oxazoline groups and contain polyester, preferably partially aromatic polyesters, as a further component can be found in DE-Al-196 06 198. They are characterized by good strength, elongation at break and impact strength. However, the low-temperature damage work of such molding compounds is not sufficient.

WO 96/06136 and EP-Bl-391 413 describe polycarbonate molding compositions which are filled with talc in an aspect ratio of 4 to 40 or 4 to 24 and a particle size of less than 44 or less than 10 μm, which is why the parts made from it warp less and have good impact strength. According to the first-mentioned document, the copolymer contained in the molding compositions should have the highest possible molecular weight. According to the latter document, amorphous polymers, including amorphous polyesters, can be mixed into the polycarbonate molding compositions. The disadvantage of the molding compositions mentioned is that they do not flow well and are difficult to process. They also have the disadvantage that the impact strength is insufficient for many applications.

EP-Al-522 397 discloses polycarbonate molding compositions which may contain polyalkylene terephthalates, which, when they are exposed to flame, do not deform and do not drip off when exposed to flame. They can be obtained by mixing their components with sulfonic acid salts and aramids. This has the disadvantage that the toughness of corresponding molding compositions is considerably reduced.

EP-Al-576 948 proposes to neutralize basic impurities which can degrade the polycarbonate and which are introduced into the molding compositions, in particular via recycled ABS, by adding polymeric resins with acid groups. Poly (meth) acrylic acid or partially saponified poly (meth) acrylates are mentioned as such. Their molecular weights (weight average M _w ) are preferably up to 500,000 g / mol. The molding compositions mentioned in EP-Al-576 948 can contain aromatic polyesters as one of their further components. This Molding compounds are not impact-resistant and tear-resistant enough for many applications.

The molding compositions disclosed in JP-A 9/137054 can contain saturated polyesters. In order to keep the polycarbonate degradation low, these molding compositions are filled with neutral talc, which however requires an additional technical process step and is therefore complex and cost-intensive.

The object of the present invention was to provide polycarbonate molding compositions which do not have the disadvantages mentioned. In particular, the polycarbonate molding compositions should be easy to process into large-scale molded parts which are suitable for use as exterior parts of the body. Since they should replace metal, polycarbonate molding compounds should be found that should meet a whole range of the highest requirements.

This task is fulfilled by the molding compounds defined at the beginning. Particular embodiments can be found in the subclaims and the description.

Component A

According to the invention, the molding compositions comprise, as component A, one or a mixture of two or more different polycarbonates. Preferred molding compositions according to the invention contain from 1 to 97.35% by weight, based on the total weight of the molding compositions of component A. Particularly preferred are molding compositions according to the invention which contain from 10 to 91.9% by weight, based on the total weight of the Molding compositions containing component A.

Halogen-free polycarbonates are preferably used as component A. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula I.

wherein Q is a single bond, a 0χ to Cs alkylene, a C ₂ to C ₃ alkylidene, a C ₃ to C _δ cycloalkylidene group, a C ₆ to C ₂ arylene group and -O-, - S- or -S0 ₂ - means and m is an integer from 0 to 2. The diphenols I may also have substituents, such as Ca The phenylene _radicals. - to C ₆ -alkyl or _Ca. - to C ₆ alkoxy.

Preferred diphenols of the formula I are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis - (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2- methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane. 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, as well as 1,1-bis- (4-hydroxyphenyl) -3,3,5- are particularly preferred. trimethylcyclohexane.

Both homopolycarbonates and copolycarbonates are suitable as component A; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.

The suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.

Polycarbonates which have relative viscosities η _re ι from 1.10 to 1.50, in particular from 1.25 to 1.40, have proven to be particularly suitable. This corresponds to average molecular weights M _w (weight average) of 10,000 to 200,000, preferably 20,000 to 80,000.

The diphenols of the general formula I are known per se or can be prepared by known processes.

The polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the interfacial process or with phosgene by the process in a homogeneous phase (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by an appropriate amount of known chain terminators. (Regarding polydiorganosiloxane-containing polycarbonates, see for example DE-OS 33 34 782).

Suitable chain terminators are, for example, phenol, p-t-butylphenol but also long-chain alkylphenols such as 4 - (1, 3-tetramethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-t-butylphenol, p-t-octylphenol, p-dodecylphenol, 2 - (3, 5 -dimethyl-hep - tyl) phenol and 4 - (3, 5-dimethylheptyl) phenol. Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine resulting, for example, from the production of the polycarbonates with phosgene by the phase boundary process, is not to be regarded as containing halogen in the sense of the invention. Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.

Component B

One or a mixture of two or more different graft polymers is used as component B in the molding compositions according to the invention, preferably in amounts of 1 to 97.35% by weight, based on the total weight of the molding compositions. Particularly preferred molding compositions according to the invention contain from 2 to 50% by weight, based on the total weight of the molding compositions, of at least one graft polymer B. According to the invention, these are based on an elastomer with a glass transition temperature of below 10 ° C., preferably below 0 ° C.

For the purposes of the present invention, an elastomer is also understood to mean mixtures of different elastomers. Natural elastomers or synthetic rubbers come as elastomers e.g. Diene rubbers, acrylate rubbers or siloxane rubbers into consideration. Among them, acrylate rubbers are preferred.

The particularly preferred graft polymers B are composed of

bi) 40 to 80% by weight, preferably 50 to 70% by weight, of a graft base made of a rubber-elastic polymer based on alkyl acrylates with 1 to 8 C atoms in the alkyl radical and with a glass transition temperature of below 0 ° C

b) 20 to 60% by weight, preferably 30 to 50% by weight, of a graft pad

b ₂ χ) 60 to 95 wt .-%, preferably 70 to 85 wt .-% styrene or substituted styrenes of the general formula II

R - C - CH ₂

wherein R is a _Ca. - to Cg alkyl group, preferably methyl or ethyl, or is hydrogen and R ^{1 is} a _Ca. represents up to Cβ-alkyl, preferably methyl or ethyl, and n has the value 1, 2 or 3 or their mixtures and

b ₂₂ ) 5 to 40% by weight, preferably 15 to 30% by weight, of at least one unsaturated nitrile, preferably acrylonitrile or methacrylonitrile or mixtures thereof.

Polymers whose glass transition temperature is below -20 ° C. are particularly preferred for the graft base i. These are elastomers based on _Ca. - To Cβ-alkyl esters of acrylic acid, which may optionally contain other comonomers.

Graft bases ba are preferred _. that are built up from

bia _. ) 70 to 99.9% by weight of at least one alkyl acrylate with 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, in particular n-butyl acrylate as the sole alkyl acrylate,

bι) 0 to 30% by weight of a further copolymerizable mono-ethylenically unsaturated monomer, such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof,

ba _.3 ) 0.1 to 5% by weight of a copolymerizable, polyfunctional, preferably bi- or trifunctional, crosslinking monomer,

the percentages by weight refer to the total weight of the graft base.

According to another preferred embodiment, the graft base can

from 66 to 79 wt.% bn,, from 20 to 30 wt.% bι ₂ ) and from 1 to 4 wt.% bχ ₃ )

put together, the weight percentages refer to the total weight of the graft base.

Suitable such bi- or polyfunctional crosslinking monomers ba _.3 ) are monomers which preferably contain two, possibly also three or more, ethylenic copolymers capable of copolymerization. Contain 7 pel bonds that are not conjugated in the 1, 3 positions. Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate or triallyl isocyanurate. The acrylic acid ester of tricyclodecenyl alcohol has proven to be a particularly favorable crosslinking monomer (cf. DE-A 12 60 135).

This type of graft base is known per se and described in the literature, for example in DE-A 31 49 358.0

Of the graft layers b ₂ , preference is given to those in which b _{2 is} styrene or α-ethylstyrene or mixtures thereof and b _{22 is} acrylonitrile or methacrylonitrile. Styrene and acrylonitrile or α-methyl-5 styrene and acrylonitrile are used as preferred monomer mixtures. The grafting pads can be obtained by copolymerizing components b ₂ ι and b ₂ .

The preparation of the graft base ba _. the graft polymer B, which is composed of the components bιχ, optionally b _i and ba _.3 0, is known per se and, for example, in the

DE-A 28 26 925, DE-A 31 49 358 and DE-A 34 14 118 are described.

The graft polymers B can be prepared, for example, by the method described in DE-PS 12 60 135.

The graft layers (graft shell) of the graft polymers can be built up in one, two or more stages.

0 In the case of the one-stage construction of the graft shell, a

Mixture of the monomers b χ and b ₂₂ in the desired weight ratio in the range from 95: 5 to 50:50, preferably from 90:10 to 65:35 in the presence of the elastomer bi, in a manner known per se (cf. e.g. DE-OS 28 26 925), preferably in emulsion, polymerized - 5 siert.

In the case of a two-stage construction of the graft shell b ₂ , the first stage generally makes up 20 to 70% by weight, preferably 25 to 50% by weight, based on b ₂ . Preferably only styrene or substituted styrenes or their mixtures (b ₂ ι) are used for their preparation.

The second stage of the graft shell generally makes up 30 to 80% by weight, in particular 50 to 75% by weight, in each case based on b, 5. For their preparation, mixtures of the monomers b ₂ ihrer and the nitriles b in the weight ratio b ₂ ι / b ₂ of generally 90:10 to 60:40, in particular 80:20 to 70:30.

The conditions of the graft polymerization are preferably chosen such that particle sizes of 50 to 700 nm (dso value of the integral mass distribution) result. Measures for this are known and e.g. described in DE-OS 28 26 925.

A coarse-particle rubber dispersion can be produced directly using the seed latex process.

In order to achieve products that are as tough as possible, it is often advantageous to use a mixture of at least two graft polymers with different particle sizes.

To achieve this, the particles of the rubber are kneaded in a known manner, e.g. by agglomeration, enlarged so that the latex is bimodal (50 to 180 nm and 200 to 700 nm).

In a preferred embodiment, a mixture of two graft polymers with particle diameters (dso value of the integral mass distribution) of 50 to 180 nm or 200 to 700 nm in a weight ratio of 70:30 to 30:70 is used.

The chemical structure of the two graft polymers is preferably the same, although the shell of the coarse-particle graft polymer can in particular also be constructed in two stages.

Mixtures of components A and B, the latter having a coarse and a finely divided graft polymer, are e.g. described in DE-OS 36 15 607. Mixtures of components A and B, the latter having a two-stage graft shell, are known from EP-A 111 260.

In addition to the already mentioned ASA rubbers, those modified with oxazoline groups described in DE-Al-146066198 are also suitable.

Component B can also be a mixture of the graft polymers mentioned with one or more different ones

Network rubbers. The proportion of network rubbers based on the total weight of the molding compositions according to the invention can be up to 20% by weight, preferably from 1 to 15% by weight.

Network rubbers based on siloxanes and acrylates or methacrylates are preferred. The preferred network rubbers generally contain

ßx) 30 to 95 wt .-%, preferably from 40 to 90 wt .-% of a network as a graft base, which

βxx) 10 to 90 wt .-%, preferably from 20 to 80 wt .-% of at least one polyorganosiloxane and

ß ₁ ) 10 to 90 wt .-%, preferably from 20 to 80 wt .-% of a polyalkyl acrylate or a polyalkyl methacrylate or mixtures thereof is formed and

ß ₂ ) 5 to 70 wt .-%, preferably from 10 to 60 wt .-% of a graft pad.

Preferred polysiloxanes are derived from cyclic organosiloxanes with preferably three to six silicon atoms. Examples of suitable siloxanes are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane or octaphenylcyclotetrasiloxane. The polysiloxanes can be composed of one or different organosiloxanes.

In addition, the polyorganosiloxanes βx generally contain from 0.1 to 30% by weight, based on βx, of at least one crosslinking agent. Trifunctional or tetrafunctional silanes such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane or tetrabutoxysilane can be used as crosslinkers. Among them, tetrafunctional silanes are particularly preferred.

Furthermore, the polyorganosiloxanes generally contain from 0 to 10% by weight, based on β _lx , of graft-active monomers. Unsaturated silanes, for example, can be used as graft-active monomers.

Preferred graft-active monomers are methacryloyl silanes. As

Examples include:

β-methacryloyloxyethyldimethoxymethylsilane γ-methacryloyloxypropylmethoxydimethylsilane γ-methacryloyloxypropyldimethoxymethylsilane γ-methacryloyloxypropyltrimethoxysilane γ-methacryloyloxypropylethoxydiethylsilan γ-methacryloyloxypropylsilane δ-methacryloyloxybutyldiethoxymethylsilane.

Processes for the preparation of polyorganosiloxanes are described, for example, in US Pat. No. 2,891,920 or 3,294,725. The polyorganosiloxanes are preferably prepared by mixing in a solvent the organosiloxanes, the crosslinking agents and, if desired, the graft-active monomers under shear with water in the presence of an emulsifying agent such as an alkyl sulfone - Acid or preferably an alkylbenzenesulfonic acid are mixed. The metal salts of alkylsulfonic acid or alkylbenzenesulfonic acid can also be used as emulsifiers.

As monomeric building blocks, the polyalkyl acrylates or polyalkyl methacrylates β ₂ generally contain alkyl acrylates or methacrylates or their mixtures, crosslinking agents and graft-active ones

Monomers, where crosslinkers and graft-active monomers can be used alone or together. The proportion of crosslinking agent and graft-active monomers is generally in the range from 0.1 to 20% by weight, based on βχ.

Examples of suitable alkyl acrylates or alkyl methacrylates are methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate or n-lauryl methacrylate. N-Butyl acrylate is particularly preferably used.

The crosslinking agent can be, for example, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or 1,4-butylene glycol dimethacrylate.

Allyl methacrylate, triallyl cyanurate or triallyl isocyanurate are examples of suitable graft-active monomers. Among them, allyl methacrylate can also act as a crosslinker.

The network is produced by adding the monomeric building blocks of component ßχ to the polyorganosiloxane ßxx, which is neutralized by adding an aqueous solution of a base such as sodium hydroxide, potassium hydroxide or calcium hydroxide. This swells the polyorganosiloxane. Then customary radical initiators are added. In the course of the polymerization reaction, a network is formed in which the components ßxx and ß ₁₂ penetrate each other. The networks can also be linked to one another via chemical bonds. Networks in which the polyorganosiloxane has a main chain made of dimethylsiloxane and β _{2 is} a polyalkyl acrylate which has a main chain made of n-butyl acrylate are very particularly preferred.

The gel content of the network is usually more than 80% (measured by extraction with toluene at 90 ° C over a period of 12 h).

The graft ß ₂ is usually made up of vinyl monomers. These include styrene, α-methylstyrene, vinyl toluene, acrylic acid esters, for example methyl acrylate, ethyl acrylate, or n-butyl acrylate, methacrylic acid esters such as methyl methacrylate or 2-ethyl methacrylate, nitriles, for example acrylonitrile or methacrylonitrile. The vinyl monomers can be used alone. Mixtures of different monomers can also be used. The monomers are generally chosen such that the graft has a glass transition temperature of at least 80 ° C., preferably in the range from 80 to 110 ° C. (determined by means of torsion pendulum measurement at a frequency of 1 Hz and a heating rate of 10 ° C./min) . Grafting pads which have a predominant proportion of methyl methacrylate are particularly preferred, preferably grafting pads with at least 85% by weight of methyl acrylate. Grafting pads with a proportion of 95 to 100% by weight of methyl methacrylate are particularly preferred. In addition to methyl methacrylate, styrene, n-butyl acrylate or cyclohexyl methacrylate are preferably used. Methyl methacrylate is very particularly preferably used alone.

Component C

As component C, the molding compositions according to the invention preferably contain from 1 to 97.35% by weight, based on the total weight of the molding compositions, of one or a mixture of two or more different copolymers which contain vinylaromatic monomers. Particularly preferred molding compositions according to the invention contain component C in proportions of 2 to 50, based on the total weight of the molding compositions. Copolymers based on styrene or substituted styrenes and unsaturated nitriles are preferred.

Both statistical and block copolymers can be considered as copolymers. Examples of suitable copolymers are polystyrene-co-acrylonitrile or terpolymers based on styrene, acrylonitrile and N-phenylmaleiimide or copolymers containing oxazoline groups. The copolymers C are particularly preferably made of

θχ) 60 to 95 wt .-%, preferably 65 to 85 wt .-% styrene or substituted styrenes of the general formula I or mixtures thereof and

c) 5 to 40% by weight, preferably 15 to 35% by weight, of at least one unsaturated nitrile, preferably acrylonitrile or methacrylonitrile or mixtures thereof

built up .

The copolymers C are resinous, thermoplastic and rubber-free. Particularly preferred copolymers C are those of styrene and acrylonitrile, of α-methylstyrene and acrylonitrile or of styrene, α-methylstyrene and acrylonitrile.

Copolymers of this type are frequently formed as by-products in the graft polymerization for the preparation of component B, especially when large amounts of monomers are grafted onto small amounts of rubber.

The copolymers C are known per se and can be prepared by radical polymerization, in particular by emulsion, suspension, solution and bulk polymerization. They have viscosity numbers in the range from 40 to 160, preferably from 60 to 110 ml / g (measured in 0.5% strength by weight solution in dimethylformamide at 23 ° C.), this corresponds to average molecular weights M _w (weight average) from 40,000 to 2,000,000.

Processes for the preparation of polymers containing oxazoline groups are also known per se. Copolymers containing oxazoline groups can e.g. by reacting copolymers containing nitrile groups with a monoamino alcohol, preferably in the presence of a catalyst such as a zinc or cadmium salt (see e.g. DE-Al-196 60 61 98).

Component D

As a further component, the molding compositions according to the invention contain one or a mixture of two or more fillers. As a rule, these are present in amounts of 0.5 to 25, preferably 1 to 20,% by weight, based on the total weight of the molding compositions. Examples of fibrous fillers are carbon fibers, potassium titanate whiskers, aramid fibers and particularly preferably glass fibers. If glass fibers are used, they can be equipped with a size and an adhesion promoter for better compatibility with the matrix material. In general, the carbon and glass fibers used have a diameter in the range from 6 to 20 μm.

Glass fibers can be incorporated both in the form of short glass fibers and in the form of continuous strands (rovings). In the finished injection molded part, the average length of the glass fibers is preferably in the range from 0.08 to 0.5 mm.

Carbon or glass fibers can also be used in the form of fabrics, mats or glass silk rovings.

Amorphous silica, carbonates such as magnesium carbonate (chalk), powdered quartz, mica, a wide variety of silicates such as clays, muscovite, biotite, suzoite, tin maletite, talc, chlorite, phlogophite, feldspar, are suitable as particulate fillers.

Calcium silicates such as wollastonite or aluminum silicates such as kaolin, especially calcined kaolin.

According to a particularly preferred embodiment, particulate fillers are used, of which at least 95% by weight, preferably at least 98% by weight, of the particles have a diameter (greatest extent), determined on the finished product, of less than 45 μm, preferably less than Have 40 microns and their so-called aspect ratio in the range of 1 to 25, preferably in the range of 2 to 20, determined on the finished product.

The particle diameter can be determined, for example, characterized in that electron micrographs of thin sections was added to the polymer mixture and at least 25, preferably at least 50 filler particles for the evaluation ^¬ the. The particle diameters can also be determined via sedimentation analysis, according to Transactions of ASAE, page 491 (1983). The weight fraction of the fillers, which is less than 40 μm, can also be measured by sieve analysis. The aspect ratio is the ratio of particle diameter to thickness (largest dimension to smallest dimension).

Particularly preferred particulate fillers are talc, kaolin, such as calcined kaolin or wollastonite, or mixtures of two or all of these fillers. Among them is talc with a proportion of at least 95% by weight of particles with a diameter of less than 40 μm and an aspect ratio of 1.5 to 25, each determined on the finished product, particularly preferred. Kaolin preferably has a proportion of at least 95% by weight of particles with a diameter of less than 20 μm and an aspect ratio of 1.2 to 20, each determined on the finished product.

Particulate fillers are very particularly preferably used as the sole fillers.

Component E

According to the invention, the molding compositions contain one or a mixture of two or more different low molecular weight halogen-free acids as component E. The proportion of these components in the molding compositions is generally from 0.05 to 2, preferably from 0.1 to 1.8 % By weight, based on the total weight of the molding compositions.

In the context of the present invention, low molecular weight is understood to mean multinuclear, for example up to pernuclear, in particular monomolecular compounds.

According to the invention, the acids are halogen-free, i.e. do not contain halogens in the molecular structure. In contrast, acids which have slight halogen-containing impurities are also included according to the invention.

Acids in the sense of the invention also mean their hydrates.

It is advantageous to use acids which are not or only slightly volatile at the processing temperatures or which do not decompose at temperatures of up to about 300.degree.

The acids can contain one, two or more, for example up to ten, acid groups.

Organic acids are preferably used. Both aromatic and aliphatic acids can be used. Aliphatic / aromatic acids can also be used. The preferred acids include palmitic acid, stearic acid, benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, sulfonic acids such as p-toluenesulfonic acid, fumaric acid, citric acid, mandelic acid or tartaric acid. Citric acid or p-toluenesulfonic acid or mixtures thereof are particularly preferably used. For example, the proportion by weight of citric acid can be from 1 to 99, preferably from 10 to 90%, and that of p-toluenesulfonic acid from 1 to 99, preferably from 10 to 90%.

Component F

According to the invention, the molding compositions contain one or a mixture of two or more different poly (alkyl) acrylates. In general, the poly (alkyl) acrylates are present in the molding compositions in proportions of 0 to 10, preferably 0.5 to 5, based on the total weight of the molding compositions.

Component F includes both homopolymers and copolymers such as statistical or block copolymers based on alkyl acrylates or acrylates or mixtures thereof.

According to a preferred embodiment, polyalkyl acrylates are used which are compatible with component C.

The compatibility of two polymer components is generally understood to mean the miscibility of the components or the tendency of one polymer to dissolve in the other polymer components (see B. Vollmert, Grundriß der makromolekular Chemie, Volume IV, p. 222 ff, E. Vollmert Verlag 1979). The solubility of two polymers can be determined indirectly, for example, by torsional vibration, DTA or DSC measurements, by the optical clarity of their mixtures or by means of nuclear magnetic resonance (NMR) relaxation methods.

Copolymers which are composed of at least two different alkyl esters, aromatic or alkyl aromatic esters of acrylic acid or methacrylic acid or mixtures thereof are particularly preferred.

In general, the esters have 1 to 10, preferably 1 to 8 carbon atoms in the alkyl radical. The alkyl radical can be either linear or branched. The alkyl radicals include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 2-ethylhexyl or cyclohexyl. Methyl methacrylate, cyclohexyl methacrylate, n-butyl acrylate or 2-ethylhexyl acrylate are preferably used. Among the aromatic esters, esters with 6 to 18 carbons are preferred, especially phenyl. Poly (alkyl) acrylates E which are from 70 to 99, in particular 16 particular from 80 to 93 wt .-% methyl methacrylate and from 1 to 30, in particular from 7 to 20 wt .-% n-butyl acrylate.

According to the invention, the poly (alkyl) acrylates E have a high molecular weight. As a rule, they have molecular weights (number average M _w ) of at least 1,000,000 g / mol (measured by means of gel permeation chromatography in tetrahydrofuran against a polystyrene standard). Preferred poly (alkyl) acrylates E have molecular weights M _w of 1,100,000 g / mol or more, for example at least 1,200,000 g / mol. In general they have

Copo'lymeren E has a glass transition temperature in the range from 40 to 125, preferably 70 to 120 ° C (determined by means of DSC measurements, at a heating rate of 10 k / min, second cycle after heating to 175 ° C and cooling to room temperature). 5

The poly (alkyl) acrylates are known per se or can be obtained by methods known per se. For example, according to the method described in H.-G. Elias, Makromoleküle, 4th ed., Huthig & Wepf, Basel 1981 described methods of suspension polymerization 0.

Component G

The molding compositions according to the invention can optionally contain one or a mixture of two or more different flame retardants. In general, these are present in proportions of 0 to 25, preferably 1 to 20,% by weight, based on the total weight of the molding compositions.

Halogen-free flame retardants are particularly preferably used. In principle, all phosphorus-containing flame retardants are particularly suitable.

For example, phosphorus compounds of the general formula 5 III

R ² , R ³ , R ⁴ independently of one another are halogen-free 0χ- to Cβ-alkyl- _c groups or halogen-free C ₆ - to C ₂ o'-aryl groups, which can be substituted one to two times by C - to C -alkyl groups mean be used.

Particularly suitable phosphorus compounds of the general formula III are, for example, tri (2,6-dimethylphenyl) phosphate, triphenyl phosphate, tricresyl phosphate,

Name diphenyl-2-ethyl-cresyl phosphate, diphenyl-cresyl phosphate and tri- (isopropylphenyl) phosphate.

In order to set an elevated Vicat temperature in the molding compositions, mixtures of the above-mentioned phosphate with, for example, triphenylphosphine oxide or tri- (2,6-dimethylphenyl) -phosphine oxide or the above-mentioned phosphine oxides can also be used alone.

Furthermore, the addition of the phosphates mentioned in DE-A 38 24 356, such as phosphoric acid bis-phenyl- (4-phenylphenyl) ester, phosphoric acid phenyl-bis- (4-phenylphenyl) ester, phosphoric acid tris- (4th -phenylphenyl) ester, phosphoric acid bis-phenyl (benzylphenyl) ester, phosphoric acid phenyl bis (benzylphenyl) ester, phosphoric acid tris (benzylphenyl) ester, phosphoric acid phenyl bis [1-phenylethyl ) -phenyl] -ester, phosphoric acid-phenyl-bis- [1-methyl-1-phenylethyl) -phenyl] -ester and phosphoric acid-phenyl-bis- [4- (1-phenylethyl) -2, 6-dimethylphenyl] - suitable for increasing the Vicat temperature of the molding compounds.

These halogen-free phosphorus compounds G are generally known (see, for example, Ulimann, Encyclopedia of Industrial Chemistry, Vol. 18, pp. 310ff, 1979, Houben-Weyl, Methods of Organic Chemistry, Bs. 12/1, p. 43, p. 136; Beilstein, Vol. 6, p. 177).

In addition, phosphoric acid esters with more than one P atom per molecule can be considered as component G. Examples are monomeric or oligomeric phosphorus compounds of the formulas IV, V or VI:

wherein

R ⁵ and R ⁷ independently of one another are optionally substituted alkyl or aryl;

R ⁶ , R ⁸ , R ¹⁰ , R ¹¹ independently of one another represent optionally substituted alkyl, aryl, alkoxy or aryloxy,

R9 represents alkylene, -S0 ₂ -, -CO-, -N = N- or - (R ¹² ) P (0) -, in which

R ^{12 stands} for optionally substituted alkyl, aryl or alkylaryl and s and t independently of one another assume an average or also integer value from 1 to 30.

Optionally substituted means that the groups can have one to five, preferably one or two, substituents, suitable substituents in compounds of the formulas (V), (VI) and (VII) being cyano, hydroxy or Cx- _4- alkyl.

Preferred alkyl radicals in compounds of the formulas (IV), (V) and (VI) are 0χ. is C ₂ o -kyl, such as methyl, ethyl, n-propyl, n-butyl, neopentyl, n-hexyl, n-octyl, n-nonyl, n-dodecyl, 2-ethylhexyl or 3, 5, 5-trimethylhexyl. Cyanoethyl is also preferred.

Preferred aryl radicals in compounds of the formulas (IV), (V) and (VI) are phenyl, naphthyl and mono- or polysubstituted radicals, such as tolyl, xylyl, mesityl or cresyl.

Preferred alkylaryl radicals in compounds of the formulas (IV), (V) and (VI) are Cχ- ₂ o -alkylaryl and in particular Cχ.χ ₂ -alkylaryl radicals, the alkyl part and aryl part being as defined above. Preferred alkoxy radicals in compounds of the formulas (IV), (V) and (VI) are Cχ- ₂ o-alkoxy radicals, the Cχ. ₂ o-alkyl part is as defined above.

Preferred aryloxy radicals in compounds of the formulas (IV), (V) and (VI) are those in which the aryl moiety is as defined above.

Preferred alkylene radicals in compounds of the formulas (IV), (V) and (VI) are Cχ- _6- alkylene radicals, such as methyl, ethylene, n-propylene and n-hexylene.

The compounds are preferably obtained by transesterification with base catalysis or by reacting phosphorus oxychloride with phenols with catalysis by magnesium or aluminum chloride. The commercially available products based on resorcinol diphenyl phosphate and the commercially available reaction products of bisphenol A and triphenyl phosphate are preferably used.

It should be noted that the technically available products are generally mixtures of different oligomers or isomers.

Mixtures of the higher phosphates and monophosphates or monophosphine oxides can also be used in any mixing ratio.

Phosphoric acid esters which can be used as component G are also those of the formula (VII)

(VII)

wherein

R ^{13 is} hydrogen or alkyl having 1 to 8 carbon atoms, preferably methyl, and _R 14

(VIII) (IX) is and

R ^{15 is} phenyl, which may be substituted by alkyl having 1 to 4 carbon atoms, phenyl, benzyl or 2-phenylethyl, and wherein m is zero and at least 1 and

R ¹⁴ must be a radical of the formula IX, in which, when n is zero, at least 2 and

R ¹⁴ must be a radical of the formula VIII, and in which m is an integer from zero to 12 and n is an integer from zero to 5, the core number of the polyphenol molecule, i.e. the number of benzene rings of the compound (VII), without the Radicals R ¹³ to R ^{15 is} not higher than 12.

Examples of phosphoric acid esters according to formula (VII) are the phosphoric acid esters of novolaks. Suitable novolaks are condensation products made from formaldehyde and phenols.

Characteristic examples of phenols are phenol, o-cresol, m-cresol, p-cresol, 2, 5-dimethyl, 3, 5-dimethyl, 2, 3, 5-trimethyl, 3, 4, 5-trimethyl , pt-butyl, pn-octyl, p-stearyl, p-phenyl, p- (1-phenylethyl) -, 1-phenylethyl -, o-isopropyl, p-isopropyl or m-isopropylphenol.

Phenol, o-cresol, p-cresol, p-t-butylphenol and o-t-butylphenol and p-octylphenol are preferably used.

Mixtures of these phenols can also be used. Novolaks which are preferably used are phenol / formaldehyde novolak, o-cresol / formaldehyde novolak, m-cresol / formaldehyde novolak, t-butylphenol / formaldehyde novolak or o-octylphenol / formaldehyde novolak. P-Cresol / formaldehyde novolak is particularly preferred.

The phosphorus compounds of the formula (VII) which are suitable according to the invention can generally be prepared by known processes (see for novolaks: Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 2, pages 193 to 292, and Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, Volume 18, pages 245 to 257; for phosphates: for example Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pages 389 to 391, 1979 and Houben-Weyl, Methods of Organic Chemistry, vol. 12/1, p. 299 to 374).

Component H

One or a mixture of different additives can moreover be present in the molding compositions according to the invention in amounts of 0 to 20, preferably 1 to 15% by weight, based on the total weight of the molding compositions. Additives typical and customary for polycarbonate molding compositions, such as colorants, e.g. Pigments, optical brighteners or fluorescent dyes, antistatic agents, antioxidants, such as sterically hindered phenols, in particular tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydroquininamate)] methane or 3,5-di-t-butyl 4-hydroxyhydrocinnamate, UV stabilizers, adhesion promoters, mold release agents such as long-chain fatty acid esters or lubricants can be considered as component H. As UV stabilizers e.g. Phosphites, hypophosphites or phosphites are used. Among them, phosphites are preferred, the three organic radicals of which are sterically hindered phenols, such as tri (2,4-di-t-butylphenyl) phosphite. These and other UV stabilizers and antioxidants which can be used as component H and processes for their preparation can be found in DE-Al-44 19 897.

Component I

The molding compositions of the invention comprise, as component I, at least one aromatic or partially aromatic polyester or mixtures thereof. In general, the molding compositions according to the invention contain component I in amounts of 0.1 to 10, preferably 0.5 to 8,% by weight, based on the total weight of the molding compositions.

In the context of the present invention, an aromatic polyester is not understood to mean polycarbonates as can be used as component A. The aromatic polyesters are derived from aromatic dihydroxy compounds and aromatic dicarboxylic acids or aromatic hydroxycarboxylic acids. Aromatic dihydroxy compounds which are suitable are the compounds of the general formula I already described under A

The preferred dihydroxy compounds include dihydroxydiphenyl, di (hydroxyphenyl) alkanes, di (hydroxyphenyl) cycloalkanes, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) sulfoxide, α, α '- Di- (hydroxyphenyl) dialkylbenzene, di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone as well as their core alkylated derivatives. Of these, 4,4'-dihydroxydiphenyl, 2,4-di (4'-hydroxyphenyl) -2-methylbutane, α, α'-di (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-di ( 3'-methyl -4'-hydroxyphenyl) propane or 2, 2 -di (3'-chloro-4'-hydroxyphenyl) propane, and in particular 2, 2 -di (4'-hydroxyphenyl) propane, 2.2 -Di (3 ', 5' -dichlorodihydroxyphenyl) propane, 1,1-di- (4'-hydroxyphenyl) cyclohexane, 3,4'-dihydroxybenzophenone, 4, 4 '-dihydroxydiphenylsulfone or 2, 2-di (3', 5'-Dimethyl-4 '- hydroxyphenyl) propane or mixtures thereof are preferred.

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

The aromatic dicarboxylic acids generally have from 8 to 30 carbon atoms. The aromatic ring or rings can be substituted, for example with one or more Cχ ~ to C ₄ alkyl radicals such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl. Preferred aromatic dicarboxylic acids are terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid. Mixtures of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid are preferred, in particular mixtures of 20 to 50 mol% isophthalic acid and 50 to 80 mol% terephthalic acid.

Semi-aromatic polyesters I are those based on aromatic dicarboxylic acids and one or more different aliphatic dihydroxy compounds.

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

Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid as described above. These polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.

Preferred dicarboxylic acids are 2, d> -naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid,

Sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids can be replaced.

Of the aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cy - Clohexanedimethylol and neopentyl glycol or mixtures thereof are preferred.

Particularly preferred partially aromatic polyesters (I) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, polyethylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred in particular.

The viscosity number of the polyesters (I) is generally in the range from 70 to 220, preferably from 100 to 150 (measured in a 0.5% by weight solution in a phenol / o-dichlorobenzene mixture (% by weight. 1: 1 at 25 ° C).

Particularly preferred are polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester. Such polyesters can be produced, for example, by the process of DE-A 44 01 055. The carboxyl end group content is usually determined by titration methods (e.g. potentiometry).

The thermoplastic molding compositions according to the invention are produced by methods known per se by mixing the components. It can be advantageous to provide individual components. The network rubbers of component B can be added separately from the other graft copolymers. Mixing the components in solution and removing the solvents is also possible. Suitable organic solvents for components A to C and E to I and the additives of group H are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene and aromatic hydrocarbons, for example toluene.

The solvent mixtures can be evaporated, for example, in evaporation extruders.

Mixing the e.g. Dry components A, B, C, D, E, F and I and optionally G and H can be carried out by all known methods. However, components A, B, C, D, E, F and I and optionally G and H are preferably mixed at temperatures from 200 to 320 ° C. by extruding, kneading or rolling the components together, the components if necessary previously being obtained from the solution obtained in the polymerization or have been isolated from the aqueous dispersion.

The thermoplastic molding compositions according to the invention can be processed by the known methods of thermoplastic processing, e.g. by extrusion, injection molding, calendering, blow molding, pressing or sintering.

The moldings according to the invention can be used for the production of moldings, fibers or films. Molded parts are preferably produced from the molding compositions according to the invention. The latter can be in small or large parts and are intended for outdoor or indoor applications. Large-scale molded parts for vehicle construction, in particular the automotive sector, are preferably produced from the molding compositions according to the invention. In particular, hub caps or exterior body parts can be produced from the molding compositions according to the invention. Examples include its fenders, tailgates, bonnets, loading areas, covers for loading areas, side walls for loading areas or car roofs, including removable or foldable car roofs or car roof parts.

The molding compositions according to the invention are notable for the fact that they are stable in processing and easy to process. The molded parts made from it are dimensionally stable and have an improved fracture behavior at low temperatures compared to the prior art. In addition, the molding compounds meet high requirements with regard to temperature stability. Examples

The mean particle size and the particle size distribution were determined from the integral mass distribution. The mean particle sizes are in all cases the weight average of the particle sizes, as they are determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z, and Z.-Polymer 250 (1972 ), Pages 782 to 796. The ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size. The mean particle diameter, which is also referred to as the ds ₀ value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the dso value. Likewise, 50% by weight of the particles then have a larger diameter than the dso value. To characterize the width of the particle size distribution of the rubber particles, in addition to the dso (average particle diameter), the dχo ~ and d ₉₀ values resulting from the integral mass distribution are used. The dχo ~ or d ₉ o ~ value of the integral mass distribution is defined according to the dso value with the difference that they are based on 10 or 90 wt .-% of the particles. The quotient Q = (d ₉ o-dχo) / dso represents a measure of the distribution width of the particle size.

The following components were used:

A ¹ ) A commercial polycarbonate based on bisphenol A with a viscosity number of 61.3 ml / g, measured on a 0.5 wt .-% solution in methylene chloride at 23 ° C.

B ¹ ) A finely divided graft polymer made from

γx) 16 g of butyl acrylate and 0.4 g of tricyclodecenyl acrylate in 150 g of water with the addition of 1 g of the sodium salt of a Cχ ₂ -Cχ ₈ paraffin sulfonic acid, 0.3 g of potassium persulfate, 0.3 g of sodium hydrogen carbonate and 0.15 g of sodium pyrophos - warmed to 60 ° C with stirring. A mixture of 82 g of butyl acrylate and 1.6 g of tricyclodecenyl acrylate was added within 3 hours 10 minutes after the start of the polymerization reaction. After the monomer additions had ended, the mixture was stirred for another hour. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40% by weight and the average particle size (weight average) became 76 nm was determined and the particle size distribution was narrow (quotient Q = 0.29).

γ ₂ ) 150 g of the polybutyl acrylate latex obtained according to ßx) were mixed with 40 g of a mixture of styrene and acrylonitrile

(Weight ratio 75:25) and 60 g of water mixed and heated with stirring after the addition of a further 0.03 g of potassium persulfate and 0.05 g of lauroyl peroxide at 65 ° C for 4 hours. After the end of the graft copolymerization, the polymerization product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream. The degree of grafting of the graft copolymer was 35% and the particle size was 91 nm.

B ² ) A coarse-particle graft polymer which was prepared as follows:

7 ₃ ) On the one hand, a mixture of 49 g of butyl acrylate and 1 g of tricyclodecenyl acrylate and, on the other hand, after adding 50 g of water and 0.1 g of potassium persulfate over the course of 3 hours, to an initial charge of 1.5 g of the latex produced according to βx) a solution of 0.5 g of the sodium salt of a C ₁₂ -C ₈ -paraffin sulfonic acid in 25 g of water at 60 ° C. Polymerization was then carried out for 2 hours. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40%. The mean particle size (weight average of the latex) was found to be 430 nm, the particle size distribution was narrow (Q = 0.1).

γ ₄ ) 150 g of the latex produced according to ß ₃ ) were with 20 g

Styrene and 60 g of water mixed and heated to 65 ° C. for 3 hours with stirring after the addition of a further 0.03 g of potassium persulfate and 0.05 g of lauroyl peroxide. The dispersion obtained in this graft copolymerization was then polymerized with 20 g of a mixture of styrene and acrylonitrile in a weight ratio of 75:25 for a further 4 hours. The reaction product was then precipitated from the dispersion using a calcium chloride solution at 95 ° C., separated off, washed with water and dried in a warm air stream. The degree of grafting of the graft copolymer was determined to be 35%; the average particle size of the latex particles was 510 nm. C ¹ ) A copolymer of styrene and acrylonitrile in a ratio by weight of 81:19 with a viscosity number of 72 ml / g (measured on a 0.5% by weight solution in dimethylformamide at 23 ° C.) by continuous solution polymerization using a process as described, for example, in the Kunststoff-Handbuch, Vieweg-Daumiller, Volume V (polystyrene), Carl-Hanser-Verlag, Munich 1969, page 124, lines 12ff.

D ¹ ) Talc (IT-Extra from Norwegian Tale), characterized in that the average particle size (Xso value) was 4.91 μm and the average particle size of 90% of all particles (Xgo value) was less than 10 , Was 82 μm, determined by means of laser diffraction, the talc in a suspension cell in a mixture of water and surfactant ^• (demineralized water / surfactant: 99/1, distributor (V-Chemievertrieb, Hannover) using a magnetic driver) was suspended at a speed of 60 rpm The pH of the aqueous suspension was 8.5.

E ¹ ) p-toluenesulfonic acid hydrate, purity 98%, melting point: 103 ° C.

^E2 ) Citric acid hydrate, purity 99%.

F ¹ ) A copolymer of 89% by weight of methyl methacrylate and 11% by weight of n-butyl acrylate, characterized by a molecular weight

(Weight average M _w ) of 1,800,000 g / mol (determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standard).

I ¹ ) Polybutylene terephthalate (Ultradur® B4500 from BASF), characterized by a viscosity number of 130 (measured in 0.5% by weight solution in a mixture of phenol / o-dichlorobenzene 1: 1).

Production of molding compounds

The components listed in the table were mixed in a twin-screw extruder (ZKS 30 from Werner and Pfleiderer) at 250 to 280 ° C, discharged as a strand, cooled and granulated. The dried granulate was processed at 250 to 280 ° C into standard small bars or ISO test specimens round disks (60 x 3 mm) at a tool temperature of 80 ° C. Application tests

The heat resistance of the samples was determined using the Vicat softening temperature. The Vicat softening temperature was determined according to DIN 53 460 with a force of 49.05 N and a temperature increase of 50 K per hour on standard small bars.

The flowability (MVI) of the molding compositions was determined in accordance with DIN 53 735 at temperatures of 260 ° C. and 5 kg load.

The notched impact strength (ak) was determined according to ISO 179 leA at room temperature.

The elongation at break was determined according to ISO 527 at a deformation rate of 50 mm / min and room temperature.

The puncture work W _s [Nm] (average of five individual measurements) was measured by means of puncture tests according to DIN 53 443 at -30 ° C. Both the energy consumption and the deformation path were determined.

The thermal expansion (CTE) was determined according to DIN 53752, method A on 2 test specimens (10 x 10 x 4 cm), the values measured in the longitudinal direction at 25 ° C are given.

The compositions and the results of the application tests of the thermoplastic molding compositions are shown in Table 1.

Table 1

Claims

claims

1. Containing molding compositions

A) at least one polycarbonate,

C) at least one copolymer containing vinyl aromatic monomers,

D) at least one filler,

E) at least one low molecular weight halogen-free acid

as well as if desired

F) at least one polyacrylate,

G) at least one flame retardant and

H) at least one additive,

characterized in that the molding compositions

I) at least one aromatic or partially aromatic polyester or mixtures thereof

contain.

2. Molding compositions according to claim 1, characterized in that component I is a polyalkylene terephthalate.

3. Molding compositions according to claim 1 or 2, characterized in that the proportion of component I.

I) 0.1 to 10% by weight, based on the total weight of the molding compositions,

is.

4. Molding compositions according to claims 1 to 3, characterized in that component B or C or B and C are oxazoline-containing polymers.

5 5. Molding compositions according to claims 1 to 4, characterized in that component D is at least one particulate filler, of which at least 95 wt .-% of all particles have a diameter (greatest dimension) of less than 45 microns and their aspect ratio in Range is 1 to 25 10.

6. Molding compositions according to claims 1 to 5, characterized in that component E is a polymethyl methacrylate with a molecular weight (number average M _n ) of at least

15 is 1,000,000 g / mol.

7. Molding compositions according to claims 1 to 6, characterized in that component F is citric acid or p-toluenesulfonic acid or a mixture thereof.

20th

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

9. Use of the molding compositions according to claim 8 for the production of 25 large-area molded parts.

10. Use of the molding compositions for the production of exterior body parts.

30 11. Molded parts, obtainable from the molding compositions according to claims 1 to 7.

35

40

45