DE102004019932A1 - Extruded sheet or plate with improved toughness - Google Patents

Abstract

The invention relates to extruded films or sheets containing a plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100 wt .-%, DOLLAR A a 10 to 89 wt .-% of a rubbery graft copolymer as component A, DOLLAR A b 10 to 89 wt .-% of a hard copolymer containing units derived from vinyl aromatic monomers, as component B, DOLLAR A c 1 to 80 wt .-% of a polycarbonate as component C and DOLLAR A. d 0 to 50 wt .-% fibrous or particulate fillers or mixtures thereof as component D, wherein DOLLAR A - component C forms the continuous phase of the plastic mixture, DOLLAR A - forms component B domains in the continuous phase of component C and DOLLAR A Component A forms particles distributed in components B and / or C, DOLLAR A being essential to the invention that, based on the total number of domains formed by components B, the number of domains formed by components B having a maximum spatial extent of less than 2 μm is in the range of 80% to 100%. DOLLAR A Furthermore, the invention relates to processes for the production of extruded films or plates according to the invention and composite layer plates or sheets, moldings and motor vehicle outer parts, comprising these extruded films or plates according to the invention.

Description

• a 10 bis 89 Gew.-% eines kautschukelastischen Pfropfcopolymerisats als Komponente A,
• b 10 bis 89 Gew.-% eines harten Copolymerisats, enthaltend Einheiten, die sich von vinylaromatischen Monomeren ableiten, als Komponente B,
• c 1 bis 80 Gew.-% eines Polycarbonats als Komponente C, und
• d 0 bis 50 Gew.-% faser- oder teilchenförmige Füllstoffe oder deren Gemische als Komponente D, wobei
• – Komponente C die kontinuierliche Phase der Kunststoffmischung bildet,
• – Komponente B Domänen in der kontinuierlichen Phase der Komponente C ausbildet und
• – Komponente A in Komponenten B und/oder C verteilte Partikel ausbildet.

The invention relates to extruded films or sheets comprising a plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100 wt .-%,

• a from 10 to 89% by weight of a rubber-elastic graft copolymer as component A,
• b 10 to 89 wt .-% of a hard copolymer containing units derived from vinyl aromatic monomers, as component B,
• c 1 to 80 wt .-% of a polycarbonate as component C, and
• d 0 to 50 wt .-% fibrous or particulate fillers or mixtures thereof as component D, wherein
• Component C forms the continuous phase of the plastic mixture,
• Component B forms domains in the continuous phase of component C and
• - Component A in components B and / or C distributed particles forms.

Farther The invention relates to processes for producing these extruded Films or sheets and composite sheets or films, moldings and Automotive exterior parts comprising these extruded sheets or plates.

At the Use of plastics in outdoor areas, where they are environmental influences such as weather, temperature fluctuations or pollution are high demands, for example, on mechanical and optical properties provided. Moldings made of plastic, these Requirements at least for certain applications or periods of use are known.

For example WO 04/00935 describes molded parts comprising a composite layer plate or foil and a back-injected, foam-backed or back-poured carrier layer made of plastic, which has a good surface quality, especially at high temperatures a slight waviness. The composite layer plate or film of these moldings has a substrate layer which is hard Copolymer component: polymers with a high α-methylstyrene content and as an optional further component polycarbonates.

The in WO 04/00935 described substrate layers, but also others extruded films or plates containing polymers based on vinyl aromatic Compounds and polycarbonate, however, have some regard to some Outdoor application, at which they are environmental influences such as weather, temperature fluctuations or pollution are not always satisfactory toughness.

task The present invention is the provision of extruded Films or sheets containing polymers based on vinyl aromatic compounds and polycarbonate having improved toughness, for example, improved Puncture resistance.

• a 10 bis 89 Gew.-% eines kautschukelastischen Pfropfcopolymerisats als Komponente A,
• b 10 bis 89 Gew.-% eines harten Copolymerisats, enthaltend Einheiten, die sich von vinylaromatischen Monomeren ableiten, als Komponente B,
• c 1 bis 80 Gew.-% eines Polycarbonats als Komponente C, und
• d 0 bis 50 Gew.-% faser- oder teilchenförmige Füllstoffe oder deren Gemische als Komponente D, wobei
• – Komponente C die kontinuierliche Phase der Kunststoffmischung bildet,
• – Komponente B Domänen in der kontinuierlichen Phase der Komponente C ausbildet und
• – Komponente A in Komponenten B und/oder C verteilte Partikel ausbildet,

gefunden, wobei erfindungswesentlich ist, dass bezogen auf die Gesamtanzahl aller von Komponente B gebildeten Domänen, die Anzahl der von Komponente B gebildeten Domänen mit einer maximalen räumlichen Ausdehnung von kleiner als 2 μm im Bereich von 80% bis 100% liegt (wobei die jeweilige Anzahl der gebildeten Domänen und deren maximale räumliche Ausdehnung anhand transmissionselektronenmikroskopischer Dünnschnittaufnahmen eines beliebigen, mindestens 20 μm² großen Bereichs der extrudierten Folie oder Platte mit Transmissionsrichtung senkrecht zur Extrusionsrichtung der Folie oder Platte in 20000-facher Vergrößerung durch Auszählen und Ausmessen bestimmt werden).Accordingly, the above-mentioned extruded sheets or plates comprising a plastic mixture comprising, based on the total weight of the components A, B, C and D, which gives a total of 100 wt .-%,

• a from 10 to 89% by weight of a rubber-elastic graft copolymer as component A,
• b 10 to 89 wt .-% of a hard copolymer containing units derived from vinyl aromatic monomers, as component B,
• c 1 to 80 wt .-% of a polycarbonate as component C, and
• d 0 to 50 wt .-% fibrous or particulate fillers or mixtures thereof as component D, wherein
• Component C forms the continuous phase of the plastic mixture,
• Component B forms domains in the continuous phase of component C and
• Component A forms components distributed in components B and / or C,

it being essential to the invention that based on the total number of domains formed by component B, the number of domains formed by component B having a maximum spatial extent of less than 2 μm is in the range of 80% to 100% (the respective number the domains formed and its maximum spatial extent of an be any, at least 20 microns ² wide range of the extruded film or sheet with the transmission direction perpendicular to the extrusion direction of the film or plate in 20000 times magnification by counting and measuring determined by transmission electron microscopy thin section photographs).

Farther have been methods of making the extruded invention Foils or sheets and composite sheets or foils, shaped parts and motor vehicle exterior parts comprising these extruded inventive Sheets or plates found.

The extruded according to the invention Films or sheets containing polymers based on vinyl aromatic Compounds and polycarbonate have improved toughness, For example, improved puncture resistance.

The extruded films or plates according to the invention, processes, composite laminate sheets or films, moldings and motor vehicle parts described in the following.

Extruded films or Plates:

• a 10 bis 89 Gew.-%, bevorzugt 15 bis 65 Gew.-%, besonders bevorzugt 15 bis 45 Gew.-% eines kautschukelastischen Pfropfcopolymerisats als Komponente A,
• b 10 bis 89 Gew.-%, bevorzugt 15 bis 65 Gew.-%, besonders bevorzugt 15 bis 45 Gew.-% eines harten Copolymerisats, enthaltend Einheiten, die sich von vinylaromatischen Monomeren ableiten, als Komponente B,
• c 1 bis 80 Gew.-%, bevorzugt 20 bis 70 Gew.-%, besonders bevorzugt 40 bis 70 Gew.-% eines Polycarbonats als Komponente C, und
• d 0 bis 50 Gew.-%, bevorzugt 0 bis 40 Gew.-%, besonders bevorzugt 0 bis 30 Gew.-% faser- oder teilchenförmige Füllstoffe oder deren Gemische als Komponente D.

The extruded films or sheets according to the invention are based on a plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100% by weight,

• a from 10 to 89% by weight, preferably from 15 to 65% by weight, particularly preferably from 15 to 45% by weight, of a rubber-elastic graft copolymer as component A,
• b is from 10 to 89% by weight, preferably from 15 to 65% by weight, particularly preferably from 15 to 45% by weight, of a hard copolymer comprising units which are derived from vinylaromatic monomers, as component B,
• c 1 to 80 wt .-%, preferably 20 to 70 wt .-%, particularly preferably 40 to 70 wt .-% of a polycarbonate as component C, and
• d 0 to 50 wt .-%, preferably 0 to 40 wt .-%, particularly preferably 0 to 30 wt .-% fibrous or particulate fillers or mixtures thereof as component D.

The Morphology of the plastic mixture on which the extruded invention Foils or plates is such that component C forms the continuous phase of the plastic mixture. In this component C formed by the continuous phase forms component B domains made, preferably spherical or have a exlongierte in the extrusion direction form. component A is in particulate Form ago, whereby these particles disperse in the continuous phase of the Component C or in the domains Component B are distributed, preferably, these particles are dispersed both in the continuous phase of component C and in the domains component B distributed.

essential morphological feature of the plastic mixture is that, related to the total number of all domains formed by component B, the Number of domains formed by component B with a maximum spatial Expansion of less than 2 μm, preferably smaller than 1.8 μm, more preferably less than 1.5 μm, in the range of 80% to 100%, preferably from 90% to 100%, more preferably from 95% to 100% lies. Under maximum spatial Extension of a domain is the biggest of all Distances between every two points on the outer edge of this domain to understand.

The respective number of domains formed and their maximum spatial extent is determined on the basis of transmission electron microscopic thin-slice exposures of any, at least 20 microns ² large area of extruded sheet or plate according to the invention with transmission direction perpendicular to the extrusion direction of the film or plate in 20000-fold magnification by counting and measuring.

The extruded according to the invention Foils or sheets generally have a total thickness of 50 μm to 5 mm, preferably of 70 microns up to 3 mm, more preferably 100 μm to 1.5 mm.

The extruded according to the invention Films or sheets are based in one embodiment on a plastic mixture containing impact resistant modified copolymers of vinylaromatic monomers and Vinyl cyanides (SAN), polycarbonate and, where appropriate, further Components.

Prefers be as impact modified SAN ASA polymers and / or ABS polymers used.

Under ASA polymers are generally understood to be impact-modified SAN polymers, in which graft copolymers of vinylaromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, on Polyalkylacrylatkautschuken in a copolymer matrix of particular Styrene and / or α-methylstyrene and acrylonitrile.

component A

• a1 1–99 Gew.-%, vorzugsweise 55–80 Gew.-%, insbesondere 55–65 Gew.-%, einer teilchenförmigen Pfropfgrundlage A1 mit einer Glasübergangstemperatur unterhalb von 0°C,
• a2 1–99 Gew.-%, vorzugsweise 20–45 Gew.-%, insbesondere 35–45 Gew.-%, einer Pfropfauflage A2 aus den Monomeren, bezogen auf A2, a21 40–100 Gew.-%, vorzugsweise 65–85 Gew.-%, Einheiten des Styrols, eines substituierten Styrols oder eines (Meth)acrylsäureesters oder deren Gemische, insbesondere des Styrols und/oder α-Methylstyrols als Komponente A21 und a22 bis 60 Gew.-%, vorzugsweise 15–35 Gew.-%, Einheiten des Acrylnitrils oder Methacrylnitrils, insbesondere des Acrylnitrils als Komponente A22.

In a preferred embodiment wherein the extruded sheets comprise ASA polymers, component A is an elastomeric graft copolymer

• a1 1-99% by weight, preferably 55-80% by weight, in particular 55-65% by weight, of a particulate grafting base A1 having a glass transition temperature below 0 ° C.,
• a2 1-99 wt .-%, preferably 20-45 wt .-%, in particular 35-45 wt .-%, of a graft A2 from the monomers, based on A2, a21 40-100 wt .-%, preferably 65- 85 wt .-%, units of styrene, of a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular of styrene and / or α-methylstyrene as component A21 and a22 to 60 wt .-%, preferably 15-35 wt. -%, units of acrylonitrile or methacrylonitrile, in particular of acrylonitrile as component A22.

The Grafting A2 consists of at least one graft shell, wherein the graft copolymer A overall has an average particle size of 50-1000 nm having.

• a11 80–99,99 Gew.-%, vorzugsweise 95 – 99,9 Gew.-%, mindestens eines C1-8-Alkylesters der Acrylsäure, vorzugsweise n-Butylacrylat und/oder Ethylhexylacrylat als Komponente A11,
• a12 0,01 – 20 Gew.-%, vorzugsweise 0,1 – 5,0 Gew.-%, mindestens eines polyfunktionellen vernetzenden Monomeren, vorzugsweise Diallylphthalat und/oder DCPA als Komponente A12.

Component A1 consists of the monomers

• a11 80-99.99% by weight, preferably 95-99.9% by weight, of at least one C1-8-alkyl ester of acrylic acid, preferably n-butyl acrylate and / or ethylhexyl acrylate as component A11,
• a12 0.01-20 wt.%, preferably 0.1-5.0 wt.%, of at least one polyfunctional crosslinking monomer, preferably diallyl phthalate and / or DCPA as component A12.

According to one embodiment of the invention the mean particle size of the component A 50 - 800 nm, preferably 50-600 nm.

According to one another embodiment of the invention is the particle size distribution of Component A bimodal, wherein 60-90 Wt .-% an average particle size of 50-200 nm and 10 - 40 Wt .-% an average particle size of 50-400 nm based on the total weight of component A.

The mean particle size or particle size distribution are the sizes determined from the integral mass distribution. The mean particle sizes according to the invention are in all cases the weight average particle size as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymere 250 (1972), pages 782-796. Ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size. The average particle diameter, which is also referred to as the d ₅₀ 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 corresponding to the d ₅₀ value. Likewise, then 50 wt .-% of the particles have a larger diameter than the d ₅₀ value. To characterize the width of the particle size distribution of the rubber particles, in addition to the d ₅₀ value (average particle diameter), the d ₁₀ and d ₉₀ values resulting from the integral mass distribution are used. The d or d ₉₀ value of the integral mass distribution is defined in accordance with the d ₅₀ value, with the difference that they are based on 10 or 90% by weight of the particles. The quotient (d 90 - d 10 ) / D 50 = Q represents a measure of the distribution width of the particle size. Emulsion polymers A which can be used according to the invention as component A preferably have Q values of less than 0.5, in particular less than 0.35.

The acrylate rubbers A1 are preferably alkyl acrylate rubbers of one or more C _1-8 -alkyl acrylates, preferably C _4-8 -alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n Butyl and 2-ethylhexyl acrylate is used. These alkyl acrylate rubbers may contain up to 30% by weight of polymers which form hard polymers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate, vinyl ethers.

The Acrylate rubbers also contain 0.01 to 20 wt .-%, preferably 0.1 to 5 wt .-%, on crosslinking, polyfunctional monomers (crosslinking monomers). Examples of this are monomers which have 2 or more double bonds capable of copolymerizing which are preferably not conjugated in the 1,3-positions are.

suitable Crosslinking monomers are, for example, divinylbenzene, diallyl maleate, Diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, Tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, Allyl acrylate, allyl methacrylate. As a particularly favorable crosslinking monomer dicyclopentadienyl acrylate (DCPA) has been found (see DE-PC 12 60 135).

Component A is a graft copolymer. The graft copolymers A have an average particle size d ₅₀ of 50-1000 nm, preferably 50-800 nm and particularly preferably 50-600 nm. These particle sizes can be achieved if the grafting base A1 of this component A has particle sizes of 50-350 nm, preferably from 50 to 300 nm and particularly preferably from 50 to 250 nm used.

The Graft copolymer A is generally one or more stages, i. a polymer composed of a core and one or more shells. The polymer consists of a basic (graft) A1 and one or - preferably - several grafted steps A2 (grafting), the so-called grafting stages or grafts.

By simple grafting or multiple stepwise grafting can one or more grafts be applied to the rubber particles, each graft a other composition may have. In addition to the grafting monomers can polyfunctional crosslinking or reactive group-containing monomers with grafted on (see, for example, EP-A 230 282, DE-AS 36 01 419, EP-A 269 861).

In a preferred embodiment be component A consists of a multi-stage graft copolymer, wherein the grafting steps are generally prepared from resin-forming monomers and have a glass transition temperature T _g above 30 ° C, preferably above 50 ° C. The multi-stage structure is used, inter alia, to achieve a (partial) compatibility of the rubber particles A with the thermoplastic B.

graft A are prepared, for example, by grafting at least one of the following Monomers A2 on at least one of the graft bases listed above or graft core materials A1.

According to one embodiment the invention, the graft A1 is 15-99 wt .-% acrylate rubber, 0.1 - 5 % By weight of crosslinker and 0-49.9 Wt .-% of one of the stated further monomers or rubbers composed.

suitable Monomers for forming the graft A2 are styrene, α-methylstyrene, (meth) acrylic acid ester, Acrylonitrile and methacrylonitrile, in particular acrylonitrile.

According to one embodiment The invention serves as the grafting base A1 crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. The crosslinked acrylic acid ester polymers should preferably have a glass transition temperature below -20 ° C, in particular below -30 ° C, own.

In a preferred embodiment the graft A2 consists of at least one graft and the outermost graft shell of it has a glass transition temperature of more than 30 ° C, where a polymer formed from the monomers of the graft A2 Glass transition temperature of more than 80 ° C would have.

suitable Manufacturing process for Graft copolymers A are the emulsion, solution, bulk or suspension polymerization. The graft copolymers A are preferred by free-radical emulsion polymerization prepared in the presence of latices of component A1 at temperatures from 20 ° C-90 ° C using water or oil-soluble Initiators such as peroxodisulfate or benzyl peroxide, or with help of redox initiators. Redox initiators are also suitable for pulxmerisation below 20 ° C.

suitable Emulsion polymerization processes are described in DE-A 28 26 925, 31 49 358 and in DE-C 12 60 135.

Of the Structure of the graft sheaths is preferably carried out in the emulsion polymerization process as described is in DE-A 32 27 555, 31 49 357, 31 49 358, 34 14 118. The defined Adjustment of the particle sizes of 50 - 1000 nm is preferably carried out according to the methods described in DE-C 12 60 135 and DE-A 28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929. The use of polymers with different Particle sizes for example, known from DE-A 28 26 925 and US-A 5,196,480.

According to the in DE-C 12 60 135 described method is first the Grafting A1 prepared by the or the according to a embodiment acrylic acid esters used in the invention and the polyfunctional, the networking effecting monomers, if necessary together with the other comonomers, in aqueous emulsion in known per se Way at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, be polymerized. It can the usual Emulsifiers, such as, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, Fatty alcohol sulfonates, higher salts fatty acids with 10 to 30 carbon atoms or resin soaps. Preferably, the sodium salts of alkyl sulfonates are used or fatty acids with 10 to 18 carbon atoms. According to one embodiment are the emulsifiers in amounts of 0.5 to 5 wt .-%, in particular of 1 - 2 Wt .-%, based on that in the preparation of the graft A1 used monomers used. In general, at a weight ratio worked from water to monomers from 2: 1 to 0.7: 1. As polymerization initiators In particular, the customary persulfates, such as potassium persulfate. However, redox systems can also be used to be used. The initiators are generally in amounts from 0.1 to 1 Wt .-%, based on that in the preparation of the graft A1 used monomers used. As further polymerization auxiliaries can the usual Buffer substances, adjusted by which pH values of preferably 6-9 such as sodium bicarbonate and sodium pyrophosphate, as well as 0-3% by weight a molecular weight regulator, such as mercaptans, terpinols or dimers a-methylstyrene, to be used in the polymerization.

The exact polymerization conditions, in particular the type, dosage and amount of the emulsifier are determined in detail within the ranges given above so that the resulting latex of the crosslinked acrylic ester polymer has a d ₅₀ value in the range of about 50-1000 nm, preferably 50-600 nm , more preferably in the range of 80-500 nm. The particle size distribution of the latex should preferably be narrow.

For the preparation of the graft polymer A is then polymerized in a next step in the presence of the resulting latex of the crosslinked acrylic acid ester polymer according to an embodiment of the invention, a monomer mixture of styrene and acrylonitrile, wherein the weight ratio of styrene to acrylonitrile in the Mo nomerengemisch according to an embodiment of the invention in the range of 100 0 to 40:60, preferably in the range of 65:35 to 85:15. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylate polymer used as the graft again in aqueous emulsion under the usual conditions described above. The graft copolymerization may suitably be carried out in the same system as the emulsion polymerization for the preparation of the graft A1, wherein, if necessary, further emulsifier and initiator may be added. The monomer mixture of styrene and acrylonitrile to be grafted on in accordance with one embodiment of the invention can be added to the reaction mixture at once, batchwise in several stages or preferably continuously during the polymerization. The graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out so that a grafting degree of 1 to 99 wt .-%, preferably 20 to 45 wt .-%, in particular 35 to 45 wt .-%, based on the Total weight of component A, resulting in the graft copolymer A. Since the graft yield in the graft copolymerization is not 100%, a slightly larger amount of the monomer mixture of styrene and acrylonitrile must be used in the graft copolymerization, as it corresponds to the desired degree of grafting. The control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is familiar to the expert and can be done, for example, by the metering rate of the monomers or by addition of the regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 et seq.) , In the emulsion graft copolymerization generally about 5 to 15 wt .-%, based on the graft copolymer, of free, ungrafted styrene / acrylonitrile copolymer. The proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method indicated above.

at the preparation of the graft copolymers A by the emulsion process are in addition to the given procedural advantages also reproducible in particle sizes possible, for example by at least partial agglomeration of the particles to larger particles. This means that in the graft copolymers A and polymers present with different particle sizes can.

In front in particular the component A of the graft base and graft shell (s) can for the each purpose of use are optimally adapted, in particular in terms of particle size.

The Graft copolymers A generally contain 1-99% by weight, preferably 55-80 and more preferably 55-65 % By weight of grafting base A1 and 1-99% by weight, preferably 20-45, particularly preferably 35 - 45 Wt .-% of the graft A2, each based on the total graft copolymer.

Under ABS polymers are generally understood to be impact-modified SAN polymers, in which diene polymers, in particular 1,3-polybutadiene, in one Copolymer matrix of in particular styrene and / or α-methylstyrene and acrylonitrile.

• a1' 10 bis 90 Gew.-% mindestens einer kautschukelastischen Pfropfgrundlage mit einer Glasübergangstemperatur unter 0°C, erhältlich durch Polymerisation von, bezogen auf A1', a11' 60 bis 100, bevorzugt 70 bis 100 Gew.-% mindestens eines konjugierten Diens und/oder C₁- bis C₁₀-Alkylacrylats, insbesondere Butadien, Isopren, n-Butylacrylat und/oder 2-Ethylhexylacrylat, a12' 0 bis 30, bevorzugt 0 bis 25 Gew.-% mindestens eines weiteren monoethylenischen ungesättigten Monomeren, insbesondere Styrol, a-Methylstyrol, n-Butylacrylat, Methylmethacrylat oder deren Mischungen, unter letztgenannten insbesondere Butadien/Styrol- und n-Butylacrylat/Styrol-Copolymere, und a13' 0 bis 10, bevorzugt 0 bis 6 Gew.-% mindestens eines vernetzenden Monomeren, vorzugsweise Divinylbenzol, Diallylmaleat, Allylester der (Meth)acrylsäure, Dihydrodicyclopentadienylacrylat, Dinvinylester von Dicarbonsäuren wie Bernstein- und Adipinsäure sowie Diallyl- und Divinylether bifunktioneller Alkohole wie Ethylenglykol oder Butan-1,4-diol,
• a2' 10 bis 60, bevorzugt 15 bis 55 Gew.-% einer Pfropfauflage A2' aus, bezogen auf A2', a21' 50 bis 100, bevorzugt 55 bis 90 Gew.-% mindestens eines vinylaromatischen Monomeren, vorzugsweise Styrol und/oder a-Methylstyrol, a22' 5 bis 35, bevorzugt 10 bis 30 Gew.-% Acrylnitril und/oder Methacrylnitril, bevorzugt Acrylnitril, a23' 0 bis 50, bevorzugt 0 bis 30 Gew.-% mindestens eines weiteren monoethylenisch ungesättigten Monomeren, vorzugsweise Methylmethacrylat und n-Butylacrylat.

In a preferred embodiment, in which the extruded films or sheets comprise ABS polymers, component A is an elastomeric graft copolymer

• a1 '10 to 90 wt .-% of at least one elastomeric graft base having a glass transition temperature below 0 ° C, obtainable by polymerization of, based on A1', a11 '60 to 100, preferably 70 to 100 wt .-% of at least one conjugated diene and or C ₁ - to C ₁₀ -alkyl acrylate, in particular butadiene, isoprene, n-butyl acrylate and / or 2-ethylhexyl acrylate, a12'0 to 30, preferably 0 to 25% by weight of at least one further monoethylenically unsaturated monomer, in particular styrene, a-methylstyrene, n-butyl acrylate, methyl methacrylate or mixtures thereof, among the latter in particular butadiene / styrene and n-butyl acrylate / styrene copolymers, and a13'0 to 10, preferably 0 to 6 wt .-% of at least one crosslinking monomer, preferably Divinylbenzene, diallyl maleate, allyl esters of (meth) acrylic acid, Dihydrodicyclopentadienylacrylat, dinvinyl esters of dicarboxylic acids such as succinic and adipic acid and diallyl and divinyl ether bifunctional alcohols such as ethylene lycol or butane-1,4-diol,
• a2 '10 to 60, preferably 15 to 55 wt .-% of a graft A2', based on A2 ', a21' from 50 to 100, preferably 55 to 90 wt .-% of at least one vinyl aromatic monomer, preferably styrene and / or a Methylstyrene, a22 'from 5 to 35, preferably 10 to 30 wt .-% of acrylonitrile and / or methacrylonitrile, preferably acrylonitrile, a23' 0 to 50, preferably 0 to 30 wt .-% of at least one further monoethylenically unsaturated monomer, preferably methyl methacrylate and n-butyl acrylate.

• a1'' 40 bis 90, bevorzugt 45 bis 85 Gew.-% einer kautschukelastischen teilchenförmigen Pfropfgrundlage A1'', erhältlich durch Polymerisation von, bezogen auf A1'' a11'' 70 bis 100, bevorzugt 75 bis 100 Gew.-% mindestens eines konjugierten Diens, insbesondere Butadien und/oder Isopren, a12'' 0 bis 30, bevorzugt 0 bis 25 Gew.-% mindestens eines weiteren monoethylenischen ungesättigten Monomeren, insbesondere Styrol, α-Methylstyrol, n-Butylacrylat oder deren Mischungen,
• a2'' 10 bis 60, bevorzugt 15 bis 55 Gew.-% einer Pfropfauflage A2'' aus, bezogen auf A2'', a21'' 65 bis 95, bevorzugt 70 bis 90 Gew.-% mindestens eines vinylaromatischen Monomeren, vorzugsweise Styrol, a22'' 5 bis 35, bevorzugt 10 bis 30 Gew.-% Acrylnitril, a23'' 0 bis 30, bevorzugt 0 bis 20 Gew.-% mindestens eines weiteren monoethylenisch ungesättigten Monomeren, vorzugsweise Methylmethacrylat und n-Butylacrylat.

In a further, preferred embodiment in which the extruded films or sheets contain ABS, component A is a graft rubber having a bimodal particle size distribution, based on A,

• a1 '' 40 to 90, preferably 45 to 85 wt .-% of a rubbery elastic particulate graft A1 ', obtainable by polymerization of, based on A1''a11''70 to 100, preferably 75 to 100 wt .-% of at least one conjugated diene, in particular butadiene and / or isoprene, a12 "0 to 30, preferably 0 to 25 wt .-% of at least one further monoethylenically unsaturated monomer, in particular styrene, α-methylstyrene, n-butyl acrylate or mixtures thereof,
• a2 '' 10 to 60, preferably 15 to 55 wt .-% of a graft A2 '', based on A2 '', a21 '' 65 to 95, preferably 70 to 90 wt .-% of at least one vinyl aromatic monomer, preferably styrene , a22 '' 5 to 35, preferably 10 to 30 wt .-% acrylonitrile, a23 '' 0 to 30, preferably 0 to 20 wt .-% of at least one further monoethylenically unsaturated monomer, preferably methyl methacrylate and n-butyl acrylate.

component B

• b1 40–100 Gew.-%, vorzugsweise 60 – 85 Gew.-%, vinylaromatischen Einheiten als Komponente B1,
• b2 bis 60 Gew.-%, vorzugsweise 15 – 40 Gew.-%, Einheiten des Acrylnitrils oder Methacrylnitrils, insbesondere des Acrylnitrils als Komponente B2.

In a preferred embodiment in which the extruded films or plates comprise ASA polymers, component B is at least one hard copolymer containing units derived from vinyl aromatic monomers, and wherein, based on the total weight of vinyl aromatic monomers of dissipative units, 0 - 100 wt .-%, preferably 40 - 100 wt .-%, particularly preferably 60 to 100 wt .-% of α-methyl styrene and 0 - 100 wt .-%, preferably 0 - 60 wt .-%, especially preferably from 0 to 40 wt .-% of styrene-derived units are included, from

• b1 40-100% by weight, preferably 60-85% by weight, of vinylaromatic units as component B1,
• b2 to 60 wt .-%, preferably 15 to 40 wt .-%, units of acrylonitrile or methacrylonitrile, in particular of the acrylonitrile as component B2.

• b1' 50 bis 100, bevorzugt 55 bis 90 Gew.-% vinylaromatischen Monomeren,
• b2' 0 bis 50 Gew.-% Acrylnitril oder Methacrylnitril oder deren Mischungen,
• b3' 0 bis 50 Gew.-% mindestens eines weiteren monoethylenisch ungesättigten Monomeren, beispielsweise Methylmethacrylat und N-Alkyl- oder N-Arylmaleinimide wie N-Phenylmaleinimid.

In a preferred embodiment wherein the extruded films or sheets comprise ABS polymers, component B is at least one hard copolymer containing units derived from vinyl aromatic monomers and wherein, based on the total weight, of vinyl aromatic monomers of derivative units, 0 - 100 wt .-%, preferably 40 - 100 wt .-%, particularly preferably 60 to 100 wt .-% of a-methyl styrene and 0 - 100 wt .-%, preferably 0 - 60 wt .-%, especially preferably 0-40 wt .-% of styrene-derived units are contained, based on B,

• b1 'from 50 to 100, preferably from 55 to 90,% by weight of vinylaromatic monomers,
• b2 'from 0 to 50% by weight of acrylonitrile or methacrylonitrile or mixtures thereof,
• b3 'from 0 to 50 wt .-% of at least one further monoethylenically unsaturated monomers, for example methyl methacrylate and N-alkyl or N-Arylmaleinimide such as N-phenylmaleimide.

• b1'' 69 bis 81, bevorzugt 70 bis 78 Gew.-% vinylaromatischen Monomeren,
• b2'' 19 bis 31, bevorzugt 22 bis 30 Gew.-% Acrylnitril,
• b3'' 0 bis 30, bevorzugt 0 bis 28 Gew.-% mindestens eines weiteren, monoethylenisch ungesättigten Monomeren, beispielsweise Methylmethacrylat oder N-Alkyl- oder N-Arylmaleinimide wie N-Phenylmaleinimid.

In a further preferred embodiment, in which the extruded films or sheets contain ABS, component B is at least one hard copolymer having a viscosity number VZ (determined according to DIN 53726 at 25 ° C. in 0.5% strength by weight solution in dimethylformamide ) from 50 to 120 ml / g, which contains units derived from vinylaromatic monomers, and wherein, based on the total weight of vinylaromatic monomers derived units, 0 - 100 wt .-%, preferably 40 - 100 wt .-% , particularly preferably 60 to 100% by weight of α-methylstyrene and 0 to 100% by weight, preferably 0 to 60% by weight, more preferably 0 to 40% by weight, of units derived from styrene, from, based on B

• b1 "'from 69 to 81, preferably from 70 to 78% by weight of vinylaromatic monomers,
• b2 "19 to 31, preferably 22 to 30 wt .-% acrylonitrile,
• b3 '' 0 to 30, preferably 0 to 28 wt .-% of at least one further monoethylenically unsaturated monomer, for example methyl methacrylate or N-alkyl or N-Arylmaleinimide such as N-phenylmaleimide.

In an embodiment are present in the ABS polymers components B side by side, in their viscosity numbers VZ at least five Units (ml / g) and / or in their acrylonitrile contents by five units (Wt .-%) differ from each other. Finally, in addition to the component B and the other embodiments Copolymers of (α-methyl) styrene and maleic anhydride or maleimides, from (α-methyl) styrene, Maleimides and methyl methacrylate or acrylonitrile, or from (α-methyl) stryol, Maleimides, methyl methacrylate and acrylonitrile.

at These ABS polymers, the graft polymers A are preferred obtained by emulsion polymerization. The mixing of the graft polymers A with the components B and optionally further additives takes place in a mixing device, wherein a substantially molten polymer mixture arises. It is advantageous, the molten polymer mixture as quickly as possible cool.

Moreover, there are manufacturing and general as special embodiments of pre described ABS polymers in the German patent application DE-A 19728629 described in detail, which is hereby incorporated by reference.

The ABS polymers mentioned can be further customary auxiliary and fillers exhibit. Such substances are, for example, lubricants or mold release agents, Waxes, pigments, dyes, flame retardants, antioxidants, Stabilizers against exposure to light or antistatic agents.

According to one preferred embodiment of Invention is the viscosity number Component B 50 - 90, preferably 60-80.

Preferably Component B is an amorphous polymer. According to one embodiment of the Invention is a component B is a mixture of a copolymer of styrene with acrylonitrile and a copolymer of a-methylstyrene used with acrylonitrile. The acrylonitrile content in these copolymers component B is while 0 - 60 wt .-%, preferably 15-40 Wt .-%, based on the total weight of component B. The component Count B also in the graft copolymerization for the preparation of the component A resulting free, ungrafted (α-methyl) styrene / acrylonitrile copolymers. ever after in the graft copolymerization for the preparation of the graft copolymer A chosen Conditions may be possible be that in the graft copolymerization already sufficient Share of component B has been formed. In general, will However, it may be necessary in the graft copolymerization obtained products with additional, separately prepared component B mix.

at this additional, separately prepared component B may preferably be a mixture of styrene / acrylonitrile copolymer with α-methylstyrene / acrylonitrile copolymer or an α-methylstyrene / styrene / acrylonitrile terpolymer act. These copolymers can individually or as a mixture for component B are used, so that the additional, separately prepared component B, for example, a mixture from a styrene / acrylonitrile copolymer and an α-methylstyrene / acrylonitrile copolymer act can. In the case where component B consists of a mixture of a styrene / acrylonitrile copolymer and an α-methylstyrene / acrylonitrile copolymer is, should preferably the acrylonitrile content of the two copolymers by not more than 1% by weight, preferably not more than 5% by weight, based on the total weight of the copolymer, differ from one another.

The additional separately prepared component B can according to the conventional Procedures are obtained. Thus, according to one embodiment the invention, the copolymerization of styrene and / or α-methylstyrene with the acrylonitrile in bulk, solution, Suspension or aqueous emulsion are performed. The component B preferably has a viscosity number of 40 to 100, preferably 50 to 90, in particular 60 to 80. The determination of the viscosity number according to DIN 53 726, thereby 0.5 g of material in 100 ml of dimethylformamide solved.

The Mixing of components A and B and optionally D, may after done in any way by all known methods. If the components A and B, for example by emulsion polymerization It has been possible to prepare the polymer dispersions obtained to mix together, to precipitate the polymers together and work up the polymer mixture. Preferably, however, takes place Mixing of components A and B by coextrusion, Kneading or rolling of the components, the components, provided previously required from the solution obtained in the polymerization or aqueous Dispersion have been isolated. The obtained in aqueous dispersion Products of the graft copolymerization (component A) may also only partially drained be and as wet crumbs be mixed with the component B, in which case during the Mixing the whole Drying of the graft copolymers takes place.

component C

Suitable components C are in principle all known per se or commercially available polycarbonates. The polycarbonates suitable as component C preferably have a molecular weight (weight average M _w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range of 10,000 to 60,000 g / mol. They are obtainable, for example, according to the processes of DE-B-1 300 266 by interfacial polycondensation or according to the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally referred to as bisphenol A, as hereinafter.

Instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyniphenyl ether. Dihydroxydiphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or Dihydroxydiphenylcycloalkane, preferably Dihydroxydiphenylcyclohexane or Dihydroxylcyclopentane, in particular 1,1-bis (4-hydroxyphe nyl) -3,3,5-trimethylcyclohexane and mixtures of the abovementioned dihydroxy compounds.

Especially preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mole% of the above aromatic dihydroxy compounds.

Particularly suitable as component C polycarbonates are those which contain units derived from Resorcinol- or Alkylresorcinolestern, as described for example in WO 00/61664, WO 00/15718 or WO 00/26274; These polycarbonates are, for example, sold by General Electric Company under the trademark SoIIX ^®.

It can also copolycarbonates according to US-A 3,737,409 are used; Of particular interest are Copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, characterized by a high heat resistance distinguished. It is also possible Use mixtures of different polycarbonates.

The average molecular weights (weight average M _w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C according to the invention are in the range of 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. The relative solution viscosities of the polycarbonates used preferably do not differ by more than 0.05, in particular not more than 0.04.

The Polycarbonates C can be used both as regrind and in granulated form.

component D

When Component D contains the extruded foils or sheets of fibrous or particulate fillers or mixtures thereof. This is preferably a commercial one available Products, such as carbon fibers and glass fibers.

usable Glass fibers can be made of E, A or C glass and are preferably with a sizing and a bonding agent. Their diameter is generally between 6 and 20 microns. It can both Continuous fibers (rovings) as well as chopped glass fibers (staple) with a length of 1 - 10 mm, preferably 3 - 6 mm, are used.

furthermore equipped can Filling or Reinforcing materials, such as glass beads, mineral fibers, whiskers, alumina fibers, mica, Quartz flour and wollastonite are added.

In addition, metal flakes (e.g., aluminum flakes from Transmet Corp.), metal powders, metal fibers, metal-coated fillers e.g. nickel-coated glass fibers and other aggregates, the electromagnetic waves shield, be mixed. Especially come aluminum flakes (K 102 Fa. Transmet) for EMI purposes (electro-magnetic interference). Furthermore, the masses with additional Carbon fibers, carbon black, in particular conductivity black, or nickel-coated C fibers are mixed.

The Plastic mixture on which the extruded films or Based on plates further contain other additives that are suitable for polycarbonates, SAN polymers and graft copolymers or mixtures thereof are typical and customary are. Examples of such additives are: dyes, Pigments, colorants, Antistatics, antioxidants, stabilizers to improve the Thermal stability, to increase the light stability, for raising the hydrolysis resistance and chemical resistance, Means against the heat decomposition and in particular the lubricants / lubricants used for the production of moldings or Moldings are appropriate. The dosing of these other additives can at any stage done the manufacturing process, but preferably to a early Time to early the stabilization effects (or other special effects) of the Take advantage of additive. heat stabilizers or oxidation inhibitors are common Metal halides (chlorides, bromides, iodides) that differs from metals derived from group I of the periodic table of elements (like Li, Na, K, Cu).

suitable Stabilizers are the usual hindered Phenols, but also vitamin E or analogous compounds. Also HALS stabilizers (hindered amine light stabilizers), benzophenones, Resorcinols, salicylates, benzotriazoles such as TinuvinRP (UV absorber 2- (2H-benzotriazole-2-yl) -4-methylphenol the CIBA) and other compounds are suitable. These are usually in amounts of up to 2% by weight (based on the total mixture of the plastic mixture) used.

suitable Lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid ester or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12-30 carbon atoms. The quantities of these additives are in the range of 0.05 - 1 Wt .-%.

Also Silicone oils, oligomeric isobutylene or the like Substances come as additives in question, the usual amounts are 0.05 to 5 wt .-%. Pigments, dyes, color-whiteners, such as ultramarine blue, phthalocyanines, Titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid also usable.

processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are becoming common in amounts of from 0.01 to 5% by weight used.

method for the production of extruded films or plates

The Production of the Extruded Inventive Foils or plates and the training of the above-described Morphology, according to the invention by mixing and extrusion the components A, B, C and, if present, D by means of a screw extruder, it is essential that the components B and C without before Foil or sheet extrusion performed melt mixture with each other - that is, without to melt the components B and C, to mix in the melt and by cooling to consolidate again - the Fed screw extruder so that the melting and mixing of components B and C together only during the extrusion takes place. Components B and C can be used with the screw extruder be supplied by separate dosage units, but it is also possible, For example, a granulate of component B and granules of Component C to mix and this granule mixture using only to feed a dosing unit to the screw extruder. Components A and, if available, D can also separately, but also in any mixture - including before and separately performed Melt mixture - with component B or component C or both component B as well as component C are fed to the screw extruder.

In a preferred embodiment the inventive method is the screw extruder as a single screw extruder with at least executed a distributive mixing screw element.

In a further preferred embodiment the inventive method is the screw extruder as a twin-screw extruder with at least executed a distributive mixing screw element.

With Exception of the features described above essential to the invention can the methods of the invention for producing the extruded films of the invention or Plates known in the art and described in the prior art Methods, e.g. Slot extrusion as adapter or die coextrusion, or laminating the layers together, and known to those skilled in the art and devices described in the prior art.

Laminated sheets or foils, molded parts and motor vehicle parts

The extruded according to the invention Films or plates are particularly suitable as a substrate layer of composite laminate sheets or foils, other than the substrate layer at least another cover layer of transparent and weather-resistant plastics, in particular selected from the group polymethyl methacrylate, SAN, polycarbonate and thermoplastic Polyurethane, exhibit. In further embodiments, the composite layer plates or films additional layers, For example, color, adhesion promoter or intermediate layers include.

The composite laminates or films mentioned and their method of preparation are known in the art and for example in WO 04/00935, DE 102004004694.8 (file reference) and the one cited in these documents State of the art in detail described why at this point expressly to this state of Technology is referenced.

The Composite laminate sheets or sheets comprising the extruded invention Sheets or plates can be used for the production of moldings. Any are Moldings accessible. Particularly preferred are these composite laminate sheets or films used for the production of moldings where it is at very good tenacity, in particular puncture resistance, arrives. Particularly preferred molded parts have composite layer plates or films comprising the extruded films of the invention or Sheets and a back-injected, foam-backed, back-poured or back-pressed carrier layer made of plastic. Thus, moldings for outdoor use, for example outside of buildings, a preferred field of application. In particular, the composite layer plates or films comprising the extruded films of the invention or Plates for the manufacture of motor vehicle parts, especially motor vehicle parts for outdoor use in the Vehicle area used. In this case, for example, the production of roof modules, hoods, fenders, door leaves, bumpers, rear fascias, as well other large exterior parts in Consideration.

The aforementioned moldings and motor vehicle outer parts and their production methods are also known to the person skilled in the art and described in detail, for example, in WO 04/00935, DE 102004004694.8 (file reference) and the prior art cited in these documents, which is why reference is expressly made to this prior art at this point.

The The invention is explained in more detail below by means of examples.

Example 1:

One ASA (components A and B) in granular form and a polycarbonate in Granule form were mixed. The granule mixture was on a screw extruder extruded into films F1. These films F1 had high puncture resistance on.

1 shows a transmission electron micrograph thin section of the extruded film F1 with transmission direction perpendicular to the extrusion direction of the film in 20,000-fold magnification.

The light gray areas ( 1 ) represent the continuous phase formed by polycarbonate, the white areas ( 2 ) represent the SAN domains, the dark particles ( 3 ) represent the graft rubber. The length of the bar shown in the figure as a scale is 1 micron.

Example 2 (for comparison):

The Example 2 was with the otherwise same materials, devices and under the same conditions as Example 1, but with the difference that the ASA (components A and B) in granular form and the polycarbonate melted together in granular form, mixed and under cooling were granulated, and the resulting granule mixture on the Screw extruders were extruded into films F1-V. These slides F1-V had a lower puncture resistance on.

2 shows a transmission electron micrograph thin section of the extruded film F1-V with transmission direction perpendicular to the extrusion direction of the film in 20000-fold magnification.

The light gray areas ( 1 ) represent the continuous phase formed by polycarbonate, the white areas ( 2 ) represent the SAN domains, the dark particles ( 3 ) represent the graft rubber. The length of the bar shown in the figure as a scale is 1 micron.

The Examples prove that the extruded films or Plates opposite known an improved toughness, in particular improved puncture resistance.

Claims (10)

Extruded sheet or sheet containing a plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100 wt .-%, a 10 to 89 wt .-% of a rubbery graft copolymer as component A, b 10 bis 89 wt .-% of a hard copolymer containing units derived from vinyl aromatic monomers, as component B, c 1 to 80 wt .-% of a polycarbonate as component C, and d 0 to 50 wt .-% fibrous or particulate Fillers or mixtures thereof as component D, wherein - component C the continuous phase of the plastic mixture bil det, - component B forms domains in the continuous phase of component C and - component A in components B and / or C distributed particles, characterized in that, based on the total number of domains formed by component B, the number of domains formed by component B has a maximum spatial extent of less than 2 microns in the range of 80% to 100% (wherein the respective number of domains formed and their maximum spatial extent by transmission electron microscopic thin section recordings of any, at least 20 microns ² large area of the extruded film or plate with a transmission direction perpendicular to the extrusion direction of the film or plate can be determined in 20000x magnification by counting and measuring). Extruded sheet or board according to claim 1, characterized in that component A comprises a1 1-99 wt .-% of a particulate graft as component A1, obtainable by polymerization of, based on A1, a11 80-99.99 wt .-%, at least one C _1-8 -alkyl ester of acrylic acid as component A11, a12 0.01-20% by weight of at least one polyfunctional crosslinking monomer as component A12, a2 1-99% by weight of a graft A2 obtainable by polymerization of to A2, a21 40 to 100 wt .-% of styrene, a substituted styrene or a (meth) acrylic acid ester or mixture thereof as component A21 and a22 to 60 wt .-% of acrylonitrile or methacrylonitrile as component A22, wherein the graft A2 from at least one Grafting consists and the graft copolymer has an average particle size of 50 - 1000 nm, and Component B comprises copolymers of b1 40-100% by weight of vinylaromatic monomers as component B1, b2 to 60% by weight of the acrylonitrile or methacrylonitrile as component B2. Extruded sheet or plate according to claim 1, characterized characterized in that component A comprises a1 '10 to 90% by weight at least one rubber-elastic graft base with a Glass transition temperature below 0 ° C as component A1 ', available by polymerization of, based on A1 ', a11 '60 to 100 wt .-% of at least one conjugated diene as component A11 ', a12 '0 to 30 wt .-% of at least one monoethylenic unsaturated Monomers as component A12 ', and a13'0 to 10 wt .-% of at least one crosslinking monomer with non-conjugated Double bonds as component A13 ', a2 '10 to 60 wt .-% of a graft as component A2, based on A2 ', a21 'from 50 to 100% by weight of at least one vinylaromatic monomers as component A21 ' a22 'from 5 to 35% by weight of acrylonitrile and / or Methacrylonitrile as component A22 ', a23 '0 to 50 wt .-% of at least one other monoethylenically unsaturated Monomers as component A23 ', and Component B comprises copolymers b1 'from 50 to 100% by weight of vinyl aromatic Monomers as component B1 ', b2'0 to 50% by weight Acrylonitrile or methacrylonitrile or mixtures thereof as a component B2 ', b3'0 to 50% by weight at least one further monoethylenically unsaturated monomer as a component B3 '. Extruded sheet or plate according to claims 1 to 3, characterized in that component B based on the total weight 40 to 100% by weight of vinyl aromatic monomer-derived units of α-methylstyrene and 0-60% by weight contains styrene-derived units. Process for producing an extruded film or plate according to one the claims 1 to 4 by mixing and extrusion of the components A, B, C and, if present, D by means of a screw extruder, characterized that the components B and C without prior melt mixture with each other supplied to the screw extruder with components A and, if present, D separately or in any mixture with components B and / or C fed to the screw extruder , and the melting and mixing of components B and C first while the extrusion takes place. Method according to claim 5, characterized in that that the screw extruder as a single screw extruder with at least a distributive mixing screw element is executed. Method according to claim 5, characterized in that that the screw extruder as a twin-screw extruder with at least a distributive mixing screw element is executed. A composite laminate sheet or film comprising an extruded one Foil or plate according to a the claims 1 to 4 as a substrate layer and a cover layer of one or selected from several plastics from the group polymethyl methacrylate, styrene-acrylonitrile copolymer, Polycarbonate and thermoplastic polyurethane. Molded part comprising a composite layer plate or film according to claim 8 and a back-injected, behind-foamed, back-poured or behind-pressed carrier layer made of plastic. Motor vehicle exterior parts, in particular roof modules, Bonnets, fenders, Bumpers, door leaves and Rear panels comprising an extruded film or plate according to a of claims 1 to 4, a composite layered sheet or film according to claim 8 and / or a molded part according to claim 9.