DE10309452A1 - Use of compositions based on impact-modified polyalkylene terephthalate / polycarbonate blends for the production of moldings - Google Patents

Abstract

The present invention relates to the use of compositions based on impact-modified polyalkylene terephthalate / polycarbonate blends for the production of semi-finished products and molded parts.

Description

The present invention relates to the use of compositions based on impact modified Polyalkylene terephthalate / polycarbonate blends for the production of semi-finished products and molded parts.

Impact-modified molding compounds, the Semi-crystalline polyesters, amorphous polycarbonates and their use as substrates for Lacquers based are known. Such molding compositions are, for example in the automotive sector for Molded parts such as bumpers, fenders, radiator grilles, Panels, rear panels, sills, spoilers, door handles, fuel filler caps, panels, horizontal components such as hoods or roof elements, door modules or similar used. Requirements for the use in automotive applications include high heat resistance, high fluidity in the melt, high impact strength even at low temperatures and good paint adhesion.

The painting of these substrates can doing about a one-coat, two-coat or multi-coat paint system respectively. Paint structures can inter alia contain the following layers: adhesive primer, master primer, Primer Surfacer, basecoats, clearcoats and / or topcoats.

For a long time, the coating was carried out with coating systems based on organic solvents, hereinafter referred to as organic coating systems, so that the substrates based on impact-modified polyalkylene terephthalate-polycarbonate blends were optimized for maximum adhesion of the organic coating systems. The state of the art here is in particular compositions based on impact-modified polybutylene terephthalate / polycarbonate blends which, in addition to the very good paint adhesion, also have high heat resistance and low-temperature impact strength. This is for example in DE 3118526 and WO 0234833.

For environmental reasons today increasingly solvent-based Varnishes replaced by water-based ones. With a so-called watery Lacquer ("Lacquer Water-based") is a significant proportion of the solvents replaced by water. Is that applied directly to the substrate Layer of solvent-based on watery changed, it happens often at the for the use of solvent-based Coating systems optimized substrates on the basis of impact modified Polyalkylene terephthalate / polycarbonate blends for poor paint adhesion.

The object of this invention was therefore the substrate based on impact modified polyalkylene terephthalate / polycarbonate blends for the Optimizing paint adhesion of hydro-based paints, with the other key properties this material class such as heat resistance, low temperature toughness, Stiffness and fluidity remain.

Surprised it has now been found that in compositions based on impact modified Blends of polycarbonate and polyalkylene terephthalates the paint adhesion of hydro-based paints while maintaining the other key properties mentioned elevated can be when the polyalkylene terephthalate components are a mixture of at least two different polyalkylene terephthalates with different alkylene chain, preferably of at least polybutylene terephthalate and polyethylene terephthalate contains. The molding compositions according to the invention stand out about it through high heat resistance, high fluidity in the melt, high rigidity, high dimensional stability and high Low temperature toughness out.

• A) 4 bis 80, vorzugsweise 10 bis 60, besonders bevorzugt 12 bis 40, insbesondere 15 bis 30 Gew.-Teile, mindestens eines Polyalkylenterephthalats, bevorzugt mindestens eines Polybutylenterephthalats,
• B) 4 bis 80, vorzugsweise 6 bis 60, besonders bevorzugt 8 bis 40, insbesondere 10 bis 30 Gew.-Teile, mindestens eines Polyalkylenterephthalats mit einer von Komponente A unterschiedlichen Alkylenkettenlänge, bevorzugt mindestens eines Polyethylenterephthalats,
• C) 10 bis 90, vorzugsweise 20 bis 80, besonders bevorzugt 25 bis 60, insbesondere 35 bis 55 Gew.-Teile, mindestens ein aromatisches Polycarbonat,
• D) 1 bis 30, vorzugsweise 3 bis 25, besonders bevorzugt 6 bis 20, insbesondere 8 bis 16 Gew.-Teile, mindestens eines kautschukelastischen Polymerisats oder Pfropfcopolymerisats,
• E) 0,1 bis 20 Gew.-Teile, bevorzugt 0,15 bis 15 Gew.-Teile, besonders bevorzugt 0,2 bis 10 Gew.-Teile üblicher Additive und Verarbeitungshilfsmittel, die zusammen 100 Gew.-Teile ergeben, gegebenenfalls zusätzlich enthaltend
• F) 0 bis 60, vorzugsweise 2 bis 45, besonders bevorzugt 4 bis 30 Gew.-Teile, mindestens eines teilchenförmigen mineralischen Füllstoffs,

zur Herstellung von lackierten Formteilen, wobei aus A) – F) Formkörper hergestellt werden und diese mit Hydrolacken lackiert werden, wobei bei mehrschichtigen Lacksystemen mit verschiedenen Lösemitteln mindestens das Lösemittel der ersten, untersten Lackschicht auf Wasserbasis bestehen muss.The invention relates to the use of compositions containing

• A) 4 to 80, preferably 10 to 60, particularly preferably 12 to 40, in particular 15 to 30 parts by weight of at least one polyalkylene terephthalate, preferably at least one polybutylene terephthalate,
• B) 4 to 80, preferably 6 to 60, particularly preferably 8 to 40, in particular 10 to 30 parts by weight of at least one polyalkylene terephthalate with an alkylene chain length different from component A, preferably at least one polyethylene terephthalate,
• C) 10 to 90, preferably 20 to 80, particularly preferably 25 to 60, in particular 35 to 55 parts by weight, at least one aromatic polycarbonate,
• D) 1 to 30, preferably 3 to 25, particularly preferably 6 to 20, in particular 8 to 16 parts by weight of at least one rubber-elastic polymer or graft copolymer,
• E) 0.1 to 20 parts by weight, preferably 0.15 to 15 parts by weight, particularly preferably 0.2 to 10 parts by weight of conventional additives and processing aids, which together add up to 100 parts by weight, optionally additionally containing
• F) 0 to 60, preferably 2 to 45, particularly preferably 4 to 30 parts by weight of at least one particulate mineral filler,

for the production of lacquered molded parts, molded bodies being produced from A) - F) and these being lacquered with hydraulic lacquers, in the case of multi-layer lacquer systems with various solvents at least the solvent of the first, bottom lacquer layer having to be water-based.

The compositions contain as component A. according to the invention or a mixture of two or more different polyalkylene terephthalates. Polyalkylene terephthalates in the sense of the invention are polyalkylene terephthalates, which is different from terephthalic acid (or their responsive Derivatives) and alkanediols, for example based on propylene glycol or derive butanediol. According to the invention, component A is preferred Polybutylene terephthalate and / or polytrimethylene terephthalate, am most preferably polybutylene terephthalate.

Polyalkylene terephthalates in the sense the invention are reaction products of aromatic dicarboxylic acid or their responsive Derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures thereof Reaction products.

Preferred polyalkylene terephthalates can be made from terephthalic acid (or their reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms manufacture according to known methods (Kunststoff-Handbuch, Vol. VIII, P. 695 FF, Karl-Hanser-Verlag, Munich 1973).

Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid and at least 80, preferably at least 90 mol%, based on the diol component, ethylene glycol and / or propanediol 1,3 and / or 1,4-butanediol radicals.

The preferred polyalkylene terephthalates can in addition to terephthalic acid residues up to 20 mol% of residues of other aromatic dicarboxylic acids 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms contain, like residues of phthalic acid, isophthalic acid, Naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, amber, Adipic, sebacic acid, azelaic acid, cyclohexanediacetic, Cyclohexane.

In addition to ethylene or propanediol-1,3- or butanediol-1,4-glycol residues, the preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms. Contain atoms, for example residues of 1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexane-dimethanol, 2,4-3-methylpentanediol, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and -1,6,2-ethylhexanediol-1,3 2,2-diethyl propanediol-1,3, hexanediol-2,5,1 4-di- (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis- (3rd -β-hydroxyethoxyphenyl) propane and 2,2-bis- (4-hydroxypropoxyphenyl) propane ( DE-A 24 07 674 , 24 07 776, 27 15 932).

The polyalkylene terephthalates can be incorporated by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acid, such as in DE-A 19 00 270 and the US-A 3,692,744 are described. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.

It is advisable not to use more than 1 mole% of the branching agent, based on the acid component.

Polyalkylene terephthalates are particularly preferred, which solely from terephthalic acid and their reactive Derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol have been prepared (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.

Preferred polyalkylene terephthalates are also copolyesters made from at least two of the above acid components and / or from at least two of the abovementioned alcohol components are produced, particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.

The polyalkylene terephthalates have generally an intrinsic viscosity of approx. 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 Parts by weight) at 25 ° C.

Those produced according to the invention can preferably be used Polyester also mixed with other polyesters and / or others Polymers are used. Mixtures are particularly preferred of polyalkylene terephthalates used with other polyesters.

Common additives such as e.g. mold release agents, Stabilizers and / or plasticizers mixed in the melt or applied to the surface.

The compositions contain as component B. at least according to the invention a polyalkylene terephthalate corresponding to component A, which of component A in length Alkylene chain of the alkanediol used differs.

At least component B is preferred a polyethylene terephthalate used, very preferred if as Component A is used at least one polybutylene terephthalate.

Polyethylene terephthalates in the sense The invention are polyalkylene terephthalates, which are derived from terephthalic acid (or their responsive Derivatives) and alkane diols based on ethylene glycol.

Preferred polyethylene terephthalates (hereinafter also abbreviated: PET) can be made from terephthalate produce acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with ethylene glycol unit according to known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Munich 1973).

Preferred polyethylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid and at least 80, preferably at least 90 mol%, based on the diol component, ethylene glycol residues.

The preferred polyethylene terephthalates can in addition to terephthalic acid residues up to 20 mol% of residues of other aromatic dicarboxylic acids 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms contain, preferably phthalic acid, isophthalic acid, Naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, amber, Adipic, sebacic acid, azelaic acid, Cyclohexanediacetic.

The preferred polyethylene terephthalates can contain up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, for example 1,3-propanediol, 1,3-propanediol, 2-1,3-propanediol, neopentyl glycol , Pentane-diol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and - 1,6,2-ethylhexanediol-1,3 2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di- (β-hydroxyethoxy) benzene, 2,2-bis- (4- hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (3-β-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane ( DE-A 24 07 674 , 24 07 776, 27 15 932). Polyethylene terephthalates can also contain up to 20 mol% of ether or polyether structures.

The polyethylene terephthalates can be incorporated by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acid, such as in DE-A 19 00 270 and the US-A 3,692,744 are described. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethane and pentaerythritol. It is advisable not to use more than 1 mol% of the branching agent, based on the acid component.

Preferred polyethylene terephthalates are also copolyesters that consist of at least two acid components and / or at least two alcohol components are produced, particularly preferred Copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.

Polyethylene terephthalates are particularly preferred, which solely from terephthalic acid and their reactive Derivatives (e.g. their dialkyl esters) and ethylene glycol have been.

Have the polyethylene terephthalates generally an intrinsic viscosity of about 0.3 to 1.5 dl / g, preferred 0.4 to 1.3 dl / g, particularly preferably 0.5 to 0.8 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.

Fast are particularly preferred Crystallizing polyethylene terephthalates, that is, polyethylene terephthalates, which according to the DSC method for isothermal crystallization at 215 ° C Crystallization times generally less than 15 minutes, preferred less than 10 minutes and particularly preferably less than 5 minutes exhibit.

A quick crystallization of the polyethylene terephthalates according to the invention is preferred by adding crystallizing agents to the polyethylene terephthalate during its manufacture or afterwards e.g. by mixing in reached the polyethylene terephthalate melt. As a crystallization agent metal salts of organic carboxylic acids are preferably used, e.g. Alkali- or alkaline earth metal salts of benzoic acid or substituted benzoic acid.

The compositions according to the invention contain as component C. a polycarbonate according to the invention or a mixture of polycarbonates.

Preferred polycarbonates are homopolycarbonates and copolycarbonates based on the bisphenols of the general formula (I), HO-Z-OH (I) wherein Z is a divalent organic radical having 6 to 30 carbon atoms and containing one or more aromatic groups.

wobei
A eine Einfachbindung, C₁-C₅-Alkylen, C₂-C₅-Alkyliden, C₅-C₆-Cycloalkyliden, -O-, -SO-, -CO-, -S-, -SO₄-, C₆-C₁₂-Arylen, an das weitere aromatische gegebenenfalls Heteroatome enthaltende Ringe kondensiert sein können,
oder ein Rest der Formel (II) oder (III)

B jeweils C₁-C₁₂-Alkyl, vorzugsweise Methyl, Halogen, vorzugsweise Chlor und/oder Brom
x jeweils unabhängig voneinander 0, 1 oder 2,
p 1 oder 0 sind, und
R¹ und R² für jedes X¹ individuell wählbar, unabhängig voneinander Wasserstoff oder C₁-C₆-Alkyl, vorzugsweise Wasserstoff, Methyl oder Ethyl,
X¹ Kohlenstoff und
m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5 bedeuten, mit der Maßgabe, dass an mindestens einen Atom X¹, R¹ und R² gleichzeitig Alkyl sind.Bisphenols of the formula (Ia) are preferred

in which
A is a single bond, C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₄ -, C ₆ -C ₁₂ arylene, to which further aromatic rings, optionally containing heteroatoms, are condensed can,
or a radical of the formula (II) or (III)

B each C ₁ -C ₁₂ alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
x each independently of the other 0, 1 or 2,
p are 1 or 0, and
R ¹ and R ^{2 can be} selected individually for each X ¹ , independently of one another hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen, methyl or ethyl,
X ¹ carbon and
m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X ¹ , R ¹ and R ^{2 are} simultaneously alkyl.

Examples of bisphenols according to the general Formula (I) are bisphenols which belong to the following groups: dihydroxydiphenyls, Bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, indane bisphenols, Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides and α, α'-bis (hydroxyphenyl) diisopropylbenzenes.

Derivatives of the bisphenols mentioned, for example by alkylation or halogenation on the aromatic Rings of the bisphenols mentioned are accessible are examples for bisphenols according to the general Formula (I).

Examples of bisphenols according to the general Formula (I) are in particular the following compounds: hydroquinone, Resorcinol, 4,4'-dihydroxydiphenyl, Bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) methane, Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) p / m-diisopropylbenzene, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane. 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (i.e. bisphenol A), 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, α, α'-bis (4-hydroxyphenyl) o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl ) -m-diisopropylbenzene (i.e. bisphenol M), α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene and Indian bisphenol.

Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates Basis of the two monomers bisphenol A and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The bisphenols described according to the general Formula (I) can by known methods, e.g. from the corresponding phenols and Ketones.

The bisphenols mentioned and processes for their preparation are described, for example, in the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 77-98, Interscience Publishers, New York, London, Sidney, 1964 and in US-A 3,028,635 , in US-A 3,062,781 , in US-A 2 999 835 , in US-A 3 148 172 , in US-A 2 991 273 , in US-A 3,271,367 , in US-A 4,982,014 , in US-A 2 999 846 , in DE-A 1 570 703 , in DE-A 2 063 050 , in DE-A 2 036 052 , in DE-A 2 211 956 , in DE-A 3 832 396 , and in FR-A1 561 518 as well as in Japanese Laid-Open Publications with the application numbers JP-A 62039 1986 JP-A 62040 1986 and JP-A 105550 1986th

1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and its preparation is described for example in US-A 4,982,014 ,

Indian bisphenols and their preparation are described, for example, in US-A 3,288,864 , in JP-A 60 035 150 and in US-A 4,334,106 , Indanbisphenols can be prepared, for example, from isopropenylphenol or its derivatives or from dimers of isopropenylphenol or its derivatives in the presence of a Friedel-Craft catalyst in organic solvents.

Polycarbonates can by known methods getting produced. Suitable processes for the production of polycarbonates are, for example, the production of bisphenols with phosgene the phase boundary method or from bisphenols with phosgene by the process in homogeneous Phase, the so-called pyridine process, or with bisphenols Kohlensäureestern after the melt transesterification process. These manufacturing processes are e.g. described in H. Schnell, "Chemistry and Physique of Polycarbonates ", Polymer Reviews, Vol. 9, pp. 31-76, Interscience Publishers, New York, London, Sidney, 1964. The production processes mentioned are also described in D. Freitag, U. Grigo, P. R. Müller, H. Nouvertne, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, Pages 648 to 718 and in U. Grigo, K. Kircher and P.R. Müller "Polycarbonate" in Becker, brown, Plastic manual, volume 3/1, polycarbonates, polyacetals, polyester, Cellulose ester, Carl Hanser Verlag Munich, Vienna 1992, pages 117 to 299 and in D.C. Prevorsek, B.T. Debona and Y. Kesten, corporate Research Center, Allied Chemical Corporation, Morristown, New Jersey 07960, "Synthesis of poly (ester carbonate) copolymers "in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980).

The melt transesterification process is particularly described, for example, in H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 44 to 51, Interscience Publishers, New York, London, Sidney, 1964 and in DE-A 1 031 512 ,

In the production of polycarbonate are preferred raw materials and auxiliary materials with a low degree used on impurities. Especially in manufacturing According to the melt transesterification process, the bisphenols used and the carbonic acid derivatives used preferably be free of alkali ions and alkaline earth ions. Such pure raw materials are available for example by the carbonic acid derivatives, for example carbonic acid esters, and the bisphenols recrystallized, washed or distilled.

The polycarbonates suitable according to the invention preferably have a weight average molar mass ( M _W ), which can be determined, for example, by ultracentrifugation or scattered light measurement, from 10,000 to 200,000 g / mol. They particularly preferably have a weight average molar mass of 12,000 to 80,000 g / mol, particularly preferably 20,000 to 35,000 g / mol.

The average molar mass of the polycarbonates according to the invention can, for example, in a known manner by an appropriate amount can be set on chain breakers. The chain terminators can be used individually or used as a mixture of different chain terminators.

Suitable chain terminators are both Monophenols as well as monocarboxylic acids. Suitable monophenols are e.g. Phenol, p-chlorophenol, p-tert-butylphenol, Cumylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as. 4- (1,1,3,3-tetramethylbutyl) -phenol or monoalkylphenols or dialkylphenols with a total of 8 to 20 C atoms in the alkyl substituents such as e.g. 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) phenol or 4- (3,5-dimethyl-heptyl) phenol. suitable Monocarboxylic acids are benzoic acid, alkylbenzoic and halobenzoic acids.

Preferred chain terminators are phenol, p-tert-butylphenol, 4- (1,1,3,3-tetramethylbutyl) phenol and cumylphenol.

The amount of chain terminators is preferred between 0.25 and 10 mol%, based on the sum of the used Bisphenols.

The polycarbonates suitable according to the invention can be branched in a known manner, preferably by the Installation of trifunctional or more than trifunctional branches. Suitable branching devices are e.g. those with three or more than three phenolic groups or those with three or more than three carboxylic acid groups.

Suitable branching agents are, for example Phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tris- (4-hydroxyphenyl) ethane, Tri- (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, 2,6-bis (2-hydroxy-5'-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, Hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl) -terephthalsäureester, Tetra (4-hydroxyphenyl) methane, Tetra- (4- (4-hydroxyphenyl-isopropyl) phenoxy) methane and 1,4-bis (4 ', 4' '- dihydroxytriphenyl) methylbenzene as well as 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, trimesic acid trichloride and α, α ', α' '- tris (4-hydroxyphenol) -1,3,5-triisopropylbenzene.

Preferred branching agents are 1,1,1-tris (4-hydroxyphenyl) ethane and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The amount of any to be used Branch is preferably 0.05 mol% to 2 mol%, based on moles of used Bisphenols.

The splitters can, for example, in the case the production of the polycarbonate by the phase interface process with the bisphenols and chain terminators in the aqueous alkaline Phase are presented, or in an organic solvent solved along with the carbonic acid derivatives be added. In the case of the transesterification process, the Branching agents are preferred together with the dihydroxyaromatics or bisphenols dosed.

Catalysts to be preferably used in the production of polycarbonate by the melt transesterification process are the ammonium salts and phosphonium salts known from the literature (see for example US-A 3,442,864 . JP-A-14742 / 72 US-A 5 399 659 and DE-A 19 539 290 ).

Copolycarbonates can also be used. For the purposes of the invention, copolycarbonates are, in particular, polydiorganosiloxane-polycarbonate block copolymers whose weight average of the molar mass ( M _W ) is preferably 10,000 to 200,000 g / mol, particularly preferably 20,000 to 80,000 g / mol (determined by gel chromatography after prior calibration by light scattering measurement or ultracentrifugation). The content of aromatic carbonate structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably 75 to 97.5% by weight, particularly preferably 85 to 97% by weight. The content of polydiorganosiloxane structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably 25 to 2.5% by weight, particularly preferably 15 to 3% by weight. The polydiorganosiloxane-polycarbonate block copolymers can be prepared, for example, starting from polydiorganosiloxanes containing α, ω-bishydroxyaryloxy end groups and having an average degree of polymerization of preferably P _n = 5 to 100, particularly preferably P _n = 20 to 80.

Common additives can be used for the polycarbonates such as. Release agent mixed in the melt or on the surface be applied. The polycarbonates used preferably contain mold release agents before compounding with the other components the molding compositions of the invention.

The compositions contain as component D) according to the invention or a mixture of two or more different rubber elastic Polymers with a glass transition temperature below -5 ° C, preferred below -15 ° C, more preferred below -30 ° C, most preferably below -50 ° C, often also as impact modifiers, Elastomers or rubbers are called.

In the component according to the invention D) are generally copolymers, preferably graft copolymers from at least two, preferably three of the following monomers: styrene, Acrylonitrile, butadiene, acrylic or methacrylic acid esters of alcohols with 1 up to 18 carbon atoms as alcohol component, vinyl acetate, ethylene, propylene, 1,3-butadiene, isobutene, isoprene and / or chloroprene. Such polymers component D) e.g. in Methods of Organic Chemistry "(Houben-Weyl), Vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, pp. 392-406 and in C.B. Bucknall, "Thoughened Plastics ", Appl. Science Publishers, London 1977. For the graft copolymers at least one outer shell is grafted onto a core.

Preferably used as component D) Graft copolymers are, for example, by grafting reaction from Styrene, acrylonitrile and / or methyl methacrylate on a graft base 1,3-butadiene, isoprene, n-butyl acrylate, styrene and / or 2-ethylhexyl acrylate, more preferably by grafting acrylonitrile, styrene and / or Methyl methacrylate on a graft base of 1,3-butadiene, isoprene, Obtained n-butyl acrylate, styrene and / or 2-ethylhexyl acrylate.

Are particularly preferred according to the invention Graft copolymers in which methyl methacrylate or a mixture of methyl methacrylate and styrene on a 1,3-butadiene-based graft or on a graft base made from a mixture of 1,3-butadiene and styrene are grafted on, also called MBS (methyl methacrylate-butadiene-styrene) rubbers be designated. According to the invention particularly graft copolymers in which acrylonitrile are also preferred or a mixture of acrylonitrile and styrene on a graft base based on 1,3-butadiene or on a graft base made from a mixture of 1,3-butadiene and grafted styrene, which is also referred to as ABS (acrylonitrile butadiene styrene) rubbers become.

Preferred as component D) also graft copolymers used in which n-butyl acrylate, n-butyl methacrylate, Ethyl acrylate, methyl acrylate, 1,3-butadiene, isoprene and / or 2-ethylhexyl acrylate on a graft base of 1,3-butadiene, isoprene, n-butyl acrylate, Styrene and / or 2-ethylhexyl acrylate are grafted on.

The monomer mixtures, which are grafted onto the graft base, also with additional ones reactive groups, such as epoxy or glycidyl, carboxyl, carboxylic anhydride, Amino and / or amide groups, functionalized monomers with one include ethylenic double bond, such as acylamide, Methacrylamide, (N, N-dimethylamino) ethyl acrylate, preferably maleic acid, fumaric acid, maleic anhydride, Allyl glycidyl ether, vinyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate.

Crosslinking monomers can also be used according to the invention polymerized into the graft base and / or into outer shells such as divinylbenzene, diallyl phthalate, dihydrodicyclopentadiene acrylate and / or 1,3-butadiene.

So-called graft-crosslinking monomers can also be used, which at least have two polymerizable double bonds, the double bonds polymerizing at different rates during the polymerization. Preferably, one double bond polymerizes at about the rate of the other monomers, the other or other double bond, on the other hand, significantly more slowly, so that this results in a certain proportion of double bonds in the rubber. When another phase is grafted on, parts of these double bonds can react with the graft monomers and thus partially chemically bind the grafted phase to the graft base. For example, ethylenically unsaturated carboxylic acid esters such as allyl acrylate, allyl methacrylate, dially maleate, diallyl fumarate or in U.S. Patent 4,148,846 called connections called.

• D.1 5 bis 95, vorzugsweise 30 bis 90 Gew.-%, wenigstens eines Vinylmonomeren auf
• D.2 95 bis 5, vorzugsweise 70 bis 10 Gew.-% einer oder mehrerer Pfropfgrundlagen mit Glasübergangstemperaturen < 10°C, vorzugsweise < 0°C, besonders bevorzugt < –20°C.

Component D preferably comprises one or more graft polymers of

• D.1 5 to 95, preferably 30 to 90 wt .-%, of at least one vinyl monomer
• D.2 95 to 5, preferably 70 to 10% by weight of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C.

The graft base D.2 generally has an average particle size (d ₅₀ value) of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm.

• D.1.1 50 bis 99 Gew.-% Vinylaromaten und/oder kernsubstituierten Vinylaromaten (wie beispielsweise Styrol, α-Methylstyrol, p-Methylstyrol, p-Chlorstyrol) und/oder Methacrylsäure-(C₁-C₈)-Alkylester (wie z.B. Methylmethacrylat, Ethylmethacrylat) und
• D.1.2 1 bis 50 Gew.-% Vinylcyanide (ungesättigte Nitrile wie Acrylnitril und Methacrylnitril) und/oder (Meth)Acrylsäure-(C₁-C₈)-Alkylester (wie z.B. Methylmethacrylat, n-Butylacrylat, t-Butylacrylat) und/oder Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren (beispielsweise Maleinsäureanhydrid und N-Phenyl-Maleinimid).

Monomers D.1 are preferably mixtures of

• D.1.1 50 to 99 wt .-% vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) alkyl esters (such as Methyl methacrylate, ethyl methacrylate) and
• D.1.2 1 to 50% by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide).

Preferred monomers D.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers D.1.2 are selected from at least one of the Monomers acrylonitrile, maleic anhydride and methyl methacrylate.

Monomers are particularly preferred D.1.1 styrene and D.1.2 acrylonitrile.

For the graft polymers D are suitable graft bases D.2, for example Diene rubbers, EP (D) M rubbers, i.e. those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.

Preferred graft bases are D.2 Diene rubbers (e.g. based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (e.g. according to D.1.1 and D.1.2), with the proviso that the glass transition temperature Component D.2 below <10 ° C, preferably <0 ° C, especially is preferably <-10 ° C.

Pure polybutadiene rubber is particularly preferred.

Particularly preferred polymers D are, for example, ABS polymers (emulsion, bulk and suspension ABS), as used, for. B. in the DE-A 2 035 390 (= US-A 3,644,574 ) or in the DE-A 2 248 242 (= GB-A 1 409 275 ) or in Ullmann, Encyclopedia of Technical Chemistry, Vol. 19 (1980), p. 280 ff. The gel fraction of the graft base D.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).

The graft copolymers D are by radical polymerization, e.g. by emulsion, suspension, solvent or bulk polymerization, preferably produced by emulsion or bulk polymerization.

ABS polymers which are particularly suitable are graft rubbers which are obtained by redox initiation using an initiator system composed of organic hydroperoxide and ascorbic acid US-A 4 937 285 getting produced.

Since in the graft reaction the graft monomers as is well known, not necessarily entirely based on the graft are grafted on, according to the invention, under graft polymers B also understood such products by (co) polymerization of the graft monomers are obtained in the presence of the graft base and incurred during processing.

Suitable acrylate rubbers according to D.2 of the polymers D are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on D.2, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C ₁ -C ₈ alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen C ₁ -C ₈ alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.

Monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as, for example, trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are Allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups exhibit.

Particularly preferred cross-linking Monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, Triacryloylhexahydro-s-triazine, triallylbenzenes. The amount of connected Monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft base D.2.

With cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base D.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base D.2 are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C ₁ -C ₆ alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base F.2 are emulsion polymers which have a gel content of at least 60% by weight.

Other suitable graft bases according to D.2 are silicone rubbers with graft-active sites, as described in the DE-A 3 704 657 . DE-A 3 704 655 . DE-A 3 631 540 and DE-A 3 631 539 to be discribed.

The gel content of the graft base D.2 is at 25 ° C in a suitable solvent determined (M. Hoffmann, H. Krömer, R. Kuhn, Polymer Analytics I and II, Georg Thieme-Verlag, Stuttgart 1977).

It also includes component D) preferably one or a mixture of two or more different Graft polymers with a graft base based on acrylates with a glass transition temperature below -5 ° C (such Graft polymers are generally referred to as acrylate rubbers and are known to the person skilled in the art) or one or a mixture of two or more different elastic block polymers, especially Two- or three-block copolymers based on vinyl aromatics and dienes, or mixtures of graft polymers and elastic block polymers, which are described in more detail as D ' and are encompassed by the general term component D.

The aforementioned also preferred acrylate rubbers D ') which can be used preferably include graft copolymers with rubber-elastic properties that consist essentially of at least 2 of the following monomers are available: (meth) acrylic acid ester with 1 to 18 carbon atoms in the alcohol component, chloroprene, 1,3-butadiene, Isopropene, styrene, acrylonitrile, ethylene, propylene and vinyl acetate, wherein the graft base contains at least one (meth) acrylic acid ester contains i.e. polymers, e.g. also in methods of organic Chemistry "(Houben-Weyl), Vol. 14/1, Georg Thieme-Verlag, Stuttgart 1961, pp. 393-406 and in C.B. Bucknall, "Thoughened Plastics ", Appl. Science Publishers, London 1977.

Preferred polymers D ') are partially crosslinked and have gel contents of over 5% by weight, preferably 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.

• D'.1) 95 bis 5, vorzugsweise 10 bis 80 Gew.-%, bezogen auf Komponente D, Pfropfauflage basierend auf mindestens einem polymerisierbaren, ethylenisch ungesättigten Monomeren als Pfropfmonomere und
• D'.2) 5 bis 95, vorzugsweise 20 bis 90 Gew.-%, bezogen auf Komponente D, Acrylatkautschuk mit einer Glasübergangstemperatur < –10°C, vorzugsweise < –20°C als Pfropfgrundlage. Besonders bevorzugt können D'.2) Polymerisate aus Acrylsäureestern oder Methacrylsäureestern enthalten, die bis zu 40 Gew.-%, bezogen auf D'.2) andere ethylenisch ungesättigte Monomere enthalten können.

Preferred acrylate rubbers D ') as component D) are graft copolymers containing

• D'.1) 95 to 5, preferably 10 to 80% by weight, based on component D, of graft based on at least one polymerizable, ethylenically unsaturated monomer as graft and
• D'.2) 5 to 95, preferably 20 to 90% by weight, based on component D, of acrylate rubber with a glass transition temperature of <-10 ° C, preferably <-20 ° C as the graft base. D'.2) may particularly preferably comprise polymers of acrylic acid esters or methacrylic acid esters which may contain up to 40% by weight, based on D'.2), of other ethylenically unsaturated monomers.

The acrylate rubbers according to D'.2 are preferably polymers made from acrylic acid alkyl esters or meth-acrylic acid alkyl esters, optionally with up to 40% by weight, based on D'.2, of other polymerizable, ethylenically unsaturated monomers. The preferred acrylic acid esters or methacrylic acid esters include C ₁ -C ₈ alkyl esters, in particular methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; and halogen alkyl esters, preferably halogen C ₁ -C ₈ alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.

Acrylic acid alkyl esters and methacrylic acid esters are preferably esters of acrylic acid or methacrylic acid with monohydric alcohols with 1 to 18 carbon atoms. Particularly preferred are methyl methacrylate, methyl ester and propyl ester, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate.

Graft monomers of the graft D'.1. are preferably selected from at least one monomer, preferably 2 or 3 monomers from the group consisting of styrene, α-methylstyrene, halogen- or methyl-core-substituted styrenes, (meth) -acrylic acid-C ₁ -C ₈ -alkyl esters, acrylonitrile, methacrylonitrile, maleic anhydride, C. ₁ -C ₄ alkyl- or phenyl-N-substituted maleimides or mixtures thereof.

• D'.1) 5 bis 95, vorzugsweise 10 bis 80, insbesondere 30 bis 80 Gew.-Teile, einer Mischung aus
• D'.1.1 50 bis 99, vorzugsweise 65 bis 90 Gew.-% Methylmethacrylat, Styrol, α-Methylstyrol, halogen- oder methylkernsubstituierten Styrolen oder Mischungen dieser Verbindungen und
• D'.1.2 1 bis 50, vorzugsweise 35 bis 10 Gew.-% Methylmethacrylat, Acrylnitril, Methacrylnitril, Maleinsäureanhydrid, C₁-C₄-alkyl- bzw. -phenyl-N-substituierten Maleinimiden oder Mischungen dieser Verbindungen auf
• D'.2) 5 bis 95, vorzugsweise 20 bis 90, insbesondere 20 bis 70 Gew.-Teilen Polymerisat auf Alkylacrylat-Basis mit einer Glasübergangstemperatur unter –10°C, vorzugsweise kleiner –20°C,

wobei die Summe der Gewichtsteile aus D'.1) und D'.2) 100 ergibt.Particularly preferred graft copolymers D ') comprise graft polymers from:

• D'.1) 5 to 95, preferably 10 to 80, in particular 30 to 80 parts by weight of a mixture of
• D'.1.1 50 to 99, preferably 65 to 90% by weight of methyl methacrylate, styrene, α-methylstyrene, halogen- or methyl-core-substituted styrenes or mixtures of these compounds and
• D'.1.2 1 to 50, preferably 35 to 10 wt .-% methyl methacrylate, acrylonitrile, methacrylonitrile, maleic anhydride, C ₁ -C ₄ alkyl or phenyl-N-substituted maleimides or mixtures of these compounds
• D'.2) 5 to 95, preferably 20 to 90, in particular 20 to 70 parts by weight of polymer based on alkyl acrylate with a glass transition temperature below -10 ° C, preferably less than -20 ° C,

where the sum of the parts by weight from D'.1) and D'.2) is 100.

• α 10 bis 70, vorzugsweise 15 bis 50, insbesondere 20 bis 40 Gew.-%, bezogen auf Pfropfpolymisat D', mindestens eines (Meth)-Acrylsäureesters oder 10 bis 70, vorzugsweise 15 bis 50, insbesondere 20 bis 40 Gew.-% eines Gemisches aus 10 bis 50, vorzugsweise 20 bis 35 Gew.-%, bezogen auf Gemisch, Acrylnitril oder (Meth)-Acrylsäureester und 50 bis 90, vorzugsweise 65 bis 80 Gew.-%, bezogen auf Gemisch, Styrol, als Pfropfauflage D'.1 auf
• β 30 bis 90, vorzugsweise 50 bis 85, insbesondere 60 bis 80 Gew.-%, bezogen auf Pfropfcopolymerisat D'), eine Pfropfgrundlage D'.2), die 70 bis 100 Gew.-% mindestens eines Alkylacrylates mit 1 bis 8 C-Atomen im Alkyrest, vorzugsweise n-Butylacrylat und/oder Methyl-n-Butylacrylat und/oder 2-Ethyl-hexylacrylat, insbesondere n-Butylacrylat als alleiniges Alkylacrylat, 0 bis 30, vorzugsweise 0 bis 15 Gew.-% eines weiteren copolymerisierbaren monoethylenisch ungesättigten Monomeren, wie Butadien, Isopren. Styrol, Acrylnitril, Methylmethacrylat oder Vinylmethylether oder deren Mischungen, 0 bis 5 Gew.-% eines copolymerisierbaren, polyfunktionellen, vorzugsweise bi- und trifunktionellen, die Vernetzung bewirkenden Monomeren, wobei sich die Gewichtsangaben auf das Gesamtgewicht der Pfropfgrundlage beziehen.

Graft copolymers D ') which are obtainable by grafting reaction of

• α 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight, based on graft polymisate D ', of at least one (meth) acrylic acid ester or 10 to 70, preferably 15 to 50, in particular 20 to 40% by weight a mixture of 10 to 50, preferably 20 to 35 wt .-%, based on the mixture, acrylonitrile or (meth) -acrylic acid ester and 50 to 90, preferably 65 to 80 wt .-%, based on the mixture, styrene, as graft D '.1 on
• β 30 to 90, preferably 50 to 85, in particular 60 to 80% by weight, based on the graft copolymer D '), a graft base D'.2) containing 70 to 100% by weight of at least one alkyl acrylate with 1 to 8 C. Atoms in the alkyl radical, preferably n-butyl acrylate and / or methyl n-butyl acrylate and / or 2-ethylhexyl acrylate, in particular n-butyl acrylate as the sole alkyl acrylate, 0 to 30, preferably 0 to 15% by weight of a further copolymerizable monoethylenically unsaturated monomers such as butadiene, isoprene. Styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof, 0 to 5% by weight of a copolymerizable, polyfunctional, preferably bifunctional and trifunctional, crosslinking monomer, the weight data relating to the total weight of the graft base.

Preferred graft polymers D ') based on acrylate rubbers are e.g. with (meth) acrylic acid alkyl esters and / or styrene and / or acrylonitrile grafted bases D'.2). acrylate n-butyl acrylate-based graft bases D'.2) are particularly preferred.

Particularly preferred graft polymers D ') based on Acrylate rubbers are in particular those that contain less than 5% by weight Polystyrene units, preferably less than 1% by weight of polystyrene units based on the total weight of the graft, particularly preferred contains no polystyrene units.

Component D) can also be a Mixture of different graft copolymers.

The gel fraction of the graft base β of the graft copolymer D ') is generally at least 20% by weight, preferably 40% by weight (measured in toluene) and the degree of grafting G generally 0.15 to 0.55.

The average particle diameter of the graft copolymer D ') is preferably 0.01 to 2 μm, more preferably 0.05 to 1.0, particularly preferably 0.1 to 0.08, in particular 0.1 to 0.4 μm.

The average particle diameter is determined, for example, on electron micrographs (TEM) of ultra-thin sections of the molding compositions according to the invention, treated with OsO ₄ and RuO ₄ , by measuring a representative amount (approx. 50) of particles.

The mean particle size d ₅₀ determined by means of ultracentrifugation (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796) is the diameter above and below which 50% by weight of the particles lie , The average particle size d _{50 of} the graft polymers D) (or D ') is preferably 0.08 to 0.6 μm, particularly preferably 0.1 to 0.4 μm.

The gel content of the graft bases D.2 (or D'.2) is at 25 ° C determined in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, polymer analysis I and II, Georg Thieme-Verlag, Stuttgart 1977).

The degree of grafting G denotes the weight ratio of grafted graft monomers to the graft base and is dimensionless.

The polymers are preferred for crosslinking D) based on acrylate rubbers can monomers with more than a polymerizable double bond can be copolymerized. preferred examples for crosslinking monomers are esters of unsaturated monocarboxylic acids 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms or saturated Polyols with 2 to 4 OH groups and 2 to 20 C atoms, e.g. ethylene glycol, allyl methacrylate; polyunsaturated heterocyclic compounds, e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate. Preferably cross-linking Monomers are allyl methacrylate, ethylene glycol dimethyl acrylate, diallyl phthalate and heterocyclic compounds containing at least 3 ethylenically unsaturated groups exhibit. Cyclic monomers are particularly preferred Monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, Triacryloylhexahydro-s-triazine, triallylbenzenes, acrylic acid esters of tricyclodecenyl alcohol.

The amount of crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight on the graft base D.2.

With cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base D.2.

The graft polymers D) can after known processes such as bulk, suspension, emulsion or bulk suspension processes getting produced.

Since in the graft reaction the graft monomers as is well known, not necessarily entirely based on the graft are grafted on, according to the invention, under graft polymers D) also understood those products which are obtained by polymerization of the Graft monomers can be obtained in the presence of the graft base.

The graft polymers D) are preferably used in compact form.

Component D) according to the invention further comprises Block polymers with rubber-elastic properties, in particular for example two (A-B) and three block copolymers (A-B-A). block copolymers A-B and A-B-A types show typical behavior of thermoplastic elastomers. The preferred block copolymers A-B and A-B-A contain one or two vinyl aromatic blocks (particularly preferably based on styrene) and a rubber block (Most preferably a diene rubber block, most preferred a polybutadiene block or isoprene block), in particular if appropriate also partially or completely can be hydrogenated.

Suitable block copolymers of the AB and ABA types are described, for example, in US-A 3,078,254 , 3 402 159, 3 297 793, 3 265 765 and 3 594 452 and in GB-A 1 264 741 , Examples of typical block copolymers of type AB and ABA are: polystyrene-polybutadiene (SBR), polystyrene-poly (ethylene-propylene), polystyrene-polyisoprene, poly (ε-methylstyrene) -polybutadiene, polystyrene-polybutadiene-polystyrene (SBR), polystyrene- Poly (ethylene-propylene) polystyrene, polystyrene-polyisoprene-polystyrene and poly (ε-methylstyrene) -polybutadiene-poly (ε-methylstyrene), as well as hydrogenated versions thereof such as, for example, and preferably hydrogenated polystyrene-polybutadiene-polystyrene (SEBS) and hydrogenated polystyrene polyisoprene (SEP). The use of corresponding hydrogenated block copolymers, optionally in a mixture with the non-hydrogenated precursor, as an impact modifier is described, for example, in DE-A 2 750 515 . DE-A 2 434 848 . DE-A 038 551 . EP-A 0 080 666 and WO-A 83/01254. Reference is hereby expressly made to the disclosure of the named publications.

Mixtures of the block polymers mentioned can can also be used.

Some are particularly preferred or completely hydrogenated block copolymers, particularly preferred are hydrogenated Polystyrene-polybutadiene-polystyrene (SEBS) and hydrogenated polystyrene-polyisoprene (SEP).

Such block polymers of type A-B and A-B-A are commercially available from a number of sources, such as. by Phillips Petroleum under the trade name SOLPRENE, from Shell Chemical Co. under the trade name KRATON, from Dexco under the trade name VECTOR and from Kuraray under the trade name SEPTON.

Component D) furthermore also comprises one or more rubber-modified graft polymers. The rubber-modified graft polymer D 'comprises a statistical (co) polymer composed of vinyl monomers D'.1, preferably according to D'.1.1 and D'.1.2, and a rubber D grafted with vinyl monomers, preferably according to D'.1.1 and D'.1.2 '.2. D is prepared in a known manner by free-radical polymerization, for example by an emulsion, bulk or solution or bulk-suspension polymerization process, for example in the US-A 3,243,481 described.

One or more graft polymers are preferred from 5 to 95, preferably 20 to 90% by weight of at least one vinyl monomer D'.1 to 95 bis 5, preferably 80 to 10 wt .-% of one or more graft bases D'.2 with glass transition temperatures <10 ° C, preferably <-10 ° C.

Preferred monomers D'.1.1 are styrene, α-methylstyrene, halogen- or alkyl nucleus-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (meth) acrylic acid C ₁ -C ₈ -alkyl esters such as methyl methacrylate, n-butyl acrylate and tert-butyl acrylate , Preferred monomers B.1.2 are unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) -acrylic acid-C ₁ -C ₈ -alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures thereof.

Particularly preferred monomers D'.1.1 are styrene, α-methylstyrene and / or methyl methacrylate, particularly preferred monomers D.1.2 are acrylonitrile, maleic anhydride and / or methyl methacrylate.

Monomers are particularly preferred D'.1.1 styrene and D'.1.2 acrylonitrile.

For the rubber-modified graft polymers D 'suitable rubbers D'.2 are, for example, diene rubbers, Acrylic, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers. Composites made from various of the rubbers mentioned are likewise suitable as a graft base.

Preferred rubbers D'.2 are diene rubbers (e.g. based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable vinyl monomers (e.g. according to D'.1.1 and D'.1.2), with the proviso that the glass transition temperature component D'.2 below 10 ° C, is preferably below -10 ° C. Pure polybutadiene rubber is particularly preferred. More copolymerizable Monomers can up to 50% by weight, preferably up to 30, in particular up to 20 % By weight (based on the rubber base D'.2) in the rubber base his.

Suitable acrylate rubbers according to D'.2 of the polymers D 'are preferably polymers of Acrylic acid alkyl esters, optionally with up to 40 wt .-%, based on D'.2 other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C ₁ to C ₈ alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halogen C ₁ -C ₈ alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base D'.2 are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C ₁ -C ₆ alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base D'.2 are emulsion polymers which have a gel content of at least 60% by weight.

Further suitable graft bases according to D'.2 are silicone rubbers with graft-active sites, as described, for example, in DE-A 3 704 657 to be discribed.

The compositions according to the invention can be used as Component E) still common Contain additives, generally up to 15, preferably in an amount of 0.01 to 10, particularly preferably 0.05 to 5, particularly preferably 0.1 to 3% by weight, based on the total weight the molding compositions can be added.

All common additives such as stabilizers (for example UV stabilizers, thermal stabilizers), antistatic agents, Flow aids, Mold release agents, fire protection additives, emulsifiers, nucleating agents, Plasticizer, lubricant, pH degrading additives (e.g. compounds containing carboxyl groups), Additives for increasing the conductivity, Dyes and pigments are possible. The above and others suitable additives are described for example in Gächter, Müller, plastic additives, 3rd edition, Hauser-Verlag, Munich, Vienna, 1989. The additives can used alone or in a mixture or in the form of masterbatches become. The additives can admixed and / or applied to the surface.

As stabilizers can Example sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary Amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, and variously substituted representatives of these Groups and their mixtures are used.

As nucleating agents e.g. Sodium phenyl phosphinate, aluminum oxide, silicon dioxide as well as preferred Talc and the nucleating agents described above are used become.

As a lubricant and mold release agent can Ester waxes, penteritol stearate (PETS), long chain fatty acids (e.g. stearic acid or behenic acid), their salts (e.g. Ca or Zn stearate) and amide derivatives (e.g. ethylene bis-stearylamide) or Montan waxes (mixtures of straight - chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes be used.

For example, phthalic acid dioctyl esters, phthalate, phthalate, Hydrocarbon oils, N- (n-butyl) benzenesulfonamide can be used.

In order to obtain conductive molding compounds can Russian, conductivity Russian, Carbon fibrils, nanoscale graphite fibers (nanotubes), graphite, conductive Polymers, metal fibers and other common additives to increase the conductivity be added.

Commercially available organic halogen compounds with synergists or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds can be used individually or as a mixture as flame retardants. Mineral flame retardants such as magnesium hydroxide or Ca-Mg carbonate hydrates (e.g. DE-A 4 236 122 ) can be used. Examples of halogen-containing, in particular brominated and chlorinated, compounds are: ethylene-1,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabrom polyacrylate, brominated polystyrene. Suitable phosphorus compounds according to WO-A 98/17720 (PCT / EP / 05705) are suitable as organic phosphorus compounds, for example triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) including oligomers and bisphenol A bis-diphenyl phosphate including oligomers (cf. eg EP-A 363 608 and EP-A 640 655 ), Melamine phosphate, melamine pyrophosphate, melamine polyphosphate and mixtures thereof. Melamine and melamine cyanurate are particularly suitable as nitrogen compounds. Examples of suitable synergists are antimony compounds, in particular antimony trioxide and antimony pentoxide, zinc compounds, tin compounds such as tin stannate and borates. Carbon formers and and tetrafluoroethylene polymers can be added. The flame retardants, optionally with a synergist, such as antimony compounds, and antidripping agents are generally used in an amount of up to 30, preferably 20% by weight (based on the total composition).

As additives, too reinforcing materials e.g. be added in the form of glass fibers.

As component F), the thermoplastic molding compositions may also contain a filler or reinforcing material or a mixture of two or more different fillers and / or reinforcing materials, for example based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate , Chalk, feldspar, barium sulfate, glass balls and / or fiber shaped fillers and / or reinforcing materials based on carbon fibers and / or glass fibers. Mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulfate and / or glass fibers are preferably used. Mineral particulate fillers based on talc, wollastonite and / or glass fibers are particularly preferred according to the invention. Fillers based on talc are most preferred.

Especially for applications where isotropy dimensional stability and high thermal dimensional stability is required, such as in automotive applications for exterior parts of the body prefers mineral fillers used, particularly preferably talc, wollastonite or kaolin.

Needle-shaped mineral ones are also particularly preferred Fillers. Under acicular mineral fillers according to the invention becomes a mineral filler with pronounced acicular character Roger that. Needle-shaped wollastonites are an example. The mineral preferably has a length: diameter ratio of 2: 1 to 35: 1, particularly preferably from 3: 1 to 19: 1, most preferred from 4: 1 to 12: 1. The average particle size of the acicular minerals according to the invention is preferably less than 20 μm, particularly preferably at less than 15 μm, particularly preferably at less than 10 μm, most preferably less than 5 μm, determined with a CILAS GRANULOMETER.

Most preferred as a component D) become mineral fillers based on talk. As mineral fillers based on talc In the context of the invention, all particulate fillers that the person skilled in the art can consider connects with talc or talc. Also come all particulate fillers that are offered commercially and their product descriptions as characteristic features containing the terms talc or talc, question.

Mineral fillers are preferred, which have a talc content according to DIN 55920 of greater than 50% by weight, preferably greater than 80% by weight, particularly preferably greater than 95% by weight and particularly preferably greater than 98% by weight based on the total mass of filler exhibit.

The mineral fillers based on talc also surface treated his. For example, you can with an adhesion promoter system e.g. be equipped on a silane basis.

The mineral fillers according to the invention based on talc preferably have an upper particle or grain size d97 smaller 50 μm, preferred less than 10, particularly preferably less than 6 and particularly preferred less than 2.5 μm. The average grain size is d50 preferably a value less than 10, preferably less than 6, particularly preferably less than 2 and particularly preferably less than 1 μm. The d97 and d50 values of the fillers D according to sedimentation analysis SEDIGRAPH D 5000 or after Sieve analysis DIN 66 165 determined.

The average aspect ratio (diameter to thickness) of the particulate fillers based on talc is preferably in the range 1 to 100, especially preferably 2 to 25 and particularly preferably 5 to 25 on electron micrographs of ultra thin sections of the finished products and measuring a representative quantity (approx. 50) of Filler particles.

The filler and / or reinforcing material can be surface modified if necessary be, for example with an adhesion promoter or adhesion promoter system e.g. based on silane. However, pretreatment is not essential required. In particular when using glass fibers, in addition to Silanes also polymer dispersions, film formers, branching agents and / or Glass fiber processing aids are used.

Glass fibers are also particularly preferred according to the invention, which generally prefers a fiber diameter between 7 and 18 between 9 and 15 μm can have as continuous fibers or as cut or ground glass fibers are added, the fibers using a suitable sizing system and an adhesion promoter or adhesion promoter system e.g. based on silane equipped could be.

q eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4
r eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2
k eine ganze Zahl von 1 bis 3, bevorzugt 1Common silane compounds for pretreatment have the general formula, for example (X- (CH2) q) k -Si- (O-C r H 2r + 1) 4-k in which the substituents have the following meaning:
x NH2-, HO-,

q is an integer from 2 to 10, preferably 3 to 4
r is an integer from 1 to 5, preferably 1 to 2
k is an integer from 1 to 3, preferably 1

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes, which are substituents X. Contain glycidyl group.

The silane compounds are generally in amounts of 0.05 to, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight based on the mineral filler for surface coating used.

The particulate fillers can be due to processing to the molding compound or molding in the molding compound or in the molding a smaller d97 or have a d50 value than those originally used Fillers. The glass fibers can due to the processing to the molding compound or molding in the molding compound or in the molding shorter length distributions than originally used on.

The particle diameter at the finished Product can can be determined, for example, by the fact that electron microscopic Images of thin sections of the polymer mixture and at least 25, preferably at least 50 filler particles for the Evaluation can be used.

The preparation of the used according to the invention Compositions are carried out by methods known per se Mixing the components. Individual components can be advantageous premix. The components are preferably mixed A to D and other components at temperatures from 220 to 330 ° C through kneading, extruding or rolling the components together.

The compositions used according to the invention can according to usual Processes for semi-finished or molded parts of all types are processed. As examples of Processing methods are extrusion and injection molding called. As examples of Semi-finished products are called foils and plates.

According to the invention, the molded parts are subsequently lacquered in their manufacture with at least one aqueous lacquer, whereby when using multilayer coating systems, in which the individual Paint layers through the use of solvent-based or aqueous Paints can be produced at least according to the invention the layer of lacquer that is applied directly to the substrate is watery.

aqueous Paint systems can contain up to 30% organic co-solvent. Current state The technology is systems with an organic co-solvent content of 10-5%. Ideally have watery Lacksysteme no co-solver.

Co-solvers are those in the paint industry paint solvent used. Among other things, you will for dispersing and also as a coalescing aid needed.

aqueous Paint systems can 1K systems, e.g. physically drying systems or systems with blocked hardeners those at elevated Temperatures are deblocked and then by a chemical reaction network, or 2K. Harden 2K systems through a chemical reaction, with one reactant already would react to storage conditions. Therefore, the components are only together shortly before application mixed. 2K systems have the disadvantage of more complex plant technology and the limited time Processability after mixing. The advantage of 2K systems is that better quality the resulting coating.

The watery ones deserve special mention here 2K PUR lacquers, which act as a crosslinking mechanism, the reaction of isocyanate groups with OH groups.

For an optimal painting result the substrate must be clean. This is done in industrial scale frequently guaranteed by the use of a "power wash system". But there is also the possibility here with the help of solvents the surface to clean.

• – Beflämmung
• – Fluorierung
• – Plasmabehandlung

oder Coronabehandlung aktiviert werden.If the surface polarity is not sufficient after cleaning, the surface can be cleaned by

• - flame treatment
• - fluorination
• - plasma treatment

or corona treatment can be activated.

There is also the possibility create a paint adhesion by using a primer.

Electrically conductive surfaces can be used generate from so-called leading primers.

The molded parts are preferred without Pretreatment after cleaning directly with an aqueous varnish painted. It is in a very particularly preferred form with the watery Paint around a color-imparting hydrobase paint. This can preferably Hydrobasis paint with a layer of a solvent-based, aqueous or solvent-free Clear lacquer coated become.

Those used according to the invention are particularly preferred Molding compounds for molded parts in the interior and exterior, preferably in the automotive exterior such as bumpers, fenders, doors or Door parts, Fuel filler caps, bonnets, covers and rear covers, air intake grilles, Spoilers, loading areas, covers for loading areas, roofs or Roof parts processed and painted with at least one hydro lacquer. The molded parts can small or large his.

Moldings or semi-finished products from the molding compositions / compositions used according to the invention conditions can also be in combination with other materials such as metal or plastic. The molding compositions according to the invention or the molded parts / semifinished products from the molding compositions used according to the invention can be made by conventional techniques of connecting and joining together several components or parts such as coextrusion, film injection molding, insert molding, gluing, welding, screwing or clamping in combination with other materials can even be used for the production of finished parts such as exterior body parts.

The moldings according to the invention can also for numerous other applications coated with hydraulic paints can be used. Examples include use in electrical and Electronics technology, as well as in the construction sector. In the areas of application mentioned can Moldings from the molding compositions according to the invention for example as lamp covers, as safety disks, as housing material for electronic Equipment, as housing material for household appliances, as Plates can be used to make covers.

The molded parts according to the invention on Basis of the molding compositions according to the invention are characterized by excellent paint adhesion. The paint liability can for example by cross-cut test, tape test and / or prefers the steam jet test according to DaimlerChrysler standard DBL 5431. The paint adhesion in the molding compositions according to the invention is in particular especially in those areas where shear friction occurs during demoulding of the molded part occurs, very critical. In addition, the Molding compositions according to the invention high requirements regarding processing stability, flowability the melt, toughness, Low temperature toughness, Rigidity, heat resistance, thermal expansion, surface quality, paintability, chemical resistance and fuel resistance.

component A

Linear polybutylene terephthalate (Pocan B 1500, commercial product from Bayer AG, Leverkusen, Germany) with an intrinsic viscosity of approx. 1.25 cm ³ / g (measured in phenol: 1,2-dichlorobenzene = 1: 1 at 25 ° C)

component B

Polyethylene terephthalate: It is polyethylene terephthalate with an intrinsic viscosity IV of 0.74 cm ³ / g and an isothermal crystallization time at 215 ° C of approx. 4.2 minutes.

The intrinsic viscosity is measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.

• 1. Aufheizen von 30°C bis 290°C mit 40°C/min,
• 2. 5 min. isotherm bei 290°C,
• 3. Kühlen von 290°C auf 215°C mit 160°C/min,
• 4. 30 min isotherm bei 215°C (Kristallisationstemperatur).

The isothermal crystallization time of PET is determined with the DSC method (differential scanning calometry) with a PERKIN ELMER DSC 7 differential scanning calometer (weight approx. 10 mg, perforated aluminum pan) with the following temperature program:

• 1. heating from 30 ° C to 290 ° C at 40 ° C / min,
• 2.5 minutes. isothermal at 290 ° C,
• 3. cooling from 290 ° C to 215 ° C at 160 ° C / min,
• 4. Isothermal for 30 min at 215 ° C (crystallization temperature).

The evaluation software is PE Thermal Analysis 4.00.

component C

Linear polycarbonate (Makrolon 2805 from Bayer AG, Leverkusen, Germany) based on bisphenol A. a viscosity ηrel. of approx.1.29 (measurement conditions: 5 g polycarbonate per liter methylene chloride, 25 ° C) and a molecular weight Mw of approx. 29,000 g / mol (determined using GPC methods against a polycarbonate standard).

component D

ABS graft copolymer (type P7528B4, Trial product from Bayer AG, Leverkusen) with a particle size of 280 up to 400 nm.

component e

Component E was used as an additive a mix of more common Stabilizers, nucleating agents and mold release agents are used.

Compounding was done on one ZSK32 twin-screw extruder (Werner and Pfleiderer) at melt temperatures from 250 to 290 ° C.

The test specimens were on an injection molding machine Arburg 320-210-500 at melt temperatures of 260 to 280 ° C and mold temperatures from 70 to 90 ° C sprayed.

The molding compositions according to the invention were tested using the following methods:
Vicat B: heat resistance or heat resistance according to DIN ISO 306 / B 120 in silicone oil.
Izod impact strength: toughness according to ISO 180 method 1 U at –50 ° C.
Izod impact strength: toughness according to ISO 180 method 1A at –20 ° C
Tension module: rigidity according to DIN / EN / ISO 527-2 / 1A.
Elongation at break: Elongation determined according to DIN / EN / ISO 527-2 / 1A.
Melt viscosity: Determined according to DIN 54811 / ISO 11443 at 280 ° C and a shear rate of 1000s ^–1 with the Viscorobo 94.00 from Göttfert after drying the granules at 120 ° C for 4 hours in a vacuum dryer.

The paint adhesion is checked through the steam jet test according to DaimlerChrysler standard 5431.

For paint adhesion, so-called friction coefficient plates with a melt temperature of 280 ° C. and a mold temperature of 60 ° C. are produced from the molding compositions according to the invention, in which shear friction is applied during the demolding process. The friction coefficient plates are round plates according to the following sketch. After the tool has been filled, the stamp is rotated by 37 ° at a stamp pressure of 50 N / cm ² in the edge region of the circle over a period of 15 s. The stamp is then removed from the surface. The coefficient of friction tool used to manufacture coefficient of friction plates is described, for example, in PCT 02/03211.

After the injection molding, the plates were stored for about 1 week at room temperature, then tempered at 80 ° C for 30 min and subsequently with the hydrobase lacquer of type 101894 (color Obsedian black, from Wörwag, Stuttgart) painted. Subsequently the plates are left for about 5 minutes at room temperature and then about 30 min at about 70 ° C dried. The dry film thickness is approximately 8 to 12 μm. Then be the plates with a solvent-based Clear varnish of type 68945 (Fa.

Wörwag, Stuttgart) painted, about 7 min at room temperature and then about 40 min at 80 ° C dried. The dry film thickness is approximately 30 μm.

The painted panels are about Stored for 1 week at room temperature. Then was in four places in the ring (following sketch), in which the shear friction during demolding the molded part was applied, a cross cut and the steam jet test carried out according to DBL standard 5431. A total of 12 tests were carried out per test performed on 4 plates of a lot.

The assessment of paint adhesion is based on DBL 5431:
0 = no failure, all right
1 = peeling up to 2 mm ² , all right
2 = peel 0.5 mm per side, all right
3 = flaking up to 40 mm ^{2 in area} , not in order
4 = Large-scale flaking up to 250 mm ² , not in order
5 = Large-scale spalling in beam size> 250 mm ² , not in order

As can be seen from Table 1 molding compositions according to the invention, which both component A, such as polybutylene terephthalate, as well as component B, such as polyethylene terephthalate (E.g. 1, 2 and 3) a lower default rate and a better rating in the steam jet test according to DBL 5431 and thus better paint adhesion the hydrocoats as the comparative examples, in which only component A or component B was used.

The mechanical properties that Heat resistance and the viscosity remain almost unaffected and in any case meet the requirements for the Molding compounds.

The composition and properties of the thermoplastic molding compositions according to the invention are shown in Table 1. Table 1

Claims (5)

Use of compositions containing A) 4 to 80, preferably 10 to 60, particularly preferably 12 to 40, in particular 15 to 30 parts by weight of at least one polyalkylene terephthalate, preferably at least one polybutylene terephthalate, B) 4 to 80, preferably 6 to 60 , particularly preferably 8 to 40, in particular 10 to 30 parts by weight of at least one polyalkylene terephthalate with an alkylene chain length different from component A, preferably at least one polyethylene terephthalate, C) 10 to 90, preferably 20 to 80, particularly preferably 25 to 60, in particular 35 to 55 parts by weight, at least one aromatic polycarbonate, D) 1 to 30, preferably 3 to 25, particularly preferably 6 to 20, in particular 8 to 16 parts by weight, at least tens of a rubber-elastic polymer or graft copolymer, E) 0.1 to 20 parts by weight, preferably 0.15 to 15 parts by weight, particularly preferably 0.2 to 10 parts by weight of conventional additives and processing aids, which together add 100 parts by weight . Parts give, optionally additionally containing F) 0 to 60, preferably 2 to 45, particularly preferably 4 to 30 parts by weight, of at least one particulate mineral filler for the production of coated molded parts, molded articles being produced from A) - F) and they are coated with hydraulic lacquers, whereby in the case of multi-layer lacquer systems with different solvents, at least the solvent of the first, lowest lacquer layer must be water-based. Use according to claim 1, the molded parts being cleaned and / or pretreated before painting become. Molded parts and / or semi-finished products made according to claim 1 and / or claim 2. Use of the molded parts according to claim 3 in the electrical and electronics technology and in the construction sector. Use of the molded parts according to claim 3 as external parts of motor vehicles.