DE102004022108A1 - Homogeneously colored, weathering-stable compositions based on impact-modified polyalkylene terephthalate / polycarbonate blends - Google Patents

Abstract

A weatherable homogeneously colored thermoplastic molding composition is disclosed. The composition that contains polyalkylene terephthalate, aromatic polycarbonate, a graft polymer based on polybutadiene, a graft polymer based on acrylate, a UV stabilizer and a coloring agent is suitable for making a variety of finished and semi finished products suitable for uses in the exterior or motor vehicles.

Description

The The present invention relates to colored, weather-stabilized Compositions based on impact-modified polyalkylene terephthalate / polycarbonate blends and molding compositions, semi-finished and molded parts produced therefrom unpainted or only coated with a transparent clearcoat for example Automotive exterior applications be used.

Schlagzähmodifzierte Molding compounds, the partially crystalline polyester, amorphous polycarbonates and graft copolymers are known. Such molding compounds For example, in the automotive sector, moldings such as bumpers, mudguards, radiator grilles, Screens, rear panels, sills, spoilers, door handles, gas caps, panels, horizontal components such as bonnets or roof elements, door modules or the like. Requirements for The use in automotive applications are high heat resistance, high flowability in the melt, good paint adhesion, high chemical resistance, high rigidity, high dimensional stability and high low temperature toughness.

The Coloring of molded parts made of impact-modified polyalkylene terephthalate / polycarbonate blends can be done by two different methods. Becoming traditional the moldings with a coloring paint, the so-called base coat, painted. Before the basecoat can the moldings optional as well have been coated with primer and / or filler. On the base coat can also optionally a transparent clearcoat can be applied. These systems are hereinafter referred to as topcoated systems. For the topcoats Systems, the intrinsic color of the molding compositions is essentially irrelevant, because the coloring is done by the basecoat.

alternative to the topcoated systems, there are systems below by colored Systems ("molded-in called "color") become. In through-colored Systems is the color of the molding in the application through the The inherent color of the molding composition determines, that is through-colored systems are not with a primer, filler or coloring basecoat varnished. optional can the through-colored However, systems should be coated with transparent clearcoat. Of the Advantage in through-colored Systems lies in the cost savings, since the working steps of the Primer with primer and / or filter and painting with coloring base coats and the associated drying accounts.

Of the Use of molded parts made of impact-modified polyalkylene terephthalate-polycarbonate blends in the automotive exterior brings high demands on the weather resistance of the material Moldings with it. Here are the resistance to photooxidation by UV irradiation (hereinafter referred to as UV stability referred to) and the resistance the materials against hydrolyzing environmental influences (hereinafter as hydrolysis stability referred) of central importance.

at Topcoated systems, the harmful UV rays are largely retained by the basecoat. In through-colored Systems, however, is not a UV blocking function of a covering basecoat given. At best, a UV-absorbing clearcoat in through-colored systems the majority of harmful Prevent UV radiation. Still have to Molding compounds that are colored through Systems have a high UV stability, which is why impact modifiers based on rubbers with conjugated dienes, such as Butadiene in ABS or MBS rubbers, not used alone can be.

Stable weather PC / polyester blends therefore use, for example, acrylate rubbers a, as described in DE-A 33 02 124.

EP-B 0 787 769 describes the use of PC / polyester blends with a Combination of AES and acrylate rubbers to molding compounds with improved weathering stability and good toughness to obtain.

The Hydrolytic stability the impact-modified Polyalkylene terephthalate / polycarbonate blends is particularly required when the molded parts made of these materials during the life of the vehicle in conditions with high outside temperature and high humidity.

US Pat. No. 5,354,791 describes the use of epoxy-substituted polyalkylene terephthalate molding compositions in combination with metal-containing phosphorus compounds in impact-modified polyalkylene terephthalate / polycarbonate blonds to improve hydrolysis stability. The improvement of the hydroly Se stability is described here by the slight change in the melt viscosity after storage of the material at 110 ° C. in water in an autoclave. The UV resistance and the surface finish are not content of US-A 5,354,791.

at dyed However, systems are not only weatherproof but also homogeneous colorability from very big Importance. Especially with impact-modified PC / polyester blends with weather-resistant acrylate impact modifiers occur in injection moldings unwanted Farbinhomogenitäten on in which are perpendicular to the flow direction during the injection molding process periodically recurring less colored areas which are optically appear lighter, with deeper colored Forming areas that are visually darker or more colorful, which are also referred to as Tiegerstreifen. For molded parts used in the final application such as automotive outer skin - e.g. Fender, Bumper, tailgate, Cover, spoiler, air intake grille, bonnet, car roof, vehicle interior, Electrical enclosure, Electronic housing, which are visually perceived by the user, these are tiger stripe effects not acceptable.

task was the development of homogeneously colored toughened Polyalkylene terephthalate / polycarbonate molding compounds with improved Weathering resistance for applications in so-called colored Systems ("molded in color ") dyed Systems are increased Requirements for the homogeneous coloring of the molding compositions or the Formed parts, since the molding material coloring at the same time for the color appearance of the finished molding is responsible in the application.

Surprised has now been found that molding compositions based on polyalkylene terephthalate / polycarbonate fulfill the task if as an impact modifier at least two different systems based on graft copolymer compositions based on acrylates on the one hand and on the basis of butadiene on the other in combination with stabilizers to increase UV resistance and used to improve the hydrolysis resistance. The moldings of the molding compositions according to the invention are distinguished by homogeneous appearance and homogeneous color impression of the surface and excellent weathering stability. In addition, the by molding compositions according to the invention high heat resistance, good flowability in the melt, good paint adhesion, high chemical resistance, high rigidity, high dimensional stability and high low temperature toughness out.

• A) 4 bis 80 Gew.-Teile, vorzugsweise 10 bis 60 Gew.-Teile, besonders bevorzugt 12 bis 50 Gew.-Teile, insbesondere 19 bis 40 Gew.-Teile, mindestens eines Polyalkylenterephthalats, bevorzugt eines Polyethylenterephthalats oder eine Polybutylenterephthalats, besonders bevorzugt eines Polybutylenterephthalats.
• B) 10 bis 90 Gew.-Teile, vorzugsweise 20 bis 80 Gew.-Teile, besonders bevorzugt 25 bis 60 Gew.-Teile, insbesondere 30 bis 60 Gew.-Teile, mindestens eines aromatischen Polycarbonats,
• C) 1,5 bis 30 Gew.-Teile, vorzugsweise 3 bis 25 Gew.-Teile, besonders bevorzugt 4 bis 20 Gew.-Teile, insbesondere 5 bis 15 Gew.-Teile, mindestens eines Pfropfpolymerisats auf Basis von Polybutadien als Kautschukkomponente.
• D) 1,5 bis 30 Gew.-Teile, vorzugsweise 3 bis 25 Gew.-Teile, besonders bevorzugt 4 bis 20 Gew.-Teile, insbesondere 5 bis 15 Gew.-Teile, mindestens eines Pfropfpolymerisats auf Basis von Acrylaten als Kautschukkomponente,
• E) 0,01 bis 5 Gew.-Teile, vorzugsweise 0,05 bis 3 Gew.-Teile, besonders bevorzugt 0,1 bis 1 Gew.-Teile eines UV-Stabilisatoren,
• F) 0,01 bis 10 Gew.-Teile, bevorzugt 0,05 bis 6 Gew.-Teile, besonders bevorzugt 0,1 bis 3 Gew.-Teile Farbmittel,
• G) 0 bis 5 Gew.-Teile, vorzugsweise 0,05 bis 3 Gew.-Teile, besonders bevorzugt 0,1 bis 2 Gew.-Teile Hydrolysestabilisatoren, bevorzugt auf Basis Epoxyverbindungen,
• H) 0 bis 54 Gew.-Teile, vorzugsweise 3 bis 34 Gew.-Teile, besonders bevorzugt 6 bis 25, insbesondere 8 bis 21 Gew.-Teile, mindestens eines teilchenförmigen mineralischen Füllstoffs,
• I) 0 bis 10 Gew.-Teile, bevorzugt 0,05 bis 3 Gew.-Teile, besonders bevorzugt 0,1 bis 0,9 Gew.-Teile weiterer Additive.

The invention relates to compositions containing

• A) 4 to 80 parts by weight, preferably 10 to 60 parts by weight, more preferably 12 to 50 parts by weight, especially 19 to 40 parts by weight, of at least one polyalkylene terephthalate, preferably a polyethylene terephthalate or a polybutylene terephthalate, especially preferably a polybutylene terephthalate.
• B) 10 to 90 parts by weight, preferably 20 to 80 parts by weight, particularly preferably 25 to 60 parts by weight, in particular 30 to 60 parts by weight, of at least one aromatic polycarbonate,
• C) 1.5 to 30 parts by weight, preferably 3 to 25 parts by weight, particularly preferably 4 to 20 parts by weight, in particular 5 to 15 parts by weight, of at least one graft polymer based on polybutadiene as the rubber component.
• D) 1.5 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 4 to 20 parts by weight, in particular 5 to 15 parts by weight, of at least one graft polymer based on acrylates as rubber component,
• E) 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 1 part by weight of a UV stabilizer,
• F) 0.01 to 10 parts by weight, preferably 0.05 to 6 parts by weight, particularly preferably 0.1 to 3 parts by weight of colorant,
• G) 0 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight of hydrolysis stabilizers, preferably based on epoxy compounds,
• H) 0 to 54 parts by weight, preferably 3 to 34 parts by weight, more preferably 6 to 25, in particular 8 to 21 parts by weight, of at least one particulate mineral filler,
• I) 0 to 10 parts by weight, preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 0.9 parts by weight of further additives.

As component A, the compositions according to the invention contain one or a mixture of two or more different polyalkylene terephthalates. Polyalkylene terephthalates in the context of the invention are polyalkylene terephthalates which are derived from terephthalic acid (or its reactive derivatives) and alkanediols, for example based on ethylene glycol, propylene glycol or butanediol. According to the invention as component A preferably polybutylene terephthalate, polytrimethylene terephthalate and / or Polyethy lenterephthalate, more preferably polybutylene terephthalate and / or polyethylene terephthalate, most preferably polybutylene terephthalate used.

polyalkylene For the purposes of the invention are reaction products of aromatic dicarboxylic acids or their reactive Derivatives (e.g., dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these Reaction products.

preferred Polyalkylene terephthalates can be prepared from terephthalic acid (or their reactive derivatives) and aliphatic or cyctoaliphatic diols having 2 to 10 C atoms according to known methods (Kunststoff-Handbuch, Vol. VIII, P. 695 ff., Karl-Hanser-Verlag, Munich 1973).

preferred Polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mole%, preferably at least 90 mole% to the diol component, ethylene glycol and / or propanediol-l, 3 and / or butanediol-1,4-residues.

The preferred polyalkylene terephthalates may be in addition to terephthalic acid residues up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms contained, such as residues of phthalic acid, isophthalic acid, Naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid.

The Preferred polyalkylene terephthalates may be in addition to ethylene or propanediol-l, 3-glycol residues or Butanediol-l, 4-glycol residues up to 20 mol .-% of other aliphatic Diols with 3 to 12 C atoms or cycloaliphatic diols with G to 21 carbon atoms, e.g. Remains of 1,3-propanediol, 2-ethylpropane-1,3-diol, neopentyl glycol, Pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-methyl-pentanediol-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.

The Polyalkylene terephthalates can by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, as they are e.g. in DE-A 19 00 270 and US-A 3,692,744 are to be branched. Examples of preferred branching agents are trimesic acid, Trimellitic acid, trimethylolethane and -propane and pentaerythritol.

It it is advisable, not more than 1 mol .-% of the branching agent, based to the acid component, too use.

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

preferred Polyalkylene terephthalates are also copolyesters which consist of at least two of the above acid components and / or at least two of the abovementioned alcohol components particularly preferred copolyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.

The Polyalkylene terephthalates generally have an intrinsic viscosity from about 0.4 to 1.5, preferably 0.5 to 1.3, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.

Prefers can the invention to be used Polyalkylene terephthalates also in admixture with other polyesters and / or other polymers are used. Especially preferred are mixtures of polyalkylene terephthalates with other polyesters, most preferably mixtures of polybutylene terephthalate with Polyethylene terephthalate used.

The Mixtures can be conventional additives such as. Mold release agents, stabilizers and / or flow agents be mixed in the melt or applied to the surface.

When Component B according to the invention contain a polycarbonate according to the invention or a mixture of polycarbonates.

Preferred polycarbonates are those 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, which contains one or more aromatic groups.

worin
A für eine Einfachbindung, C₁-C₅-Alkylen, C₂-C₅-Alkyliden, C₅-C₆-Cycloalkyliden, -O-, -SO-, -CO-, -S-_; -SO₂-, C₆-C₁₂-Arylen steht, an das weitere aromatische gegebenenfalls Heteroatome enthaltende Ringe kondensiert sein können.
oder für einen Rest der Formel (II) oder (III)

steht, und
B für jeweils C₁-C₁₂-Alkyl, vorzugsweise Methyl, Halogen, vorzugsweise Chlor und/oder Brom steht,
x jeweils unabhängig voneinander für 0, 1 oder 2 steht,
p für 1 oder 0 steht,
R¹ und R² für jedes X¹ individuell wählbar ist und unabhängig voneinander für Wasserstoff oder C₁-C₆-Alkyl, vorzugsweise Wasserstoff, Methyl oder Ethyl stehen,
X¹ für Kohlenstoff steht und
m für eine ganze Zahl von 4 bis 7, bevorzugt für 4 oder 5 steht, mit der Maßgabe, dass an mindestens einem Atom X¹, R¹ und R² gleichzeitig für Alkyl stehen.Preference is given to bisphenols of the formula (Ia)

wherein
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 ₂ -, C ₆ -C ₁₂ -arylene, to which more aromatic optionally heteroatom-containing rings may be condensed.
or a radical of the formula (II) or (III)

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

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

Also Derivatives of said bisphenols, for example by alkylation or halogenation on the aromatic rings of said bisphenols accessible are, are examples of 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-phenyl-ethane, 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 (ie, 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 (ie bisphenol M), α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene and indanebisphenol.

Especially 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 based on the two monomers bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

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

The abovementioned bisphenols and processes for their preparation belong to the prior art,
so also the 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
and the indanbisphenols. Indanibisphenols can be prepared, for example, from isopropenylphenol or its derivatives or from diners of isopropenylphenol or its derivatives in the presence of a Friedel-Craft catalyst in organic solvents.

polycarbonates can be prepared by known methods. Suitable methods for the production of polycarbonates are, for example, the preparation from bisphenols with phosgene according to the phase interface method or from bisphenols with phosgene by the method in homogeneous Phase, the so-called pyridine process, or from bisphenols mt Kohlensäureestern after the melt transesterification process. These production methods are e.g. described in H. Schnell, "Chemistry and Physis of Polycarbonates ", Polymer Reviews, Vol. 9, pp. 31-76, Interscience Publishers, New York, London, Sidney, 1964.

The Melt transesterification process is specifically described in H. Quick, "Chemistry and Physics of Polycarbonates ", Polymer Reviews, Vol. 9, pp. 44 to 51, Interscience Publishers, New York London Sidney, 1964.

at The production of polycarbonate are preferred raw materials and Excipients used with a low level of impurities. In particular, in the preparation of the melt transesterification process should 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 ester, and the bisphenols recrystallized, washed or distilled.

The polycarbonates to be used 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. More preferably, they have a weight average molecular weight of 12,000 to 80,000 g / mol, more preferably 20,000 to 35,000 g / mol.

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

suitable Chain terminators are both monophenols and monocarboxylic acids. suitable Monophenols are e.g. Phenol, p-chlorophenol, p-tert-butylphenol, Cumylphenol or 2,4,6-tribromophenol, and long-chain alkylphenols, e.g. 4- (1,1,3,3-tetramethylbutyl) -phenol or monoalkylphenols or dialkylphenols having a total of 8 to 20 C atoms in the alkyl substituents such as. 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 to be used Kettenabbrechem is preferably between 0.25 and 10 mol%, based on the sum of the bisphenols used in each case.

The used according to the invention Polycarbonates can be branched in a known manner, preferably by the Incorporation of trifunctional or more than trifunctional branching agents. Suitable branching agents are e.g. those with three or more than three phenolic groups or those having three or more than three carboxylic acid groups.

According to the invention suitable Branches are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tr- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tris (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-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -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 and 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.

Prefers Branches to be used are 1,1,1-tris (4-hydroxyphenyl) ethane and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The Amount of optionally used branching agent is preferred 0.05 mol% to 2 mol%, based on moles of bisphenols used.

The Branches can For example, in the case of production of the polycarbonate after Phase boundary process with the bisphenols and the chain terminators in the aqueous alkaline Phase are submitted, or in an organic solvent solved together with the carbonic acid derivatives be added. In the case of the transesterification process, the Branching agent preferably together with the dihydroxyaromatics or bisphenols dosed.

Prefers catalysts to be used in the production of polycarbonate after the melt transesterification process are known from the literature Ammonium salts and phosphonium salts.

Copolycarbonates can also be used according to the invention. Copolycarbonates according to the invention are in particular polydiorganosiloxane-polycarbonate block copolymers whose weight average molar mass ( M _w ) is preferably 10,000 to 200,000 g / mol, more preferably 20,000 to 50,000 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, more 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, more preferably 15 to 3% by weight. The polydiorganosiloxane-polycarbonate block copolymers can be prepared, for example, starting from polydiorganosiloxanes containing α, ω-bis-hydroxyaryloxy end groups having an average degree of polymerization of preferably from P _n = 5 to 100, more preferably P _n = 20 to 60.

The Polydiorganosiloxane-polycarbonate block polymers may also be a mixture of Polydiorganosiloxane-polycarbonate block copolymers with conventional be polysiloxane-free thermoplastic polycarbonates, wherein the total content of polydiorganosiloxane structural units in this Mixture preferably 2.5 to 25 wt .-% is.

worin
Ar gleiche oder verschiedene difunktionelle aromatische Reste sind und
R und R¹ gleich oder verschieden sind und lineares Alkyl, verzweigtes Alkyl, Alkenyl, halogeniertes lineares Alkyl, halogeniertes verzweigtes Alkyl, Aryl oder halogeniertes Aryl, vorzugsweise Methyl, bedeuten und
n den mittleren Polymerisationsgrad von bevorzugt 5 bis 100, besonders bevorzugt 20 bis 60, bedeutet.Such polydiorganosiloxane-polycarbonate block copolymers are characterized in that they contain, on the one hand, aromatic carbonate structure units (1) and, on the other hand, aryloxy end group-containing polydiorganosiloxanes (2) in the polymer chain,

wherein
Ar are identical or different difunctional aromatic radicals and
R and R ^{1 are the} same or different and are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, preferably methyl, and
n is the average degree of polymerization of preferably 5 to 100, particularly preferably 20 to 60, means.

Alkyl in the above formula (2) is preferably C ₁ -C ₂₀ alkyl, alkenyl in the above formula (2) is preferably C ₂ -C ₆ alkenyl; Aryl in the above formulas (1) and (2) is preferably C ₆ -C ₁₄ aryl. Halogenated in the above formula means partially or fully chlorinated, brominated or fluorinated.

Examples for alkyls, Alkenyls, aryls, halogenated alkyls and halogenated aryls are Methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, Chloromethyl, perfluorobutyl, perfluorooctyl and chlorophenyl.

such Polydiorganosiloxane polycarbonate block copolymers and their preparation belong to the state of the art.

preferred Polydiorganosiloxane-polycarbonate block copolymers may be e.g. are prepared by α, ω-Bishydroxyaryloxyendgruppen-containing Polydiorganosiloxanes along with other bisphenols, optionally with the concomitant use of branching agents in the usual amounts, e.g. after this Two-phase boundary process (as described, for example, in H. Schnell, "Chemistry and Physis of Polycarbonates ", Polymer Reviews, Vol. 9, pp. 31-76, Interscience Publishers, New York, London, Sidney, 1964). As Starting materials for this synthesis used α, ω-Bishydroxyaryloxyendgruppen-containing Polydiorganosiloxanes and their preparation are described, for example, in US-A 3,419,634.

The Polycarbonates can be conventional additives such as. Mold release agent mixed in the melt or on the surface be applied. The polycarbonates to be used preferably contain already release agent before compounding with the other components the molding compositions according to the invention.

When Component C) according to the invention, a graft polymer or a Mixture of two or more graft copolymers used, the by graft polymerization of at least one vinyl monomer a graft base based on olefinically unsaturated Olefin polymers or olefinically unsaturated olefin copolymers to be obtained.

• C1) 5 bis 95 Gew.-%, vorzugsweise 10 bis 80 Gew.-%, insbesondere 20 bis 50 Gew.-%, wenigstens eines Vinylmonomeren auf
• C2) 95 bis 5 Gew.-%, vorzugsweise 90 bis 20, insbesondere 80 bis 20 Gew.-% einer oder mehrerer Pfropfgrundlagen mit Glasübergangstemperaturen der Kautschukkomponente <–10°C, bevorzugt <–20°C, besonders bevorzugt <–30°C auf Basis von kautschukelastischen olefinisch ungesättigten Olefin(co-)polymerisaten.

According to the invention used as component C) are graft polymers of

• C1) 5 to 95 wt .-%, preferably 10 to 80 wt .-%, in particular 20 to 50 wt .-%, of at least one vinyl monomer on
• C2) 95 to 5 wt .-%, preferably 90 to 20, in particular 80 to 20 wt .-% of one or more graft bases with glass transition temperatures of the rubber component <-10 ° C, preferably <-20 ° C, particularly preferably <-30 ° C based on elastomeric olefinically unsaturated olefin (co) polymers.

The graft base C2) generally has an average particle size (d ₅₀ value) of 0.05 to 5 μm, preferably 0.10 to 2 μm, particularly preferably 0.15 to 1 μm.

• C1.1) aus 50 bis 99 Gew.-Teilen, vorzugsweise 60 bis 80 Gew.-Teilen Vinylaromaten und/oder kernsubstituierte Vinylaromaten wie Styrol. α-Methylstyrol, p-Methylstyrol, p-Chlorstyrol und/oder Acrylsäure-(C₁-C₈)-alkylester und/oder Methacrylsäure-(C₁-C₈)-alkylester wie Methylmethacrylat und Ethylmethacrylat und
• C1.2) 1 bis 50 Gew.-Teilen, vorzugsweise 40 bis 20 Gew.-Teilen Vinylcyanide (ungesättigte Nitrile wie Acrylnitril und Methacrylnitril) und/oder (Meth)acrylsäure-(C₁-C₈)-alkylester wie Methylmethacrylat, n-Butylacrylat, t-Butylacrylat und/oder Derivate, wie Anhydride und Imide ungesättigter Carbonsäuren, beispielsweise Maleinsäureanhydrid und N-Phenylmaleinimid.

Monomers C1) are preferably mixtures

• C1.1) from 50 to 99 parts by weight, preferably 60 to 80 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics such as styrene. α-methylstyrene, p-methylstyrene, p-chlorostyrene and / or acrylic acid (C ₁ -C ₈ ) -alkyl esters and / or methacrylic acid (C ₁ -C ₈ ) -alkyl esters such as methyl methacrylate and ethyl methacrylate and
• C1.2) 1 to 50 parts by weight, preferably 40 to 20 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters such as methyl methacrylate, n Butyl acrylate, t-butyl acrylate and / or derivatives such as anhydrides and imides of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.

Especially preferred monomers C 1.1) are selected from at least one of Monomeric styrene, α-methylstyrene, Methyl methacrylate, particularly preferred monomers C2.2) are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.

Particularly preferred monomers are C.1.1 styrene and C 1.2 acrylonitrile and C.1.1 styrene and C1.2 Methyl methacrylate.

preferred Grafting Bases C.2 are diene rubbers (for example based on butadiene, Isoprene, etc.) or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable Monomers (e.g., according to C.1.1 and C.1.2), with the proviso that the glass transition temperature the component E.2 below <-10 ° C, preferably <-20 ° C, especially preferably <-30 ° C is and that the grafting over olefinically unsaturated Groups.

Especially Preference is given to using pure polybutadiene rubber.

Especially preferred polymers C are e.g. ABS polymers (emulsion, Bulk and suspension ABS), as known to those skilled in the literature are known, for example, from Ullmann, Encyclopedia of Technical Chemistry, Vol. 19 (1980), p. 280 ff Grafting is E.2 at least 30% by weight, preferably at least 40% by weight (in toluene measured).

The Graft copolymers C) are obtained by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably prepared by emulsion or bulk polymerization.

Especially suitable graft rubbers are also ABS polymers by Redox initiation with an organic hydroperoxide initiator system and ascorbic acid according to US-A 4 937 285 are produced.

There in the grafting reaction the grafting monomers are not necessarily known Completely are grafted onto the graft, be under the invention Graft polymers C) are also understood to be those products obtained by (Co) polymerization of the graft monomers in the presence of the grafting base be recovered and incurred in the workup.

Particularly preferred polymers C) the expert as known MBS rubbers are known, such as those sold by the company. Rohm and Haas under the name Paraloid ^® EXL 2600, Paraloid EXL 2650 or Paraloid ^® EXL 2691, for example, and the example in EP A 0 985 682 can be described.

When Component D) are inventively one or a mixture of two or more graft copolymers used by graft polymerization of at least one vinyl monomer based on a grafting base on rubber-elastic acrylate polymers or on rubber-elastic acrylate copolymers to be obtained.

• D1) 5 bis 95 Gew.-%, vorzugsweise 10 bis 80 Gew.-%, insbesondere 20 bis 50 Gew.-%, wenigstens eines Vinylmonomeren auf
• D2) 95 bis 5 Gew.-%, vorzugsweise 90 bis 20, insbesondere 80 bis 20 Gew.-% einer oder mehrerer Pfropfgrundlagen mit Glasübergangstemperaturen der Kautschukkomponente < 10°C, bevorzugt < 0°C, besonders bevorzugt < –10°C auf Basis von kautschukelastischen Acrylatpolymerisaten oder Acrylatcopolymerisaten.

According to the invention used as component D) are graft polymers of

• D1) 5 to 95 wt .-%, preferably 10 to 80 wt .-%, in particular 20 to 50 wt .-%, of at least one vinyl monomer on
• D2) 95 to 5 wt .-%, preferably 90 to 20, in particular 80 to 20 wt .-% of one or more graft bases with glass transition temperatures of the rubber component <10 ° C, preferably <0 ° C, particularly preferably <-10 ° C. Base of rubber-elastic acrylate polymers or acrylate copolymers.

The graft base D2) generally has an average particle size (d ₅₀ value) of 0.05 to 5 μm, preferably 0.10 to 2 μm, particularly preferably 0.15 to 1 μm.

• D1.1) aus 50 bis 99, vorzugsweise 60 bis 80 Gew.-Teilen Vinylaromaten und/oder kernsubstituierte Vinylaromaten wie Styrol, α-Methylstyrol, p-Methylstyrol, p-Chlorstyrol und/oder Acrylsäure-(C₁-C₈)-alkylester und/oder Methacrylsäure-(C₁-C₈)-alkylester wie Methylmethacrylat und Ethylmethacrylat und
• D1.2) 1 bis 50, vorzugsweise 40 bis 20 Gew.-Teilen Vinylcyanide (ungesättigte Nitrile wie Acrylnitril und Methacrylnitril) und/oder (Meth)acrylsäure-(C₁-C₈)-alkylester wie 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

• D1.1) from 50 to 99, preferably 60 to 80 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene and / or acrylic acid (C ₁ -C ₈ ) - alkyl esters and / or methacrylic acid (C ₁ -C ₈ ) alkyl esters such as methyl methacrylate and ethyl methacrylate and
• D1.2) 1 to 50, preferably 40 to 20 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t Butyl acrylate and / or derivatives such as anhydrides and imides of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.

Especially preferred monomers D 1.1) are selected from at least one of Monomeric styrene, α-methylstyrene, Methyl methacrylate, particularly preferred monomers D1.2) are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.

Especially preferred monomers are D.1.1 styrene and D 1.2 acrylonitrile.

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

to Networking can Monomers copolymerized with more than one polymerizable double bond become. Preferred examples of Crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, such as e.g. ethylene glycol, Allyl methacrylate: polyunsaturated heterocyclic compounds, e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes, dicyclopentadiene, 5-ethylidenenorbornene; 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 Have groups.

Especially preferred crosslinking monomers are the cyclic monomers "triallyl cyanurate, Triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft base D.2.

at cyclic crosslinking monomers having at least 3 ethylenically unsaturated Groups, it is advantageous, the amount to less than 1 wt .-% of the graft D.2 restrict.

Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft D.2, z. For example, acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl-C ₁ -C ₆ -alkyl ethers, methyl methacrylate. Preferred acrylate rubbers as grafting base D.2 are emulsion polymers which have a gel content of at least 60% by weight. The preparation of the grafting base D.2. can be done in one step or in several steps. For the grafting reaction, it is also possible to use a mixture of different grafting bases as described. In particular, it is also possible to use various grafting bases which are inferior in average particle size.

Particularly preferred as component D) according to the invention are ASA rubbers, as described, for example, in WO 2000046296, in US Pat EP 0960145 or in DE 42 299 13 are described.

When Component E) contain the compositions according to the invention UV stabilizers as described, for example, in Gächter, Müller, Kunststoff-Additive, 3rd edition, Hanser-Verlag, Munich, Vienna, 1989 and in the Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001, pp. 97-137, 141-154, 178-183, 188-192, 369-372, 389-394. The UV stabilizers can used alone or mixed or in the form of masterbatches become.

preferred used according to the invention UV stabilizers are sterically hindered phenols, sterically hindered Amines (HALS = Hindered Amine Light Stabilizer), hydroquinones, aromatic secondary Amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as various substituted representatives of these Groups and their mixtures.

Especially preference is given to sterically hindered amines of the HALS type, benzotriazoles, Benzotriazines and Bezopyrimidines.

The HALS-type sterically hindered amines to be preferably used can be derived from the general structure shown in (3)

Each of these can be independent of one another:
Y: H, acyl, O-radical, alkyl, alkenyl, alkoxyalkyl, arylalkyl,
X ² : -OR, NR ₂ , maleimide,
R ⁷ and R ⁸ independently of one another = H, alkyl, alkenyl, arylalkyl, preferably = H
R ³ , R ⁴ , R ⁵ , R ⁶ independently of one another H, alkyl, phenyl, alkylaryl, aromatic heterocycle containing oxygen, sulfur or nitrogen; preferably R ³ -R ^{6 are} methyl

The preferably used HALS stabilizers are described for example in US 4895901 . US 4210612 and US 5015682 ,

The Benzotriazoles preferably to be used are general derive from the structure shown in (4).

In this case, R ⁹ and R ^{10 can be selected} independently of one another from the group consisting of H, alkyl (in particular methyl, ethyl, propyl), cycloalkyl, halogen, haloalkyl, alkoxy, alkylene, aryl, alkyl-aryl or a combination thereof.

Particularly preferred are R ⁹ = R ¹⁰ = (2-phenyl) isopropyl, R ⁹ = H and R ¹⁰ = 2- (2,4,4-trimethyl) pentyl, R ⁹ = H and R ¹⁰ = methyl, R ⁹ = R ¹⁰ = t-butyl, R ⁹ = t-butyl and R ¹⁰ = methyl, R ⁹ = R ¹⁰ = 2- (2-methyl) -butyl, R ⁹ = iso-butyl and R ¹⁰ = 2- ( 2,4,4-trimethyl) pentyl.

The present invention preferably to be used benzotriazoles described are sold, for example by Ciba Specialty Chemicals, Basel, Switzerland under the trade name Tinuvin ^® product.

The preferably used hydroxyphenyltriazine and -pyrimidine UV stabilizers consist of two phenyl and one resorcinol group bound to a triazine or pyrimidine ring as described in US Pat US 6,239,276 and U.S. 5,597,854 , The preferred hydroxyphenyltriazines and -pyrimidines can be generally derived from the general structure shown in (5).

In formula (5), A can be N or CH and R ¹¹ to R ¹⁸ independently of one another from the group consisting of H, alkyl (in particular methyl, ethyl, propyl), cycloalkyl, halogen, haloalkyl, alkoxy, alkylene, aryl, Alkyl aryl or combination of these be selected.

Examples of commercially available representatives of the preferably used hydroxyphenyltriazines are Tinuvin ^® 1577 (CAS number 147315-50-2, Ciba Spezialcheimkalien, Basel, Switzerland) or Cyasorb ^® UV 1164 (Cyctec Industries).

When Component F), the compositions of the invention contain conventional colorants and / or Pigments, e.g. Titanium dioxide, ultramarine blue, iron oxide, carbon black, Phthalocyanines, quinacridones, perylenes, nigrosine and anthraquinones and their derivatives are used. Particularly suitable also the colorants for improvement described in US Pat. No. 6,476,158 the shine after weathering. The colorants and / or pigments can be used in Substance are added or as masterbatches, for example in component A), component B), component C), polyethylene, polypropylene, Waxing or paraffin.

The used according to the invention Colorants are also described, for example, in Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001, pp. 822-850.

When Component G) can the compositions according to the invention at least difunctional, low molecular weight and oligomeric compounds containing at least one epoxide group feature.

Preferred epoxy-containing compounds as component G are generally:
Polyglydicyl or poly (β-methylglycidyl) ether obtainable by reacting a compound having at least two free alcoholic or phenolic hydroxyl groups and / or phenolic hydroxy groups and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.

ether of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, Propane-1,2-diol, or poly (oxypropylene) glycols, propane-1,3-diol, Butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-1,5-diol, hexane-1,6-diol, Hexane-2,4,6-triol, glycerol, 1,1,1-trimethylpropane, bistrimethylolpropane, Pentaerythritol, sorbitol, as well as polyepichlorohydrins.

she But also derived for example from cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, Bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1,1-bis (hydroxymethyl) cyclohex-3-ene or they have aromatic Cores such as N, N-bis-82-hydroxyethyl) -aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.

The Epoxy compounds can also derived from mononuclear phenols, such as of resorcinol or hydroquinone; or they are based on polynuclear Phenols such as bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 4,4'-dihydroxydiphenylsulfone or condensation products obtained under acidic conditions phenols with formaldehyde such as phenol novolacs.

2. Difunctional, cycloaliphatic epoxy-containing compounds containing the structural fragment shown in (6)

In Formula (6) may be R independently selected from each other from the group containing H, alkyl, aryl, halogen, haloalkyl, Alkoxy, carboalkoxy, carbonyl and n be selected from 0 to 8, preferably 0 up to 2.

Preferred examples from the class of cycloaliphatic epoxide-containing compounds which may optionally be used according to the invention are 3,4-epoxycyclohexyl-3,4-epoxycyclohexylcarboxylate (commercial product ERL 4221 from Union Carbide), bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, 3, 4-Ep oxi-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexane carboxylate, 2,3-epoxycyclohexyl-3,4-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) -butyl- 3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexyl-ethylene oxide.

Third Poly (N-glycidyl) compounds obtainable by dehydrochlorination the reaction products of epichlorohydrin with amines. In these Amines are, for example, aniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane, but also N, N, O-triglycidyl-m-aminophenyl or N, N, O-triglycidyl-p-aminophenol.

To However, the poly (N-glycidyl) compounds also include N, N'-diglycidyl derivatives of cycloalkylene ureas, such as ethyleneurea or 1,3-propyleneurea and N, N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.

Prefers usable nitrogen compounds are also nitrogen-containing Heterocycles such as triazines, berbraic acids, hydantoins, uracils, pyromellithsäurediimide, piperidines, piperazines, piperazinediones and isocyanurates.

When Component H) can the thermoplastic molding compositions, 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 beads and / or fibrous fillers and / or reinforcing materials based on carbon fibers and / or glass fibers. Preference is given to 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 used. Particular preference is given according to the invention mineral particulate fillers based on talc, wollastonite and / or glass fibers. Most Preference is given to fillers based on talc.

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

Especially also needle-shaped are preferred mineral fillers. Under acicular mineral fillers is a mineral according to the invention filler with pronounced acicular nature Understood. As an example, needle-shaped wollastonites are mentioned. Preferably, the mineral has a length: diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, most preferably from 4: 1 to 12: 1. The mean particle size of the acicular minerals according to the invention is preferably less than 20 μm, more preferably at less than 15 microns, more preferably at less than 10 μm, most preferably less than 5 microns, determined with a CILAS GRANULOMETER.

At the most preferred as component H) are mineral fillers based on talc. As mineral fillers based on talc For the purposes of the invention, all particulate fillers are considered which are those skilled in the art connects with talc or talc. Also come all particulate fillers, the be offered commercially and their product descriptions as characterizing features include the terms talc or talc, in question.

Prefers are mineral fillers, which has a content of talc according to DIN 55920 of greater than 50% by weight, preferably greater than 80% by weight, more 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 be. You can, for example with a primer system e.g. be equipped on a silane basis.

The used according to the invention mineral fillers based on talc preferably have an upper particle or d97 size smaller 50 μm, preferred less than 10 μm, more preferably less than 6 microns and particularly preferably less than 2.5 microns. As mean particle size d50 becomes preferably a value smaller than 10 μm, preferably less than 6 μm, more preferably less than 2 microns and more preferably selected less than 1 micron. The d97 and d50 values from the fillers after sedimentation analysis SEDIGRAPH D 5000 resp. 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, particularly preferably 2 to 25 and particularly preferably 5 to 25, determined by electron micrographs of ultrathin sections of the finished products and measuring a representative amount (about 50) of filler particles.

Of the filler and / or reinforcing material may optionally be surface modified be, for example, with a primer or primer system e.g. on a silane basis. The pretreatment is not necessarily required. In particular, when using glass fibers in addition to Silanes and polymer dispersions, film formers, branching and / or Fiber processing aids are used.

Especially preferred According to the invention also glass fibers are used, which generally have a fiber diameter between 7 and 18 μm, preferably between 9 and 15 microns to have. These can be as Continuous fibers or added as cut or ground glass fibers be with the fibers with a suitable sizing system and a primer system, e.g. be equipped on a silane basis can.

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 1.Common silane compounds for pretreatment with a sizing system have, for example, the general formula (X- (CH2) q) k -Si- (O-C r H 2r + 1) 4-k in which the substituents have the following meanings:

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 contain a glycidyl group as substituent X.

The Silane compounds can generally in amounts of 0.05 to 2 wt .-%, preferably 0.5 to 1.5 wt .-% and in particular 0.8 to 1 wt .-% based on the mineral filler for surface coating be used.

The particulate fillers can due to the processing to the molding compound or molding in the molding compound or in the molding have a smaller d97 or 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 as originally have used.

The Particle diameters on the finished product can thereby be achieved, for example be determined that electron micrographs of thin sections taken up of the polymer mixture and at least 25, preferably at least 50 filler particles for the Evaluation are used.

The Compositions of the invention can as component I) continue usual Contain additives which are generally up to 15 wt .-%, preferably in an amount of 0.01 to 10 wt .-%, particularly preferably 0.05 to 5 wt .-%, particularly preferably 0.1 to 3 wt .-%, based on the Total weight of the molding compositions, can be added.

All usual Additives such as e.g. Stabilizers (for example heat stabilizers), Antistatic agents, flow aids, Mold release agents, fire protection additives, emulsifiers, nucleating agents, Plasticizers, lubricants, pH lowering additives (e.g., carboxyl groups containing compounds), additives for increasing the conductivity can come into question. The above and other suitable additives are described for example in Gächter, Müller, plastic additives, 3rd edition, Hanser-Verlag, Munich, Vienna, 1989. The additives can used alone or mixed or in the form of masterbatches become. The additives can mixed and / or applied to the surface.

As stabilizers, for example, sterically hindered phenols and / or phosphites, hydroquinone ne, aromatic secondary amines such as diphenylamines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, as well as various substituted representatives of these groups and mixtures thereof can be used.

When Nucleating agents can e.g. Sodium phenylphosphinate, alumina, silica and preferred Talcum and the nucleating agents described earlier used become.

When Lubricants and mold release agents 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 from 28 to 32 carbon atoms) and low molecular weight polyethylene or Polypropylene waxes are used.

When Plasticizers can for example, dioctyl phthalate, phthalate, phthalate, Kohlemvasserstofföle, N- (n-butyl) benzenesulfonamide can be used.

Around conductive Can get molding compounds Russian, conductivity Russian, Carbon fibrils, nanoscale graphite fibers (nanotubes), graphite, conductive Polymers, metal fibers and other common additives to increase the conductivity be added.

When Flame retardants can commercial organic halogen compounds with synergists or commercial organic Nitrogen compounds or organic / inorganic phosphorus compounds individually or used in a mixture. Also mineral flame retardant additives such as magnesium hydroxide or Ca-Mg-carbonate hydrates (e.g., DE-A 4,236 122) be used. As halogen-containing, in particular brominated and chlorinated compounds may be mentioned by way of example: ethylene-1,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate, Tetrachlorobisphenol A oligocarbonate, pentabromopolyacrylate, brominated Polystyrene. As organic phosphorus compounds are the phosphorus compounds according to WO-A 98/17720 suitable, e.g. Triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) including Oligomers and bisphenol A bis-diphenyl phosphate including oligomers (see for example EP-A 0 363 608 and EP-A 0 640 655), melamine phosphate, Melamine pyrophosphate, melamine polyphosphate and mixtures thereof. When Nitrogen compounds are in particular melamine and melamine cyanurate question. As synergists are e.g. Antimony compounds, in particular Antimony trioxide and antimony pentoxide, zinc compounds, tin compounds such as. Tin stannate and borates suitable. Carbon formers and and tetrafluoroethylene polymers may be added. The Flame retardant, optionally with a synergist, such as antimony compounds, and anti-dripping agents are generally up to an amount of 30% by weight, preferably 20% by weight (based on the total composition) used.

When Additives can also reinforcing materials e.g. be added in the form of glass fibers.

object The invention further provides a process for the preparation of the compositions, the use of the composition according to the invention for the production of semi-finished products and molded parts as well as from them Semi-finished and molded parts.

The Preparation of the compositions of the invention takes place by known methods by mixing the components. It may be advantageous to premix individual components. The Premixing can take place both as a dry blend and through joint kneading, extruding or rolling the components. Furthermore, the mixing of individual components, in particular of stabilizers, additives and colorants already during the Synthesis of the invention used Polymers take place. Preferably, the mixing of the components is done A to D and other constituents at temperatures of 220 to 330 ° C through joint kneading, extruding or rolling the components.

The Compositions of the invention can according to usual Process be processed into semi-finished products or moldings of all kinds. As examples of Processing methods are extrusion methods and injection molding methods called. As examples of Semi-finished products are called films and plates.

The molded parts are particularly suitable for applications that are visible and visually important due to the high color homogeneity. The moldings can be used unpainted according to the invention or coated with a transparent clearcoat system. Of course, the moldings but also be painted with a coloring basecoat. The molded parts can be small or large parts and used for exterior or interior applications. Preference is given to large-size molded parts for vehicle construction, in particular the automotive sector. In particular, from the molding compositions of the invention exterior body parts such as fenders, tailgates, hoods, bumpers, cargo areas, covers for cargo areas, car roofs, air intake grille, spoilers or other body parts can be made.

moldings or semi-finished products of the molding compositions / compositions according to the invention can also in combination with other materials such. Metal or plastic are located. The molding compositions according to the invention or the moldings / semi-finished products of the molding compositions according to the invention can by usual Techniques of joining and assembling multiple components or Parts such as e.g. Coextrusion, film backsplash, overmolding of Inserting, gluing, welding, screwing or stapling in Composite with other materials or yourself for the manufacture finished parts such as e.g. Body Exterior parts are used.

The molding compositions according to the invention can also for numerous other applications are used. For example be called the use in the electrical and electronic engineering, as well as in the construction sector. In the applications mentioned moldings can from the molding compositions according to the invention for example as lamp covers, as safety discs, as housing material for electronic Equipment, as housing material for home appliances, as Plates are used for making covers.

The Compositions of the invention are characterized by a very good color homogeneity and by very good weathering stability. Furthermore fulfill they have high requirements with regard to processing stability, flowability the melt, toughness, Low temperature toughness, Stiffness, heat resistance, thermal expansion, surface quality, paintability, Chemical resistance and Fuel resistance.

component A

Polybutylene terephthalate type A1:
It is polybutylene terephthalate with an intrinsic viscosity IV of 0.93 cm ³ / g, commercial product Pocan ^® B1300 from Bayer AG, Leverkusen.

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

component B

Polycarbonate Type B1:
Linear polycarbonate (Makrolon ^® 2405 from Bayer AG, Leverkusen, Germany) based on bisphenol A with a viscosity rel. of about 1.29 (measurement conditions: 5 g of polycarbonate per liter of methylene chloride, 25 ° C) and a molecular weight Mw of about 29 000 g / mol (determined by GPC methods against polycarbonate standard).

Component C1

It is Paraloid ^® EXL 2650 from Rohm and Haas Germany GmbH, Frankfurt.

Component C2

It is a graft copolymer of acrylonitrile and styrene on a grafting base of polybutadiene, intermediate of Bayer AG, Leverkusen with a Polybutadienanteil of 75 -wt% and a Styrene content in the shell of 28% by weight.

Comparison component V1

This is the AES rubber Royaltuf ^® 970 E (formerly Blendex ^® WX 270) Crompton Corporation, Crompton GmbH Germany, Bergkamen

Component D1

It is a graft copolymer of styrene on a graft base and Acrynlnitril of partially crosslinked polybutyl acrylate, Centrex ^® 57 WBA, intermediate product of Bayer Corp., Pittsburgh.

Component D2

It is Paraloid ^® EXL 3361 of Messrs. Rohm & Haas Germany, Frankfurt

Component E

It is Tinuvin ^® 350 of the company. Ciba Geigy, Basel.

component F

These are carbon black, type Black ^Pearls® 800 from Cabot GmbH, Hanau.

component G

It is Araldite ^® GT 7071 from Huntsman Advanced Materials GmbH Germany, Bergkamen.

Besides are commercially available as additives Processing aids used.

compounding were carried out on a ZSK32 twin-screw extruder (Werner and Pfleiderer) at melt temperatures of 250 to 290 ° C.

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

The tests of the molding compositions according to the invention were carried out according to the following methods:
Vicat B: Heat dimensional stability 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 -23 ° C.
Notched Izod impact strength: Toughness according to ISO 180 Method 1 A at 23 ° C
Tensile modulus and tensile strength according to DIN / EN / ISO 527-2 / 1A.
MVR: Flowability according to DIN / ISO 1133 at 260 ° C and 5 kg.

Color homogeneity: Determination of the color homogeneity of the surface by visual inspection.
"+" Means homogeneous coloring without formation of stripes of lower color intensity perpendicular to the flow direction (tiger stripes)
"O" means a largely homogeneous coloring with easy formation of stripes of lower color intensity perpendicular to the flow direction
"-" means inhomogeneous coloring with strong formation of stripes perpendicular to the flow direction.

The Assessment of color homogeneity was carried out on 150 × 105 × 1.6 mm plates, those with a melt temperature of 270 ° C, a mold temperature from 80 ° C and a filling speed of 50 mm / s over a movie on a 105 mm side were made.

As Table 1 shows the molding compositions according to the invention the required combination of very good color homogeneity and good hydrolytic stability at the same time good mechanical properties. Compared to Comparative Examples 2 and 3 are the molding compositions of the invention about that In addition, significantly more UV-stable, because the proportion of UV-sensitive components C is significantly lower.

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

Claims (9)

A composition comprising A) 4 to 80 parts by weight of at least one polyalkylene terephthalate, B) 10 to 90 parts by weight of at least one aromatic polycarbonate, C) 1.5 to 30 parts by weight of at least one graft polymer based on polybutadiene as rubber component, D) 1.5 to 30 parts by weight of at least one graft polymer based on acrylates as rubber component, E) 0.01 to 5 wt Parts UV stabilizers, F) 0.01 to 10 parts by weight of colorant G) 0 to 5 parts by weight of hydrolysis stabilizers, H) 0 to 54 parts by weight of at least one particulate mineral filler, I) 0 to 10 Parts by weight of further additives. A composition according to claim 1, wherein C) composed of graft polymers of C1) from 5 to 95% by weight, at least one vinyl monomer C2) 95 to 5 wt .-% of a or more grafting bases with glass transition temperatures of the rubber component <-10 ° C based on of elastomeric olefinically unsaturated olefin (co) polymers. A composition according to claim 1 or?, Wherein D) is composed of graft polymers of D1) 5 bis 95 wt .-%, at least one vinyl monomer on D2) 95 to 5 % By weight of one or more graft bases with glass transition temperatures the rubber component <10 ° C based of acrylate rubbers. Compositions according to one or more of the preceding Claims, wherein polyethylene terephthalate is used as component A. Use of the compositions according to one or more of the preceding claims for the production of moldings. Process for the production of molded parts, molding compounds or semi-finished products, characterized in that compositions containing A) 4 to 80 parts by weight of at least one polyalkylene terephthalate, B) 10 to 90 parts by weight of at least one aromatic polycarbonate, C) 1.5 to 30 parts by weight of at least one graft polymer based on of polybutadiene as a rubber component, D) 1.5 to 30 parts by weight at least one graft polymer based on acrylates as Rubber component E) 0.01 to 5 parts by weight of UV stabilizers, F) 0.01 to 10 parts by weight of colorant G) 0 to 5 parts by weight of hydrolysis stabilizers, H) 0 to 54 parts by weight of at least one particulate mineral filler, I) 0 to 10 parts by weight of further additives. Molding compounds, semi-finished products or molded parts available from Containing compositions A) 4 to 80 parts by weight at least a polyalkylene terephthalate, E) 10 to 90 parts by weight at least an aromatic polycarbonate, F) 1.5 to 30 parts by weight at least one graft polymer based on polybutadiene as Rubber component G) 1.5 to 30 parts by weight of at least one Graft polymer based on acrylates as rubber component, e) 0.01 to 5 parts by weight of UV stabilizers, F) 0.01 to 10 parts by weight colorants G) 0 to 5 parts by weight of hydrolysis stabilizers, H) 0 to 54 parts by weight of at least one particulate mineral filler, I) 0 to 10 parts by weight of further additives. Moldings according to claim 7, characterized in that it is painted with a clearcoat become. Use of the moldings according to claims 7 and 8 in automotive exterior applications.