EP2766429A1 - Stabilized polyamide/abs molding masses - Google Patents

Abstract

The invention relates to thermoplastic molding masses, containing the following components: a) 3 to 91.8 wt% of a polyamide as component A, b) 3 to 91.8 wt% of a styrene copolymer as component B, c) 5 to 91.8 wt% of an impact-modifying graft rubber as component C, d) 0.2 to 1.5 wt% of a compound of formula (I) as component D, e) 0 to 0.9 wt% of a mixture of formula (II) as component E, wherein n = 7 to 8, f) 0 to 0.9 wt% of an additional stabilizer component F, g) 0 to 25 wt% of one or more styrene copolymers, which have units derived from 0.5 to 5 wt% of maleic anhydride, as component G, and optionally additional additives. According to the invention, said molding masses have advantageous weathering properties.

Description

 Stabilized polyamide-ABS molding compounds

description

The present invention relates to thermoplastic molding compositions comprising at least one polyamide, at least one styrene copolymer and at least one impact-modifying graft rubber having olefinic double bonds in the rubber phase.

Stabilized thermoplastic molding compositions based on acrylonitrile-butadiene-styrene copolymers (ABS) have been known for years and can be used widely due to their favorable property profile for many applications. Thermoplastic molding compositions are also known in the literature which contain polyamides, graft rubbers and at least one styrene-based copolymer (EP-A 0 202 214, EP-A 0 784 080, EP-A 0 402 528, WO 2005/071013). Such thermoplastic molding compositions are used in particular in the production of moldings, moldings, films, fibers and foams, wherein, for example, the moldings can be used as motor vehicle components.

In EP-A 1 263 855 stabilized molding compositions are disclosed which, in addition to a polyethylene or polypropylene or their copolymer, also compounds of the formulas (I), (II), (III), (IV), (V) or (VI) of the present invention in combination with an acrylate rubber-modified vinyl aromatic copolymer (so-called "ASA" = acrylonitrile / styrene / acrylic ester) or polyamide in amounts up to 1 .5%. However, no butadiene-rubber-modified molding compositions are described. A disadvantage of the known compositions is u. a. the low notched impact strength of the molding compounds.

US Pat. No. 4,692,486 discloses stabilizer mixtures comprising compounds of the formulas (I) and (III) of the present application for polypropylene, polyurethane and polystyrene, the amounts of the individual stabilizer components used being less than or equal to 0.1% by weight. A disadvantage of this embodiment is the low impact strength of the molding compositions.

The application DE-A 103 16 198 discloses stabilizer mixtures for different types of thermoplastic polymers, such as polypropylene. The stabilizer mixtures are ternary mixtures. For the three components of this stabilizer mixture, a variety of possible generic and special compounds is described in each case. Stabilizer mixtures which also contain compounds of the formulas (I), (II) and (III) of the present application are described as only one of many possibilities. Each of the three stabilizer components may preferably be present in amounts of from 0.05 to 1% by weight, based on the organic material. A disadvantage of this embodiment is the strong decrease of the multi-axial toughness during weathering.

The object of the present invention is to provide improved molding compositions based on polymer blends of polyamide with acrylonitrile / butadiene / styrene copolymers. Accordingly, there are provided improved thermoplastic molding compositions containing (or also consisting of): a) 3 to 91, 8% by weight of at least one polyamide as component A, b) 3 to 91.8% by weight of one or more styrene copolymers which have no units derived from maleic anhydride, as component B, c) 5 to 91, 8 wt .-% of one or more impact-modifying graft rubbers with olefinic double bond in the rubber phase, as component C, d) 0.2 to 1, 5 wt .-% of a compound of formula (I) as component D: e) 0 to 0.9% by weight of a mixture of the formula (II) as component E:

 n = 2 to 20,

in particular the formula below f) 0 to 0.9% by weight of a compound of the formula (III) as component F:

 or 0 to 0.9% by weight of a compound of the formula (IV):

 n = 2 to 20

or 0 to 0.9% by weight of a compound of the formula (VI):

n = 2 to 20,

0 to 25 wt .-%, but often 1 to 25 wt .-% of one or more styrene copolymers, based on the total component G, from 0.5 to 5 wt .-% of maleic anhydride derived units, as a component G

0 to 40% by weight of one or more further rubbers,

0 to 40 wt .-% of one or more additives which are different from the components D, E, F, G, and H, as component I, and

0 to 40% by weight of one or more fibrous or particulate fillers as component J.

The following applies to the molding compositions as a proviso that, if component E is just 0 wt .-% (that is, no component E is present), the component F of 0.01 to 0.9 wt .-%, preferably 0.1 to 0.8 wt .-%, particularly preferably 0.2 to 0.8% by weight of one or more of the compounds III, IV, V or VI, wherein the wt .-% each based on the total weight of the components A to J and these together give 100 wt .-%.

Preference is also given to those molding compositions which contain from 0.2 to 1, 5 wt .-%, often 0.3 to 1, 1 wt .-% of component D, and additionally 0.1 to 0.8 wt .-% of component E (such as Cyasorb 3853). The invention also relates to a thermoplastic molding composition, characterized in that the swelling index of component C is from 7 to 20. The invention also relates to a thermoplastic molding composition in which component B is a copolymer of acrylonitrile, styrene and / or α-methylstyrene, phenylmaleimide, methyl methacrylate or mixtures thereof. The invention also relates to a thermoplastic molding composition, in which component C is a mixture of an acrylonitrile-butadiene-styrene (ABS) graft polymer which contains from 50 to 80% by weight, based on C, of an elastomer-crosslinked butadiene polymer B1 and From 50 to 20% by weight, based on C, of a graft shell C2 of a vinylaromatic monomer and one or more polar, copolymerizable, ethylenically unsaturated monomers, optionally a further copolymerizable, ethylenically unsaturated monomer in a weight ratio of 85:15 to 65:35 contains.

The invention also relates to a thermoplastic molding composition, wherein the average particle diameter of component C is between 50 and 800 nm.

The invention also relates to a thermoplastic molding composition, wherein components D to E are used in a weight ratio of 4: 1 to 0.25: 1. The invention also relates to a thermoplastic molding composition, wherein the vinylaromatic component in C2 is styrene or α-methylstyrene.

The invention also relates to a thermoplastic molding composition, wherein acrylonitrile and / or alkyl methacrylates and / or alkyl acrylates having C 1 to C ₈ alkyl radicals are used as the ethylenically unsaturated component in C 2.

The invention also relates to a thermoplastic molding composition, wherein component C is a rubber which has a bimodal particle size distribution.

The invention also relates to a thermoplastic molding composition, wherein component G comprises 1, 0 to 2.5 wt .-% of maleic anhydride derived units.

The invention also relates to a thermoplastic molding composition, wherein component G has from 1, 7 to 2.3 wt .-% of maleic anhydride derived units.

The invention also relates to a thermoplastic molding composition, wherein component A has from 0.05 to 0.5 wt .-% triacetonediamine (TAD) end groups. The invention also provides a process for the preparation of thermoplastic molding compositions as described above, wherein the components A, B, C, D and G, and optionally E, F, H, I and J, at temperatures of 100 to 300 ° C and a pressure of 1 to 50 bar in any order mixed together, then kneaded and extruded. The subject matter also relates to a process for the production of thermoplastic molding compositions, in which first a part of component C is premixed with a part of component B to give a masterbatch in a ratio of 1: 1 to 1: 2 and subsequently mixed with further components A, B, C, D and G, and optionally E, F, H, I and J, mixed into the thermoplastic molding composition.

The use of the o.g. thermoplastic molding compositions for the production of moldings, films or fibers is also an object of the invention as well as the use of the thermoplastic molding compositions for the production of moldings for automotive components or parts of electronic equipment.

The invention also relates to the shaped bodies, fibers or films containing or consisting of a thermoplastic molding composition as described above. The invention also relates to processes for the preparation of these molding compositions, their use for the production of films, moldings or fibers and these films, moldings or fibers themselves. Due to the inventively essential special selection of the individual components and their specific proportions, the molding compositions according to the invention over the known stabilized molding compositions improved weather resistance, ie an improved heat, light and / or oxygen resistance on. The objects, methods and uses of the invention are described in more detail below.

The molding compositions of the invention preferably contain, based on the total weight (mass) of the components A, B, C, D, G (necessary components) and optionally E, F, H, I and J (optional components), which total weight is 100 percent by weight results:

3 to 91.8 wt .-%, preferably 25 to 75 wt .-%, particularly preferably 30 to 70 wt .-% of the component A

 3 to 91, 8 wt .-%, preferably 10 to 40 wt .-%, particularly preferably 14 to 30 wt .-% of component B,

 5 to 91, 8 wt .-%, preferably 10 to 40 wt .-%, particularly preferably 14 to 35 wt .-% of the component C,

0.2 to 1, 5 wt .-%, preferably 0.2 to 1, 2 wt .-%, particularly preferably 0.3 to 1, 1 wt .-% of component D, e) 0 to 0.9 wt .-%, preferably 0.2 to 0.8 wt .-%, particularly preferably 0.2 to 0.7 wt .-% of the component E,

 with the proviso that when component E is 0% by weight (ie no component E is present), the component F is from 0.01 to 0.9% by weight, preferably from 0.1 to 0.8% by weight, more preferably 0.2 to 0.8% by weight of one or more of

Compounds III, IV, V or VI,

f) 0 to 0.9 wt .-%, preferably 0.1 to 0.8 wt .-%, particularly preferably 0.2 to 0.8 wt .-% of the component F

g) 1 to 25 wt .-%, preferably 2 to 10 wt .-%, particularly preferably 3 to 7 wt .-% of the component G.

h) 0 to 30 wt .-%, preferably 0 to 20 wt .-%, often 3 to 20 wt .-%, particularly preferably 5 to 17 wt .-% of the component H,

i) 0 to 40 wt .-%, preferably 0 to 30 wt .-%, in particular 0 to 17 wt .-% of the component I, and

j) 0 to 50% by weight, preferably 0 to 40% by weight, in particular 10 to 35% by weight of component J.

Instead of the upper limit of 91, 8 wt .-% for the components A, B and C, this is often 90.8 wt .-% and preferably 90 wt .-%.

A molding composition according to the invention consists, for example, based on the total weight of all components, which give a total weight of 100 percent by weight in total:

a.) 30 to 45 wt .-% of component A.

b.) 14 to 20 wt .-% of component B,

c) 14 to 35% by weight of component C,

d) 0.3 to 1, 1 wt .-% of component D,

e) 0 to 0.9% by weight, preferably 0.2 to 0.7% by weight, of component E,

f) 0.2 to 0.8 wt .-% of component F

g) 3 to 7 wt .-% of component G.

h) 0 to 20% by weight of component H,

i) 0 to 17% by weight of component I,

j) 0 to 40 wt .-% of the component J, with the proviso that when component E is just 0 wt .-%, the component F of 0.2 to 0.8 wt .-% of one or more of the compounds III, IV, V or VI.

Often, the composition contains both a component D and (at least) a component E (in particular the substance Cyasorb 3853). The weight ratio of component D to component E is often in the range from 4: 1 to 0.25: 1, preferably 4: 1 to 1: 1, more preferably 3: 1 to 1: 1. The weight ratio of component E to F, as far as component F is present, is often in the range of 2: 1 to 0.5: 1.

Component A: As component A, the thermoplastic molding compositions according to the invention comprise one or more polyamides. This component A is often contained in an amount of 30 to 70 wt .-% in the molding compositions. As component A, a polyamide is often used, of whose end groups at least one of the piperidine compound triacetonediamine (TAD) can be derived. The polyamide has, based on the entire component A, 0.05 to 0.5 wt .-%, preferably 0.1 to 0.2 wt .-%, of triacetonediamine (TAD) end groups.

Component A may be TAD-free polyamides, TAD-containing polyamides or else mixtures of TAD-terminated polyamides with polyamides without TAD end groups. Overall, it may be preferred, based on the component A, 0.1 to 0.2 wt .-% triacetonediamine end groups. Preference is given to 0.14 to 0.18 wt .-% TAD end groups, in particular 0.15 to 0.17 wt .-% TAD end groups. It is also possible to use mixtures of two or more different polyamides as component A. For example, polyamides of different basic structure but the same end group can be used. But it is also possible to use polyamides having the same backbone and end groups, which are derived from different piperidine compounds. Furthermore, it is possible to use mixtures of polyamides having different contents of end groups derived from the piperidine compounds (such as TAD).

Polyamides are understood as meaning homopolymers or copolymers of synthetic, long-chain polyamides which contain, as an essential constituent, recurring amide groups in the polymer main chain. Examples of such polyamides are:

Nylon 6 (polycaprolactam), nylon 6,6 (polyhexamethylene adipamide),

 Nylon 4,6 (polytetramethylene adipamide),

 Nylon 5,10 (polypentamethylene adipamide),

Nylon 6,10 (polyhexamethylene sebacamide), nylon 7 (polyeneantholactam), Nylon 1 1 (polyundecanolactam), nylon 12 (polydodecanolactam).

These polyamides are known to carry the generic name nylon. The preparation of polyamides can be carried out in principle by two known methods.

In the polymerization of dicarboxylic acids and diamines, as well as in the polymerization of amino acids, the amino and carboxyl end groups of the starting monomers or starting oligomers react with each other to form an amide group and water. The water can then be removed from the polymer mass. In the polymerization of carboxylic acid amides, the amino and amide end groups of the starting monomers or starting oligomers react with each other to form an amide group and ammonia. The ammonia can then be removed from the polymer mass. Suitable starting monomers or starting oligomers for the preparation of polyamides are, for example:

) C ₂ - to C ₂₀ -, preferably C ₃ - to C ₈ - amino acids, such as 6-aminocaproic acid, 1 1 -aminoundecanoic acid, and their dimers, trimers, tetramers, pentamers or hexamers,

(2) C ₂ to C ₂₀ amino acid amides, such as 6-aminocaproic acid amide, 1-amino undecanamide and their dimers, trimers, tetramers, pentamers or hexamers,

(3) reaction products of (3a) C ₂ - to C ₂₀ -, preferably C ₂ - to C ₂ - alkyldiamines such as tetramethylenediamine or preferably Hexamethylendia- min, with

(3b) a C ₂ - to C ₂₀ -, preferably C ₂ - to C ₄ -aliphatic dicarboxylic acid, such as sebacic acid, decanedicarboxylic acid or adipic acid, and their dimers, trimers, tetramers, pentamers or hexamers,

(4) reaction products of (3a) with (4b) of a C ₈ - to C ₂₀ -, preferably C ₈ - to C ₂ aromatic dicarboxylic acid or derivatives thereof, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, preferably isophthalic acid or terephthalic acid, as well as their dimers, trimers, tetramers, pentamers or hexamers,

(5) reaction products of (3a), with (5b) a C ₉ - to C ₂₀ -, preferably C ₉ - to C ₈ -aryl-aliphatic dicarboxylic acid or derivatives thereof, for example such as o-, m- or p-phenylenediacetic acid, as well as their dimers, trimers, tetramers, pentamers or hexamers,

(6) reaction products of (6a) C ₆ - to C ₂ o-, preferably C ₆ - to C ₀ aromatic diamines, such as, m- or p-phenylenediamine, with (3b) and their

Dimers, trimers, tetramers, pentamers or hexamers,

(7) reaction products of (7a), C ₇ - o- to C _2, preferably C ₈ - to C ₈ - a- rylaliphatischen diamines such as m- or p-xylylenediamine, with (3b) as well as their dimers, trimers, tetramers , Pentamers or hexamers,

(8) Monomers or oligomers of a C ₂ to C ₂ o, preferably C ₂ to C ₈ arylaliphatic or preferably aliphatic lactam, such as enantholactam, undecanolactam, dodecanolactam or caprolactam, as well as homopolymers, copolymers or mixtures thereof Starting monomers or starting oligomers.

Preference is given to those starting monomers or starting oligomers which in the polymerization to the polyamides nylon 6; Nylon 6,6; Nylon 4,6; Nylon 5,10; Nylon 6,10; Nylon 7; Nylon 1 1; Nylon 12; especially nylon 6 and nylon 6,6.

The optionally present triacetonediamine (TAD) end groups are derived from 4-amino-2,2,6,6-tetramethylpiperidine. The TAD can be attached to the polyamide via an amino or carboxyl group. It may also be, for example, 4-carboxy-2,2,6,6-tetramethylpiperdine.

The polymerization of the monomers for the polyamides A is known per se or can be carried out by known processes. For example, the polymerization or polycondensation of the starting monomers, for example in the presence of the piperidine compounds, can be carried out under customary process conditions, it being possible for the reaction to take place continuously or batchwise. The piperidine compounds can - if present - but also with a chain regulator, as it is commonly used for the production of polyamides, combined. Information on suitable methods can be found, for example, in In WO 1995/28443, WO 1999/41297 or DE-A-198 12 135. The TAD compound is bound to the polyamide by reaction of at least one of the amide-forming groups. The secondary amino groups of the piperidine ring systems do not react because of steric hindrance. It is also possible to use polyamides prepared by co-polycondensation of two or more of the above monomers or their components, e.g. B. copolymers of: adipic acid, isophthalic acid or terephthalic acid and

 Hexamethylenediamine or copolymers of caprolactam,

 Terephthalic acid and hexamethylenediamine.

Such partially aromatic copolyamides contain from 40 to 90% by weight of units derived from terephthalic acid and hexamethylenediamine. A small proportion of the terephthalic acid, preferably not more than 10% by weight, of the total aromatic dicarboxylic acids used may be replaced by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position. A partially aromatic polyamide is nylon 9T, which is derived from nonanediamine and terephthalic acid.

As monomers it is also possible to use cyclic diamines such as those of the general formula (VII)

in the

R ^{1 is} hydrogen or a C ¹ -C ₄ -alkyl group,

R ^{2 is} a Ci - C ₄ alkyl group or hydrogen, into consideration. Particularly preferred diamines of the formula (VII) are bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) -2,2-propane or bis (4-amino-3- methylcyclohexyl) -2,2-propane.

Further diamines of the formula (VII) which may be mentioned are 1,3,3 or 1,4-cyclohexanediamine or isophoronediamine. In addition to the units derived from terephthalic acid and hexamethylenediamine, the partly aromatic copolyamides contain units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine. The proportion of units derived from ε-caprolactam is up to 50% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units derived from adipic acid and hexamethylenediamine, up to 60 wt .-%, preferably 30 to 60 wt .-% and in particular 35 to 55 wt .-% is. The copolyamides may also contain both units of ε-caprolactam and units of adipic acid and hexamethylenediamine; in this case, care must be taken that the proportion of units which are free of aromatic groups is at least 10% by weight, preferably at least 20% by weight. The ratio of the units derived from ε-caprolactam and from adipic acid and hexamethylenediamine is subject to no particular restriction. Polyamides having from 50 to 80, in particular from 60 to 75,% by weight of units derived from terephthalic acid and hexamethylenediamine and from 20 to 50, preferably from 25 to 40,% by weight of units derived from ε -Caprolactam derived. The preparation of partially aromatic copolyamides can, for. Example, according to the method described in EP-A 0 129 195 and EP-A 0 129 196.

Preferred partially aromatic polyamides are those which have a content of triamine units, in particular units of dihexamethylenediamine of less than 0.555% by weight, ie 0 to 0.554% by weight, preferably 0 to 0.45% by weight, particularly preferably 0 to 0.3% by weight.

Preference is given to using linear polyamides having a melting point above 200.degree. C. as component A.

Preferred polyamides are also Polyhexamethylenadipinsäureamid, Polyhexa- methylensebacinsäureamid and polycaprolactam and polyamide 6 / 6T and polyamide 66 / 6T and polyamides containing cyclic diamines as comonomers.

The polyamides generally have a relative viscosity of 2.0 to 5, determined on a 1 wt .-% solution in 96 wt .-% sulfuric acid at 23 ° C, which corresponds to a number average molecular weight of 15,000 to 45,000 , Polyamides having a relative viscosity of from 2.4 to 3.5, in particular from 2.5 to 3.4, are preferably used.

Also suitable are polyamides, the z. B. by condensation of 1, 4-diaminobutane with adipic acid are available at elevated temperature (polyamide 4.6). Manufacturing process for polyamides of this structure are z. In EP-A 038 094, EP-A 038 582 and EP-A 039 524. Preferred polyamides are also described in the experimental section.

Component B: As component B, the thermoplastic molding compositions according to the invention contain one or more styrene copolymers. In this case, any suitable comonomers can be present in the copolymers in addition to styrene. Preferably component B is a styrene-acrylonitrile copolymer (SAN), alpha-methylstyrene-acrylonitrile copolymer or N-phenylmaleimide-styrene copolymer. The components often have a viscosity number VZ equal to or less than 85 ml / g. The viscosity number (VZ) is measured according to DIN 53727 at 25 ° C, as 0.5 wt .-% solution in dimethylformamide; This measuring method also applies to all viscosity numbers mentioned below.

The component B, in particular the SAN, is often contained in an amount of 14 to 30 wt .-% in the molding composition. Preferred components B are composed of 50 to 90% by weight, preferably 60 to 85% by weight, in particular 70 to 83% by weight, styrene and 10 to 50% by weight, preferably 15 to 40% by weight , in particular 17 to 30% by weight, acrylonitrile and optionally 0 to 5 wt .-%, preferably 0 to 4 wt .-%, in particular 0 to 3 wt .-%, of further monomers, wherein the wt .-% in each case are based on the weight of component B and together give 100 wt .-%.

Further preferred components B are composed of 50 to 90 wt .-%, preferably 60 to 80 wt.%, In particular 65 to 78 wt .-%, α-methylstyrene and 10 to 50 wt .-%, preferably 20 to 40 Wt .-%, in particular 22 to 35 wt .-%, acrylonitrile, and optionally 0 to 5 wt .-%, preferably 0 to 4 wt .-%, in particular 0 to 3 wt .-%, of further monomers, wherein the % By weight in each case based on the weight of component B and together give 100% by weight.

Components B which are likewise preferred are mixtures of these styrene-acrylonitrile copolymers or α-methylstyrene-acrylonitrile copolymers with N-phenylmaleimide-styrene copolymers or N-phenylmaleimide-styrene-acrylonitrile terpolymers. As the other monomers mentioned above, usable are all copolymerizable monomers such as p-methylstyrene, t-butylstyrene, vinylnaphthalene, alkylacrylates and / or alkylmethacrylates, for example those having C 1 to C ₈ alkyl radicals, N-phenylmaleimide or mixtures thereof. The copolymers of component B, preferably the S-AN copolymers, can be prepared by known methods. You can z. B. by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. They have viscosity numbers in the range of 40 to 160 ml / g, which corresponds to average molecular weights Mw (weight average) of 40,000 to 2,000,000 g / mol. Component C:

Component C used is one or more rubber-elastic graft copolymers of vinylaromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, on polybutadiene rubbers. The amount of component C is often 14 to 35 wt .-% of the molding composition according to the invention.

A method for characterizing the crosslinking state of crosslinked polymer particles is the measurement of the swelling index (Q1), which is a measure of the swellability of a more or less strongly crosslinked polymer by a solvent. Typical swelling agents are, for example, methyl ethyl ketone or toluene. The Q1 of the graft copolymer C of the molding compositions according to the invention usually lies in the range Q1 = 7 to 20. Preference is given to a Q1 of from 8 to 15, more preferably from 8 to 13 in toluene.

To determine the swelling index, an aqueous dispersion of the graft copolymer C is dried on a plate at 80 ° C. under a slight vacuum (600 to 800 mbar) and nitrogen atmosphere overnight. Of the approximately 2mm thick remaining film then a 1 cm ² large slice is cut and swollen in 50ml toluene (or methyl ethyl ketone) in a penicillin glass overnight. The supernatant toluene is filtered off with suction, the swollen film is weighed and dried overnight at 80.degree.

The weight of the dried film is determined. The swelling index results from the quotient of the weights of the swollen gel and the dried gel. Component C preferably consists of one or more impact-modifying graft rubbers with an olefinic double bond in the rubber phase. The graft polymer C is composed of a "soft" elastomeric, particulate "grafting base" C1, and a "hard grafting pad" C2.

The grafting base C1 is contained in a proportion of 40 to 90, preferably 45 to 85 and particularly preferably 50 to 80 wt .-%, based on the component C. The grafting base C1 is obtained by polymerization of, based on C1, 70 to 100, preferably 75 to 100 and particularly preferably 80 to 100 wt .-% of at least one conjugated diene C1 1, and 0 to 30, preferably 0 to 25 and particularly preferably 0 to 10% by weight of at least one further monoethylenically unsaturated monomer. The conjugated dienes C1 1 are butadiene, isoprene, chloroprene or mixtures. Preference is given to butadiene or isoprene or mixtures thereof, especially butadiene.

In addition, the constituent C1 of the molding compositions may contain, at the expense of the monomers C1, further monomers C12 which vary the mechanical and thermal properties of the core within a certain range. Examples of such monoethylenically unsaturated comonomers are: styrene, alpha-methylstyrene, acrylonitrile, maleic anhydride, acrylic acid, methylacrylic acid, maleic acid or fumaric acid. Styrene, α-methylstyrene, n-butyl acrylate or mixtures thereof are preferably used as monomers C12, particularly preferably styrene and n-butyl acrylate or mixtures thereof and very particularly preferably styrene. Styrene or n-butyl acrylate or mixtures thereof are used in particular in amounts of together up to 20 wt .-%, based on C1. In a particular embodiment, a graft base is used, based on C1:

 C1 1 70 to 99.9, preferably 90 to 99 wt .-% butadiene, and

 C12 0.1 to 30, preferably 1 to 10 wt .-% styrene. The graft C2 is contained in a proportion of 10 to 60, preferably 15 to 55 and particularly preferably 20 to 50 wt .-%, based on the component C.

The graft C2 is obtained by polymerization of, based on C2:

C21 65 to 95, preferably 70 to 90 and particularly preferably 72 to 85 wt .-% of at least one vinyl aromatic monomer;

 C22 5 to 35, preferably 10 to 30 and particularly preferably 15 to 28 wt .-% acrylonitrile;

 C23 0 to 30, preferably 0 to 20 and particularly preferably 0 to 15 wt .-% of at least one further monoethylenically unsaturated monomer.

As vinylaromatic monomers it is possible to use styrene and / or alpha-methylstyrene. Suitable further monomers C23 are the monomers mentioned above for component C12. In particular, methyl methacrylate and acrylates such as n-butyl acrylate are suitable. Especially suitable as monomer C23 is methyl methacrylate MMA, wherein an amount of up to 20 wt .-% MMA, based on C2, is preferred.

The graft polymers are often prepared by the process of emulsion polymerization. Usually polymerized at 20 to 100 ° C, preferably 30 to 90 ° C. In general, conventional emulsifiers are used, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, higher fatty acid salts of 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or rosin soaps. The alkali metal salts, in particular the Na and K salts, of alkylsulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.

As a rule, the emulsifiers are used in amounts of from 0.5 to 5% by weight, in particular from 0.5 to 3% by weight, based on the monomers used in the preparation of the grafting base C1. So much water is preferably used to prepare the dispersion that the finished dispersion has a solids content of from 20 to 50% by weight. Usually, a water / monomer ratio of 2: 1 to 0.7: 1 is used.

To start the polymerization reaction, all radical formers are suitable which decompose at the chosen reaction temperature, ie both those which thermally decompose alone, as well as those which do so in the presence of a redox system. Suitable polymerization initiators are preferably free-radical initiators, for example peroxides, such as preferably peroxosulfates (for example sodium persulfate or potassium persulfate) and azo compounds, such as azodiisobutyronitrile.

 However, it is also possible to use redox systems, in particular those based on hydroperoxides, such as cumene hydroperoxide.

As a rule, the polymerization initiators are used in an amount of from 0.1 to 1% by weight, based on the graft-base monomers C1 1 and C12. The free-radical generators and also the emulsifiers are added to the reaction batch, for example batchwise as a total amount at the beginning of the reaction, or divided into several portions batchwise at the beginning and at one or more later times, or added continuously over a certain time interval. The continuous addition may also be along a gradient, e.g. ascending or descending, linear or exponential, or may be stepwise (step function).

It is also possible to use molecular weight regulators, such as, for example, ethylhexyl thioglycolate, n- or t-dodecyl mercaptan or other mercaptans, terpinols and dimeric α-methylstyrene or other compounds suitable for controlling the molecular weight. The molecular weight regulators are added to the reaction mixture batchwise or continuously, as described above for the free-radical formers and emulsifiers. To maintain a constant pH, which is preferably from 6 to 9, it is possible to use buffer substances such as Na 2 HPO 4 / NaH 2 PO 4, sodium bicarbonate or buffers based on citric acid / citrate. Regulators and buffer substances are used in the usual amounts, so that further information is unnecessary.

In a particularly preferred embodiment, a reducing agent is added during the grafting of the grafting base C1 with the monomers C21 to C23. In a particular embodiment, the graft base can also be prepared by polymerization of the monomers C1 in the presence of a finely divided latex (so-called "seed latex procedure" of the polymerization). This latex is presented and may consist of elastomeric polymer-forming monomers, or of other monomers, as they have already been mentioned. Suitable seed latices consist for example of polybutadiene or polystyrene.

In another preferred embodiment, it is possible to prepare the graft base C1 in the so-called feed process. In this process, a certain proportion of the monomers C1 is initially charged and the polymerization is started, after which the remainder of the monomers ("feed fraction") C1 is added as feed during the polymerization.

The feed parameters (shape of the gradient, amount, duration, etc.) depend on the other polymerization conditions. Analogously, the statements made here for the addition of the radical starter or emulsifier apply as well. In the feed process, the proportion of monomers present is preferably from 5 to 50, particularly preferably from 8 to 40,% by weight, based on C 1. The feed fraction of C1 is preferably allowed to run in within 1 to 18 hours, in particular 2 to 16 hours, very particularly 4 to 12 hours.

Furthermore, graft polymers having a plurality of "soft" and "hard" shells, e.g. of the structure C1 -C2-C1 -C2, or C2-C1 -C2, especially in the case of larger particles.

The exact polymerization conditions, in particular the type, amount and dosage of the emulsifier and the other polymerization aids are preferably chosen so that the resulting latex of the graft polymer C, an average particle size, defined by the d50 value of the particle size distribution, from 80 to 800, preferably 80 to 600 and more preferably 85 to 400 measured by HDC (W Wohlleben and H. Schuch in Measurement of Particle Size Distribution of Polymer Latexes, 2010, Editors: Luis M. Gugliotta and Jorge R. Vega, p - 153). The reaction conditions are preferably coordinated so that the polymer particles of C have a bimodal particle size distribution, ie a size distribution with two more or less pronounced maxima. The first maximum is more pronounced (comparatively narrow peak) than the second and is generally from 25 to 200, preferably from 60 to 170, particularly preferably from 70 to 150 nm. The second maximum is generally from 150 to 800, preferably from 180 to 700, more preferably 200 to 600 nm. The second maximum (150 to 800 nm) is at larger particle sizes than the first maximum (25 to 200 nm). Preferably, the bimodal particle size distribution is achieved by (partial) agglomeration of the polymer particles. This can be done, for example, as follows: polymerizing the monomers C1, which form the core, to a conversion of usually at least 90, preferably greater than 95%, based on the monomers used. This turnover is usually reached after 4 to 20 hours. The obtained rubber latex has a mean particle size d50 of at most 200 nm and a narrow particle size distribution (almost monodisperse system).

In the second stage, the rubber latex is agglomerated. This is usually done by adding a dispersion of an acrylic ester polymer. Dispersions of copolymers of (C 1 -C ₄ -alkyl) esters of acrylic acid, preferably of ethyl acrylate, with monomers forming from 0.1 to 10% by weight of polar polymers, such as, for example, acrylic acid, methacrylic acid, acrylamide or methacrylamide, N-methylol, are preferred - methacrylamide or N-vinylpyrrolidone used. Preferred is a composition of 80 to 98% ethyl acrylate and 2 to 20% methacrylamide, more preferred is a composition of 90 to 98% ethyl acrylate and 2 to 10% methacrylamide. If appropriate, the agglomerating dispersion may also contain several of the stated acrylic ester polymers.

The concentration of the acrylic ester polymers in the dispersion used for agglomeration should generally be between 3 and 40% by weight. In the agglomeration, 0.2 to 20, preferably 1 to 5 parts by weight of the agglomerating dispersion are used per 100 parts of the rubber latex, calculated in each case on solids. The agglomeration is carried out by adding the agglomerating dispersion to the rubber. The rate of addition is usually not critical, generally it takes about 1 to 30 minutes at a temperature between 20 and 90 ° C, preferably between 30 and 75 ° C.

Apart from an acrylic ester polymer dispersion, the rubber latex may also be agglomerated by other agglomerating agents such as acetic anhydride. Also an agglomeration by pressure or freezing (pressure or freezing agglomeration) is possible. The methods mentioned are known to the person skilled in the art.

Under the conditions mentioned, only a part of the rubber particles is agglomerated, resulting in a bimodal distribution. In general, more than 50, preferably between 75 and 95% of the particles (number distribution) are present in the non-agglomerated state after agglomeration. The resulting partially agglomerated rubber latex is relatively stable so that it can readily be stored and transported without coagulation occurring.

In order to achieve a bimodal particle size distribution of the graft polymer C, it is also possible to prepare two different graft polymers C and C ", which differ in their average particle size, separately in the usual way and to add the graft polymers C and C" in the desired ratio ,

Usually, the polymerization of the grafting base C1 is carried out by selecting the reaction conditions so that a grafting base results in a certain state of crosslinking.

Examples of essential parameters for this purpose are the reaction temperature and duration, the ratio of monomers, regulators, free radical initiators and, for example, in the feed process, the feed rate and the amount and time of addition of regulator and initiator.

One method for characterizing the crosslinking state of crosslinked polymer particles is the measurement of the swelling index Q1, which is a measure of the swellability of a more or less strongly crosslinked polymer by a solvent. Typical swelling agents are, for example, methyl ethyl ketone or toluene. The Q1 of the ungrafted inventive molding compositions C1 is usually in the range Q1 = 10 to 60, preferably 15 to 55 and particularly preferably 20 to 50 in toluene.

Another method for characterizing the state of crosslinking is the measurement of NMR relaxation times of the mobile protons, the so-called T2 times. The more networked a particular network is, the lower its T2 times. Typical T2 times for the graft bases C1 according to the invention are mean T2 times in the range from 2.0 to 4.5 ms, preferably 2.5 to 4.0 ms and particularly preferably 2.5 to 3.8 ms, measured on filmed samples at 80 ° C. Another measure of the characterization of the grafting base and its state of crosslinking is the gel content, ie that part of the product which is crosslinked and thus insoluble in a certain solvent. It makes sense to determine the gel content in the same solvent as the swelling index. Usual gel contents of the graft bases C1 according to the invention are in the range from 50 to 90%, preferably from 55 to 85% and particularly preferably from 60 to 80%.

The determination of the swelling index is carried out, for example, according to the following procedure: About 0.2 g of the solid of a graft base dispersion filmed by evaporation of the water are swollen in a sufficiently large amount (for example 50 g) of toluene. After e.g. The toluene is filtered off with suction for 24 h and the sample is weighed out. After drying the sample in vacuo is weighed again. The swelling index is the ratio of the weight after the swelling process to the weight dry after re-drying. Accordingly, the gel fraction is calculated from the ratio of the dry weight after the swelling step to the weight before the swelling step (x 100%).

The T2 time is determined by measuring the NMR relaxation of a dewatered and filmed sample of the graft base dispersion. For example, the sample is flashed overnight at e.g. Dried at 60 ° C. for 3 h in vacuo and then measured at 80 ° C. using a suitable measuring instrument (for example Bruker Minispec apparatus). Comparable are only samples that were measured by the same method, since the relaxation is significantly temperature-dependent. The preparation of the graft C2 can be done under the same conditions as the preparation of the graft c1, where it is possible to produce the overlay C2 in one or more steps. For example, in a two-stage grafting reaction, styrene or α-methylstyrene alone can be polymerized first, followed by polymerization of styrene and acrylonitrile in two consecutive steps. This two-stage grafting (initially styrene, then styrene / acrylonitrile) is a preferred embodiment. Further details of the preparation of the graft polymers C are described in DE 12 60 135 and 31 49 358.

It is advantageous to carry out the graft polymerization onto the graft base C1 in turn in aqueous emulsion. It can be carried out in the same system as the polymerization of the grafting base, wherein further emulsifier and initiator can be added. These need not be identical to the emulsifiers or initiators used to prepare the graft base C1. For example, it may be expedient to use a persulfate as initiator for the preparation of the graft base C1, but a redox initiator system for the polymerization of the graft shell C2 use. For the choice of emulsifier, initiator and polymerization auxiliaries said in the preparation of the grafting C1 said. The monomer mixture to be grafted on can be added to the reaction mixture all at once, batchwise in several stages, or preferably continuously during the polymerization.

Insofar as the grafting of the grafting base C1 does not give grafted polymers of the monomers C2, the amounts which as a rule are less than 10% by weight of C2 are assigned to the mass of the component C.

The graft copolymers C according to the invention can be used as they are obtained in the reaction mixture, for example as a latex emulsion or dispersion. Alternatively and as it is preferred for most applications, but they can also be worked up in a further step. Measures for processing are known to the person skilled in the art.

This includes, for example, the graft copolymers C being isolated from the reaction mixture, e.g. by spray-drying, shearing or by precipitation with strong acids or by nucleating agents such as inorganic compounds e.g. Magnesium sulfate. However, the graft copolymers C present in the reaction mixture can also be worked up by dehydrating them in whole or in part. It is also possible to carry out the workup by means of a combination of the measures mentioned. The Q1 of the graft copolymers is usually in the range Q1 = 7 to 20, preferably 8 to 15 and particularly preferably 8 to 13

The mixing of the components B and C for the preparation of the molding composition can be carried out in any manner by all known methods. If these components have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, then jointly precipitate the polymers and work up the polymer mixture. Preferably, however, the mixing of these components is carried out by coextruding, kneading or rolling the components, the components, if necessary, having previously been isolated from the solution or aqueous dispersion obtained during the polymerization. The products B of the graft copolymerization obtained in aqueous dispersion can also be only partially dewatered and mixed as a moist crumb with the hard matrix B, during which the complete drying of the graft copolymers C takes place during the mixing. Component D:

Component D of the molding compositions of the invention is a compound of the formula (I):

This sterically hindered amine (CAS number 52829-07-9) and its preparation are described in the literature (US 4,396,769 and literature cited therein). Displaced persons will ben from BASF under the name Tinuvin ^® 770. The amount of component D is often from 0.3 to 1, 1 wt .-% of the molding composition.

Component E: Component E of the molding compositions of the invention is a compound of the formula (II):

n = 2 to 20, especially the formula below

These sterically hindered amines, such as. CAS number 167078-06-0, and the preparation are known to those skilled in the art and described in the literature (Carlsson, Journal of Polymer Science, Polymer Chemistry Edition (1982), 20 (2), 575-82). Distributed is the product CAS number 167078-06-0 z. B. from Cytec Industries under the designation Cyasorb ^® 3853. The sterically hindered amine of the formula (II) can also be in polypropylene at concentrations of 1 to 60% are present as sold for example, from Cytec Industries under the name Cyasorb ^® 3853 PP5, and Be incorporated polypropylene. The amount of component E is often 0.2 to 0.7 wt .-% of the molding composition. Component F: As component F of the molding compositions of the invention, a compound of formula (III) can be used:

This sterically hindered amine (CAS number 71878-19-8) and its preparation are described in the literature (EP-A 093 693 and literature cited therein). Sold it by BASF SE under the name Chimassorb ^® 944th

As a further component F of the molding compositions of the invention, a compound of formula (IV) can be used:

 n = 2 to 20

This sterically hindered amine (CAS number 101357-37-3) and its preparation are described in the literature (US Pat. No. 5,208,132 and literature cited therein). It is sold by ADEKA under the name Adeka Stab ^® LA-68. As a further component F of the molding compositions of the invention, a compound of formula (V) can be used:

 n = 2 to 20

This sterically hindered amine (CAS number 82451-48-7) and its preparation are described in the literature (US 4,331,586 and the references cited therein). Sold it by Cytec Industries under the name Cyasorb ^® UV 3346th

As a further component F of the molding compositions of the invention, a compound of formula (VI) can be used:

This sterically hindered amine (CAS number 192268-64-7) and its preparation are described in the literature (EP-A 0 782 994 and literature cited therein). It is sold by BASF SE under the name Chimassorb ^® 2020.

The amount of component F is often (if present) 0.2 to 0.8 wt.% Of the molding composition. Component G: As component G, the thermoplastic molding compositions according to the invention also contain styrene copolymers, based on the total component G, from 0.5 to 5 wt .-%, preferably 1, 0 to 2.5, in particular 1.7 to 2.3 wt .-%, derived from maleic anhydride units. This proportion of units is particularly preferably from 2.0 to 2.2% by weight, especially about 2.1% by weight.

More preferably, component G is a styrene-acrylonitrile-maleic anhydride terpolymer or a styrene-N-phenylmaleimide-maleic anhydride terpolymer. In the terpolymer, the proportion of acrylonitrile, based on the total terpolymer, is preferably 10 to 30% by weight, more preferably 15 to 30% by weight, in particular 20 to 25% by weight. The remainder is styrene and the third monomer.

The copolymers generally have molecular weights M _w in the range from 30,000 to 500,000 g / mol, preferably from 50,000 to 250,000 g / mol, in particular from 70,000 to 200,000 g / mol, determined by GPC using tetrahydrofuran (THF) as the eluent and with polystyrene calibration.

The copolymers of component G can be prepared by free-radical-forming polymerization of the corresponding monomers. The preparation is explained in more detail, for example, in WO 2005/040281, page 10, line 31 to page 11, line 8.

Further, as component G and styrene-N-phenylmaleimide-maleic anhydride terpolymers can be used. Reference may be made to the descriptions in EP-A 0 784 080 and DE-A 100 24 935, as well as to DE-A 44 07 485, description of the local component B on pages 6 and 7.

The component G is often contained in an amount of 3 to 7 wt .-% in the molding composition.

Component H:

The molding compositions according to the invention may have an additional component H which contains at least one rubber (rubber other than component C). Optionally, mixtures of two or more rubbers can be used. The thermoplastic molding compositions preferably comprise an additional rubber if component H is present in the molding compositions according to the invention. As component H (rubber H) are ungrafted or grafted, non-particulate rubbers without core-shell structure, which have functional groups which can react with the end groups of component A (polyamide) Suitable functional groups are, for example:

 Carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide, carboxylic acid imide, amino, hydroxyl, epoxy, urethane and oxazoline groups.

Suitable monomers for introducing the functional groups are, for example, maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacrylate. These monomers can be reacted, for example in the presence of a free radical initiator such as cumene hydroperoxide, with the starting rubber, for example in the melt or in solution, for example grafted, by methods known to those skilled in the art.

As rubbers H, for example, copolymers of α-olefins are suitable which have functional groups which can react with the end groups of component A. The α-olefins are usually monomers having 2 to 8 C atoms, preferably ethylene and propylene, in particular ethylene. Particularly suitable comonomers are alkyl acrylates or alkyl methacrylates which are derived from alcohols having 1 to 8 C atoms, preferably from ethanol, butanol or ethylhexanol, and reactive comonomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or glycidyl (meth) acrylate and furthermore vinyl esters, in particular Vinyl acetate, into consideration. Mixtures of different comonomers can also be used. Particularly suitable are copolymers of ethylene with ethyl or butyl acrylate and acrylic acid and / or maleic anhydride.

Another preferred embodiment of these rubbers H are ethylene-propylene copolymers ("EP rubbers") which have functional groups which can react with the end groups of component A.

Particularly preferred rubbers H are those based on ethylene and octene, which have functional groups which can react with the end groups of component A. Considering for example the commercial product Fusabond ^® MN 493D from DuPont are, in particular with maleic anhydride grafted ethylene-octene copolymers.

These copolymers can be prepared in a high-pressure process at a pressure of from 400 to 4500 bar or by grafting the comonomers onto a poly-α-olefin. the. The proportion of the α-olefin in the copolymer is usually in the range of 99.95 to 55% by weight.

Suitable rubbers H are, for example, composed of ethylene, propylene and a diene ("EPDM rubber") which have functional groups which can react with the end groups of component B). As EPDM rubbers are preferably used those which have a glass transition temperature in the range of -60 to -40 ° C. The EPDM rubbers have only a small number of double bonds per 1000 C atoms, in particular 3 to 10 double bonds per 1000 C atoms. Examples of such EPDM rubbers are terpolymers of at least 30% by weight of ethylene, at least 30% by weight of propylene and from 0.5 to 15% by weight of a non-conjugated diolefinic component. As a functionalized EPDM rubber is, for example, the Royaltuf ^® 485 Chemtura in question. As the diene component for EPDM rubbers, diolefins having at least 5 carbon atoms such as 5-ethylidenenorbornene, dicyclopentadiene, 2,2,1-dicyclopentadiene and 1,4-hexadiene are usually used. Also suitable are polyalkyleneamers such as polypentamer, polyoctenamer, polydodecanamer or mixtures of these substances. Also suitable are partially hydrogenated polybutadiene rubbers in which at least 70% of the residual double bonds are hydrogenated. Typically, EPDM rubbers have a Mooney viscosity ML _1-4 (100 ° C) of 25 to 120. They are commercially available.

Suitable rubbers H are furthermore those of vinylaromatic monomers and dienes, for example styrene and butadiene or isoprene, it being possible for the dienes to be completely or partially hydrogenated, which have functional groups which are able to react with the end groups of component A. For example, such copolymers may be random or have a block structure of vinyl aromatic blocks and diene blocks, or may have a tapered structure (gradient from polymer poor to high in value along the polymer chain). The copolymers can be linear, branched or star-shaped. The block copolymers may have two or more blocks, and the blocks may also be random or tapered.

Suitable styrene-butadiene copolymers are, for example, diblock copolymers styrene-butadiene ("SB"), triblock copolymers styrene-butadiene-styrene ("SBS") and in particular hydrogenated triblock copolymers styrene-ethenebutene-styrene ("SEBS"). Such copolymers of styrene and dienes are available for example as Styrolux ^® or Styroflex ^® of BASF SE. Functionalized with anhydride groups styrene Ethenbuten- block copolymers are commercially available, for example, as Kraton ^® FG-1901 FX. The abovementioned block copolymers are customarily prepared by sequential anionic polymerization. In this case, for example, first styrene is polymerized with an organolithicon compound as initiator to form a styrene block, then butadiene is added and a butadiene block is polymerized onto the styrene block, optionally subsequently styrene is added again and a styrene block is polymerized. A possible hydrogenation of the diene blocks is usually carried out catalytically under hydrogen pressure.

Component I:

In addition to the components A, B, C, D, E, F, G and H molding compositions of the invention one or more, different from the components D, E, F, G and H additives or additives that are typical for plastic mixtures and in use included.

As such additives or additives may be mentioned, for example: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the resistance to hydrolysis and chemical resistance, means against the heat decomposition and in particular the lubricants / lubricants used for the production Of moldings or moldings are appropriate. The dosing of these other additives can be done at any stage of the manufacturing process, but preferably at an early stage, to take advantage of the stabilizing effects (or other specific effects) of the additive at an early stage. Heat stabilizers or oxidation inhibitors are usually metal halides (chlorides, bromides, iodides), which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).

Stabilizers which are suitable as component I are the customary hindered phenols, but also "vitamin E" or compounds of analogous construction. Also suitable are benzophenones, resorcinols, salicylates, benzotriazoles and other compounds. , preferably 0.01 to 2 wt .-% (based on the total weight of the molding compositions of the invention) used.

Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12 to 30 carbon atoms. The amounts of these additives are, if present, in the range of 0.05 to 1 wt .-% (based on the total weight of the molding compositions of the invention). Also, silicone oils, oligomeric isobutylene or similar substances are suitable as additives, the usual amounts are - if present - 0.05 to 5 wt .-% (based on the total weight of the molding compositions of the invention). Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are also usable.

Processing aids, lubricants and antistatic agents are usually used in amounts of 0 to 2 wt .-%, preferably 0.01 to 2 wt .-% (based on the total weight of the molding compositions of the invention).

Of the component I, the molding materials, e.g. 0 to 17 wt .-%, often 0 to 5 wt .-%, which may often be soot.

Component J:

As component J, the molding compositions according to the invention of the other components A to I different fibrous or particulate fillers or mixtures thereof. These are preferably commercially available products, for example carbon fibers and glass fibers.

Useful glass fibers may be of E, A or C glass and are preferably equipped with a size and a primer. Their diameter is generally between 6 and 20 μηη. Both endless fibers and chopped glass fibers (staple) or so-called "rovings with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used.

Furthermore, fillers or reinforcing materials such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powder and wollastonite can also be added as component J.

In addition to the components A, B, C, D, E, F, G and optionally H, I and J, the molding compositions according to the invention may in principle also contain other polymers.

The molding compositions of the invention can be prepared by any of the known methods. Preferably, however, the mixing of the components by melt-mixing, for example, common extrusion, kneading or rolling of the components, z. B. at temperatures in the range of 160 to 400 ° C, preferably from 180 to 280 ° C. In a preferred embodiment, the components may have previously been partially or completely isolated from the reaction mixtures obtained in the respective production steps. For example, the graft copolymers C can be mixed as wet crumbs with a granulate of the vinyl aromatic copolymer B, in which case the complete drying takes place during mixing to the described graft copolymers.

The components can be supplied in each case in pure form to suitable mixing devices, in particular extruders, preferably twin-screw extruders. However, it is also possible for individual components, for example B and C, to be premixed first and then mixed with further components B or C or other components, for example D and E. The component B can be used as a pre-separately prepared component. It is also possible to dose the rubber and the vinyl aromatic copolymer independently.

In one embodiment, a concentrate, for example components D and E in component B is first prepared (so-called additive batches or masterbatches) and then mixed with the desired amounts of the remaining components. The molding compositions can be processed, for example, into granules by methods known to the person skilled in the art, or else directly into, for example, shaped bodies.

The molding compositions of the invention can be processed into films, moldings or fibers. These films, moldings or fibers are particularly suitable for outdoor use, i. under the influence of the weather, suitable. These films, moldings or fibers can be prepared by the known methods of thermoplastic processing from the molding compositions of the invention. In particular, the production by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, pressing sintering, deep drawing or sintering, preferably by injection molding, take place.

The molding compositions of the invention have over the known stabilized molding compositions again improved weathering resistance, i. a further improved heat, light and / or oxygen resistance on. This applies in particular to molding masks containing the special components A-i, A-ii, B-i, C-i, D-i, E-i, F-i, F-ii, G-i and / or l-i mentioned in the experimental section.

The invention will be explained in more detail with reference to the following examples and claims. A) Measurement methods:

The notched impact strength of the products was determined at room temperature on ISO rods according to ISO 179 1 eA.

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

The surface gloss of all samples was measured according to DIN 67530 at 60 ° viewing angle.

As a measure of the weather resistance was on test specimens (60 x 60 x 2mm, prepared according to ISO 294 in a family tool, at a melt temperature of 260 ° C and a mold temperature of 60 ° C) weathering according to xenon test according to ISO 4892/2, method A, outside, performed. The samples were not subjected to additional treatment after weathering. After the weathering time of 300 h and 600 h (h = hour) mentioned in Table 1, the surface was assessed on the basis of the gray value (5: no change, 1: massive change) according to ISO 105-A02 (1993).

As a further measure of the weather resistance, the change in the color space ΔΕ was calculated according to DIN 52 336 from ΔΙ_, Aa and Ab according to DIN 6174.

As a further measure of the weathering resistance, the puncture or the multi-axial toughness was measured on flakes (60 × 60 × 2 mm, produced according to ISO 294 in a family mold, at a melt temperature of 260 ° C. and a mold temperature of 60 ° C.) according to ISO 6603 -2 determined at room temperature.

B) starting materials

Components or products preceded by "V-" are not inventive and are for comparison.

As component A (or V-A for comparison) were used:

A-i: The polyamide was a polyamide 6, obtained from ε-caprolactam, with a

Viscosity number of 150 ml / g (measured 0.5% by weight in 96% strength ferric acid), commercially available, for example, from BASF SE® under the name Ultramid® B 3.

A-ii: The polyamide was a polyamide 6, obtained from ε-caprolactam, with a

 Viscosity number of 130 ml / g (measured 0.5 wt .-% in 96% sulfuric acid) and a proportion of triacetonediamine of 0.16 wt .-% used.

V-A-ii from Lyondell Basell Industries AF S.C.A. commercially available polypropylene Moplen® HP500N.

V-A-iii: a polystyrene marketed by BASF SE under the name Polystyrol® 158K.

As component B was used:

Bi: a styrene-acrylonitrile copolymer with 75 wt .-% of styrene and 25 wt .-% acrylonitrile and a viscosity number of 80 ml / g (determined in 0.5 wt .-% DMF solution at 25 ° C. ). As component C (or V-C for comparison) were used:

C-i: a butadiene graft rubber, whose synthesis in DE 197 28 629 A1 as

 Example A6 will be described. C-ii 41826.4g of butadiene and 1293.6g of styrene are in the presence of 432g

Tert. Dodecylmercaptan (TDM), 31 1 g of potassium salt of C12-C20 fatty acids, 82 g of potassium persulfate, 147 g of sodium bicarbonate and 58400 g of water at 65 ° C to a polybutadiene latex polymerized. In detail, the procedure was as described in EP-A 62901, Ex. 1, p. 9, Z. 20 to p. 10 Z. 6 wherein the TDM in deviation thereof in a

Portion was given at the beginning of the reaction. The turnover was 98%. The mean particle size d _{50 of} the latex was 134 nm, the swelling index was 20.3. The T ₂ time determined by NMR was from 3.8 to 2.9 ms.

 To agglomerate the latex, 35,000 g of the resulting latex were added

65 ° C by addition of 2700g of a dispersion (solids content 10 wt .-%) of 96 wt .-% ethyl acrylate and 4 wt .-% methacrylic acid amide agglomerated. Ci ₂ The agglomerated latex were added ₂ -C ₂ o-fatty acids and 17g potassium 9000g water 130g potassium salt of Ci. Subsequently, 18667 g of styrene and 4666 g of acrylonitrile were added at 75 ° C within 4 hours with stirring. The conversion, based on the grafting monomers, which is almost quantitative. The obtained

Graft polymer dispersion had a bimodal particle size distribution. A first maximum of the particle size distribution was 166nm, a second maximum in the range 442nm.

 The obtained dispersion was added with an aqueous dispersion of an antioxidant and then coagulated by adding a magnesium sulfate solution. The coagulated rubber was removed by centrifugation from the dispersion water and washed with water. This gave a rubber with about 30 wt .-% adherent or trapped residual water.

This gave a swelling index of 8.8 for C-i in toluene.

VC-ii: The preparation was carried out according to component Ci, but with 44 g tert-dodecyl mercaptan (TDM) instead of 432 g tert-dodecylmercaptan (TDM). The T ₂ time determined by NMR was from 3.5 to 2.5 ms. After the in

C ₂ described grafting resulted in a swelling index of 6.3 in toluene. The mean particle size was determined to be 316nm.

As component D (or V-D for comparison) were used:

Di: a compound of formula (I), commercialized by BASF SE under the name Tinuvin ^® 770th

VD-ii: A compound of formula (XII), commercially sold by BASF under the name Tinuvin ^® SE 765th

As component E was used:

Ei: a compound of formula (IIa), commercially sold by Cytec Industries under the designation Cyasorb ^® 3853rd

As component F (or VF for comparison) were used: a compound of formula (III), commercialized by BASF SE under the name Chimassorb ^® 944th

a compound of formula (V), commercially sold by Cytec Industries under the designation Cyasorb ^® UV 3346th

a high molecular weight sterically hindered amine of formula (XIII), CAS number 106990-43-6, sold commercially by SABO SpA under the name ^® Sabostab 1 nineteenth

As component G was used:

G-i: a styrene-acrylonitrile-maleic anhydride terpolymer having a composition of: 74.4% by weight of styrene; 23.5% by weight of acrylonitrile and 2.1% by weight

% Maleic anhydride (according to infrared measurement) and a viscosity number of 66 ml / g (determined in 0.5% strength by weight DMF solution at 25 ° C.).

As component I was used: l-i: carbon black type Black Pearls 880, sold commercially by Cabot Corporation.

Preparation of the molding compositions and moldings: The components A, B, C, D, E, F, G and I (respective parts by weight see Table 1) were homogenized in a twin-screw extruder (ZSK30 from. Werner & Pfleiderer) at 280 ° C and extruded a water bath. The extrudates were granulated and dried. From the granules was prepared on an injection molding machine at 260 ° C melt temperature and 60 ° C tool surface temperature test specimens ago and determined the properties listed in Table 1.

Table 1: Composition and properties of the molding compositions

(preceded V: for comparison)

Example V-1 2 3 4 5 V-6 V-7 V-8 V-9 V-10 V-1 1

composition

 A-i 40 40 40 40 40 40 40

A-ii 40

 V-A-iii 98.8

 V-A-iv 98.8 98

 B-i 19 18 18 18 18 18 18 18

C-i 35 35 35 35 35 35 35

V-C-ii 35

 D-i 0.5 0.5 0.5 0.5 0.1 0.1 0.5 0.5 0.5

V-D-ii 0.5

 E-i 0.5 0.25 0.5 0.1 0.1 0.5 0.5 0.5

 F-i 0.25

 F-ii 0.5

 V-F-iii 0.5

G-i 5 5 5 5 5 5 5 5 l-i 1 1 1 1 1 1 1 1 1 1 1 ak (kJ / m2) 49 53 51 54 48 2 2 2 29 52 50

Vicat B [° C] 102 100 99 101 99 86 101 99 100 101 100

Gloss 91 91 93 92 91 85 102 103 83 92 91

Gray value

to

0 h BWZ 5 5 5 5 5 5 5 5 5 5 5 300 h BWZ 1 4 4 4 4 5 5 5 3 2 2 600 h BWZ 1 4 4 4 4 5 1 3 1 1 1

ΔΕ after 0 h BWZ 0 0 0 0 0 0 0 0 0 0 0

300 h BWZ 17 0 0 0 0 1 2 1 8 10 9

600 h BWZ 18 1 0 0 1 1 2 2 13 15 12

puncture

to

0 h BWZ 45 42 44 40 33 4 1 1 36 46 45

300 h BWZ 13 33 37 34 26 2 0 1 21 22 28

600 h BWZ 5 27 29 27 17 0 0 0 9 12 14

The examples show that the molding compositions according to the invention comprising at least the components A, B, C, D and G have improved weather resistance compared to the known stabilized molding compositions, i. have improved heat, light, and / or oxygen resistance. The compositions are each given in parts by weight and the abbreviation BWZ stands for weathering time. An application of component D-i in combination with component E-i proves particularly favorable.

Claims

claims

□ plastic molding composition comprising the following components: a) from 3 to 91, 8% by weight of at least one polyamide, as component A b) from 3 to 91, 8% by weight of one or more styrene copolymers which have no units derived from maleic anhydride, as component B c) from 5 to 91, 8 wt .-% of one or more impact-modifying graft rubbers with olefinic double bond in the rubber phase, as component C d) 0.2 to 1, 5 wt .-% of a compound of formula (I ) as component D: e) 0 to 0.9% by weight of a mixture of the formula (II) as component E:

0 to 0.9% by weight of a compound of the formula (III) as component F:

or 0 to 0.9% by weight of a compound of the formula (IV):

 where n

or 0 to 0.9% by weight of a compound of the formula (V):

n = 2 to 20 or 0 to 0.9% by weight of a compound of the formula (VI):

where n = 2 to 20 g) 1 to 25 wt .-% of one or more styrene copolymers, based on the total component G, 0.5 to 5 wt .-% of maleic anhydride derived units, h) 0 to 40% by weight of one or more further Rubbers, i) 0 to 40% by weight of one or more additives other than components D, E, F, G and H, as component I, and j) 0 to 40% by weight of one or more fibrous or particulate fillers, as component J, with the proviso that when component E is just 0 wt .-%, the component F 0.01 to 0.9 wt .-%, preferably 0.1 to 0.9 wt. %, particularly preferably 0.2 to 0.9% by weight, of one or more of the compounds III, IV, V or VI, the percentages by weight being based on the total weight of the components A to J and together 100% by weight.

2. Thermoplastic molding composition according to claim 1, characterized in that the swelling index of the component C is from 7 to 20.

3. Thermoplastic molding composition according to claim 1 or 2, characterized in that is used as component B is a copolymer of acrylonitrile, styrene and / or α-methylstyrene, phenylmaleimide, methyl methacrylate or mixtures thereof.

4. A thermoplastic molding composition according to any one of claims 1 to 3, characterized in that is used as component C, a mixture of an acrylonitrile-butadiene-styrene (ABS) graft polymer, the 50 to 80 wt .-% based on C of a Elastomer-crosslinked butadiene polymer B1 and 50 to 20

Wt .-% based on C of a graft shell C2 of a vinyl aromatic monomer and one or more polar, copolymerizable, ethylenically unsaturated monomers, optionally a further copolymerizable, ethylenically unsaturated monomer in a weight ratio of 85:15 to 65:35.

5. Thermoplastic molding composition according to one of claims 1 to 4, characterized in that the average particle diameter of component C is between 50 to 800 nm.

6. Thermoplastic molding composition according to one of claims 1 to 5, characterized in that one uses the components D to E in a weight ratio of 4: 1 to 0.25: 1.

7. Thermoplastic molding composition according to one of claims 1 to 6, characterized in that is used as the vinyl aromatic component in C2 styrene or α-methyl styrene.

8. A thermoplastic molding composition according to any one of claims 1 to 7, character- ized in that is used as the ethylenically unsaturated component in C2 acrylonitrile and / or alkyl methacrylates and / or alkyl acrylates having C 1 - to C ₈ - alkyl radicals.

9. Thermoplastic molding composition according to one of claims 1 to 8, character- ized in that is used as component C is a rubber having a bimodal particle size distribution.

10. A thermoplastic molding composition according to any one of claims 1 to 9, characterized in that component G comprises 1, 0 to 2.5 wt .-% of maleic anhydride derived units.

1 1. Thermoplastic molding composition according to claim 10, characterized in that component G has from 1, 7 to 2.3 wt .-% of maleic anhydride derived units.

12. Thermoplastic molding composition according to one of claims 1 to 1 1, characterized in that component A from 0.05 to 0.5 wt .-% triacetonediamine (TAD) end groups.

13. A process for preparing thermoplastic molding compositions according to any one of claims 1 to 12, characterized in that the components A, B, C, D and G, and optionally E, F, H, I and J, at temperatures of 100 mixed to 300 ° C and a pressure of 1 to 50 bar in any order with each other, then kneaded and extruded.

14. Use of thermoplastic molding compositions according to any one of claims 1 to 12 for the production of moldings, films or fibers.

15. Shaped body, fibers or films containing or consisting of a thermoplastic molding composition according to one of claims 1 to 12.