MXPA00000011A - Low individual color thermoplastic molding material - Google Patents

Abstract

The invention relates to thermoplastic molding material containing the constituents A) to F), 5 to 80 wt.%of a graft polymer A) with a bimodal particle size distribution, 20 to 95 wt.%of a thermoplastic polymer B) with a viscosity VZ of 50 to 120 ml/g and optionally other thermoplastic polymers C), D) and/or E) based on at least one vinyl-aromatic monomer, and optionally additives F). The inventive material can be obtained by 1) producing the graft polymers A) according to the emulsion polymerization method, 2) mixing the graft polymer A) with polymer B) and, insofar as they are available, the other constituents C), D), E) and/or F) in a mixing device, whereby a substantially molten polymer mixture arises and 3) rapidly cooling the substantially molten polymer mixture.

Description

COMPOSITIONS OF THERMOPLASTIC MOLDING WHICH HAVE LITTLE INTRINSIC COLOR The present invention relates to thermoplastic molding compositions comprising, as components A) to F), based on the total weight of the molding composition, A) from 5 to 80% by weight. weight of a graft polymer A) having a bimodal distribution of particle sizes made from, based on A), al) from 40 to 90% by weight of the elastomeric particulate graft base (a), which can be obtained by polymerization of, based on al), there) from 70 to 100% by weight of at least one conjugated diene, al2) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and al3) from 0 to 10% by weight weight, preferably from 0.01 to 5% by weight, and particularly from 0.02 to 2% by weight, of at least one crosslinking monomer, polyfunctional and a2) from 10 to 60% by weight of a graft a2) made from , based on a2), a21) of 65 to 95% by weight of at least one vinylaromatic monomer, a22) d 5 to 35% by weight of acrylonitrile, a23) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and, a24) from 0 to 10% by weight, preferably from 0.01 to 5% by weight, and particularly from 0.02 to 2% by weight, of at least one polyfunctional crosslinking monomer and B) from 20 to 95% by weight of a thermoplastic polymer B) having a viscosity index VN (determined in accordance with DIN 53726 at 25 ° C , at 0.5% by weight in dimethylformamide) from 50 to 120 ml / g, produced from, based on B), bl) from 69 to 81% by weight of at least one vinylaromatic monomer, b2) from 19 to 31% by weight weight of acrylonitrile, and b3) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and C) from 0 to 50% by weight of a thermoplastic polymer C) having a VN viscosity number of 50 to 120 mg / 1 made of, based on C), cl) from 69 to 81% by weight of at least one vinylaromatic monomer, c2) from 19 to 31% by weight of acrylonitrile and c3) from 0 to 30% by weight of at least another m monoethylenically unsaturated monomer, where components B) and C) differ in their VN viscosity indexes by at least 5 units [ml / g], or in their acrylonitrile content by at least 5 units [wt%], or in both characteristics, viscosity index VN and content of acrylonitrile, by at least 5 units and D) from 0 to 95% by weight of a thermoplastic polymer D) made of, based on D), di) of 63 to less than 69% by weight of at least one vinylaromatic monomer, d2) of more than 31 to 37% by weight of acrylonitrile and d3) from 0 to 40% by weight of at least one other monoethylenically unsaturated monomer and E) from 0 to 50 % by weight of a thermoplastic polymer E) made of, based on E), the) from 4 to 96% by weight of at least one vinylaromatic monomer, e2) from 4 to 96% by weight of at least one selected monomer within of the class consisting of methyl methacrylate, maleic anhydride and maleimides and e3) from 0 to 50% by weight of acrylonitrile, where the polymer E) is different from polymers B) and from C) and D) if present and F) from 0 to 50% by weight of additives F), which can be obtained by 1) the preparation of the graft polymers [sic] ] A) by emulsion polymerization, 2) the mixture of graft polymer A) with polymer B) and the other components C), D), E) and / or F) if present, in a mixing apparatus, providing an essentially melted polymer mixture; and 3) rapid cooling of the essentially melted polymer mixture. The invention further relates to a process for the preparation of thermoplastic molding compositions, the use of thermoplastic molding compositions to produce molded products, and finally molded products produced from thermoplastic molding compositions. Molded products made from ABS (polybutadiene rubber particles grafted with polystyrene-acrylonitrile in a polystyrene-acrylonitrile matrix) have good mechanical properties, for example, a high resistance and hardness and especially, due to the low transition temperature to glass Tg of the polybutadiene, a good resistance to impacts, even at low temperatures. However, ABS polymers, especially those prepared by emulsion polymerization, often have an intrinsic color, such as yellowish to brown. This intrinsic color can, for example, be expressed using the Yellowness Index (Yl), which for ABS polymers of this type having a remarkable intrinsic color is from about 30 to more than 50. The Y Yellowness Index here depends on several factors, including the rubber content of ABS. In addition, yellowish / brown discolorations, for example, are frequent during the preparation of the molding compositions and their further processing to provide the molded articles, and during the use of the molded articles. The yellowing or browning is favored by the high temperatures, as they are, for example, during the molding by injection or during the mixing with additives in an extruder; the higher the intrinsic color of the ABS pellets not processed for injection or extrusion molding, the more noticeable the yellowing or the brown coloration. Particularly, there are problems in the coloring of polymers subject to yellowing since the yellow tone disrupts the desired shade (unsatisfactory color fidelity) or requires the use of large amounts of expensive colorants (increased pigmentation costs). A low depth of color is therefore often observed in pigmented ABS molding compositions, and results from its high level of light scattering. Since the initial level of intrinsic color and the color depth of the pigmented molded article are responsible for the perceived color of the molded article, intrinsic color and yellowness greatly reduce the usefulness of the molding compositions. EP-A 6341 proposes the processing of an acrylonitrile rubber in an extruder filled with inert gases, such as N2 or C02, the yellow tone of the polymer being reduced in this way. The operation of an extruder under inert conditions is disadvantageous, since the expensive and complicated procedure becomes. DE-B-2503966 proposes ABS molding compositions whose color stability is improved by the additional use of a C? -C8 alcohol during the emulsion polymerization of butadiene. The magnitude of the yellow tone reduction, however, is not always satisfactory. In addition, alcohol can have a negative effect on certain properties of the molding compositions. DE-B-2427960 discloses ABS molding compositions of some of the rubber particles from which they have been agglomerated by the addition of a binder dispersion to the finely divided polybutadiene latex, and which therefore has a broad or bimodal distribution of particle sizes. DE-A-3505749 proposes that a polybutadiene rubber grafted with styrene and acrylonitrile is precipitated from its latex by the addition of a sulfur-containing graft product based on polybutadiene, improving the thermal stability of the polybutadiene rubber when it has been precipitated and converted into molding compositions. The important content of sulfur compounds, however, frequently gives the molding compositions an unpleasant odor. EP-A-678531 discloses ABS molding compositions with a polybutadiene graft rubber having a bimodal distribution of particle sizes, where styrene and acrylonitrile, the monomers grafted onto the polybutadiene particles, are introduced predominantly during the first part of the monomer feed time. Although ABS compositions of this type have a high strength and are easy to process, they present a remarkable yellow tone. WO 95/22570 presents a process for the preparation of an ABS polymer in which a partially agglomerated finely divided emulsion rubber latex is prepared and the now bimodal latex is grafted in SAN emulsion. The graft polymer is then separated from the aqueous phase, in melted form with a SAN matrix polymer, the AN content of the graft structure of SAN and the SAN matrix differ by no more than about 6% by weight . During the removal of the water and / or the mixture in the melt form of the graft polymers and SAN matrix, a further partial agglomeration of the graft particles is carried out. Molding compositions of this type also have an intrinsic yellowish color which has a disadvantage. It is an object of the present invention to solve the disadvantages described and particularly to offer molding compositions that have little intrinsic color, that is, a low initial level of the yellow tone, and in addition to that, a low tendency to yellowing. Particularly, the molding compositions should have only a yellow color even after a prolonged thermal aging or as a result of thermal processing (for example, during injection molding or mixing in an extruder). A further object is to provide molding compositions which have a good pigment-applying ability and, after the pigment application, show a very small discrepancy between the desired shade and the actual shade, and which require small amounts of dyes for their pigmentation. The pigmented molding compositions should have a good depth of color, and for this reason the non-pigmented molding composition should have a very low light scattering. The low level of intrinsic color desirable for the object of the present invention can be defined by a Yellowness Index Yl of = 25 and / or an absorption of <0.1%. The color depth, that is to say, the low level of light scattering, desirable for the object of the invention can be defined by scattering values less than 4.9. The given numerical values are naturally based on the non-pigmented molding composition and are determined in accordance with the examples. A further object is to offer molding compositions whose low level of intrinsic color is not achieved with adverse effect on its other beneficial properties, for example, mechanical properties, such as strength and rigidity, or its level of surface gloss. Particularly, an object is to provide molding compositions whose mechanical properties, such as hardness, and also impact resistance at low temperature and rigidity are improvements compared to prior art molding compositions. We have found that this object is achieved through the thermoplastic molding compositions defined at the beginning. The invention also provides a process for preparing the thermoplastic molding compositions, the use of the thermoplastic molding compositions for the production of molded parts, and finally the molded parts produced from the thermoplastic molding compositions. It will now be apparent that the total of the components A) to F), the total of the monomers all) to al3), the total of the monomers a21) to 24), the total of the monomers bl) to b3), the total of the monomers cl) to c3), the total of the monomers di) to d3), and the total of the monomers el) to e3) is in each case 100% by weight.

Component A) is a graft copolymer having a bimodal particle size distribution and is present in novel molding compositions in a proportion of 5 to 80% by weight, preferably 10 to 70% by weight, especially of 15 to 60% by weight, based on the total weight of components A) and B) and, if present C), D), E), and F). The graft polymer A) is constituted by a graft base of elastomeric al) "soft" particles, and a "hard" graft a2). The graft base a) is present in a proportion of 40 to 90% by weight, preferably 45 to 85% by weight, and particularly 50 to 80% by weight, based on component A). The graft base a) is obtained by polymerization, based on al), from 70 to 100% by weight, preferably from 75 to 100% by weight, and particularly from 80 to 100% by weight, at least a conjugated diene, al2) from 0 to 30% by weight, preferably from 0 to 25% by weight, and particularly from 0 to 20% by weight, of at least one other monethylenically unsaturated monomer, and al3) from 0 to 10% by weight weight, preferably 0.01 to 5% by weight and particularly 0.02 to 2% by weight, of at least one polyfunctional crosslinking monomer. Examples of conjugated dienes all) are butadiene, isoprene, chloroprene and mixtures thereof. The use of butadiene or isoprene or mixtures thereof is preferred, and butadiene is especially preferred. The constituent al) of the molding compositions may also contain, with corresponding reduction of the monomers therefrom, other monomers (2) which vary the mechanical and thermal properties of the core within a certain range. Examples of such monoethylenically unsaturated comonomers are: vinylaromatic monomers, such as ethylene and styrene derivatives of the formula I where R1 and R2 are hydrogen or C? -C8 alkyl and n is 0, 1, 2, or 3; methacrylonitrile, acrylonitrile; Acrylic acid, methacrylic acid, and also dicarboxylic acid, such as for example maleic acid and fumaric acid, and their anhydrides, such as maleic anhydride; Monomers with nitrogen functionality, such as, for example, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinylaniline, acrylamide; Ci-Cio alkyl acrylate, such as for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, ethylhexyl acrylate, and the corresponding C1-C10 alkyl methacrylates, and hydroxyethyl acrylate; (A) aromatic and araliphatic acrylates, such as, for example, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, and 2-methacrylate. phenoxyethyl; N-substituted maleimides, such as, for example, N-methyl-, N-phenyl- and N-cyclohexylmaleimide; unsaturated ethers, such as, for example, methyl vinyl ether and mixtures of these monomers. Preferred al2) monomers are styrene, alpha-methylstyrene, n-butyl acrylate or mixtures of these, styrene and n-butyl acrylate or mixtures thereof, particularly and essentially styrene being preferred. The styrene or n-butyl acrylate or mixtures thereof are preferably used in amounts, in total up to 20% by weight, based on (a). The graft base a) may contain crosslinking monomers al3). Possible polyfunctional al3 crosslinking monomers are monomers having at least two ethylenically unsaturated double bonds which are not conjugated in position 1, 3. Examples which may be mentioned are triallyl cyanurate, divinylbenzene, divinyl esters of dicarboxylic acids, such as, for example, diallyl, diallyl fumarate, diallyl phthalate, and likewise allyl and methacrylate acrylate, dihydrodicyclopentadienyl acrylate, diallyl ethers, and divinyl ethers of bifunctional alcohols, such as those of ethylene glycol and of 1,4-butanediol, and diesters of polyhydric alcohols with acrylic and methacrylic acid, such as, for example, butanediol diacrylate, ethylene glycol diacrylate and hexanediol dimethacrylate. In a particular embodiment, use is made of a grafting base made up, on the basis of al), of) from 70 to 99.9% by weight, preferably from 90 to 99% by weight of butadiene, and al2) from 0.1 to 30% by weight, preferably 1 to 10% by weight, of styrene. The graft a2) is present in a proportion of 10 to 60% by weight, preferably 15 to 55% by weight, and particularly 20 to 50% by weight, based on component A). The graft a2) is obtained by polymerization, based on a2), a21) from 65 to 95% by weight, preferably from 70 to 90% by weight, and particularly from 75 to 85% by weight, of at least one vinylaromatic monomer, a22) from 5 to 25% by weight, preferably from 10 to 30% by weight, and particularly from 15 to 25% by weight of acrylonitrile, a23) from 0 to 30% by weight, preferably from 0 to 30% by weight, 20% by weight, and particularly from 0 to 15% by weight, of at least one additional monoethylenically unsaturated monomer, and a24) from 0 to 10% by weight, preferably from 0.01 to 5% by weight, and particularly from 0.02 to 2% by weight. % by weight, of at least one crosslinking monomer, polyfunctional. Examples of vinylaromatic monomers a21) are styrene and styrene derivatives of the formula (I) where R1 and R2 are hydrogen or C? -C8 alkyl and n is 0.1 2, or 3. The use of styrene is preferred. Examples of other monomers a23) are the monomers given above for component a2). Methyl methacrylate and acrylates, such as n-butyl acrylate, are particularly suitable. Methyl methacrylate MMA is particularly suitable as monomer a23), with an amount of up to 20% by weight of MMA being preferred, based on a2). The graft a2) can comprise crosslinking monomers a24). Examples of crosslinking monomers, polyfunctional a24) are the monomers given above for al3). The graft polymers are prepared by emulsion polymerization, usually at a temperature of 20 to 100 ° C, preferably 30 to 80 ° C. A further use is usually made of customary emulsifiers, for example, alkali metal salts of alkyl- or alkylarylsulfonic acids, alkyl sulfate, fatty alcohol sulfonates, salts of higher fatty acids having from 10 to 30 carbon atoms or sulfosuccinates , ether sulfonates or resin soaps. It is preferred to use the alkali metal salts, particularly the Na and K salts, of alkylsulfonates or fatty acids having from 10 to 18 carbon atoms. The emulsifiers are generally used in amounts of 0.5 to 5% by weight, particularly 0.5 to 3% by weight, based on the monomers used for the preparation of the graft base a). In the preparation of the dispersion, it is preferable to use enough water to give the finished dispersion a solids content of 20 to 50% by weight. A water / monomer ratio of 2: 2 to 0.7: 1 is usually employed. Suitable generators of free radicals to initiate polymerization are those that decompose at the selected reaction temperature, that is, both those that decompose themselves and those that decompose in the presence of a redox system. Examples of preferred polymerization initiators are free radical generators such as peroxides, preferably peroxosulfates (such as sodium or potassium peroxosulfates) and azo compounds, such as azodiisobutyronitrile. It is also possible, however, to use redox systems, especially those based on hydroperoxides, such as eumeno hydroperoxide. The polymerization initiators are generally used in amounts of 0.1 to 1% by weight, based on the graft base monomers all) and al2). The free radical generators and also the emulsifiers and, if appropriate, the molecular weight regulators (see following paragraph) are added to the reaction mixture, for example, in batches as a total amount at the beginning of the reaction or in stages , divided into several portions, at the beginning and once or several times after, or continuously over a defined period.The continuous addition can also follow a gradient, which can for example rise or fall and be linear or exponential or even stepwise It is also preferable to include in the molecular weight regulators of the reaction, such as ethylhexyl thioglycolate, n-dodecyl or t-dodecyl mercaptan or other mercaptans, terpinoles and dimeric alpha-methylstyrene or other compounds suitable for regulating the molecular weight Molecular weight regulators can be added to the reaction mixture in batches or continuously, as described up, for free radical generators and emulsifiers. If molecular weight regulators are used in the polymerization, during the preparation of the graft base a) either during the preparation of the a2) graft or during the preparation of al) and a2), in the previously described manner can be added. Details regarding the graft are provided at a later stage below. For a constant pH, preferably from 6 to 9, it is possible for the reaction to include regulatory substances such as Na2HP04 / NaH2P04 sodium hydrogen carbonate or regulators based on citric acid / citrate. Regulators and buffer substances are used in the usual amounts, and additional details on this point are therefore unnecessary. In a particularly preferred embodiment, a reductant is added during grafting of the graft base a) with the monomers a21) to a23). In a particular embodiment, it is also possible to prepare the graft base by polymerizing the monomers a) in the presence of a finely divided latex (the sown latex polymerization method). This latex is the initial charge and can be made from monomers that form elastomeric polymers or from other monomers mentioned above. Suitable seeded latexes are made from, for example, polybutadiene or polystyrene. Latex strewn with polystyrene is particularly preferred. In another preferred embodiment, the graft base a) can be prepared by the feeding method. In this process, the polymerization is initiated using a certain proportion of monomers a), and the rest of the monomers a) (the feed portion) is added as a feed during the polymerization. The feeding parameters (gradient shape, quantity, duration, etc.) depend on other polymerization conditions. The principles of the descriptions provided in relation to the addition method of the free radical initiator and / or emulsifier are again relevant here. In the feeding process the proportion of the monomers a) in the initial charge is preferably 5 to 50% by weight, particularly 8 to 40% by weight, based on (a). The feed portion of a) is preferably fed within a period of 1 to 18 hours, particularly from 2 to 16 hours, especially from 4 to 12 hours. Graft polymers having several "soft" and "hard" shells, for example of the structure a) -a2) -al) -a2) or a2) -al) -a2), are also suitable, especially when the particles They are of relatively large size. The precise polymerization conditions, particularly the type, amount, and method of addition of the emulsifier and the other polymerization aids are preferably selected such that the latex resulting from the graft polymer A has an average particle size, defined by the dso of the distribution of particle sizes, from 80 to 800 [lagoon], preferably from 80 to 600"lagoon", and especially from 85 to 400 [lagoon]. The reaction conditions are preferably balanced such that the polymer particles have a bimodal particle size distribution, ie, a particle size distribution having two maximums whose distinctive characteristics may vary. The first maximum is more distinct (comparatively narrow peak) than the second maximum, and is generally within a range of 25 to 200 nm, preferably 60 to 170 nm, and particularly 70 to less than 150 nm. The second maximum is wider in comparison and is generally within a range of 150 to 800 nm, preferably 180 to 700, especially from 200 to 600 nm. The second maximum aguí (from 150 to 800 nm) is found in particle sizes larger than the first maximum (25 to 200 nm). The bimodal distribution of particle sizes is preferably achieved by the (partial) agglomeration of the polymer particles. This can be achieved, for example, by the following procedure: the monomers a) which form the core are polymerized at a conversion of usually at least 90%, generally greater than 95% based on the monomers used. This conversion is usually achieved in a period of 4 to 20 hours. The resulting rubber latex has an average particle size dso not greater than 200 nm, preferably less than 150 nm, and a narrow particle size distribution (virtually monodisperse system). In the second stage, the rubber latex is agglomerated. This is usually carried out by the addition of a dispersion of an acrylate polymer. Preference is given to the use of dispersions of C?-C4 alkyl acrylate copolymers, preferably ethyl acrylate, with 0.1 to 10% by weight of monomers that form polar polymers, examples being acrylic acid, methacrylic acid, acrylamide, methacrylamide, methacrylamide of n-methylol, and n-vinylpyrrolidone. A copolymer of 90 to 96% by weight of ethyl acrylate and 4 to 10% by weight of methacrylamide is especially preferred. The agglomeration dispersion may, if desired, also contain more than one of the aforementioned acrylate polymers. In general, the concentration of the acrylate polymers in the dispersion used for agglomeration should be within a range of 3 to 40% by weight. For the agglomeration, from 0.2 to 20% by weight, preferably from 1 to 5% by weight of the binder dispersion are used for each 100 parts of rubber latex, the calculation in each case based on the solids. The agglomeration is carried out by the addition of the binder dispersion to the rubber. The rate of addition is usually not a critical factor, and the addition is usually carried out for a period of 1 to 60 minutes and at a temperature of 20 to 90 ° C, preferably 30 to 75 ° C. In addition to an acrylate polymer dispersion, it is also possible to use other binder agents, such as acetic anhydride, for the agglomeration of rubber latex. Agglomeration by pressure or by freezing is also possible. The methods mentioned are known to the person skilled in the art. Under the conditions mentioned, the rubber latex is only partially agglomerated, providing a bimodal distribution. More than 40%, preferably 45 to 95% of the particles (distribution by number) are generally in the non-agglomerated state after agglomeration. The partially agglomerated rubber latex is relatively stable, and therefore it is easy to store and transport without coagulation occurring. To achieve a bimodal distribution of particle sizes of graft polymer A) it is also possible to prepare, separately from each other in the usual manner, two different graft polymers A ') and A ") which differ in their average size of particle, and mix the graft polymers A ') and A ") in the desired mixing ratio. The polymerization of the graft base a) is usually carried out under selected reaction conditions to provide a graft base having a particular cross-linked nature. Examples of parameters that are important for this are the temperature of the reaction and the duration of said reaction, the proportion of monomers, regulator, free radical initiator and, for example, in the feed process, the feed rate and the amount and moment of addition of regulator and initiator. One method for describing the crosslinked nature of the crosslinked polymer particles is the measurement of the swelling index. Ql, which is a measurement of the solvent swelling capacity of a polymer that has a certain degree of crosslinking. Examples of customary swelling agents are methyl ethyl ketone and toluene. The Ql of the novel molding compositions is usually within a range Ql = from 10 to 60, preferably from 15 to 55 and especially from 20 to 50. Another method to describe the magnitude of the crosslinking is the measurement of time T2, the NMR relaxation times of protons capable of movement. The most frequently reticulated is a particular network, the lower its times T2 for the graft bases al) according to the invention are within a range of 2.0 to 5.0 ms, preferably from 2.5 to 4.5 ms and particularly from 2.5 to 4.0 ms, measured at 80 ° C on samples in film form. The gel content is another criterion for describing the graft base and its extent of crosslinking, and it is the proportion of crosslinked material and therefore insoluble in a particular solvent. It is useful to determine the gel content in the solvent also used to determine the swelling index. The gel content of the graft bases a) in accordance with the present invention are usually within a range of 50 to 90%, preferably 55 to 95% and particularly 60 to 85%. The following method can for example be used to determine the swelling index: about 0.2 g of the solid from a graft base dispersion converted to a film by the evaporation of water is swollen in a sufficient amount of toluene (e.g. g). Then, for example, 24 hours later the toluene is removed with suction and the sample is weighed. The weighing process is repeated after drying the sample in vacuum. The swelling index is the ratio between the weight of the sample after the swelling procedure and the weight of the dry sample after the second drying. The gel content is calculated correspondingly from the ratio between the dry weight after the swelling step and the weight of the sample before the swelling step (x 100%).

The time T12 is determined by measuring the NMR relaxation of a sample of the graft base dispersion from which the water has been removed and which has been converted into a film. For this purpose, the sample, for example, is dried in the air overnight, at a temperature of 60 ° C for 3 hours under vacuum and then studied at a temperature of 80 ° C using a suitable measuring device, for example , Bruker minispec. It is only possible to compare samples studied by the same method, since the relaxation depends significantly on the temperature. The graft a2) can be prepared under the same conditions as those used for the preparation of the graft base a) and can be prepared in one or several processing steps. In a two-step graft, for example, it is possible to polymerize styrene and / or alpha-methylstyrene alone, and then styrene and acrylonitrile, in two sequential stages. This two-stage grafting (first styrene, then styrene / acrylonitrile) is a preferred embodiment. Further details regarding the preparation of the graft polymers A are given in DE-A 12 60 135 and DE-A 31 49 358. In turn, it is advantageous to carry out the graft polymerization in the graft base at the same time. ) in aqueous emulsion. It can be carried out in the same system used for the polymerization of the graft base, and emulsifier and initiator can be added additionally. These do not have to be identical with the emulsifiers and / or initiators used for the preparation of the graft base a). For example, it may be convenient to employ a persulfate as initiator for the preparation of the graft base a) but a redox initiator system for polymerization of graft a2). Otherwise, what was said for the preparation of the graft base a) is applicable for the selection of emulsifier, initiator and polymerization aids. The monomer mixture on which it is to be grafted may be added to the reaction mixture once in portions in more than one step or preferably continuously during the polymerization. The establishment of desired properties can be beneficial during polymerization of the graft a2) add crosslinking monomers a24) and molecular weight regulators in accordance with that described above. If molecular weight regulators are included when graft a2) is prepared, the amounts are from 0.001 to 5% by weight, preferably from 0.005 to 2% by weight, and particularly from 0.01 to 2% by weight, based on the monomers a21) to a24). The regulators are added either at the beginning of the grafting reaction or subsequently, all at once or in several steps in identical or different portions, uniformly during the feeding time, or together with the graft monomers a21) a a24) during the entire feeding time or during a particular section of feeding time. Under (al), more details were provided on the form of addition. In the embodiment of the graft preparation a2) in two stages, in accordance with that described in a previous step mentioned above, it is possible, for example, to add a regulator in the first stage and a reticular a24) in the second stage, or well the other way around It is also possible to employ both a regulator and a crosslinker in both stages. The ratio between the regulator and the crosslinker a24) in the steps may be identical or different. What was said in an earlier stage above applies to the form of addition of the regulator and reticulator during the preparation of the graft base a) and graft a2). The two materials here can be introduced in the same way or in different ways. If grafted polymers are not produced from the monomers a2) during grafting of the graft base a), the amounts, which are generally less than 20% by weight, preferably less than 15% by weight, of a2) are attributed to the weight of component A). Component B) is a thermoplastic polymer and is present in novel molding compositions in a proportion of 20 to 95% by weight, preferably 30 to 90% by weight and particularly 40 to 85% by weight, based on the total of components A) and B), and, if present, C), D), E), and F). Component B) is obtained by polymerization, based on B), b) from 69 to 81% by weight, preferably from 70 to 68% by weight and particularly from 70 to 77% by weight, of at least one monomer vinylaromatic b2) from 19 to 31% by weight, preferably from 22 to 30% by weight, and particularly from 23 to 30% by weight of acrylonitrile b3) from 0 to 30% by weight, preferably from 0 to 28% by weight, weight, of at least one other monoethylenically unsaturated monomer. Suitable vinylaromatic monomers b) are styrene and styrene derivatives of the formula (I) according to that described for component a21). Preference is given to the use of styrene and / or alpha-methylstyrene. In a preferred embodiment, the graft a2) of the graft polymer A) consists essentially of, based on A2) [sic]), a21) from 75 to 85% by weight of styrene and / or alpha-methylstyrene a22) of 15 to 25% by weight of acrylonitrile, and the thermoplastic polymer B) consists essentially of, based on B), bl) from 71 to 78% by weight of styrene, and b2) from 22 to 29% by weight of acrylonitrile. In a particular embodiment, component B) consists of two polymers B ') and B ". Polymer B') corresponds here to polymer B) described above, where vinylaromatic monomers b1 'are only those of the formula (I) ) having R1 and R2 as hydrogen, ie, non-alkylated vinylaromatics, styrene is preferred as monomer b1 ') in B') Polymer B ") corresponds to polymer B) described above, where vinylaromatic polymers bl") it is only those of the formula (I) having R 1 and R 2 as alkyl Ci-Cs, ie, alkylated vinylaromatics, alpha-methylstyrene, monomer b ") in B" is preferred.) Polymer B ") is preferably a alpha-methylstyrene-acrylonitrile copolymer. If component B) comprises components B ") and B '" [sic]), it is particularly preferably a copolymer of styrene-acrylonitrile B') and a polymer of alpha-methylstyrene-acrylonitrile B "). ) consists of B ') and B "), the ratio B') / B") is preferably from 99: 1 to 1:99, preferably from 95: 5 to 5:95, the other monomers b3) can be the monomers mentioned above for component a2) Particularly suitable monomers are methyl methacrylate and N-alkyl- and / or N-arylmaleimide such as N-phenylmaleimide, polymers B), which due to their main components of styrene and acrylonitrile are Generally known as SAN polymers, they are known and in some cases also commercially available Component B) has a viscosity index VN (determined in accordance with DIN 53 726 at a temperature of 25 ° C in a solution of 0.5% component. B) in dimethylformamide) from 50 to 120 mn / g, preferably from 52 to 110 ml / g particularly from 55 to 105 ml / g. It is obtained in a known manner by emulsion polymerization, precipitation, suspension, solution, in bulk, with polymerization in bulk and in solution being preferred. Details of these procedures are described, for example, in Kunststoffhandbuch, ed. R. Vieweg and G. Daumiller, Vol. V "Polystyrol", Carl-Hanser-Verlag Munich, 1969, page 118 et seq. Component C is also a thermoplastic polymer and is present in the novel molding compositions in a proportion of 0 to 50% by weight, preferably from 0 to 48% by weight, and particularly from 0 to 45% by weight, based on in the total of components A) and B), and, if present, C), D), E) and F).

Component C is obtained by polymerization, based on C), cl) from 69 to 81% by weight, preferably from 71 to 78% by weight, and particularly from 72 to 77% by weight, of at least one vinylaromatic monomer, c2) from 19 to 31% by weight, preferably from 22 to 29% by weight, and particularly from 23 to 28% by weight of acrylonitrile, and c3) from 0 to 40% by weight, preferably 0 to 30% by weight of at least one other monoethylenically unsaturated monomer. Suitable vinylaromatic monomers cl) are styrene and styrene derivatives of the formula (I), in accordance with that described for component a21). The use of styrene is preferred. The other monomers c3) can be the monomers mentioned above for the al2) components. Particularly suitable monomers are methyl methacrylate, maleic anhydride and n-phenylmaleimide. Component C) has a viscosity index VN of 50 to 120 ml / g, preferably of 52 to 110 ml / g and particularly of 55 to 105 ml / g. It is obtained in a known manner by bulk polymerization, in solution, suspension, precipitation or emulsion, with bulk polymerization and solution polymerization being preferred. Details of these procedures are provided, for example, in Kunststoffhandbuch, ed. R. Vieweg and G. Daumiller, Vol. V "Polystyrol", Carl-Hanser-Verlag Munich, page 118 et seq.

Components B) and C) are therefore SAN-type polymers that incorporate a comparatively small amount of acrylonitrile (not more than 31% by weight). According to the invention, the difference between B) and C) is - whether the viscosity indices VN of B ') and C) differ by at least 5 units [ml / g] (in this case, the molar masses means M of B) and C) are different between them), - either that the contents of nitrile acid of B) and C) (monomers b2) and c2), respectively) differ by at least units [percentage of weight], - or that both characteristics mentioned above, viscosity index VN and content of nitrile acid, differ by at least 5 units. Component D) is also a thermoplastic polymer and is present in the novel molding compositions in a proportion of 0 to 95% by weight, preferably from 0 to 80% by weight, and particularly from 0 to 70% by weight, in base in the total of components A) and B), and C), D), E), and F) if present. Component D) is obtained by polymerization, based on D), di) from 63 to less than 69% by weight, preferably from 64 to 68% by weight, of at least one vinylaromatic monomer, d2) from 31 to 37 % by weight, preferably from 32 to 37% by weight, of acrylonitrile, d3) from 0 to 40% by weight, preferably from 0 to 30% by weight, of at least one other monoethylenically unsaturated monomer. Suitable vinylaromatic monomers di) are styrene and styrene derivatives of the formula (I), in accordance with that described for component a21). Preferably styrene and / or alpha-methylstyrene is used, particularly styrene. The other monomer d3) can be the monomers mentioned above for component a21). Particularly suitable monomers are methyl methacrylate, maleic anhydride, N-phenylmaleimide and other N-substituted maleimides. Accordingly, component D), such as components B) and C), is a SAN polymer but differs from B) and C) by a low content of vinylaromatic monomers di) and a high content of acrylonitrile d2) (more than 31). % in weigh) . Component D) generally has a viscosity index VN of 55 to 110 ml / g, preferably of 56 to 105 ml / g and particularly of 58 to 103 ml / g. The component D) is obtained in a known manner by bulk polymerization, in solution, suspension, precipitation or emulsion. Details of these procedures are described, for example in Kunststoffhandbuch, ed. R. Vieweg and G. Daumiller, Vol. V "Polystyrol", Carl-Hanser-Verlag Munich 1969, page 118 et seq. The component E) is also a thermoplastic polymer and is present in the novel molding compositions in a proportion of 0 to 50% by weight, preferably from 0 to 40% by weight, and particularly from 0 to 30% by weight, based on the total weight of components A), and B), and C), D), E) and F) if they are present. Component E) is obtained by polymerization, based on E), the) from 4 to 96% by weight, preferably from 8 to 92% by weight, and particularly from 10 to 90% by weight, of at least one vinylaromatic monomer, e2) from 4 to 96% by weight, preferably from 8 to 92% by weight, and particularly from 10 to 90% by weight, of at least one monomer selected from the class consisting of maleic anhydride, maleimides , C 1 -C 20 alkyl acrylates and C 1 -C 2 alkyl methacrylates, e 3) from 0 to 50% by weight, preferably from 0 to 40% by weight, and particularly from 0 to 30% by weight of acrylonitrile. Suitable vinylaromatic monomers (a) are styrene and styrene derivatives of the formula (I), in accordance with that described for a21). Preferably, styrene and / or alpha-methylstyrene is used. Among the C1-C20 alkyl methacrylates (one of the monomers e2)), methyl methacrylate MMA is preferred. Particularly preferred components E) are copolymers of styrene and maleic anhydride either of styrene and maleimides, or of styrene, maleimides and MMA or of styrene, maleimides and acrylonitrile, or of styrene, maleimides, MMA and acrylonitrile. According to the invention, the monomers el) to e3) are selected in such a way that the polymer E) differs from the polymers B) and, if they are also present in the molding compositions C) and D). The polymers E) can serve to increase the thermal resistance of the thermoplastic molding compositions. Component E) generally has a VN viscosity index of 50 to 120 ml / g, preferably 55 to 110 ml / g. Component E) is obtained in a known manner by bulk polymerization, in solution, suspension, precipitation or emulsion. Details of these procedures are described, for example, in Kunststoffhandbuch, ed. R. Vieweg and G. Daumiller, Vol. V "PoLystyrol", Carl-Hanser-Verlag Munich, 1969, pages 118 et seq. Component F) consists of additives that are present in the novel thermoplastic molding compositions in a proportion of 0 to 50% by weight, preferably 0.1 to 45% by weight and particularly 0.2 to 30% by weight, based on the total of components A) and B), and C), D), E) and F) if present. Component F) includes lubricants or mold release agents, waxes, pigments, dyes, flame-retardant substances, antioxidants, stabilizers to counteract the action of light and heat, matting agents to obtain a matt surface on the articles moldings, anti-dripping agents, fillers in fibers or powder, reinforcing agents in fibers and powder, antistatic substances and other usual additives, in accordance with what is described, for example, in Plastics Additives Handbook, ed. Gachter and Müller, fourth edition, Hanser Publ., Munich, 1996, or mixtures thereof. Here are some examples. Examples of suitable lubricants and mold release agents are stearic acids, stearyl alcohol, esters or stearic acid amides, silicone oils, mountain waxes, as well as lubricants based on polyethylene and polypropylene. Examples of pigments are titanium dioxide, phthalocyanines, ultramarine blue, iron oxide, and carbon black, and the entire class of organic pigments. For the purposes of the present invention, colorants are all colorants that can be used for the transparent, semitransparent or non-transparent coloration of polymers, particularly those suitable for coloration of styrene copolymers. Colorants of this type are known to the person skilled in the art. Examples of pyro-retardant agents are halogen or phosphorus-containing compounds known to those skilled in the art, magnesium hydroxide and other customary compounds or mixtures of these compounds. Red phosphorus is also adequate. Particularly suitable antioxidants are sterically hindered mononuclear or polynuclear phenolic antioxidants, which may be substituted in various ways, and also bridging through substituents. These include not only monomeric compounds but also oligomeric compounds that can constitute more than one fundamental phenol unit. Hydroquinones and substituted compounds that are hydroquinone analogs are also suitable as well as antioxidants based on tocopherols and their derivatives. Mixtures of different antioxidants can also be used. In principle, it is possible to use any compound that is commercially available or suitable for styrene copolymers, such as Topanol ® or Irganox ®. Along with the phenolic antioxidants mentioned as examples above, it is possible to employ co-stabilizers, particularly co-stabilizers containing phosphorus or sulfur. Such co-stabilizers containing phosphorus or sulfur are known to those skilled in the art and are commercially available. Examples of suitable stabilizers to counteract the action of light are several substituted resorcinols, salicylates, benzotriaols, benzophenones, and HALS (hindered amine light stabilizers), commercially available, for example, as Tinuvin®. Possible agents that produce a matt surface are either inorganic materials such as talcum, glass beads or metal carbonates (such as MgC0 and CaCo3) or polymer particles, particularly spherical particles with a diameter dso (weight average) greater than lum, based, for example, on methyl methacrylate, styrene compounds, acrylonitrile or mixtures thereof. It is also possible to use polymers comprising copolymerized acidic and / or basic monomers. Examples of suitable antidrug agents are polymers of tetrachlorethylene (Teflon®) and ultra-high molecular weight polystyrene (molecular weight Mw greater than 2,000,000). Examples of fiber and / or particulate fillers are carbon fibers or glass fibers in the form of glass fabrics, glass mats or glass fiber yarns, cut glass or glass beads and wollastonite, fibers of particular interest being preferred. glass. If glass fibers are used, they can be supplied with a size and a coupling agent for greater compatibility with the components of the mixture. The glass fibers can be incorporated either in the form of short fiberglass or in the form of continuous yarns (yarns).

Fillers in suitable particles are carbon black, amorphous silicic acid, magnesium carbonate (chalk), quartz powder, mica, mica [sic], bentonite, talc, feldspar or particular calcium silicates, such as wollastonite. and kaolin. Examples of suitable antistatic agents are amine derivatives, such as, for example, N, N-bis (hydroxyalkyl) alkylamines or -alkylene amines, polyethylene glycol esters, copolymers of ethylene oxide and propylene oxide (in particular two-block or three-block copolymers) of ethylene oxide blocks and propylene oxide block), and glycerol mono- and distearates, and mixtures thereof. The individual additives are used in the usual amounts in each case, and further details of this point are therefore unnecessary. Details regarding the preparation of the thermoplastic molding compositions are as follows: Graft polymers having bimodal particle size distributions are prepared by emulsion polymerization, in accordance with that described above for component A). In accordance with what has been described above, suitable measures are taken in order to establish the bimodal distribution of particle sizes, the (partial) agglomeration of the polymer particles being preferred, as mentioned above, by the addition of a polyacrylate dispersion having a binder effect. Instead of this, or in combination with the (partial) agglomeration, it is possible to use other suitable measures familiar to the person skilled in the art in order to establish the bimodal particle size distribution. The resulting dispersion of graft polymer A) can either be directly mixed with components B) to F) or prepared before this. This last method is preferred. The dispersion of the graft polymer A) is prepared in a manner known per se. The graft polymer A) is usually first precipitated from the dispersion, for example, by the admission of acids (for example acetic acid, hydrochloric acid, or sulfuric acid) or salt solutions (such as, for example, calcium chloride, magnesium sulfate or alum) that can cause precipitation or by freezing (coagulation by freezing). Precipitation by high cutting forces, known as cutting precipitation, is also possible; the high cutting forces are created here, for example, by means of rotor / stator systems or by pressing the dispersion through a narrow space. The aqueous phase can be removed in a customary manner, for example by sieving, filtering, decanting or centrifuging. This preliminary removal of the dispersion water provides graft polymers A) which are wet with water and have a residual water content of up to 60% by weight, based on A), where the waste water can, for example, either adhere externally on the graft polymer or encased therein. After this, the graft polymer can, if required, be dried in a known manner, for example, by means of hot air, or by using a pneumatic dryer. It is also possible to treat the dispersion by means of spray drying. According to the invention, the graft polymers A) are mixed in a mixing apparatus with the polymer B) and the other components C), D), E) and / or F) if present, providing a mixture of polymers essentially melted. The term "essentially melted" means that the polymer blend may also contain, in addition to the predominantly melted (softened) fraction, a certain proportion of solid constituents, for example, non-molten fillers and reinforcing materials, such as glass fibers, for example. , metallic flakes or non-melted pigments, dyes, etc. The term "melted" refers to the polymer mixture flowing at least to a certain extent, that is, that is softened at least to the point of having plastic properties. The mixing apparatuses used are known to the person skilled in the art. Components A) and B) and C), D), E), and F), if used, can be mixed, for example, by extrusion, kneading or winding of said components, components A) to F) have previously isolated, if necessary, from the solution resulting from the polymerization or from the aqueous dispersion. If one or more components are incorporated in the form of an aqueous dispersion or an aqueous or non-aqueous solution, the water or the solvent is removed from the mixing apparatus, preferably an extruder through a volatile substances removal unit. . Examples of mixing apparatuses for the novel process are internal heated mixers of discontinuous operation with or without rammers, continuous operation kneaders, such as continuous internal mixers, equipment for forming screw compounds having axial oscillating screws, Banburry mixers, and Also extruders, roller mills, rollers mixing don the rollers are heated and calenders. It is preferred to use an extruder as a mixing apparatus. Single or double screw extruders, for example, are especially suitable for extrude melting. A double screw extruder is preferred. In some cases, the mechanical energy introduced by the mixing apparatus during the mixing process is sufficient to cause the mixture to melt, and therefore, it is not necessary to heat the mixing apparatus. Otherwise, the mixing apparatus is generally heated. The temperature depends on the chemical and physical properties of components A) and B) and C), D), E), and F) if present, and must be selected in such a way that an essentially melted polymer mixture is produced. To avoid thermal degradation of the polymer mixture, on the other hand, the temperature should not be excessive. The mechanical energy introduced can, however, still be sufficient to require a cooling of the mixing apparatus. The mixing apparatus usually operates at a temperature within a range of 150 to 300 ° C, preferably 180 to 300 ° C. In a preferred embodiment, the graft polymer A) is mixed with the polymer B) and the other components C), D), E), and / or F), if present in an extruder, the dispersion of the graft polymer A) is introduced into the extruder without prior removal of the dispersion water. Water is usually removed along the extruder through adequate ventilation systems. Examples of ventilation systems are vents equipped with retaining screws (which avoid the emergence of the polymer mixture). In another also preferred embodiment, the graft polymer A) is mixed with the polymer B) and the other components C), D), E), and / or F), if present, in an extruder, the graft polymer. A) having previously been separated from the dispersion water, for example, by sieving, filtering, decanting or centrifugation. This preliminary removal of the dispersion water provides graft polymers A) moistened with water and having a residual water content of up to 60% by weight, based on A), where the waste water can, for example, either externally adhere on the graft polymer or be enclosed there. The waste water present can then, in accordance with what is described above, be removed as steam through ventilation systems in the extruder. In a particularly preferred embodiment, however, the waste water in the extruder is not only removed as steam; instead, a certain part of the wastewater is mechanically removed in the extruder and exits the extruder in the liquid phase. The polymer B) and, if present, the components C), D), E), and / or F), are fed to the same extruder, in such a way that the product extruded in the process is the finished molding composition. The process (compression process) will be described in more detail below: For this process, the graft polymer is separated from the dispersion water in advance, for example, by sieving, pressure, filtration, decanting, sedimentation or centrifugation, or by drying that involves heat to a certain point. The graft polymer from which the water has been partially removed in this way and which contains up to 60% by weight of waste water is then introduced into the extruder. The introduced material is carried by the screw against a delay element which acts as an obstacle and is generally located at the end of a "compression section". This zone of restricted flow accumulates a pressure that presses the water out of the graft polymer. Pressure differences can accumulate, depending on the rheological behavior of the rubber, varying the placement of the screw elements, kneading elements or other delay elements. In principle, any commercially available element that serves to increase the pressure in the apparatus is adequate. Examples of possible delay elements are: - transport screw elements, pushed - screw element having a passage opposite to the direction of transport, including screw elements that have large pitch transport threads (pitch larger than the diameter of the screw) opposite to the transport direction (they are known as LGS elements) - kneading blocks that have kneading discs of different steps that have no transport purpose - kneading blocks that have a conveying step to after kneading blocks which have a transport passage - barrel disks, eccentric disks and blocks configured from them - neutral delay disks (baffles) - mechanically adjustable restriction devices (sliding barrels, radial restriction devices, center restriction devices). Two or more of the delay elements may be combined with each other. The retardation effect of the restricted flow zone can also be adapted to the respective graft rubber by adjusting the length and intensity of the individual delay elements. In the understanding section described, the screw elements located before the restricted flow zone (before the first delay element) are generally constructed as conventional transport screws. In a preferred embodiment, transport screws are used whose pitch increases towards the restricted flow area, i.e. they become steeper. This design causes a relatively high pressure build-up and is known as a transition section, which can be beneficial for the removal of water from certain rubber. In another preferred embodiment, the pressure builds up without a pre-transition section, i.e., immediately before and / or in the restricted flow zone (i.e., the transport screw has a constant passage in the compression section). In the compression section, it is preferable if all the design parameters and operating parameters of the extruder are balanced in such a way that, even when the elastomeric material is worn and compressed at the selected rotation speed of the screw, it is not plasticized or melted partially, neither is it totally melted, or if it is, it is only a subordinate quantity. The compression section of the extruder preferably contains, to increase the pressure, screw elements having a passage opposite the transport direction and / or the appropriate kneading blocks. The water squeezed from the graft polymer in the compression section leaves the extruder in the liquid phase and not in the form of vapor. In a less preferred embodiment, up to 20% by weight of the water removed in this section emerges as steam. The compression section is equipped with one or more water removal holes, which are normally under atmospheric pressure. The expression "under atmospheric pressure" indicates that water arises from the orifices of water removal under atmospheric pressure. The water removal holes are preferably located on the upper side of the extruder but arrangements that are lateral or face to low are also possible. The water removal holes are also preferably equipped with an apparatus that prevents discharge of the graft polymer A) transported. For this purpose, retaining screws are particularly preferred. The water removal holes are designed in a manner known per se. It is preferable to use water removal holes whose dimensions are selected in such a way that they can not be blocked by the contents of the extruder. Cut-outs or perforations in the extruder barrel are particularly preferably used as water removal holes. In a particularly preferred embodiment, the water removal holes are not Seiher frames or similar quick locking components, such as screens. In accordance with the previously described, the Seiher frames have in fact susceptibility to blockage. The water removal hole associated with the delay elements are usually located at a distance of at least one screw diameter, preferably from 1 to 4 mm, and very particularly preferably from 1 to 2 mm, upstream of the element. of delay, or else in the case in which more than one delay element is used, upstream of the first delay element. For the purposes of the invention, the distance is the path length from the middle part of the water removal hole to the beginning of the first delay element. The temperature of the discharged water is generally from 20 to 95 ° C and preferably from 25 to 70 ° C, measured at the discharge orifice. In the first compression section, depending on the elastomer component and the residual water initially present, from 2 to 90% by weight, preferably from 20 to 80% by weight, of the residual water initially present is usually removed. In a preferred embodiment, the extruder is not heated in the feed sections or in the compression sections. In one embodiment, the extruder is cooled in these particular sections. Graft polymer A) with partial water removal is carried through the restricted flow zones and passes to the next extruder section. In a preferred embodiment for the preparation of some modified thermoplastic for impacts, a second compression section follows the first compression section that we have just described, said second compression section again consists of a transport section and a restricted flow zone that acts as an obstruction. The same details for the first compression section are essentially applied to the second compression section, particularly as to the distance of the water removal orifice from the restricted flow area downstream. The water expelled by compression generally exits the extruder through all the water removal holes present. Depending on the properties of the elastomer component and according to its residual water content it is also possible, however, that the water that has been expelled is discharged only from one or a few available water removal holes, and the other water removal holes are "dry" that is, they do not expel water or almost no water. This has not been proven to be a disadvantage. The proportion of the residual water not mechanically removed by compression can be removed in the form of steam in accordance with a usual manner through the ventilation system in the extruder. It is preferable that at least 30% by weight of the waste water (which, for example, can adhere externally to the graft polymer A) and / or be contained therein) is removed by compression in the extruder in the form of liquid water. 30 to 90% by weight of the waste water is generally removed as a liquid by compression, and 10 to 70% by weight in the form of vapor through ventilation systems. In the described compression process, the polymer B) and, if the polymers C), D), and / or E) are present, are fed in the form of a polymer melt. The polymer melt can be fed by means of an extruder or by means of a technically simpler transport equipment, such as melting pumps or feed screws. The polymer melting of B) is applied to the extruder after the compression sections. The mixture of graft polymers A), which has been subjected to the squeezing process but is not yet in the melted state, and the melting of polymers D) are melted and homogenized in downstream sections comprising the mixture, kneading, and / or other plasticizer elements. In WO-A 98/13412, for example more details on the compression process are found. If an extruder is used as mixing apparatus for components A) and B), and if present, C), D), E) and F), the different sections of the extruder can, as is generally known, be heated or cooled individually in such a way that an ideal temperature profile is adjusted along the screw axis. The person skilled in the art will also be familiar with the fact that the individual sections of the extruder can generally have different lengths. The temperatures and lengths to be chosen for the individual sections in a particular case differ according to the chemical and physical properties of components A) and B), and, if present, C), D), E) and F), as well as of its mixing proportions. This also applies to the speed of rotation of the screw, which can vary within a wide range. Speeds of rotation of the extruder screws in the range of 100 to 350 min. "1 can be mentioned by way of example In accordance with the present invention, the essentially melted polymer mixture prepared in the mixing apparatus from the components A ) and B), and, if present, C), D), E) and F), is subjected to a rapid cooling.The rapid cooling is carried out usually carrying the polymer mixture essentially melted (receives the abbreviated term "melting of polymers" below) in contact with a medium or a cold surface "cold" here implies a temperature that is sufficiently below the polymer melting temperature for the polymer melt to cool rapidly when it is carried The term "cold" therefore does not always mean that it is cooled down., a polymer melt at a temperature of 200 ° C can be subjected to a rapid cooling with water that has been previously heated, for example, from 30 to 90 ° C. The decisive factor is that the difference between the polymer melting temperature and the temperature of the cold medium or cold surface is sufficient for rapid cooling of the mixture. "fast" means that within a period of time from 0 to 10 seconds, preferably from 0 to 5 seconds, and particularly from 0 to 3 seconds, the polymer melt is transformed from the melted state to the solid and cooled state. The polymer melt is preferably cooled rapidly using a cold medium. Means of this type can be gases or liquids. Examples of cold gaseous media (hereinafter referred to as cooling gases) are cooled or fresh air or, particularly, in the case of fusions of polymers that are easily oxidized, gases, such as carbon dioxide, nitrogen or noble gases, for example. . It is preferred to use nitrogen or air as the cooling gas. The cooling gas is generally blown onto the melt discharge of polymer from the mixing apparatus. Cold liquid media (hereinafter referred to as "cooling liquids") may be organic or inorganic cooling liquids. Examples of suitable organic cooling liquids are oils and other high melting liquid organic materials that do not interact chemically or physically (eg swelling, solvent attack, etc.) with the polymer melt to be cooled, ie they are chemical and physically inert to the polymer melt. It is preferred to employ inorganic cooling liquids, particularly aqueous solutions and water. It is especially preferred to use water, which can be cooled (freezing point at room temperature), set at room temperature or heated (from room temperature to boiling point). The cooling liquid is generally sprayed on the melt of unloaded polymers; or the polymer melt is discharged from the mixing apparatus directly into a bath of the cooling liquid. It is also possible to apply the cooling liquid on the discharge polymer melt in the form of a wide jet of liquid (flood). The spraying of the polymer melt with a cooling liquid is especially advantageous when the mixing apparatus employed is an apparatus that produces the formation of sheets (for example roller mills, mixing rollers, and calenders) the polymer melt discharged in The shape of a film solidifies when sprayed with a cooling liquid, to provide the formation of leaves. The polymer melt is especially preferably discharged directly from the mixing apparatus in a bath of the cooling liquid, very particularly preferably in a water bath. It is also possible, and in some cases preferable, that the polymer melt is discharged from the mixing apparatus to be first only slightly cooled by its contact with a cooling glass [sic], for example by blowing heated air thereon. or an inert gas such as, for example, nitrogen gas. This solidifies only the outer surface of the melt, but the inner part of the polymer remains melted. The actual rapid cooling is then carried out by bringing the melt, previously solidified on the surface, into contact with a cooling liquid, for example water, whereby the internal part of the melt hardens. The extruded articles of the polymer melt discharged from the die head of the extruder can, for example, be surface-initially solidified by blowing air over them and then carried to a water bath, where the cooling is carried out. real fast. The polymer melt that has been hardened by rapid cooling can be further processed in a manner known to those skilled in the art. The solidified polymer is generally ground by granulation, milling, cutting or other processes. In a particularly preferred embodiment, rapid cooling and grinding are carried out by the submerged granulation process. In the submerged granulation, the polymer melt is discharged from the mixing apparatus through a die plate where the holes (nozzles) are preferably round and placed in the shape of a circle. The dice plate is located under the water (either in another cooling liquid or it is sprayed with water or another cooling liquid), and this can be carried out in an inert gas. Immediately behind the die plate, on its external side, there is a cutting apparatus, preferably rotating blades, which separate the polymer as it is discharged. The polymer is therefore separated by rotating blades and rapidly cooled in water (or other cooling liquid), generally solidifying to provide to a certain extent round, pearl-like grains. The placement of holes that have a shape different from the circular shape and the shapes of the holes that are not round, however, are frequently found on a dice plate. In another embodiment, a process known as granulation of extruded product from under water is employed. For this purpose, the melt is discharged as extruded product from a die plate and is immediately humidified and rapidly cooled by a stream of water or cooling liquid, and then introduced, through a slope, into a water bath. water or cooling liquid bath, and after cooling, granules are formed. In a very particularly preferred embodiment, an extruder is used as mixing apparatus for components A) and B), and, if present, C), D), E), and F), with the low water granulation that we just described. The discharge orifice of the extruder in this mode is therefore a die plate located under water (or sprayed with water) and having a cutting apparatus, particularly rotating blades. Accordingly, thermoplastic molding compositions comprising components A) and B) described above and, if present, C), D), E) and F), with butadiene as all-conjugated diene, are obtainable by means of 1 ) preparing the graft polymers A) by emulsion polymerization to provide a polymer A) which is wet with water and contains up to 60% by weight, based on A), of residual water, 2) mixing the graft polymer A ), wet with water, with the other components B) to F) in an extruder to provide an essentially melted polymer mixture and by squeezing at least 30% by weight of the residual water of the wet graft polymer A) of liquid water, accumulated pressure in the extruder, 3) rapid cooling of the polymer mixture essentially melted through the granulation process under water. The novel thermoplastic molding compositions can be processed by the known methods of thermoplastic processing, ie, for example, by extrusion, injection molding, calendering, blow molding, compression molding, or sintering. The novel molding compositions have good mechanical properties, particularly good strength and also good resistance to low temperatures and a balanced ratio between strength and stiffness. Its transition from rubber to glass is improved. The compositions have little intrinsic color (yellowness index YK25), and only a low tendency to form yellow and show only a slight yellowing, even after prolonged thermal aging or as a result of thermal processing. The molding compositions when dyed also have a good color depth (low light scattering, with dispersion values less than 4.9). EXAMPLES 1. Preparation of the graft polymer A) 1.1. Preparation of the graft base a) 43120 g of the monomer mixture provided in table 1 were polymerized at a temperature of 65 ° C in the presence of tert-dodecyl mercaptan (TDM), 311 g of a potassium salt of C 12 fatty acids -C20, 82 g of potassium persulfate, 147 g of sodium hydrogencarbonate and 580000 g of water, to provide a polybutadiene latex. The amount of TDM in percent by weight, based on the monomer mixture, together with the procedure for the addition of monomers and TDM appear in table 1 or in "procedure" below. Otherwise, the procedure was in accordance with that described in EP-A 62901, example 1, page 9, line 20 - page 10, line 6. The conversion was 95% or greater, and the average particle size d5o of latex of 80120 nm, and the swelling index was greater than 18. The T2 time determined by NMR was 2.5 to 3.8 ms. The solids content was 41% by weight. Procedure: Version 0: The initial charge consisted of 1% by weight of TDM, the entire amount of styrene and n-butyl acrylate (if these comonomers are used) and a sufficient amount of butadiene to make the initial charge represent 16.6% by weight of the total amount of monomer. Starting one hour after the start of the polymerization, the rest of the butadiene was introduced in a period of 5 hours. TDM was introduced in a single portion at the beginning of the polymerization. Version 1: The total amount of styrene and 20% by weight of butadiene, and % by weight of the TDM formed the initial charge, the remaining 80% of the butadiene was introduced in a period of 5 hours, adding 20% by weight of the remaining TDM per hour. Version 2: Like version 0, but the TDM was introduced in 3 portions of equal size at the beginning, in the middle, and at the end of the feeding phase of the rest of the butadiene. Version 3: Like version 0, but with 1.2% by weight of TDM. Version 4: Like version 0, but with additional introduction of 0.5% by weight of TDM 10 minutes after the beginning of the feeding of the rest of the butadiene. Version 5: Like version 4, but the initial charge consisted only of a sufficient amount of butadiene to make the initial charge represent 12.5% by weight of the total amount of monomer. Version 6: Like version 3, but the initial load comprised only a sufficient amount of butadiene to make the initial charge represent 12.5% by weight of the total amount of monomer. Version 7: As version 3, but the initial charge additionally comprised 0.2% by weight of butanediol diacrylate. Version 8: The amount of an initial charge of a seeded latex comprising particles of polystyrene with a particle size of 29nm, water, regulator salts and potassium persulfate (solids content: 33%) was sufficient to make the content of polystyrene will reach 1.9% by weight, based on the monomers of the graft base al). A monomer mixture was added dropwise over a period of 80 minutes. It consisted of 0.33% by weight of TDM and the total amount of monomeric styrene and a sufficient amount of butadiene to make it represent 16.6% by weight of the total amount of monomer. The rest of the butadiene was then introduced within a period of 6.5 hours. 0.33% by weight of TDM, respectively, was added after 2.5 hours and after 6.5 hours. To agglomerate the latex, 35,000 g of the resulting latex (partial agglomeration) was agglomerated at a temperature of 65 ° C by the addition of 2870 g and a dispersion (solids content: 10% by weight) of 96% by weight of ethyl acrylate and 4% by weight of methacrylamide sulfate. Table 1: Grafting base E emplo Kl K2 K3 K4 K5a K5b K6 K7 Monomers [% by weight] • butadiene 100 97 95 97 95 95 93 90 • Styrene 0 0 0 3 5 5 7 10 • n-butyl acrylate 0 3 5 0 0 0 0 0 TDM regulator [% by weight] 2) 1 1 1 1 1 1 1 1 Procedure: Version No. 00 0 0 0 1 0 0 0 Properties • swelling index 32 14 23 12 43 18 21 25 • Gel content [%] 70 90 76 92 62 81 78 73 • Light scattering 82 82 78 78 78 88 85 74 Example K8 K9 K10 Kll K12 K13 K14 Kla Monomers [% by weight] • Butadiene 93 93 93 93 93 93.1 100 100 • Styrene 7 7 7 7 7 1.9 + 51 '0 0 • n-butyl acrylate 0 0 0 0 0 0 0 0 TDM regulator [% in 1.2 1 + 0.5 1 + 0.5 1.2 1.2 1 weight] 2) Procedure: Version No. 3 Properties • swelling index 22 31 26 41 32 38 29 • Gel content [%] 79 66 74 66 74 - 72 • Light scattering 85 85 86 86 87 - 77 - not determined 1) 1.9% by weight as sowing polystyrene (in the form of seeded latex), 5% by weight as monomers 2)% by weight of TDM based on the monomers 3) several batches were prepared which were further processed. See Table 5 1.1. Preparation of the graft a2) 9300 g of water, 130 g of the potassium salt of C12-C20 fatty acids and 17 g of potassium peroxodisulfate were added to agglomerated latex. The procedure then followed one of the following versions: graft version 1: 8970 g of the graft monomer mixture presented in table 2, were added, with stirring, at a temperature of 75 ° C in a period of 4 hours. Graft version 2: the total amount of the graft monomer mixture presented in Table 2 was 8970 g. First, at 75 ° C and with stirring, a sufficient amount of styrene was added to cause the amount of styrene to reach 30% by weight of the total amount of the graft monomers. After waiting for 30 minutes, a monomer mixture was made from the rest of the styrene and the total amount of acrylonitrile or methyl methacrylate was added within a period of two hours. Graft version 3: as graft version 1, but 0.5% by weight of TDM was added to the monomer mixture.

After two additional hours, the conversion, based on the graft monomers, was virtually quantitative in each case. The resulting dispersion of graft polymers, which had a bimodal particle size distribution, had an average particle size dso of 150 to 350 mm and d90 of 400 to 600 nm. The particle size distribution presented a first maximum in a range of 50 to less than 150 nm and a second maximum in the range of 200 to 600 nm. The density of the smaller graft polymer particles (maximum maximum of 50 to less than 150) was 0.90 to 0.93 g / cm3, the density of the large particles (second maximum of 200 to 600 nm) was 0.96 to 0.98 g / cm3. The resulting dispersion was mixed with an aqueous dispersion of an oxidant, and then coagulated by the addition of a solution of magnesium sulfate. The coagulated rubber was centrifuged from the dispersion water and washed with water, providing a rubber with approximately 30% by weight of adhered or integrated water. Table 2: graft polymer and graft A) finished Component: Al A2 A3 A4 A5 A6 A7 A8 Grafting base of Kl Kl Kl Kl Kl K4 K5a Kla Example Monomers [% by weight] • styrene 83 80 78 75 70 80 80 80 acrylonitrile 17 20 22 25 30 20 20 20 • methyl methacrylate 0 0 0 0 0 0 0 0 Start version with No. 1 1 1 1 1 1 1 1 Properties of the graft polymer • yellowness index 9.0 9.3 - - 19.9 13.6 15.7 - Yl • swelling index i) • gel content [%] i) Component: A9 AlO All Al2 Al3 Al4 Al5 Grafting base of K5b K6 K8 K9 K10 Kll K12 Example Monomers [% by weight] • Styrene 80 80 86 80 80 80 80 • Acrylonitrile 20 20 14 20 20 20 20 • methyl methacrylate 0 0 0 0 0 0 0 0 Start version with No. 1 properties of the graft polymer • yellowness index Yl - • swelling index 8 10 11 10 10 • gel content [%] 89 89 87 83 88 84 85 Component: Al6 Al7 Al8 Al9 A20 Grafting base of K13 K3 K14 K14 K14 Example Monomers [% by weight] • styrene 80 86 80 84. 6 72 • acrylonitrile 20 14 20 15. 4 0 • methyl methacrylate 0 0 0 0 28 Start version with No. 3 2 1 2 2 properties of the graft polymer • yellowness index Yl - • swelling index 14 14 11 12 16 • gel content [%] 74 89 86 84 81 - not determined 1) several batches of the graft base Kla were used. See table 5. 2. Preparation of polymers B), C), D) and E) The thermoplastic polymers B) to E) were prepared by continuous solution polymerization, according to that described in Kunstsoff-Handbuch, ed. R. Vieweg and G. Daumiller, Vol. V, "Polystyrol", Carl-Hanser-Verlag, Munich, 1969, pages 122-124. Table 3 provides the formulations and properties. Table 3 Components B) to D) Component Bl B2 B3 Cl Monomers [Weight percentage] Styrene 75 75 0 75 Alpha-methyl styrene 0 0 70 0 Acrylonitrile 25 26 30 25 Viscosity index VN [ml / g] 67 80 80 80 Component C2 DI Monomers [weight percentage] Styrene 75 67 Alpha-methyl styrene 0 0 Acrylonitrile 25 33 Viscosity index VN [ml / g] 100 60 The component El is a copolymer of 63% by weight of styrene, 13% by weight of acrylonitrile and 25% by weight of N-phenylmaleimide having a Vicat B softening point of 144 ° C. Component E2 is a copolymer of 59% by weight of styrene and 41% by weight of N-phenylmaleimide. 3. Preparation of component F) Component Fl 60% by weight of a pigment made from titanium dioxide and 40% by weight of component B2 were intimately mixed in a kneader, discharged and granulated after cooling. 4. Preparation of the mixtures 4.1. Mixing after pre-drying of graft rubber A), examples 1 and 2 Graft rubber A) containing waste water was dried using hot air under vacuum and mixed intimately with the other components B) to F) in a Werner extruder and Pfleiderer ZSK 30 at a temperature of 250 ° C and 250 min "1, at a production of 10 kg / h The molding composition was extruded and the melted polymer mixture was subjected to rapid cooling which was carried out in a bath of water at a temperature of 30 ° C. The hardened molding composition was formed into granules 4.2 Mixing without prior drying of the graft rubber A), examples 3 to 35 C Graft rubber A) containing waste water was introduced into a Werner extruder and Pfleiderer ZSK where the front of the two transport screws were equipped with delay elements that accumulate pressure. A considerable part of the wastewater was mechanically removed by compression in this way and exited the extruder in liquid form through water removal holes. The other components D) to F), in the form of their fusions were added to the extruder downstream of the restricted flow areas, and intimately mixed with the waterless component A). The residual water still present was removed in the form of steam through ventilation holes in the back of the extruder. The extruder was operated at a rotation speed of 250 min "1, and with a performance of 80 kg / h or 250 kg / h, the diameter of the extruder screws that were used were selected accordingly. was extruded, and the polymer mixture and melt polymer mixture was subjected to rapid cooling In Examples 7 to 28, rapid cooling was carried out by means of low water granulation using a submerged GALA granulator : The extruder die plate was placed under water at a water temperature of 60 ° C. The polymer was discharged as melt extruded products in a water bath and was cut by rotating blades located directly on the outside of the die plate This provided beads of polymers in the form of beads In Examples 3 to 6 and 29 to 35 C, a quench is carried out in accordance with the following: the die die plate was placed in the direct vicinity of a water bath at 30 ° C. The melt extruded products discharged from the die plate were briefly carried through the air and then directly into the water bath, where they cooled rapidly. The cooled products were granulated in a conventional granulator. The components used and their amounts appear in tables 4 to 7. 5. Measurements made The rate of swelling of the graft base: a film was prepared from the aqueous dispersion of the graft base by evaporation of water. 0.2 g of this film was mixed with 50 g of toluene, and after 24 hours the toluene was removed with suction from the swollen sample, and the sample was weighed. The weighing operation was repeated after drying the sample for 16 hours under vacuum at a temperature of 110 ° C. The following were calculated: swelling index Ql = swollen sample weight After solvent removal With suction Weight of the sample dried in Vacuum Gel content = weight of the sample dried in vacuum 100% initial weight of the sample before swelling Rubber particle latex sizes: The average particle size provided is the average particle size in weight in accordance with an analytical ultracentrifuge by the method of W. Scholtan and H. Lange, Kolloid-Z, und Z. -Polymer 250 (1972) pages 782-796. The ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it is possible to deduce what percentage by weight of the particle has a diameter that is equal to or less than a particular size. The dio is the particle diameter for which the diameter of 10% by weight of all the particles is smaller and the diameter of 90% by weight is greater. The opposite applies to the dgo: 90% by weight of all particles have a smaller diameter and 10% by weight a diameter greater than d90. The weight average particle diameter dso and the volume average particle diameter T50 are the particle diameter for which the particle diameter d, respectively, 50% by weight and 50% by volume of all particles is greater and that, respectively, 50% by weight and 50% by volume is smaller, dio- and d50 and d90 describe the width Q of the particle size distribution, where Q = (dgo-dio) / dso. The smaller the Q, the narrower the distribution. Time T2 time T2 was measured by measuring the NMR relaxation of a sample without water converted to a film. For this purpose, the sample was dried in the air overnight, dried at a temperature of 60 ° C under vacuum for 3 hours, and was studied using a Brucker minispec equipment at 80 ° C. yellowness index Yl, the yellowness index Yl was determined by determining the color co-ordinates X, Y, Z in accordance with DIN 5033, using a standard illuminant of 65 and a standard observer 10 °, and the following definition equation : Yl = (131.48 X - 116.46 Z) / Y viscosity index VN: was determined in accordance with DIN 53726 in a 0.5% by weight solution of the polymer in dimethylformamide. MVR melt index: was determined in accordance with DIN 53735/30, at a melting temperature of 220 ° C, and a load of 10 kg and 21.6 kg, respectively. To determine the mechanical and brightness values below, the following test samples were injection molded from the granules: standard small samples (see DIN 53453), fungiform samples, discs with a diameter of 60 mm and a thickness of 2 mm, and rectangular samples with a thickness of 2mm. In each case, unless stated otherwise, the melting temperature was 250 ° C and the mold temperature was 60 ° C. Brightness: ISO 2813 was determined in rectangular samples of 40 x 60 mm with an angle of incidence of 45 °, using a Byk Microgloss measuring device. a ?: Was the impact resistance determined with Charpy a notches? in small standard samples through a flexural impact test in accordance with ISO 179-2 / leA (S) at 23 ° C, 10 ° C and -30 ° C. an: Impact resistance of Charpy an was determined in small standard samples in accordance with ISO 179-2 / lfU at a temperature of -30 ° C. Vicat: the softening point of Vicat was determined in small sheets pressed in accordance with ISO 306 / B using a load of 50 N and a heating rate of 50 K / h. aD: the penetration energy aD was determined in accordance with ISO 6603-2 on discs or rectangular samples that emit 40 x 40 mm through the Plastechon test at a temperature of -30 ° C and 23 ° C, the samples were produced at fusion temperatures of 220, 250 and 280 ° C. Resistance to tension, ultimate tensile strength, elongation to breaking and modulus of elasticity: these values were determined in accordance with ISO 527 in fungiform samples at a temperature of 23 ° C. Light scattering and absorption: flat staggered samples were injection molded from the granules at a melting temperature of 240 ° C and at a mold temperature of 80 ° C, the thinnest step is 1 mm thick and the thickest step is 2 mm thick. To determine the dispersion and absorption, measurements were made in the staggered samples in both white and black backgrounds, using a Hunter Ultrascan VIS spectrophotometer from these measurements, using the BCS color measurement system, absorption and specific dispersions were calculated for wavelengths within a range of 400 to 700 nm. 6. Results of the measurements The results of the measurements are given in Tables 4 to 7. Table 4 and Table 6 comprise mixtures of several components A and several components B. Table 5 comprises mixtures of component A8 with several components B .

Table 7 comprises a mixture in accordance with the present invention and, by way of comparison, a molding composition not in accordance with the present invention with the same rubber content. Table 4: Mixes and measurement results. The quantities of components are all parts by weight Example 1 2 3 4 5 6 Component A 31 Al 32 A2 33 Al 33 A2 33 A3 30 A4 Component B 69 B2 28 Bl 67 B2 67 B2 67 B2 70 B2 yellowness index Yl 19.7 20.5 23.8 24.1 24.2 25.3 Brightness [%] 74 73 73 73 72 72 a? (23 ° C) [kj / m2] 24 21 23 24 25 21 a? (- 30 ° C) [kJ / m2] 10 9 11 12 12 12 a? (- 30 ° C) [kJ / m2] - - 180 180 164 155 Vicat [° C] 98 98 99 99 100 101 MVR 220/102) [mi / 10 min] 1 122 11 5 5 5 5 aD (220 ° C / 23 ° C) 1) [Nm] 7 7 19 21 20 20 aD (220 ° C / 23 ° C) 1) [Nm] 2 1 8 8 6 3 aD (220 ° C / 23 ° C ) 1) [Nm] 14 7 22 22 23 20 aD (220 ° C / 23 ° C) 1) [Nm] 5 3 13 15 16 15 aD (220 ° C / 23 ° C) 1) [Nm] 18 15 20 21 20 21 aD (220 ° C / 23 ° C) 1) [Nm] 8 8 10 7 12 10 Resistance to tension 4 433 44 45 46 46 47 (23 ° C) [MPa] Final strength at 33 35 31 33 34 35 tension (23 ° C) [Mpa] Elongation at break (23 ° C) [%] Modulus of elasticity 2170 2200 2140 2120 2130 2170 (23 ° C [MPa] Dispersion 3.44 3.46 -Absorption [%] 0.023 0.021 - Example 7 8 9 10 11 Component A 28.5 Al 23.5 Al 30 Al 43 Al 30 A6 Component B 71.5 Bl 76.5 Bl 38 Bl 57 B2 70 Bl 32 B3 Component F yellowness index Yl 19.8 15.5 24.5 20.8 22.3 Brightness [%] a? ( 23 ° C) [kJ / m2] 23 16 26 46 17 a? (-30 ° C) [kJ / m2] 10 9 29 7 an (-30 ° C) [kJ / m2] 120 90 100 160 140 Vicat [ ° C] 97 99 101 93 97 MVR 220/102) [ml / 10 min] 19 24 9 4 17 aD (220 ° C / 23 ° C) 1) [Nm] 16 2 9 19 21 aD (220 ° C / -30 ° C) 1) [ Nm] 5 0.5 11 7 aD (250 ° C / 23 ° C) 1) [Nm] 20 22 23 16 aD (250oC / -30oC) 1 '[Nm] 7 4 18 8 aD (280 ° C / 23 ° C ) 1) [Nm] 25 20 22 23 21 aD (280oC / -30oC) 1 '[Nm] 11 8 15 10 Resistance to 47 51 48 39 50 voltage (23 ° C) [MPa] Final resistance to 40 40 38 28 39 tension (23 ° C) [Mpa] Elongation at rompi2.4 2.6 2.9 3.0 2.9 ment (23 ° C) [%] Modulus of elasticity 2270 2460 2210 1820 2340 (23 ° C [MPa] Dispersion 3.30 3 .15 3.18 3.67 3.14 Absorption [%] 0.023 0., 023 0.033 0.029 0.026 Example 12 13 14 Component A 30 A7 28 Al 26 Component B 70 Bl 72 B2 48 Bl 26 B2 Component F 5 Fl yellowness index Yl 22.4 Brightness [%] a? (23 ° C) [kJ / m2] 8 26 19 a? (-30 ° C) [kJ / m2] 6 9 8 an (-30 ° C) [kJ / m2] 75 120 114 Vicat [° C] 95 - 98 MVR 220/102) [ml / 10 min] 19 10 15 aD (220 ° C / 23oC) 1) [Nm] 4 - -aD (220 ° C / -30 ° C) 1) [Nm] 2 - -aD (250oC / 23 ° C) 1 > [Nm] 5 - 15 aD (250 ° C / -30 ° C) 1J [Nm] 3 - 5 aD (280 ° C / 23 ° C) 1) [Nm] 25 - 8 aD (280 ° C / -30 ° C) 1) [Nm] 9 - 4 Tensile strength 46 47 48 (23 ° C) [MPa] Final strength at 38 40 38 tension (23 ° C) [Mpa] Elongation at break 2.8 2.6 2.7 (23 ° C) [%] Modulus of elasticity 2190 2400 2350 (23 ° C) [MPa] Dispersion 3.12 Absorption [%] 0.026 1) melting temperature / temperature test 2) melting temperature [° C] / load [kg] - not determined Table 5: Mixtures and measurement results. The quantities of components are all parts by weight Example 15 16 17 18 Component A8 25.5 33.0 38.4 49.3 • from lot 1 2 3 4 Kla No. • swelling index 31 36 28 35 from lot Kla • time T2 from lot 3.15 3.53 3.25 3.29 Kla [ms] • swelling index 10.7 11.7 11.0 10.7 from A8 Component B 75.5 Bl 67.0 Bl 61.6 Bl 50.7 B yellowness index Yl 18.8 20.1 19.0 18.4 a? (250 ° C / 23 ° C) 1) [kJ / m2] 13 20 31 34 a? (250 ° C / 23 ° C) 1) [ kJ / m2] 7 9 12 18 Vicat [° C] 98 96 94 88 MVI 220/102) [ml / 10 min] 21 16 10 - MVI 220 / 21.62) [ml / min] - - - 23 aD (250oC / 23oC) 1) [N / m] 7 36 32 40 Light scattering 3.6 3.7 3.8 - Absorption [%] 0.038 0.041 0.041 - Example 19 20 21 Component A8 41.0 31.1 40 .0 • from batch Kla No. 5 6 7 • swelling index 27 28 39 batch Kla • time T2 of lot Kla 3.26 3.28 [ms] • swelling index of A8 1 100..77 11.6 - Component B 59.0 B2 68.9 B2 15.0 Bl 45.0 B3 yellowness index Yl 18.4 18.7 27.4 a? (250oC / 23oC) 1) [kJ / m2] 33 21 37 a? (250oC / 23oC) 1) [kJ / m2] - - 13 Vicat [° C] 96 100 101 MVI 220/102) [ml / 10 min] 3 6 -MVI 220 / 21.62) [ ml / min] - - 10 aD (250 ° C / 23 ° C) 1 '[N / m] 33 35 29 Light scattering 3.86 3.7 -Absorption [%] 0.038 0.040 __ 1) melting temperature / test temperature 2 ) melting temperature [° C] / load [kg] - not determined Table 6: Mixtures and measurement results. The amounts of the components are all parts by weight Example 22 23 24 25 Component A 28.5 Al 28.6 AlO 27.6 A12 27.5 A12 Component B 71.5 B2 71.4 B2 72.4 B2 72.5 B2 yellowness index Yl 23.5 19.6 17.7 22.4 a? (250 ° C / 23 ° C) 1) [kJ / m2] 24 20 21 24 aK (25O oC / -30 ° C) 1) [kJ / m2] Vicat [° C] 99 101 99 99 MVI 220/102) [ml / 10 min] MVI 220 / 21.62) [ml / min] aD (250oC / 23oC) 1) [N / m] 38 36 39 33 Light scattering 3.06 2.99 2.86 3.03 Absorption [%] 0.047 0.040 0.036 0.045 Example 26 27 28 29 Component A 27.3 Al3 26.3 Al4 27.0 Al 6 29.5 Al6 Component B 72.7 B2 73.7 B2 73.0 B2 70.5 Bl yellowness index Yl 22.6 23.2 22.8 22.1 a? (250 ° C / 23 ° C) 1, [kJ / m2] 20 23 23 22 a? (250oC / -30oC) 1) [kJ / m2] Vicat [° C] 99 100 100 100 MVI 220/102) [ml / 10 min] 7 12 MVI 220 / 21.62) [ml / min] aD (250 ° C / 23 ° C) 1, [N / m] 36 37 38 43 Light scattering 3.03 3.14 2.83 3.15 Absorption [%] 0.047 0.046 0.044 0.049 Example 30 31 32 33 Component A 27.6 Al 6 44.0 Al8 45.4 Al9 42.5 A20 Component B 72.4 Bl 56.0 Bl 54.6 Bl 57.5 Bl yellowness index Yl 22.0 24.6 23.2 19.0 a? (250 ° C / 23 ° C) 1) [kJ / m2] 22 37 30 11 a? (250 ° C / -30oC) 1) [kJ / m2] 8 - - - Vicat [° C] 96 - MVI 220/102) [ml / 10 min] 12 MVI 220 / 21.62 > [ml / min] 30 27 59 aD (250oC / 23oC) 1) [N / m] 22 29 28 25 Light scattering 3.35 - - Absorption [%] 0.039 - 1) melting temperature / test temperature 2) melting temperature [° C] / load [kg] - not determined Table 7: mixes and measurement results. The amounts of components are all parts by weight. Example 34 35c (comparison) Component A 29.9 A8 30.1 A5 Component B 70.1 Bl 0 Component D 0 69.9 DI Yellowness Index Yl 18.1 38.4 a? (250 ° C / 23 ° C) 1) [kJ / m2] 21 17 a? (250 ° C / 10 ° C) 1) [kJ / m2] 19 12 a? (250 ° C / -30 ° C) 1) [kJ / m2] 8 6 Vicat [° C] 97 99 MVI 220/102) [ml / 10 min] 18 16 aD (250 ° C / 23 ° C) 1 ) (N / m) 31 25 light scattering 3.6 Absorption [%] 0.036 0.080 1) melting temperature / test temperature 2) melting temperature [° C] / load [kg] - not determined The tables show that the compositions Novelty castings have little intrinsic color (low yellowness index below 25 and absorption less than 0.1%) and can be easily colored (light scattering less than 4.9) the novel molding compositions have at the same time a good resistance to impacts, including at low temperature (high values for an, a? and aD), and its flow capacity can be adjusted within a wide range (MVI values). Table 7 provides a direct comparison of two molding compositions with a direct rubber content of 30 + [sic] 0.1% by weight. The novel molding composition of Example 34 comprises, as the matrix polymer, the SAN Bl polymer with a low content of acrylonitrile according to the invention of 25% by weight. The molding composition of Example 35c, which is not according to the invention, comprises, instead of Bl low in acrylonitrile, the DI polymer rich in acrylonitrile with 33% by weight of acrylonitrile. The novel molding composition of Example 34 has a considerably lower Yellowness Index (18.1 instead of 38.4) and at the same time has a significantly better impact resistance (a? Of 21/19/8 kJ / m2 instead of 17). / 12/6 kJ 2 to 23/20 / -30 ° C, and aD of 31 instead of 25 N / m to 23 ° C). Compared to the prior art molding compositions, the impact resistance of novel molding compositions is therefore not simply comparable but remarkably better. The reduction in intrinsic color that is achieved therefore is not accompanied by a deterioration of the mechanical properties. On the contrary, these mechanical properties are improved.

Claims (1)

1. CLAIMS A thermoplastic molding composition comprising, as components A) to F), A) from 5 to 80% by weight of a graft polymer A) having a bimodal distribution of particle sizes made from, based on A) , a) from 40 to 90% by weight of the elastomeric particulate graft base a), which can be obtained by polymerization of, based on (a)) from 70 to 100% by weight of at least one conjugated diene, al2) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and al3) from 0 to 10% by weight, preferably from 0.01 to 5% by weight, and particularly from 0.02 to 2% by weight, of at least a crosslinking monomer, polyfunctional and a2) from 10 to 60% by weight of a graft a2) made from, based on a2), a21) from 65 to 95% by weight of at least one vinylaromatic monomer, a22) from 5 to 35% by weight of acrylonitrile, a23) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and, a24) from 0 to 10% by weight, of p reference of 0.01 to 5% by weight, and particularly of 0.02 to 2% by weight, of at least one polyfunctional crosslinking monomer and B) of 20 to 95% by weight of a thermoplastic polymer B) having a viscosity index VN (determined in accordance with DIN 53726 at 25 ° C, at 0.5% by weight in dimethylformamide) from 50 to 120 ml / g, produced from, based on B), bl) from 69 to 81% by weight of at least one vinylaromatic monomer, b2) from 19 to 31% by weight of acrylonitrile, and b3) from 0 to 30% by weight of at least one other monethylenically unsaturated monomer and C) from 0 to 50% by weight of a thermoplastic polymer C) having a VN viscosity index of 50 to 120 mg / 1 made from, based on C), cl) from 69 to 81% by weight of at least one vinylaromatic monomer, c2) from 19 to 31% by weight of acrylonitrile and c3 ) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer, where components B) and C) differ in their VN viscosity indices by at least 5 units [ml / g], either in its content of acrylonitrile by at least 5 units [% by weight], or in both characteristics, viscosity index VN and content of acrylonitrile, by at least 5 units and D) from O to 95% by weight of a thermoplastic polymer D) made of, based on D), di) from 63 to less than 69% by weight of at least one vinylaromatic monomer, d2) of more than 31 to 37% by weight of acrylonitrile and d3) from 0 to 40% by weight of at least one other monoethylenically unsaturated monomer and E) from 0 to 50% by weight of a thermoplastic polymer E) made of, based on E), the) from 4 to 96% by weight weight of at least one vinylaromatic monomer, e2) from 4 to 96% by weight of at least one monomer selected from the class consisting of methyl methacrylate, maleic anhydride and maleimides and e3) from 0 to 50% by weight of acrylonitrile , where polymer E) is different from polymers B) and C) and D) if present and F) from 0 to 50% by weight of additives F), which can be obtained rse by 1) the preparation of graft polymers [sic] A) by emulsion polymerization, 2) the mixture of graft polymer A) with polymer B) and the other components C), D), E) and / or F) if present, in a mixing apparatus, providing an essentially melted polymer mixture, and 3) rapid cooling of the essentially melted polymer mixture. A thermoplastic molding composition according to claim 1, wherein the conjugated diene all) is butadiene. A thermoplastic molding composition according to claim 1, or in accordance with claim 2, wherein the vinylaromatic monomer a21) and bl) and, if components C), D) and / or E) are present, cl) , di), and the), is styrene or either alpha-methylstyrene or a mixture of styrene and alpha-methylstyrene. A thermoplastic molding composition according to any of claims 1 to 3, wherein the graft a2) consists essentially of, based on a2), a21) from 75 to 85% by weight of styrene and / or alpha-methylstyrene a22 ) from 15 to 25% by weight of acrylonitrile and the thermoplastic polymer B) consists essentially of, based on B), bl) from 71 to 78% by weight of styrene b2) from 22 to 29% by weight of acrylonitrile. A thermoplastic molding composition according to any of claims 1 to 4, wherein the monoethylenically unsaturated al2) monomer is styrene or n-butyl acrylate or a mixture thereof. A thermoplastic molding composition according to claim 5, wherein an initial charge comprises a charge of the styrene in polymerized form as a latex seeded with polystyrene and another part of the polystyrene is incorporated in the form of monomeric styrene through copolymerization. A thermoplastic molding composition according to any of claims 1 to 6 wherein a bimodal particle size distribution of graft polymer A) has two maximums in particle sizes of 25 to 200 nm on one side and 150 to 800 nm on the other hand. The thermoplastic molding composition according to any of claims 1 to 7, wherein the bimodal particle size distribution of the graft polymer A is achieved by the agglomeration of the polymer particles. A thermoplastic molding composition according to any of claims 1 to 8, wherein, in step 1), the graft base is prepared in emulsion using at least one molecular weight regulator. A thermoplastic molding composition according to any of claims 1 to 9, wherein in step 1), the graft a2) is prepared in emulsion using at least one molecular weight regulator. . A thermoplastic molding composition according to any of claims 1 to 10, wherein the graft a2) comprises polyfunctional crosslinking monomers a24) and is prepared in emulsion using at least one molecular weight regulator. . A thermoplastic molding composition according to any of claims 1 to 11, wherein the graft a2) is prepared in two steps of different constitutions of monomers. . A thermoplastic molding composition according to any of claims 1 to 12, wherein the process step 1) provides a graft polymer A) wet with water and containing up to 60% by weight, based on A) of water residual. A thermoplastic molding composition according to any of claims 1 to 13, wherein the process step 2) employs an extruder as the mixing apparatus, and at least 30% by weight of the residual water in the wet graft polymer at ) is squeezed out of the extruder in the form of liquid water. A thermoplastic molding composition according to any of claims 1 to 14, wherein the process step 3 employs the granulation process under water for rapid cooling, using water or another cooling liquid. A thermoplastic molding composition according to any of claims 1 to 14, wherein, in step 3), the essentially melted polymer mixture is discharged into air or an inert gas, and is then rapidly cooled by putting it into contact with water or with another refrigerant. A process for the preparation of a thermoplastic molding composition according to any of claims 1 to 16, wherein the processing conditions are those set forth in claim 1. The use of a thermoplastic composition according to any one of claims 1 to 16 to produce molded objects. A molded object produced from a thermoplastic molding composition according to any of claims 1 to 11. SUMMARY OF THE INVENTION Thermoplastic molding compositions comprise, as components A) to F), A) from 5 to 80% by weight of a graft polymer A) having a bimodal particle size distribution made from, based on A), al) from 40 to 90% by weight of a graft base of elastomeric particles a), which can be obtained by polymerization of, based on al), from 70 to 100% by weight of at least one conjugated diene, al2) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and al3) from 0 to 10% by weight, preferably from 0.01 to 5% by weight, and particularly from 0.02 to 2% by weight, of at least one crosslinked, polyfunctional monomer, and a2) from 10 to 60% by weight of a graft a2) made of, based on a2), a21) from 65 to 95% by weight of at least one vinylaromatic monomer, a22 ) from 5 to 35% by weight of acrylonitrile, a23) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer, and a24) from 0 to 10% by weight, from 0.01 to 5% by weight, and particularly 0.02 to 2% by weight, of at least one polyfunctional crosslinked monomer and B) of 20 to 95% by weight of a thermoplastic polymer B) having a viscosity index VN of 50 to 120 ml / g, produced from, based on B), bl) from 69 to 81% by weight of at least one vinylaromatic monomer, b2) from 19 to 31% by weight of acrylonitrile, and b3) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer, and, if desired, additional thermoplastic polymers C), D) and / or E) based on at least one vinylaromatic monomer and, if desired, additives F), which they may be obtained by 1) the preparation of the graft polymers [sic] A by emulsion polymerization, 2) the mixture of graft polymer A) with polymer B) and the other components C), D), E) and / or F) if present, in a mixing apparatus, providing an essentially melted mixture of polymers, and 3) rapid cooling of the essential mixture melted mind of polymers.