THERMOPLASTIC ABS MOLDING COMBO WITH A GOOD COMBINATION OF PROCESSABILITY AND SURFACE QUALITY

Description

[0001] The present invention relates to a mixture P of ABS grafting rubbers, a method for its production, and its use. Furthermore, the invention comprises thermoplastic molding compounds F containing the mixture P, a method for producing the thermoplastic molding compounds F, molded parts obtainable therefrom, and their use.

[0002] For many years, acrylonitrile butadiene styrene copolymers (ABS) and ABS-type molding compounds, which may contain further comonomers (as building blocks) and / or further thermoplastic components, have been used as thermoplastic molding compounds for the production of molded parts for various applications.

[0003] The range of properties of these thermoplastic molding compounds can be varied widely. Of particular interest for many applications is the fact that such molding compounds exhibit exceptionally high toughness (e.g., impact strength and / or notched impact strength). Furthermore, good processability (thermoplastic flowability, MVR), heat resistance, and a very good surface gloss, and especially very good gloss stability, are desirable.

[0004] From WO 2001 / 62848, polymer compositions are known which include a graft rubber polymer (I) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a polybutadiene latex (A) with a mean particle diameter d 50 of 230 to 330 nm and a graft rubber polymer (II) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a polybutadiene latex (B) with a mean particle diameter d 50 of 340 to 480 nm, optionally a graft rubber polymer (III) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a polybutadiene latex (C), and a rubber-free copolymer of styrene and acrylonitrile. The polybutadiene latexes (A) and (B) are obtained by seed polymerization using a polybutadiene latex (C) with a mean particle diameter of 10 to 220 nm as the seed latex. The amount of seed latex used is not disclosed.

[0005] The weight ratio of the graft rubber polymers (I):(II) is preferably 70:30 to 35:65 (e.g., also 50:50). The weight ratio of the graft rubber polymers [(I) +(II)]:(III) is preferably 25:75 to 65:35.

[0006] In exemplary graft rubber polymer mixtures of (I), (II) and (III) the weight ratio [(I) +(II)] : (III) is 50:50; the calculated proportion of the polybutadiene latex (C) used - based on polybutadiene latexes (A), (B) and (C) - is 46.3 wt.%.

[0007] The polymer compositions known from WO 2001 / 62848 exhibit high toughness (impact strength and / or notched impact strength) and good processability (thermoplastic flowability, MVR). However, the surface gloss, especially the gloss under practical conditions (280°C / 50°C), as well as the gloss stability, still require improvement.

[0008] In light of the ever-increasing demands placed on plastic materials and new application areas, ABS graft polymers with specific property combinations are increasingly required. Crucial for many properties of ABS graft polymers is their particle size distribution, which can be particularly favorably controlled if at least one graft polymer is produced by direct growth in a seeding process. A disadvantage of the direct growth process, however, is the long cycle times required to produce large particles. This involves maintaining elevated reaction conditions for extended periods, which promotes the formation of 4-vinylcyclohexene (VCH), a Diels-Alder product that is often formed as an undesired side reaction during butadiene polymerization, in amounts ranging from 1 to 2 wt% (based on the solids content of the latex).

[0009] 4-Vinylcyclohexene has a strong odor and is potentially carcinogenic. Furthermore, like the unreacted monomers, it is classified as a volatile organic compound (VOC). If the VOCs are not removed or avoided through complex processes, which is generally associated with increased effort (in terms of process technology and / or energy consumption) and / or compromises in product properties (e.g., thermal stress, reduced rubber efficiency), the molding compounds produced from the graft polymers will still contain VOCs. These volatile organic compounds can be released into the ambient air. Due to the toxicity of VOCs, this is undesirable from both a health and environmental perspective. Therefore, the market demands graft copolymers and the molding compounds produced from them with a low VOC content while maintaining consistent processing and application properties.

[0010] WO 2014 / 170407 describes ABS graft copolymers and molding compounds containing them, exhibiting good impact strength and improved surface gloss. The graft base (butadiene latex, d 50 : 80 to 120 nm) is agglomerated using an acrylate / acrylamide copolymer.

[0011] The agglomerated butadiene latex (bimodal d 50 : 80 to 120 nm and 350 to 550 nm) is then grafted with styrene and acrylonitrile by means of emulsion polymerization.

[0012] A disadvantage is that the production of the aforementioned ABS graft copolymers, unlike graft copolymers whose butadiene latex was formed by seed polymerization, is technically more complex (additional production and storage of the starting materials and the agglomerating copolymer) and that the gloss stability of injection-molded parts is unsatisfactory and in need of improvement.

[0013] Therefore, there is a need to provide ABS graft copolymers and corresponding molding compounds that exhibit good toughness (impact strength and / or notched impact strength), good processability (thermoplastic flowability, MVR), and very good surface gloss, and in particular, very good gloss stability. Furthermore, the VOC content of the ABS graft copolymers, especially the 4-vinylcyclohexene content, should be as low as possible (max. 4000 ppm), and the manufacturing process should be economical (shortest possible production times or batch durations) and environmentally advantageous.

[0014] The problem was solved by the present invention according to the claims.

[0015] An object of the invention is a mixture P containing (or consisting of): (I) at least one graft rubber PI obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, preferably 80:20 to 65:35, wherein styrene and / or acrylonitrile may be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of at least one polybutadiene latex A having a mean particle diameter d 50 of 230 to 330 nm, preferably 240 to 320 nm, particularly 250 to 310 nm, and at least one polybutadiene latex B having a mean particle diameter d 50 of 340 to 480 nm, preferably 350 to 470 nm, particularly 360 to 460 nm, wherein the polybutadiene latexes A and B are joined by means of Seed polymerization (radical emulsion polymerization using a seed latex) starting from at least one, preferably one, polybutadiene latex C (as seed latex) with a mean particle diameter d 50 of 10 to 220 nm, preferably 20 to 210 nm,(II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, preferably 80:20 to 65:35, wherein styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of at least one polybutadiene latex C with a mean particle diameter d 50 of 10 to 220 nm, preferably 30 to 200 nm, and (III) optionally one or more additives and / or processing aids D, , characterized by the fact that With reference to the polybutadiene latexes A to C used (each calculated as the solid part of the latexes), the sum of which is 100 wt.% - the proportion of polybutadiene latex C is 36 to 43 wt.%, and the weight ratio A:B of the polybutadiene latizes A and B is 1.1:1 to 5:1 (calculated as the solid of latizes A and B, respectively).

[0016] A mixture P according to the invention is preferred, wherein the proportion of polybutadiene latex C is 37 to 43 wt.%, particularly preferably 38 to 42 wt.%, most preferably 39 to 42 wt.%.

[0017] A mixture P according to the invention is also preferred, wherein the weight ratio A:B of the polybutadiene latizes A and B used is preferably 1.3:1 to 4.5:1, often 2.5:1 to 4:1.

[0018] A preferred mixture P according to the invention is one in which the polybutadiene latex A was obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) as described above, and in which the polybutadiene latex C was used in an amount of 1.90 to 4.50 wt.%, preferably 2.40 to 3.80 wt.%, based on the total amount of monomer (ia butadiene amount) used to produce polybutadiene latex A.

[0019] Furthermore, a mixture P according to the invention is preferred, wherein the polybutadiene latex B was obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) as previously described, and wherein the polybutadiene latex C was used in an amount of 0.75 to 1.55 wt.%, preferably 0.95 to 1.35 wt.%, based on the total amount of monomer (ia butadiene amount) used to produce polybutadiene latex B.

[0020] Preferably, the mixture P consists of the aforementioned components (I) and (II) (grafting rubbers PI and P-II) and optionally component (III) (one or more additives and / or processing aids D).

[0021] In another preferred embodiment, the mixture P consists of components (I) and (II) (grafting rubbers PI and P-II) and component (III) (one or more additives and / or processing aids D).

[0022] The terms "graft rubber", "graft rubber polymer" and "graft rubber polymer" are to be understood in the broadest sense as synonymous with a graft copolymer consisting of a graft base (core) made of polybutadiene latex and a graft shell made of thermoplastic material based on styrene and acrylonitrile, and optionally the previously described comonomers (i.e. alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide).

[0023] Similarly, the terms "butadiene latex," "polybutadiene latex," "butadiene polymer latex," and "butadiene polymerate latex" are to be understood here in the broadest sense as synonymous with particulate particles that consist primarily, and therefore at least 50 wt%, of butadiene units. The term "latizes" is to be understood here as synonymous with emulsions and dispersions in the broadest sense.

[0024] It will generally be understood by those skilled in the art that "styrene", "acrylonitrile", "butadiene", etc. refer to the structural units derived from the respective monomer that are embedded in the (co)polymer structure.

[0025] Weight specifications, specifications and definitions of weight ratios, specifications in weight percent (wt%) and specifications in parts by weight (wt-parts) throughout the application generally refer to the respective weights of the dry substance (calculated as a solid), therefore excluding any liquids contained or absorbed (e.g., water, electrolyte solution and unbound monomers). "Weight ratio" and "mass ratio" are to be understood synonymously.

[0026] As used herein, the values ​​given in weight percent (wt%) are to be understood as meaning that the entire composition (e.g., of mixture P or molding compound F) always amounts to 100 wt%. If a composition comprises or contains a certain proportion of one or more components, the proportion of one or more other unspecified components is consequently 100 wt% less (minus) the proportion of the one or more specified components.

[0027] If a composition consists of certain components, the total proportion of these components is 100% by weight. A person skilled in the art will easily determine what the proportions of the remaining components can be when the proportions of other components are specified.

[0028] The mean particle diameter d50 of the polybutadiene lacites can be determined by disk centrifugation measurements as described in the examples. The particle diameter d50, also referred to as the d50 value of the integral mass distribution, is defined as the value at which 50 wt% of the particles have a smaller diameter and 50 wt% of the particles have a larger diameter than the d50 value.

[0029] To measure the particle size distribution using the CPS Instruments DC 24000 disc centrifuge, equipped with a low-density disc, a 17.1 mL aqueous sugar solution with a density gradient of 8 to 20 wt% sucrose was used in the centrifuge disc to achieve stable particle flotation behavior. For calibration, a polybutadiene latex with a narrow distribution and a mean particle size of 405 nm was used. The measurements were performed at a disc rotation speed of 24,000 rpm by injecting 0.1 mL of a dilute rubber dispersion into a 24% aqueous sucrose solution. The mass distribution of the particle diameters was calculated using Mie theory. Grafting rubbers PI and P-II

[0030] The graft rubber PI is preferably obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 in the presence of polybutadiene latices A and B. Preferably, the styrene:acrylonitrile weight ratio is 77:23 to 70:30. An exemplary embodiment of a graft rubber PI can also be found in the experimental example section below.

[0031] The graft rubber P-II is preferably obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 in the presence of polybutadiene latex C. A styrene:acrylonitrile weight ratio of 77:23 to 70:30 is particularly preferred. Preferred embodiments of a graft rubber P-II can also be found in the experimental example section below.

[0032] The polybutadiene latex A has a mean particle diameter d 50 of 230 to 330 nm, preferably of 240 to 320 nm, and particularly of 250 to 310 nm. Preferably, the polybutadiene latex A has a gel content of 30 to 80 wt.%, particularly preferably 40 to 75 wt.%, and particularly 45 to 70 wt.%.

[0033] In a preferred embodiment, the polybutadiene latex A has a mean particle diameter d 50 of 240 to 320 nm, in particular 250 to 310 nm, and a gel content of 30 to 80 wt.%, preferably 40 to 75 wt.%, in particular 45 to 70 wt.%. Particularly preferably, the polybutadiene latex A has a mean particle diameter d 50 of 250 to 310 nm and a gel content of 45 to 70 wt.%.

[0034] A particularly preferred embodiment of polybutadiene latex A can also be found in the experimental example section below.

[0035] The specified values ​​for the respective gel contents can be determined by the usual procedure using the wire cage method in toluene (see Houben-Weyl, Methods of Organic Chemistry, Macromolecular Substances, Part 1, p. 307 (1961), Thieme Verlag Stuttgart).

[0036] The gel content of the polybutadiene latizes A, B and C and optionally other latizes can be adjusted in a manner known in principle by applying suitable reaction conditions (e.g. high reaction temperature and / or polymerization up to high conversion and, if necessary, the addition of crosslinking agents to achieve a high gel content, or, e.g., low reaction temperature and / or termination of the polymerization reaction before excessive crosslinking occurs and, if necessary, the addition of molecular weight regulators such as n-dodecyl mercaptan or t-dodecyl mercaptan to achieve a low gel content).

[0037] The polybutadiene latex B has a mean particle diameter d 50 of 340 to 480 nm, preferably of 350 to 470 nm, and particularly of 360 to 460 nm. Preferably, the polybutadiene latex B has a gel content of 50 to 95 wt.%, and particularly of 55 to 90 wt.%.

[0038] In a preferred embodiment, the polybutadiene latex B has a mean particle diameter d 50 of 350 to 470 nm, in particular 360 to 460 nm, and a gel content of 50 to 95 wt.%, in particular 55 to 90 wt.%. Particularly preferably, the polybutadiene latex B has a mean particle diameter d 50 of 360 to 460 nm and a gel content of 55 to 90 wt.%.

[0039] A preferred embodiment of polybutadiene latex B can also be found in the experimental example section below.

[0040] The at least one, preferably one, polybutadiene latex C has a mean particle diameter d 50 of 10 to 220 nm, preferably of 20 to 210 nm, and particularly of 30 to 200 nm. Preferably, the polybutadiene latex C has a gel content of 30 to 98 wt.%, preferably 40 to 95 wt.%, and particularly of 50 to 94 wt.%.

[0041] In a preferred embodiment, the polybutadiene latex C has a mean particle diameter d 50 of 20 to 210 nm, in particular 30 to 200 nm, and a gel content of 30 to 98 wt.%, preferably 40 to 95 wt.%, in particular 50 to 94 wt.%.

[0042] The polybutadiene latex C particularly preferably has a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 94 wt.%.

[0043] When using a polybutadiene latex C with a mean particle diameter d50 above 80 nm, preferably above 90 nm, and particularly preferably above 100 nm, this polybutadiene latex C itself is also preferably produced by seed polymerization. The seed latex C' (preferably a polybutadiene latex) used for this purpose preferably has a mean particle diameter d50 of 10 to 70 nm, more preferably 20 to 60 nm. The gel content of the seed latex C' is 10 to 95 wt.%, preferably 20 to 90 wt.%, and particularly preferably 30 to 85 wt.%.

[0044] Preferably, the polybutadiene latex C is obtained by seed polymerization starting from at least one, preferably one, seed latex C', preferably one polybutadiene seed latex (as seed latex C'), as described above, wherein the seed latex C' was used in an amount of 4.00 to 9.00 wt.%, preferably 5.50 to 7.50 wt.%, based on the total amount of monomer used (i.e., butadiene amount) for the production of polybutadiene latex C.

[0045] A preferred embodiment of polybutadiene latex C can be found in the experimental example section below.

[0046] A mixture P according to the invention is preferably comprising (or consisting of) as described above. (I) at least one graft rubber PI obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 in the presence of: at least one polybutadiene latex A having a mean particle diameter d 50 of 250 to 310 nm and a gel content of 45 to 70 wt.%, and at least one polybutadiene latex B having a mean particle diameter d 50 of 360 to 460 nm and a gel content of 55 to 90 wt.%, wherein the polybutadiene latexes A and B are prepared by seed polymerization starting from at least one, preferably one, polybutadiene latex C having a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 94 wt.%.-% (as seed latex) were obtained, and the weight ratio A:B of the polybutadiene latexes A and B used is 1.3:1 to 4.5:1 (each calculated as solid of the latexes used); (II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 80:20 to 65:35 in the presence of at least one polybutadiene latex C with a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 92 wt.%, wherein - based on the polybutadiene latexes A to C used (each calculated as the solid of the latexes), the sum of which adds up to 100 wt.% - the proportion of polybutadiene latex C is 38 to 42 wt.%, (III) at least one rubber-free copolymer matrix P-III of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 95:5 to 50:50, wherein styrene is partially (< 50 wt.-%) can be replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride, (IV) optionally one or more additives and / or processing aids D. .

[0047] A mixture P according to the invention as described above containing (or consisting of): is particularly preferred. (I) at least one graft rubber PI obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 in the presence of: at least one polybutadiene latex A having a mean particle diameter d 50 of 250 to 310 nm and a gel content of 45 to 70 wt.%, and at least one polybutadiene latex B having a mean particle diameter d 50 of 360 to 460 nm and a gel content of 55 to 90 wt.%, wherein the polybutadiene latexes A and B are prepared by seed polymerization starting from at least one, preferably one, polybutadiene latex C having a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 94 wt.%.-% (as seed latex) were obtained, and wherein the weight ratio A:B of the polybutadiene latexes A and B used is 1.3:1 to 4.5:1, often 2.5:1 to 4:1 (each calculated as the solid of the latexes used); (II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 80:20 to 65:35 in the presence of at least one polybutadiene latex C with a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 92 wt.%, wherein - based on the polybutadiene latexes A to C used (each calculated as the solid of the latexes), the sum of which adds up to 100 wt.% - the proportion of polybutadiene latex C is 39 to 42 wt.%; (III) at least one rubber-free copolymer matrix P-III of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 95:5 to 50:50, wherein styrene is partially (< 50 wt.%)-%) can be replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride, (IV) optionally one or more additives and / or processing aids D. .

[0048] The weight ratio PI:P-II of the grafting rubbers PI and P-II in the mixture P according to the invention is preferably 62.5:37.5 to 52:48, particularly preferably 60:40 to 53:47, most preferably 58:42 to 54:46, and in particular 55:45.

[0049] In this context, too, the weight ratio refers to the solids of the polybutadiene lacites. These can be determined gravimetrically after drying (e.g., at a temperature of 100 to 200°C for 5 to 60 minutes (e.g., in a circulating air drying oven)).

[0050] Polybutadiene latexes A and B, and optionally C, are produced independently of each other using a seed polymerization process. This process involves the emulsion polymerization of butadiene (at least 50 wt.% and optionally other comonomers) to first produce a finely divided polybutadiene (co)polymer as seed latex. This seed latex is then further polymerized to larger particles by further reaction with butadiene (and optionally other comonomers) (see, e.g., Houben-Weyl, Methods of Organic Chemistry, Macromolecular Substances, Part 1, p. 339 (1961), Thieme Verlag Stuttgart). The seed batch process or the seed feed process is preferably employed.

[0051] Polybutadiene latex C is used as seed latex for polybutadiene latexes A and B.

[0052] The preferred polybutadiene latex C is made from: 50 to 100 wt.%, preferably 80 to 100 wt.%, in particular 90 to 100 wt.%, butadiene, and 0 to 50 wt.%, preferably 0 to 20 wt.%, in particular preferably 0 to 10 wt.%, of monomers copolymerizable with butadiene (therefore co-monomers), preferably monomers selected from the group consisting of: styrene, acrylonitrile, isoprene, chloroprene, alpha-methylstyrene, C1-C4 alkylstyrenes, C1-C8 alkyl acrylates, C1-C8 alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene and combinations of two or more thereof, in particular styrene and / or acrylonitrile.

[0053] Polybutadiene latex C, made from: is particularly preferred. 90 to 100 wt.% butadiene, and 0 to 10 wt.% styrene and / or acrylonitrile.

[0054] Polybutadiene latex C, a butadiene homopolymer latex, is particularly preferred.

[0055] A particularly preferred embodiment of the composition of a polybutadiene latex C can also be found in the experimental example section below.

[0056] The polybutadiene latex A is preferably produced from: 50 to 100 wt.%, preferably 80 to 100 wt.%, in particular 90 to 100 wt.%, butadiene; and 0 to 50 wt.%, preferably 0 to 20 wt.%, in particular preferably 0 to 10 wt.%, of monomers copolymerizable with butadiene (co-monomers), preferably monomers selected from the group consisting of: styrene, acrylonitrile, isoprene, chloroprene, alpha-methylstyrene, C1-C4 alkylstyrenes, C1-C8 alkyl acrylates, C1-C8 alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene and combinations of two or more thereof, in particular styrene and / or acrylonitrile.

[0057] Particularly preferred is the polybutadiene latex A made from: 90 to 100 wt.% butadiene, and 0 to 10 wt.% styrene and / or acrylonitrile.

[0058] A preferred embodiment of the composition of a polybutadiene latex A can also be found in the experimental example section below.

[0059] Preferably, the polybutadiene latex B is produced from: 50 to 100 wt.%, preferably 80 to 100 wt.%, in particular 90 to 100 wt.%, butadiene; and 0 to 50 wt.%, preferably 0 to 20 wt.%, in particular preferably 0 to 10 wt.%, of monomers copolymerizable with butadiene (therefore co-monomers), preferably monomers selected from the group consisting of styrene, acrylonitrile, isoprene, chloroprene, alpha-methylstyrene, C1-C4 alkylstyrenes, C1-C8 alkyl acrylates, C1-C8 alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene and combinations of two or more thereof, in particular styrene and / or acrylonitrile.

[0060] Particularly preferred is the polybutadiene latex B made from: 90 to 100 wt.% butadiene, and 0 to 10 wt.% styrene and / or acrylonitrile.

[0061] A particularly preferred embodiment of the composition of a polybutadiene latex B can also be found in the experimental example section below.

[0062] For the production of polybutadiene latex A and polybutadiene latex B, at least one, preferably one, polybutadiene latex C with a mean particle diameter d 50 of 10 to 220 nm, preferably 20 to 210 nm, particularly preferably 30 to 200 nm, is used as seed latex in each case (independently of each other).

[0063] The grafting rubber PI preferably consists of: 15 to 60 wt.%, in particular 20 to 50 wt.%, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof, and 40 to 85 wt.%, in particular 50 to 80 wt.%, of a graft base consisting of the polybutadiene latizes A and B, wherein the weight ratio A:B of the polybutadiene latizes A and B is 1.1:1 to 5:1, particularly preferably 1.3:1 to 4.5:1, often 2.5:1 to 4:1 (each calculated as the solid of latizes A and B).

[0064] The solids content of the polybutadiene lacites can be determined gravimetrically after drying (approximately at 50 to 150°C for 5 to 60 min (e.g. in a circulating air drying oven)).

[0065] The grafting rubber PI is particularly preferably composed of: 20 to 50 wt.% of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35, and 50 to 80 wt.% of a graft base consisting of the polybutadiene latizes A and B, wherein the weight ratio A:B of the polybutadiene latizes A and B is 1.1:1 to 5:1, preferably 1.3:1 to 4.5:1, often 2.5:1 to 4:1 (each calculated as the solid of latizes A and B).

[0066] The grafting rubber PI is particularly preferably composed of: 20 to 50 wt% of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35, and 50 to 80 wt% of a graft base consisting of the polybutadiene latizes A and B, wherein the weight ratio A:B of the polybutadiene latizes A and B is 1.3:1 to 4.5:1, often 2.5:1 to 4:1 (each calculated as the solid of latizes A and B).

[0067] Particularly preferably, the graft shell of the graft rubber PI consists solely of styrene and acrylonitrile in the aforementioned styrene:acrylonitrile weight ratios. Thus, the graft shell of the graft rubber PI is obtained by emulsion polymerization of styrene and acrylonitrile alone, i.e., without partial replacement of styrene and acrylonitrile by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide, or mixtures thereof. Preferred embodiments of the composition of the graft rubber PI are also described in the experimental example section below.

[0068] The grafting rubber P-II preferably consists of: 15 to 60 wt.%, in particular 20 to 50 wt.%, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile may be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof, and 40 to 85 wt.%, in particular 50 to 80 wt.%, of a graft base of polybutadiene latex C.

[0069] The P-II grafting rubber is particularly preferably composed of: 20 to 50 wt.% of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35, and 50 to 80 wt.% of a graft base made of polybutadiene latex C.

[0070] The graft shell of graft rubber P-II most preferably consists only of styrene and acrylonitrile in the aforementioned styrene:acrylonitrile weight ratios. Thus, the graft shell of graft rubber P-II is obtained by emulsion polymerization of styrene and acrylonitrile alone, i.e., without partial replacement of styrene and acrylonitrile by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide, or mixtures thereof.

[0071] A particularly preferred embodiment for the composition of the grafting rubber P-II can also be found in the experimental example section below.

[0072] Optionally, the grafting rubbers PI and P-II used according to the invention, or the mixture P according to the invention, may contain conventional additives and / or processing aids D.

[0073] The additives and / or processing aids D can be used in usual quantities, preferably in an amount of 0.2 to 5.0, more preferably 0.3 to 4.0 parts by weight, based on 100 parts by weight of the mixture consisting of components (I) and (II). Antioxidants and / or thermal stabilizers are often used as additives and / or processing aids D.

[0074] The inventive method for producing mixture P comprises the following steps: (i) Providing at least one polybutadiene latex C with a mean particle diameter d 50 of 10 to 220 nm; (ii) Producing at least one polybutadiene latex A with a mean particle diameter d 50 of 230 to 330 nm and at least one polybutadiene latex B with a mean particle diameter d 50 of 340 to 480 nm by seed polymerization from the polybutadiene latex C of step (i); (iii) Producing a graft rubber PI by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile are partially (< 50 wt.(i) (i) can replace the polybutadiene latex C from step (ii) by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of the polybutadiene latexes A and B from step (ii); (iv) prepare a graft rubber P-II by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of the polybutadiene latex C from step (i); (v) optionally mix the emulsions containing the graft rubbers PI and P-II from steps (iii) and (iv); (vi) work up the graft rubbers PI and P-II from steps (iii) and (iv) or step (v); and (vii) if step (v) is not present, mixing the grafting rubbers PI and P-II from step (vi); . wherein in step (iii) the weight ratio A:B of the polybutadiene latexes A and B used is 1.1:1 to 5:1, preferably 1.3:1 to 4.5:1, (each calculated as the solid of the latexes A and B), and in step (v) or (vii) - based on the polybutadiene latexes A to C used (each calculated as the solid of the latexes), the sum of which is 100 wt.% - the proportion of the at least one polybutadiene latex C is 36 to 43 wt.%, preferably 37 to 43 wt.%, particularly preferably 38 to 42 wt.%.

[0075] A preferred method according to the invention for producing the mixture P is wherein the polybutadiene latex C in step (i) was obtained by seed polymerization starting from at least one, preferably one, seed latex C', preferably a polybutadiene seed latex (as seed latex C'), seed latex C' (preferably a polybutadiene latex) with a mean particle diameter d 50 of 10 to 70 nm, preferably 20 to 60 nm, and wherein the seed latex C' was used in an amount of 4.00 to 9.00 wt.%, preferably 5.50 to 7.50 wt.%, based on the total amount of monomer used (iA butadiene amount) for the production of polybutadiene latex C.

[0076] A further preferred method according to the invention for producing the mixture P is wherein in step (ii) the polybutadiene latex C for the production of the polybutadiene latex A was used in an amount of 1.90 to 4.50 wt.%, preferably 2.40 to 3.80 wt.%, based on the total amount of monomer (ia butadiene amount) used for the production of polybutadiene latex A.

[0077] A further preferred method according to the invention for producing the mixture P is wherein in step (ii) the polybutadiene latex C for the production of the polybutadiene latex B was used in an amount of 0.75 to 1.55 wt.%, preferably 0.95 to 1.35 wt.%, based on the total amount of monomer (ia butadiene amount) used for the production of polybutadiene latex B.

[0078] A method for producing the mixture P is particularly preferred according to the invention, wherein the polybutadiene latex C in step (i) was obtained by seed polymerization starting from at least one, preferably one, seed latex C', preferably a polybutadiene seed latex (as seed latex C'), seed latex C' (preferably a polybutadiene latex) with a mean particle diameter d 50 of 10 to 70 nm, preferably 20 to 60 nm, and wherein the seed latex C' was used in an amount of 5.50 to 7.50 wt.%, preferably 4.00 to 9.00 wt.%, based on the total amount of monomer used (iA butadiene amount) for the production of polybutadiene latex C; in step (ii) the polybutadiene latex C was used to produce the polybutadiene latex A in an amount of 1.90 to 4.50 wt.%, preferably 2.40 to 3.80 wt.%, based on the total amount of monomer (ia butadiene amount) used to produce polybutadiene latex A; and in step (ii) the polybutadiene latex C was used to produce the polybutadiene latex B in an amount of 0.75 to 1.55 wt.%.-%, preferably 0.95 to 1.35 wt.%, was used, based on the total amount of monomer used (ia butadiene amount) for the production of polybutadiene latex B. .

[0079] Conventional anionic emulsifiers can be used independently as emulsifiers in the production of polybutadiene latizes A, B, and C (steps (i) and (ii) of the process according to the invention) and / or in the emulsion polymerization for the production of graft rubbers PI and P-II (steps (iii) and (iv) of the process according to the invention). Alkyl sulfates, alkyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturated fatty acids, and alkaline disproportionated or hydrogenated abietic or talloleic acids, or mixtures thereof, are preferred as emulsifiers. Emulsifiers with carboxyl groups (e.g., salts of C10-C18 fatty acids, disproportionated abietic acid, emulsifiers according to DE-OS 36 39 904 and DE-OS 39 13 509) are preferably used.

[0080] In a further preferred embodiment, alkaline soaps of sodium and potassium salts of disproportionated and / or dehydrogenated and / or hydrogenated and / or partially hydrogenated resins (rosin) with a dehydroabietic acid content of at least 30 wt.% and an abietic acid content of at most 1 wt.% can be used as emulsifiers.

[0081] Salts, acids and bases can still be used as additive D in the emulsion polymerization of polybutadiene latizes A, B and C, e.g. sulfuric acid, phosphoric acid, solutions of sodium hydroxide, potassium hydroxide, sodium and potassium salts of sulfates and phosphates, in particular tetrasodium pyrophosphate can be used.

[0082] Additionally, molecular weight regulators can be used in the production of polybutadiene latizes A, B, and C and / or in the emulsion polymerization for the production of graft rubbers PI and P-II, preferably in amounts of 0.01 to 2 wt.%, particularly preferably in amounts of 0.05 to 1 wt.% (in each case based on the total amount of monomer in the emulsion polymerization). Suitable molecular weight regulators are, for example, alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan; dimeric α-methylstyrene; and terpinolene.

[0083] Any initiators that decompose at the chosen reaction temperature to form radicals can be used as initiators in the synthesis of polybutadiene latizes A, B, and C. Typically, initiators that decompose thermally on their own or those that decompose in the presence of a redox system can be used.

[0084] Preferably, in the emulsion polymerization of styrene and acrylonitrile (and optionally alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) for the production of the graft rubbers PI and P-II (steps (iii) and (iv) of the process according to the invention) - independently of each other - at least one organic and / or inorganic peroxide compound, preferably at least one inorganic peroxide compound, is used as an initiator.

[0085] Suitable organic and / or inorganic peroxide compounds (comprising at least one peroxide group ROOH and / or ROOR) include, for example, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, ammonium, potassium, and sodium persulfate. In particular, inorganic peroxide salts, such as peroxodisulfates (persulfates), perphosphates, and perborates of ammonium, sodium, or potassium, are used as initiators. Sodium and / or potassium persulfates are especially preferred as initiators.

[0086] The polymerization temperature in the emulsion polymerization of styrene and acrylonitrile (and optionally alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) for the production of the graft rubbers PI and P-II (steps (iii) and (iv) of the process according to the invention) is - independently of each other - generally 25 to 99°C, preferably 40 to 90°C, particularly preferably 54 to 85°C.

[0087] Preferably, however, the graft polymerization (emulsion polymerization of styrene and acrylonitrile) is carried out such that the temperature difference between the beginning and end of the dosing of the initiator is at least 10 °C, preferably at least 15 °C and particularly preferably at least 20 °C.

[0088] The production of the graft rubbers PI and P-II (steps (iii) and (iv) of the process according to the invention) is carried out by means of emulsion polymerization by supplying the graft base and continuously dosing the monomers.

[0089] The monomers of the graft shell of the graft rubber PI, i.e. styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile from 95:5 to 50:50, whereby styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, are added separately or as a monomer mixture continuously to the polybutadiene latizes A and B in the given amounts and polymerized.

[0090] The monomers of the graft shell of the graft rubber P-II, i.e. styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile from 95:5 to 50:50, whereby styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, are added separately or as a monomer mixture continuously to the polybutadiene latex C in the given amounts and polymerized.

[0091] In the production of the graft rubber PI and in the production of the graft rubber P-II (steps (iii) and (iv) of the process according to the invention) the dosing of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) and the dosing of the initiator can be started simultaneously, independently of each other.

[0092] In the production of the graft rubber PI and in the production of the graft rubber P-II in steps iii) and iv) of the process according to the invention, the dosage of styrene and acrylonitrile can be carried out independently of each other within 2 to 6 hours, preferably 4 to 6 hours.

[0093] Furthermore, in the production of the graft rubber PI and in the production of the graft rubber P-II in steps iii) and iv) of the process according to the invention, the dosage of the entire quantity of the initiator can be carried out independently of each other within 2 to 6 hours, preferably 4 to 6 hours.

[0094] For example, at least one organic and / or inorganic peroxide compound, preferably at least one inorganic peroxide compound, particularly preferably at least one inorganic peroxide salt, and most preferably sodium and / or potassium persulfate, can be used as an initiator.

[0095] The total amount of initiator is often 0.1 to 1.0 parts by weight, preferably 0.2 to 0.9 parts by weight, particularly preferably 0.3 to 0.7 parts by weight (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latizes).

[0096] Often, steps (iii) and (iv) of the inventive process for producing the mixture P as described above additionally include a post-reaction time of 1.5 to 2.5 hours, preferably 2 hours, after the end of all dosages.

[0097] A preferred method according to the invention for producing the mixture P is wherein step (v) is present, i.e. the emulsions containing the grafting rubbers PI and P-II from steps (iii) and (iv) are mixed.

[0098] The processing of the resulting dispersion of the graft rubber PI or P-II in step vi) of the process according to the invention can be carried out according to a method known to those skilled in the art. For example, the processing is carried out by precipitation of the graft rubbers and separation of the dispersion water.

[0099] For this purpose, the grafting rubbers PI and P-II can be mixed in the desired ratio and then precipitated together or co-precipitated, or the grafting rubbers PI and P-II can be processed or precipitated separately and then used in the desired ratio for the mixture P according to the invention.

[0100] Preferably, the processing is carried out by co-precipitation of the graft rubbers PI and P-II and separation of the dispersion water, wherein the graft rubbers PI and P-II are mixed in the desired ratio and then co-precipitated.

[0101] For precipitation, any coagulating agent can be added. For example, coagulation can be achieved using an electrolyte solution (e.g., a salt solution, an acid solution, or a salt and acid solution). Preferred aqueous electrolyte solutions are those containing one or more salts selected from the group consisting of: magnesium sulfate, kieserite, pentahydrite, hexahydrite, epsomite (Epsom salt), calcium chloride, sodium chloride, or mixtures of two or more of these, and / or one or more acids (in particular, sulfuric acid and / or acetic acid). For example, coagulation can be achieved using a magnesium sulfate / sulfuric acid solution (e.g., containing 1 wt% magnesium sulfate and 0.07 wt% sulfuric acid in water).

[0102] The water of dispersion can be separated in the usual manner, for example by sieving, filtration, decanting, or centrifugation. After separation of the water of dispersion, a moist graft polymer is obtained, which typically has a residual water content of up to 60 wt%. The graft polymer can be used dried, partially dried, or moist for the production of the thermoplastic molding compound according to the invention.

[0103] To protect the graft rubbers PI and P-II from thermal damage during reprocessing, and to ensure safe and hazard-free reprocessing, it is often common practice to add antioxidants as component (III). For example, one or more phenolic antioxidants (see also Additives D), as well as any other substances that increase the thermal resistance of the graft rubbers PI and P-II, can preferably be added after emulsion polymerization. Typically, these antioxidants, e.g., in the form of one or more emulsions or dispersions, are mixed with the graft rubber PI and / or P-II by stirring.

[0104] Typically, the antioxidants are used in quantities of up to 4 parts by weight, based on 100 parts by weight of the mixture consisting of components (I) and (II).

[0105] Preferably, the work-up according to step (vi) of the inventive process for the production of the mixture P is carried out by (vi-1) cases (where applicable, co-cases) of the graft rubbers PI and P-II from the emulsion comprising these graft rubbers from steps (iii) and (iv) or step (v), (vi-2) dewatering the precipitated graft rubbers PI and P-II from step (vi-1) by filtration or centrifugation, and (vi-3) if necessary, drying the dewatered graft rubbers PI and P-II from step (vi-2).

[0106] The optional step (vi-3) includes drying the dehydrated grafting rubbers PI and P-II from step (vi-2).

[0107] In a preferred embodiment, the method according to the invention comprises step (vi-3), preferably step (vi-3'): drying the dehydrated graft rubbers PI and P-II from step (vi-2), wherein a graft rubber powder is obtained which has a residual moisture content of less than or equal to 5 wt.%.

[0108] Preferably, the moisture-moist grafting rubbers with a residual moisture content of less than or equal to 25% by weight are dried using a drying gas, wherein the grafting rubber is moved in the drying gas (e.g., carried along by the flowing drying gas) and the drying gas has a temperature in the range of 50 to 160 °C, preferably 55 to 155 °C, particularly preferably 60 to 150 °C. Preferably, air, nitrogen, or any mixture thereof is used as the drying gas.

[0109] In a preferred embodiment, the drying of the dewatered graft rubbers PI and P-II in step (vi-3) is carried out using a fluidized bed dryer and / or a flash dryer. In particular, the drying in step (vi-3) is carried out as described in WO 2017 / 093468 A1.

[0110] Fluidized bed dryers and flash dryers are familiar to those skilled in the art. In particular, they are drying devices for free-flowing, particulate materials, as described in Krischer / Kröll, Trocknungstechnik, Zweiter Band, Trockner und Trocknungsverfahren (Springer-Verlag, 1959).

[0111] In particular, the drying in step (vi-3) is carried out using a fluidized bed dryer, wherein the drying gas has a temperature in the range of 50 to 100 °C, preferably 55 to 90 °C, particularly preferably 60 to 85 °C, and the mean residence time of the graft rubbers PI and P-II in the fluidized bed dryer is 1 to 60 min, preferably 5 to 50 min, particularly preferably 10 to 40 min.

[0112] In particular, the drying in step (vi-3) is carried out using a flash dryer, wherein the drying gas has a temperature in the range of 100 to 160 °C, preferably 110 to 155 °C, particularly preferably 130 to 150 °C, and the mean residence time of the graft rubbers PI and P-II in the flash dryer is typically 1 to 300 seconds, preferably 1 to 120 seconds, particularly preferably 5 to 60 seconds.

[0113] In a preferred embodiment, the dried grafting rubber powder obtained in step (vi-3) has a residual moisture content in the range of 0.01 to 5 wt.%, preferably 0.05 to 2 wt.%, and particularly preferably 0.1 to 1 wt.%.

[0114] A particularly preferred method according to the invention for producing the mixture P is one in which step (v) is provided, and the work-up according to step (vi) is carried out by (vi-1) Co-precipitating the graft rubbers PI and P-II from the emulsion containing these graft rubbers from step (v), (vi-2) separating the precipitated graft rubbers PI and P-II (mixture P) from step (vi-1) by filtration or centrifugation, and (vi-3) optionally drying the separated graft rubbers PI and P-II (mixture P) from step (vi-2).

[0115] According to an alternative preferred embodiment, the moist, dehydrated graft rubbers PI and P-II obtained after step (vi-2) can be mixed with a melt of thermoplastic components containing a rubber-free copolymer P-III and optionally non-vinyl aromatic thermoplastic polymers T and / or additives and / or processing aids D' (for example in a kneading reactor) (szB EP-A 0867463).

[0116] Reference is made to the previously mentioned details of the emulsion polymerization according to steps (ii), (iii) and (iv), the work-up, in particular the precipitation and dehydration, of the graft rubbers PI and P-II according to step (vi) or steps (vi-1), (vi-2) and (vi-3) of the process according to the invention for the preparation of the mixture P.

[0117] Another object of the invention is a mixture P obtained by the inventive method. Thermoplastic molding compound F

[0118] Another aspect of the invention is a thermoplastic molding compound F containing the components (a) to (c): (a) a mixture P according to the invention comprising: (I) at least one graft rubber PI obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile are partially (< 50 wt.-%) can be replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as an initiator, in the presence of: at least one polybutadiene latex A with a mean particle diameter d 50 of 230 to 330 nm and at least one polybutadiene latex B with a mean particle diameter d 50 of 340 to 480 nm, wherein the polybutadiene latexes A and B were obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) with a mean particle diameter d 50 of 10 to 220 nm; (II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile are partially (< 50 wt.-%) can be replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as an initiator, in the presence of at least one polybutadiene latex C with a mean particle diameter d 50 of 10 to 220 nm, and (III) optionally one or more additives and / or processing aids D, characterized in that, with reference to the polybutadiene latexes A to C used (each calculated as the solid of the latexes), their sum is 100 wt.% - the proportion of polybutadiene latex C is 36 to 43 wt.%, and the weight ratio A:B of the polybutadiene latexes A and B used is 1.1:1 to 5:1 (each calculated as the solid of the latexes A and B); (b) at least one rubber-free copolymer P-III (= matrix copolymer) of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene is partially (< 50 wt.-%) can be replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride; and (c) optionally one or more additives and / or processing aids D'. .

[0119] The thermoplastic molding compound F can comprise any quantity of component (a) - of the mixture P according to the invention containing the grafting rubbers PI and P-II.

[0120] The thermoplastic molding compound F can comprise any amount of component (b) - the rubber-free copolymer P-III.

[0121] Preferred thermoplastic molding compounds F according to the invention contain: a) 10 to 60 wt.% mixture P according to the invention; b) 40 to 90 wt.% copolymer P-III; and c) 0 to 20 wt.% additives and / or processing aids D'; where the proportions of components a) to c) add up to 100 wt.%.

[0122] Particularly preferred thermoplastic molding compounds F according to the invention contain: a) 15 to 50 wt.%, preferably 20 to 40 wt.%, mixture P according to the invention; b) 50 to 80 wt.%, preferably 60 to 80 wt.%, copolymer P-III; and c) 0 to 10 wt.%, preferably 0 to 5 wt.%, additives and / or processing aids D'; where the proportions of components a) to c) add up to 100 wt.%.

[0123] If component (c) is present, its proportion is usually at least 0.01 wt.%, preferably at least 0.05 wt.%, particularly preferably at least 0.1 wt.%.

[0124] The molding compound F according to the invention can further optionally d) contain one or more thermoplastic polymers TP not composed of vinyl monomers.

[0125] The proportion of thermoplastic polymers TP, based on 100 parts by weight of components a) and b) (i.e., the total mass of the mixture P and the rubber-free copolymer P-III), can comprise 0 to 1000 parts by weight, preferably 0 to 700 parts by weight, particularly preferably 0 to 500 parts by weight, and especially 0 to 100 parts by weight.

[0126] Preferably, the thermoplastic molding compound F consists of the aforementioned components (a) and (b), and optionally (c) and / or (d). Rubber-free copolymer matrix P-III

[0127] The at least one rubber-free matrix component P-III (component (b)) is at least a copolymer of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 95:5 to 50:50, wherein styrene can be partially (< 50 wt%) replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride.

[0128] Preferably, the rubber-free matrix component P-III is at least a copolymer of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 65:35 to 80:20, wherein styrene can be partially replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride.

[0129] Particularly preferred is the rubber-free matrix component P-III, which is at least a copolymer of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 68:32 to 77:23, wherein styrene can be partially replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride.

[0130] Particularly preferred is the rubber-free matrix component P-III, which is at least a copolymer of styrene and acrylonitrile in the aforementioned styrene:acrylonitrile weight ratios, wherein the copolymer is a copolymer of styrene and acrylonitrile alone (i.e., no substitution by other comonomers).

[0131] Equally preferred is the rubber-free matrix component P-III, which is at least a copolymer (or terpolymer) of styrene, acrylonitrile and maleic anhydride, preferably in a weight ratio of styrene:acrylonitrile:maleic anhydride of 65:34:1 to 70:25:5.

[0132] Furthermore, the rubber-free matrix component P-III is particularly preferred as a mixture of at least one copolymer of styrene and acrylonitrile alone in the aforementioned styrene:acrylonitrile weight ratios and at least one copolymer (or terpolymer) of styrene, acrylonitrile and maleic anhydride in the weight ratio styrene:acrylonitrile:maleic anhydride of 65:34:1 to 70:25:5.

[0133] The at least one rubber-free matrix component P-III preferably has a mean molar mass Mw (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000 and / or an intrinsic viscosity [η] of 20 to 110 ml / g (measured in dimethylformamide at 25°C).

[0134] Rubber-free matrix components P-III are known and can be produced by radical polymerization, in particular by emulsion, suspension, solution, or bulk polymerization. Details on the production of such rubber-free matrix components are described, for example, in DE-A 24 20 358, DE-A 27 24 360, and DE-A 1 971 3509. Initiation can be carried out purely thermally or by the addition of initiators, in particular peroxides. Matrix components P-III produced by bulk or solution polymerization are particularly preferred.

[0135] A preferred embodiment of a rubber-free copolymer P-III can also be found in the experimental example section below. Thermoplastic polymers TP

[0136] In addition to thermoplastic components made from vinyl monomers – such as component (b) – the use of polycondensates, such as aromatic polycarbonates, aromatic polyester carbonates, polyesters, and polyamides as a rubber-free copolymer matrix in the molding compound is also possible. These are then used as thermoplastic polymers TP (optional component (c)).

[0137] Numerous suitable thermoplastic polycarbonates and polyester carbonates are known (see, for example, DE-A 14 95 626, DE-A 22 32 877, DE-A 27 03 376, DE-A 27 14 544, DE-A 30 00 610, DE-A 38 32396, and in particular DE-A 100 08 420 and WO 2012 / 022710).

[0138] Aromatic polycarbonates and / or aromatic polyester carbonates suitable according to the invention, used as thermoplastic polymers T, are known from the literature or can be produced according to processes known from the literature (for the production of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, as well as DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the production of aromatic polyester carbonates, see, for example, DE-A 3 077 934).

[0139] Aromatic polycarbonates can be produced, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, using an interfacial process, optionally with the use of chain terminators, such as monophenols, and optionally with the use of trifunctional or more than trifunctional branchers, such as triphenols or tetraphenols. Alternatively, they can be produced via a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate.

[0140] Diphenols for the production of aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of formula (I) where A a single bond, C 1 to C 5 alkylenes, C 2 to C 5 alkylidenes, C 5 to C 6 cycloalkylidenes, -O-, -SO-, -CO-, -S-, -SO 2-, C 6 to C 12 arylenes, to which further aromatic rings, optionally containing heteroatoms, may be fused, or a residue of formula (II) or (III) B each C 1 to C 12 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine X each independently of each other 0, 1 or 2, p 1 or 0, and R 5< and R 6< for each X 1 individually selectable, independently of each other hydrogen or C 1 to C 6 -alkyl, preferably hydrogen, methyl or ethyl, X1 carbon and m an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1< , R 5< and R 6< are simultaneously alkyl.

[0141] Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C 1 -C 5 -alkanes, bis-(hydroxyphenyl)-C 5 -C 6 -cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones and α,α-bis-(hydroxyphenyl)-diisopropyl benzenes as well as their nuclear-brominated and / or nuclear-chlorinated derivatives.

[0142] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, and their di- and tetrabrominated or chlorinated derivatives, such as 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.

[0143] The diphenols can be used individually or in any mixture. The diphenols are known from the literature or can be obtained through methods known from the literature.

[0144] Suitable chain termination compounds for the production of thermoplastic aromatic polycarbonates include, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]-phenol, 4-(1,3-tetramethyl-butyl)-phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain terminators to be used is generally between 0.5 mol-% and 10 mol-%, based on the total moles of the diphenols used.

[0145] The thermoplastic aromatic polycarbonates have mean weight-average molar masses (Mw, measured e.g. by GPC, ultracentrifuge or light scattering measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably 24,000 to 32,000 g / mol.

[0146] The thermoplastic aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the total amount of diphenols used, of trifunctional or more than trifunctional compounds, for example those with three or more phenolic groups.

[0147] Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates as thermoplastic polymer T, 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of diphenols to be used, of polydiorganosiloxanes with hydroxyaryloxy end groups can also be employed. These are known (US 3,419,634) and can be produced according to processes known from the literature. The production of copolycarbonates containing polydiorganosiloxanes is described in DE-A 3,334,782.

[0148] Preferred polycarbonates, besides the bisphenol-A homopolycarbonates, are the copolycarbonates of bisphenol-A with up to 15 mol%, based on the molar totals of diphenols, other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.

[0149] Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

[0150] Particularly preferred are mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1.

[0151] In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally used as a bifunctional acid derivative.

[0152] In addition to the monophenols already mentioned, other suitable chain terminators for the production of aromatic polyester carbonates include their chlorocarbonate esters, the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C 1 to C 22 alkyl groups or by halogen atoms, and aliphatic C 2 to C 22 monocarboxylic acid chlorides.

[0153] The amount of chain terminators is 0.1 to 10 mol-% in each case, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic dichloride in the case of monocarboxylic acid chloride chain terminators.

[0154] Aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

[0155] The aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).

[0156] Branching agents can include, for example, tri- or multi-functional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-napthalin tetracarboxylic acid tetrachloride, or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used), or tri- or multi-functional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)heptane, 1,3,5-tri-(4-hydroxyphenyl)benzene, 1,1,1-tri-(4-hydroxyphenyl)ethane, tri-(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, tetra(4-hydroxyphenyl)methane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-Hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-bis[4,4'-dihydroxytri-phenyl)-methyl]-benzene, in amounts of 0.01 to 1,0 mol-% based on the diphenols used. Phenolic branching agents can be added with the diphenols, acid chloride branching agents can be added together with the acid dichlorides.

[0157] In thermoplastic aromatic polyester carbonates, the proportion of carbonate structural units can vary arbitrarily. Preferably, the proportion of carbonate groups is up to 100 mol%, particularly up to 80 mol%, and most preferably up to 50 mol%, based on the sum of ester and carbonate groups. Both the ester and carbonate components of the aromatic polyester carbonates can be present in the form of blocks or statistically distributed within the polycondensate.

[0158] The relative solution viscosity (η rel ) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g polycarbonate or polyester carbonate in 100 ml methylene chloride solution at 25°C).

[0159] Furthermore, thermoplastic polymers T (component (c)) include polyamides, which are produced wholly or partly from lactams with 7-12 C atoms in the ring, optionally using one or more of the above-mentioned starting components.

[0160] Particularly preferred semi-crystalline polyamides are polyamide-6 and polyamide-6,6 and their mixtures. Well-known amorphous polyamides can also be used. They are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, m- and / or p-xylylenediamine, bis-(4-aminocyclohexyl)methane, bis-(4-aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 3-aminomethyl,3,5,5,-trimethylcyclohexylamine, 2,5- and / or 2,6-bis-(aminomethyl)norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and / or 2,4,4-trimethyladipic acid. Isophthalic acid and terephthalic acid.

[0161] Copolymers obtained by polycondensation of several monomers are also suitable, as are copolymers produced by adding aminocarboxylic acids such as ε-aminocaproic acid, ω-aminoundecanoic acid or ω-aminolauric acid or their lactams.

[0162] Particularly suitable amorphous polyamides are those produced from isophthalic acid, hexamethylenediamine and other diamines such as 4,4'-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, 2,5- and / or 2,6-bis-(aminomethyl)norbornene; or from isophthalic acid, 4,4'-diaminodicyclohexylmethane and ε-caprolactam; or from isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurinlactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine.

[0163] Instead of pure 4,4'-diaminodicyclohexylmethane, mixtures of the positional isomers of diaminodicyclohexylmethanes can also be used, consisting of 70 to 99 mol% of the 4,4'-diamino isomer, 1 to 30 mol% of the 2,4'-diamino isomer, 0 to 2 mol% of the 2,2'-diamino isomer, and optionally correspondingly higher condensed diamines obtained by hydrogenation of technical-grade diaminodiphenylmethane. Up to 30% of the isophthalic acid can be replaced by terephthalic acid.

[0164] The polyamides preferably have a viscosity number (VZ, determined according to ISO 307 on 0.5 wt.% solution in concentrated sulfuric acid (96 wt.% H 2 SO 4 at 25°C) of 90-150 ml / g, particularly preferably of 105-135 ml / g. Additives and / or processing aids D'

[0165] As component (c), the necessary or appropriate additives and / or processing aids D' can be added to the molding compounds according to the invention during production, preparation, further processing and final forming.

[0166] Examples of additives and / or processing aids D' are lubricants, release agents, waxes, pigments, dyes, flame retardants, antioxidants, UV stabilizers, fibrous or powdered fillers, fibrous or powdered reinforcing agents, as well as antistatic agents and mixtures thereof.

[0167] Examples of suitable lubricants and release agents include stearic acids, stearyl alcohol, stearic acid esters, stearamides, as well as silicone oils, montan waxes, and those based on polyethylene or polypropylene. These lubricants and release agents are generally used in amounts of up to 4% by weight, preferably up to 3% by weight, based on 100% by weight of the molding compound consisting of components (a), (b), and (c).

[0168] Examples of pigments include titanium dioxide, phthalocyanines, ultramarine blue, iron oxides and soot, as well as the entire class of organic and inorganic pigments.

[0169] For the purposes of the present invention, dyes are all dyes that can be used for the transparent, semi-transparent, or opaque coloring of polymers, in particular dyes suitable for coloring styrene copolymers. Such dyes are known to those skilled in the art. These pigments and dyes are generally used in amounts up to 20 wt.%, preferably up to 10 wt.%, based on 100 wt.% of the molding compound consisting of components (a), (b), and (c).

[0170] Examples of suitable flame retardants are antimony oxides such as Sb 2 O 3 and / or halogenated organic compounds.

[0171] Particularly suitable antioxidants are sterically hindered mono- or polynuclear phenolic antioxidants, which can have various substituents and also exhibit bridging via substituents. These include both monomeric and oligomeric compounds, which can be composed of two or more phenolic building blocks. It is also possible to use hydroquinones or hydroquinone analogues or substituted compounds, or other antioxidants based on tocopherols or their derivatives. Mixtures of different antioxidants are also possible. Generally, the antioxidants are used in amounts up to 4 wt%, based on 100 wt% of the molding compound consisting of components (a), (b), and (c). In principle, all commercially available compounds or those suitable for styrene copolymers can be used.

[0172] Along with the phenolic antioxidants mentioned above as examples, so-called costabilizers, especially those containing phosphorus or sulfur, can be used simultaneously. These phosphorus- or sulfur-containing costabilizers are familiar to skilled workers and commercially available.

[0173] Examples of suitable antioxidants include: Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as, for example, and preferably, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, 3-thiaoundecanol, 3-thiapentadecanol, trimethylolpropane, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with the aforementioned mono- or polyhydric alcohols, and esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, with the aforementioned mono- or polyhydric alcohols. Alcohols, esters of β-(3,5-Dicyclohexyl-4-hydroxyphenyl)-propionic acid with the aforementioned mono- or polyhydric alcohols.

[0174] Preferred antioxidants are 3,3'-thiodipropionic acid dioctadecyl ester (CAS No. 693-36-7), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3) and the butylated reaction product of p-cresol and dicyclopentadiene (CAS No. 68610-51-5).

[0175] Examples of suitable stabilizers against the effects of light include various substituted resorcinols, salicylates, benzotriazoles, benzophenones and HALS (hindered amine sunscreens), e.g., those commercially available as Tinuvin.

[0176] Preferred substances are Tinuvin 770 DF 1, bis(2,2,6,6,6-Tetramethyl-4-piperidyl)sebaceate (CAS No. 52829-07-9), Tinuvin P, 2-(2H-Benzotriazol-2-yl)-p-cresol (CAS No. 2H 2440-22-4), Cyasorb UV 3853, 2,2,6,6,6-Tetramethyl-4-piperidinyl stearate (CAS No. 167078-06-0), Hostavin N 845 (CAS No. 86403-32-9) and mixtures thereof.

[0177] These stabilizers can generally be used in amounts of up to 4 wt.%, preferably up to 3 wt.%, based on 100 wt.% of the molding compound consisting of components (a), (b) and (c).

[0178] Examples of fibrous or powdered fillers include carbon fibers and glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads, and wollastonite, especially glass fibers.

[0179] When glass fibers are used, they may be modified with a size and an adhesion promoter to improve compatibility with the components of the mixture. The incorporated glass fibers may be in the form of short glass fibers or continuous strands (rovings). These fillers may generally be used in amounts of up to 20 wt.%, preferably up to 10 wt.%, based on 100 wt.% of the molding compound consisting of components (a), (b), and (c).

[0180] Unless explicitly stated otherwise, the individual additives and / or processing aids D' are used in quantities customary for a person skilled in the art, so that it is unnecessary to provide further details in this context.

[0181] Another aspect of the present invention is a method for producing a thermoplastic molding compound F according to the invention.

[0182] According to the inventive method, the thermoplastic molding compound F is produced by mixing the components (a), (b) and optionally (c) and / or (d), and compounding in the melt, preferably at a temperature of 200 to 300°C.

[0183] In the process according to the invention, the respective components are mixed in a known manner and melt-compounded and melt-extruded at suitable temperatures, in particular at 200°C to 300°C, in conventional units such as internal kneaders, extruders and twin-screw extruders.

[0184] The mixing of the individual components can take place in a known manner, both successively and simultaneously, both at approximately 20°C (room temperature) and at higher temperatures.

[0185] The thermoplastic molding compound F according to the invention can be produced either directly by mixing the respective components or by using concentrates / precompounds of these components. These concentrates are produced in a known manner at suitable temperatures, in particular at 200°C to 300°C, in conventional equipment such as internal kneaders, extruders and twin-screw extruders. Molded body and use

[0186] Furthermore, other objects of the invention include a method for producing molded bodies from the molding compounds according to the invention, molded bodies produced from the molding compounds according to the invention, and the use of the molding compounds and / or the molded bodies according to the invention.

[0187] The molding compounds according to the invention can be used to produce molded parts of any kind. These can be produced, for example, by injection molding, extrusion, and blow molding. Another processing method is the production of molded parts by deep drawing from previously produced sheets or films and film back injection molding.

[0188] Examples of such molded parts include films, profiles, housing components of all kinds, for example for household appliances such as juicers, coffee machines, mixers, televisions; for office machines such as monitors, printers, copiers, notebooks, flat screens; bodywork or interior components for commercial vehicles, especially for the automotive sector; plates, pipes, electrical installation channels, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic components such as switches, plugs and sockets.In particular, the molding compounds according to the invention can also be used to produce the following molded bodies: interior components for rail vehicles, ships, aircraft, buses and other motor vehicles, exterior body parts in the automotive sector, housings for electrical appliances containing small transformers, housings for information processing and transmission devices, housings and coverings for medical devices, massage devices and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, thermally insulated transport containers, devices for keeping or caring for small animals, molded bodies for sanitary and bathroom equipment, cover grilles for ventilation openings, molded bodies for garden sheds and tool sheds, housings for garden tools.

[0189] The examples and claims shown below explain the invention. Examples Polybutadiene latex C

[0190] Polybutadiene latex C is anionically stabilized and has a mean particle diameter (d50) of 125 nm and a gel content of 93 wt%. It is produced using 6.0 wt% (calculated as solids), based on the amount of butadiene used, of a polybutadiene seed latex C' with a mean particle diameter (d50) of 49 nm as the seed by radical emulsion polymerization. The production of one batch of polybutadiene latex C takes 32 hours. The solids content is 40 wt%. Polybutadiene Latex A

[0191] Polybutadiene latex A is anionically stabilized and has a mean particle diameter (d50) of 305 nm and a gel content of 60 wt%. It is produced using 3.1 wt% (calculated as solids), based on the amount of butadiene used, of polybutadiene seed latex C with a mean particle diameter (d50) of 125 nm by radical emulsion polymerization. The production of a single batch of polybutadiene latex A takes 50 hours. The solids content is 48 wt%. Polybutadiene latex B

[0192] Polybutadiene latex B is anionically stabilized and has a mean particle diameter d50 of 395 nm and a gel content of 82 wt%. It is produced using 1.15 wt% (calculated as solids), based on the amount of butadiene used, of polybutadiene seed latex C with a mean particle diameter d50 of 125 nm by radical emulsion polymerization. The production of a single batch of polybutadiene latex B takes 95 hours. The solids content is 50 wt%.

[0193] Table 1 shows an average batch time [h] for the production of polybutadiene latices A to C, which is determined as follows:

[0194] The wt% given refers to the solid content of the latizes A to C in the mixtures P or the thermoplastic molding compounds F, and the sum of the wt% of the polybutadiene latizes A to C equals 100%. Production of ABS graft rubbers (ABS graft copolymers) Grafting rubber P-II-1

[0195] 51.5 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex C with a mean particle diameter d 50 of 125 nm and a gel content of 93 wt.%, which was produced using 6.0 wt.% of a polybutadiene seed latex C' with a mean particle diameter d 50 of 49 nm as seed by radical emulsion polymerization, was brought to a solids content of approximately 27 wt.% with deionized water.

[0196] The polybutadiene latex C was heated to 60°C and mixed with 0.25 parts by weight of potassium peroxodisulfate (dissolved in water). Then, 48.5 parts by weight of a mixture of 74.5% by weight styrene, 25.5% by weight acrylonitrile, and 0.1 parts by weight tert-dodecyl mercaptan were added at a constant rate over 5 hours. Simultaneously, 1 part by weight (calculated as solids) of the sodium salt of a resin acid mixture (commercial product Burez DRS S70 E, from Lawter BVBA, B-9130 Kallo, Belgium (specification data: acid value: 11 mg KOH / g, abietic acid content: < 1%, dehydroabietic acid content: 38%), dissolved in alkaline water) was added at a constant rate over a period of 5 hours. In parallel, 0.25 parts by weight of potassium peroxodisulfate (dissolved in water) were dosed over a period of 5 hours.

[0197] During the first 3 hours, the reaction temperature was increased from 60°C to 81°C. After all doses were completed, a two-hour post-reaction period at 81°C followed. The graft rubber was then cooled to room temperature. The solids content of the graft rubber, determined gravimetrically (drying in a circulating air drying oven at 180°C for 23 minutes), was 34.3 wt.%. Grafting rubber PI-1

[0198] 30 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex A with a mean particle diameter d 50 of 305 nm and a gel content of 60 wt%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, and 30 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex B with a mean particle diameter d 50 of 395 nm and a gel content of 82 wt%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, were mixed and brought to a solids content of approximately 27 wt% with deionized water.

[0199] The mixture of polybutadiene latizes A and B was heated to 60°C and mixed with 0.25 wt parts potassium peroxodisulfate (dissolved in water). Then, 40 wt parts of a monomer mixture consisting of 74.5 wt% styrene, 25.5 wt% acrylonitrile, and 0.12 wt parts tert-dodecyl mercaptan were added at a constant rate over 5 hours. Simultaneously, 1 wt part (calculated as a solid) of the sodium salt of a resin acid mixture (commercial product Burez DRS S70 E, from Lawter BVBA, B-9130 Kallo, Belgium (specification data: acid value: 11 mg KOH / g, abietic acid content: < 1%, dehydroabietic acid content: 38%), dissolved in alkaline water) was added at a constant rate over a period of 5 hours. In parallel, 0.25 parts by weight of potassium peroxodisulfate (dissolved in water) were dosed over a period of 5 hours.

[0200] During the first 3 hours, the reaction temperature was raised from 60°C to 81°C. After all doses were added, a two-hour post-reaction period at 81°C followed. The grafted rubber latex was then cooled to room temperature.

[0201] The gravimetrically determined solids content (drying in a circulating air drying oven at 180°C, 23 minutes) of the grafting rubber PI-1 was 35.0 wt.%. Grafting rubber PI-2

[0202] The product is manufactured according to the PI-1 grafting rubber specification, using 36 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex A with a mean particle diameter d 50 of 305 nm and a gel content of 60 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, and 24 parts by weight (calculated as solids) of a stabilized emulsified polybutadiene latex B with a mean particle diameter d 50 of 395 nm and a gel content of 82 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization. Grafting rubber PI-3

[0203] The product is manufactured according to the specification for grafting rubber PI-1, using 39 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex A with a mean particle diameter d 50 of 305 nm and a gel content of 60 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, and 21 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex B with a mean particle diameter d 50 of 395 nm and a gel content of 82 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization. Grafting rubber PI-4

[0204] The product is manufactured according to the specification for grafting rubber PI-1, using 42 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex A with a mean particle diameter d 50 of 305 nm and a gel content of 60 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, and 18 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex B with a mean particle diameter d 50 of 395 nm and a gel content of 82 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization. Grafting rubber PI-5

[0205] The product is manufactured according to the specification for grafting rubber PI-1, using 45 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex A with a mean particle diameter d 50 of 305 nm and a gel content of 60 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, and 15 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex B with a mean particle diameter d 50 of 395 nm and a gel content of 82 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization. Grafting rubber PI-6

[0206] The product is manufactured according to the specification for grafting rubber PI-1, using 48 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex A with a mean particle diameter d 50 of 305 nm and a gel content of 60 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization, and 12 parts by weight (calculated as solids) of an anionically stabilized polybutadiene latex B with a mean particle diameter d 50 of 395 nm and a gel content of 82 wt.%, which was produced using a polybutadiene seed latex C with a mean particle diameter d 50 of 125 nm by radical emulsion polymerization. Grafting rubber compound P-1

[0207] The latizes of the grafting rubbers P-II-1 and PI-1 were mixed by stirring in a weight ratio of 35% : 65%, calculated as solids, and at the same time 1.0 wt% of a phenolic antioxidant (Irganox 1076, BASF SE), based on the total solids content of the grafting rubber mixture, was added to this mixture of grafting rubbers in the form of a dispersion and mixed.

[0208] The resulting graft rubber mixture P-1 was then precipitated with a magnesium sulfate / sulfuric acid solution. The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt% and the concentration of sulfuric acid was 0.07 wt%. The concentration of the graft rubber mixture P-1, containing the graft rubbers P-II-1 and PI-1 in the dispersion, was 16 wt%.

[0209] Coagulation was carried out by first adding the magnesium sulfate / sulfuric acid solution and then, while stirring, adding the stabilized graft rubber mixture and subsequently heating to 95°C. Mixture P-1 was separated from the aqueous phase by vacuum filtration and washed with 1000 parts by weight of water. The resulting moist powder was dried at 70°C in a circulating air drying oven to a residual moisture content of < 1 wt% (gravimetric determination). The material was obtained as a fine powder with a mean particle size d50 of approximately 400 µm. The particle size d50 was determined by sieve analysis according to ISO 3310-1 using the following sieves: 63, 100, 150, 200, 300, 500, 800, and 2000 µm. Grafting rubber compound P-2

[0210] The latizes of the grafting rubbers P-II-1 and PI-1 were mixed by stirring in a weight ratio of 40% : 60%, calculated as solids, and at the same time 1.0 wt% of a phenolic antioxidant (Irganox 1076, BASF SE), based on the total solids of the grafting rubber mixture, was added and mixed to this mixture of grafting rubber latizes in the form of a dispersion.

[0211] The resulting graft rubber mixture was then precipitated with a magnesium sulfate / sulfuric acid solution. The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt%, and the concentration of sulfuric acid was 0.07 wt%. The concentration of graft rubber mixture P-2, containing graft rubbers P-II-1 and PI-1 in the dispersion, was 16 wt%. Coagulation was carried out by first adding the stabilized graft rubber mixture to the magnesium sulfate / sulfuric acid solution while stirring, and then heating to 95°C. Mixture P-2 was separated from the aqueous phase by vacuum filtration and washed with 1000 parts wt of water. The resulting moist powder was dried at 70°C in a circulating air drying oven to a residual moisture content of < 1 wt% (gravimetric determination). The material was supplied in the form of a fine powder with a mean particle size d 50 of approximately...400 µm was obtained. The determination of the particle size d 50 was carried out by sieve analysis according to ISO 3310-1 with the following sieves: 63, 100, 150, 200, 300, 500, 800 and 2000 µm. Grafting rubber mixtures P-3, P-4, P-5, P-6, P-7

[0212] The latex of grafting rubber P-II-1 and one latex each of grafting rubbers PI-1, PI-3 to PI-6 were mixed by stirring in a weight ratio of 45% : 55%, calculated as solids. Simultaneously, 1.0 wt% of a phenolic antioxidant (Irganox 1076, BASF SE), based on the total solids content of the grafting rubber mixture, was added to this mixture in the form of a dispersion and mixed. This resulted in one latex of each grafting rubber mixture P being obtained: Grafting rubber mixture P-3 containing grafting rubbers P-II-1 and PI-1, grafting rubber mixture P-4 containing grafting rubbers P-II-1 and PI-3, grafting rubber mixture P-5 containing grafting rubbers P-II-1 and PI-4, grafting rubber mixture P-6 containing grafting rubbers P-II-1 and PI-5, grafting rubber mixture P-7 containing grafting rubbers P-II-1 and PI-6.

[0213] The resulting graft rubber mixtures were then precipitated with a magnesium sulfate / sulfuric acid solution. The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt%, and the concentration of sulfuric acid was 0.07 wt%. The concentration of graft rubber mixtures P-3, P-4, P-5, P-6, and P-7 in the dispersion was 16 wt% each. Coagulation was carried out by first adding the stabilized graft rubber mixture to the magnesium sulfate / sulfuric acid solution while stirring, and then heating to 95°C. Graft rubber mixtures P-3, P-4, P-5, P-6, and P-7 were each separated from the aqueous phase by vacuum filtration and washed with 1000 wt% water.

[0214] The resulting moist powder was dried at 70°C in a circulating air drying oven until a residual moisture content of < 1 wt% (gravimetric determination) was achieved. The material was obtained as a fine powder with a mean particle size d50 of approximately 400 µm. The particle size d50 was determined by sieve analysis according to ISO 3310-1 using the following sieves: 63, 100, 150, 200, 300, 500, 800, and 2000 µm. Grafting rubber mixtures P-8, P-9, P-10, P-11, P-12, P-13, P-14

[0215] The latizes of the grafting rubbers P-II-1 and PI-2 were mixed by stirring in the ratios specified in Table 1, calculated as solids, and at the same time 1.0 wt% of a phenolic antioxidant (Irganox 1076, BASF SE), based on the total solids of the grafting rubber mixture, was added and mixed to this mixture of grafting rubber latizes in the form of a dispersion.

[0216] In each case, a latex of a graft rubber mixture P-8, P-9, P-10, P-11, P-12, P-13 or P-14 was obtained.

[0217] The respective graft rubber mixture obtained was then precipitated with a magnesium sulfate / sulfuric acid solution.

[0218] The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt%, and the concentration of sulfuric acid was 0.07 wt%. The concentration of the graft rubber mixtures P-8, P-9, P-10, P-11, P-12, P-13, and P-14 in the dispersion was 16 wt%. Coagulation was carried out by first adding the stabilized graft rubber mixture to the magnesium sulfate / sulfuric acid solution while stirring, and then heating to 95°C. The graft rubber mixtures P-8, P-9, P-10, P-11, P-12, P-13, and P-14 were each separated from the aqueous phase by vacuum filtration and washed with 1000 parts by weight of water. The resulting moist powder was dried at 70°C in a circulating air drying oven until a residual moisture content of < 1 wt% (gravimetric determination) was achieved. The material was obtained as a fine powder with a mean particle size d50 of approximately 400 µm.The determination of the particle size d 50 was carried out by sieve analysis according to ISO 3310-1 with the following sieves: 63, 100, 150, 200, 300, 500, 800 and 2000 µm. Grafting rubber compound P-15 (analogous to WO 2001 / 62848, examples 8-10)

[0219] The latizes of the grafting rubbers P-II-1 and PI-1 were mixed by stirring in a weight ratio of 50% : 50%, calculated as solids, and at the same time 1.0 wt% of a phenolic antioxidant (Irganox 1076, BASF SE), based on the total solids of the grafting rubber mixture, was added and mixed to this mixture of grafting rubber latizes in the form of a dispersion.

[0220] The resulting graft rubber mixture was then precipitated with a magnesium sulfate / sulfuric acid solution. The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt%, and the concentration of sulfuric acid was 0.07 wt%. The concentration of graft rubber mixture P-15, containing graft rubbers P-II-1 and PI-1 in the dispersion, was 16 wt%. Coagulation was carried out by first adding the stabilized graft rubber mixture to the magnesium sulfate / sulfuric acid solution while stirring, and then heating to 95°C. Mixture P-15 was separated from the aqueous phase by vacuum filtration and washed with 1000 parts wt of water. The resulting moist powder was dried at 70°C in a circulating air drying oven to a residual moisture content of < 1 wt% (gravimetric determination). The material was supplied in the form of a fine powder with a mean particle size d 50 of approximately...400 µm was obtained. The determination of the particle size d 50 was carried out by sieve analysis according to ISO 3310-1 with the following sieves: 63, 100, 150, 200, 300, 500, 800 and 2000 µm. Production of ABS molding compounds and molded parts Rubber-free copolymer matrix P-III-1

[0221] A statistical styrene / acrylonitrile copolymer (styrene-acrylonitrile weight ratio 73:27) with a weight-averaged molar mass Mw of 106,000 g / mol and a number-averaged molar mass Mn of 15,000 g / mol was used as the rubber-free copolymer matrix P-III-1. The rubber-free copolymer matrix P-III-1 was obtained by radical solution polymerization with peroxide initiation and exhibited an oligomer content of 1.0 wt% for oligomers with a molar mass less than 1000 g / mol. The molar masses Mw and Mn, as well as the oligomer content, were determined by gel permeation chromatography using tetrahydrofuran as the solvent and polystyrene for calibration. For the determination of the oligomer content in statistical styrene / acrylonitrile copolymer, see: K. Kirchner, H. Schlapkohl, Makromol. Chem. 177 (1976) 2031 -2042, "The Formation of Oligomers in the Thermal Copolymerization of the Styrene / Acrylonitrile System". Rubber-free copolymer matrix P-III-2

[0222] A statistical styrene / acrylonitrile copolymer (styrene-acrylonitrile weight ratio 76.5:23.5) with a weight-averaged molar mass Mw of 145,000 g / mol and a polydispersity of Mw / Mn < 3 was used as the rubber-free copolymer matrix P-III-2. The molar masses Mw and Mn were determined by gel permeation chromatography using tetrahydrofuran as the solvent and polystyrene for calibration. The rubber-free copolymer matrix P-III-2 was obtained by radical solution polymerization and exhibited a thermoplastic flow rate (MVR) of 40 ml / 10 minutes at 220°C and 10 kg. Rubber-free copolymer matrix P-III-3

[0223] A statistical styrene / acrylonitrile copolymer (styrene-acrylonitrile weight ratio 75:25) with a weight-averaged molar mass Mw of 185,000 g / mol and a polydispersity of Mw / Mn < 3 was used as the rubber-free copolymer matrix P-III-3. The molar masses Mw and Mn were determined by gel permeation chromatography using tetrahydrofuran as the solvent and polystyrene for calibration. The rubber-free copolymer matrix P-III-3 was obtained by radical solution polymerization and exhibited a thermoplastic flow rate (MVR) of 10 ml / 10 minutes at 220°C and 10 kg. Rubber-free copolymer matrix P-III-4

[0224] A statistical terpolymer of styrene, acrylonitrile and maleic anhydride (styrene-acrylonitrile-maleic anhydride weight ratio 66.4:31.5:2.1) produced by radical solution polymerization was used as the rubber-free copolymer matrix P-III-4, which has a thermoplastic flowability (MVR) of 18-26 ml / 10 minutes at 220°C and 10 kg. Polycarbonate (T-1):

[0225] Linear polycarbonate based on bisphenol A with a weight-averaged molecular weight Mw of 27,500 g / mol was used. The molar mass Mw was determined by gel permeation chromatography with methylene chloride as solvent at 25°C. Polyamide (T-2):

[0226] Polyamide 6 with a viscosity number of 105-135 ml / g was used. The viscosity number (VZ) of the polyamide was determined according to ISO 307 using a 0.5 wt% solution in concentrated sulfuric acid (96 wt% H₂SO₄) at 25°C. Thermoplastic molding compounds F1 to F15

[0227] For the production of the molding compounds, the graft rubber mixtures P-1 to P-14 described above were each used in a quantity of 30.0 parts by weight. 30 parts by weight of graft rubber mixture and 70 parts by weight of styrene / acrylonitrile copolymer P-III-1 were mixed together with 2.0 parts by weight of ethylene bisstearylamide, 0.30 parts by weight of magnesium stearate, and 0.15 parts by weight of a polydimethylsiloxane with a viscosity of 1000 mPas (measured at 25°C) in a ZSK 25 extruder (manufacturer Coperion) at 250°C, yielding molding compounds F1 to F15. After granulation of the molding compounds F1 to F15, they were processed into molded parts and tested (see Table 1).

[0228] The following properties of the molding compounds F and molded bodies were determined: Charpy impact strength at room temperature (ak RT) according to DIN EN ISO 179-2 / 1eA (unit: kJ / m²) Thermoplastic flowability: MVR (220 / 10) at 220°C and 10 kg load according to ISO 1133 (unit: cm³ / 10 min) Vicat softening temperature B / 50 according to ISO 306 (unit °C) Ball indentation hardness according to ISO 2039-1 (unit MPa or N / mm²) Tensile modulus, E-modulus Et (unit MPa or N / mm²) from a tensile test according to EN ISO 527-1 Gloss at 20°C according to DIN EN ISO 2813, the melt and mold temperatures used for injection molding the test plates are given in degrees Celsius. According to the invention, gloss stability is defined as the quotient of the gloss at 20°C under unfavorable but practical (280°C / 50°C) injection molding conditions divided by the gloss at 20°C under optimal (250°C / 80°C) injection molding conditions (the value is given in percent).d 50: To measure the particle size distribution of rubber latex (polybutadiene latex) using the DC 24000 disc centrifuge from CPS Instruments Inc., equipped with a low-density disc, an aqueous sugar solution of 17.1 mL with a density gradient of 8 to 20 wt% sucrose was used in the centrifuge disc to achieve stable particle flotation behavior. For calibration, a polybutadiene latex with a narrow distribution and a mean particle size of 405 nm was used. The measurements were performed at a disc rotation speed of 24,000 rpm by injecting 0.1 mL of a dilute rubber dispersion into a 24% aqueous sucrose solution. The mass distribution of the particle diameters was calculated using Mie theory.Rubber effectiveness (KE number) (dimensionless): A measure of the performance of the graft rubber, defined as the sum of impact strength at room temperature (ak RT) and thermoplastic flowability (MVR (220 / 10)). The higher the KE number value, the better the rubber effectiveness.

[0229] The DIN, ASTM and ISO standards mentioned herein are preferably the versions current as of July 2022. 4-Vinyl-1-Cyclohexene (VCH) content of grafting rubber mixtures P

[0230] The 4-vinyl-1-cyclohexene (VCH) content in the graft rubber mixtures P is determined by headspace gas chromatography. For this purpose, the latex samples (mixtures of graft flatizes PI and P-II) are mixed with internal standards (mesitylene and butyronitrile), diluted with dimethyl sulfoxide (5 g DMSO per 1 g latex), dispersed, and heated at 94°C for 30 minutes using a PerkinElmer Clarus 680 gas chromatograph. The analysis uses columns A (30 m capillary column Elite-WAX, 0.32 mm diameter, 1 µm film thickness) and B (30 m capillary column DB-WAX, 0.32 mm diameter, 1 µm film thickness), an FID detector, and helium as the carrier gas. The headspace temperatures are: oven 100°C / needle 110°C / transfer line 150°C. The content is given in ppm based on the solid content of the graft rubber compound P (see table).

[0231] The molding compounds of Examples 4, 5, and 11-14 according to the invention (see Table 1) have a very good surface quality and a gloss that depends only slightly on the injection molding parameters (= high gloss stability). For injection molding, it is crucial that not only is a perfect gloss achieved on the molded parts under optimal injection molding conditions, but also that an acceptable gloss is maintained even under less than ideal, or even unfavorable, injection molding conditions commonly encountered in practice. This allows for time savings, thereby reducing costs and increasing the capacity of an injection molding machine. Very good injection molding conditions are defined as a combination of a melt temperature of 250°C and a mold temperature of 80°C, while poor injection molding conditions are defined as a combination of a melt temperature of 280°C and a mold temperature of 50°C.

[0232] The molding compounds F4, F5, F11 to F14 according to the invention exhibit good surface quality even under less than ideal, poor injection molding conditions and contain only small amounts of volatile organic compounds (VOCs) in the form of 4-vinylcyclohexene. Furthermore, the graft copolymer mixtures P-8, P-9, P-4 to P-7 according to the invention and the molding compounds F4, F5, F11 to F14 produced therefrom show good toughness (impact strength and / or notched impact strength) and simultaneously good processability (thermoplastic flowability, MVR), which is also reflected in good rubber effectiveness (KE number). In addition, the average batch time for the production of the butadiene latizes A, B, and C, which are used for the graft copolymer mixtures P according to the invention, is relatively short, which is advantageous from both an economic and ecological perspective. Table 1: Composition and properties of the grafting rubber mixtures P and the molding compounds F Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 VB 1)< VB 1)< VB 1)< erf 2)< erf 2)< VB 1)< VB 1)< VB 1)< VB 1)< VB 1)< erf 2)< erf 2)< erf 2< ) erf 2)< VB 1)< Composition of graft rubber mixture P P-1 P-2 P-3 P-8 P-9 P-10 P-11 P-12 P-13 P-14 P-4 P-5 P-6 P-7 P-15 Pfropflatex P-II-1 [wt.%] 35 40 45 40 45 50 55 60 65 70 45 45 45 45 50 Pfropflatex PI-1 [wt.%] 65 60 55 50 Pfropflatex PI-2 [wt.%] 60 55 50 45 40 35 30 Pfropflatex PI-3 [wt.%] 55 Pfropflatex PI-4 [wt.%] 55 Pfropflatex PI-5 [wt.%] 55 Pfropflatex PI-6 [wt.%] 55 Butadiene latex C content [%] 31,6 36,4 41,2 36,4 41,3 46,2 51,2 56,3 61,5 66,7 41,2 41,2 41,2 41,2 45,8 Butadiene latex A content [%] 34,2 31,8 29,4 38,2 35,2 32,3 29,3 26,2 23,1 20,0 38,2 41,2 44,1 47,0 27,1 Butadiene latex B content [%] 34,2 31,8 29,4 25,4 23,5 21,5 19,5 17,5 15,4 13,3 20,6 17,6 14,7 11,8 27,1 Total Butadiene Latex A, B, C [%] 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Average batch duration of polybutadiene latex 59,7 57,8 55,8 54,9 53,1 51,4 49,6 47,7 45,9 44,0 51,9 50,5 49,2 47,9 54,0 VCH content grafting rubber mixture P [ppm] 4380 4120 3880 3960 3710 3480 3220 2990 2730 2500 3640 3580 3490 3430 3620 Table 1: Composition and properties of the grafting rubber mixtures P and the molding compounds F Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 VB 1)< VB 1)< VB 1)< erf 2)< erf 2)< VB 1)< VB 1)< VB 1)< VB 1)< VB 1)< erf 2)< erf 2)< inherit 2)< erf 2)< VB 1< ) Composition of graft rubber mixture P P-1 P-2 P-3 P-8 P-9 P-10 P-11 P-12 P-13 P-14 P-4 P-5 P-6 P-7 P-15 Pfropflatex P-II-1 [wt.%] 35 40 45 40 45 50 55 60 65 70 45 45 45 45 50 Pfropflatex PI-1 [wt.%] 65 60 55 50 Pfropflatex PI-2 [wt.%] 60 55 50 45 40 35 30 Pfropflatex PI-3 [wt.%] 55 Pfropflatex PI-4 [wt.%] 55 Pfropflatex PI-5 [wt.%] 55 Pfropflatex PI-6 [wt.%] 55 Butadiene latex C content [%] 31,6 36,4 41,2 36,4 41,3 46,2 51,2 56,3 61,5 66,7 41,2 41,2 41,2 41,2 45,8 Butadiene latex A content [%] 34,2 31,8 29,4 38,2 35,2 32,3 29,3 26,2 23,1 20,0 38,2 41,2 44,1 47,0 27,1 Butadiene latex B content [%] 34,2 31,8 29,4 25,4 23,5 21,5 19,5 17,5 15,4 13,3 20,6 17,6 14,7 11,8 27,1 Total Butadiene Latex A, B, C [%] 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Average batch duration of polybutadiene latex 59,7 57,8 55,8 54,9 53,1 51,4 49,6 47,7 45,9 44,0 51,9 50,5 49,2 47,9 54,0 VCH content grafting rubber mixture P [ppm] 4380 4120 3880 3960 3710 3480 3220 2990 2730 2500 3640 3580 3490 3430 3620

Claims

1. Mixture P containing: (I) at least one graft rubber P-I obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of at least one polybutadiene latex A with an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B with an average particle diameter d50 of 340 to 480 nm, wherein the polybutadiene latexes A and B have been obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) with an average particle diameter d50 of from 10 to 220 nm; (II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of the at least one polybutadiene latex C with an average particle diameter d50 of from 10 to 220 nm; and (III) optionally one or more additives and / or processing aids D, characterized in that, based on the polybutadiene latexes A to C used (in each case calculated as solids of the latices), the sum of which is 100% by weight, the proportion of polybutadiene latex C is 36 to 43% by weight, and the weight ratio A:B of the polybutadiene latices A and B is from 1.1:1 to 5:1 (in each case calculated as solids of the latices A and B), wherein the average particle diameter d50 is determined by disk centrifugation measurement.

2. Mixture P according to claim 1, characterized in that the proportion of polybutadiene latex C is 37 to 43% by weight, preferably 38 to 42% by weight, particularly preferably 39 to 42% by weight.

3. Mixture P according to claim 1 or 2, characterized in that the weight ratio A:B of the polybutadiene latices A and B used is 1.3:1 to 4.5:1.

4. Mixture P according to any one of claims 1 to 3, characterized in that the polybutadiene latex A was obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C, and the polybutadiene latex C was used in an amount of 1.90 to 4.50% by weight, preferably 2.40 to 3.80% by weight, based on the total amount of monomer used for the preparation of polybutadiene latex A.

5. Mixture P according to any one of claims 1 to 4, characterized in that the polybutadiene latex B was obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C, and the polybutadiene latex C was used in an amount of 0.75 to 1.55% by weight, preferably 0.95 to 1.35% by weight, based on the total amount of monomer used to prepare polybutadiene latex B.

6. Mixture P according to any one of claims 1 to 5, characterized in that the polybutadiene latex C was obtained by seed polymerization starting from at least one, preferably one, seed latex C', preferably a polybutadiene seed latex (as seed latex C'), and the seed latex C' was used in an amount of 4.00 to 9.00% by weight, preferably 5.50 to 7.50% by weight, based on the total amount of monomer used to prepare polybutadiene latex C.

7. Mixture P according to any one of claims 1 to 6, characterized in that the graft rubber P-I was obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 80:20 to 65:35 in the presence of the polybutadiene latexes A and B; and the graft rubber P-II was obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 80:20 to 65:35 in the presence of the polybutadiene latex C.

8. Mixture P according to one of claims 1 to 7, characterized in that the polybutadiene latex A has an average particle diameter d50 of 240 to 320 nm, in particular 250 to 310 nm, and a gel content of 30 to 80% by weight, preferably 40 to 75% by weight, in particular 45 to 70% by weight; the polybutadiene latex B has an average particle diameter d50 of 350 to 470 nm, in particular 360 to 460 nm, and a gel content of 50 to 95% by weight, in particular 55 to 90% by weight; and the polybutadiene latex C has an average particle diameter d50 of 20 to 210 nm, in particular 30 to 200 nm, and a gel content of 30 to 98% by weight, preferably 40 to 95% by weight, in particular 50 to 92% by weight, wherein the gel content is determined by the wire cage method in toluene according to the description.

9. Mixture P according to any one of claims 1 to 8, wherein the graft rubber P-I consists of: 15 to 60% by weight, in particular 20 to 50% by weight, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof; and 40 to 85% by weight, in particular 50 to 80% by weight, of a graft base from the polybutadiene latices A and B; and the graft rubber P-II consists of: 15 to 60% by weight, in particular 20 to 50% by weight, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof; and 40 to 85% by weight, in particular 50 to 80% by weight, of a graft base of polybutadiene latex C.

10. Process for preparing a mixture P according to any one of claims 1 to 9, comprising the following steps: (i) providing at least one polybutadiene latex C with an average particle diameter d50 of 10 to 220 nm; (ii) preparing at least one polybutadiene latex A with an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B with an average particle diameter d50 of 340 to 480 nm by seed polymerization from the polybutadiene latex C from step (i); (iii) preparing a graft rubber P-I by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of the polybutadiene latices A and B from step (ii), (iv) preparing a graft rubber P-II by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, in the presence of the polybutadiene latex C from step (i); (v) optionally mixing the emulsions containing the graft rubbers P-I and P-II from steps (iii) and (iv); (vi) processing the graft rubbers P-I and P-II from steps (iii) and (iv) or step (v); and (vii) if step (v) is not present, mixing the graft rubbers P-I and P-II from step (vi); • wherein in step (iii) the weight ratio A:B of the polybutadiene latices A and B used is 1.1:1 to 5:1, preferably 1.3:1 to 4.5:1 (in each case calculated as solids of the latices A and B), and • wherein in step (v) or (vii) - based on the polybutadiene latices A to C used (in each case calculated as solids of the latices), the sum of which is 100% by weight - the proportion of the at least one polybutadiene latex C is 36 to 43% by weight, preferably 37 to 43% by weight, particularly preferably 38 to 42% by weight.

11. Process for preparing a mixture P according to claim 10, wherein the processing according to step (vi) comprises: (vi-1) precipitation (optionally co-precipitation) of the graft rubbers P-I and P-II from the emulsion comprising these graft rubbers from steps (iii) and (iv) or step (v); (vi-2) separation of the precipitated graft rubbers P-I and P-II from step (vi-1) by filtration or centrifugation; and (vi-3) optionally, drying of the separated graft rubbers P-I and P-II from step (vi-2).

12. Mixture P according to any one of claims 1 to 9, obtained by the process according to claim 10 or 11.

13. Thermoplastic molding composition F containing components (a) to (c): (a) mixture P according to any one of claims 1 to 9 or claim 12; (b) at least one rubber-free copolymer P-III of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, preferably 80:20 to 65:35, wherein styrene can be partially replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride; and (c) optionally one or more additives and / or processing aids D'.

14. Thermoplastic molding composition F according to claim 13, further comprising (d) one or more thermoplastic polymers TP not composed of vinyl monomers selected from the group consisting of: aromatic polycarbonates, aromatic polyester carbonates, polyesters, and polyamides.

15. Process for preparing a thermoplastic molding composition F according to claim 13 or 14, wherein components (a), (b) and optionally (c) and / or (d) are mixed and compounded in the melt, preferably at a temperature of 200 to 300 °C.

16. Molded article of a molding composition F according to claim 13 or 14 obtainable by injection molding, extrusion, blow molding or thermoforming.

17. Use of a molding composition F according to claim 13 or 14 or a molded article according to claim 16 for housing parts or components in the household, office, automotive and / or garden sector.