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

Description

[0001] The present invention relates to ABS grafting rubbers with high latex stability and a method for their production, as well as thermoplastic ABS molding compounds containing these with a good combination of processability and surface quality, as well as a method for their production, furthermore molded bodies obtainable from the thermoplastic molding compound according to the invention, and their use.

[0002] For 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 surface gloss are desirable.

[0004] EP-A 0845496 describes a mixture of two ABS graft copolymers, I and II. Graft copolymer I is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a butadiene polymer latex A (particle diameter d50: ≤ 330 nm) and a butadiene polymer latex B (d50: ≥ 370 nm). Graft copolymer II is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a butadiene polymer latex C (d50: 110 to 150 nm). The graft polymerization is carried out by inorganic peroxide salt initiation in each case, whereby the graft base and 0.5 parts by weight of peroxide salt are initially added, and the monomer mixture is added over 4 hours. This is followed by post-polymerization for another 4 hours.

[0005] Furthermore, ABS molding compounds containing the ABS graft copolymer mixture and rubber-free SAN copolymers are described.

[0006] WO 2001 / 62848 discloses a polymer composition comprising I) a graft copolymer (I) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a butadiene polymer latex (A) with a mean particle diameter d50 of 230 to 330 nm, wherein the latex (A) was obtained by seed polymerization; II) a graft copolymer (II) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a butadiene polymer latex (B) with a d50 of 340 to 480 nm, wherein the latex (B) was obtained by seed polymerization using latex (C); III) a graft copolymer (III) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a butadiene polymer latex (C) with a mean particle diameter d50 of 80 to 220 nm, wherein the latex (C) was obtained by seed polymerization; and as seed latex for (A) and (B), as well as (IV) a rubber-free SAN copolymer.The graft polymerization is carried out by means of inorganic peroxide salt initiation, wherein the butadiene polymer latices (A) and (B), or (C), and 0.5 wt parts of peroxide salt are placed, and the monomer mixture is added over 6 hours.

[0007] WO 2016 / 184765 and WO 2017 / 093468 describe a mixture of two ABS graft copolymers BI and B-II, wherein graft copolymer BI is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a polybutadiene graft base B1-A (mean particle diameter d 50 : 230 to 330 nm) and a polybutadiene graft base B1-B (d 50 : 340 to 480 nm), wherein the graft bases B1-A and B1-B were obtained by seed polymerization, and graft copolymer B-II is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a polybutadiene graft base B1-C (d 50 : 10 to 220 nm). Emulsion polymerization is carried out particularly within 2 to 10 hours, e.g., 3 to 7 hours. As an example, graft polymerization is performed by inorganic peroxide salt initiation, where the graft base and 0.25 wt.Parts of peroxide salt are added, then the monomer mixture is added over 5 hours, and in parallel, 0.25 parts by weight of peroxide salt are dosed over a period of 5 hours. Furthermore, ABS molding compounds containing the ABS graft copolymer mixture and rubber-free SAN copolymers are described.

[0008] WO 2018 / 197377 also discloses a mixture of two ABS graft copolymers BI and B-II as previously described. Graft copolymers BIa and B-II are obtained by adding 0.5 parts by weight of peroxide salt to the graft bases B1-A and B1-B, or B1-C, and then adding styrene and acrylonitrile over 6 hours. Graft copolymers BIb are obtained by adding styrene and acrylonitrile to the graft bases B1-A and B1-B over 4 hours, and simultaneously adding peroxide and ascorbate over 9 hours. Furthermore, ABS molding compounds containing the ABS graft copolymer mixture and SAN copolymers are described.

[0009] A disadvantage of ABS graft copolymers obtained according to the state of the art is often a number of flecks that is too high for the required quality of the ABS molding compounds.

[0010] Spots can form at various stages during the manufacturing process, for example, during the grafting of the rubber base with graft monomers through coagulation. These coagulates then form the basis for the spots contained in ABS-type molding compounds in the subsequent manufacturing process. The formation of these spots is fundamentally unavoidable, but must be reduced to improve surface quality.

[0011] Therefore, there is a need to provide ABS grafting rubbers with higher latex stability and lower coagulation. Furthermore, there is a need to provide ABS molding compounds with improved surface quality, particularly a lower number of specks, as well as an energy- and resource-efficient process for producing the ABS grafting copolymers or the ABS molding compounds.

[0012] These problems are solved by the ABS grafting rubber compound, the ABS molding compound, and the method according to the claims, as described in the invention. The invention relates to a mixture of polymers.

[0013] 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, using at least one organic and / or inorganic, preferably 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, preferably 240 to 320 nm, particularly 250 to 310 nm, and at least one polybutadiene latex B with a mean particle diameter d 50 of 340 to 480 nm, preferably 350 to 470 nm nm, in particular 360 to 460 nm, wherein the polybutadiene latexes A and B are polymerized by seed polymerization starting from at least one, preferably one,(II) polybutadiene latex C (as seed latex) with a mean particle diameter d 50 of 10 to 220 nm, preferably 20 to 210 nm, particularly 30 to 200 nm, were obtained; (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, using at least one organic and / or inorganic peroxide compound as an initiator, in the presence of the 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 in that - independently of each other - in the production of the graft rubber PI and in the production of the graft rubber P-II,The dosing of the monomers – i.e., styrene and acrylonitrile, optionally partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide – and the dosing of the initiator are started simultaneously; the dosing of the monomers is carried out continuously within 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, particularly 4 hours; and the entire quantity of the initiator is dosed within 4.50 to 5.25 h, preferably 4.75 to 5.25 h, particularly 5 h, wherein the dose rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, particularly 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total quantity of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the dose rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0014] Preferably, the mixture P consists of the aforementioned components (I) and (II) (grafting rubber PI and P-II), and optionally component (III) (additives and / or processing aids D).

[0015] 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).

[0016] 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.

[0017] It is generally 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.

[0018] 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.

[0019] As used herein, the values ​​expressed in weight percent (wt%) are to be understood as meaning that the entire composition (e.g., of mixture P or molding compound F) always constitutes 100 wt%. If a composition comprises or contains a certain proportion of one or more components, the proportion of one or more other unnamed components is consequently 100 wt% less (minus) the proportion of the one or more named components. If a composition consists of certain components, the total proportion of these components is 100 wt%. A person skilled in the art will readily determine what the remaining components might be when the proportions of other components are specified.

[0020] The mean particle diameter d50 can be determined by disc centrifuge measurement 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.

[0021] To measure the particle diameter distribution using the DC 24000 disc centrifuge from CPS Instruments Inc., 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. A polybutadiene latex with a narrow distribution and a mean particle size of 405 nm was used for calibration. 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

[0022] Preferably, the graft rubber PI is 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.

[0023] An exemplary embodiment of a grafting rubber PI can also be found in the experimental example section below.

[0024] 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. A preferred embodiment of graft rubber P-II is also described in the experimental example section below.

[0025] 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.%.

[0026] According to 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.%.

[0027] A particularly preferred embodiment of polybutadiene latex A can also be found in the experimental example section below.

[0028] The stated values ​​for the respective gel contents can be determined using the standard procedure by wire cage assay in toluene (see Houben-Weyl, Methods of Organic Chemistry, Macromolecular Substances, Part 1, p. 307 (1961), Thieme Verlag Stuttgart). The gel contents of polybutadiene latices A, B, and C, and optionally other latices, can be adjusted in a generally known manner by applying suitable reaction conditions (e.g., high reaction temperature and / or polymerization to high conversion, and optionally 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 optionally the addition of molecular weight regulators such as n-dodecyl mercaptan or t-dodecyl mercaptan to achieve a low gel content).

[0029] 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.%.

[0030] According to 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.%.

[0031] A preferred embodiment of polybutadiene latex B can also be found in the experimental example section below.

[0032] 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 92 wt.%.

[0033] According to 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 92 wt.%.

[0034] 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 92 wt.%.

[0035] When using polybutadiene latex C with mean particle diameters d50 above 80 nm, preferably above 90 nm, and preferably above 100 nm, this polybutadiene latex C itself is preferably produced by seed polymerization. For this purpose, a polybutadiene latex with a mean particle diameter d50 of 10 to 60 nm, preferably 20 to 50 nm, is preferably used. The seed latex C' (preferably a polybutadiene latex) used for this purpose preferably has a mean particle diameter d50 of 10 to 60 nm, preferably 20 to 50 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.%.

[0036] A preferred embodiment of polybutadiene latex C can also be found in the experimental example section below.

[0037] 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 using at least one inorganic peroxide compound as an initiator, 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 92 wt.%.-% (as seed latex) obtained, wherein the weight ratio of the solids of the polybutadiene latexes A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 60:40 to 40:60; (II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile from 80:20 to 65:35 using at least one inorganic peroxide compound as an initiator, in the presence of the at least one polybutadiene latex C having a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 92 wt%; and (III) optionally one or more additives and / or processing aids D; . wherein the weight ratio of the grafting rubbers PI:P-II is from 70:30 to 35:65, preferably 55:45 to 60:40.

[0038] 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 (and optionally other comonomers) to first produce a finely divided polybutadiene (co)polymer as seed latex, which 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). This is preferably carried out using either the seed batch process or the seed feed process.

[0039] Polybutadiene latex C is used as seed latex for polybutadiene latexes A and B.

[0040] 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.

[0041] Polybutadiene latex C, made from: is particularly preferred. 90 to 100 wt.% butadiene, and 0 to 10 wt.% styrene and / or acrylonitrile.

[0042] Particularly preferred is the polybutadiene latex C, a butadiene homopolymer latex. A particularly preferred embodiment of the composition of a polybutadiene latex C can also be found in the experimental example section below.

[0043] 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.

[0044] Polybutadiene latex A, made from: is particularly preferred. 90 to 100 wt.% butadiene, and 0 to 10 wt.% styrene and / or acrylonitrile.

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

[0046] 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.

[0047] Polybutadiene latex B, made from: is particularly preferred. 90 to 100 wt.% butadiene, and 0 to 10 wt.% styrene and / or acrylonitrile.

[0048] A particularly preferred embodiment of the composition of a polybutadiene latex B can also be found in the experimental example section below.

[0049] 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).

[0050] The weight ratio of the solid components of polybutadiene latices A and B can be varied within wide limits. In principle, any weight ratio is possible.

[0051] Preferably the weight ratio of the solids of the polybutadienelatices A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, in particular 60:40 to 40:60.

[0052] In this context, the weight ratio refers to the solids of the polybutadiene latices. These can be determined gravimetrically after drying (approximately at 50 to 150°C for 5 to 60 minutes (e.g., in a circulating air drying oven)).

[0053] A preferred embodiment for the weight ratio of the solids of the polybutadiene latices A:B can also be found in the experimental example section below.

[0054] 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 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 consisting of polybutadienelates A and B.

[0055] 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 polybutadienelatices A and B.

[0056] The grafting rubber PI is particularly preferably made 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 polybutadienelatices A and B, wherein the weight ratio of the solids of polybutadienelatices A:B is 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 60:40 to 40:60.

[0057] The graft shell of the graft rubber PI is particularly preferably composed 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.

[0058] A preferred embodiment for the composition of the graft rubber PI can also be found in the experimental example section below.

[0059] 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 wt. 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.

[0060] 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.

[0061] 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.

[0062] A particularly preferred embodiment for the composition of the grafting rubber P-II can also be found in the experimental example section below.

[0063] The weight ratio of the grafting rubbers PI and P-II to each other in the mixture P according to the invention can be varied within wide limits. In principle, any weight ratio is possible.

[0064] A mixture P according to the invention is preferred, wherein the weight ratio of the grafting rubbers PI:P-II is 90:10 to 10:90, particularly preferably 80:20 to 20:80, and especially 70:30 to 35:65.

[0065] A mixture P according to the invention is particularly preferred, wherein the weight ratio of the grafting rubbers PI:P-II is 55:45 to 60:40.

[0066] In this context, too, the weight ratio refers to the solids of the polybutadiene latices. 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)).

[0067] A particularly preferred embodiment for the weight ratio of the solids of the grafting rubbers PI:P-II can also be found in the experimental example section below.

[0068] Conventional anionic emulsifiers can be used independently as emulsifiers in the production of polybutadiene latexes A, B, and C and / or in the emulsion polymerization for the production of graft rubbers PI and P-II. Preferably, 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 used 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.

[0069] 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.

[0070] Salts, acids and bases can still be used as additive D in the emulsion polymerization of polybutadienelates 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.

[0071] Additionally, molecular weight regulators can be used in the production of polybutadienelatices 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.

[0072] Any initiators that decompose at the chosen reaction temperature to form radicals can be used as initiators in the production of polybutadiene latices 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.

[0073] According to the invention, 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, at least one organic and / or inorganic peroxide compound, preferably at least one inorganic peroxide compound, is used as an initiator, independently of one another. Suitable organic and / or inorganic peroxide compounds (comprising at least one peroxide group ROOH and / or ROOR) are, 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.

[0074] The polymerization temperature for 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 is - independently of each other - generally 25 to 99°C, preferably 40 to 90°C, particularly preferably 54 to 85°C.

[0075] 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.

[0076] Furthermore, the graft polymerization is preferably carried out such that within 100 to 180 minutes, preferably within 110 to 150 minutes, particularly preferably within 110 to 140 minutes, and most preferably within 110 to 130 minutes, after the start of dosing the initiator and the monomers, a temperature minimum is passed which has a temperature that is at least 1 to 10°C, preferably 2 to 8°C, and particularly preferably 4 to 6°C, lower than the temperature at the start of dosing.

[0077] The above preferred graft polymerization is particularly preferably carried out such that the temperature at the beginning of the dosing of the initiator and the monomers is 58 to 68°C, preferably 59 to 66°C, particularly preferably 60 to 64°C; the temperature of the minimum temperature, which is passed within 100 to 180 minutes, preferably within 110 to 150 minutes, particularly preferably within 110 to 140 minutes, most preferably within 110 to 130 minutes, after the beginning of the dosing of the initiator and the monomers, is 54 to 64°C, preferably 55 to 62°C, particularly preferably 56 to 58°C; and the temperature at the end of the dosing of the initiator is 75 to 90°C, preferably 78 to 85°C.

[0078] According to the invention, the graft rubbers PI and P-II are produced by means of emulsion polymerization by supplying the graft base and continuously dosing the monomers.

[0079] According to the invention, 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, wherein styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, separately or as a monomer mixture, are added continuously to the polybutadienelates A and B in the given amounts and polymerized.

[0080] According to the invention, 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, wherein styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, separately or as a monomer mixture continuously added to the polybutadiene latex C in the given amounts and polymerized.

[0081] 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 are started simultaneously and independently of each other during the production of the graft rubber PI and during the production of the graft rubber P-II.

[0082] According to the invention, the dosage of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) is carried out independently of each other during the production of the graft rubber PI and during the production of the graft rubber P-II within 3.50 to 4.25 hours.

[0083] According to the invention, the total amount of the initiator is dosed independently of each other during the production of the graft rubber PI and during the production of the graft rubber P-II within 4.50 to 5.25 hours, wherein the dose rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, particularly 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices) and thereafter 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0084] Preferably, in the production of graft rubber PI and in the production of graft rubber P-II, the dosage of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) is carried out independently of each other within 3.75 to 4.25 hours, and the dosage of the entire quantity of the initiator is carried out within 4.75 to 5.25 hours, wherein the dosage rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, particularly 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight (based on the total quantity of monomer in the emulsion polymerization and the solid of the polybutadiene latices) per hour, and thereafter 0.03 to 0.08 parts by weight per hour. The quantity is parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0085] Particularly preferably, in the production of graft rubber PI and in the production of graft rubber P-II, the dosage of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) is carried out independently of each other within 3.75 to 4.25 hours, in particular 4.00 hours, and the dosage of the entire quantity of the initiator is carried out within 4.75 to 5.25 hours, in particular 5.00 hours, wherein the dosage rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, is 0.4 to 0.6 parts by weight (based on the total quantity of monomer in the emulsion polymerization and the solid of the polybutadiene latices) per hour, and thereafter 0.05 to 0.06 parts by weight. The amount of parts by weight per hour is [amount missing].

[0086] 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 latices).

[0087] As previously described, according to the invention, 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, is used as the initiator.

[0088] The processing of the resulting dispersion of graft rubber PI or P-II is carried out according to a method known to those skilled in the art. For example, processing is carried out by precipitation of the graft rubbers and separation of the dispersion water. For this purpose, the graft rubbers PI and P-II can be mixed in the desired ratio and then co-precipitated, or the graft 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.

[0089] 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.

[0090] Any coagulating agent can be added to precipitate the solution. For example, coagulation can be achieved using an electrolyte solution (e.g., a salt solution, an acid solution, or a salt and acid solution).

[0091] 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 thereof, and / or one or more acids (in particular, sulfuric acid and / or acetic acid). For example, coagulation can be carried out using a magnesium sulfate / sulfuric acid solution (e.g., containing 1 wt% magnesium sulfate and 0.07 wt% sulfuric acid in water).

[0092] 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.

[0093] 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. The additives and / or processing aids D may be used in conventional 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).

[0094] Antioxidants and / or thermal stabilizers are often used as additives and / or processing aids.

[0095] 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.

[0096] 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).

[0097] Another aspect of the present invention is a method for producing the mixture P according to the invention.

[0098] The process is characterized according to the invention in that, independently of one another, during the production of the graft rubber PI and the production of the graft rubber P-II, the dosing of the monomers – i.e., of styrene and acrylonitrile, optionally partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide – and the dosing of the initiator are started simultaneously; furthermore, the dosing of the monomers is carried out continuously within 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, in particular 4 hours; and the entire quantity of the initiator is dosed within 4.50 to 5.25 hours, preferably 4.75 to 5.25 hours, particularly 5 hours, wherein the dose rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, particularly 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight.-parts per hour, (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the dosage rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0099] 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 on the polybutadiene latex C from 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.-%) 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 the polybutadiene latexes A and B from step (ii); (iv) preparation of 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, using at least one organic and / or inorganic peroxide compound as an initiator, in the presence of the polybutadiene latex C from step (i); wherein in steps (iii) and (iv) - independently of each other - the dosage of the monomers - i.e.of styrene and acrylonitrile, optionally replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide - and the dosing of the initiator are started simultaneously; the dosing of the monomers is carried out continuously within 3.50 to 4.25 hours; the entire amount of initiator is dosed within 4.50 to 5.25 hours, wherein the dosing rate of the initiator in the first 20 to 40 minutes is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour, (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the dosing rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.-parts per hour; (v) if necessary, mixing the emulsions containing the graft rubbers PI and P-II from steps (iii) and (iv); (vi) reprocessing 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 graft rubbers PI and P-II from step (vi).

[0100] A preferred method according to the invention for producing the mixture P as described above is wherein in steps (iii) and (iv) - independently of each other - The monomers are dosed continuously over 3.75 to 4.25 hours, in particular 4 hours; the entire quantity of the initiator is dosed over 4.75 to 5.25 hours, in particular 5 hours, wherein the dosage rate of the initiator is 0.25 to 0.75 parts by weight per hour for the first 25 to 35 minutes, in particular 30 minutes, and thereafter the dosage rate of the initiator is 0.03 to 0.08 parts by weight per hour.

[0101] A particularly preferred method according to the invention for producing the mixture P as described above is wherein steps (iii) and (iv) are carried out independently of each other - The monomers are dosed continuously over a period of 3.75 to 4.25 hours, in particular 4 hours; the entire quantity of the initiator is dosed over a period of 4.75 to 5.25 hours, in particular 5 hours, wherein the dosage rate of the initiator is 0.4 to 0.6 parts by weight per hour for the first 25 to 35 minutes, in particular 30 minutes, and thereafter the dosage rate of the initiator is 0.05 to 0.06 parts by weight per hour.

[0102] A method according to the invention is particularly preferred in which, in steps (iii) and (iv) - independently of each other - at least one inorganic peroxide salt selected from the group consisting of peroxodisulfate (persulfate), perphosphate and perborate of ammonium, sodium and / or potassium, preferably sodium and / or potassium persulfate, is used.

[0103] 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.

[0104] Preferably, in the emulsion polymerization in steps (iii) and (iv) of the process according to the invention for the preparation of mixture P, the temperature is 40 to 90 °C, particularly 55 to 85 °C. Furthermore preferably, in the emulsion polymerization in steps (iii) and (iv) of the process according to the invention for the preparation of mixture P, the temperature difference between the beginning and end of the reaction is at least 10 °C, preferably at least 15 °C, and particularly preferably at least 20 °C.

[0105] 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.

[0106] 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).

[0107] The optional step (vi-3) includes drying the dehydrated grafting rubbers PI and P-II from step (vi-2).

[0108] 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.%.

[0109] 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.

[0110] 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.

[0111] 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).

[0112] 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.

[0113] 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.

[0114] 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.%.

[0115] 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).

[0116] 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) (see EP-A 867 463).

[0117] 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.

[0118] Another object of the invention is a mixture P obtained by the inventive method. Thermoplastic molding compound F

[0119] Another aspect of the invention is a thermoplastic molding compound F containing (or consisting of) the components (a) to (d): (a) a mixture P according to the invention comprising (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, 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 - independently of each other - in the production of the graft rubber PI and in the production of the graft rubber P-II, the dosage of the monomers - i.e.Styrene and acrylonitrile, optionally partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, - and the dosing of the initiator is started simultaneously; the dosing of the monomers is carried out continuously within 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, particularly 4 hours; The entire quantity of the initiator is dosed within 4.50 to 5.25 h, preferably 4.75 to 5.25 h, particularly 5 h, wherein the dose rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, particularly 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the dose rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.-parts per hour; (b) at least one rubber-free copolymer matrix P-III of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene may be partially (< 50 wt%) replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride; (c) optionally one or more non-vinyl monomer thermoplastic polymers T; and (d) optionally one or more additives and / or processing aids D'. .

[0120] Preferably, the thermoplastic molding compound F consists of the aforementioned components (a) and (b), and optionally (c) and / or (d).

[0121] Component (a) is the mixture P according to the invention as described above. Rubber-free copolymer matrix P-III

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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).

[0126] 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.

[0127] 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.

[0128] 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).

[0129] 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.

[0130] A preferred embodiment of a rubber-free copolymer P-III can also be found in the experimental example section below. Thermoplastic polymers T

[0131] 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 T (optional component (c)).

[0132] 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).

[0133] 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-A 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).

[0134] Aromatic polycarbonates can be produced, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic 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. Production via a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate is also possible.

[0135] 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, X 1< 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1 are particularly preferred.

[0145] In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally used as a bifunctional acid derivative.

[0146] 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.

[0147] 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.

[0148] Aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

[0149] 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).

[0150] 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.

[0151] 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.

[0152] 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).

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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'

[0159] As component (d), 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.

[0160] 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.

[0161] 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 parts by weight, preferably up to 3 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c).

[0162] Examples of pigments include titanium dioxide, phthalocyanines, ultramarine blue, iron oxides and soot, as well as the entire class of organic and inorganic pigments.

[0163] 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 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c).

[0164] Examples of suitable flame retardants are antimony oxides such as Sb 2 O 3 and / or halogenated organic compounds.

[0165] 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 analogs or substituted compounds, or other antioxidants based on tocopherols or their derivatives. Mixtures of different antioxidants can also be used. Generally, the antioxidants are used in amounts up to 4 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c). In principle, all commercially available compounds or those suitable for styrene copolymers can be used.

[0166] 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.

[0167] 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; esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)-propionic acid with the aforementioned mono- or polyhydric alcohols.

[0168] 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).

[0169] 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.

[0170] 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.

[0171] These stabilizers are generally used in quantities up to 4 parts by weight, preferably 3 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c).

[0172] Examples of fibrous or powdered fillers include carbon fibers and glass fibers in the form of glass fabrics, glass mats or glass fiber rovings, chopped glass, glass beads, and wollastonite, particularly glass fibers. 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 are generally used in amounts of up to 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c).

[0173] 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.

[0174] Preferably the thermoplastic molding compound F according to the invention contains (or the thermoplastic molding compound F consists of) components (a) to (d): (a) a mixture P according to the invention as described above comprising (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 80:20 to 65:35 using at least one inorganic peroxide compound as an initiator, 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 92 kg-% (as seed latex) obtained, wherein the weight ratio of the solids of the polybutadiene latexes A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 60:40 to 40:60; (II) at least one graft rubber P-II obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile from 80:20 to 65:35 using at least one inorganic peroxide compound as an initiator, in the presence of the at least one polybutadiene latex C having a mean particle diameter d 50 of 30 to 200 nm and a gel content of 50 to 92 wt%; and (III) optionally one or more additives and / or processing aids D; wherein the weight ratio of the graft rubbers PI:P-II is 70:30 to 35:65, preferably 55:45 to 60:40. (b) at least one rubber-free copolymer matrix P-III of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 80:20 to 65:35; wherein styrene is partially (< 50 wt.-%) can be replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride; (c) optionally one or more non-vinyl monomer thermoplastic polymers T; and (d) optionally one or more additives and / or processing aids D'. .

[0175] The thermoplastic molding compound F can comprise any quantity of component (a) – the mixture P according to the invention containing the graft rubbers PI and P-II. Preferably, the thermoplastic molding compound F comprises 1 to 60 parts by weight, in particular 5 to 50 parts by weight, of the mixture P. Here, the parts by weight are 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).

[0176] The thermoplastic molding compound F can comprise any quantity of component (b) – the rubber-free copolymer P-III. Preferably, the thermoplastic molding compound F comprises 40 to 99 parts by weight, in particular 50 to 95 parts by weight, of rubber-free copolymer P-III. Here, the parts by weight are 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).

[0177] The thermoplastic molding compound F particularly preferably comprises 1 to 60 parts by weight, in particular 5 to 50 parts by weight, of the mixture P and 40 to 99 parts by weight, in particular 50 to 95 parts by weight, of rubber-free copolymer P-III. Here, the parts by weight are 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).

[0178] The thermoplastic molding compound F can optionally comprise any quantity of non-vinyl monomer thermoplastic polymers T. Preferably, the thermoplastic molding compound comprises 0 to 1000 parts by weight, more preferably 0 to 700 parts by weight, more preferably 0 to 500 parts by weight, and more particularly 0 to 100 parts by weight, of non-vinyl monomer thermoplastic polymers T. Here, the parts by weight are 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).

[0179] The thermoplastic molding compound F may optionally comprise any quantity of additives and / or processing aids D'. Often, the thermoplastic molding compound F comprises 0 to 10 parts by weight, preferably 0 to 7.5 parts by weight, and particularly preferably 0 to 5 parts by weight, of additives and / or processing aids D'. Here, the parts by weight are 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).

[0180] According to one embodiment, the thermoplastic molding compound F according to the invention comprises or consists of: (a) 1 to 60 parts by weight, in particular 5 to 50 parts by weight, of the mixture P according to the invention containing grafting rubbers PI and P-II; (b) 40 to 99 parts by weight, in particular 50 to 95 parts by weight, of rubber-free copolymer P-III; (c) 0 to 250 parts by weight, preferably 0 to 200 parts by weight, more preferably 0 to 150 parts by weight, in particular 0 to 100 parts by weight, of thermoplastic polymers T not composed of vinyl monomers; and (d) 0 to 50 parts by weight, preferably 0 to 10 parts by weight, in particular 0 to 5 parts by weight, of additives D'.

[0181] Preferably, the thermoplastic molding compound F according to the invention contains 4.5 to 57.5 wt.%, in particular 22.5 to 45 wt.%, of component (a) (mixture P according to the invention containing graft rubbers PI and P-II). In the aforementioned molding compound, the weight ratio of the graft rubbers PI:P-II in the mixture P is preferably 90:10 to 10:90, particularly preferably 80:20 to 20:80, in particular 70:30 to 35:65.

[0182] Above and below, the percentage by weight refers to the molding compound F containing (preferably consisting of) the components (a), (b), (c) and (d), the sum of which equals 100% by weight.

[0183] Preferably, if component (c) (thermoplastic polymers T) is not present or is present in a quantity not exceeding 10 wt.%, the thermoplastic molding compound F according to the invention contains 22.5 to 95.5 wt.%, in particular 55.5 to 77.5 wt.%, of at least one rubber-free copolymer matrix P-III (component (b)).

[0184] Preferably, if component (c) is present in more than 10 wt.%, the thermoplastic molding compound F according to the invention contains 15 to 40 wt.%, in particular 15 to 35 wt.%, of at least one rubber-free copolymer matrix P-III (component (b)).

[0185] According to a preferred embodiment, the thermoplastic molding compound F contains no more than 10 wt.%, in particular (largely) no non-vinyl monomer thermoplastic polymers T (component (c)).

[0186] According to a further preferred embodiment, the thermoplastic molding compound F contains 30 to 55 wt.%, in particular 35 to 50 wt.%, thermoplastic polymers T (component (c)) not composed of vinyl monomers.

[0187] Preferably, the thermoplastic molding compound F contains no more than 10 wt.%, in particular no more than 5 wt.%, or (largely) no additives and / or processing aids D'. If additives and / or processing aids D' are present, their proportion is at least 0.01 wt.%.

[0188] According to a preferred embodiment, the thermoplastic molding compound F according to the invention contains (or the thermoplastic molding compound F consists of): (a) 4.5 to 57.5 wt.% of the mixture P according to the invention containing graft rubbers PI and P-II; (b) 22.5 to 95.5 wt.% of rubber-free copolymer P-III; (c) 0 to 10 wt.% of non-vinyl monomer thermoplastic polymers T; and (d) 0 to 10 wt.%, 0 to 5 wt.%, of one or more additives and / or processing aids D'; where the sum of components (a) to (d) is 100 wt.%.

[0189] In the aforementioned molding compound, the weight ratio of the grafting rubbers PI:P-II in the mixture P is preferably 70:30 to 35:65.

[0190] According to the aforementioned preferred embodiment, the thermoplastic molding compound F according to the invention preferably contains (or preferably consists of): (a) 22.5 to 45 wt.% of the inventive mixture P containing grafting rubbers PI and P-II; (b) 55.5 to 77.5 wt.% of at least one rubber-free copolymer matrix P-III; and (d) 0 to 10 wt.%, preferably 0 to 5 wt.%, of one or more additives and / or processing aids D'; where the sum of components (a), (b) and (d) is 100 wt.%.

[0191] In the aforementioned molding compound, the weight ratio of the grafting rubbers PI:P-II in the mixture P is preferably 70:30 to 35:65.

[0192] According to a further preferred embodiment, the thermoplastic molding compound F according to the invention contains (or the thermoplastic molding compound F consists of): (a) 4.5 to 57.5 wt.% of the inventive mixture P containing graft rubbers PI and P-II; (b) 15 to 40 wt.% of at least one rubber-free copolymer matrix P-III; (c) 25 to 55 wt.% of one or more non-vinyl monomer thermoplastic polymers T; and (d) 0 to 10 wt.%, preferably 0 to 5 wt.%, of one or more additives and / or processing aids D'; where the sum of components (a) to (d) is 100 wt.%.

[0193] In the aforementioned molding compound, the weight ratio of the grafting rubbers PI:P-II in the mixture P is preferably 70:30 to 35:65.

[0194] According to the aforementioned preferred embodiment, the thermoplastic molding compound F according to the invention particularly preferably contains (or the thermoplastic molding compound F according to the invention particularly preferably consists of): (a) 22.5 to 34.5 wt.% of the inventive mixture P containing graft rubbers PI and P-II; (b) 15 to 35 wt.% of at least one rubber-free copolymer matrix P-III; (c) 25.5 to 50 wt.% of one or more non-vinyl monomer thermoplastic polymers T; and (d) 0 to 10 wt.%, preferably 0 to 5 wt.%, of one or more additives and / or processing aids D; where the sum of components (a) to (d) is 100 wt.%.

[0195] In the aforementioned molding compound, the weight ratio of the grafting rubbers PI:P-II in the mixture P is preferably 70:30 to 35:65.

[0196] A preferred embodiment for the composition of the thermoplastic molding compound F can also be found in the experimental example below.

[0197] Another aspect of the present invention is a method for producing a thermoplastic molding compound F according to the invention.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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

[0202] Furthermore, other aspects 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.

[0203] 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.

[0204] 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.

[0205] The examples and claims shown below explain the invention. Examples Manufacturing ABS grafting rubbers Grafting rubber P-II-L1

[0206] 50 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with a mean particle diameter d 50 of 113 nm (polybutadiene latex C) and a gel content of 91 wt.%, which was produced using a polybutadiene seed latex with a mean particle diameter d 50 of 49 nm by radical seed polymerization, was reduced with deionized water to a solids content of approximately 27 wt.%.

[0207] The polybutadiene latex was heated to 60°C. Then, 50 parts by weight of a mixture of 74.5 wt% styrene, 25.5 wt% acrylonitrile, and 0.1 wt% tert-dodecyl mercaptan were dosed evenly over 4 hours. Simultaneously, 1.3 parts 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) were dosed over a period of 4 hours. In parallel, 0.5 parts by weight of potassium peroxodisulfate (dissolved in water) were dosed over a period of 5 hours, with the dosage rate being 0.5 parts by weight per hour in the first 30 minutes and 0.056 parts by weight per hour in the following 270 minutes.The temperature control was designed so that a minimum temperature of 56°C was reached within 2 hours of the start of dosing. Subsequently, the reaction temperature was raised until a temperature of 81°C was reached at the end of the initiator dosing.

[0208] 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 gravimetrically determined solids content (dried in a circulating air drying oven at 180°C for 23 minutes) of the graft rubber was 34.4 wt.%. L2 grafting rubber

[0209] 50 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with a mean particle diameter d 50 of 113 nm and a gel content of 91 wt.%, which was produced using a polybutadiene seed latex with a mean particle diameter d 50 of 49 nm by radical seed polymerization, was reduced with deionized water to a solids content of approximately 27 wt.%.

[0210] The polybutadiene latex was heated to 60°C and mixed with 0.25 parts by weight of potassium peroxodisulfate (dissolved in water). After 30 minutes, 50 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, 1.3 parts 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 6 hours.

[0211] Over the course of 6 hours, the reaction temperature was increased from 60°C to 81°C without reaching a minimum temperature of 56°C. After all doses were completed, a two-hour post-reaction period at 81°C followed. Subsequently, the graft rubber was cooled to room temperature. The solids content of the graft rubber, determined gravimetrically (drying in a forced-air drying oven at 180°C for 23 minutes), was 34.2 wt%. Grafting rubber PI-L3

[0212] 36 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with a mean particle diameter d50 of 299 nm and a gel content of 60 wt% (Polybutadiene Latex A), which was produced using a polybutadiene seed latex (Polybutadiene Latex C) with a mean particle diameter d50 of 113 nm by radical emulsion polymerization, and 24 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with a mean particle diameter d50 of 371 nm and a gel content of 82 wt% (Polybutadiene Latex B), which was produced using a polybutadiene seed latex with a mean particle diameter d50 of 113 nm (Polybutadiene Latex C) by radical emulsion polymerization, were mixed and diluted with deionized water to a solids content of approximately 27% by weight was achieved.

[0213] The polybutadiene latices mixture was heated to 60°C. Then, 40 parts by weight of a monomer mixture consisting of 74.5% by weight styrene, 25.5% by weight acrylonitrile, and 0.12 parts by weight tert-dodecyl mercaptan were dosed evenly over 4 hours. Simultaneously, 1.3 parts 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 dosed over a period of 4 hours. In parallel, 0.5 parts by weight of potassium peroxodisulfate (dissolved in water) were dosed over a period of 5 hours, with the dosage rate being 0.5 parts by weight per hour in the first 30 minutes and 0.056 parts by weight per hour in the following 270 minutes.

[0214] The temperature control was designed so that a minimum temperature of 56°C was reached within 2 hours of the start of dosing. Subsequently, the reaction temperature was raised until a temperature of 80°C was reached at the end of the initiator dosing.

[0215] After all doses were completed, a two-hour post-reaction period at 80°C followed. The grafting rubber was then cooled to room temperature. The gravimetrically determined solids content (dried in a circulating air drying oven at 180°C for 23 minutes) of the grafting rubber was 34.8 wt.%. Grafting rubber L4

[0216] 36 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with a mean particle diameter d 50 of 299 nm and a gel content of 60 wt%, which was produced using a polybutadiene seed latex with a mean particle diameter d 50 of 113 nm by radical emulsion polymerization, and 24 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with a mean particle diameter d 50 of 371 nm and a gel content of 82 wt%, which was produced using a polybutadiene seed latex with a mean particle diameter d 50 of 113 nm by radical emulsion polymerization, were mixed and brought to a solids content of approximately 27 wt% with deionized water.

[0217] The polybutadiene latices mixture was heated to 60°C and mixed with 0.25 parts by weight of potassium peroxodisulfate (dissolved in water). After 30 minutes, 40 parts by weight of a monomer mixture consisting of 74.5% by weight styrene, 25.5% by weight acrylonitrile, and 0.12 parts by weight tert-dodecyl mercaptan were added at a constant rate over 5 hours. Simultaneously, 1.3 parts by weight (calculated as solids) of the sodium salt of a resin acid mixture (commercial product Burez DRS S70 E, manufactured by 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 6 hours.

[0218] Over the course of 6 hours, the reaction temperature was increased from 60°C to 80°C without reaching a minimum temperature of 56°C. After all doses were completed, a two-hour post-reaction period at 80°C followed. Subsequently, the graft copolymer latex was cooled to room temperature. The solids content of the graft copolymer latex, determined gravimetrically (drying in a forced-air drying oven at 180°C for 23 minutes), was 34.9 wt%. Production of graft rubber mixture P1 from graft rubbers P-II-L1 and PI-L3

[0219] The grafting rubbers P-II-L1 and PI-L3 were mixed by stirring in a weight ratio of 45% : 55%, calculated as solids. To this mixture (= grafting rubber mixture P1 from P-II-L1 / PI-L3), 1.0 wt% of a phenolic antioxidant (Irganox® < 1076, BASF SE), based on the total solids content of the grafting rubber mixture P, was added in the form of a dispersion and mixed.

[0220] The 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 the graft rubber mixture P1 in the precipitated dispersion was 16 wt%. Precipitation was carried out by first adding the stabilized graft rubber mixture P1 to the magnesium sulfate / sulfuric acid solution while stirring, and then heating to 95°C. The graft rubber mixture P1 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). Production of graft rubber mixture V1 (not according to the invention) from graft rubbers L2 and L4

[0221] Grafting rubbers L2 and L4 were mixed by stirring in a weight ratio of 45% : 55%, calculated as solids. To this mixture V1 of grafting rubbers L2 / L4, 1.0 wt% of a phenolic antioxidant (Irganox® < 1076, BASF SE), based on the total solids content of the grafting rubber mixture, was added in the form of a dispersion and mixed.

[0222] The 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 the graft rubber mixture L2 / L4 in the precipitated dispersion was 16 wt%. Precipitation 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 mixture V1 of graft rubbers L2 and L4 was separated from the aqueous phase by vacuum filtration and washed with 1000 wt parts 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). Production of ABS molding compounds Rubber-free copolymer matrix P-III-A1

[0223] 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-A1. The rubber-free copolymer matrix P-III-A1 was obtained by radical solution polymerization with peroxide initiation and exhibited an oligomer content of 1.0 wt% with a molar mass of 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 fraction in statistical styrene / acrylonitrile copolymer, see: K. Kirchner, H. Schlapkohl, Makromol. Chem. 177 (1976) 2031-2042, "The Formation of Oligomers in the Thermal Copolymerisation of the Styrene / Acrylonitrile- System". Rubber-free copolymer matrix P-III-A2

[0224] 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-A2. 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-A2 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-A3

[0225] 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-A3. 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-A3 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-A4

[0226] 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-A4, which has a thermoplastic flowability (MVR) at 220°C and 10 kg of 18-26 ml / 10 minutes. Polycarbonate (T-1):

[0227] 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):

[0228] 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 ABS molding compounds F1-F4

[0229] The polymer components described above were mixed in the amounts specified in Table 2 (in wt.%) together with 2 wt. parts ethylene bisstearylamide, 0.30 wt. parts magnesium stearate and 0.15 wt. parts of a polydimethylsiloxane with a viscosity of 1000 mPas (measured at 25°C) in an extruder ZSK 25 (manufacturer Coperion) at 250°C to form the molding compounds F1-F4 and, after granulation, processed into molded parts. Thermoplastic PC / ABS molding compounds F5-F6

[0230] The polymer components described above were mixed in the amounts specified in Table 3 (in wt.%) together with 0.75 wt. parts pentaerythritol tetrastearate, 0.12 wt. parts Irganox ®< B900 (BASF SE) and 0.1 wt. parts Irganox ®< 1076 (BASF SE) in a ZSK 25 extruder (manufacturer Coperion) at 270°C to form the molding compounds F5 and F6 and, after granulation, processed into molded parts. Thermoplastic PA-ABS molding compounds F7-F8

[0231] The polymer components described above were mixed in the amounts specified in Table 4 (in wt.%) together with 0.5 wt. parts Irganox B802 (BASF SE) and 1.0 wt. parts Irganox 1076 (BASF SE) in an extruder ZSK 25 (manufacturer Coperion) at 260°C to form the molding compounds F7 and F8 and, after granulation, processed into molded bodies.

[0232] Molding compounds F1-F8 and the resulting molded parts were obtained. The molded parts comply with the specifications of the respective testing standards.

[0233] The following properties of the molding compounds or molded bodies were determined: Impact strength at room temperature (ak RT) and at -30°C (ak -30°C) according to DIN EN ISO 179-2 / 1eA (unit: kJ / m²) Thermoplastic flowability (cm³ / 10 min): MVR (220 / 10) at 220°C and 10 kg load according to ISO 1133, unit: cm³ / 10 min) MVR (260 / 5) at 260°C and 5 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, Young's modulus Et (unit MPa or N / mm²)N / mm²< ) from a tensile test according to EN ISO 527-1 Raw tone: The assessment of the intrinsic color / raw tone was carried out by determining the Yellowness Index (YI) according to ASTM method E313. The melting and molding temperatures used for the injection molding of the test plates are given in degrees Celsius. Gloss at 20° and 60° according to DIN EN ISO 2813. The melting and molding temperatures used for the injection molding of the test plates are given in brackets in degrees Celsius. d50: For the measurement of the particle diameter d50 with the DC 24000 disc centrifuge from CPS Instruments Inc., which is equipped with a low-density disc, an aqueous sugar solution of 17.1 mL with a density gradient of 8 to 20 wt% sucrose in the centrifuge disc was used to achieve stable flotation behavior of the particles. For calibration, a polybutadiene latex with a narrow distribution and a mean particle size of 405 nm was used.Measurements were performed at a disk rotation speed of 24,000 rpm by injecting 0.1 mL of a diluted rubber dispersion into a 24% aqueous sucrose solution. The mass distribution of the particle diameters was calculated using Mie theory. Rubber effectiveness 1 (KE number 1) (dimensionless): a measure of the graft rubber's performance, defined as the sum of the room-temperature impact strength (ak RT) and the thermoplastic flowability (MVR (220 / 10)). The higher the KE number 1 value, the better the rubber effectiveness. Rubber effectiveness 2 (KE number 2) (dimensionless): a measure of the graft rubber's performance, defined as the product of the room-temperature impact strength (ak RT) and the modulus of elasticity. The higher the KE number 2 value, the better the rubber effectiveness.Spot Test: Surface quality was determined by measuring the number of spots in the ranges < 250 µm, 250–450 µm, and > 450 µm (unit 1 / m²), with a lower spot count indicating a better result. Surface examinations were performed using a Collin extruder type 25 x 25 L / D and attached OCS cameras, type FSA 100 (OCS Optical Control Systems GmbH, Wullener Feld 24, 58454 Witten, Germany), with a resolution of 50 µm. The material was melted, extruded through a 150 mm wide-slot die with a 2.0 mm die gap, guided through several guide rollers, and wound onto a reel as a ribbon. During this process, the ribbon passed the cameras, where the particles on the surface were quantitatively analyzed using reflected light. The inspected area where the number of specks was measured was 1.0 m².Hydrolysis resistance: The change in MVR, measured according to ISO 1133 at 260°C with a 5 kg injection load, serves as a measure of the hydrolysis resistance of the manufactured compositions during 7 days of storage of the granules at 95°C and 100% relative humidity ("FWL storage"). The increase in the MVR value compared to the MVR value before the corresponding storage is calculated as ΔMVR (hydr.), which is defined by the following formula: . Δ MVR hyrdr = MVR nach FWL − Lagerung − MVR vor Lagerung MVR vor Lagerung • 100 % Processing stability: The change (in percent) in the MVR, measured according to ISO 1133 at 260°C with a 5 kg ram load and a 15-minute residence time of the melt under exclusion of air at a temperature of 300°C (IMVR), serves as a measure of the processing stability of the compositions produced in this way. The resulting value ΔMVR(proc.) is calculated using the following formula: Δ MVR proc . = MVR nachSchmelzelagerung − MVR vor Lagerung MVR vor Lagerung • 100 %

[0234] The DIN, ASTM and ISO standards mentioned herein are preferably the most current versions as of June 2022.

[0235] The latex stability of the grafting rubber latexes P-II-L1, PIL, L2, and L4 was determined as follows: An Ultra-Turrax device type T45 from Janke & Kunkel (600W, 10,000 RPM nominal speed) was immersed in a 100ml beaker containing 50g of latex and switched on. The time until the latex was completely coagulated was measured using a stopwatch.

[0236] The more time that passes until the latex has completely coagulated, the higher the latex stability. Table 1: Stability of grafted rubber latices grafted rubber latex Latex stability [s] P-II-L1 used according to the invention 88 L2 Comparison 63 PI-L3 used according to the invention 101 L4 Comparison 54

[0237] It was surprisingly found (see Table 1) that the grafting rubber latices P-II-L1 and PI-L3 of the inventive mixture P1 exhibit significantly higher latex stability than the grafting rubber latices L2 and L4 (comparison V1). This is particularly advantageous because latices with higher latex stability form less coagulate during the production and processing process, which reduces the yield and, moreover, has to be disposed of as waste.

[0238] The production of the graft rubber latices P-II-L1 and PI-L3 or the mixture P1 according to the invention is also carried out by a more efficient (shortened cycle times) and more environmentally friendly process (less coagulate / waste). Table 2: Composition and test data of the molding compounds F1-F4 Molding compounds F1 F2 F3 F4 according to the invention Comparison according to the invention Comparison composition Grafting rubber compound P1 [wt.%] 30 40 Grafting rubber compound V1 [wt.%] 30 40 Rubber-free copolymer matrix P-III-A1 [wt.%] 70 70 60 60 Ethylene bisstearylamide [wt.%] 2,0 2,0 2,0 2,0 Magnesium stearate [wt.%] 0,30 0,30 Polydimethylsiloxane (viscosity 1000 cSt) [wt.%] 0,15 0,15 0,15 0,15 Measurement results Impact strength at room temperature (ak RT) [kJ / m²<] 18,1 17,9 24,4 24,3 MVR (220°C / 10 kg) [cm 3< / 10 min] 33,2 32,5 23,1 22,5 KE number 1 (ak RT+ MVR) 51,3 50,4 47,5 46,8 Hardness [N / mm²<] 107 109 90 92 E-modulus [N / mm²<] 2291 2298 2019 1998 Tensile strength (SB) [N / mm²<] 45,0 45,0 42,1 41,8 Breaking stress (SR) [N / mm²<] 32,2 32,5 30,1 30,2 Elongation at break (DR) [%] 48,1 39,3 22,4 20,1 Gloss at 20° (240°C / 80°C) [%] 92 83 96 91 Gloss at 60° (240°C / 80°C) [%] 99 97 99 99 Raw clay (240°C / 80°C) 25,2 24,8 30,1 33,8 Number of specks <250 µm [1 / m 2< ] 119 781 84 139 Number of specks: 250-450 µm [1 / m 2< ] 11 148 19 31 Number of specks >450 µm [1 / m 2< ] 4 81 6 13 KE number 2 (E-module x ak RT) 41467 41134 49264 48551

[0239] The test results for the molding compounds F1-F4 (see Table 2) surprisingly revealed that the molding compounds F1 and F3 according to the invention, which contain the grafting rubber compound P1 according to the invention, exhibit improved surface quality (in particular fewer specks and higher gloss) compared to the non-inventive molding compounds F2 and F4, while otherwise having comparable properties. Furthermore, the rubber effectiveness (KE number 1 and KE number 2) of the molding compounds according to the invention is also higher than that of the comparison examples. Table 3: Composition and test data of the molding compounds F5-F6 Molding compounds F5 F6 according to the invention Comparison composition Grafting rubber compound P1 [wt.%] 25,5 Grafting rubber compound V2 [wt.%] 25,5 Rubber-free copolymer matrix P-III-A2 [wt.%] 31,5 31,5 Polycarbonat [wt.%] 43 43 Pentaerythritol tetrastearate [wt.%] 0,75 0,75 Irganox B900 [wt.%] 0,12 0,12 Irganox 1076 [wt.%] 0,10 0,10 Measurement results Impact strength at room temperature (ak RT) [kJ / m²<] 42,6 43,3 MVR (260°C / 5 kg) [cm 3< / 10 min] 21,8 15,4 KE number 1 (ak RT+ MVR) 64,4 58,7 ΔMFR (hydr.) [%] 50,6 102,3 Gloss at 20° (260°C / 80°C) [%] 94 94 Raw clay (260°C / 80°C) 23,4 22,9 Raw clay (300°C / 80°C) 30,4 30,5 Table 4: Composition and test data of the molding compounds F7-F8 Molding compounds F7 F8 according to the invention Comparison composition Grafting rubber compound P1 [wt.%] 34 Grafting rubber compound V2 [wt.%] 34 Rubber-free copolymer matrix P-III-A1 [wt.%] 5 5 Rubber-free copolymer matrix P-III-A3 [wt.%] 8 8 polyamide [wt.%] 47 47 Rubber-free copolymer matrix P-III-A4 [wt.%] 6 6 Irganox B802 [wt.%] 0,5 0,5 Irganox 1076 [wt.%] 1,0 1,0 Measurement results Impact strength at room temperature (ak RT) [kJ / m²<] 62,9 61,9 MVR (260°C / 5 kg) [cm 3< / 10 min] 23,8 27,1 IMVR (300°C / 5Kg - 15min VWZ) [cm 3< / 10 min] 139,1 174,9 ΔMVR (proc.) [%] 485 546 Gloss at 20° (250°C / 50°C) [%] 94 93 Raw clay (250°C / 50°C) 28,8 29,1

[0240] The test results of the molding compounds F5-F8 (see Tables 3 and 4) surprisingly revealed that the molding compounds F5 and F7 according to the invention, which contain the grafting rubber mixture P1 according to the invention, are characterized - in comparison to the non-inventive molding compounds F6 and F8 - by improved hydrolysis stability (F5) and improved melt and processing stability (F7), respectively, with otherwise comparable properties.

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, using at least one organic and / or inorganic, preferably inorganic, peroxide compound as initiator, 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 were obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) with an average particle diameter d50 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 can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the at least one polybutadiene latex C with an average particle diameter d50 of 10 to 220 nm, preferably 30 to 200 nm; and (III) optionally one or more additives and / or processing aids D; wherein the average particle diameter d50 is determined by disk centrifuge measurement, characterized in that - independently of one another - during the preparation of the graft rubber P-I and during the preparation of the graft rubber P-II, • the dosing of the monomers and the dosing of the initiator are started simultaneously; • the monomers are dosed continuously within 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, in particular 4 hours; • the entire amount of initiator is dosed within 4.50 to 5.25 h, preferably 4.75 to 5.25 h, in particular 5 h, wherein the dosing rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latexes), and thereafter the dosing rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

2. Mixture P according to claim 1, wherein the graft rubber P-I was obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of from 80:20 to 65:35 in the presence of 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 from 80:20 to 65:35 in the presence of polybutadiene latex C.

3. Mixture P according to claim 1 or 2, wherein 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.

4. Mixture P according to any one of claims 1 to 3, wherein the weight ratio of the solids of the polybutadiene latexes A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, in particular 60:40 to 40:60.

5. Mixture P according to any one of claims 1 to 4, wherein the weight ratio of the graft rubbers P-I:P-II is 90:10 to 10:90, preferably 80:20 to 20:80, more preferably 70:30 to 35:65.

6. Mixture P according to any one of claims 1 to 5, 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 comprising the polybutadiene latices A and B; und 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.

7. Process for preparing a mixture P according to any one of claims 1 to 6, 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 having an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B having an average particle diameter d50 of 340 to 480 nm by seed polymerization on the polybutadiene latex C from step (i); (iii) preparing a graft rubber P-I by emulsion polymerization of styrene and acrylonitrile in a 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, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the polybutadiene latexes A and B from step (ii); (iv) preparing a graft rubber P-II by emulsion polymerization of styrene and acrylonitrile in a 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, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the polybutadiene latex C from step (i); wherein in steps (iii) and (iv) - independently of one another - • the dosing of the monomers and the dosing of the initiator are started simultaneously; • the dosing of the monomers takes place continuously within 3.50 to 4.25 hours; • the entire amount of the initiator is dosed within 4.50 to 5.25 hours, wherein the dosing rate of the initiator in the first 20 to 40 minutes is 0.25 to 0.75 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latexes), and thereafter the dosing rate of the initiator is 0.03 to 0.08 parts by weight per hour; (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 available, mixing the graft rubbers P-I and P-II from step (vi).

8. Process for preparing a mixture P according to claim 7, wherein in steps (iii) and (iv) - independently of one another - the emulsion polymerization is carried out in such a way that within 100 to 180 minutes, preferably 110 to 150 minutes, after the start of dosing of the initiator and the monomers, a temperature minimum is passed through which has a temperature which is at least 1 to 10 °C, preferably 2 to 8 °C, lower than the temperature at the start of dosing.

9. Process for preparing a mixture P according to claim 8, wherein the temperature at the beginning of the dosing of the initiator and the monomers is 58 to 68°C, preferably 59 to 66°C; the temperature at the minimum temperature is 54 to 64°C, preferably 55 to 62°C, and the temperature at the end of the dosing of the initiator is 75 to 90°C, preferably 78 to 85°C.

10. Process for preparing a mixture P according to claim 7, wherein the dosing rate of the initiator in the first 20 to 40 minutes is 0.4 to 0.6 parts by weight per hour, and thereafter the dosing rate of the initiator is 0.05 to 0.06 parts by weight per hour.

11. Process for preparing a mixture P according to any one of claims 7 to 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. Process for preparing a mixture P according to any one of claims 7 to 11, wherein step (v) is present.

13. Mixture P according to any one of claims 1 to 6, obtained by the process according to any one of claims 7 to 12.

14. Thermoplastic molding composition F containing components (a) to (d): (a) mixture P according to any one of claims 1 to 6 or claim 13; (b) at least one rubber-free copolymer matrix 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; (c) optionally at least one thermoplastic polymer T not composed of vinyl monomers; and (d) optionally one or more additives and / or processing aids D'.

15. Thermoplastic molding composition F according to claim 14, wherein the at least one thermoplastic polymer T not composed of vinyl monomers is selected from the group consisting of: aromatic polycarbonates, aromatic polyester carbonates, polyesters, and polyamides.

16. Thermoplastic molding composition F according to claim 14 or 15 containing: (a) 4.5 to 57.5% by weight of the mixture P according to any one of claims 1 to 6 or claim 10; (b) 22.5 to 95.5% by weight of rubber-free copolymer P-III; (c) 0 to 10% by weight of thermoplastic polymers T not composed of vinyl monomers; and (d) 0 to 10% by weight of one or more additives and / or processing aids D'; wherein the sum of components (a) to (d) is 100% by weight.

17. Thermoplastic molding composition F according to claim 14 or 15 containing: (a) 4.5 to 57.5% by weight of the mixture P according to any one of claims 1 to 6 or claim 10; (b) 15 to 40% by weight of at least one rubber-free copolymer matrix P-III; (c) 25 to 55% by weight of one or more thermoplastic polymers T not composed of vinyl monomers; and (d) 0 to 10% by weight of one or more additives and / or processing aids D'; wherein the sum of components (a) to (d) is 100% by weight.

18. Process for preparing a thermoplastic molding composition F according to any one of claims 14 to 17, 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.

19. Molded article of a molding composition F according to any one of claims 14 to 17 obtainable by injection molding, extrusion, blow molding or deep drawing.

20. Use of a molding composition F according to any one of claims 14 to 17 or a molded article according to claim 19 for housing parts or components in the household, office, automotive and / or garden sector.