Acrylonitrile styrene acrylate copolymer composition with improved ultraviolet resistance

Abstract

A thermoplastic molding composition P comprising: AB: at least one graft copolymer composition AB consisting of at least one thermoplastic copolymer A and at least one graft copolymer B; c: at least one hindered amine light stabilizer as component C; d: at least one antioxidant as component D; e: optionally at least one co-stabilizer as component E; f: optionally at least one ultraviolet absorber as component F; and G: optionally at least one further additive as component G, the content of at least one of components E and F being at least 0.05% by weight based on the molding composition P.

Description

[0001] describe

[0002] Impact-modified molding compositions, such as acrylonitrile styrene acrylate (ASA) and its blends with other thermoplastic polymers, are widely used in many areas, such as the automotive industry, the electronics industry or household goods. These thermoplastic polymer compositions are popular because of their property profile combining good impact strength, melt flow properties and high weathering stability.

[0003] In order to improve the weathering stability of ASA formulations for outdoor applications, UV stabilizers, such as hindered amine light stabilizers (HALS) compounds or UV absorbers, are usually used. Some documents, such as US 4,692,486, US 9,701,813, EP-B 2593510 and DE-A 10316198, disclose how to use HALS stabilizers and combinations thereof as UV absorbers and light stabilizers. For example, combined formulations of UV absorbers, HALS stabilizers and antioxidants are disclosed in US 2003 / 0074833, US 7,084,197, US 6,800,676, WO 2007 / 113248 and DE 103 08 506A.

[0004] However, new research has found that ASA compositions with known UV stabilizer formulations cannot meet the high weather resistance required for high gloss outdoor applications. In view of this demand, the inventors have studied some combinations of polymer additives, and the UV stability of their ASA polymer compositions has been improved.

[0005] The present invention relates to a thermoplastic molding composition P, comprising (or consisting of) the following composition:

[0006] AB: 83 to 99.93% by weight, based on the weight of the molding composition P, of at least one graft copolymer composition as component AB consisting of:

[0007] A: 30 to 80% by weight, based on the weight of components AB, of at least one thermoplastic copolymer as component A, which is made from the following components:

[0008] A1; 50 to 95% by weight of monomer A1, based on the weight of copolymer A, which is selected from styrene, α-methylstyrene and a mixture of styrene and at least one other monomer selected from α-methylstyrene, p-methylstyrene and C1-C8 alkyl (meth) acrylate;

[0009] A2; 5 to 50% by weight of monomer A2, based on the weight of copolymer A, wherein the monomer A2 is selected from acrylonitrile and a mixture of acrylonitrile and at least one other monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids;

[0010] B: 20 ​​to 70% by weight, based on the weight of component AB, of at least one graft copolymer as component B, which comprises:

[0011] B1: 50 to 90% by weight, based on the weight of the graft copolymer B, of at least one graft base B1 obtained by emulsion polymerization of:

[0012] B11: 70 to 99.9% by weight, based on the weight of the graft base B1, of at least one C1-C8 alkyl (meth)acrylate as monomer B11;

[0013] B12: 0.1 to 10% by weight, based on the weight of the graft base B1, of at least one multifunctional crosslinking monomer B12;

[0014] B13: 0 to 29.5% by weight, based on the weight of the graft base B1, of at least one other copolymerizable monomer B13, which is preferably selected from styrene, α-methylstyrene, C1-C4 alkylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, C9-C 20 Alkyl methacrylates and vinyl methyl ethers;

[0015] wherein the total weight of B11+B12+B13 is 100% of the at least one graft base B1; and

[0016] B2: 10 to 50% by weight, based on the weight of the graft copolymer B, of at least one graft shell B2, obtainable by emulsion polymerization of the following components in the presence of at least one graft base B1:

[0017] B21: 50 to 100% by weight, based on the weight of the graft shell B2, of a monomer B21 selected from styrene, α-methylstyrene and a mixture of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C4-alkyl(meth)acrylates;

[0018] B22: 0 to 50% by weight, based on the weight of the graft shell B2, of a monomer B22 selected from acrylonitrile and mixtures of acrylonitrile with at least one further monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids;

[0019] B23: 0 to 20% of at least one further copolymerizable monomer B23;

[0020] wherein the total weight of B21+B22+B23 is 100% of the at least one graft shell B2;

[0021] wherein the total weight of the graft base B1 and the graft shell B2 is 100% by weight of the at least one graft copolymer B;

[0022] C: as component C, 0.01 to 2.5% by weight, based on the weight of the molding composition P, of at least one hindered amine light stabilizer;

[0023] D: 0.01 to 1.0% by weight, based on the weight of the molding composition P, of at least one antioxidant as component D, which is selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof:

[0024]

[0025] in

[0026] R1 to R5 each independently represent a hydrogen atom or an alkyl group having 1 to 70 carbon atoms, wherein the hydrocarbon group optionally contains at least one heteroatom selected from O and S, and wherein at least one of the substituents R1 and R5 is a hydrocarbon group having at least 3 carbon atoms;

[0027] E: 0 to 2.5% by weight, based on the weight of the molding composition P, of at least one stabilizer E selected from phosphorus-containing or sulfur-containing stabilizers;

[0028] F: 0 to 3% by weight, based on the weight of the molding composition P, of at least one UV absorber as component F; and

[0029] G: 0 to 8% by weight, based on the weight of the molding composition P, of at least one further additive as component G;

[0030] wherein the sum of components A to G accounts for 100% by weight of the molding composition P, and

[0031] The content of at least one of components E and F is at least 0.05% by weight, based on the weight of the molding composition P.

[0032] The graft copolymer B preferably has a weight-average particle size dw of at least 50 nm, preferably at least 80 nm, more preferably at least 90 nm, which can be measured, for example, by means of an ultracentrifuge (Scholtan).

[0033] In a preferred embodiment, at least one graft copolymer composition AB consists of:

[0034] A: 30 to 80% by weight, based on the graft copolymer composition AB, of at least one thermoplastic copolymer selected from poly(styrene-acrylonitrile) (SAN), poly(α-methylstyrene / acrylonitrile) (AMSAN) and mixtures thereof as component A; and

[0035] B: 20 ​​to 70% by weight, based on the graft copolymer composition AB, of at least one graft copolymer B comprising:

[0036] B1: Based on the graft copolymer B, 50 to 90% by weight, preferably 55 to 90% by weight, more preferably 55 to 65% by weight, at least one graft base B1 obtained by emulsion polymerization of the following components.

[0037] B11: 70 to 99.9% by weight, preferably 87 to 99.5% by weight, of n-butyl acrylate as monomer B11, based on the graft base B1.

[0038] B12: 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 2.5% by weight, based on the graft base B1, of at least one polyfunctional crosslinking monomer B12;

[0039] B13: 0 to 29.5% by weight, preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight, based on the graft base B1, of at least one other copolymerizable monoethylenically unsaturated monomer B13, which is preferably selected from styrene, α-methylstyrene, C1-C4 alkylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, C9-C 20 Alkyl methacrylates and vinyl methyl ethers;

[0040] wherein the sum of B11 and B12 is equal to 100 weight % of B1; and

[0041] B2: 10 to 50% by weight, preferably 10 to 45% by weight, more preferably 35 to 45% by weight, based on the graft copolymer B, of at least one graft shell B2, obtained by emulsion polymerization in the presence of at least one graft base B1:

[0042] B21: 50 to 95% by weight, more preferably 65 to 80% by weight, most preferably 75 to 80% by weight, of the monomer B21 styrene, based on the graft shell B2; and

[0043] B22: 5 to 50% by weight, more preferably 20 to 35% by weight, most preferably 20 to 25% by weight, based on the graft shell B2, of at least one monomer B22 selected from acrylonitrile or a mixture of acrylonitrile with at least one further monomer selected from methacrylonitrile;

[0044] B23: 0 to 20% of at least one further copolymerizable monomer B23;

[0045] wherein the sum of B21, B22 and B23 is equal to 100% by weight of the at least one graft shell B2;

[0046] wherein the sum of the graft base B1 and the graft shell B2 is equal to 100% by weight of the graft copolymer B, and

[0047] The at least one graft copolymer B has a weight average particle size dw of 50 to 1000 nm, preferably 50 to 900 nm, in particular 80 to 700 nm.

[0048] Another object of the present invention is to use the thermoplastic molding composition P as described herein for producing molded articles.

[0049] In another aspect, the present invention also relates to a shaped article comprising the thermoplastic molding composition P described herein.

[0050] According to the invention, the thermoplastic molding composition P comprises:

[0051] AB: at least one graft copolymer composition AB, consisting of at least one thermoplastic copolymer A and at least one graft copolymer B;

[0052] C: at least one hindered amine light stabilizer as component C;

[0053] D: at least one antioxidant as component D;

[0054] E: Optionally, at least one co-stabilizer as component E;

[0055] F: Optionally, at least one UV absorber as component F; and

[0056] G: Optionally, at least one other additive as component G,

[0057] The content of at least one of components E and F, based on the weight of the molding composition P, is at least 0.05% by weight.

[0058] The thermoplastic molding composition P therefore preferably comprises from 0.05 to 2.5% by weight of at least one costabilizer as component E and / or from 0.05 to 3% by weight of at least one UV absorber as component F.

[0059] In one embodiment, the thermoplastic molding composition P comprises:

[0060] AB: 87 to 99.89% by weight, based on the molding composition P, of at least one graft copolymer composition as component AB;

[0061] C: as component C, 0.01 to 2.5% by weight, based on the molding composition P, of at least one hindered amine light stabilizer;

[0062] D: 0.05 to 0.5% by weight, based on the molding composition P, of at least one antioxidant as component D, the antioxidant being selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0063] E: 0.05 to 2.0% by weight, based on the molding composition P, of at least one costabilizer E selected from phosphorus- or sulfur-containing costabilizers; and

[0064] G: 0 to 8% by weight, based on the molding composition P, of at least one further additive as component G;

[0065] Components A to G account for 100% by weight of the molding composition P.

[0066] In one embodiment, the thermoplastic molding composition P comprises:

[0067] AB: 92.65 to 99.2% by weight of at least one graft copolymer composition as component AB, based on the molding composition P;

[0068] C: 0.1 to 0.75% by weight, based on the molding composition P, of at least one hindered amine light stabilizer as component C;

[0069] D: 0.2 to 0.6% by weight, based on the molding composition P, of at least one antioxidant as component D, the antioxidant being selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0070] E: 0.5 to 1.0% by weight, based on the molding composition P, of at least one costabilizer E selected from phosphorus- or sulfur-containing costabilizers; and

[0071] G: 0 to 5% by weight, based on the molding composition P, of at least one further additive as component G;

[0072] Components A to G account for 100% by weight of the molding composition P.

[0073] In one embodiment, the thermoplastic molding composition P comprises:

[0074] AB: 92.6 to 98.39% by weight of at least one graft copolymer composition as component AB, based on the molding composition P;

[0075] C: 0.01 to 0.1% by weight, based on the molding composition P, of at least one hindered amine light stabilizer as component C;

[0076] D: 0.1 to 0.3% by weight, based on the molding composition P, of at least one antioxidant as component D, which is selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0077] E: 1.5 to 2.0% by weight, based on the molding composition P, of at least one costabilizer E selected from phosphorus- or sulfur-containing costabilizers; and

[0078] G: 0 to 5% by weight, based on the molding composition P, of at least one further additive as component G;

[0079] Components A to G account for 100% by weight of the molding composition P.

[0080] In one embodiment, the thermoplastic molding composition P comprises:

[0081] AB: 93.8 to 99.8% by weight of at least one graft copolymer composition as component AB, based on the molding composition P;

[0082] C: 0.1 to 0.4% by weight, based on the molding composition P, of at least one hindered amine light stabilizer as component C;

[0083] D: 0.05 to 0.3% by weight, based on the molding composition P, of at least one antioxidant as component D, which is selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0084] E: 0.05 to 0.5% by weight, based on the molding composition P, of at least one costabilizer E selected from phosphorus- or sulfur-containing costabilizers; and

[0085] G: 0 to 5% by weight, based on the molding composition P, of at least one further additive as component G;

[0086] Components A to G account for 100% by weight of the molding composition P.

[0087] In one embodiment, the thermoplastic molding composition P comprises:

[0088] AB: 92.7 to 98.4% by weight, based on the molding composition P, of at least one graft copolymer composition as component AB;

[0089] C: 1.5 to 2.0% by weight, based on the molding composition P, of at least one hindered amine light stabilizer as component C;

[0090] D: 0.05 to 0.15% by weight, based on the molding composition P, of at least one antioxidant as component D, which is selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0091] E: 0.05 to 0.15% by weight, based on the molding composition P, of at least one costabilizer E selected from phosphorus- or sulfur-containing costabilizers; and

[0092] G: 0 to 5% by weight, based on the molding composition P, of at least one further additive as component G;

[0093] Components A to G account for 100% by weight of the molding composition P.

[0094] In one embodiment, the thermoplastic molding composition P comprises:

[0095] AB: 91.25 to 97.65% by weight of at least one graft copolymer composition as component AB, based on the molding composition P;

[0096] C: 0.75 to 1.25% by weight, based on the molding composition P, of at least one hindered amine light stabilizer as component C;

[0097] D: 0.1 to 0.5% by weight, based on the molding composition P, of at least one antioxidant as component D, which is selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0098] E: 1.5 to 2.0% by weight, based on the molding composition P, of at least one costabilizer E selected from phosphorus- or sulfur-containing costabilizers; and

[0099] G: 0 to 5% by weight, based on the molding composition P, of at least one further additive as component G;

[0100] Components A to G account for 100% by weight of the molding composition P.

[0101] In an alternative embodiment, the thermoplastic molding composition P comprises:

[0102] AB: 87 to 99.79% by weight, preferably 91.5 to 99.69% by weight, more preferably 95 to 99.59% and typically 96.6 to 99.4%, of at least one graft copolymer composition as component AB, based on the molding composition P;

[0103] C: as component C, 0.1 to 1% by weight, preferably 0.15 to 0.9% by weight, more preferably 0.2 to 0.8% and typically 0.3 to 0.7%, based on the molding composition P, of at least one hindered amine light stabilizer;

[0104] D: 0.01 to 1% by weight, preferably 0.03 to 0.9% by weight, more preferably 0.04 to 0.8% and typically 0.05 to 0.7% by weight, based on the molding composition P, of at least one antioxidant as component D, the antioxidant being selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (II) and mixtures thereof;

[0105] F: as component F, 0.1 to 3% by weight, preferably 0.13 to 2.2% by weight, more preferably 0.16 to 1.4% and typically 0.2 to 1% by weight, based on the molding composition P, of at least one UV absorber; and

[0106] G: as component G, 0 to 8% by weight, preferably 0.01 to 7.5% by weight, more preferably 0.1 to 7% and typically 0.5 to 6.5% by weight, based on the molding composition P, of at least one further additive;

[0107] wherein components A to G account for 100% by weight of the molding composition P,

[0108] Components A to G of the thermoplastic molding composition P are described in further detail below.

[0109] Graft copolymer composition AB

[0110] The thermoplastic molding composition P according to the invention comprises, as component AB, from 83 to 99.98% by weight, based on the molding composition P, of at least one graft copolymer composition.

[0111] At least one graft copolymer composition AB comprises (or consists of) at least one thermoplastic copolymer as component A and at least one graft copolymer as component B, and has the following composition:

[0112] A: 30 to 80% by weight, preferably 40 to 75% by weight, more preferably 50 to 65% by weight, most preferably 55 to 65% by weight, based on the graft copolymer composition AB, of at least one thermoplastic copolymer as component A, which is prepared from:

[0113] A1: 50 to 95% by weight, preferably 55 to 80% by weight, more preferably 60 to 75% by weight, typically 62 to 68% by weight, based on copolymer A, of a monomer A1 selected from styrene, α-methylstyrene and a mixture of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C8 alkyl(meth)acrylates;

[0114] A2: 5 to 50% by weight, preferably 20 to 45% by weight, more preferably 25 to 40% by weight, typically 32 to 38% by weight, based on copolymer A, of a monomer A2 selected from acrylonitrile and a mixture of acrylonitrile with at least one further monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids;

[0115] B: 20 ​​to 70%, preferably 25 to 60%, more preferably 35 to 50%, usually 35 to 45% of at least one graft copolymer B, based on the weight percentage of the graft copolymer composition AB, wherein the graft copolymer B comprises:

[0116] B1: 50 to 90%, preferably 52 to 80%, more preferably 54 to 70%, usually 55 to 65% by weight of at least one graft base B1, based on the weight percentage of the graft copolymer B, which is obtained by emulsion polymerization of the following components:

[0117] B11: 70 to 99.9% by weight, preferably 87 to 99.5% by weight, more preferably 87.5 to 99% by weight, based on the graft base B1, of at least one C1-C8 alkyl (meth)acrylate as monomer B11;

[0118] B12: 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 2.5% by weight, based on the graft base B1, of at least one polyfunctional crosslinking monomer B12;

[0119] B13: Based on the graft base B1, 0 to 29.5% by weight, preferably 0 to 20% by weight, more preferably 0 to 10% by weight of at least one other copolymerizable monoethylenically unsaturated monomer B13, which is preferably selected from styrene, α-methylstyrene, C1-C4 alkylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, C9-C 20 Alkyl methacrylates and vinyl methyl ethers;

[0120] wherein the total weight of B11+B12+B13 is 100% of the at least one graft base B1; and

[0121] B2: 10 to 50% by weight, preferably 20 to 48% by weight, more preferably 30 to 46% by weight, typically 35 to 45% by weight, based on the graft copolymer B, of at least one graft shell B2, obtained in the presence of at least one graft base B1 by emulsion polymerization:

[0122] B21: 50 to 100% by weight, preferably 60 to 90% by weight, more preferably 70 to 80% by weight, typically 73 to 77% by weight, based on the graft shell B2, of monomers B21 selected from styrene, α-methylstyrene and mixtures of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C4-alkyl(meth)acrylates;

[0123] B22: 0 to 50% by weight, preferably 10 to 40% by weight, more preferably 20 to 30% by weight and typically 23 to 27% by weight, based on the graft shell B2, of a monomer B22 selected from acrylonitrile and mixtures of acrylonitrile with at least one further monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids;

[0124] B23: 0 to 20% of at least one further copolymerizable monomer B23, based on the graft shell B2; wherein the total weight of B21+B22+B23 is 100% of the at least one graft shell B2;

[0125] The total weight of the graft base B1 and the graft shell B2 is 100% of the at least one graft copolymer B.

[0126] Thermoplastic Copolymer A

[0127] The thermoplastic copolymer A is preferably a resin containing no rubber.

[0128] In a preferred embodiment of the present invention, monomer A1 is styrene or α-methylstyrene, and monomer A2 is acrylonitrile. In an alternative embodiment of the present invention, monomer A1 is a mixture of styrene and α-methylstyrene, and monomer A2 is acrylonitrile. The mixture, based on the total amount of monomer A1, preferably contains at least 10% by weight, preferably at least 50% by weight, and most preferably at least 90% by weight of styrene.

[0129] Particularly preferred are thermoplastic copolymers A made from (i.e. consisting of):

[0130] 50 to 95% by weight, preferably 55 to 80% by weight, more preferably 60 to 75% by weight, typically 62 to 68% by weight, based on the total copolymer A, of monomers A1 selected from styrene, α-methylstyrene or a mixture of styrene and α-methylstyrene, and

[0131] 5 to 50% by weight, preferably 20 to 45% by weight, more preferably 25 to 40% by weight and typically 32 to 38% by weight, based on the total copolymer A, of monomer A2 selected from acrylonitrile or a mixture of acrylonitrile and methacrylonitrile.

[0132] The most preferred thermoplastic copolymer A comprises 35 wt% or less of acrylonitrile based on the total weight of the copolymer A.

[0133] The weight average molecular weight MW of copolymer A (determined by gel permeation chromatography based on polystyrene) is usually in the range of 15,000 to 200,000 g / mol, preferably in the range of 30,000 to 150,000 g / mol. The viscosity value VN of copolymer A is preferably in the range of 50 to 100 g / cm 3 In the range of 55 to 85 g / cm 3 range (determined according to DIN 53726 at 25° C., 0.5% by weight of dimethylformamide).

[0134] Poly(styrene-acrylonitrile) (SAN) and poly(α-methylstyrene / acrylonitrile) (AMSAN) are known and their preparation, for example by free radical polymerization, in particular by emulsion, suspension, solution and bulk polymerization, is well described in the literature.

[0135] The synthesis of thermoplastic copolymers A is described, for example, in DE-A 24 20 358 and DE-A 27 24 360. Suitable thermoplastic copolymers are also described in DE-A 1 971 3509.

[0136] The synthesis of the thermoplastic copolymer A can be achieved by thermal initiation or by adding an initiator (especially a free radical initiator, such as a peroxide). Suitable thermoplastic copolymers A are preferably prepared by bulk or solution polymerization. The copolymers can be added individually or as any mixture.

[0137] Graft copolymer B

[0138] According to the invention, the graft copolymer composition AB comprises at least one graft copolymer B, in particular an ASA graft rubber, which comprises 50 to 90% by weight, preferably 55 to 90% by weight, based on the graft copolymer B, of at least one graft base B1, and 10 to 50% by weight, preferably 10 to 45% by weight, based on the graft copolymer B, of at least one graft shell B2, preferably one to three graft shells B2, the sum of the graft base B1 and the graft shells B2 being equal to 100% by weight.

[0139] In a preferred embodiment of the present invention, the graft copolymer B comprises 10 to 50% by weight, preferably 10 to 45% by weight, most preferably 35 to 45% by weight, based on the total graft copolymer B, of at least one graft shell B2 obtained by emulsion polymerization of:

[0140] B21: 50 to 95%, preferably 65 to 80%, typically 75 to 80%, based on the graft shell B2, of at least one monomer B21 selected from styrene, α-methylstyrene or a mixture of styrene with another monomer selected from α-methylstyrene, p-methylstyrene, C1-C4-alkyl(meth)acrylates (e.g. methyl methacrylate, ethyl methacrylate), preferably selected from styrene, α-methylstyrene or a mixture of styrene with α-methylstyrene or methyl methacrylate, and

[0141] B22: 5 to 50% by weight, preferably 20 to 35% by weight, typically 20 to 25% by weight, based on the graft shell B2, of at least one monomer B22 selected from acrylonitrile or acrylonitrile mixtures and at least one further monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids (for example maleic anhydride, phthalic anhydride) and imides of unsaturated carboxylic acids (for example N-substituted maleimides, such as N-cyclohexylmaleimide and N-phenylmaleimide), preferably selected from acrylonitrile or a mixture of acrylonitrile and methacrylonitrile;

[0142] The total weight of B21 and B22 is equal to 100%.

[0143] Preferably, the graft copolymer B comprises a graft base B1 of crosslinked polybutyl acrylate rubber as described above and exactly one graft shell B2, which is obtained by emulsion polymerization of monomers B21 and B22 (as described above, especially styrene or acrylonitrile) in the presence of the graft base B1 (single graft shell B2). Further preferably, the graft copolymer B comprises a graft base B1 as described above (which comprises a crosslinked polybutyl acrylate rubber) and two graft shells B2′ and B2″, wherein B2′ is obtained by emulsion polymerization of monomers B21 (especially styrene) in the presence of the graft base B1, and the graft shell B2″ is obtained by subsequent emulsion polymerization of monomers B21 and B22 (as described above), especially styrene and acrylonitrile, in the presence of the graft base B1 to which B2′ is already grafted (i.e. two-stage grafting).

[0144] Particularly preferably, the graft base B1 is obtained by emulsion polymerization as follows:

[0145] B11: preferably 87 to 99.5% by weight, based on the graft base B1, of at least one C4-C8-alkyl (meth)acrylate, more preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, most preferably n-butyl acrylate alone.

[0146] B12: 0.5 to 5% by weight, preferably 0.5 to 3% by weight, most preferably 1 to 2.5% by weight, based on the graft base B1, of at least one multifunctional crosslinking monomer B12, preferably selected from isoprene, butadiene, chloroprene, alkyldiol di(meth)acrylate, allyl(meth)acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and dihydrodicyclopentadienyl acrylate (DCPA), particularly preferably allyl(meth)acrylate and / or dihydrodicyclopentadienyl acrylate (DCPA);

[0147] B13: Based on the graft base B1, 0 to 29.9% by weight, preferably 0 to 10% by weight, most preferably 0.5 to 10% by weight, of at least one other copolymerizable monoethylenically unsaturated monomer B13, which is preferably selected from styrene, α-methylstyrene, C1-C4-alkylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, C9-C 20 Alkyl methacrylates and vinyl methyl ethers;

[0148] The total weight of B11, B12 and B13 is 100%.

[0149] Preferred monomers B11 for preparing the graft base B1 are alkyl acrylates and / or alkyl methacrylates, wherein the alkyl group has 1 to 8 carbon atoms, preferably 4 to 8 carbon atoms. Particularly preferred monomers B11 are n-butyl acrylate and / or 2-ethylhexyl acrylate, most preferably n-butyl acrylate. The alkyl acrylates are preferably used alone as monomers B11.

[0150] In order to crosslink the C1-C8 alkyl (meth) acrylate monomer B11 and thus the graft base B1, the monomer B11 is polymerized in the presence of a multifunctional crosslinking monomer B12, the amount of which is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, preferably 0.5 to 3% by weight, preferably 1 to 4% by weight, more preferably 1 to 2.5% by weight, based on the graft base B1. Suitable monomers B12 are especially multifunctional crosslinking monomers, which can be copolymerized with the above-mentioned monomers (especially B11 and B13). Suitable multifunctional crosslinking monomers B12 contain two or more, preferably two or three, more preferably exactly two olefinic double bonds, which are preferably not 1,3 conjugated. Examples of suitable multifunctional crosslinking monomers B12 are allyl (meth) acrylate, divinylbenzene, carboxylic acid diallyl esters, such as maleic acid diallyl ester, fumaric acid diallyl ester and phthalic acid diallyl ester.

[0151] Acrylic esters of tricyclodecenol (dihydrodicyclopentadienyl acrylate, DCPA), as described in DE-A 1 260 135, also represent preferred polyfunctional crosslinking monomers B12.

[0152] In particular, the multifunctional cross-linking monomer B12 is at least one selected from the following: allyl (meth)acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and dihydrodicyclopentadienyl acrylate (DCPA), preferably selected from allyl (meth)acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate and dihydrodicyclopentadienyl acrylate (DCPA), and particularly preferably selected from allyl (meth)acrylate and dihydrodicyclopentadienyl acrylate (DCPA).

[0153] In a preferred embodiment, 1 to 2.5 wt. %, preferably 1.5 to 2.1 wt. %, based on the graft base B1, of dihydrodicyclopentadienyl acrylate (DCPA) is used alone as monomer B12 or mixed with another of the above-mentioned monomers B12, in particular with allyl (meth)acrylate.

[0154] Furthermore, the graft base B1 may optionally comprise one or more copolymerizable monoethylenically unsaturated monomers B13 which are different from B11 and B12. The monomers B13 may be selected, for example, from styrene, acrylonitrile, methyl methacrylate and vinyl methyl ether.

[0155] In a preferred embodiment, at least one graft base B1 is obtained by emulsion polymerization of:

[0156] B11: 90 to 99.9% by weight, preferably 97 to 99.5% by weight, based on the graft base B1, of at least one C1-C8 alkyl (meth)acrylate, preferably n-butyl acrylate;

[0157] B12: 0.1 to 10%, preferably 0.5 to 3%, most preferably 1 to 2.5%, based on the graft base B1, of at least one multifunctional crosslinking monomer B12 selected from isoprene, butadiene, chloroprene, alkyldiol di(meth)acrylate, allyl(meth)acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate and dihydrodicyclopentadienyl acrylate (DCPA), particularly preferably allyl(meth)acrylate and / or dihydrodicyclopentadienyl acrylate (DCPA);

[0158] The total weight of B11 and B12 is equal to 100% of B1.

[0159] Graft bases B1 comprising monomers B11, B12 and optionally B13 and processes for their preparation are known and described in the literature, for example in DE-A 28 26 925, DE-A 31 49 358 and DE-A 34 14 118.

[0160] The graft polymerization for synthesizing the graft shell B2 (e.g. B2′ and B2″) can conveniently be carried out in the same vessel as the emulsion polymerization for synthesizing the graft base B1. During the reaction, additives such as emulsifiers, pH buffers and initiators can be added. The monomers of the graft shell, in particular the monomers B21 and B22, can be added to the reaction mixture all at once or in stages during the polymerization, preferably in a continuous manner. When the monomers B21 and / or B22 are added in several steps, a multilayer graft shell B2 is usually obtained.

[0161] Suitable emulsifiers, buffers and initiators are described in WO 2015 / 150223 and WO 2015 / 078751.

[0162] In a preferred embodiment, the graft copolymer B (only one graft layer B2) comprises:

[0163] B1: 50 to 70% by weight, preferably 55 to 65% by weight, typically 58 to 65% by weight, based on the graft copolymer B, of at least one graft base (as described above);

[0164] B2: 30 to 50% by weight, preferably 35 to 45% by weight, typically 35 to 42% by weight, based on the graft copolymer B, of at least one graft shell B2, obtained by emulsion polymerization in the presence of at least one graft base B1:

[0165] B21: 50 to 95% by weight, preferably 65 to 80% by weight, more preferably 75 to 80% by weight, based on the graft base B2, of a monomer B21 selected from styrene, α-methylstyrene or a mixture of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C4-alkyl(meth)acrylates (e.g. methyl methacrylate, ethyl methacrylate), preferably selected from styrene, α-methylstyrene or a mixture of styrene with α-methylstyrene or methyl methacrylate; and

[0166] B22: 5 to 50% by weight, preferably 20 to 35% by weight, typically 20 to 25% by weight, of monomers B22, based on the graft shell B2, selected from acrylonitrile or a mixture of acrylonitrile with at least one further monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids (for example maleic anhydride, phthalic anhydride) and imides of unsaturated carboxylic acids (for example N-substituted maleimides such as N-cyclohexylmaleimide and N-phenylmaleimide), preferably selected from acrylonitrile or a mixture of acrylonitrile and methacrylonitrile;

[0167] The total weight of the graft base B1 and the graft shell B2 is equal to 100% by weight of the graft copolymer B.

[0168] In a preferred embodiment of the present invention, the graft copolymer B (comprising a double-layer graft shell of B2′ and B2″) comprises:

[0169] B1: 50 to 70% by weight, preferably 60 to 70% by weight, based on the graft copolymer B, of at least one graft base B1 as described above;

[0170] B2′: 10 to 30% by weight, preferably 10 to 20% by weight, typically 10 to 15% by weight, based on the graft copolymer B, of at least one graft shell B2′, obtained in the presence of the graft base B1 by emulsion polymerization of:

[0171] B21′: 100% by weight of monomers B21′, based on the graft shell B2′, selected from styrene, α-methylstyrene or a mixture of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C4-alkyl(meth)acrylates (e.g. methyl methacrylate, ethyl methacrylate); and

[0172] B2″: 20 to 40% by weight, preferably 20 to 30% by weight, typically 25 to 30% by weight, based on the graft copolymer B, of at least one graft shell B2″, which is also obtained by emulsion polymerization in the presence of the graft base B1 grafted with B2′:

[0173] B21″: 50 to 95% by weight, preferably 65 to 80% by weight, typically 70 to 80% by weight, based on the graft shell B2″, of monomers B21″ selected from styrene, α-methylstyrene or mixtures of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C4-alkyl(meth)acrylates (e.g. methyl methacrylate, ethyl methacrylate), preferably selected from styrene, α-methylstyrene or mixtures of styrene with α-methylstyrene or methyl methacrylate; and

[0174] B22″: 5 to 50% by weight, preferably 20 to 35% by weight, more preferably 20 to 30% by weight, based on the graft shell B2″, of at least one monomer B22″ selected from acrylonitrile or a mixture of acrylonitrile with at least one further monomer selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids (e.g. maleic anhydride, phthalic anhydride) and imides of unsaturated carboxylic acids (e.g. N-substituted maleimides, such as N-cyclohexylmaleimide and N-phenylmaleimide).

[0175] Preferably, the monomers B21, B21′ and B21″ are styrene or a mixture of styrene and α-methylstyrene.

[0176] Preferably, monomers B22 and B22″ are acrylonitrile or a mixture of acrylonitrile and at least one other monomer, wherein the other monomer is selected from the group consisting of methacrylonitrile, maleic anhydride, N-cyclohexylmaleimide, and a mixture of other monomers of N-phenylmaleimide, more preferably acrylonitrile or a mixture of acrylonitrile and at least one other monomer selected from the group consisting of methacrylonitrile and maleic anhydride.

[0177] Monomers B23 and B23″ can be selected from copolymerizable ethylenically unsaturated monomers, such as C1-C8 alkyl methacrylate, C9-C 20 Alkyl methacrylate, and a multifunctional crosslinking monomer selected from isoprene, butadiene, chloroprene, alkyl glycol di(meth)acrylate, allyl(meth)acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, and dihydrodicyclopentadienyl acrylate (DCPA).

[0178] In a more preferred embodiment of the present invention, monomers B21, B21′ and B21″ are styrene, and monomers B22 and B22′ are acrylonitrile.

[0179] The graft copolymers B (obtained in latex form) generally have a weight-average particle size dw of 50 to 1000 nm, preferably 90 to 700 nm. The particle size of the latex particles can be controlled during the synthesis by suitable methods known from the literature, for example DE-A 2826925.

[0180] Typically, the average particle size can be measured by ultracentrifugation (e.g., as described in W. Scholtan, H. Lange, Kolloid-ZuZ, Polymer, 250, 1972, pp. 782-796) or using hydrodynamic chromatography HDC (e.g., as described in W. Wohlleben, H. Schuch, "Measurement of the particle size distribution of polymer latexes", 2010, ed.: L. Gugliotta, J. Vega, pp. 130-153). Average particle size d 50 The value of the particle size distribution curve where 50% of the particles (e.g., polyacrylate latex) have a diameter smaller than this d 50 value, while the diameter of the other 50% of the particles is larger than this d 50 Value. Similarly, for example, d 90 A value indicates that 90% of all particles have a diameter smaller than this value. The average particle size (mass average, dw) can be determined by turbidity measurements as described in Lange, Journal of Colloids and Polymers, Vol. 223, No. 1.

[0181] In one embodiment of the present invention, the weight-average particle size dw distribution of the graft copolymer B is unimodal.

[0182] However, in an alternative embodiment of the present invention, the graft copolymer B may be present in a multimodal weight-average particle size dw distribution, more preferably in a bimodal weight-average particle size dw distribution, i.e. in the form of a mixture of at least two different graft copolymers BI and B-II, wherein the weight-average particle sizes dw of the graft copolymers BI and B-II are different.

[0183] The graft copolymer B comprises in particular at least one of the graft copolymers BI and B-II, wherein:

[0184] The weight average particle size dw of the graft copolymer BI is 50 to 180 nm, preferably 80 to 150 nm, typically 90 to 100 nm (small size ASA rubber), and

[0185] The weight average particle size dw of the graft copolymer B-II is 200 to 800 nm, preferably 300 to 700 nm, usually 400

[0186] To 600nm (large size ASA rubber).

[0187] Suitable large-size crosslinked C1-C8 alkyl (meth) acrylate polymer graft bases B1-II can be produced according to known methods for producing large-size dispersions, conveniently by seeded polymerization, such as the method described in DE 1911 882 for producing ASA polymers. According to this method, a small-size crosslinked acrylate latex (seed latex) having an average particle size dw of 50 to 180 nm, preferably less than 120 nm, is subjected to further polymerization. The reaction conditions selected (see "Journal of Applied Polymer Science", Vol. 9 (1965), pp. 2929 to 2938) only allow the existing (seed) latex particles to grow further without forming new latex particles. An initiator is usually used, and the particle size of the resulting graft copolymer B-II (large-size rubber) can be adjusted by varying the weight ratio of seed latex to monomer. The small-size crosslinked acrylate latex is obtained by emulsion polymerization of C1-C8 alkyl (meth) acrylate, crosslinking monomer and optionally other comonomers, emulsifiers and possible buffers.

[0188] The graft copolymer B-II is preferably obtained by emulsion polymerization of styrene or α-methylstyrene and acrylonitrile in the presence of a previously prepared large-scale graft base B1-II.

[0189] In order to produce the thermoplastic resin of the present invention, graft copolymers BI and B-II can be combined, in particular in step d (mixing the components). The weight ratio of graft copolymers BI and B-II can vary within a wide range. Preferably, the graft copolymer is a mixture of graft copolymers BI and B-II, wherein the weight ratio of graft copolymer BI: graft copolymer B-II is 90:10 to 10:90, preferably 80:20 to 20:80, and most preferably 70:30 to 35:65.

[0190] Preferably, the graft copolymers BI and B-II are prepared and separated separately, or the graft copolymers BI and B-II are prepared separately, then separated together, and then mixed.

[0191] It is also possible to obtain graft copolymers with different particle sizes, in particular bimodal particle size distributions of 50 to 180 nm and 200 to 800 nm, by known agglomeration processes. For example, graft copolymers with large and small particle sizes are described in DE-A 3615607.

[0192] In a preferred embodiment of the present invention, the weight average particle size dw of the graft copolymer B is at least 50 nm. The inventors have found that when the weight average particle size dw of the graft copolymer B is at least 50 nm, improved mechanical properties are exhibited under artificial weathering conditions. When the weight average particle size dw is at least 80 nm, more preferably at least 90 nm, the graft copolymer B can achieve better performance.

[0193] Furthermore, it is possible to use graft copolymers B which have two or more different graft shells B2. Graft copolymers having a multilayer graft shell are described, for example, in EP-A 0111260 and WO 2015 / 078751.

[0194] The monomers B21 and B22 used for the emulsion polymerization of the graft copolymer B are preferably a mixture of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, typically 80:20 to 65:35.

[0195] Furthermore, molecular weight regulators can be used for the production of the graft base B1 and / or for the emulsion polymerization of the at least one graft copolymer B, preferably in an amount of 0.01 to 2% by weight, typically 0.05 to 1% by weight (relative to the total amount of monomers used for the emulsion polymerization). Suitable molecular weight regulators are, for example, alkyl mercaptans (e.g. n-dodecyl mercaptan, tert-dodecyl mercaptan), dimeric α-methylstyrene and terpinolene.

[0196] Suitable initiators for the production of the graft base B1 and / or for the emulsion polymerization of the at least one graft copolymer B are any initiators. Preference is given to using at least one organic and / or inorganic peroxide compound (containing at least one peroxide group ROOH and / or ROOR) as initiator. In particular, inorganic peroxide salts such as aluminum, sodium or potassium persulfates, perphosphates or perborates can be used. Most preferred are sodium persulfate and potassium persulfate.

[0197] In a preferred embodiment of the present invention, an inorganic peroxide salt, preferably an inorganic persulfate, preferably sodium persulfate and / or potassium persulfate, is used for the emulsion polymerization of the graft copolymer B.

[0198] As emulsifiers for the emulsion polymerization for producing the graft base B1 and / or the at least one graft copolymer B, classic anionic emulsifiers can be used. Preferably, the emulsifiers are alkyl sulfates, alkyl sulfonates, aryl alkyl sulfonates, soaps of saturated or unsaturated fatty acids and alkaline disproportionated or hydrated rosin acids or tall oil acids or mixtures thereof. Preferably, emulsifiers containing carboxyl groups (e.g. C 10 -C 18 Salts of fatty acids, salts of disproportionated rosin acid or tall oil acid, and emulsifiers according to DE-OS 36 39 904 and DE-OS 39 13 509).

[0199] Suitable buffers are usually used to prepare the graft copolymers B, for example sodium carbonate or sodium bicarbonate. Suitable emulsifiers, buffers and initiators are also mentioned in WO 2015 / 150223 and WO 2015 / 078751.

[0200] The temperature during the emulsion polymerization of the graft copolymer B is generally 25 to 160° C., preferably 40 to 90° C. Suitable emulsifiers are as described above. During the reaction, typical temperature control can be applied, such as an isothermal process, preferably keeping the temperature difference between the start and the end of the reaction less than 20° C., preferably less than 15° C., most preferably less than 5° C.

[0201] The production of the graft copolymer B, especially the graft copolymers BI and B-II, in the present invention is carried out by emulsion polymerization. Common embodiments of emulsion polymerization, including batch or continuous mode, are well known to those skilled in the art.

[0202] In particular the monomers for the graft shell B2, ie the monomers B21 and B22, are added successively to the graft base B2 in suitable amounts and weight ratios, either individually or as a monomer mixture. The monomers are generally added to the graft base B1 in a manner known to the person skilled in the art.

[0203] Hindered amine light stabilizer (component C)

[0204] The thermoplastic molding compositions P according to the invention further comprise, as component C, 0.01 to 2.5% by weight, based on the weight of the molding composition P, of at least one hindered amine light stabilizer.

[0205] The thermoplastic molding composition P comprises at least one hindered amine light stabilizer component C, preferably selected from compounds of the following formula (I):

[0206]

[0207] in

[0208] R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

[0209] R2 represents a hydrocarbon group having 5 to 30 carbon atoms, wherein the hydrocarbon group preferably contains at least one heteroatom selected from N and O; and

[0210] R3, R4, R5, R6, R7, R8, R9, and R10 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;

[0211] and a mixture of a hindered amine light stabilizer component C represented by formula (I).

[0212] Hindered amine light stabilizers (HALS) are well known in the art. Known examples include bis-(2,2,6,6-tetramethylpiperidinyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidinyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate bis-(1,2,2,6,6-pentanemethylpiperidinyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N′-(2,2,6,6-tetramethylpiperidinyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-s-triazine, Tris-(2,2,6,6-tetramethylpiperidinyl)-nitrile triacetate, tetrakis-(2,2,6,6-tetramethylpiperidinyl)-nitrile triacetate, -(2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate, 1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone), bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.

[0213] In one embodiment, the thermoplastic molding composition P comprises at least one hindered amine light stabilizer component C-1 and optionally a further hindered amine light stabilizer component C-2 which is different from the hindered amine light stabilizer component C-1.

[0214] In a preferred embodiment, the at least one hindered amine light stabilizer component C-1 is selected from compounds having the following formula (Ia):

[0215]

[0216] in

[0217] R1 each independently represents -H or -CH3; and

[0218] n represents an integer from 1 to 8, preferably from 3 to 5, in particular 4;

[0219] and mixtures thereof.

[0220] In a preferred embodiment, the two substituents R1 are identical. More preferably, both substituents R1 represent a methyl group -CH3.

[0221] Particularly preferred representatives of the hindered amine light stabilizer component C-1 according to formula (Ia) include bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (CAS No.: 52829-07-9) and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (CAS No.: 41556-26-7) and mixtures thereof.

[0222] In one embodiment, the thermoplastic molding composition P comprises at least two hindered amine light stabilizers component C-1 selected from compounds of formula (Ia).

[0223] In one embodiment, the thermoplastic molding composition P comprises at least one hindered amine light stabilizer component C-1 selected from compounds having formula (Ia) and at least one additional hindered amine light stabilizer component C-2 different from the hindered amine light stabilizer component C-1.

[0224] Preferably, the hindered amine light stabilizer component C-2, if present, is selected from sterically hindered monopiperidine derivatives having a molecular weight of 400 to 600 g / mol and sterically hindered piperidine derivatives having a molecular weight > 600 g / mol and mixtures thereof.

[0225] Preferred examples of hindered amine light stabilizer component C-2 are selected from poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CAS-No. 71878-19-8), 2,2,6,6-tetramethyl-4-piperidinyl-octadecanoate, 2,2,6,6-tetramethyl-4-piperidinyl-eicosanoate and mixtures thereof.

[0226] Particularly preferred combinations include:

[0227] (i) bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7) and

[0228] (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7 or 82919-37-7);

[0229] (ii) mixtures of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7), poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CAS No. 71878-19-8) and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7 or 82919-37-7);

[0230] (iii) a mixture of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7) and poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CAS No. 71878-19-8); and

[0231] (iv) A mixture of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7) and 2,2,6,6-tetramethyl-4-piperidinyl octadecanoate (CAS No. 52829-07-9).

[0232] More preferred combinations include:

[0233] (i) bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7) and bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7 or 82919-37-7), in a weight ratio of 1:2 to 2:1, preferably 1:1.2 to 1.2:1;

[0234] (ii) a mixture of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7), poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CAS No. 71878-19-8) and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (CAS No. 41556-26-7 or 82919-37-7) in a weight ratio of 3:1:1 to 7:1:3, preferably 4:1:1.5 to 6:1:2.5;

[0235] (iii) a mixture of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7) and poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (CAS No. 71878-19-8) in a weight ratio of 3:1 to 1:1, preferably 2.5:1 to 1.5:1; and

[0236] (iv) a mixture of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (CAS No. 41556-26-7) and 2,2,6,6-tetramethyl-4-piperidinyl octadecanoate (CAS No. 52829-07-9) in a weight ratio of 1:5 to 1:10, preferably 1:7 to 1:8.

[0237] Antioxidant (Component D)

[0238] The thermoplastic molding compositions P according to the invention comprise, as component D, 0.01 to 1.0% by weight, based on the weight of the molding composition P, of at least one sterically hindered phenolic antioxidant.

[0239] The antioxidant component D is selected from the sterically hindered phenolic antioxidants of general formula (II) and mixtures thereof:

[0240]

[0241] in

[0242] R1 to R5 each independently represent a hydrogen atom or an alkyl group having 1 to 70 carbon atoms, wherein the hydrocarbon group optionally contains at least one heteroatom selected from O and S, and at least one of the substituents R1 and R5 is a hydrocarbon group having at least 3 carbon atoms.

[0243] In a preferred embodiment, at least one of the substituents R1 and R5 represents a branched hydrocarbon group having 3 to 20 carbon atoms, more preferably a branched hydrocarbon group having 3 to 10 carbon atoms. In a preferred embodiment, at least one of the substituents R1 and R5 represents a branched hydrocarbon group having 3 to 10 carbon atoms, preferably selected from sec-propyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, cyclohexyl and dicyclopentadienyl. In a particularly preferred embodiment, the substituent R1 represents tert-butyl.

[0244] In a preferred embodiment, at least one of the substituents R2 to R5, in particular R3 and / or R5, represents a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group optionally contains at least one heteroatom selected from O and S. In a preferred embodiment, the substituent R3 represents a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group preferably contains at least one heteroatom selected from O and S. In an alternative preferred embodiment, the substituent R5 represents a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group optionally contains at least one heteroatom selected from O and S, and wherein the hydrocarbon group preferably contains a cyclic hydrocarbon group. In another alternative preferred embodiment, the substituents R3 and R5 each represent a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group preferably contains at least one heteroatom selected from O and S, in particular S.

[0245] In another preferred embodiment, R2, R4 and optionally R5 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, in particular 1 to 4 carbon atoms, provided that at least one of the substituents R2, R4 and R5 is not hydrogen.

[0246] In one embodiment of the present invention, the antioxidant component D is selected from sterically hindered phenolic antioxidants of the general formula (II-a) and mixtures thereof:

[0247]

[0248] in

[0249] R3 represents a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group preferably contains at least one heteroatom selected from O and S; and

[0250] R2, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of the substituents R2, R4 and R5 is not hydrogen.

[0251] In an alternative preferred embodiment of the present invention, the antioxidant component D is selected from sterically hindered phenolic antioxidants of the general formula (II-a) and mixtures thereof, wherein

[0252] R5 represents a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group includes a cyclic hydrocarbon group, more preferably a polycyclic hydrocarbon group, and wherein the hydrocarbon group preferably contains at least one heteroatom selected from O and S; and

[0253] R2, R3 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein at least one of the substituents R2, R3 and R4, in particular R3, is not hydrogen. Preferably, R3 is selected from -CH3 and C2H6, in particular -CH3.

[0254] Particularly preferred representatives of the sterically hindered phenolic antioxidant represented by formula (II-a) as component D include octadecyl 3-(3,-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No.: 2082-79-3, such as the commercially available octadecyl 3-(3,-di-tert-butyl-4-hydroxyphenyl) propionate produced by BASF, Germany 1076), pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (CAS-No.: 6683-19-8, such as commercially available 1010, produced by BASF SE, Germany), ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (CAS-No.: 36443-68-2, such as commercially available 245, produced by BASF SE, Germany), 4,4′-thiobis(2-(tert-butyl)-5-methylphenol) (CAS-No.: 96-69-5, such as commercially available BB12P and R), poly(dicyclopentadiene-co-p-cresol) (butylated reaction product of p-cresol and dicyclopentadiene, preferably having an average molecular weight of 650 g / mol, CAS No.: 68610-51-5, such as commercially available from Omnova Solutions L), pentaerythritol tetrakis [3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionate (CAS-No. 2082-79-3), ethylenebis (ethylene oxide) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate) (CAS-No. 36443-68-2). Particularly preferred are pentaerythritol tetrakis [3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionate (CAS-No. 2082-79-3), ethylenebis (ethylene oxide) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate) (CAS-No. 36443-68-2), 4, 6-bis (dodecylthiomethyl) - o-cresol (CAS-No. 110675-26-8) and mixtures thereof. More preferred is ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (CAS-No. 36443-68-2).

[0255] In an alternative embodiment of the present invention, the antioxidant component D is selected from sterically hindered phenolic antioxidants of the general formula (II-b) and mixtures thereof:

[0256]

[0257] in

[0258] R1, R2 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and wherein at least one of the substituents R1, R2 and R4 is not hydrogen; and

[0259] R6 and R7 each independently represent an alkyl group having 1 to 20 carbon atoms, preferably 8 to 16 carbon atoms.

[0260] Particularly preferred representatives of sterically hindered phenol antioxidants according to formula (II-b) as component D include 4,6-bis(dodecylthiomethyl)-o-cresol (CAS No. 110675-26-8).

[0261] In one embodiment, the thermoplastic molding composition P comprises at least one sterically hindered phenolic antioxidant selected from ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate (CAS No. 36443-68-2) and 4,6-bis(dodecylthiomethyl)-o-cresol (CAS No. 110675-26-8) as component D, and at least one co-stabilizer E selected from tris(2,-di-tert-butylphenol) phosphite (CAS No. 31570-04-4).

[0262] Stabilizer (component E)

[0263] In addition to the phenolic antioxidant D, the thermoplastic molding composition further comprises 0 to 2.5% by weight (based on the total weight of the molding composition P) of at least one auxiliary stabilizer E selected from phosphorus-containing or sulfur-containing auxiliary stabilizers. If the UV absorber component F is not present in the molding composition P, the auxiliary stabilizer component E is present in an amount of at least 0.05% by weight, based on the total weight of the molding composition P. Phosphorus auxiliary stabilizers or sulfur-containing auxiliary stabilizers can be used alone or in combination with one another.

[0264] Particularly suitable phosphorus-containing co-stabilizers include phosphite components of the general formula (III):

[0265]

[0266] wherein R1 to R3 each independently represent an aryl group, which is optionally substituted by a hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. In a preferred embodiment, R1, R2 and R3 each represent a phenyl group having 1 to 3 alkyl groups as substituents, the alkyl groups having 3 to 10 carbon atoms. Particularly preferred phosphorus-containing stabilizers include tris (4-nonylphenyl) phosphite (TNPP, CAS-No. 3050-88-2), tris (2,-di-tert-butylphenol) phosphite (CAS-No. 31570-04-4, such as commercially available 168, BASF SE, Germany) and mixtures thereof.

[0267] Suitable sulfur-containing co-stabilizers include thiodicarboxylic acids of the general formula (IV):

[0268]

[0269] in

[0270] R1 is independently selected from hydrocarbon radicals having 1 to 30 carbon atoms, preferably linear hydrocarbon radicals having 5 to 20 carbon atoms, and optionally containing oxygen atoms, in particular in the form of a carboxyl function,

[0271] R2 is independently selected from a hydrocarbon group having 1 to 30 carbon atoms, preferably a straight chain hydrocarbon group having 10 to 20 carbon atoms, and

[0272] m is independently an integer from 1 to 8, preferably from 2 to 4, especially 2.

[0273] In one embodiment, suitable sulfur-containing co-stabilizers include thiodicarboxylic acids of formula (IV-a):

[0274]

[0275] in

[0276] R1 and R2 are independently selected from hydrocarbon groups having 1 to 30 carbon atoms, preferably linear hydrocarbon groups having 10 to 20 carbon atoms, and n and m independently represent integers of 1 to 8, preferably 2 to 4, in particular 2. Particularly preferred sulfur-containing stabilizers of formula (IV-a) include didodecyl thiodipropionate (Irganox PS 800, BASF SE), ditetradecyl thiodipropionate (CAS No. 123-28-4; Irganox PS 801, BASF SE), dioctadecyl thiodipropionate (CAS No. 693-36-7; Irganox PS 802, BASF SE) and mixtures thereof.

[0277] In another preferred embodiment, suitable sulfur-containing co-stabilizers include thiodicarboxylic acids of general formula (IV-b):

[0278]

[0279] in

[0280] R1 is selected from a hydrocarbon group having 1 to 30 carbon atoms, preferably a linear hydrocarbon group having 5 to 15 carbon atoms, and m is an integer from 1 to 8, preferably from 2 to 4, especially 2. Particularly preferred sulfur-containing stabilizers of formula (Vb) include 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecylthio)propionate] (CAS-No. 29598-76-3, 412S, Rianlon, China).

[0281] In one embodiment of the present invention, at least one co-stabilizer E is selected from tris(2,-di-tert-butylphenol)phosphite (CAS No. 31570-04-4), 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecylthio)propionate] (CAS No. 29598-76-3) and mixtures thereof.

[0282] In a preferred embodiment, the thermoplastic molding composition P comprises at least one sterically hindered phenolic antioxidant component D selected from 4,6-bis(dodecylthiomethyl)-o-cresol (CAS No. 110675-26-8), and at least one co-stabilizer E selected from tris(2,-di-tert-butylphenol)phosphite (CAS No. 31570-04-4).

[0283] If component E is present in combination with component F, the amount of phosphorus-containing auxiliary stabilizer and / or sulfur-containing auxiliary stabilizer is generally in the range of 0.01 to 2.2%, typically 0.05 to 1%. Preferably, in this case, the amount of phosphorus-containing auxiliary stabilizer and / or sulfur-containing auxiliary stabilizer is less than 0.5% by weight, more preferably less than 0.3% by weight, based on the molding composition P.

[0284] UV absorber (component F)

[0285] The thermoplastic molding composition P according to the invention may comprise at least one UV absorber as component F in an amount of 0 to 3% by weight of the molding composition P. If no co-stabilizer component E is present in the molding composition P, the UV absorber component F is present in an amount of at least 0.05% by weight, based on the total weight of the molding composition P. The UV absorber generally comprises at least one organic or inorganic component, the UV absorption band of which is at least in the wavelength range of ≤500 nm, preferably ≤380 nm, in particular in the wavelength range of 200 nm to 500 nm, preferably 200 to 380 nm.

[0286] Known UV absorbers that meet the UV absorption band requirements include 2-(2-hydroxyphenyl)-2H-benzotriazole, such as the known commercially available hydroxyphenyl-2H-benzotriazole and benzotriazole, such as those disclosed in the following U.S. Patent Nos.: 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905. For example:

[0287] 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 5-chloro-2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-4- 2-(3-tert-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-phenyl)-2H-benzotriazole, 2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole, dodecyl 2-(2-hydroxy-5 -methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonyl-ethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-α-cumylethyl)-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole, 2,2′-methylene-bis(4-tert-octyl-(6-2H-benzotriazol-2-yl)phenol), 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole, 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-di-α-cumylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole, 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl- 4-hydroxyhydrocinnamic acid methyl ester, 5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole and 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole. ,

[0288] Preferred ultraviolet absorbers include compounds containing a benzotriazole group, which are represented by the following formula (C):

[0289]

[0290] in

[0291] R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from a hydrogen atom, a halogen atom and an alkyl group having 1 to 5 carbon atoms, which is a particularly suitable UV absorber component F.

[0292] As a preferred embodiment, component F (if present) comprises 2-(2H-benzotriazol-2-yl)-4-methylphenol (CAS No. 2440-22-4, available as P is commercially available from BASF SE, Germany), which is represented by the following formula (Va):

[0293]

[0294] Other suitable UV absorbers include 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol ( 326), which is represented by the following formula (Vb):

[0295]

[0296] In one embodiment of the present invention, the UV absorber component F comprises or consists of compounds of formula (V), (Va), (Vb) and mixtures thereof. Preferably, the UV absorber component F comprises or consists of compounds of formula (Va).

[0297] Other additives (component G)

[0298] The thermoplastic molding composition P of the invention comprises as optional component G 0 to 8% by weight, based on the weight of the molding composition P, of at least one further additive, wherein additive G is different from components C, D, E and F contained in the thermoplastic molding composition P.

[0299] As used herein, one or more other additives G may be any additive that can be used in the molding composition P. Suitable additives G include all substances commonly used for processing or finishing polymers, such as plasticizers, lubricants, mold release agents, dyes, pigments, fillers and UV stabilizers. These other added substances can be mixed at any stage of the manufacturing operation, but are preferably mixed at an early stage in order to benefit from the stabilizing effect (or other specific effect) of the added substances as early as possible.

[0300] Additive G can be added to the molding compound as an auxiliary and processing additive in an amount of 0 to 8% by weight, preferably 0.01 to 7.5% by weight, more preferably 0.1 to 7% and typically 0.5 to 6.5% by weight.

[0301] The additive G may be added in the form of a masterbatch, which is a polymer matrix comprising the additive G. In a preferred embodiment, the additive G is added in the form of a masterbatch, which comprises 10 to 70 wt %, preferably 20 to 60 wt % of the additive G or a mixture thereof (based on the total amount of the masterbatch) and 30 to 90 wt %, preferably 40 to 80 wt % of a copolymer of a vinyl aromatic olefin and acrylonitrile as a matrix polymer (based on the total amount of the masterbatch). Preferably, the matrix polymer is selected from poly(styrene-acrylonitrile) (SAN), poly(α-methylstyrene / acrylonitrile) (AMSAN) and / or poly(styrene-methyl methacrylate) (SMMA).

[0302] Examples of additives G include, for example, antistatic agents, antioxidants, flame retardants, stabilizers for improving thermal stability, stabilizers for increasing light stability, stabilizers for enhancing hydrolysis resistance and chemical resistance, anti-thermal decomposition agents, and dyes, pigments, lubricants and release agents particularly for producing molded bodies / articles, with the proviso that additive G is different from components C, D, E and F disclosed herein.

[0303] Examples of suitable antistatic agents include amine derivatives such as N,N-bis(hydroxyalkyl)alkylamines or -alkyleneamines, polyethylene glycol esters, copolymers of ethylene oxide and propylene oxide (particularly diblock or triblock copolymers of ethylene oxide blocks and propylene oxide blocks), glyceryl monostearate and distearate, and mixtures thereof.

[0304] Examples of suitable antioxidants include sterically hindered monocyclic or polycyclic phenolic antioxidants different from component E, which may contain various substituents and may also be bridged by substituents. These include not only monomeric compounds, but also oligomeric compounds, which may be composed of multiple phenolic units. Hydroquinone and hydroquinone analogs are also suitable, and substituted compounds thereof are also suitable, and antioxidants based on tocopherol and its derivatives are also suitable. Mixtures of different antioxidants can also be used. In principle, any commercially common or suitable compound for styrene copolymers can be used.

[0305] Examples of suitable flame retardants include halogen-containing or phosphorus-containing compounds known to those skilled in the art, as well as magnesium hydroxide and other commonly used compounds, or mixtures thereof.

[0306] Examples of suitable light stabilizers include various substituted resorcinols, salicylates, benzophenones, vitamin E and compounds of similar structure and butylated condensation products of p-cresol and dicyclopentadiene. Other suitable compounds include, for example, thiocarboxylates. C6-C6 thiopropionic acid may also be used. 20 Alkyl esters, in particular stearates and laurates. It is also possible to use dilauryl thiodipropionate (dilauryl thiodipropionate), distearyl thiodipropionate (distearyl thiodipropionate) or mixtures thereof.

[0307] Suitable matting agents include not only inorganic substances, such as talc, glass beads or metal carbonates (eg MgCO3, CaCO3), but also polymer particles, in particular with a diameter D 50 Spherical particles larger than 1 μm are based, for example, on methyl methacrylate, styrene compounds, acrylonitrile or mixtures thereof. Furthermore, it is also possible to use polymers which comprise copolymerized acidic and / or basic monomers.

[0308] Examples of suitable anti-drip agents include polytetrafluoroethylene (Teflon) polymers and ultra-high molecular weight polystyrene (weight average molar mass Mw greater than 2,000,000).

[0309] Examples of powdered fillers include carbon fibers or glass fibers in the form of glass fabrics, glass mats or glass yarn rovings, chopped glass, glass beads and wollastonite, with glass fibers being particularly preferred. When glass fibers are used, they may be treated with sizing agents and coupling agents to improve compatibility with the blending components. The added glass fibers may be short glass fibers or continuous filaments (rovings).

[0310] Examples of suitable particulate fillers include amorphous silica, magnesium carbonate, quartz powder, mica, bentonite, talc, feldspar, or in particular calcium silicates (eg wollastonite) and kaolin.

[0311] Suitable lubricants and release agents include stearic acid, stearyl alcohol, stearic acid esters, polyolefin waxes and / or generally higher fatty acids, derivatives thereof and corresponding fatty acid mixtures, the fatty acid mixtures comprising 1 to 45 carbon atoms. In another preferred embodiment, the composition includes an amide compound with formula R1-CONH-R2, wherein R1 and R2 are each independently selected from aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 30 carbon atoms, preferably 12 to 24 carbon atoms, particularly 16 to 20 carbon atoms. In another preferred embodiment of the present invention, the composition can also include a fatty acid ester compound with formula R3-CO-OR4, wherein R3 and R4 are each independently selected from aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 45 carbon atoms, preferably 15 to 40 carbon atoms, particularly 25 to 35 carbon atoms. Also particularly suitable is ethylenebis(stearamide).

[0312] In another preferred embodiment, the thermoplastic polymer composition P may contain organic, inorganic or mixed phosphates, in particular alkali metal or alkaline earth metal phosphates, such as Ca3(PO4)2 and / or organic phosphates of alkyl or aryl groups having 1 to 12 carbon atoms. These phosphates can conveniently be added in the form of a masterbatch, for example in combination with a polyolefin wax and / or an olefin / styrene copolymer.

[0313] In one embodiment of the present invention, the thermoplastic molding composition may contain phenolic antioxidants that do not meet the specifications of component E. Preferably, the amount of phenolic antioxidants other than component E is less than 0.5% by weight, more preferably less than 0.1% by weight, based on the molding composition P. In a preferred embodiment, the weight ratio of hindered phenolic antioxidants in component E to phenolic antioxidants other than component E is less than 1:1, more preferably less than 2:1. Suitable examples of phenolic antioxidants other than component E include 2,6-di-tert-butyl-p-cresol, TBK, commercially available from Raschig GmbH, Germany.

[0314] The molding composition P may also contain dyes, pigments or colorants as optional component G. Suitable dyes, pigments or colorants are any dyes, pigments or colorants which can be used for transparent, semi-transparent or opaque coloring of polymers, in particular dyes which are suitable for coloring styrene copolymers. Such dyes, pigments and colorants are known to those skilled in the art and include, for example, carbon black, titanium dioxide and mixed-phase metal oxide pigments.

[0315] Preparation of molding composition P

[0316] The method according to the invention may have any procedural steps suitable for carrying out the claimed method.

[0317] In a preferred embodiment, the step of compounding the components comprises at least the following steps:

[0318] (i) adding components A to C and E and / or F and optionally G in predetermined amounts to an optionally heatable mixing device; and

[0319] (ii) mixing components A to C and E and / or F and, if present, component G in the optionally heatable mixing apparatus at a temperature above the glass transition point of components A and B to obtain a molding composition P.

[0320] Optionally, step (ii) may be preceded by a step of preparing a homogeneous particulate material mixture from components A to G. However, when adding them to the optional heatable mixing device without prior mixing, homogeneous mixing can generally also be achieved in the optional heatable mixing device.

[0321] Each of components A to G (in terms of their solids) may be provided in the form of a particulate material having different particle sizes and particle size distributions (eg, pellets, granules and / or powders).

[0322] Components A to G may be added to the mixing device in the desired amounts and weight ratios as previously described and optionally mixed prior to mixing step (ii) to obtain a homogeneous mixture of particulate materials. In a preferred embodiment, this may take from 1 to 60 minutes, preferably from 1 to 20 minutes, especially from 2 to 10 minutes, depending on the amount of particulate material to be mixed.

[0323] The homogenous particulate material mixture thus obtained is transferred to an optionally heatable mixing device and mixed therein to produce a substantially liquid molten polymer mixture.

[0324] "Substantially liquid molten" means that the polymer mixture, in addition to the main liquid molten (softened) part, may also contain a certain proportion of solid components, such as unmelted fillers and reinforcing materials, such as glass fibers, metal flakes, or unmelted pigments, colorants, etc. "Liquid molten" means that the polymer mixture has at least low fluidity and is therefore at least softened to the extent of having plasticity.

[0325] The mixing apparatus used is known to the person skilled in the art. Components A to D and E and / or F and, if present, G, which must be isolated from the aqueous dispersion or the aqueous solution obtained in the polymerization, can be mixed, for example, by coextrusion, kneading or calendering.

[0326] Examples of mixing apparatus for carrying out the process include discontinuously operated heated internal kneading apparatuses with or without RAM, continuously operated kneaders (e.g. continuous internal kneaders), screw kneaders with axially vibrating screws, Banbury kneaders, in addition to extruders, and also roll mills, mixing roll mills with heated rolls and calenders.

[0327] The preferred mixing device used is an extruder or a kneader. Particularly suitable for melt extrusion are, for example, single-screw or twin-screw extruders. Twin-screw extruders are preferred. In some cases, the mechanical energy introduced by the mixing device during the mixing process is sufficient to melt the mixture, which means that the mixing device does not have to be heated. Otherwise, the mixing device usually needs to be heated.

[0328] The temperature depends on the chemical and physical properties of components A to G and should be selected to produce a substantially liquid molten polymer mixture. On the other hand, the temperature should not be too high to prevent thermal damage to the polymer mixture. However, the mechanical energy introduced may also be so high that the mixing device may even need to be cooled. The mixing device is usually operated at 150 to 400, preferably 170 to 300°C.

[0329] In a preferred embodiment, a heatable twin-screw extruder is used with a speed of 50 to 150 rpm, preferably 60 to 100 rpm. In a preferred embodiment, an extrusion temperature of 170 to 270° C., preferably 210 to 260° C., is used to obtain a molding composition P. The molding composition P can be used directly, for example, in a molding process, preferably an injection molding process, or can be processed into granules, which can then be subjected to a molding process. The molding process is preferably carried out at a temperature of 170 to 270° C., in particular 210 to 260° C., to produce a molded article.

[0330] The processing can be carried out by known thermoplastic processing methods, in particular by thermoforming, extrusion, injection molding, calendering, blow molding, compression molding, press sintering, deep drawing or sintering, preferably by injection molding.

[0331] application

[0332] The thermoplastic molding composition P can be used to produce molded articles for various purposes. In view of the increased weathering stability, it is particularly preferred for outdoor applications or applications exposed to ultraviolet radiation. The molded articles comprising the thermoplastic molding composition P can include, for example, components or articles of electronic devices, household items and exterior and / or interior automotive parts, in particular for the production of visible components or articles. Preferred applications are for exterior automotive parts, such as front grilles or side mirrors.

[0333] The invention will be further illustrated by examples and patent claims.

[0334] Example

[0335] 1. Example containing an ultraviolet absorber (component F)

[0336] Element

[0337] Component AB-1: A polymer mixture of the following ingredients:

[0338] 57% by weight of a styrene / acrylonitrile (SAN) copolymer, wherein the styrene / acrylonitrile weight ratio S / AN is 65 / 35 and the viscosity number VN is 80 (measured in 0.5% methyl ethyl ketone solution at 23° C.), as component A

[0339] 41% by weight of a unimodal ASA graft copolymer having a weight average particle size dw of 100 nm as component B, and

[0340] As component G, 2% by weight of additives (lubricants) were used.

[0341] Component AB-2: A polymer mixture of the following ingredients:

[0342] 57% by weight of a styrene / acrylonitrile (SAN) copolymer, wherein the styrene / acrylonitrile weight ratio S / AN is 65 / 35 and the viscosity number VN is 80 (measured in 0.5% methyl ethyl ketone solution at 23° C.), as component A

[0343] 41% by weight of a unimodal ASA graft copolymer having a weight average particle size dw of 400 nm as component B, and

[0344] As component G, 2% by weight of additives (lubricants) were used.

[0345] Component C-1: Bis(2,2,6,6-tetramethyl-4-piperidinyl)decanedioic acid (CAS No. 52829-07-9), hindered amine light stabilizer (HALS), commercially available 770, product of BASF SE, Germany.

[0346] Component D-1: Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3), a sterically hindered phenol antioxidant, commercially available 1076, product of BASF SE.

[0347] Component E-1: tris(4-nonylphenyl)phosphite (TNPP, CAS No. 3050-88-2), co-stabilizer.

[0348] Component E-2: tris(2,4-di-tert-butylphenol)phosphite (CAS No. 31570-04-4), stabilizer, commercially available 168, product of BASF SE.

[0349] Component F-1: 2-(2H-benzotriazol-2-yl)-4-methylphenol (CAS No. 2440-22-4), UV absorber, commercially available P, product of BASF SE, Germany.

[0350] Component G-1: 2,6-di-tert-butyl-p-cresol (CAS No. 128-37-0), commercially available TBK, product of Raschig GmbH, Germany.

[0351] preparation

[0352] The above ingredients were mixed at a temperature of 250° C. in a twin-screw extruder (model ZSK-30, produced by Coperion GmbH, Germany) according to the specific weight ratios given in Tables 1 and 2 to prepare a thermoplastic molding composition.

[0353] Several sets of samples were prepared by injection molding (temperature: 250°C).

[0354] Table 1. Examples 1 to 9 (Examples marked as Ref are comparative examples, not examples of the present invention)

[0355]

[0356] Table 2 gives further examples which differ from Examples 1 to 9 in particular in the graft copolymer compositions AB.

[0357] Table 2. Examples 10 to 12 (Examples marked as Ref are comparative examples, not examples of the present invention)

[0358] Element Example 10(Ref) Example 11 Example 12(Ref) AB-2 99.00 98.82 99.26 C-1 0.5 0.5 0.06 D-1 --- 0.06 0.06 E-1 --- 0.1 0.1 F-1 0.5 0.5 0.5 G-1 --- 0.02 0.02

[0359] Artificial weathering and testing

[0360] To measure the weathering resistance, the Xenotest 1200 weathering test was carried out according to ISO 4892 / 2 Method A (external) on the test specimens (prepared in a mold series according to ISO 294 at a melt temperature of 250° C.). After the weathering times specified in Tables 3 and 4, respectively, the impact strength of the unnotched test specimens was measured in a pendulum impact test according to ISO 180.

[0361] Table 3. Impact strength αn (unit: kJ / m2) of Examples 1 to 9 after artificial weathering (nb=no break; examples marked as Ref are not examples according to the present invention but are comparative examples)

[0362]

[0363] The data in Table 3 show that the compositions of the present invention exhibit improved mechanical stability after artificial weathering, as shown by a comparison of Examples 1 and 5. Particularly excellent results were obtained for compositions comprising HALS component C-1, an equivalent of 0.5 wt. % of UV absorber F-1, antioxidant D-1, and less than 0.5 wt. % of component G-1 (see Examples 2 and 5), which can be attributed to the synergistic effect of the combination of components C, D, and F.

[0364] 2. Embodiments containing stabilizer (E)

[0365] Starting from the above experimental data, further examples were carried out without UV absorber F and evaluated by the design of experiments (DoE) method with the help of a computer program.

[0366] Components

[0367] Component AB-3: A polymer mixture of the following components:

[0368] 54.8% by weight of a styrene / acrylonitrile (SAN) copolymer, wherein the styrene / acrylonitrile weight ratio S / AN is 65 / 35 and the viscosity number VN is 80 (measured in 0.5% methyl ethyl ketone solution at 23° C.), as component A

[0369] 39.7 wt. % of a unimodal ASA graft copolymer as component B, and

[0370] 5.5% by weight of additives (pigments, plasticizers, release agents) as component G.

[0371] Component AB-4: A polymer mixture of the following components:

[0372] 33.5% by weight of a styrene / acrylonitrile (SAN) copolymer, wherein the styrene / acrylonitrile weight ratio S / AN is 65 / 35 and the viscosity number VN is 80 (measured in 0.5% methyl ethyl ketone solution at 23° C.), as component A,

[0373] 4.6 wt. % of a styrene / acrylonitrile (SAN) copolymer, wherein the styrene / acrylonitrile weight ratio S / AN is 76 / 24 and the viscosity number VN is 64 (measured in 0.5 % methyl ethyl ketone solution at 23° C.), as component A,

[0374] 27.2% by weight of α-methylstyrene / acrylonitrile (AMSAN) copolymer as component A,

[0375] 32.4 wt% of a bimodal ASA graft copolymer as B component, and

[0376] 2.3 wt. % additives (pigments, plasticizers, mold release agents) as G component.

[0377] Component C-1: Bis(2,2,6,6-tetramethyl-4-piperidinyl)decanedioic acid (CAS No. 52829-07-9), hindered amine light stabilizer (HALS), commercially available product 770, purchased from BASF SE, Germany.

[0378] Component C-2: poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) (CAS No. 71878-19-8, 70624-18-9 (USA)), HALS is a commercially available product 944, purchased from BASF SE, Germany.

[0379] Component C-3: 2,2,6,6-tetramethyl-4-piperidinyl stearate (CAS No. 167078-06-0), HALS is a commercially available product 3853, purchased from Solvay, Belgium.

[0380] Component C-4: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No. 41556-26-7 or 82919-37-7), hindered amine light stabilizer (HALS) is a commercially available product UV-292 was purchased from Li'anlong Company, China.

[0381] Component D-2: Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (CAS No. 2082-79-3), antioxidant, product name 1010, purchased from Li’anlong Company, China.

[0382] Component D-3: Ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (CAS No. 36443-68-2), antioxidant, product name 245, purchased from Li’anlong Company, China.

[0383] Component D-4: 2,4-bis[(dodecylthio)methyl]-6-methylphenol (CAS No. 110675-26-8), an antioxidant, product name 1726, purchased from Li’anlong Company, China.

[0384] Component E-2: tris(2,4-di-tert-butylphenol)phosphite (CAS No. 31570-04-4), stabilizer, product name 168, purchased from BASF SE, Germany.

[0385] Component E-3: 2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]propane-1,3-diylbis[3-(dodecylthio)propionate] (CAS No. 29598-76-3), co-stabilizer, trade name 412S, purchased from Li’anlong Company, China.

[0386] preparation

[0387] The thermoplastic molding compositions were prepared by mixing in a twin-screw extruder (model ZSK-30, Coperion GmbH, Germany) at Tm=250°C according to the specific weight ratios given in Table 4. Several groups of sample rod-shaped plaques were prepared by injection molding (Tm: 250°C).

[0388] Artificial weathering and testing

[0389] Weathering test is based on The Kalahari test of standard PV3929 is a test performed by artificial weathering of the test specimens. After weathering, the color shift dE of the test specimens is evaluated. The initial color and the residual color after artificial weathering are determined by color measurement according to DIN 6174. The test results are summarized in Table 4.

[0390] Furthermore, the test samples were visually evaluated after weathering, and the evaluation method was as follows:

[0391]

[0392] The test results are summarized in Table 4.

[0393] Table 4. Compositions of Examples 13 to 63 and Comparative Examples 1 and 2; Results of weathering experiments (nd = not determined).

[0394]

[0395] Table 4 (continued)

[0396]

[0397] The experimental results summarized in Table 4 were further evaluated using a computer program and the following combination was determined to be the preferred formulation:

[0398] sample C-1 C-2 C-3 C-4 D-3 D-4 E-2 Recipe 1 0.75 0.15 --- 0.3 --- 0.15 1.9 Recipe 2 --- --- --- 0.4 --- 0.4 0.75 Recipe 3 0.02 0.01 --- --- 0.15 --- 2 Recipe 4 0.02 --- 0.15 --- --- 0.1 0.1 Recipe 5 1 --- --- 1 --- 0.1 0.1

Claims

1. A thermoplastic molding composition P, comprising: AB: 83 to 99.93% by weight, based on the molding composition P, of at least one graft copolymer composition AB consisting of: A: Based on composition AB, 30 to 80% by weight of at least one thermoplastic copolymer A, which is made from the following ingredients: A1: 50 to 95% by weight of monomer A1, based on copolymer A, wherein the monomer A1 is selected from styrene, α-methylstyrene, and a mixture of styrene and at least one other monomer selected from α-methylstyrene, p-methylstyrene and C1-C8 alkyl (meth) acrylate; A2: 5 to 50% by weight of a monomer A2, based on the copolymer A, wherein the monomer A2 is selected from acrylonitrile and a mixture of acrylonitrile and at least one other monomer, wherein the other monomer is selected from methacrylonitrile, acrylamide, vinyl methyl ether, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids; B: 20 ​​to 70% by weight, based on composition AB, of at least one graft copolymer B comprising: B1: Based on the graft copolymer B, 50 to 90% by weight of at least one graft base B1 obtained by emulsion polymerization of: B11: 70 to 99.9% by weight, based on the graft base B1, of at least one C1-C8 alkyl (meth)acrylate as monomer B11; B12: 0.1 to 10% by weight, based on the graft base B1, of at least one polyfunctional crosslinking monomer B12; B13: 0 to 29.5% by weight, based on the graft base B1, of at least one other copolymerizable monomer B13; wherein the total weight of B11+B12+B13 accounts for 100% of the at least one grafted base B1; and B2: 10 to 50% by weight, based on the graft copolymer B, of at least one graft shell B2, which is obtained by emulsion polymerization in the presence of at least one graft base B1 and has the following composition: B21: 50 to 100% by weight of a monomer B21, based on the graft shell B2, selected from styrene, α-methylstyrene and a mixture of styrene with at least one further monomer selected from α-methylstyrene, p-methylstyrene and C1-C4 alkyl (meth)acrylates B22: 0 to 50% by weight of a monomer B22, based on the graft shell B2, selected from acrylonitrile and a mixture of acrylonitrile with at least one other monomer selected from methacrylonitrile, acrylonitrile, Amines, vinyl methyl ethers, anhydrides of unsaturated carboxylic acids and imides of unsaturated carboxylic acids; B23: 0 to 20%, based on the graft shell B2, of at least one further copolymerizable monomer B23; wherein the total weight of B21+B22+B23 accounts for 100% of the at least one graft shell B2; wherein the total weight of the graft base B1 and the graft shell B2 accounts for 100% of the at least one graft copolymer B; C: as component C, 0.01 to 2.5% by weight, based on the molding composition P, of at least one hindered amine light stabilizer; D: 0.01 to 1.0% by weight, based on the molding composition P, of at least one antioxidant as component D, selected from the group consisting of sterically hindered phenolic antioxidants of the general formula (I) and mixtures thereof: in R1 to R5 each independently represent a hydrogen atom or an alkyl group having 1 to 70 carbon atoms, wherein the hydrocarbon group optionally contains at least one heteroatom selected from O and S, and wherein at least one of the substituents R1 and R5 is a hydrocarbon group having at least 3 carbon atoms; E: 0 to 2.5% by weight, based on the molding composition P, of at least one stabilizer E, selected from phosphorus- or sulfur-containing stabilizers; F: 0 to 3% by weight, based on the molding composition P, of at least one UV absorber as component F; and G: 0 to 8% by weight of at least one further additive as component G, based on the molding composition P; wherein components A to G account for 100% by weight of the molding composition P, and At least one of components E and F is present in an amount of at least 0.05% by weight, based on the molding composition P.

2. The thermoplastic molding composition P according to claim 1, wherein the thermoplastic molding composition P comprises at least one hindered amine light stabilizer component C selected from the group consisting of compounds of the following formula (Ia): in R1 each independently represents -H or -CH3; and n represents an integer from 1 to 8; and mixtures thereof.

3. Thermoplastic molding composition P according to claim 1 or 2, wherein the thermoplastic molding composition P comprises at least one hindered amine light stabilizer component C-1 selected from compounds having the following formula (Ia): in R1 each independently represents -H or -CH3; and n represents an integer from 1 to 8; and mixtures thereof, and At least one additional hindered amine light stabilizer component C-2 that is different from the hindered amine light stabilizer component C-1.

4. Thermoplastic molding composition P according to claim 3, wherein the hindered amine light stabilizer component C-2 is selected from sterically hindered monopiperidine derivatives with a molecular weight of 400 to 600 g / mol and sterically hindered piperidine derivatives with a molecular weight> 600 g / mol and mixtures thereof.

5. Thermoplastic molding composition P according to any one of claims 1 to 4, wherein the antioxidant as component D comprises (or consists of) sterically hindered phenolic antioxidants of the general formula (Ia) and mixtures thereof: in R3 represents a hydrocarbon group having 5 to 70 carbon atoms, wherein the hydrocarbon group preferably contains at least one heteroatom selected from O and S; and R2, R4 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and wherein at least one of the substituents R2, R4 and R5 is not hydrogen.

6. Thermoplastic molding composition P according to any one of claims 1 to 5, wherein the antioxidant as component D comprises (or consists of) sterically hindered phenolic antioxidants of the general formula (Ib) and mixtures thereof: in R1, R2 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and wherein at least one of the substituents R2, R4 and R5 is not hydrogen; and R6 and R7 each independently represent an alkyl group having 1 to 20 carbon atoms, preferably 8 to 16 carbon atoms.

7. Thermoplastic molding composition P according to any one of claims 1 to 6, wherein the phosphorus- or sulfur-containing costabilizer (E) comprises (or consists of) a phosphite component of the general formula (III): Wherein R1 to R3 each independently represent an aryl group, which may optionally be substituted by a hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. In a preferred embodiment, R1, R2 and R3 each represent a phenyl group having 1 to 3 alkyl groups having 3 to 10 carbon atoms as substituents.

8. Thermoplastic molding composition P according to any one of claims 1 to 7, wherein the phosphorus- or sulfur-containing costabilizer (E) comprises (or consists of) a thiodicarboxylic acid of the general formula (IV): in R1 is independently selected from hydrocarbon radicals having 1 to 30 carbon atoms, preferably linear hydrocarbon radicals having 5 to 20 carbon atoms, and optionally containing oxygen atoms, in particular in the form of a carboxyl function, R2 is independently selected from a hydrocarbon group having 1 to 30 carbon atoms, preferably a straight chain hydrocarbon group having 10 to 20 carbon atoms, and m independently represents an integer of 1 to 8, preferably 2 to 4, especially 2.

9. The thermoplastic molding composition P according to any one of claims 1 to 8, wherein the ultraviolet absorber component F comprises (or consists of) a benzotriazole moiety represented by the following formula (V): in R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 5 carbon atoms.

10. The thermoplastic molding composition P according to any one of claims 1 to 9, comprising as component D at least one antioxidant, which comprises (or consists of) a sterically hindered phenolic antioxidant of the general formula (Ib), and at least one stabilizer as component E, which comprises (or consists of) a phosphite component of the general formula (IV).

11. The thermoplastic molding composition P according to any one of claims 1 to 10, comprising as component D at least one antioxidant, which comprises (or consists of) a sterically hindered phenolic antioxidant of the general formula (Ia), and at least one stabilizer as component E, which comprises (or consists of) a phosphite component of the general formula (IV).

12. Thermoplastic molding composition P according to any one of claims 4 to 11, comprising at least two hindered amine light stabilizer components C-1 selected from compounds having the following formula (Ia): in R1 each independently represents -H or -CH3; and n represents an integer from 1 to 8; and mixtures thereof.

13. Thermoplastic molding composition P according to any one of claims 1 to 12, wherein at least one graft copolymer composition AB consists of: A: 30 to 80 wt % of at least one thermoplastic copolymer selected from poly(styrene-acrylonitrile) (SAN), poly(α-methylstyrene / acrylonitrile) (AMSAN) and mixtures thereof, as component A, based on the graft copolymer composition AB; and B: 20 ​​to 70% by weight, based on the graft copolymer composition AB, of at least one graft copolymer B comprising: B1: 50 to 90% by weight, based on the graft copolymer B, of at least one graft base B1 obtained by emulsion polymerization of: B11: 70 to 99.9% by weight of n-butyl acrylate, based on the graft base B1, as monomer B11; B12: 0.1 to 10% by weight, based on the graft base B1, of at least one multifunctional crosslinking monomer B12; selected from allyl (meth) acrylate and / or dihydrodicyclopentadienyl acrylate (DCPA); wherein the sum of B11 and B12 is equal to 100 weight % of B1; and B2: 10 to 50% by weight, based on the graft copolymer B, of at least one graft shell B2, obtainable by emulsion polymerization in the presence of at least one graft base B1: B21: 50 to 95% by weight of monomer B21, based on the graft shell B2, styrene; and B22: 5 to 50% by weight, based on the graft shell B2, of at least one monomer B22 selected from acrylonitrile or a mixture of acrylonitrile with at least one further monomer selected from methacrylonitrile; wherein the sum of the graft base B1 and the graft shell B2 is equal to 100% by weight of the graft copolymer B, and Wherein, at least one graft copolymer B has a weight average particle size dw of 50 to 1000 nm.

14. Use of a thermoplastic molding composition P according to any one of claims 1 to 13 for producing molded articles.

15. Moulded article comprising the thermoplastic moulding composition P according to any one of claims 1 to 13.

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