Plastics composition

Abstract

The present invention relates to a plastics composition comprising 5 to 50 wt.% of at least one first thermoplastic styrene-butadiene copolymer, 5 to 25 wt.% of at least one amorphous plastic, 5 to 30 wt.% of at least one polyolefin and 4 to 30 wt.% of at least one thermoplastic elastomer, and to a molded product, in particular a children's toy, which consists of or comprises the plastics composition.

Description

[0001] Plastic composition

[0002] The present invention relates to a plastic composition and a shaped article, in particular a children's toy, comprising this plastic composition.

[0003] Plastic compositions are versatile and can contain a variety of different substances that influence the physical and chemical properties of the plastic composition. Depending on the application, the plastic composition must meet different basic requirements.

[0004] Due to their adjustable plastic deformability and hardness, plastic compositions are often used to form the basis for molded articles, especially children's toys.

[0005] The plastic compositions known from the prior art for the production of molded articles usually contain halogen-containing polymers, such as polyvinyl chloride, since these are readily and inexpensively available and advantageous physical properties can be easily achieved.

[0006] However, such plastic compositions known from the prior art are disadvantageous because the halogen-containing polymers they contain can be harmful to humans and the environment. The use of halogen-containing polymers can be particularly disadvantageous when using plastic compositions in molded articles, especially children's toys, since the requirements for the compatibility of children's toys are particularly high.

[0007] In addition, some plastic compositions known from the state of the art are easily breakable or provide no indication before breakage, so that mechanical overload is not detectable before the molded body breaks. Therefore, the molded body can break without warning, forming sharp edges and small parts that can be swallowed.

[0008] Demoulding of known plastic compositions during injection moulding can also be difficult in some cases.

[0009] Furthermore, the molded bodies, comprising the plastic compositions known from the prior art, are often not colorable or paintable with water-based paints or varnishes.

[0010] Some of the plastic compositions do not have good resilience, which means that these molded bodies do not return to their original position quickly and / or completely when deformed.

[0011] The object of the present invention is therefore to eliminate the above-mentioned disadvantages of the prior art. In particular, the object of the present invention is to provide a plastic composition which is compatible with humans and the environment. Furthermore, the components of the plastic composition should be inexpensive and easy to obtain and the plastic composition should meet the basic physical and chemical requirements, particularly with regard to hardness and fragility, for molded articles, in particular children's toys. The plastic composition should also have good resilience. After deformation has occurred, the molded part should return to its original position as quickly and completely as possible. In addition, the plastic composition should make it possible to provide molded articles whose surfaces are smooth and can be colored or painted with water-based paints or varnishes.can be painted. Good demolding of the plastic composition during the injection molding process should be possible.

[0012] The above object is achieved by a plastic composition according to claim 1, ie by a plastic composition comprising 5 to 50 wt.% of at least one first thermoplastic styrene-butadiene copolymer, 5 to 25 wt.% of at least one amorphous plastic, 5 to 30 wt.% of at least one polyolefin and 4 to 30 wt.% of at least one thermoplastic elastomer.

[0013] Such a plastic composition is particularly distinguished by the fact that it essentially eliminates halogen-containing polymers, making it safe for humans and the environment, while its components are still inexpensive and readily available. Furthermore, such a plastic composition meets the basic requirements regarding hardness and brittleness, as the plastic composition is white-refracting, allowing potential mechanical overloads to be detected before a potential fracture occurs. Furthermore, the plastic composition exhibits good demolding during the injection molding process, which is caused by high shrinkage.

[0014] Furthermore, molded bodies made from the plastic composition can be colored or painted with water-based paints or varnishes. The plastic composition also exhibits good recovery properties, allowing any deformation of a molded body made from it to return to its original position as quickly and completely as possible.

[0015] Advantageous further developments are described in the subclaims.

[0016] Numerous specific details are discussed below to provide a thorough understanding of the subject matter. However, it will be apparent to one skilled in the art that the subject matter can be practiced and recreated without these specific details.

[0017] All features of one embodiment may be combined with features of another embodiment if the features of the different embodiments are compatible.

[0018] The terminology used in the description of the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the subject matter. As used in this description and the claims, the singular forms "a," "an," and "the" are intended to include the plural forms, unless the context clearly dictates otherwise. The reverse is also true, meaning that the plural forms are intended to include the singular forms. It is also understood that the term "and / or," as used herein, refers to and includes all possible combinations of one or more of the related listed elements.It is further understood that the terms "includes," "including," "comprises," and / or "comprising," when used in the present description and claims, specify the presence of the stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0019] In the present description and claims, the terms "includes", "comprises" and / or "comprising" may also mean "consisting of", that is, the presence or addition of one or more other features, steps, operations, elements, components and / or groups is excluded.

[0020] For the purposes of the invention, the quantity % by weight refers (unless otherwise stated) to the proportion of the respective component based on the total weight of the plastic composition.

[0021] The plastic composition according to the invention comprises 5 to 50 wt.%, preferably 10 to 45 wt.%, particularly preferably 15 to 45 wt.%, in particular 20 to 36 wt.%, of at least one thermoplastic styrene-butadiene copolymer.

[0022] Thermoplastic polymers are known to those skilled in the art as polymers that can be permanently deformed within a certain temperature range.

[0023] The copolymer can be a random copolymer, alternating copolymer, block copolymer, graft copolymer, or a mixture of the above-mentioned copolymers. Random copolymers, alternating copolymers, block copolymers, and graft copolymers are known to those skilled in the art.

[0024] Particular preference is given to multiblock copolymers in which at least one of the blocks is polystyrene. At least one of the other blocks is typically a polybutadiene, polyisoprene, or polyisobutene. The copolymer can be a triblock copolymer of the ABA structure, in which the A block is typically polystyrene and the B block is typically composed of polybutadiene, polyisoprene, or polyisobutene (SBS, SIS, SiBS). Alternatively, the styrene monomers in the A block can be partially or completely replaced by styrene derivatives, such as o-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, or vinylnaphthalene, such as 1-vinylnaphthalene and 2-vinylnaphthalene. The B block can also alternatively contain mixtures of dienes, such as SIBS (B block consisting of a mixture of butadiene and isoprene). Furthermore, the copolymer consisting of styrene and diene monomers can also be used as a hydrogenated derivative.The units of the B blocks can be partially or fully hydrogenated. Preferred copolymers are polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), polystyrene-block-poly(ethylene-co-propylene)-block-polystyrene (SEPS), and polystyrene-block-poly(ethylene-co-(ethylene-propylene))-block-polystyrene (SEEPS). In addition to triblock copolymers, diblock, tetrablock, or multiblock copolymers made from the aforementioned monomers of styrene, styrene derivatives (A blocks) and butadiene, isoprene, isobutylene, and their mixtures (B blocks) in various sequences of A and B blocks (e.g., BAB, ABA-B, etc.) can also be used.

[0025] Suitable commercially available thermoplastic styrene-butadiene copolymers are available, for example, under the trade names of the manufacturers and product series Dynasol - Calprene®, Kraton - Kraton®, and LCY - Globalprene®. For example, thermoplastic styrene-butadiene copolymer is commercially available as the commercial product Calprene 719 of the Calprene® product series.

[0026] The plastic composition according to the invention comprises 5 to 25 wt.%, preferably 9 to 23 wt.%, or 9 to 22 wt.%, more preferably 7 to 20 wt.% and even more preferably 10 to 20 wt.%, of at least one amorphous plastic.

[0027] Suitable amorphous plastics are preferably essentially all polymers, in particular halogen-free polymers, which are known to the person skilled in the art for the production of plastic compositions.

[0028] Polystyrene, polymethyl methacrylate, styrene-acrylonitrile and acrylonitrile-butadiene-styrene are particularly preferred.

[0029] Amorphous plastics, within the meaning of the invention, are defined as plastics with a degree of crystallization of 0 to 3%. The degree of crystallization is measured according to DIN EN ISO 11357 (2023). The plastic composition according to the invention comprises 5 to 30 wt. %, preferably 5 to 20 wt. %, more preferably 5 to 16 wt. %, and even more preferably 5 to 15 wt. %, of at least one polyolefin.

[0030] Polyolefins are saturated hydrocarbons that are usually produced from alkenes such as ethylene, propylene, 1-butene or isobutene by chain polymerization.

[0031] The polyolefins are preferably homopolymers, random copolymers, but also block copolymers, such as thermoplastic elastomers based on polyolefin block copolymers (TPO), with homopolymers or random copolymers being preferred, which are preferably prepared from alkenes, which are preferably aliphatic alkenes.

[0032] Particularly preferred are non-elastomeric polyolefins, i.e., those that do not exhibit elastomeric properties. Polyolefin thermoplastics are more preferred.

[0033] Polyolefins can, for example, be homopolymers or random copolymers of olefins. Examples include: copolymers of polyethylene, such as HDPE (high-density polyethylene), MDPE (medium-density polyethylene), LDPE (low-density polyethylene), LLDPE (linear low-density polyethylene), VLDPE (very low-density polyethylene); a homopolymer of propylene (hPP); a random copolymer of propylene and ethylene (rPP); and combinations of the same. Homopolymers of propylene (hPP) are commercially available, and any of these available hPPs can be used according to the invention.

[0034] The plastic composition according to the invention is preferably characterized in that the at least one polyolefin comprises at least one polyethylene, preferably a high-density polyethylene, a low-density polyethylene, and / or a linear low-density polyethylene. High-density polyethylene, also known as HDPE, typically has a density of 930 to 970 kg / m3 , measured according to ISO 1183-2 (2019).

[0035] Low-density polyethylene, also known as LDPE, typically has a density of 917 to 930 kg / m 3 , measured according to ISO 1183-2 (2019).

[0036] Linear low-density polyethylene, also known as LLDPE, typically differs from LDPE in that LLDPE is less branched than LDPE.

[0037] An embodiment comprising polyethylene as polyolefin is preferred.

[0038] Preferred is an embodiment which comprises high-density polyethylene as polyolefin.

[0039] HDPEs are commercially available under the trade names of manufacturers and product series DOW - DOW™, ORLEN Unipetrol - LITEN®, SABIC - SABIC®, and LyondellBasell - Hostalen®. For example, HDPE is commercially available as Sabic HDPE CC 2056 from the SABIC® product series.

[0040] The plastic composition according to the invention comprises 4 to 30 wt.%, preferably 5 to 30 wt.%, preferably 7 to 20 wt.%, more preferably 7 to 15 wt.%, or 4 to 12 wt.%, of at least one thermoplastic elastomer.

[0041] Elastomers are known to those skilled in the art as polymers that are dimensionally stable but elastically deformable, with a glass transition temperature below room temperature.

[0042] Suitable thermoplastic elastomers are essentially all halogen-free elastomers known to those skilled in the art for the production of plastic compositions. Particular preference is given to copolyester-based (TPC) or polyurethane-based (TPU) thermoplastic elastomers.

[0043] Thermoplastic copolyesters (TPCs) are generally copolyesters in the form of copolymers that have monomer units in the polymer main chain that are linked via ester groups (-C(=O)-O-). Such thermoplastic copolyester elastomers can be produced by polycondensation. Such copolyesters are preferably multiblock copolyesters, which generally have crystalline segments of hard blocks (X) and amorphous segments of soft blocks (Y). Suitable monomer components for constructing hard blocks (X) and soft blocks (Y) in multiblock copolyesters are known to those skilled in the art.

[0044] Preferred TPCs of the present invention are linear multiblock polyesters with a random distribution of high-melting, hard polyester blocks and low-melting, soft polyester blocks. The hard blocks form crystalline regions, while the soft blocks form amorphous regions, which result in elastic behavior at the application temperatures of the TPC.

[0045] Suitable TPCs are commercially available under the trade names of the manufacturers and product series TICONA - Riteflex®, P. GROUP - PIBIFLEX®, DSM - Arnitel®, Kolon - KOPEL-PEL®, PTS - Uniflex®, Ria-Polymers - Riaflex®, LG Chem - KEYFLEX®, and DuPont - Hytrel®. For example, TPC is commercially available as Arnitel EL 630-08 from the Arnitel® product series.

[0046] Thermoplastic polyurethane elastomers (TPUs) are generally polyurethanes in the form of copolymers, which have monomer units in the polymer main chain linked via urethane groups (-NH-(C=O)-O-). Such thermoplastic polyurethane elastomers can be produced by polyaddition. Such polyurethane elastomers are preferably multiblock polymers, which generally have crystalline segments of hard blocks (X) and amorphous segments of soft blocks (Y). Suitable monomer components for constructing hard blocks (X) and soft blocks (Y) in multiblock polyurethanes are known to those skilled in the art. Suitable TPUs are commercially available, for example, under the trade names of the manufacturers and product series BASF - Elastollan®, Covestro - Desmopan®, Hunstman - AVALON®, Lubrizol - Estane®. For example, TPU is commercially available as the commercial product Elastollan 1160 D 50 000 of the Elastollan® product series.

[0047] The plastic composition according to the invention is preferably characterized in that the amorphous plastic comprises polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer and / or styrene-methyl(meth)acrylate copolymer.

[0048] The copolymers mentioned may be random copolymers, alternating copolymers, block copolymers, graft copolymers or a mixture of the above-mentioned copolymers.

[0049] An embodiment comprising polystyrene as an amorphous plastic is preferred.

[0050] Polystyrene, for example, is available under the name “Polystyrene Crystal 1810”.

[0051] The plastic composition according to the invention is preferably characterized in that the at least one thermoplastic elastomer comprises a thermoplastic polyester elastomer and / or a thermoplastic polyurethane elastomer, more preferably a thermoplastic polyester elastomer.

[0052] Preferred is an embodiment which comprises polyester elastomer (TPC) as thermoplastic elastomer.

[0053] Preferred TPCs of the present invention are linear multiblock polyesters with a random distribution of high-melting, hard polyester blocks and low-melting, soft polyester blocks. The hard blocks form crystalline regions, while the soft blocks form amorphous regions, which result in elastic behavior at the application temperatures of the TPC. The hard polyester blocks are preferably composed of short-chain dicarboxylic acids with fewer than 4 carbon atoms or aromatic dicarboxylic acids or mixtures of dicarboxylic acids. Aromatic dicarboxylic acids are preferred, particularly preferably isophthalic acid or terephthalic acid. The alcohol component is preferably also difunctional and consists of short-chain alkyldiols or short-chain polyoxyalkylenediols with fewer than 3 repeating units or mixtures of different diols.Short-chain diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferred, with 1,4-butanediol being particularly preferred. The soft polyester blocks preferably consist of aliphatic or aromatic dicarboxylic acids, preferably aromatic dicarboxylic acids, and most preferably isophthalic acid or terephthalic acid. To create soft regions in the TPC, different types of diols can be used: polyether diols such as polyethylene glycols, polypropylene glycols, polyethylene-copropylene glycols, polytetramethylene glycols, or soft polyester diols composed of alkanedicarboxylic acids, for example, adipic acid or sebacic acid, and alkanediols, or polycaprolactone diols or aliphatic polycarbonate diols.

[0054] The plastic composition according to the invention is preferably characterized in that the plastic composition further comprises at least one thermoplastic styrene block copolymer.

[0055] The plastic composition preferably comprises at least one thermoplastic styrene block copolymer in an amount of greater than 0 wt.% and / or at most 10 wt.%, more preferably in an amount of greater than 0 to 10 wt.%, even more preferably in an amount of 2 to 10 wt.%.

[0056] In another preferred embodiment, the plastic composition comprises at least one thermoplastic styrene block copolymer in an amount of greater than 0 to 13 wt.%, or greater than 0 to 8 wt.%, more preferably 6 to 13 wt.%. Preferably, the at least one thermoplastic styrene block copolymer comprises a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, and / or a styrene-ethylene-ethylene-propylene-styrene block copolymer.

[0057] Preferred is an embodiment which comprises styrene-ethylene-butylene triblock copolymer as thermoplastic styrene block copolymer.

[0058] Preferably, the at least one thermoplastic styrene block copolymer has been modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%.

[0059] More preferably, the at least one thermoplastic styrene block copolymer comprises a styrene-ethylene-butylene triblock copolymer which has been modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%.

[0060] A styrene-ethylene-butylene triblock copolymer modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, is available, for example, under the name "Kraton FG 1901 GT".

[0061] The plastic composition according to the invention is preferably characterized in that the plastic composition is substantially free of halogen-containing polymers, such as polyvinyl chloride.

[0062] The term "essentially free of halogen-containing polymers" in the sense of the invention refers to a plastic composition whose proportion of halogen-containing polymers is in a range from 0 to 2 wt.%, preferably from 0 to 1 wt.% and in particular from 0 to 0.5 wt.%.

[0063] Preferably, the plastic composition contains no halogen-containing polymers, such as polyvinyl chloride, except for unavoidable impurities. In particular, the plastic composition is free of halogen-containing polymers, such as polyvinyl chloride.

[0064] The plastic composition according to the invention is preferably characterized in that the plastic composition additionally comprises at least one additive, wherein the at least one additive is more preferably selected from a group consisting of fillers, antioxidants e.g. pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (e.g. Irganox® 1010), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g. Irganox® 1076) stabilizers e.g. 2-[4,6-bis(2,4-dimethylphenyl)-l,3,5-triazin-2-yl]-5-(octyloxy)phenol (e.g. Tinuvin® 1400), poly-(4-hydroxy-2,2,6,6-tetramethyl-l-piperidineethanol-alt-succinic acid) (e.g. Tinuvin® 622 SF) and / or oil, especially white oil.

[0065] As stated above, the plastic composition is preferably free of halogen-containing polymers. However, this "halogen-free" nature does not apply to the additives, so halogen-containing additives, as long as they are not polymers, may contain halogens.

[0066] In particular, the plastic composition additionally comprises at least one filler.

[0067] Preferably, the filler is selected from CaCO3 and / or BaSO4, preferably from CaCO3.

[0068] In particular, the plastic composition additionally comprises at least one filler selected from CaCO3 and / or BaSO4, preferably from CaCO3, in an amount of 20 to 35 wt.%, preferably 22 to 30 wt.%.

[0069] In another preferred embodiment, the plastic composition additionally comprises at least one filler in an amount of 15 to 40 wt.%, in particular 17 to 35 wt. In particular, the plastic composition additionally comprises CaCCh as a filler in an amount of 15 to 40 wt.%, in particular 17 to 35 wt.

[0070] In particular, the plastic composition additionally comprises BaSC as filler in an amount of 15 to 40 wt.%, in particular 17 to 35 wt.%.

[0071] CaCOs, for example, is available under the name "Omyacarb 1 T-AV".

[0072] In particular, the plastic composition additionally comprises at least one white oil in an amount of 0 to 15 wt.%, preferably greater than 0 to 15 wt.%, preferably 0 to 7.5 wt.%, in particular greater than 0 to 7.5 wt.%, or 1 to 10 wt.%.

[0073] White oil, for example, is available under the name “Pionier 2071 EE”.

[0074] The plastic composition according to the invention is preferably characterized in that the plastic composition has a tensile strength of 10 MPa to 30 MPa, preferably of 13 MPa to 25 MPa, wherein the tensile strength is determined according to DIN 53504 (2017).

[0075] A test specimen shape S2 according to DIN 53504 (2017) is used. The test specimens are punched out perpendicular to the melt flow direction using a punching knife.

[0076] The plastic composition according to the invention is preferably characterized in that the plastic composition has a hardness [Shore D] of 30 to 60, preferably of 35 to 50, wherein the hardness [Shore D] is determined according to ISO 868 (2003).

[0077] The test duration is 3 seconds. The plastic composition according to the invention is preferably characterized in that the plastic composition has an elongation at break of 400 to 700%, preferably 450 to 700%, more preferably 550 to 650%, wherein the elongation at break is determined according to DIN 53504 (2017).

[0078] A test specimen shape S2 according to DIN 53504 (2017) is used. The test specimens are punched out perpendicular to the melt flow direction using a punching knife.

[0079] In particular, the present invention relates to a plastic composition comprising

[0080] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0081] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0082] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene and

[0083] 5 to 30 wt.%, preferably 7 to 20 wt.%, of at least one thermoplastic polyester.

[0084] In particular, the present invention relates to a plastic composition comprising

[0085] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0086] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0087] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene and

[0088] 4 to 30 wt.%, preferably 4 to 12 wt.%, or 7 to 15 wt.%, of at least one thermoplastic elastomer.

[0089] In particular, the present invention relates to a plastic composition comprising 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0090] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0091] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0092] 5 to 30 wt.%, preferably 7 to 20 wt.%, of at least one thermoplastic polyester and at least one filler selected from CaCO3 and / or BaSO4, preferably from CaCO3, in an amount of 20 to 35 wt.%, preferably 22 to 30 wt.%.

[0093] In particular, the present invention relates to a plastic composition comprising

[0094] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0095] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0096] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0097] 5 to 30 wt.%, preferably 7 to 20 wt.%, of at least one thermoplastic polyester and at least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40 wt.%, preferably 17 to 35 wt.%.

[0098] In particular, the present invention relates to a plastic composition comprising

[0099] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0100] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0101] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0102] 4 to 30 wt.%, preferably 4 to 12 wt.%, or 7 to 15 wt.%, of at least one thermoplastic polyester and at least one filler, in particular CaCCh and / or BaSC, preferably CaCCh, in an amount of 15 to 40 wt.%, preferably 17 to 35 wt.%.

[0103] In particular, the present invention relates to a plastic composition comprising

[0104] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0105] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0106] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0107] 5 to 30% by weight, preferably 7 to 20% by weight, of at least one thermoplastic polyester,

[0108] 2 to 10 wt.% of a styrene-ethylene-butylene triblock copolymer modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, and at least one filler selected from CaCO3 and / or BaSO4, preferably from CaCO3, in an amount of 20 to 35 wt.%, preferably 22 to 30 wt.%.

[0109] In particular, the present invention relates to a plastic composition comprising

[0110] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0111] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0112] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0113] 5 to 30% by weight, preferably 7 to 20% by weight, of at least one thermoplastic polyester,

[0114] 2 to 10 wt.% of a styrene-ethylene-butylene triblock copolymer modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, and at least one filler, in particular CaCCh and / or BaSC, preferably CaCCh, in an amount of 15 to 40 wt.%, preferably 17 to 35 wt.%.

[0115] In particular, the present invention relates to a plastic composition comprising

[0116] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0117] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0118] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0119] 4 to 30 wt.%, preferably 4 to 12 wt.%, or 7 to 15 wt.%, of at least one thermoplastic polyester,

[0120] 2 to 10 wt.% of a styrene-ethylene-butylene triblock copolymer modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, and at least one filler, in particular CaCCh and / or BaSC, preferably CaCCh, in an amount of 15 to 40 wt.%, preferably 17 to 35 wt.%.

[0121] In particular, the present invention relates to a plastic composition comprising

[0122] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0123] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0124] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0125] 4 to 30% by weight, preferably 7 to 20% by weight, of at least one thermoplastic polyester, greater than 0 to 13% by weight, preferably 6 to 13% by weight, of a styrene-ethylene-butylene triblock copolymer which has been modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, and at least one filler, in particular CaCCh and / or BaSC, preferably CaCCh, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0126] In particular, the present invention relates to a plastic composition comprising

[0127] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer,

[0128] 5 to 25% by weight, preferably 7 to 20% by weight, of at least one polystyrene,

[0129] 5 to 30 wt.%, preferably 5 to 20 wt.%, of at least one high-density polyethylene,

[0130] 4 to 30% by weight, preferably 4 to 12% by weight, or 7 to 15% by weight, of at least one thermoplastic polyester, greater than 0 to 13% by weight, preferably 6 to 13% by weight, of a styrene-ethylene-butylene triblock copolymer which has been modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, and at least one filler, in particular CaCCh and / or BaSC, preferably CaCCh, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0131] The present invention also relates to a shaped body, in particular a children's toy, comprising the plastic composition described above or consisting of the plastic composition described above.

[0132] All definitions and embodiments described above for the plastic composition apply analogously to the molded body, in particular to the children's toy.

[0133] The molded bodies are preferably produced by injection molding. Injection molding processes are known to those skilled in the art.

[0134] The present plastic composition is advantageous in that it does not impose any special requirements on the injection molding process, but rather allows the plastic composition to be used in existing processes. Thus, the replacement of halogen-containing plastic compositions with the plastic composition according to the invention is readily possible.

[0135] Furthermore, the present invention relates to the use of the plastic composition described above for producing a shaped body, in particular a children's toy.

[0136] Preferably, the molded body, in particular the children's toy, is colored or painted with a water-based varnish or a water-based paint.

[0137] All definitions and embodiments described above for the plastic composition apply analogously to the use according to the invention.

[0138] The present invention is explained in more detail below using some non-limiting examples.

[0139] Examples

[0140] Tables 1 to 18 describe nine plastic compositions according to the invention and their physical properties by way of example.

[0141] Tables 19 and 20 describe an exemplary, known plastic composition not according to the invention and its physical properties.

[0142] Table 21 summarizes the physical properties of a typical PVC composition.

[0143] The proportions described in the tables are % by weight and refer to the total weight of the respective plastic composition.

[0144] The hardness [Shore D] was determined according to ISO868 (2003).

[0145] The elongations at break [%] and the tensile strengths [MPa] were determined according to DIN53504 (2017) (test specimen shape according to DIN 53504 = S2; test specimens are produced by punching perpendicular to the flow direction of the plastic melt).

[0146] The densities [g cm -3 ] were determined according to DIN EN ISO 1183-1 (A) (2019).

[0147] The shrinkages [s Mp ] were determined according to DIN EN ISO 294-4 (2003) and refers to the shrinkage of the respective composition during the injection molding process.

[0148] The gloss levels [GE] were determined according to DIN EN ISO 2813 (2015) at 60°.

[0149] The remaining deformations [A / ] were determined using a three-point bending test. The test setup corresponded to the apparatus defined in DIN 178 (2019). Test specimens measuring 3.00 mm x 12.5 mm x 125 mm were used to measure the recovery. Before the measurement, a preload of 1 N was applied to the specimen to ensure full-surface contact of the test indenter. The point at which the preload of 1 N was reached was defined as the force zero point. The deflection was carried out in a force-controlled manner at a rate of 20 N / s up to a maximum deflection of 8 mm measured from the force zero point (loading phase). After the deflection, the specimen was unloaded in a force-controlled manner at a rate of 20 N / s until the preload of 1 N was reached (unloading phase). Since the materials do not behave ideally elastically, this results in a measurable permanent deformation (A / ).The permanent deformation (A / ) is measured from the zero point of force before the start of the measurement to the unloading point of the respective cycle. The index indicates the respective cycle in which the permanent deformation was measured. A total of four cycles were measured with one and the same sample. The cycles consisted of the respective loading and unloading phases. Preliminary studies have shown that the permanent deformation measured in the fourth cycle provides the most statistically significant values ​​with regard to the recovery properties of the plastic composition.

[0150] The return speeds [ RÜC k] was determined using the same setup as the residual deformations mentioned above. This results in a speed (mm min -1) of the loading and unloading phases. The speed of the unloading phase is assumed to be a measure of the speed of recovery. The index indicates the respective cycle in which the speed was determined. Previous studies have shown that the speed of the unloading phase in the second cycle provides the most statistically significant values ​​in terms of the recovery speed.

[0151] Table 1 : Example composition 1

[0152] Table 2 : Physical properties of Example Composition 1

[0153] Table 3: Example composition 2

[0154] Table 4: Physical properties of Example Composition 2

[0155] Table 5: Example composition 3

[0156] Table 6: Physical properties of Example Composition 3

[0157] Table 7: Example composition 4

[0158] Table 8: Physical properties of Example Composition 4

[0159] Table 9: Example composition 5

[0160] Table 10: Physical properties of example composition 5

[0161] Table 11 : Example composition 6

[0162] Table 12: Physical properties of example composition 6

[0163] Table 13: Example composition 7

[0164] Table 14: Physical properties of example composition 7

[0165]

[0166] Table 15: Example composition 8

[0167] Table 16: Physical properties of example composition 8

[0168] Table 17: Example composition 9

[0169] Table 18: Physical properties of example composition 9 Table 19: Comparative example composition 10

[0170] Table 20: Physical properties of comparative example composition 10

[0171] Table 21: Physical properties of a typical PVC composition The results show that for the essentially halogen-free

[0172] Plastic compositions, excellent values ​​regarding hardness, density, tensile strength and elongation at break compared to conventional plastic compositions. Molded articles made from these

[0173] Plastic composites are therefore very suitable as children's toys. Furthermore, molded articles made from these plastic composites can be easily colored or painted with water-based paints or varnishes.

Claims

Claims 1. A plastic composition comprising 5 to 50 wt.% of at least one thermoplastic styrene-butadiene copolymer, 5 to 25 wt.% of at least one amorphous plastic, 5 to 30 wt.% of at least one polyolefin and 4 to 30 wt.% of at least one thermoplastic elastomer.

2. Plastic composition according to claim 1, characterized in that the at least one polyolefin comprises at least one polyethylene, preferably a high-density polyethylene, a low-density polyethylene and / or a linear low-density polyethylene.

3. Plastic composition according to any one of the preceding claims, characterized in that the amorphous plastic comprises polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer and / or styrene-methyl (meth)acrylate copolymer.

4. Plastic composition according to any one of the preceding claims, characterized in that the at least one thermoplastic elastomer comprises a thermoplastic polyester elastomer and / or a thermoplastic polyurethane elastomer.

5. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition further comprises at least one thermoplastic styrene block copolymer, preferably in an amount of greater than 0 wt.% to 13 wt.%, more preferably in an amount of 6 wt% to 13 wt%.

6. Plastic composition according to claim 5, characterized in that the styrene block copolymer comprises a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, and / or a styrene-ethylene-ethylene-propylene-styrene block copolymer.

7. Plastic composition according to claim 5 or 6, characterized in that the styrene block copolymer has been modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%, preferably wherein the styrene block copolymer comprises a styrene-ethylene-butylene triblock copolymer which has been modified with maleic anhydride, so that the proportion of modification is preferably 0.2 to 3%.

8. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition is substantially free of halogen-containing polymers.

9. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition additionally comprises at least one additive, wherein the at least one additive is preferably selected from a group consisting of fillers, antioxidants, stabilizers and / or oil, in particular white oil.

10. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition additionally comprises at least one filler, preferably selected from CaCO3 and / or BaSO4, in particular in an amount of 15 to 40 wt.%, preferably in an amount of 20 to 35 wt.%.

11. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition additionally comprises at least one white oil in an amount of 0 to 15 wt.%.

12. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition has a tensile strength of 10 MPa to 30 MPa, preferably of 13 MPa to 25 MPa, wherein the tensile strength is determined according to DIN53504 (2017).

13. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition has a hardness [Shore D] of 30 to 60, preferably of 35 to 50, wherein the hardness [Shore D] is determined according to ISO868 (2003).

14. Plastic composition according to any one of the preceding claims, characterized in that the plastic composition has an elongation at break of 400 to 700%, in particular 450 to 700%, preferably 550 to 650%, wherein the elongation at break is determined according to DIN53504 (2017).

15. A molded article, in particular a children's toy, comprising a plastic composition according to any one of claims 1 to 14 or consisting of the plastic composition according to any one of claims 1 to 14.

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