Plastic composition

Abstract

The invention relates to a plastic composition comprising 5 to 50% by weight of at least one first thermoplastic styrene-butadiene copolymer, 5 to 25% by weight of at least one amorphous plastic, 5 to 30% by weight of at least one polyolefin and 4 to 30% by weight of at least one thermoplastic elastomer, the invention further relates to a molded article, in particular a toy for children, consisting of the plastic composition or comprising the plastic composition.

Description

Technical Field

[0001] This invention relates to plastic compositions and molded articles comprising the plastic compositions, particularly children's toys. Background Technology

[0002] Plastic compositions have a wide range of applications and can contain a variety of different substances that affect their physical and chemical properties. Depending on the application, plastic compositions must meet different basic requirements.

[0003] Due to their adjustable plasticity, deformability, and hardness, plastic compositions are frequently used as the basis for molded products, especially children's toys.

[0004] Plastic compositions known in the art for the preparation of molding articles typically contain halogenated polymers, such as polyvinyl chloride, because they are readily available and inexpensive, and readily achieve favorable physical properties.

[0005] However, these plastic compositions known in the prior art are disadvantageous because the halogenated polymers they contain may be harmful to humans and the environment. The use of halogenated polymers may be unprofitable, especially when using plastic compositions in molded products, particularly children's toys, where the requirements for child-friendliness are particularly stringent.

[0006] Furthermore, plastic compositions known from the prior art are partially brittle or show no signs of breaking beforehand, making mechanical overload invisible before molded parts break. Therefore, molded parts can break without warning, resulting in sharp edges and small, potentially swallowable parts.

[0007] In addition, demolding can sometimes be difficult when using injection molding methods for known plastic compositions.

[0008] Furthermore, molded articles containing plastic compositions known from the prior art often cannot be colored or painted with water-based inks or paints.

[0009] Plastic compositions sometimes do not have good recovery ability, so these molded articles do not quickly and / or completely return to their original position when deformed. Summary of the Invention

[0010] The objective of this invention is therefore to eliminate the aforementioned disadvantages of the prior art. In particular, the objective is to provide a plastic composition that is compatible with humans and the environment. Furthermore, the components of the plastic composition should be inexpensive and readily available, and the plastic composition should meet the basic physical and chemical requirements for molded articles, especially children's toys, particularly regarding hardness and brittleness. In addition, the plastic composition should have good resilience. After deformation, the molded part should return to its original position as quickly and completely as possible. Furthermore, it should be possible, with the aid of the plastic composition, to provide molded articles with smooth surfaces that can be colored or painted with water-based inks or paints. Good demolding of the plastic composition should be possible in the injection molding method.

[0011] The above-mentioned task is solved by the plastic composition according to claim 1, that is, 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.

[0012] A key characteristic of such plastic compositions is the substantial elimination of halogen-containing polymers, making them compatible with humans and the environment, while their components remain inexpensive and readily available. Furthermore, such plastic compositions meet fundamental requirements regarding hardness and brittleness because they are white and refractive, allowing for the identification of potential mechanical overloads before possible breakage. Additionally, the plastic compositions exhibit excellent demolding properties due to high shrinkage during injection molding.

[0013] Furthermore, molded articles formed from the plastic composition can be colored or painted with water-based inks or paints. Additionally, the plastic composition has good resilience, thus allowing any deformation of the molded articles formed from it to return to their original position as quickly and completely as possible.

[0014] Advantageous embodiments are described in the dependent claims.

[0015] Many specific details will be discussed below to provide a full understanding of the subject matter. However, it will be apparent to those skilled in the art that the subject matter can be practiced and processed even without these specific details.

[0016] When the features of different implementation schemes are compatible, all the features of one implementation scheme can be combined with the features of another implementation scheme.

[0017] The terminology used in the description of this disclosure is for the purpose of describing certain embodiments only and should not be construed as limiting the subject matter. As used in this specification and claims, unless the context clearly specifies otherwise, the singular forms “an,” “a,” and “the” should be understood to include the plural forms as well. Conversely, the plural forms also include the singular forms. It should also be understood that the term “and / or” as used herein refers to and includes all possible combinations of one or more of the associated listed elements. It should also be understood that, when used in this specification and claims, the terms “containing,” “covering,” “comprising,” and / or “including” detail the presence of a given feature, step, operation, element, and / or component, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0018] In this specification and claims, the terms “containing,” “comprising,” and / or “including” may also mean “consisting of,” that is, excluding the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0019] In the context of this invention, the quantity specification % by weight (unless otherwise stated) refers to the share of each component based on the total weight of the plastic composition.

[0020] The plastic composition according to the invention comprises 5 to 50% by weight, more preferably 10 to 45% by weight, particularly preferably 15 to 45% by weight, especially 20 to 36% by weight of at least one thermoplastic styrene-butadiene copolymer.

[0021] Thermoplastic polymers are polymers known to those skilled in the art to be permanently deformable within a certain temperature range.

[0022] The copolymer can be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or a mixture of the above copolymers. Random copolymers, alternating copolymers, block copolymers, and graft copolymers are known to those skilled in the art.

[0023] Particularly preferred herein are multi-block copolymers, wherein at least one block is polystyrene. At least one of the other blocks is typically polybutadiene, polyisoprene, or polyisobutylene. The copolymer can be a triblock copolymer of structure ABA, wherein block A is typically polystyrene and block B is typically composed of polybutadiene, polyisoprene, or polyisobutylene (SBS, SIS, SiBS). Alternatively, in block A, the styrene monomer can be partially or completely replaced by styrene derivatives, such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, or vinylnaphthalene, such as 1-vinylnaphthalene and 2-vinylnaphthalene. Alternatively, block B can also contain a mixture of dienes, such as SIBS (a B-block of a mixture of butadiene and isoprene). Furthermore, copolymers composed of styrene monomers and diene monomers can also be used as hydrogenated derivatives. In this case, the units of block B can be present in a partially or fully hydrogenated form. Preferred examples herein include polystyrene block-poly(ethylene-co-butene) 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 copolymers, tetrablock copolymers, or multiblock copolymers may also be used, consisting of monomers of styrene, styrene derivatives (A blocks), and butadiene, isoprene, isobutylene, and mixtures thereof (B blocks) in different sequences of A and B blocks (e.g., BAB, ABAB, etc.).

[0024] Suitable commercially available thermoplastic styrene-butadiene copolymers, for example, under the manufacturer's trade name and product series Dynasol- Kraton- and LCY- Available. For example, thermoplastic styrene-butadiene copolymer as a product series. The commercial product Calprene 719 is commercially available.

[0025] The plastic composition according to the invention comprises 5 to 25% by weight, more preferably 9 to 23% by weight, or 9 to 22% by weight, even more preferably 7 to 20% by weight, and still more preferably 10 to 20% by weight of at least one amorphous plastic.

[0026] Suitable amorphous plastics are preferably all polymers known to those skilled in the art for preparing plastic compositions, especially halogen-free polymers.

[0027] Polystyrene, polymethyl methacrylate, styrene-acrylonitrile, and acrylonitrile-butadiene-styrene are particularly preferred.

[0028] In the context of this invention, amorphous plastics are defined as plastics having a crystallinity of 0 to 3%. Crystallinity is measured according to DIN ENISO 11357 (2023).

[0029] The plastic composition according to the invention contains 5 to 30% by weight, more preferably 5 to 20% by weight, even more preferably 5 to 16% by weight, and even more preferably 5 to 15% by weight of at least one polyolefin.

[0030] Polyolefins are saturated hydrocarbons that are typically prepared by chain polymerization of olefins such as ethylene, propylene, 1-butene or isobutene.

[0031] Preferably, the polyolefin is a homopolymer, a random copolymer, or a block copolymer, such as a thermoplastic elastomer based on a polyolefin block copolymer (TPO), wherein a homopolymer or random copolymer is preferred, which is preferably prepared from an olefin, said olefin being preferably an aliphatic olefin.

[0032] Particularly preferred are non-elastic polyolefins, i.e., those that do not possess elastic properties. More preferred are thermoplastic polyolefins.

[0033] Polyolefins can be, for example, 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), and VLDPE (very low-density polyethylene); homopolymers of propylene (hPP); random copolymers of propylene and ethylene (rPP); and combinations of the same homopolymers of propylene (hPP) are commercially available, and each of these available hPPs can be used according to the invention.

[0034] The plastic composition according to the invention is preferably characterized in that at least one polyolefin comprises at least one polyethylene, preferably high-density polyethylene, low-density polyethylene and / or linear low-density polyethylene.

[0035] High-density polyethylene, also known as HDPE, typically has a strength of 930 to 970 kg / m² as measured according to ISO 1183-2 (2019). 3 The density.

[0036] Low-density polyethylene, also known as LDPE, typically has a strength of 917 to 930 kg / m³ as measured according to ISO 1183-2 (2019). 3 The density.

[0037] Linear low-density polyethylene, also known as LLDPE, typically differs from LDPE in that LLDPE has a lower degree of branching than LDPE.

[0038] The preferred embodiment is one that includes polyethylene as a polyolefin.

[0039] The preferred embodiment is one that includes high-density polyethylene as the polyolefin.

[0040] HDPE, for example, is named after the manufacturer's trade name and product series DOW-DOW. TM ORLEN Unipetrol- SABIC- LyondellBasell- Commercially available. For example, HDPE as a product line. The commercial product Sabic HDPE CC 2056 is commercially available.

[0041] The plastic composition according to the invention contains 4 to 30% by weight, preferably 5 to 30% by weight, more preferably 7 to 20% by weight, even more preferably 7 to 15% by weight, or 4 to 12% by weight of at least one thermoplastic elastomer.

[0042] Those skilled in the art know that elastomers are shape-stable but elastically deformable polymers, wherein their glass transition temperature is below room temperature.

[0043] Suitable thermoplastic elastomers are basically all halogen-free elastomers known to those skilled in the art for the preparation of plastic compositions.

[0044] Thermoplastic elastomers based on copolyester (TPC) or polyurethane (TPU) are particularly preferred here.

[0045] Thermoplastic copolyesters (TPCs) are typically copolyesters in copolymer form, having monomer units linked by ester groups (-C(=O)-O-) in the polymer backbone. Such thermoplastic copolyester elastomers can be prepared by polycondensation. These copolyesters are preferably multiblock copolyesters, typically having crystalline segments from hard blocks (X) and amorphous segments from 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.

[0046] The preferred TPC of this invention is a linear multiblock polyester with a random distribution of high-melting-point hard polyester blocks and low-melting-point soft polyester blocks. In this case, the hard blocks form crystalline regions, and the soft blocks form amorphous regions, which determines the elastic behavior at the application temperature of the TPC.

[0047] Suitable TPCs include those based on the manufacturer's trade name and product series TICONA- P.GROUP- DSM- Kolon-KOPEL- PTS- Ria-Polymers- LG Chem- and DuPont- Commercially available. For example, TPC as a product line. The commercial product Arnitel EL 630-08 is commercially available.

[0048] Thermoplastic polyurethane elastomers (TPUs) are typically polyurethane copolymers having monomer units linked by urethane groups (-NH-(C=O)-O-) in the polymer backbone. Such thermoplastic polyurethane elastomers can be prepared by addition polymerization. These polyurethane elastomers are preferably multiblock polymers, typically having crystalline segments from hard blocks (X) and amorphous segments from 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.

[0049] Suitable TPUs include those from manufacturers such as BASF and their trade names and product lines. Covestro- Hunstman- Lubrizol- Commercially available. For example, TPU as a product line. The commercial product Elastollan 1160 D 50,000 is commercially available.

[0050] 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-(meth)acrylate copolymer.

[0051] The copolymer may be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or a mixture of the above copolymers.

[0052] The preferred embodiment is one that incorporates polystyrene as an amorphous plastic.

[0053] Polystyrene is available, for example, under the name "Polystyrene Crystal 1810".

[0054] The plastic composition according to the invention is preferably characterized in that at least one thermoplastic elastomer comprises a thermoplastic polyester elastomer and / or a thermoplastic polyurethane elastomer, more preferably a thermoplastic polyester elastomer.

[0055] The preferred embodiment is one in which polyester elastomer (TPC) is used as the thermoplastic elastomer.

[0056] The preferred TPC of the present invention is a linear multiblock polyester having a random distribution of high-melting-point hard polyester blocks and low-melting-point soft polyester blocks. In this case, the hard blocks form crystalline regions, and the soft blocks form amorphous regions, which determines the elastic behavior at the application temperature of the TPC. The hard polyester blocks are preferably composed of short-chain dicarboxylic acids or aromatic dicarboxylic acids or mixtures of dicarboxylic acids having fewer than 4 carbon atoms. Aromatic dicarboxylic acids are preferred, and isophthalic acid or terephthalic acid are particularly preferred. The alcohol component is preferably also bifunctional and consists of short-chain alkyl diols or short-chain polyoxyalkylene diols or mixtures of different diols having fewer than 3 repeating units. Short-chain diols are preferred, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanediol, and is particularly preferred, 1,4-butanediol. The soft polyester blocks are preferably composed of aliphatic dicarboxylic acids or aromatic dicarboxylic acids, more preferably aromatic dicarboxylic acids, and very particularly preferably isophthalic acid or terephthalic acid. To create soft regions in TPC, different types of diols can be used, such as polyether diols like polyethylene glycol, polypropylene glycol, polyethylene-co-propylene glycol, polytetramethylene glycol, or soft polyester diols composed of alkane dicarboxylic acids, such as adipic acid or sebacic acid, and alkane diols, or polycaprolactone diols or aliphatic polycarbonate diols.

[0057] The plastic composition according to the invention is preferably characterized in that it further comprises at least one thermoplastic styrene block copolymer.

[0058] Preferably, the plastic composition contains at least one thermoplastic styrene block copolymer in an amount greater than 0% by weight and / or a maximum of 10% by weight, more preferably in an amount greater than 0 to 10% by weight, and even more preferably in an amount of 2 to 10% by weight.

[0059] In another preferred embodiment, the plastic composition contains at least one thermoplastic styrene block copolymer in an amount greater than 0 to 13% by weight, or greater than 0 to 8% by weight, and more preferably 6 to 13% by weight.

[0060] Preferably, at least one thermoplastic styrene block copolymer comprises styrene-ethylene-butene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer and / or styrene-ethylene-ethylene-propylene-styrene block copolymer.

[0061] The preferred embodiment is one in which a styrene-ethylene-butene triblock copolymer is used as a thermoplastic styrene block copolymer.

[0062] Preferably, at least one thermoplastic styrene block copolymer is modified with maleic anhydride, such that the modification percentage is preferably 0.2% to 3%.

[0063] More preferably, at least one thermoplastic styrene block copolymer comprises a styrene-ethylene-butene triblock copolymer modified with maleic anhydride, such that the modification percentage is preferably 0.2 to 3%.

[0064] The styrene-ethylene-butene triblock copolymer is modified with maleic anhydride to such that the modified proportion is preferably 0.2 to 3%, for example, it is available under the name "Kraton FG 1901GT".

[0065] The plastic composition according to the invention is preferably characterized in that it is substantially free of halogen-containing polymers, such as polyvinyl chloride.

[0066] The term "substantially free of halogenated polymers" in the sense of this invention refers to plastic compositions in which the proportion of halogenated polymers is in the range of 0 to 2% by weight, preferably 0 to 1% by weight, and especially 0 to 0.5% by weight.

[0067] Preferably, apart from unavoidable impurities, the plastic composition does not contain halogenated polymers, such as polyvinyl chloride. In particular, the plastic composition does not contain halogenated polymers, such as polyvinyl chloride.

[0068] The plastic composition according to the invention is preferably characterized in that the plastic composition further comprises at least one additive, wherein the at least one additive is further preferably selected from the group consisting of: fillers, antioxidants such as pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (e.g. 1010), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g.) 1076), stabilizers such as 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octoxy)phenol (e.g. 1400), poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol-alt-succinic acid) (e.g.) 622SF) and / or oil, especially white oil.

[0069] As mentioned above, plastic compositions are preferably free of halogen-containing polymers. However, this "halogen-free" requirement does not apply to additives; therefore, halogen-containing additives can contain halogens as long as they are not polymers.

[0070] In particular, the plastic composition also contains at least one filler.

[0071] Preferably, the filler is selected from CaCO3 and / or BaSO4, with CaCO3 being the most preferred.

[0072] In particular, the plastic composition further comprises at least one filler selected from CaCO3 and / or BaSO4, preferably selected from CaCO3, in an amount of 20 to 35% by weight, preferably 22 to 30% by weight.

[0073] In another preferred embodiment, the plastic composition further comprises 15 to 40% by weight, particularly 17 to 35% by weight, at least one filler.

[0074] In particular, the plastic composition further contains 15 to 40% by weight, especially 17 to 35% by weight, of CaCO3 as a filler.

[0075] In particular, the plastic composition further contains 15 to 40% by weight, especially 17 to 35% by weight, of BaSO4 as a filler.

[0076] CaCO3 can be obtained, for example, by the name "Omyacarb 1T-AV".

[0077] In particular, the plastic composition further comprises at least one white oil in an amount of 0 to 15% by weight, preferably greater than 0 to 15% by weight, more preferably 0 to 7.5% by weight, especially greater than 0 to 7.5% by weight, or 1 to 10% by weight.

[0078] White oil, for example, is available under the name "Pionier 2071EE".

[0079] The plastic composition according to the invention is preferably characterized in that it has a tensile strength of 10 MPa to 30 MPa, more preferably 13 MPa to 25 MPa, wherein the tensile strength is determined according to DIN 53504 (2017).

[0080] Here, the test specimen shape S2 according to DIN 53504 (2017) is used, and the specimen is punched perpendicular to the melt flow direction by means of a punch.

[0081] The plastic composition according to the invention is preferably characterized in that the plastic composition has a hardness [Shore D] of 30 to 60, more preferably 35 to 50, wherein the hardness [Shore D] is determined according to ISO 868 (2003).

[0082] The test lasted for 3 seconds.

[0083] 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).

[0084] Here, the test specimen shape S2 according to DIN 53504 (2017) is used, and the specimen is punched perpendicular to the melt flow direction by means of a punch.

[0085] The present invention particularly relates to plastic compositions comprising the following:

[0086] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0087] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0088] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one high-density polyethylene, and

[0089] 5 to 30% by weight, more preferably 7 to 20% by weight, of at least one thermoplastic polyester.

[0090] The present invention particularly relates to plastic compositions comprising the following:

[0091] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0092] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0093] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one high-density polyethylene, and

[0094] At least one thermoplastic elastomer, comprising 4 to 30% by weight, more preferably 4 to 12% by weight, or 7 to 15% by weight.

[0095] The present invention particularly relates to plastic compositions comprising the following:

[0096] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0097] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0098] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0099] 5 to 30% by weight, more preferably 7 to 20% by weight, of at least one thermoplastic polyester, and

[0100] At least one filler, selected from CaCO3 and / or BaSO4, preferably selected from CaCO3, in an amount of 20 to 35% by weight, preferably 22 to 30% by weight.

[0101] The present invention particularly relates to plastic compositions comprising the following:

[0102] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0103] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0104] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0105] 5 to 30% by weight, more preferably 7 to 20% by weight, of at least one thermoplastic polyester, and

[0106] At least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0107] The present invention particularly relates to plastic compositions comprising the following:

[0108] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0109] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0110] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0111] 4 to 30% by weight, more preferably 4 to 12% by weight, or 7 to 15% by weight of at least one thermoplastic polyester, and

[0112] At least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0113] The present invention particularly relates to plastic compositions comprising the following:

[0114] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0115] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0116] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0117] 5 to 30% by weight, more preferably 7 to 20% by weight, of at least one thermoplastic polyester.

[0118] 2 to 10% by weight of a styrene-ethylene-butene-triblock copolymer modified with maleic anhydride, wherein the modification fraction is preferably 0.2 to 3%, and

[0119] At least one filler, selected from CaCO3 and / or BaSO4, preferably from CaCO3, in an amount of 20 to 35% by weight, preferably 22 to 30% by weight.

[0120] The present invention particularly relates to plastic compositions comprising the following:

[0121] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0122] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0123] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0124] 5 to 30% by weight, more preferably 7 to 20% by weight, of at least one thermoplastic polyester.

[0125] 2 to 10% by weight of a styrene-ethylene-butene triblock copolymer modified with maleic anhydride, wherein the modification fraction is preferably 0.2 to 3%, and

[0126] At least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0127] The present invention particularly relates to plastic compositions comprising the following:

[0128] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0129] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0130] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0131] 4 to 30% by weight, more preferably 4 to 12% by weight or 7 to 15% by weight of at least one thermoplastic polyester,

[0132] 2 to 10% by weight of a styrene-ethylene-butene triblock copolymer modified with maleic anhydride, wherein the modification fraction is preferably 0.2 to 3%, and

[0133] At least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0134] The present invention particularly relates to plastic compositions comprising the following:

[0135] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0136] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0137] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0138] 4 to 30% by weight, more preferably 7 to 20% by weight, of at least one thermoplastic polyester.

[0139] Greater than 0 to 13% by weight, more preferably 6 to 13% by weight, of a styrene-ethylene-butene triblock copolymer modified with maleic anhydride, such that the modification percentage is preferably 0.2 to 3%, and

[0140] At least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0141] The present invention particularly relates to plastic compositions comprising the following:

[0142] 5 to 50% by weight, preferably 20 to 40% by weight, of at least one thermoplastic styrene-butadiene copolymer.

[0143] 5 to 25% by weight, more preferably 7 to 20% by weight, of at least one type of polystyrene.

[0144] 5 to 30% by weight, more preferably 5 to 20% by weight, of at least one type of high-density polyethylene.

[0145] 4 to 30% by weight, more preferably 4 to 12% by weight, or 7 to 15% by weight of at least one thermoplastic polyester,

[0146] Greater than 0 to 13% by weight, more preferably 6 to 13% by weight, of a styrene-ethylene-butene triblock copolymer modified with maleic anhydride, such that the modification percentage is preferably 0.2 to 3%, and

[0147] At least one filler, in particular CaCO3 and / or BaSO4, preferably CaCO3, in an amount of 15 to 40% by weight, preferably 17 to 35% by weight.

[0148] Furthermore, the present invention relates to molded articles, particularly children's toys, which comprise or are composed of the aforementioned plastic composition.

[0149] All the above definitions and embodiments for plastic compositions are similarly applicable to molded articles, especially to children's toys.

[0150] In this case, the molded article is preferably prepared by injection molding. Injection molding is a method known to those skilled in the art.

[0151] This plastic composition is advantageous in this respect because it does not have special requirements for the injection molding method, but rather allows the use of the plastic composition in existing processes. Therefore, it is perfectly acceptable to replace halogen-containing plastic compositions with the plastic composition according to the invention.

[0152] Furthermore, the present invention relates to the use of the above-mentioned plastic composition in the preparation of molded articles, especially children's toys.

[0153] Preferably, in this case, the molded articles, especially children's toys, are colored or painted with water-based paints or water-based inks.

[0154] All the above definitions and embodiments for plastic compositions are similarly applicable to the uses according to the invention.

[0155] The invention will be described in more detail below with the aid of some non-limiting embodiments. Example

[0156] The novel plastic compositions according to the invention and their physical properties are exemplarily described in Tables 1 to 18.

[0157] Exemplary known plastic compositions not based on the invention and their physical properties are described in Tables 19 and 20.

[0158] The physical properties of conventional PVC compositions are summarized in Table 21.

[0159] The proportions described in the table are by weight % and are based on the total weight of the individual plastic compositions.

[0160] Hardness [Shore D] is determined according to ISO 868 (2003).

[0161] Elongation at break [%] and tensile strength [MPa] were determined according to DIN 53504 (2017) (test specimen shape according to DIN 53504 = S2; specimens were prepared by stamping perpendicular to the flow direction of the plastic melt).

[0162] Density [g cm] -3 Determined according to DIN ENISO 1183-1(A)(2019).

[0163] Shrinkage rate [s] MpThe shrinkage is determined according to DIN EN ISO 294-4 (2003) and is related to the shrinkage of each composition in the injection molding process.

[0164] Gloss [GE] was measured at 60° according to DIN EN ISO 2813 (2015).

[0165] Residual deformation [Δl] was determined using a three-point bending test. The experimental setup in this case corresponds to the equipment defined according to DIN 178 (2019). A specimen measuring 3.00 mm × 12.5 mm × 125 mm was used for measurement reset. Before measurement, an initial force of 1 N was applied to the specimen, thereby ensuring full surface contact of the test punch. The point at which the initial force of 1 N was reached was defined as the zero force point. Offset was controlled with a force of 20 N / s until the maximum offset measured from the zero force point (load phase) was 8 mm. After offset, the specimen was released controlled with a force of 20 N / s until the initial force of 1 N was reached (release phase). Because the material does not exhibit ideal elastic behavior, this results in measurable permanent deformation (Δl). Permanent deformation (Δl) was measured from the zero force point before the start of measurement until the release point of the corresponding cycle. This index represents the corresponding cycle for measuring permanent deformation. A total of four cycles were measured using the same specimen. Each cycle consisted of a loading phase and an unloading phase. Preliminary tests showed that the permanent deformation measured in the fourth cycle returned to the most statistically significant value regarding the recovery properties of the plastic composition.

[0166] The recovery rate was determined using the same structure as the residual deformation described above. 恢复 This results in the speed (mm min) of the loading and unloading phases of each cycle. -1 The rate of the unloading phase is considered a measure of the recovery rate. This index represents the corresponding period for which the rate is measured. Preliminary experiments showed that the rate of the unloading phase in the second cycle returned the most statistically significant value regarding the recovery rate.

[0167] Table 1: Composition 1 of Example

[0168] Composition 1 Commercial products describe 28.91％ Calprene 701 Thermoplastic butadiene / styrene copolymer 0.20％ Irganox 1010 antioxidants 0.20％ Irgafos 168 stabilizer 15.94％ Polystyrene Crystal 1810 polystyrene 11.88％ Arnitel EL 630-08 Polyester elastomer resin 26.94％ Omyacarb 1T-AV CaCO3 <!-- 9 -->]]> 9.85％ Liten MB 71 polyethylene 6.08％ Pionier 2071EE White oil

[0169] Table 2: Physical properties of composition 1 in Example

[0170] Hardness [Shore D] 44 Density [g cm -3 ]]]> 1.18 Tensile strength [MPa] 12.2 Elongation at break [%) 512 [% Mp [% 0.85 Gloss (60°) [GE] 3.7 [mm] delta l4 1.36 v 恢复,2 [mm min -1 ]]]> 675

[0171] Table 3: Example Composition 2

[0172]

[0173]

[0174] Table 4: Physical properties of composition 2 in Example

[0175] Hardness [Shore D] 42 Density [g cm -3 ]]]> 1.24 Tensile strength [MPa] 11.9 Elongation at break [%) 492 sMp[%] 1.1 Gloss (60°) [GE] 2.6 [mm] delta l4 1.34 v 恢复,2 [mm min -1 ]]]> 818

[0176] Table 5: Example Composition 3

[0177]

[0178]

[0179] Table 6: Physical properties of composition 3 in Example

[0180] Hardness [Shore D] 42 Density [g cm -3 ]]]> 1.11 Tensile strength [MPa] 12.4 Elongation at break [%) 595 [% Mp [% 0.8 Gloss (60°) [GE] 3.2 [mm] delta l4 1.26 v 恢复,2 [mm min -1 ]]]> 767

[0181] Table 7: Example Composition 4

[0182]

[0183] Table 8: Physical properties of composition 4 in Example

[0184]

[0185]

[0186] Table 9: Example Composition 5

[0187]

[0188] Table 10: Physical properties of composition 5 in Example

[0189]

[0190]

[0191] Table 11: Example Composition 6

[0192]

[0193] Table 12: Physical properties of composition 6 in Example

[0194] Hardness [Shore D] 43 Density [g cm -3 ]]]> 1.23 Tensile strength [MPa] 11.0 Elongation at break [%) 412 S Mp [%]]]> 0.8 Gloss (60°) [GE] 2.8 [mm] delta l4 1.42 <![CDATA[v 恢复,2 [mm min. -1 ]]> 856

[0195] Table 13: Example Composition 7

[0196]

[0197]

[0198] Table 14: Physical properties of composition 7 in Example

[0199] Hardness [Shore D] 46 <![CDATA[Density [g cm -3 > 1.24 Tensile strength [MPa] 20.4 Elongation at break [%) 558 <![CDATA[S Mp [%]]]> 0.7 Gloss (60°) [GE] 4.5 <![CDATA[Δl4[mm]]]> 1.37 <![CDATA[v 恢复,2 [mm min. -1 ]]> 697

[0200] Table 15: Example Composition 8

[0201]

[0202]

[0203] Table 16: Physical properties of composition 8 in Example

[0204] Hardness [Shore D] 46 <![CDATA[Density [g cm -3 > 1.13 Tensile strength [MPa] 12.8 Elongation at break [%) 539 <![CDATA[S Mp [%]]]> 0.7 Gloss (60°) [GE] 6.4 <![CDATA[Δl4[mm]]]> 1.16 <![CDATA[v 恢复,2 [mm min. -1 ]]> 713

[0205] Table 17: Example Composition 9

[0206] Composition 9 Commercial products describe 35.20％ Kraton D 1155 ES Thermoplastic butadiene / styrene copolymer 0.20％ Irganox 1010 antioxidants 0.20％ Irgafos 168 stabilizer 20.76％ Polystyrene Crystal 1810 polystyrene 11.26％ Arnitel EL 630-08 Polyester elastomer resin 17.95％ Omyacarb 1 T-AV <![CDATA[CaCO3]]> 14.43％ Liten MB 71 polyethylene

[0207] Table 18: Physical properties of composition 9 in Example

[0208]

[0209]

[0210] Table 19: Comparative Composition 10

[0211] Composition 10 Commercial products describe 36.15％ Calprene 540 Thermoplastic butadiene / styrene copolymer 0.29％ Irganox 1010 antioxidants 0.29％ Irgafos 168 stabilizer 32.54％ Edistir N 3910 polystyrene 25.31％ Albasoft 70 <![CDATA[BaSO4]]> 5.42％ Pionier 2071EE White oil

[0212] Table 20: Physical properties of comparative example composition 10

[0213] Hardness [Shore D] 38 <![CDATA[Density [g cm -3 > 1.19 Tensile strength [MPa] 11.7 Elongation at break [%) 562 <![CDATA[S Mp [%]]]> 0.3 Gloss (60°) [GE] 21 <![CDATA[Δl4[mm]]]> 1.27 <![CDATA[v 恢复，2 [mm min. -1 ]]> 592

[0214] Table 21: Physical properties of typical PVC compositions

[0215]

[0216]

[0217] The results show that, compared with conventional plastic compositions in the prior art, the essentially halogen-free plastic compositions exhibit superior values ​​in terms of hardness, density, tensile strength, and elongation at break. Therefore, molded articles made from these plastic compositions are ideal as children's toys. Furthermore, molded articles made from these plastic compositions can be colored or painted very well with water-based inks or paints.

Claims

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

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

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

4. The 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. The 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 greater than 0% to 13% by weight, more preferably in an amount of 6% to 13% by weight.

6. The plastic composition according to claim 5, characterized in that, The styrene block copolymers include styrene-ethylene-butene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, and / or styrene-ethylene-ethylene-propylene-styrene block copolymers.

7. The plastic composition according to claim 5 or 6, characterized in that, The styrene block copolymer is modified with maleic anhydride, such that the modification percentage is preferably 0.2% to 3%, and preferably the styrene block copolymer comprises a styrene-ethylene-butene triblock copolymer, wherein the styrene-ethylene-butene triblock copolymer is modified with maleic anhydride, such that the modification percentage is preferably 0.2% to 3%.

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

9. The plastic composition according to any one of the preceding claims, characterized in that, The plastic composition further comprises at least one additive, wherein the at least one additive is preferably selected from the group consisting of: fillers, antioxidants, stabilizers and / or oils, especially white oils.

10. The plastic composition according to any one of the preceding claims, characterized in that, The plastic composition further comprises at least one filler, preferably selected from CaCO3 and / or BaSO4, especially in an amount of 15 to 40% by weight, more preferably in an amount of 20 to 35% by weight.

11. The plastic composition according to any one of the preceding claims, characterized in that, The plastic composition further comprises at least one white oil in an amount of 0 to 15% by weight.

12. The 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 13 MPa to 25 MPa, wherein the tensile strength is determined according to DIN 53504 (2017).

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

14. The 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%, particularly 450 to 700%, preferably 550 to 650%, wherein the elongation at break is determined according to DIN 53504 (2017).

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

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