THERMOPLASTIC ELASTOMER COMPOSITION WITH LOW DENSITY AND GOOD MECHANICAL PROPERTIES USING UNCOATED HOLLOW GLASS SPHERES

Description

[0001] The present invention relates to a thermoplastic elastomer composition according to claim 1. The present invention also relates to a method for producing a thermoplastic elastomer using the thermoplastic elastomer composition according to the invention, as well as to the thermoplastic elastomer obtained thereby. Furthermore, the invention relates to various uses of the thermoplastic elastomer where a thermoplastic elastomer with low density and yet good mechanical properties is required.

[0002] Thermoplastic elastomers are required in many applications and for the production of various components. Often, weight reduction is desirable, necessitating the use of low-density thermoplastic elastomers. However, this reduction in density should not compromise mechanical properties or processability. Furthermore, it is desirable that low-density thermoplastic elastomers do not require foaming processes and can be processed using standard injection molding or extrusion methods.

[0003] Vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylacyloxysilanes, and methacryloxyalkylalkoxysilanes are known to be suitable for the radical grafting of polyolefins. These so-called organofunctional silanes are suitable for the surface modification of mineral and metallic surfaces because almost all of these surfaces exhibit hydroxyl groups that typically form covalent bonds with alkoxysilanes (Si-OR + HO-Y → Si-OY + HO-R), thus enabling bonding between the surface and the silane. Since the surface of hollow glass spheres is covered with Si-OH groups that can react with the alkoxysilanes or acyloxysilanes, these compounds are ideally suited for attaching hollow glass spheres to polymers.

[0004] To date, manufacturing processes are known in which non-functionalized glass spheres are bonded to the elastomeric phase of a thermoplastic elastomer via a functionalized elastomer. This is achieved by using grafted SBC instead of grafted polypropylene. However, the resulting thermoplastic elastomers often lack sufficiently good mechanical properties.

[0005] Manufacturing processes for reducing the density of pure, elastomer-free thermoplastic compositions are known in which a functional group is first applied to the surface of hollow glass spheres, to which a thermoplastic is then coupled using an emulsion process. The glass spheres, functionalized by the emulsion process and coated with the thermoplastic, must subsequently be dried and insulated before they can be embedded in additional thermoplastic for which a density reduction is desired. This multi-stage process is not only technically complex but also time-consuming and expensive. Furthermore, methods for reducing the density of thermoplastics cannot be readily transferred to thermoplastic elastomers, as the latter consist of at least two phases.

[0006] Furthermore, the same applicants of the present invention have already filed a patent application, namely in the as yet unpublished application with application number DE 10 2017 122 314, which discloses a low-density thermoplastic elastomer composition with good mechanical properties. This composition comprises a styrene block copolymer (SBC), a polyolefin functionalized with an organic acid anhydride, and hollow glass spheres surface-treated or surface-coated with a silane-based agent. The applicants have consistently assumed that the surface coating of the hollow glass spheres is necessary to bond them to the thermoplastic phase, thus providing a thermoplastic elastomer (TPE) that is both lightweight and exhibits good mechanical properties.Comparative tests using a functionalized SBC instead of the functionalized polyolefin did lead to a weight reduction of the resulting TPE, but with unsatisfactory results. Therefore, it was assumed that it was necessary to ensure that the hollow glass spheres were bonded to the polyolefin used. For this purpose, surface-coated hollow glass spheres and a functionalized polyolefin were used in the preliminary application, enabling bonding between them.

[0007] Surprisingly, the inventors of the present application have now discovered that lightweight thermoplastic elastomers with comparable mechanical properties can also be produced without the use of surface-treated or surface-coated hollow glass spheres, provided that the polyolefin or TPC is nevertheless present as a functionalized polyolefin or functionalized TPC.

[0008] KR 2014 0145009 A relates to a polypropylene resin composition comprising 60 to 97 wt.% highly crystalline polypropylene resin, 1 to 20 wt.% of a rubber component, 1 to 10 wt.% of a polypropylene resin grafted with glycidyl methacrylate and 1 to 10 wt.% glass beads.

[0009] KR 2014 0145010 A concerns a composition comprising 60 to 97 wt.% of a high isotactic polypropylene, 1 to 20 wt.% of a rubber component, 1 to 10 wt.% hair crystals and 1 to 10 wt.% glass particles.

[0010] US 2014 / 0163154 A1 concerns improved-feel polypropylene compositions and a process for their manufacture, wherein the composition comprises a mixture of reactor TPO and filler. The compositions may also include homopolymer polypropylene, random copolymer polypropylene, polyamide 6, ethylene-C-NER1-α-olefin plastomer, plastomer-propylene-ethylene copolymer, SEBS triblock thermoplastic elastomer, maleic anhydride-grafted PP, anti-scratch additives, antioxidants, UV stabilizers, and dyes.

[0011] The present invention solves the problem of providing a thermoplastic elastomer or an alternative composition that has a low density (preferably < 0.9 g / cm³) and whose mechanical properties are within a range that makes it suitable for a wide variety of applications. Furthermore, the thermoplastic elastomers can be produced in a simpler, more cost-effective, and faster manner than when previously using surface-coated hollow glass spheres.

[0012] The thermoplastic elastomer composition according to the invention has a styrene block copolymer (SBC), a polyolefin or a thermoplastic elastomer based on copolyester, and uncoated hollow glass spheres, wherein the polyolefin or thermoplastic elastomer based on copolyester is functionalized by grafting reaction with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, a methacryloxyalkylacyloxysilane or with an anhydride of an organic acid (functionalized polyolefin or TPC), wherein the thermoplastic elastomer composition may additionally contain a non-functionalized polyolefin or a non-functionalized thermoplastic elastomer based on copolyester (TPC), and wherein the weight ratio of the sum of non-functionalized polyolefin or non-functionalized TPC and functionalized polyolefin or functionalized TPC to SBC is in the range of 15:100 to 140:100.

[0013] The thermoplastic elastomer composition according to the invention can be processed as a simple mixture of its components to form a thermoplastic elastomer, for example in an extruder. No complex intermediate steps or isolation of intermediate products are necessary for this.

[0014] According to the present application, a thermoplastic elastomer is understood to be one that consists of a polymer mixture (blend) comprising an elastomer and a thermoplastic or thermoplastic elastomer, and which at its service temperature has properties similar to those of vulcanized rubber, but which can be processed and reprocessed at elevated temperatures like a thermoplastic polymer.

[0015] Since the thermoplastic elastomer compositions according to the invention comprise a styrene block copolymer (SBC) as the elastomeric component, they are also referred to herein as thermoplastic elastomer compositions based on styrene block copolymer (TPS). The same applies to the thermoplastic elastomers according to the invention.

[0016] It is assumed that, due to their components, the thermoplastic elastomers produced from the thermoplastic composition according to the invention have a thermoplastic phase and an elastomeric phase, wherein the elastomeric phase comprises the SBC and the thermoplastic phase comprises the functionalized polyolefin or the functionalized TPC. It appears that the uncoated hollow glass spheres, as well as the coated hollow glass spheres of DE 10 2017 122 314, exhibit an affinity for the thermoplastic phase and not for the elastomeric phase when a functionalized polyolefin or TPC is used. Comparative tests with functionalization of the elastomer instead of the polyolefin or TPC have yielded TPEs with significantly inferior mechanical properties.

[0017] The hollow glass spheres used to produce the thermoplastic elastomer according to the invention are uncoated, i.e., those that have no coating on their surface. In the present invention, coating is understood to mean a functionalization step that follows the production of the hollow glass spheres. An uncoated hollow glass sphere is one whose surface is formed from the glass itself.

[0018] In particular, the present invention also relates to an embodiment in which, in the thermoplastic elastomer composition according to the invention, the styrene block copolymer is a triblock copolymer in which the two terminal blocks are made of polystyrene and the middle block is made of a polymer other than polystyrene. It is preferred that the middle block of the triblock copolymer is made of a polyolefin. The styrene block copolymer is preferably one selected from the group consisting of SEBS, SEPS, SBS, SEEPS, SiBS, SIS, SIBS, or a mixture thereof. Furthermore, it is preferred that the styrene block copolymer is not functionalized with an anhydride of an organic acid, a vinyl alkoxysilane, a vinyl acyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane.Preferably, the styrene block copolymer is one that is not grafted with an anhydride of an unsaturated organic acid, a vinyl alkoxysilane, a vinyl acyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane. The styrene block copolymer is preferably not a grafted styrene block copolymer. The styrene block copolymer is preferably not a functionalized styrene block copolymer. The styrene block copolymer usable according to the invention is described in more detail below.

[0019] In a further embodiment of the present invention, it is preferred that in the thermoplastic elastomer composition according to the invention the functionalization of the functionalized polyolefin or TPCs is carried out by an anhydride of an unsaturated organic dicarboxylic acid, preferably an organic 1,2-dicarboxylic acid, or by a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane.

[0020] The anhydride of an unsaturated organic carboxylic acid or a vinyl alkoxysilane, a vinyl acyloxysilane, a methacryloxyalkyl alkoxysilane, or a methacryloxyalkyl acyloxysilane is preferably bonded to the polyolefin or TPC by radical grafting. For this purpose, an anhydride of an unsaturated organic carboxylic acid or a vinyl alkoxysilane, a vinyl acyloxysilane, a methacryloxyalkyl alkoxysilane, or a methacryloxyalkyl acyloxysilane is "grafted" onto a suitable polyolefin or TPC (grafting process). Preferably, an anhydride of an unsaturated organic acid or a vinyl alkoxysilane, a vinyl acyloxysilane, a methacryloxyalkyl alkoxysilane, or a methacryloxyalkyl acyloxysilane is used that has a reactive double bond; in the case of the anhydride, for example, maleic anhydride; in the case of the organosilanes, they are explicitly vinyl- or methacrylic acid-functionalized organosilanes.Further details about the polyolefin or TPC grafted with an anhydride of an unsaturated organic carboxylic acid or an alkoxy or acyloxysilane, as well as its preparation by grafting reaction, are described below and in the . Figs. 1 and 2 shown.

[0021] Fig. 1 shows the grafting reaction of a polyolefin or TPC 1 with a vinyl or methacryloxysilane 2 in the presence of a radical initiator 3 to form a vinyl or methacryloxysilane-grafted polyolefin or TPC 4.

[0022] The same shows Fig. 2 the grafting reaction of a polyolefin or TPC 1 with maleic anhydride (MAH) 5 in the presence of a radical initiator 3 to form a MAH-grafted polyolefin or TPC 6.

[0023] In Fig. 3 The bonding of the glass hollow spheres 7 to the functionalized polyolefin or TPC 4 is shown, which according to the equation in Fig. 1 was manufactured.

[0024] In a further embodiment of the present invention, the functionalized polyolefin in the thermoplastic composition according to the invention is preferably a functionalized polypropylene. Most preferably, the functionalized polyolefin is a polypropylene grafted / grafted with maleic anhydride (MAH-g-PP).

[0025] In a further embodiment of the present invention, the thermoplastic elastomer composition can additionally comprise a polyolefin or TPC, which is preferably not functionalized with an anhydride of an organic carboxylic acid (non-functionalized polyolefin or TPC). Particularly preferred is the non-functionalized polyolefin polypropylene or polyethylene, and more preferably polypropylene. Polyolefins usable according to the invention are described below. It is also preferred that the non-functionalized polyolefin is added to a composition according to the invention in which a functionalized polyolefin is used. Likewise, it is preferred that the non-functionalized TPC is used in a composition according to the invention in which a functionalized TPC is present.

[0026] In one embodiment, it is preferred that the composition according to the invention uses a polyolefin functionalized by a grafting reaction with an anhydride of an unsaturated organic acid. In this embodiment, the resulting thermoplastic elastomer is suitable for adhesion to polypropylenes or polyamides.

[0027] In a further embodiment, it is preferred that the composition according to the invention uses a polyolefin functionalized by grafting with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane. In this embodiment, the resulting thermoplastic elastomer is particularly suitable for adhesion to polypropylenes. If adhesion to polyamides is desired, this can be achieved by additionally adding a polyolefin functionalized by grafting with an anhydride of an unsaturated organic acid.

[0028] In a further embodiment, it is preferred that the composition according to the invention includes a TPC functionalized by a grafting reaction with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane, or with an anhydride of an unsaturated organic acid, preferably an anhydride of an unsaturated organic acid, and even more preferably maleic anhydride. In this embodiment, the resulting thermoplastic elastomer is preferably used for adhesion to polar thermoplastics, such as ABS, PC, PC / ABS, PA, or SAN.

[0029] The thermoplastic elastomer composition may also contain a plasticizer. Suitable plasticizers that can be used according to the invention are described further below.

[0030] Furthermore, the thermoplastic elastomer composition according to the invention can also contain further additives, such as a stabilizer, an auxiliary substance, a dye, another filler that is not a hollow glass sphere, and / or a compatibility enhancer. These are also described in more detail below.

[0031] The present invention also relates to a process for producing a thermoplastic elastomer based on a styrene block copolymer. In this process, the components of the thermoplastic elastomer composition according to the invention are mixed together at a temperature in the range of 150°C to 240°C, preferably in the range of 180°C to 220°C.

[0032] The method according to the invention is described in more detail below.

[0033] The present invention also relates to a thermoplastic elastomer obtainable or obtained according to the inventive method. The thermoplastic elastomer according to the invention is characterized by a hardness ranging from a Shore A hardness of 40 to a Shore D hardness of 30, a low density ranging from 0.5 to 1.1 g / cm³, a tensile strength of at least 2.0 MPa, an elongation at break of at least 100%, and a compression set at room temperature after 72 hours of less than 70%. All of the aforementioned (preferred) features of the elastomer composition according to the invention shall also apply to the thermoplastic elastomer according to the invention.

[0034] The present invention also relates to the use of a polyolefin or TPC for the production of a thermoplastic elastomer composition or a thermoplastic elastomer according to the invention, wherein the polyolefin or TPC is functionalized by grafting reaction with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane or an unsaturated anhydride of an organic carboxylic acid.

[0035] Furthermore, the present invention also relates to the use of uncoated hollow glass spheres for the production of a thermoplastic elastomer composition or a thermoplastic elastomer according to the invention.

[0036] It is known that thermoplastic elastomers are not only suitable as standalone materials for the manufacture of various products and articles. Rather, the special characteristic of this material class is its ability to bond with thermoplastics (rigid plastics or hard components) without the use of additional adhesives, adhesion promoters, or adhesion-promoting processes such as corona treatments. Furthermore, it is known that the composition of the respective TPE (soft component) determines its ability and strength to bond with the selected hard component. Therefore, providing TPEs with suitable properties for bonding with other thermoplastics is almost always a task for TPE manufacturers.

[0037] The present invention therefore also relates to the use of a thermoplastic elastomer according to the invention for producing a composite material with a thermoplastic (hard component), such as polyolefin, polyamide, or another polar thermoplastic, or for the adhesion of the thermoplastic elastomer composition according to the invention to one of these thermoplastics. In other words, the present invention also relates to a method for producing a composite material from the thermoplastic elastomer according to the invention and a thermoplastic, such as polyolefin, polyamide, or another polar thermoplastic, wherein the thermoplastic elastomer composition is bonded to the thermoplastic. In the use according to the invention, or...The inventive process uses injection molding, multi-component injection molding, injection molding insert molding, extrusion, co-extrusion, or compression molding as a processing method for manufacturing the articles, wherein injection molding, multi-component injection molding, injection molding insert molding, extrusion, and co-extrusion are preferred, and multi-component injection molding is particularly preferred. As described above, the use of functionalized polyolefin is particularly suitable for adhesion to polypropylene or polyamide as a thermoplastic rigid component. As also described above, the use of functionalized TPC is particularly suitable for adhesion to polar thermoplastics.

[0038] Thus, the present invention also relates to a composite material made of a thermoplastic elastomer according to the invention and a thermoplastic, particularly preferably a polyamide, polyolefin or another polar thermoplastic, such as ABS, PC, PC / ABS or SAN.

[0039] The present invention also relates to the use of a thermoplastic elastomer according to the invention and / or the use of a composite material according to the invention as a component or molded body in the interior and exterior of automobiles, industrial equipment, industrial tools, power tools for professional and / or private use, household appliances, consumer electronics products, medical consumables and devices, sporting goods, containers for hygiene products and cosmetics, sealing materials or preparations of consumer goods.

[0040] The aforementioned components used in the thermoplastic elastomer compositions or thermoplastic elastomers according to the invention, as well as in the uses and processes according to the invention, are described in more detail below: A: Styrene block copolymer B: Functionalized polyolefin or functionalized TPC C: Hollow glass spheres D: Polyolefin or TPC (both non-functionalized) E: Plasticizer F: Stabilizer, additive, colorant Component A: Styrene block copolymer

[0041] According to the invention, the term "styrene block copolymer" (SBC) refers to a multi-block copolymer, wherein at least one of the blocks is polystyrene. At least one of the other blocks is typically polybutadiene, polyisoprene, or polyisobutene. The SBC can be a tri-block copolymer of the ABA structure, wherein the A-block is typically polystyrene and the B-block is typically composed of polybutadiene, polyisoprene, or polyisobutene (SBS, SIS, SiBS). Alternatively, in the A-block, the styrene monomers can be partially or completely replaced by derivatives of styrene, such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, or vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene. The B-block can also alternatively contain mixtures of dienes such as SIBS (B-block made from a mixture of butadiene and isoprene).Furthermore, SBCs consisting of styrene and diene monomers can also be used as hydrogenated derivatives. In these cases, the B-block units are partially or completely hydrogenated. 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) are preferred examples. 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, ABAB, etc.) can also be used. Preferred SBCs are composed of triblock copolymers ABA.

[0042] SBCs according to the invention preferably have a weight-averaged molecular weight (Mw) of 50,000 to 1,000,000 g / mol, particularly preferably of 100,000 to 500,000 g / mol.

[0043] The SBC is present in the thermoplastic elastomer composition or in the thermoplastic elastomer according to the invention preferably in an amount in the range of 12 wt.% to 30 wt.%, more preferably in a range of 15 wt.% to 25 wt.% and most preferably in a range of 18 wt.% to 23 wt.%, based on the total weight of the thermoplastic elastomer composition or the thermoplastic elastomer. Component B: functionalized polyolefin or functionalized TPC

[0044] According to the invention, the polyolefin or TPC is functionalized with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, a methacryloxyalkylacyloxysilane, or an anhydride of an unsaturated organic acid, as described above. Preferably, the functionalization takes place by grafting, wherein a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, a methacryloxyalkylacyloxysilane, or an anhydride of an unsaturated organic acid is grafted onto a suitable polyolefin. After the grafting reaction with a vinylalkoxysilane, the polyolefin or TPC is present as a 2-ethylalkoxysilane-modified polyolefin or TPC.After grafting with a methacryloxyalkylalkoxysilane, the polyolefin or TPC exists as a 2-methylpropenoylalkylalkoxysilane-modified polyolefin or TPC. After grafting with a methacryloxyalkylacyloxysilane, the polyolefin or TPC exists as a 2-methylpropenoylalkylacyloxysilane-modified polyolefin or TPC. After grafting with an anhydride of an unsaturated organic acid, the polyolefin or TPC exists as a 1,2-dicarboxylic acid-modified polyolefin or TPC. These are the reaction products of the reaction of polyolefin or TPC with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, a methacryloxyalkylacyloxysilane, or an anhydride of an unsaturated organic acid using radical initiators, according to the reaction equations in the [references]. Figs. 1 and 2 , which have already been described above.

[0045] Grafting generally refers to the process of adding other molecular building blocks (here, vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane, methacryloxyalkylacyloxysilane, or the anhydride of an unsaturated organic carboxylic acid) to the already existing molecular chains of a primary polymer (here, polyolefin or TPC). Such functionalized polymers are also called "graft polymers." Graft polymers can be produced in various ways, for example, by mixing the primary polymer with the molecular building blocks to be grafted in a desired ratio and then generating radicals through the decomposition of peroxides or by irradiation, preferably with peroxides. This process creates radical sites on the primary polymer to which the grafted molecular building blocks attach.For this to occur, the anhydride of the organic carboxylic acid must have a reactive site where the radical site of the primary polymer can attack. Grafting can also partially occur if a mixture of the primary polymer and the molecular building blocks to be grafted is subjected to intensive mechanical-thermal treatment. The grafting reaction of polymers is preferably carried out in a solid-phase reactor, rolling mill, extruder, or in a reactor in solution or emulsion, and is known to those skilled in the art in the field of thermoplastics. For polyolefins or TPCs, the reaction is preferably carried out in a solid-phase reactor or extruder.

[0046] In the present invention, a polyolefin is understood to be a polymer produced from alkenes such as ethylene, propylene, 1-butene, or isobutene by chain polymerization. Saturated polymers are preferably produced from the unsaturated alkenes by polymerization.

[0047] According to the invention, the polyolefins can be homopolymers, statistical copolymers, but also block copolymers, such as polyolefin block copolymers (OBC), wherein homopolymers or statistical copolymers are preferred according to the invention, which are preferably produced from alkenes, which are preferably aliphatic alkenes.

[0048] Particularly preferred are non-elastomeric polyolefins, i.e., those that do not exhibit elastomeric properties. Thermoplastic polyolefins are even more preferred.

[0049] Commercially available polyolefins, described below, can be used as a base for grafting: Polyolefins can be, for example, homopolymers or statistical 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 statistical copolymer of propylene and ethylene (rPP); and combinations thereof.

[0050] Suitable polyolefins for the invention, as a basis for functionalization with the anhydride of a dicarboxylic acid, are primarily those suitable for injection molding. Suitable polyolefins are those with good flow properties and stiffness.

[0051] Homopolymers of propylene (hPP) are commercially available, and any of these available hPPs can be used according to the invention. The use of hPP is preferred according to the invention.

[0052] Commercially available HPPs include, for example, LyondellBasell products sold under the trade name Moplen®, such as Moplen® HP500N and Moplen® HP501L.

[0053] Statistical polypropylene copolymers (rPP) are also commercially available, and any of these rPPs can be used according to the invention. Ethylene and / or butene are preferred as comonomers.

[0054] Polyethylenes of varying densities, such as HDPE, MDPE, LDPE, LLDPE, and VLDPE, can be used according to the invention. These are readily available commercially.

[0055] However, it is particularly preferred according to the invention that the polyolefin is one comprising propylene in its repeating units. Even more preferably, the polyolefin is an hPP.

[0056] The OBCs usable as polyolefins according to the invention are block copolymers whose blocks are composed of olefin monomers as repeating units. The OBCs according to the invention have at least two different polymer blocks. These blocks can be composed of one type of olefin or of two or more types of olefin. The olefins used to construct the OBCs usable according to the invention are aliphatic olefins, such as ethylene, propylene, or butylene, with ethylene and propylene being preferred according to the invention. Particularly preferred are the OBCs usable according to the invention composed exclusively of aliphatic olefins as so-called repeating units. According to the invention, those OBCs that have an aromatic residue are excluded from the definition of the invention (such are known to those skilled in the art as TPS (thermoplastic elastomers based on styrene)).Particularly preferred for the application described herein, or for the composition according to the invention, are OBCs whose blocks are composed of or consist of polypropylene, polyethylene, or a statistical ethylene / propylene copolymer. Such OBCs are commercially available, for example, under the trade name Hifax CA 10 A from LyondellBasell. Also particularly preferred are the polyolefin block copolymers described in detail in US 8,481,637 B2 (referred to therein as "olefin block copolymers, OBCs"), to which reference is made here in full. These are polymers that have alternating blocks of a hard (very rigid) and a soft (highly elastomeric) segment. Such products are marketed by Dow Elastomers under the trade name INFUSE™. In particular, the types recommended for use with TPE are preferred (INFUSE™ 9010, 9007, 9107, 9807).

[0057] Further examples of OBCs usable according to the invention are so-called hydrogenated diene block copolymers. Such polymers preferably have polymer blocks consisting of hydrogenated polybutadiene or hydrogenated polyisoprene.

[0058] According to the invention, it is preferred that the OBCs are used together with a non-elastomeric polyolefin.

[0059] Preferably, suitable TPCs (copolyester-based TPEs) according to the invention are generally copolyesters in the form of copolymers, which have monomer building blocks in the polymer main chain that are linked via ester groups (-C(=O)-O-). Such thermoplastic copolyester elastomers can be produced by polycondensation. These 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. The copolyesters preferably used according to the invention have melting points or softening points in the range of 160°C to 300°C, preferably 165°C to 270°C, and particularly preferably 170°C to 220°C.Preferred TPCs of the present invention are linear multiblock polyesters with a statistical 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, resulting in elastic behavior at the application temperatures of the TPCs. The hard polyester blocks are preferably composed of short-chain dicarboxylic acids with fewer than 4 carbon atoms, aromatic dicarboxylic acids, or mixtures of dicarboxylic acids. Aromatic dicarboxylic acids are preferred, particularly isophthalic acid or terephthalic acid. The alcohol component is preferably also difunctional and consists of short-chain alkyl diols or short-chain polyoxyalkylene diols 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; 1,4-butanediol is particularly preferred. The soft polyester blocks preferably consist of aliphatic or aromatic dicarboxylic acids, more preferably of aromatic dicarboxylic acids, and most preferably of isophthalic acid or terephthalic acid. To create soft regions in the TPCs, different types of diols are used, including polyether diols such as polyethylene glycols, polypropylene glycols, polyethylene-copropylene glycols, and polytetramethylene glycols, or soft polyester diols composed of alkanodicarboxylic acids, for example, adipic acid or sebacic acid, and alkanediols, or polycaprolactone diols or aliphatic polycarbonate diols. However, mixtures of diols can also be used.Preferably, hard TPC regions are composed of terephthalic acid and short-chain diols, particularly preferably 1,4-butanediol, combined with soft regions, preferably composed of terephthalic acid and polyether diols, most preferably polytetramethylene glycol. The copolyesters suitable as component B in the compositions according to the invention can be produced by methods known to those skilled in the art or are commercially available. Suitable commercially available copolyesters are, for example, TICONA - Riteflex®, P.GROUP - PIBIFLEX®, DSM - Arnitel®, Kolon - KOPEL®, PTS - Uniflex®, Ria-Polymers - Riaflex®, LG Chem. - KEYFLEX®, and DuPont - Hytrel®.

[0060] If an anhydride of an unsaturated organic acid is used for the grafting reaction, maleic anhydride is particularly preferred.

[0061] In the case of using a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane for the grafting reaction, a mono-, di-, or tri-alkoxy or -acyloxysilane may be used, with a trialkoxysilane or triacyloxysilane being preferred. The alkoxy groups may be substituted or unsubstituted alkoxy groups. C1-8 alkoxy groups are preferred, with methoxy, ethoxy, or propoxy groups being more preferred, and methoxy groups being most preferred. The acyloxy groups may be C1-8 acyloxy groups, with C1-3 acyloxy groups being more preferred, and the acetyloxy group being most preferred. The latter groups preferably remain bonded to the silicon atom of the silane after grafting. In order for a silane to be grafted, the alkoxysilane to be grafted has another group that has a double bond or an epoxy group.This group can be, for example, a substituted or unsubstituted vinyl, epoxy, or alkylacrylic group (alkyl = C1-5 alkyl, with C1-3 alkyl being preferred and methyl being particularly preferred), which can also be bonded to the silicon atom of the silane via one of the following groups: -(CH2)n-O- or -(CH2)n-, where n- is 1 to 5, more preferably 1 to 3, and even more preferably 3, with n-propyl being most preferred. In the case of the -(CH2)n-O- group, the oxygen atom bonds to the silicon atom of the silane. Such graftable silanes are available, for example, under the trade name Geniosil® from Wacker.

[0062] Preferred vinylsilanes are: vinyltrialkoxysilanes (specifically vinyltrimethoxysilane, vinyltriethoxysilane), vinylalkyldialkoxysilanes (specifically vinyldimethoxymethylsilane), and vinyltricarboxysilanes (specifically vinyltriacetoxysilane). These are shown in the following formulas (I) to (III): wherein R2 to R5 are each independently alkyl groups, preferably methyl or ethyl groups.

[0063] Preferred methacryloxyalkylalkoxysilanes and methacryloxyalkylacyloxysilanes are: 3-methacryloxypropyl-trialkoxysilane or methacryloxymethyl-trialkoxysilane (specifically 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyl-trimethoxysilane, methacryloxymethyl-triethoxysilane), 3-methacryloxypropylalkyldialkoxysilane or methacryloxymethyl-alkyldialkoxysilane (specifically methacryloxymethyl-dimethoxymethylsilane), 3-methacryloxypropyl-tricarboxysilane or methacryloxymethyltricarboxysilane (specifically 3-methacryloxypropyltriacetoxysilane). These are shown in the following formulas (IV) to (VI): wherein R1 is an alkylene group, preferably a methylene or propylene group; and R2 to R5 are each independently alkyl groups, preferably methyl or ethyl groups.

[0064] The amount of anhydride of an unsaturated organic carboxylic acid in the grafted polyolefin is in the range of 0.1 wt.% to 5 wt.%, more preferably in the range of 0.5 wt.% to 2 wt.%, based on the total weight of the polyolefin that is functionalized with an anhydride of an organic carboxylic acid.

[0065] The amount of vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane or methacryloxyalkylacyloxysilane in the grafted polyolefin is in the range of 0.5 wt.% to 5 wt.%, more preferably in the range of 1 wt.% to 4 wt.%, based on the total weight of the polyolefin that is functionalized with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane.

[0066] According to the invention, polypropylene, and especially hPP, is preferably used as the polyolefin. A polypropylene grafted with maleic anhydride is also known in the trade as MAH-g-PP. Such an MAH-g-PP is known under the trade name "Scona®< TPPP" and is available, for example, as types "Scona®< TPPP 2112 GA" or "Scona®< TPPP 8112 GA".

[0067] The amount of anhydride of an unsaturated organic carboxylic acid in the grafted TPC is in the range of 0.1 wt.% to 5 wt.%, more preferably in the range of 0.5 wt.% to 2 wt.%, based on the total weight of the TPC that is functionalized with an anhydride of an organic carboxylic acid.

[0068] Such a MAH-g-TPC is known under the trade name "Scona ®< TPHY" and is available, for example, as "Scona ®< TPHY 45602 PCX".

[0069] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of functionalized polyolefin or TPC to SBC is preferably in the range of 15:100 to 140:100, more preferably in the range of 20:100 to 98:100. Component C: Hollow glass spheres

[0070] The hollow glass spheres usable for the thermoplastic elastomer composition or the thermoplastic elastomer according to the invention have a glass shell and a hollow core, and can be filled with gas at atmospheric pressure or reduced pressure. The glass shell contains silicon dioxide as its main component and can contain sodium oxide, magnesium oxide, calcium oxide, boron oxide, phosphorus oxide, and the like as additional components.

[0071] The hollow glass spheres can be essentially round, but can also deviate from this shape, e.g., have an elliptical shape, and / or have craters or dents in the surface. It is preferred that the hollow glass spheres have a ratio of shortest axis to longest axis of ≥ 0.85, more preferably 0.90, and most preferably 0.95.

[0072] Since high shear forces are present during the mixing of the thermoplastic elastomer composition according to the invention, hollow glass spheres can break. This breakage must be avoided by appropriately selecting the isostatic collapse strength. The hollow glass spheres preferably have an isostatic collapse strength (10 volume%) of 55 MPa or more, more preferably 69 MPa or more, and most preferably 100 MPa or more. The "isostatic collapse strength (10 volume%)" is defined according to ASTM D-3102-78, whereby an appropriate quantity of the hollow glass spheres is immersed in glycerin and the pressure is increased until 10 volume% has collapsed.

[0073] The mean diameter is preferably in the range of 10 µm to 70 µm, more preferably in the range of 10 µm to 35 µm. The mean diameter can be determined using a commercially available laser diffraction particle size analyzer.

[0074] The hollow glass spheres preferably have a density of 0.9 g / cm³ or less, more preferably 0.6 g / cm³ or less, and 0.3 g / cm³ or more. This refers to the actual density of the hollow glass spheres and not the bulk density. The actual density of the hollow glass spheres is determined using a pycnometer, such as the AccuPyc II 1340 from Micromeritics.

[0075] Hollow glass spheres suitable for use according to the invention are available from 3M. Preferably, hollow glass spheres of type iM16K are used according to the invention.

[0076] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of glass hollow spheres to SBC is preferably in the range of 30:100 to 250:100, more preferably in the range of 50:100 to 150:100. Component D: Polyolefin or TPC (non-functionalized)

[0077] Here, the same polyolefins or TPCs can be used as mentioned above for functionalized polyolefin or functionalized TPC (however, here they are non-functionalized).

[0078] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of polyolefin or TPC (each not functionalized) to SBC is preferably in the range of 0:100 to 105:100, more preferably up to 80:100.

[0079] The weight ratio of the sum of polyolefin or TPC (each non-functionalized) and functionalized polyolefin or functionalized TPC to SBC is in the range of 15:100 to 140:100. Component E: Plasticizer

[0080] Suitable plasticizers are generally known to those skilled in the art. Suitable plasticizers for nonpolar elastomers (e.g., SBCs) include technical or medical mineral or white oils, virgin oils such as soybean or rapeseed oil, and alkylsulfonyl esters, particularly alkylsulfonylphenyl esters, wherein the alkyl substituents contain linear and / or branched alkyl chains with > 5 carbon atoms. Also suitable are di- or tri-alkyl esters of melitic acid, wherein the alkyl substituents preferably contain linear and / or branched alkyl chains with > 4 carbon atoms. Furthermore, alkyl esters of di-, tri-, and higher polycarboxylic acids, wherein the alkyl substituents are preferably linear and / or branched alkyl chains, are also used as suitable plasticizers. Examples include adipic acid di-2-ethylhexyl ester and tributyl O-acetyl citrate. Furthermore, carboxylic acid esters of mono- and / or polyalkylene glycols can also be used as plasticizers, such as ethylene glycol adipate.According to the invention, technical or medical mineral or white oils are preferably used. Shell Catenex T 145 S is one example of a technical mineral oil.

[0081] Suitable plasticizers can also be mixtures of the described substance classes.

[0082] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of plasticizer to SBC is preferably in the range of 50:100 to 300:100, more preferably in the range of 100:100 to 250:100. Component F: Additives such as stabilizers, auxiliary substances and colorants

[0083] Suitable additives include, but are not limited to, processing aids, metal soaps, fatty acids and fatty acid derivatives, paraffin waxes, microcrystalline waxes, lubricants, demolding agents, flame retardants, fume suppressants, adhesion promoters, marking agents, minerals, crystallization accelerators and retarders, anti-fogging agents, antistatic agents, as well as biocides and fungicides.

[0084] Examples of process aids and stabilizers that can be used include: aging or ozone protection agents such as ozone protection waxes, stabilizers such as heat stabilizers, weathering stabilizers; oxidation protection agents, antioxidants, UV stabilizers, other light stabilizers, antifoaming agents, lubricants, dispersants, release agents, anti-blocking agents, radical scavengers, metal deactivators, and also additives such as foaming aids, blowing agents, impact modifiers, adhesion promoters and viscosity modifiers.

[0085] Furthermore, additives such as color masterbatches, pigments, dyes, e.g. titanium dioxide, lithophone, zinc oxide, iron oxide, ultramarine blue, chromium oxide, antimony sulfite can be used.

[0086] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of the sum of all additives to SBC is preferably in the range of 0.1:100 to 50:100, more preferably in the range of 0.5:100 to 25:100.

[0087] Production of the compositions according to the invention: The thermoplastic elastomer compositions according to the present invention can be produced by mixing the components A, B, C, D, E and F – insofar as they are present in the compositions. The mixing can be carried out using mixing systems known in rubber and plastics technology, such as kneaders, internal mixers, e.g., internal mixers with intermeshing or tangential rotor geometry, as well as in continuously mixing systems such as mixing extruders, e.g., mixing extruders with 2 to 4 or more screw drives (e.g., twin-screw extruders).

[0088] When carrying out the manufacturing process according to the invention, it is important to ensure that the mixing temperature is high enough to allow components B and D – if used according to the invention – to be brought into the plastic state without being damaged in the process. This is ensured if a temperature above the highest melting or softening temperature of components B and D – if used according to the invention – is selected. At the same time, adequate energy input must be ensured, which is determined by the rotational speed and throughput in the extruder (see examples).

[0089] Mixing the components – insofar as they are present in the compositions – is particularly preferred and is carried out at a temperature in the range of 150°C to 240°C and preferably 180°C to 220°C.

[0090] The terms "comprise", "contain" and "have" used in the present application are also intended to include the term "consist of" in every instance in which they are used, so that these embodiments are also disclosed in this application. Examples:

[0091] Determination methods and definitions: The density is determined according to DIN EN ISO 1183-1.

[0092] The Shore hardness is determined according to DIN EN ISO 868 and DIN ISO 7619-1.

[0093] The tensile strength and elongation at break are determined according to DIN 53504 / ISO 37. In contrast to ISO 37, the S2 bar is tested with a feed rate of 200 mm / min.

[0094] The determination of the compression set is carried out according to DIN ISO 815-1, method A.

[0095] The tear resistance is determined according to ISO 34-1.

[0096] The adhesion of the thermoplastic elastomer compositions to PA6 is determined according to VDI 2019: The PA6 used is Frianyl B3 V2 NC1102 from Nilit Plastics. The adhesion of the thermoplastic elastomer compositions to polypropylene (PP) (type: Moplen® < HP501L; manufacturer: Basell Polyolefins) is also determined according to VDI 2019.

[0097] The melt flow index is determined according to DIN EN ISO 1133. Extruder and injection molding parameters:

[0098] The thermoplastic elastomers of the present invention are produced in a continuous process on a twin-screw extruder (48 L / D). The hollow glass spheres are fed via a side feeder. The extruder speed is 500 rpm, and the throughput is 20 kg / h. The set temperature profile ranges from 170 to 190°C. The extrudate is granulated for subsequent injection molding or extrusion processing.

[0099] The test specimens are manufactured using injection molding with a temperature profile of 180 to 200°C. Examples of implementation:

[0100] Table 1 lists the abbreviations used for the components employed in the examples and comparison examples: Table 1: component raw material A SBC B1 Polyolefin, functionalized with an anhydride of an organic carboxylic acid B2 Polyolefin, functionalized with an alkoxy or acyloxysilane C Glass hollow spheres D Polyolefin (non-functionalized) E Plasticizers F Additive G silanized glass hollow spheres H SBC, functionalized with an anhydride of an organic carboxylic acid Examples and comparative examples:

[0101] Production of thermoplastic elastomer compositions and elastomers (according to the invention and not according to the invention):

[0102] Thermoplastic elastomers are produced according to the manufacturing method described above, using the components listed in Tables 3 and 4. Table 2 specifies the manufacturers and types of the components used. Tables 5 and 6 list the mechanical properties and processability values. Table 2: Raw materials used component raw material Manufacturer type A SBC (not functionalized) TSRC Taipol SEBS 6151 B1 Polyolefin (functionalized) BYK Scona TPPP 2112 GA B2 1) LyondellBasell 1) Moplen HP501L 2) Wacker 2) Geniosil GF 31 C Glass hollow spheres (uncoated) 3M iM16K D Polyolefin (non-functionalized) LyondellBasell Moplen HP501L E Plasticizers Shell Shell Catenex T 145 S F Additive: Process stabilizer BASF Irgafos 168 G Glass hollow spheres (functionalized) Hoffmann Mineral iM16K ASHM H SBC (functionalized) BYK Scona TSKD 9103* *Malenic anhydride grafted SEBS Production of polyolefin B2:

[0103] The functionalized polyolefin B2 is produced by grafting the polypropylene Moplen®< HP501L with the silane Geniosil®< GF 31. For this purpose, 0.06 wt% Peroxan®< HXY-85W (85% in white oil) is dissolved in 5 wt% liquid Geniosil GF 31 and fed to Moplen®< HP501L in a twin-screw extruder at room temperature. The wt% values ​​refer to the amount of polypropylene used. Mixing takes place under slow heating in the mixing zone, initially to 160°C. The temperature is then increased to 200°C, during which radical grafting occurs. Volatile components are removed by vacuum degassing. Table 3: Compositions Comparative example 1 Comparative example 2 Example 1 Comparative example 3 Example 2 raw material component [Weight percentages] [Weight percentages] [Weight percentages] [Weight percentages] [Weight percentages] SBC (not functionalized) A 100 100 100 100 100 Polyolefin (functionalized) B1 92 92 23 31 Glass hollow spheres (uncoated) C 136 136 115 Polyolefin (non-functionalized) D 92 9 Plasticizers E 200 200 200 200 200 Additive: Process stabilizer F 0,26 0,26 0,26 0,23 0,23 silanized glass hollow spheres G 136 115 Comparative example 1: without interacting groups on polyol tin and hollow glass spheres; comparative examples 2 and 3: with interacting groups on polyolefin and hollow glass spheres; examples 1 and 2: with functionalized polyolefin, but uncoated hollow glass spheres; Table 4: Compositions Example 3 Comparative example 4 Comparative example 5 raw material component [Weight percentages] [Weight percentages] [Weight percentages] SBC (not functionalized) A 100 50 50 Polyolefin (functionalized) B1 B2 64 Glass hollow spheres (uncoated) C 131 136 Polyolefin (non-functionalized) D 92 92 Plasticizers E 200 200 200 Additive: Process stabilizer F 0,25 0,26 0,26 Glass hollow spheres (silanized) G 136 SBC (functionalized) H 50 50 Example 3: with functionalized polyolefin, but uncoated glass hollow spheres; Comparative example 4: with functionalized SBC, but uncoated glass hollow spheres; Comparative example 5: with non-functionalized polyolefin, but uncoated glass hollow spheres; Table 5: Mechanical values ​​of the examples from Table 3: Mechanical values Comparative example 1 Comparative example 2 Example 1 Comparative example 3 Example 2 Value Unit density g / cm³< 0,717 0,723 0,724 0,728 0,722 hardness ShA 78 87 87 59 61 Tensile strength MPa 3 5 4,9 2,9 2,9 Elongation at break % 587 200 237 293 304 Tear resistance N / mm 14,5 20,7 22,1 10,9 11,6 Compression set at 23°C / 72h % 53 35 33 10 13 Compression set at 70°C / 24h % 69 47 42 22 24 Compression set at 100°C / 24h % 81 80 81 71 68 Melting flow index 230°C / 5 kg cm 3< / 10 min 112 74,5 79,5 18,1 9,4 Liability N / mm PP: 3.5 PA6: 4.2

[0104] The values ​​for density, hardness, tensile strength, elongation at break and tear resistance were recorded at room temperature. Table 6: Mechanical values ​​of the examples from Table 4: Mechanical values Example 3 Comparative example 4 Comparative example 5 Value Unit density g / cm³< 0,728 0,747 0,724 hardness ShA 78 84 84 Tensile strength MPa 4,1 2,6 2,8 Elongation at break % 245 169 36 Tear resistance N / mm 15,5 17,4 16,2 Compression set at 23°C / 72h % 22 58 57 Compression set at 70°C / 24h % 34 88 82 Compression set at 100°C / 24h % 81 96 92 Melting flow index 230°C / 5 kg cm 3< / 10 min 204,2 190 Liability N / mm PP: 3.8

[0105] The values ​​for density, hardness, tensile strength, elongation at break and tear resistance were recorded at room temperature.

Claims

1. Thermoplastic elastomer composition, which comprises • a styrenic block copolymer (SBC), • a polyolefin or a copolyester-based thermoplastic elastomer (TPC), and • uncoated hollow glass spheres, wherein the polyolefin or the copolyester-based thermoplastic elastomer is functionalized by a grafting reaction with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane, wherein the thermoplastic elastomer composition can additionally contain a non-functionalized polyolefin or a non-functionalized copolyester-based thermoplastic elastomer (TPC), and wherein the weight ratio of the sum of non-functionalized polyolefin or non-functionalized TPC and functionalized polyolefin or functionalized TPC to SBC is in the range of 15:100 to 140:100.

2. Thermoplastic elastomer composition according to claim 1, wherein the styrenic block copolymer is a triblock copolymer, in which the two terminal blocks are formed of polystyrene and the middle block is formed of a polymer other than polystyrene.

3. Thermoplastic elastomer composition according to claim 2, wherein the middle block of the triblock copolymer is formed by a polyolefin.

4. Thermoplastic elastomer composition according to any of claims 1 to 3, wherein the styrenic block copolymer is a SEBS, SEPS, SBS, SEEPS, SIS, SiBS or SIBS.

5. Thermoplastic elastomer composition according to any of claims 1 to 4, wherein the styrenic block copolymer is not grafted with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane.

6. Thermoplastic elastomer composition according to any of claims 1 to 5, wherein the anhydride of an unsaturated organic acid is preferably an anhydride of an organic unsaturated dicarboxylic acid, preferably an organic unsaturated 1,2-dicarboxylic acid.

7. Thermoplastic elastomer composition according to any of claims 1 to 6, which additionally contains a plasticizer.

8. Process for producing a thermoplastic elastomer, wherein the components of a thermoplastic elastomer composition according to any of claims 1 to 7 are mixed together at a temperature in the range of 150°C to 240°C.

9. Thermoplastic elastomer obtainable by a process according to claim 8.

10. Use of a polyolefin or TPC for producing a thermoplastic elastomer composition according to any of claims 1 to 7 or a thermoplastic elastomer according to claim 9, wherein the polyolefin or TPC is functionalized with an anhydride of an organic carboxylic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane.

11. Use of uncoated hollow glass spheres for producing a thermoplastic elastomer composition according to any of claims 1 to 7 or a thermoplastic elastomer according to claim 9.

12. Use of a thermoplastic elastomer according to claim 9 for producing a composite material with a thermoplastic.

13. Composite material made of a thermoplastic elastomer according to claim 9 and a thermoplastic.

14. Use of a thermoplastic elastomer according to claim 9 and / or a composite material according to claim 13 as a component or shaped body in the field of automobile interiors and exteriors, industrial equipment, industrial tools, power tools for professional and / or private use, household appliances, products in the field of consumer electronics, medical consumables and devices, sporting goods, containers for hygiene articles and cosmetics, sealing materials or preparations of consumer goods.