Lightweight thermoplastic elastomer as a damping material for protectors

Abstract

The invention relates to a thermoplastic elastomer composition containing the components: A1) a double-bond-containing styrene-isoprene-styrene block copolymer and / or A2) a styrene-ethylene-ethylene / propylene-styrene block copolymer, B) a hydrogenated styrene block copolymer which is functionalized by means of a grafting reaction and which is functionalized with an anhydride of an unsaturated organic acid, a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkyl acyloxysilane, and C) hollow glass spheres. The invention also relates to a method for producing a thermoplastic elastomer using the thermoplastic elastomer composition and to the thermoplastic elastomer obtained thereby.

Description

[0001] 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co . KG

[0002] Lightweight thermoplastic elastomer as a damping material for protectors

[0003] The present invention relates to a thermoplastic elastomer composition and a resulting thermoplastic elastomer (TPE) that combines excellent elastic and damping properties with low weight. The present invention also relates to a method for producing the thermoplastic elastomer and its use as a damping material for protectors, in particular sports protectors.

[0004] Up to now, protectors have mainly been made of PU foams, which are very light but have poor damping properties at 40 °C and become stiff at -10 °C.

[0005] Protectors made of elastomeric thermoplastic polyurethane (TPU) also have significant weaknesses; for one thing, they are very heavy, and for another, they are very stiff at low temperatures, not least due to their high inherent hardness.

[0006] Recently, it has become apparent that thermoplastic elastomers can also possess damping properties and can therefore be used as protectors in protective clothing and equipment, particularly in sports. Weight reduction is also desirable here, so the thermoplastic elastomers used should have a low density. Furthermore, it is desirable that no foaming processes are necessary for the production of a low-density thermoplastic elastomer, and that they are manufactured using [28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG]

[0007] They can be processed using standard injection molding or standard extrusion processes.

[0008] It is well known that styrene block copolymers can exhibit good damping properties. However, no product has yet been established on the market that combines all the requirements for protectors in a single material.

[0009] as little weight as possible;

[0010] Flexible even at low temperatures;

[0011] very good damping behavior in an application range of -10 to +40 °C .

[0012] Patent application WO 2021 / 236914 Al describes a vibration-damping TPE material containing at least one non-hydrogenated styrene-isoprene block copolymer (SIS) and either at least one hydrogenated SIS or a styrene-ethylene / butylene-styrene block copolymer (SEBS), as well as at least one tackifier. This TPE material is also suitable for higher temperatures but offers no significant damping properties at low temperatures. Furthermore, this patent application does not use hollow glass spheres or glass spheres for weight reduction.

[0013] Maleic anhydride, vinylalkoxysilanes, vinylacyloxysilanes, methacryloxyalkylacyloxysilanes, and methacryloxyalkylalkoxysilanes are known to be suitable for the radical grafting of styrene block copolymers. These so-called organofunctional silanes are suitable for the surface modification of mineral and metallic surfaces, since almost all of these surfaces exhibit hydroxyl groups that typically form covalent bonds with alkoxysilanes.28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG

[0014] (Si-OR + HO-Y -> Si-OY + HO-R) and thus enable the bond 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, the alkoxysilanes and the acyloxysilanes are ideally suited for bonding hollow glass spheres to polymers.

[0015] The object of the present invention is to provide a thermoplastic elastomer which has good elastic and damping properties in a temperature range of -10 °C to +40 °C and also has a low weight, in order to be used as comfortable protectors, in particular sports protectors.

[0016] The problem according to the invention is solved by a thermoplastic elastomer composition or a resulting thermoplastic elastomer comprising the following components:

[0017] Al ) a double-bonded styrene-isoprene-styrene block copolymer (SIS) , and / or

[0018] A2 ) a styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS) , as well as

[0019] B) a hydrogenated styrene block copolymer functionalized by grafting reaction, which is functionalized with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane, and

[0020] C) Hollow glass spheres.28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co . KG

[0021] By combining the two components Al) and / or A2) and B), a material can be provided that exhibits good damping properties at both low temperatures down to -10 °C and high temperatures up to +40 °C. Furthermore, by using the graft-functionalized component B) and incorporating hollow glass spheres, a low density and thus a low weight of the material can be achieved without significantly compromising its damping properties and elasticity.

[0022] 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.

[0023] According to the present application, a thermoplastic elastomer is understood to be a polymer composition 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.

[0024] In a further embodiment of the thermoplastic elastomer composition according to the invention, it is preferred that the styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS) of component A2 is not functionalized by a grafting reaction with an anhydride of an unsaturated organic acid, or a vinyl alkoxysilane, or a vinyl acyloxysilane, or a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane. In other words, 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0025] the styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS) of component A2 ) differs from the functionalized hydrogenated styrene block copolymer of component B).

[0026] In one embodiment of the thermoplastic elastomer composition according to the invention, it is preferred that only component Al) , i.e., the double-bond-containing styrene-isoprene-styrene block copolymer (SIS) , is used. However, any mixture of both polymers of components Al) and A2) as well as only the styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS) of component A2) can also be used. The SIS in component Al) primarily ensures good damping properties at temperatures above or equal to 0 °C. Therefore, the presence of SIS as component Al) is generally sufficient for good performance across the entire temperature range. However, if improved damping properties and flexibility at temperatures below 0 °C are desired, a mixture of SIS and SEEPS is recommended.

[0027] In a further embodiment of the thermoplastic elastomer composition according to the invention, it is preferred that the hydrogenated styrene block copolymer from component B) functionalized by grafting reaction is a styrene-ethylene / butylene-styrene block copolymer (SEBS) functionalized by grafting reaction. The functionalizing group ensures the incorporation of the glass hollow spheres via their surface.

[0028] The thermoplastic elastomer composition according to the invention can additionally comprise as component D) a further styrene block copolymer, which is not formed by a grafting reaction with an anhydride of an unsaturated organic acid or 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0029] The styrene block copolymer is functionalized with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane and is different from components Al), A2), and B), as well as the optional component E) listed below. This styrene block copolymer preferably has a relatively low styrene content in the range of 5 wt.% to 18 wt.%, more preferably in the range of 10 wt.% to 15 wt.%, based on the total weight of the polymer. The presence of such a styrene block copolymer improves the processability of the thermoplastic elastomer composition and creates a pleasant feel in the resulting thermoplastic elastomer according to the invention.

[0030] The thermoplastic elastomer composition according to the invention can additionally comprise a styrene-butadiene-styrene block copolymer (SBS) as component E). Such a polymer preferably has a relatively high Shore hardness. By increasing its addition to the thermoplastic composition according to the invention, its hardness can thus be adjusted accordingly.

[0031] Furthermore, the thermoplastic elastomer composition according to the invention can additionally contain a plasticizer. A plasticizer ensures improved processability during the production of the thermoplastic elastomer composition according to the invention. Suitable plasticizers that can be used according to the invention are also described below.

[0032] The glass hollow spheres used to produce the thermoplastic elastomer according to the invention are preferably uncoated, i.e., those that have no coating on their 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0033] The surface of the glass hollow spheres is defined in the present invention as a functionalization step that occurs after the production of the glass hollow spheres. An uncoated glass hollow sphere is one whose surface is formed from the glass itself.

[0034] 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 SEBS 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.

[0035] The anhydride of an unsaturated organic carboxylic acid or a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane is preferably attached to SEBS by radical grafting. For this purpose, an anhydride of an unsaturated organic carboxylic acid or a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane is grafted onto a suitable SEBS (grafting process). Preferably, an anhydride of an unsaturated organic acid or a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane is used that has a reactive double bond; in the case of the anhydride, for example, maleic anhydride; in the case of the organosilanes, explicitly vinyl- or methacrylic acid-functionalized organosilanes.Further details about the SEBS, which is made with an anhydride of an unsaturated organic carboxylic acid or an alkoxy or 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co . KG.

[0036] The preparations for acyloxysilane grafting, as well as for preparation by grafting reaction, are described further below and shown in Figs. 1 and 2.

[0037] Fig. 1 shows the grafting reaction of a SEBS 1 (here simplified as a polyethylene chain) with a vinyl or methacryloxysilane 2 in the presence of a radical initiator 3 to form a vinyl or methacryloxysilane-grafted SEBS 4.

[0038] Similarly, Fig. 2 shows the grafting reaction of a SEBS 1 (here simplified as a polyethylene chain) with malic anhydride (MAH) 5 in the presence of a radical initiator 3, resulting in the formation of a MAH-grafted SEBS 6.

[0039] Fig. 3 shows the connection of the glass hollow spheres 7 to the functionalized SEBS 4 (here simplified as a polyethylene chain) which was produced according to the equation in Fig. 1.

[0040] 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.

[0041] In a further embodiment, the present invention also relates to a thermoplastic elastomer composition according to the invention and to a thermoplastic elastomer according to the invention, comprising the following components: Al) and / or 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0042] A2 ) as well as B) and C) as well as - optionally - the components D) , E) , F) and G) consists .

[0043] The present invention also relates to a method for producing a thermoplastic elastomer. 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. The method according to the invention is described in more detail below.

[0044] The present invention also relates to a thermoplastic elastomer that is obtainable or obtained according to the inventive method. All mentioned (preferred) features of the elastomer composition according to the invention shall also apply to the thermoplastic elastomer according to the invention.

[0045] The present invention also relates to the use of a thermoplastic elastomer according to the invention as a damping material for protectors / sports protectors and protectors in the military sector, for electronic components, electrical components (e.g. vibration damping of drills), for sound insulation, in vehicle technology and in the transport sector, in the construction sector, in household appliance technology (e.g. for vibration damping of washing machines and tumble dryers), for industrial machines, for firearms, for devices in healthcare and medicine, in military transport and for military equipment.

[0046] Furthermore, the present invention also relates to a damping material, in particular a protector, made of a 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0047] thermoplastic elastomer according to the invention or obtainable from a thermoplastic elastomer composition according to the invention.

[0048] 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:

[0049] Al ) double bond-containing styrene-isoprene-styrene block copolymer (SIS)

[0050] A2 ) Styrene-ethylene-ethylene / propylene-styrene block copolymer (non-functionalized)

[0051] B) functionalized hydrogenated styrene block copolymer C) glass hollow spheres

[0052] D) further styrene block copolymer (non-functionalized) E) styrene-butadiene-styrene block copolymer (SBS)

[0053] F) Plasticizers

[0054] G) Additive

[0055] Components Al ) and A2 ) :

[0056] The total amount of the sum of components Al) and A2) in the thermoplastic elastomer composition or in the thermoplastic elastomer according to the invention is preferably in an amount in the range of 10 wt.% to 60 wt.%, more preferably in a range of 15 wt.% to 50 wt.%, and even more preferably in a range of 20 wt.% to 45 wt.%, based on the total weight of the thermoplastic elastomer composition or the thermoplastic elastomer. 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0057] Component Al ): double bond-containing styrene-isoprene-styrene block copolymer (SIS)

[0058] According to the invention, a “double-bonded styrene-isoprene-styrene block copolymer” is a multi-block copolymer of structure ABA, wherein the A-block is typically polystyrene and the B-block is typically composed of isoprene units. 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.

[0059] According to the invention, double-bond-containing styrene-isoprene-styrene block copolymers (SIS) preferably have a weight-averaged molecular weight (Mw) of 50,000 to 500,000 g / mol, particularly preferably of 100,000 to 200,000 g / mol. Furthermore, the styrene content is preferably in the range of 15 wt.% to 25 wt.%, more preferably in the range of 18 wt.% to 22 wt.%, based on the total weight of the polymer. The glass transition temperature is preferably in the range of -18 °C to 15 °C, more preferably in the range of -5 °C to 10 °C. The Shore A hardness is preferably in the range of 55 Shore A to 95 Shore A, more preferably in the range of 75 Shore A to 90 Shore A.

[0060] Styrene-isoprene-styrene block copolymers (SIS) containing double bonds can be those of the Hybrar™ type from Kuraray, specifically the 5000 series. Hybrar™ 5127 is particularly preferred according to the invention. .28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG

[0061] Component A2 ): Styrene-ethylene-ethylene / propylene-styrene block copolymer

[0062] According to the invention, a “styrene-ethylene-ethylene / propylene-styrene block copolymer” is understood to be a multi-block copolymer of structure ABA, wherein the A-block is typically polystyrene and the B-block is typically composed of ethylene and ethylene / propylene units. Furthermore, it preferably has no double bonds. 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.

[0063] Styrene-ethylene-ethylene / propylene-styrene block copolymers (SEEPS) according to the invention preferably have a weight-averaged molecular weight (Mw) in the range of 110,000 to 500,000 g / mol, particularly preferably in the range of 120,000 to 250,000 g / mol. Furthermore, the styrene content is preferably in the range of 9 wt.% to 15 wt.%, more preferably in the range of 11 wt.% to 13 wt.%, based on the total weight of the polymer. The glass transition temperature is preferably in the range of -45 °C to -20 °C, more preferably in the range of -40 °C to -25 °C. The Shore A hardness is preferably in the range of 32 Shore A to 50 Shore A, more preferably in the range of 38 Shore A to 44 Shore A.

[0064] Styrene-ethylene-ethylene / propylene-styrene block copolymers (SEEPS) can be those of the Hybrar™ type from Kuraray, 28310-PT-WO, January 19, 2026, Kraiburg TPE GmbH & Co. KG

[0065] so-called 7000 series are used. Hybrar™ 7311F is particularly preferred according to the invention.

[0066] Component B): functionalized hydrogenated styrene block copolymer

[0067] According to the invention, a "functionalized hydrogenated styrene block copolymer" is understood to be a multi-block copolymer, wherein at least one of the blocks is polystyrene. At least one of the further blocks is preferably a block consisting of ethylene / butylene units. Furthermore, it preferably has no double bonds. The SBC can be a tri-block copolymer of the structure ABA, wherein the A-block is typically polystyrene and the B-block is typically composed of ethylene / butylene units. 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 vinylnaphthalene such as 1-vinylnaph-thalin and 2-vinylnaphthalene.The hydrogenated styrene block copolymer is preferably produced by hydrogenating a triblock copolymer of structure ABA, in which the B-block contains double bonds. According to the invention, the hydrogenated styrene block copolymer is functionalized as described below.

[0068] According to the invention, the functionalized hydrogenated styrene block copolymer is functionalized with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, a methacryloxyalkylacyloxysilane, or an anhydride of an unsaturated organic acid, as described above. The functionalization preferably takes place 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0069] This is achieved by grafting, in which a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, a methacryloxyalkylacyloxysilane, or an anhydride of an unsaturated organic acid is grafted onto a suitable functionalized hydrogenated styrene block copolymer. After the grafting reaction with a vinylalkoxysilane, the functionalized hydrogenated styrene block copolymer exists as a 2-ethyl-alkoxysilane-modified functionalized hydrogenated styrene block copolymer. After the grafting reaction with a methacryloxyalkylalkoxysilane, the functionalized hydrogenated styrene block copolymer exists as a 2-methyl-propenoyl-al-kylalkoxysilane-modified functionalized hydrogenated styrene block copolymer.After grafting with a methacryloxyalkylacyloxysilane, the functionalized hydrogenated styrene block copolymer exists as a 2-methyl-propenoyl-al-kylacyloxysilane-modified functionalized hydrogenated styrene block copolymer. After grafting with an anhydride of an unsaturated organic acid, the functionalized hydrogenated styrene block copolymer exists as a 1,2-dicarboxylic acid-modified functionalized hydrogenated styrene block copolymer. These are the reaction products of the reaction of functionalized hydrogenated styrene block copolymer with a vinylalkoxysilane, a vinylacyloxysilane, a methacryloxyalkylalkoxysilane, or a methacryloxyalkylacyloxysilane, or an anhydride of an unsaturated organic acid using radical initiators, according to the reaction equations in Figures 1 and 2, which have already been described above. 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG.

[0070] Grafting generally refers to the process of grafting other molecular building blocks (here, vinylalkoxysilane, vinylacyloxysilane, methacryloxyalkylalkoxysilane, methacryloxyalkylacyloxysilane, or the anhydride of an unsaturated organic carboxylic acid) onto pre-existing molecular chains of a primary polymer (here, an unfunctionalized hydrogenated styrene block copolymer). 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 subsequently 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 functionalized hydrogenated styrene block copolymer, the reaction is preferably carried out in the melt (extrusion).

[0071] If an anhydride of an unsaturated organic acid is used for the grafting reaction, maleic anhydride is particularly preferred. 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0072] 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. Ci-8 alkoxy groups are preferred, with methoxy, ethoxy, or propoxyg groups being more preferred, and methoxy groups being most preferred. The acyloxy groups may be Ci-g acyloxy groups, with Ci-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 = Ci-5-alkyl, with Ci-3-alkyl being preferred and methyl being particularly preferred), which may also include one of the following groups - (CH2). n - 0- or - (CH2) n _ can be bonded to the silicon atom of the silane, where n = 1 to 5, more preferably 1 to 3 and even more preferably 3, with n-propyl being most preferred. In the case of group - (CH2) n -O- binds the oxygen atom to the silicon atom of the silane. Such graftable silanes are available, for example, under the trade name Geniosil® from Wacker.

[0073] Preferred vinylsilanes are: vinyltrialkoxysilanes (specifically vinyltrimethoxysilane, vinyltriethoxysilane), vinylalkyldialkoxysilanes (specifically vinyldimethoxymethylsilane), 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0074] Vinyltricarboxysilanes (specifically vinyltriacetoxysilane). These are shown in the following formulas (I) to (III):

[0075]

[0076] III

[0077] wherein R2 to R5 are each independently alkyl groups, preferably methyl or ethyl groups.

[0078] Preferred methacryloxyalkylalkoxysilanes and methacryloxyal-kylacyloxysilanes are: 3-methacryloxypropyl-trialkoxysilane or methacryloxymethyl-trialkoxysilane (specifically 3-methacryloxy-loxypropyl-trimethoxysilane, 3-methacryloxypropyl-triethoxysilane, methacryloxymethyl-trimethoxysilane, methacryloxymethyl-triethoxysilane) , 3-Methacryloxypropyl-alkyldialkoxysilane or methacryloxymethyl-alkyldialkoxysilane (specifically methacryloxymethyl-dimethoxymethylsilane), 3-methacryloxypropyl-tri-carboxysilane or methacryloxymethyl-tricarboxysilane (specifically: 3-methacryloxypropyl-triacetoxysilane). These are shown in the following formulas (IV) to (VI): 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0079]

[0080] wherein RI is an alkylene group, preferably a methylene or propylene group; and R2 to R5 are each independently alkyl groups, preferably methyl or ethyl groups.

[0081] The amount of anhydride of an unsaturated organic carboxylic acid in the grafted functionalized hydrogenated styrene block copolymer 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 functionalized 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0082] hydrogenated styrene block copolymer functionalized with an anhydride of an organic carboxylic acid.

[0083] The melt flow index (230 °C, 5 kg) of the functionalized hydrogenated styrene block copolymer is preferably in the range of 10 cm 3 / 10 min to 40 cm 3 / 10 min, more strongly preferred in the area of ​​15 cm 3 / 10 min to 35 cm 3 / 10 min.

[0084] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of the sum of components Al ) and A2 ) to component B) is preferably in the range of 100 : 5 to 100 : 25, more preferably in the range of 100 : 7 to 100 : 23 and most preferably in the range of 100 : 10 to 100 : 20.

[0085] Hydrogenated styrene block copolymers of the Scona TSKD type from BYK can be used. Scona TSKD 9103 is particularly preferred according to the invention.

[0086] Component C): Hollow glass spheres

[0087] 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.

[0088] The hollow glass spheres can be essentially round, but can also deviate from this shape, e.g., the shape of an ellipse. 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0089] exhibit, 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.

[0090] Since high shear forces are exerted during the mixing of the thermoplastic elastomer composition according to the invention, hollow glass spheres can break. This breakage must be avoided by correctly 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.

[0091] The mean diameter is preferably in the range of 10 pm to 70 pm, more preferably in the range of 10 pm to 35 pm. The mean diameter can be determined using a commercially available laser diffraction particle size analyzer.

[0092] The hollow glass spheres preferably have a density of 0.9 g / cm³. 3 or less, preferably 0.6 g / cm³ 3 or less, and 0.3 g / cm² 3 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. 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG

[0093] Hollow glass spheres suitable for use according to the invention are available from 3M. Preferably, hollow glass spheres of type 1M16K are used according to the invention.

[0094] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of the sum of components Al ) and A2 ) to component C) is in the range of 100 : 5 to 100 : 80, more preferably in the range of 100 : 10 to 100 : 70, even more preferably in the range of 100 : 20 to 100 : 60 and most preferably in the range of 100 : 30 to 100 : 50.

[0095] Component D): further styrene block copolymer (non-functionalized)

[0096] The thermoplastic elastomer composition according to the invention can contain, in addition to the components Al ) , A2 ) and B), a further styrene block copolymer which is different from the components Al ) , A2 ) , B) and E).

[0097] 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 comprises 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 vinylnaphthalene such as 1-28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0098] Vinylnaphthalene and 2-vinylnaphthalene can be substituted. The B-block can also alternatively contain mixtures of dienes. Furthermore, SBCs consisting of styrene and diene monomers can also be used as hydrogenated derivatives. In this case, the B-block units are partially or completely hydrogenated. Styrene-ethylene / butylene-styrene block copolymers (SEBS), styrene-ethylene / propylene-styrene block copolymers (SEPS), and styrene-ethylene-ethylene / propylene-styrene block copolymers (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 mixtures thereof (B-blocks) in different sequences of A- and B-blocks (e.g., BAB, ABAB, etc.) can alternatively be used. Preferred SBCs are composed of triblock copolymers ABA. According to the invention, the SBC is particularly preferably a SEBS or a SEPS.

[0099] In principle, any styrene block copolymer that differs from components Al), A2), B), and E) can be used as the additional styrene block copolymer. However, for improved processability of the thermoplastic elastomer composition, it has proven advantageous to use a styrene block copolymer whose Shore A hardness is preferably in the range of 25 Shore A to 45 Shore A and more preferably in the range of 30 Shore A to 40 Shore A. Furthermore, the additional styrene block copolymer preferably has a relatively low styrene content in the range of 5 wt.% to 18 wt.%, more preferably in the range of 10 wt.% to 15 wt.%, based on the total weight of the polymer. The melt flow index (230 °C / 2160 g) is preferably in the range of 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0100] Range from 1 g / 10 min to 6 g / 10 min and more preferably in the range from 1.5 g / 10 min to 5 g / 10 min.

[0101] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of the sum of components Al ) and A2 ) to component D) is in the range of 100 : 0 to 100 : 80, more preferably in the range of 100 : 10 to 100 : 75, even more preferably in the range of 100 : 20 to 100 : 70, even more preferably in the range of 100 : 30 to 100 : 65 and most preferably in the range of 100 : 40 to 100 : 60, provided that it is contained in the composition or the thermoplastic elastomer.

[0102] Other styrene block copolymers that can be used include, for example, polymers from the Kraton™ G series by Kraton (e.g., Kraton™ Gl 645 V) or corresponding polymers from the Septon™ 200, 4000 and 8000 series by Kuraray (e.g., Septon™ 4055 or 4077).

[0103] Component E): Styrene-butadiene-styrene block copolymer

[0104] According to the invention, a "styrene-butadiene-styrene block copolymer" is understood to be a multi-block copolymer of the ABA structure, wherein the A-block is typically polystyrene and the B-block is typically composed of polymerized butadiene units. Alternatively, in the A-block, the styrene monomers 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 vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene. It is also possible that the B-28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0105] The block is built not only from butadiene units but also from styrene units.

[0106] The melting volume rate (200 °C / 5 kg) of the styrene-butadiene-styrene block copolymer (SBS) is preferably in the range of 7 cm³. 3 / 10 min to 15 cm 3 / 10 min and even more strongly preferred in the area of ​​9 cm 3 / 10 min to 13 cm 3 / 10 min. The modulus of elasticity is preferably in the range of 1000 MPa to 1800 MPa and more preferably in the range of 1200 MPa to 1600 MPa. The Shore D hardness is preferably in the range of 40 Shore D to 90 Shore D, more preferably in the range of 50 Shore D to 75 Shore D, and even more preferably in the range of 58 Shore D to 68 Shore D.

[0107] The A-blocks of the styrene-butadiene-styrene block copolymer (SBS) are preferably composed of styrene units, and the B-block is preferably composed of 40% to 100% butadiene units and 0% to 60% by weight of styrene units. Particularly preferably, the A-blocks of the styrene-butadiene block copolymer (SBS) are composed of styrene units, and the block is composed of 40% to 80% by weight of butadiene units and 20% to 60% by weight of styrene units.

[0108] The butadiene unit content in the styrene-butadiene-styrene block copolymer (SBS) is preferably in the range of 15 wt.% to 35 wt.%, particularly preferably in the range of 20 wt.% to 30 wt.%, in each case based on the total weight of the styrene-butadiene-styrene block copolymer (SBS).

[0109] The styrene unit content in the styrene-butadiene-styrene block copolymer (SBS) is preferably in the range of 65 wt.% to 85 wt.%, particularly preferably in the range of 70 wt.%. 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0110] up to 80 wt. -%, each based on the total weight of the styrene-butadiene-styrene block copolymer (SBS) .

[0111] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of the sum of components Al ) and A2 ) to component E) is in the range of 100 : 0 to 100 : 120, more preferably in the range of 100 : 10 to 100 : 110, even more preferably in the range of 100 : 30 to 100 : 100 and most preferably in the range of 100 : 40 to 100 : 95, provided that it is contained in the composition or the thermoplastic elastomer.

[0112] Styrolux 684D from Ineos Styrolution, for example, can be used as a styrene-butadiene-styrene block copolymer.

[0113] Component F): Plasticizer

[0114] 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. Furthermore, di- or tri-alkyl esters of mellitic acid are suitable, wherein the alkyl substituents preferably contain linear and / or branched alkyl chains with > 4 carbon atoms. Additionally, 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 .28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0115] Furthermore, carboxylic acid esters of mono- and / or polyalkylene glycols, such as ethylene glycol adipate, can also be used as plasticizers. According to the invention, technical or medical mineral or white oils are preferably used. Shell Catenex T 145 S from Shell GmbH is one example of a technical mineral oil.

[0116] Suitable plasticizers can also be mixtures of the described substance classes.

[0117] In the thermoplastic elastomer composition or thermoplastic elastomer according to the invention, the weight ratio of the sum of the components Al ) and A2 ) to the plasticizer is preferably in the range of 100 : 10 to 100 : 90, more preferably in the range of 100 : 20 to 100 : 80 and most preferably in the range of 100 : 30 to 100 : 60, if contained in the composition or the thermoplastic elastomer.

[0118] Component G): Additives such as stabilizers, auxiliary substances and colorants and other fillers

[0119] Suitable additives include, for example, but not exclusively, 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.

[0120] The following can be used as process aids and stabilizers, for example: aging or 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0121] Ozone protection agents such as ozone protection waxes, stabilizers such as heat stabilizers, weathering stabilizers; oxidation protection agents, antioxidants, UV stabilizers, other light protection agents, antifoaming agents, lubricants, dispersants, release agents, anti-blocking agents, radical scavengers, metal deactivators, and also additives such as foaming agents, blowing agents, impact modifiers, adhesion promoters and viscosity modifiers.

[0122] 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.

[0123] Inorganic fillers are preferably used as additional fillers, which simplify the processing of the thermoplastic elastomer composition according to the invention.

[0124] Examples include, for example, carbon black, chalk (calcium carbonate), kaolin, silica, talc (magnesium silicate), aluminum oxide hydrate, aluminum silicate, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, barium sulfate, zinc carbonate, calcined kaolin (e.g., Polestar® 200 P), calcium oxide, magnesium oxide, titanium dioxide, aluminum oxide, zinc oxide, silanized kaolins, silanized silica, coated chalk, treated kaolins, pyrogenic silica, hydrophobized pyrogenic silica (e.g., Aerosil® 972), synthetic amorphous precipitated silica (silica), industrial carbon black, graphite, nanoscale fillers such as carbon nanofibrils, platelet-shaped nanoparticles, or nanoscale silicon dioxide hydrates and minerals. If an additional filler is used, calcium carbonate is preferred, for example from Omya28310-PT-WO, January 19, 2026, Kraiburg TPE GmbH & Co. KG.

[0125] GmbH (Omyacarb 5AV) , used . Since the aforementioned additional fillers increase the density of the thermoplastic elastomer composition according to the invention, they are preferably not included in the thermoplastic elastomer composition.

[0126] Production of the compositions according to the invention:

[0127] The thermoplastic elastomer compositions according to the present invention can be produced by mixing the components Al), A2), B), C), D), E), F), and G) – 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).

[0128] When carrying out the manufacturing process according to the invention, it is important to ensure that the mixing temperature is high enough to allow the components with the highest hardness 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 the hardest component is selected. At the same time, adequate energy input must be ensured, which is determined by the rotational speed and throughput in the extruder. 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG

[0129] Mixing the components - insofar as they are present in the compositions - is particularly preferred at a temperature in the range of 150°C to 240°C and preferably 180°C to 220°C.

[0130] 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 forms of implementation are also disclosed in this application.

[0131] Examples:

[0132] Methods of determination and definitions:

[0133] The Shore A and Shore D hardness are determined according to DIN ISO 48-4.

[0134] The weight-averaged molecular weight is determined by conventional gel permeation chromatography.

[0135] The glass transition temperature is determined using DSC.

[0136] The determination of the melt flow index and the melt volume rate is carried out according to ISO 1133.

[0137] Tensile strength is defined as the maximum mechanical tensile stress that a material can withstand before it breaks / tears. It is determined in a tensile test from the maximum tensile force achieved, relative to the original cross-section of the (standardized) 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0138] Sample strength calculated and specified in MPa. Tensile strength is measured according to DIN 53504 / ISO 37.

[0139] Elongation at break is a material property that indicates the permanent elongation at fracture relative to the initial gauge length. In materials testing, elongation at break is one of many parameters and characterizes a material's deformability. It is the elongation at break relative to the initial gauge length L. o The permanent change in length AL of a specimen after fracture in a tensile test. This change in length is expressed as a percentage. The elongation at break is measured according to DIN 53504 / ISO 37.

[0140] The loss factor tan 5 describes a material's ability to dampen vibrations and shock loads and is calculated as the quotient of the loss modulus E" and the elastic modulus E'. The loss modulus E" and the storage modulus E' are measured using dynamic mechanical analysis (DMA). This analysis was performed on a Netzsch DMA 242 instrument in accordance with DIN 53513 (March 1990) and DIN 53545 (December 2016). A round specimen with a height of 6.0 mm was measured at a compressive force of 6.0 N, a deformation amplitude of 30 pm, and a frequency of 50 Hz. Measurements were taken within a temperature range of -40°C to +60°C at a heating rate of 2 K / min.

[0141] Extruder and injection molding parameters:

[0142] The thermoplastic elastomers of the present invention are produced in a continuous process on an intermeshing, co-rotating twin-screw extruder (46 L / D). The hollow glass spheres are fed via 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG

[0143] A side feeder is added. The extruder speed is 600 rpm, and the throughput is 500 kg / h for the production system used. The set temperature profile ranges from 190 to 170°C in the feed zone to the discharge zone and is maintained at a consistent temperature profile by means of a temperature control system. The resulting plastic melt is filtered by a 200 µm filter system and processed into granules via a granulation unit. The produced granules are used as semi-finished products for subsequent injection molding or extrusion processing.

[0144] Examples of implementation:

[0145] Table 1 lists the abbreviations used for the components employed in the examples and comparison examples: 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG

[0146] Table 1:

[0147]

[0148] Examples and comparative examples:

[0149] Production of thermoplastic elastomer compounds and elastomers (according to the invention and not according to the invention):

[0150] Thermoplastic elastomers are produced according to the manufacturing process described above, using the components listed in Tables 3 and 4. Table 2 specifies the manufacturer and type of the components used. Tables 5 and 6 list the measured parameters. 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co. KG

[0151] Table 2:

[0152]

[0153] 28310-PT-WO January 19, 2026

[0154] Kraiburg TPE GmbH & Co. KG

[0155] Table 3:

[0156]

[0157] 28310-PT-WO January 19, 2026

[0158] Kraiburg TPE GmbH & Co. KG

[0159] Table 4:

[0160]

[0161] 28310-PT-WO January 19, 2026

[0162] Kraiburg TPE GmbH & Co. KG

[0163] Table 5 .

[0164]

[0165] 28310-PT-WO January 19, 2026

[0166] Kraiburg TPE GmbH & Co. KG

[0167] Table 6.

[0168] <

[0169]

[0170] 28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co . KG

[0171] The thermoplastic elastomer composition from Example 3 according to the invention already exhibits significant damping behavior at the starting point of the measurements. Half the maximum of the first loss factor, tan 5, lies outside the measured range. As expected, Example 3 also shows two different maxima of the tan 5 values, which arise from the two components Al and A2 and result in the thermoplastic elastomer composition according to the invention exhibiting good damping properties over a wide temperature range. Between the two maxima, the value for the loss factor is consistently at least 0.6, and thus above half the tan 5 of both maxima, which is why only a large range can be specified in Table 4.

[0172] Examples 3 and 4 according to the invention demonstrate that the use of component A2 leads to an improvement in the damping properties at low temperatures. With a higher proportion of component A2, the maxima of the loss factor Tan 5 shift into the low-temperature range.

Claims

28310-PT-WO January 19, 2026 Kraiburg TPE GmbH & Co . KG Patent claims 1. Thermoplastic elastomer composition comprising the following components: Al ) a double-bonded styrene-isoprene-styrene block copolymer , and / or A2 ) a styrene-ethylene-ethylene / butylene-styrene block copolymer, as well as B) a hydrogenated styrene block copolymer functionalized by grafting reaction, which is functionalized with an anhydride of an unsaturated organic acid or a vinyl alkoxysilane or a vinyl acyloxysilane or a methacryloxyalkyl alkoxysilane or a methacryloxyalkyl acyloxysilane, and C) Hollow glass spheres.

2. Thermoplastic elastomer composition according to claim 1, wherein the hydrogenated styrene block copolymer of component A2 ) is not functionalized by grafting reaction with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane .

3. Thermoplastic elastomer composition according to claim 1 or 2, wherein the hydrogenated styrene block copolymer functionalized by grafting reaction from component 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG B) is a styrene-ethylene / butylene-styrene block copolymer functionalized by grafting reaction.

4. Thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the anhydride of an unsaturated organic acid is an anhydride of an organic 1,2-dicarboxylic acid.

5. Thermoplastic elastomer composition according to one of claims 1 to 4, which additionally comprises as component E) a styrene-butadiene-styrene block copolymer .

6. Thermoplastic elastomer composition according to any one of claims 1 to 5, which additionally comprises as component D) a further styrene block copolymer which is not functionalized by grafting reaction with an anhydride of an unsaturated organic acid or a vinylalkoxysilane or a vinylacyloxysilane or a methacryloxyalkylalkoxysilane or a methacryloxyalkylacyloxysilane and which is different from components Al ) , A2 ) , B) and E) .

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

8. Thermoplastic elastomer composition according to any one of claims 1 to 7, wherein the weight ratio of the sum of components Al) and A2) to component B) is in the range of 100:5 to 100:

25. .28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG 9. Thermoplastic elastomer composition according to any one of claims 1 to 8, wherein the weight ratio of the sum of components Al ) and A2 ) to component C) is in the range of 100 : 5 to 100 : 80 .

10. Thermoplastic elastomer composition according to any one of claims 1 to 9, wherein the glass hollow spheres are uncoated glass hollow spheres.

11. Method for producing a thermoplastic elastomer, wherein the components of a thermoplastic elastomer composition according to any one of claims 1 to 10 are mixed together at a temperature in the range of 150°C to 240°C.

12. Thermoplastic elastomer obtainable by a method according to claim 11.

13. Use of a thermoplastic elastomer composition according to any one of claims 1 to 10 or of a thermoplastic elastomer according to claim 12 as a damping material for protectors / sports protectors and protectors in the military sector, for electronic components, electrical components, for sound insulation, in vehicle technology and in the transport sector, in the construction sector, in household appliance technology, for industrial machines, for firearms, for devices in healthcare and medicine, in military transport and for military equipment.

14. Damping material, in particular a protector, made of a thermoplastic elastomer according to claim 12 or 28310-PT-WO 19 January 2026 Kraiburg TPE GmbH & Co. KG available from a thermoplastic elastomer composition according to any one of claims 1 to 10.

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