Thermoplastic elastic compositions and their use as shoe sole materials

Abstract

This invention relates to thermoplastic elastomer compositions comprising an aromatic thermoplastic polyurethane and a block copolymer, said block copolymer comprising at least one polymer block consisting essentially of repeating units derived from at least one vinyl aromatic monomer and at least one polymer block consisting essentially of repeating units derived from isobutylene, isobutylene derivatives, and / or mixtures thereof. The thermoplastic elastomer compositions exhibit improved anti-slip properties and can be advantageously used as materials requiring anti-slip properties, preferably as sole materials for shoes, particularly safety shoes.

Description

[0001] This invention relates to thermoplastic elastomer compositions comprising an aromatic thermoplastic polyurethane and a block copolymer, said block copolymer comprising at least two polymer blocks, one of which is a polymer block consisting essentially of repeating units derived from at least one vinyl aromatic monomer, and the other of a polymer block consisting essentially of repeating units derived from isobutylene, isobutylene derivatives, and / or mixtures thereof. The thermoplastic elastomer compositions have improved anti-slip properties and are suitable for use as materials requiring anti-slip performance, preferably as sole materials for shoes, particularly safety shoes.

[0002] Despite the superior mechanical properties and ease of processing of thermoplastic polyurethane (TPU) outsole materials, the slip resistance of TPU outsoles remains a technical challenge that needs improvement. There are various methods to improve the slip resistance of outsole materials, one of which is by adjusting the sole profile.

[0003] The methods disclosed in US 2,065,386 and US 2,160,601 are to improve slip resistance by using anti-slip devices nailed or screwed onto the heel. The methods taught in US 2009 / 0249652 and US 2010 / 0088929 are to improve the slip resistance of the sole by creating certain patterns on the sole.

[0004] To date, existing technologies have not explored solutions to this problem through material selection and chemical properties.

[0005] US 2001 / 0046588 relates to an anti-slip surface consisting of individual, unconnected uneven portions made of an anti-slip polymer material, which does not form a continuous film on the surface of a thermoplastic product. US 2006 / 0100378 discloses a shoe sole whose material includes polyvinyl chloride, plasticizer expanding powder, and stabilizer foaming powder to increase its anti-slip properties.

[0006] CN 110283298 relates to an anti-slip thermoplastic polyurethane comprising 50-70 parts by weight of a polyol as component A, the chain end of which is capped with hydroxyl groups, 10-20 parts by weight of a polyisocyanate as component B, 1.5-3.5 parts by weight of a 2-12C linear diol as component C, 0.05 to 1 part by weight of an organosilicon as component D, the chain end of which has a reactive group that reacts with the isocyanate, 15 to 30 parts by weight of a diethylene glycol dibenzoate as component E, and 0.001 to 0.1% by weight of a catalyst.

[0007] CN 105086422 discloses a long glass fiber reinforced thermoplastic polyurethane (TPU) anti-slip shoe sole, comprising 90 to 110 parts by weight of elastic TPU, 20 to 40 parts by weight of glass fiber, 0.5 to 1 part by weight of anti-abrasion agent, 2.5 to 4 parts by weight of crosslinking agent, 0.5 to 1 part by weight of bridging agent, 4 to 6 parts by weight of compatibilizer, 1 to 3 parts by weight of activator, 0.4 to 0.6 parts by weight of antioxidant, 0.4 to 0.6 parts by weight of flow aid, and 1 to 2.5 parts by weight of foaming agent.

[0008] This invention improves the chemical properties of TPU material blends, particularly increasing the anti-slip performance of the outsole, without relying on the contour of the sole.

[0009] Thermoplastic elastomer compositions comprising thermoplastic polyurethane and styrene block copolymers are known. US2010 / 0160545 relates to a thermoplastic elastomer based on a blend of styrene block copolymer and thermoplastic polyurethane made from aliphatic diisocyanate, which has excellent light transmittance, transparency and adhesion, the latter being suitable for adhesion to engineered thermoplastic compounds with multi-component polymer structures.

[0010] WO 2016 / 130639 discloses thermoplastic elastomer formulations comprising blends of thermoplastic elastomers with different chemical properties, which, as blends, exhibit damping characteristics over a wide temperature range and a wide range of vibration frequencies.

[0011] WO 2018 / 200510 relates to a damping material comprising (A) a thermoplastic elastomer compound of polyester-type thermoplastic polyurethane; and (B) a styrene-isobutylene-styrene block copolymer not exceeding about 30% by weight of the compound. When tested according to ASTM D1003 with a 3mm thick, injection-molded sample, the compound has a haze not exceeding about 60% (mm).

[0012] US 2010 / 010171 A1 relates to a composition comprising (a) an anionic block copolymer of a monoalkenyl aromatic hydrocarbon and isoprene, and (b) a thermoplastic polyurethane elastomer. It discloses that the SIS block copolymer is highly effective in modifying the hardness of TPU. Furthermore, it discloses that blends of TPU and the SIS block copolymer can produce optically transparent compositions.

[0013] WO 2009 / 069666 A1 relates to a thermoplastic styrene elastomer composition for the production of molded articles temporarily fixed and bonded to an olefin resin substrate. The thermoplastic styrene elastomer composition is characterized by comprising a styrene block copolymer (A), polypropylene (B), and a thermoplastic polyurethane elastomer (C).

[0014] US 2016 / 230000 A1 relates to a thermoplastic elastomer compound comprising a styrene block copolymer and a high softening point tackifier. The block copolymer has a copolymer tan Delta Peak Temperature, and the thermoplastic elastomer compound has a compound tan Delta Peak Temperature. The compound's tan Delta Peak Temperature is higher than the copolymer's tan Delta Peak Temperature. The thermoplastic elastomer compound exhibits damping properties.

[0015] US 2018 / 118870 A1 relates to a polymer composition comprising 60 to 85 parts by weight of thermoplastic polyurethane and 15 to 40 parts by weight of polyolefin, wherein the sum of the parts by weight of thermoplastic polyurethane and the parts by weight of polyolefin is 100 parts by weight. Based on a total of 100 parts by weight of thermoplastic polyurethane and polyolefin, it further comprises 1 to 15 parts by weight of a hydrogenated block copolymer derived from a vinyl aromatic monomer and a conjugated diene monomer.

[0016] Minor modifications to TPU unexpectedly produced a significant impact on gliding properties. A high coefficient of friction, a key indicator of slip resistance, is an important aspect of the polyurethane industry's competitiveness against other materials. This invention provides a solution to the slipping problem of TPU outsoles, and this solution is well-suited to the chemistry and processing of TPU.

[0017] In standard anti-slip tests, the inventors surprisingly observed a significant improvement in anti-slip properties when applied to the outsole of shoes. The thermoplastic polyurethane composition for safety shoes, comprising at least one other styrene block copolymer as disclosed herein, was tested using the test method of “EN ISO 13287 (2020) Personal Protective Equipment”.

[0018] The composition can be obtained by mixing materials in a prescribed ratio, for example by simply mixing the materials manually or by using dry mixing, extrusion or any other method to produce a polymer blend. The final product obtained by injection molding of the blended thermoplastic elastomer composition (E) is a transparent, translucent or opaque and homogeneous sole material without any defects or delamination.

[0019] This invention relates to a thermoplastic elastomer composition (E) comprising...

[0020] (or its components):

[0021] (a) 40 to 99% by weight of at least one aromatic thermoplastic polyurethane (A);

[0022] (b) 1 to 60% by weight of at least one block copolymer (B), comprising:

[0023] (B-1) At least one polymer block (B-1) consists essentially of repeating units derived from at least one vinyl aromatic monomer, and

[0024] (B-2) At least one polymer block (B-2) consists essentially of repeating units derived from isobutylene, isobutylene derivatives, and / or mixtures thereof, wherein at least one block copolymer (B) is preferably at least partially hydrogenated; and

[0025] (c) 0 to 10% by weight of at least one optional additive (C),

[0026] Components (A), (B), and (C) together constitute 100% by weight of the thermoplastic elastomer composition (E).

[0027] The thermoplastic elastomer composition (E) has a glass transition temperature Tg(E) < 0°C, calculated according to the following formula:

[0028]

[0029] in

[0030] w(A) is the mass (weight) fraction of component A.

[0031] w(B) is the mass (weight) fraction of component B.

[0032] Tg(A) is the glass transition temperature of pure component A, measured in Kelvin.

[0033] Tg(B) is the glass transition temperature of pure component B, expressed in Kelvin.

[0034] Tg(E) is the glass transition temperature of composition E, expressed in Kelvin.

[0035] Tg(A) and Tg(B) are determined by dynamic mechanical analysis at 1 Hz according to ISO 6721-2, wherein the thermoplastic elastomer composition (E) has a resilience of 25% to 60% according to DIN 53512, and wherein the at least one aromatic thermoplastic polyurethane (A) is at least one transparent, translucent or opaque aromatic thermoplastic polyurethane (A).

[0036] The thermoplastic elastomer composition (E) can be prepared by extrusion, dry mixing and / or manual mixing of components (A), (B) and optional (C).

[0037] The thermoplastic elastomer composition (E) is characterized in that it passes the SRA test according to the DIN EN 13287 (2020) standard for personal protective equipment. When used as a sole material, according to EN 13287, the heel slip SRA value is ≥0.28 and the forward smooth SRA value is ≥0.32. The thermoplastic elastomer composition (E) is further characterized in that it passes the SRB test according to the DIN EN 13287 (2020) standard for personal protective equipment, when used as a sole material, the heel slip SRB value is ≥0.13 and the forward smooth SRB value is ≥0.18. Therefore, the thermoplastic elastomer composition (E) is characterized in that, when used as a sole material, it passes the SRC test according to the EN 13287 (2020) standard for personal protective equipment.

[0038] Traditional polyester-based TPU typically passes the SRA test for personal protective equipment (PPE) under EN 13287, but fails the SRB test. Polyether-based TPU usually fails both tests. Therefore, for traditional TPU sole materials, the outsole profile is usually modified to pass these two tests, thus limiting design freedom when using traditional TPU sole materials.

[0039] The inventors have surprisingly discovered that the thermoplastic elastomer composition (E) described herein is suitable for use as a footwear material and passes the SRA, SRB, and SRC tests according to the EN 13287 (2020) personal protective equipment standard. This property is achieved by adding the block copolymer (B) disclosed herein.

[0040] However, on the other hand, it was found that TPU compositions containing other styrene copolymers such as poly(acrylonitrile-butadiene-styrene) (ABS) and poly(b-styrene-b-ethylene-b-butene-b-styrene) (SEBS) failed to pass the SRA, SRB and SRC tests for personal protective equipment in accordance with EN 13287 (2020) under the same conditions.

[0041] The present invention also relates to the use of the thermoplastic elastomer composition (E) of the present invention in the production of outsole or outsole components. In another aspect, the present invention relates to articles (T) formed from the said thermoplastic elastomer composition (E). Preferably, the articles (T) are obtained by molding, extrusion, thermoforming, lamination, calendering, and / or 3D printing processes. In a particular embodiment, the article (T) is a sole material, particularly as a sole material for safety shoes.

[0042] The following will describe in detail the thermoplastic elastomer composition (E), its composition, and its preparation and use.

[0043] Thermoplastic elastomer composition (E)

[0044] The thermoplastic elastomer composition (E) of the present invention comprises (or consists of):

[0045] (a) 40 to 99% by weight, preferably 50 to 95% by weight, particularly 55 to 85% by weight of at least one aromatic thermoplastic polyurethane (A);

[0046] (b) 1 to 60% by weight, preferably 5 to 50% by weight, particularly 15 to 45% by weight, of at least one block copolymer (B) comprising:

[0047] (B-1) At least one polymer block (B-1) consists essentially of repeating units derived from at least one vinyl aromatic monomer, and

[0048] (B-2) At least one polymer block (B-2) consists essentially of repeating units derived from isobutylene, isobutylene derivatives, and / or mixtures thereof, wherein at least one block copolymer (B) is preferably at least partially hydrogenated; and

[0049] (c) 0 to 10% by weight, preferably 0.1 to 7% by weight, particularly 0.5 to 5% by weight, at least one optional additive (C),

[0050] The total of components (A), (B), and (C) constitutes 100% by weight of a thermoplastic elastomer composition (E).

[0051] The thermoplastic elastomer composition (E) has a glass transition temperature (Tg(E)) < 0°C, typically < -10°C, preferably < -20°C, more preferably < -30°C, and particularly < -40°C. Surprisingly, thermoplastic elastomer compositions (E) with a glass transition temperature (Tg(E)) higher than the application temperature (i.e., typically higher than 10°C or 0°C) exhibit poorer anti-slip properties.

[0052] As MPSepe described in “Thermal Analysis of Polymers”, Rapra Review Reports, Vol. 8, No. 11, 1997, the damping ("tan delta") of a material is the ratio between its loss modulus (E") and storage modulus (E'). Therefore, as the value of tan delta increases, the viscous response of the material is relatively greater than that of the elastic response, thus providing greater damping.

[0053] When a tan delta curve is graphically described relative to temperature or frequency at a given temperature, it has a significant peak at a specific temperature, called the tan delta peak temperature, which can represent or correspond to the glass transition temperature (Tg) of the material.

[0054] The glass transition temperature Tg(E) was determined according to ISO 6721-2 by dynamic mechanical analysis (DMA) at 1 Hz by measuring the glass transition temperatures Tg of components A and B.

[0055] Then, the glass transition temperature Tg(E) of composition E is calculated according to the following equation:

[0056]

[0057] in,

[0058] w(A) is the mass (weight) fraction of component A.

[0059] w(B) is the mass (weight) fraction of component B.

[0060] Tg(A) is the glass transition temperature of pure component A, and its unit is Kelvin.

[0061] Tg(B) is the glass transition temperature of pure component B, and its unit is Kelvin.

[0062] Tg(E) is the glass transition temperature of composition E, measured in Kelvin.

[0063] For a composition (E) containing multiple components (A, B, ..., X), each component has a separate glass transition temperature, and the glass transition temperature Tg(E) of the composition (E) is calculated according to the following equation:

[0064]

[0065] in

[0066] w(X) is the mass (weight) fraction of component X.

[0067] Tg(X) is the glass transition temperature of pure component X in Kelvin, and

[0068] w(A), w(B), Tg(A), Tg(B), and Tg(E) are defined as above.

[0069] This method is further described in: “Prediction of glass transition temperature: binary blends and copolymers”; W. Brostow, R. Chiu, A. Vassilikou-Dova; Materials Communications 62 (2008); 3152-3155.

[0070] The at least one aromatic thermoplastic polyurethane (A) is at least one transparent, translucent or opaque aromatic thermoplastic polyurethane (A), preferably having a Shore A value of <85 according to DIN ISO 7619-1, more preferably ≤75, and more preferably ≤70.

[0071] Unless otherwise stated, Shore hardness is determined according to DIN ISO 7619-1 (2012).

[0072] In one embodiment of the invention, the thermoplastic elastomer composition (E) comprises (or consists of) the following components:

[0073] (a) 40 to 99% by weight of polyether-type aromatic thermoplastic polyurethane (A-2) as the at least one aromatic thermoplastic polyurethane (A), preferably 50 to 95% by weight, particularly 55 to 85% by weight, having a Shore A hardness of shore A 20 to shore D 80, preferably shore A < 85.

[0074] (b) 1 to 60% by weight of at least one block copolymer (B), preferably 5 to 50% by weight, particularly 15 to 45% by weight; and

[0075] (c) at least one additive (C) of 0 to 10% by weight, preferably 0.1 to 7% by weight, particularly 0.5 to 5% by weight.

[0076] Components (A), (B), and (C) together constitute 100% by weight of the thermoplastic elastomer composition (E).

[0077] In an alternative embodiment of the invention, the thermoplastic elastomer composition (E) comprises (or consists of) the following components:

[0078] (a) 40-99% by weight of polyester-type aromatic thermoplastic polyurethane (A-1) as the at least one aromatic thermoplastic polyurethane (A), preferably 50 to 95% by weight, more preferably 55 to 85% by weight, particularly 70 to 85% by weight, having a Shore hardness of shore A 20 to shore D 80, preferably shore A < 85.

[0079] (b) 1 to 60% by weight of at least one block copolymer (B), preferably 5 to 50% by weight, more preferably 15 to 45% by weight, particularly 15 to 30% by weight; and

[0080] (c) at least one additive (C) of 0 to 10% by weight, preferably 0.1 to 7% by weight, particularly 0.5 to 5% by weight.

[0081] Components (A), (B), and (C) together constitute 100% by weight of the thermoplastic elastomer composition (E).

[0082] In another alternative embodiment of the invention, the thermoplastic elastomer composition (E) comprises (or consists of) the following components:

[0083] (a) 40 to 99 wt% of polycarbonate-type aromatic thermoplastic polyurethane (A-3), as the at least one aromatic thermoplastic polyurethane (A), according to DIN ISO 7619-1, having a Shore A value of <85, preferably 50 to 95 wt%, more preferably 55 to 85 wt%, particularly 70 to 85 wt%.

[0084] (b) 1 to 60% by weight of at least one block copolymer (B), preferably 5 to 50% by weight, more preferably 15 to 45% by weight, particularly 15 to 30% by weight; and

[0085] (c) at least one additive (C) of 0 to 10% by weight, preferably 0.1 to 7% by weight, particularly 0.5 to 5% by weight.

[0086] Components (A), (B), and (C) together constitute 100% by weight of the thermoplastic elastomer composition (E).

[0087] In one embodiment of the invention, the thermoplastic elastomer composition (E) preferably contains >30% by weight of at least one block copolymer (B), for example, 31 to 50% by weight or 32 to 45% by weight.

[0088] The Shore hardness of the thermoplastic elastomer composition (E), according to DIN ISO 7619-1, is preferably ≤70 Shore A, more preferably ≤65 Shore A, and especially ≤60 Shore A.

[0089] The thermoplastic elastomer composition (E) has a rebound resilience of 25% to 60%, preferably 30% to 55%, and particularly 30% to 50%, according to DIN 53512. The inventors have surprisingly discovered that thermoplastic elastomer compositions (E) with rebound values ​​in this range, particularly between 30% and 50%, exhibit excellent results in terms of anti-slip properties.

[0090] The thermoplastic elastomer composition (E) preferably does not contain a large amount, i.e., no more than 5% by weight (based on the total weight of the thermoplastic elastomer composition (E), more preferably no more than 2% by weight, and particularly no more than 1% by weight), of (styrene-ethylene-butene-styrene) block copolymers (SEBS), (styrene-ethylene-propylene-styrene) block copolymers (SEPS), (styrene-ethylene-ethylene-propylene-styrene) block copolymers (SEEPS), (styrene-butadiene-styrene) block copolymers (SBS) and / or (acrylonitrile-butadiene-styrene) copolymers (ABS). More preferably, the thermoplastic elastomer composition (E) is free of (styrene-ethylene-butene-styrene) block copolymer (SEBS), (styrene-ethylene-propylene-styrene) block copolymer (SEPS), (styrene-ethylene-ethylene-propylene-styrene) block copolymer (SEEPS), (styrene-butadiene-styrene) block copolymer (SBS) and / or (acrylonitrile-butadiene-styrene) copolymer (ABS), i.e., its content is 0% by weight (based on the total weight of the thermoplastic elastomer composition (E) of said block copolymers).

[0091] In a further preferred embodiment, the thermoplastic elastomer composition (E) preferably does not contain a large amount (i.e., no more than % by weight, based on the total weight of the thermoplastic elastomer composition (E), more preferably no more than 2% by weight, and particularly no more than 1% by weight) of styrene block copolymers other than the block copolymer (B) described herein. More preferably, the thermoplastic elastomer composition (E) does not contain any styrene block copolymers other than the block copolymer (B) described herein, i.e., it contains 0% by weight of styrene block copolymers other than the block copolymer (B) described herein based on the total weight of the thermoplastic elastomer composition (E).

[0092] In a further preferred embodiment, the thermoplastic elastomer composition (E) preferably does not contain a large amount (i.e., no more than 5% by weight, based on the total weight of the thermoplastic elastomer composition (E)), more preferably no more than 2% by weight, and particularly no more than 1% by weight, of a polymer other than the block copolymer (B) described herein that comprises repeating units derived from vinyl aromatic monomers (especially repeating units of styrene monomers). More preferably, the thermoplastic elastomer composition (E) does not contain (i.e., 0% by weight, based on the total weight of the thermoplastic elastomer composition (E)) a polymer comprising repeating units derived from vinyl aromatic monomers (especially styrene monomers) other than the block copolymer (B) described herein.

[0093] The block copolymer (B) may contain, based on the total weight of the block copolymer (B), up to 5% by weight of other polymers selected from poly(styrene-b-isoprene-b-styrene) and poly(styrene-b-isobutylene-b-butadiene-b-styrene), preferably not exceeding 2% by weight. However, preferably, the block copolymer (B) and the thermoplastic elastomer composition (E) do not contain polymers selected from poly(styrene-b-isoprene-b-styrene) and poly(styrene-b-isobutylene-b-butadiene-b-styrene).

[0094] In a further preferred embodiment, the thermoplastic elastomer composition (E) preferably does not contain a large amount of polyolefin (i.e., no more than 5% by weight, based on the total weight of the thermoplastic elastomer composition (E), more preferably no more than 3% by weight, and particularly no more than 2% by weight of polyolefin). More preferably, based on the total weight of the thermoplastic elastomer composition (E), the thermoplastic elastomer composition (E) does not contain polypropylene, i.e., it contains 0% by weight of polypropylene.

[0095] The thermoplastic elastomer composition (E) described herein is advantageously used as a sole material for the production of outsoles or outsole portions of shoes. Surprisingly, the thermoplastic elastomer composition (E) according to the invention, when used as a sole material, passes the SRA, SRB, and SRC tests of EN 13287 (2020). The material of the present invention exhibits superior performance compared to conventional materials. For example, when used as a sole material, the thermoplastic elastomer composition (E) has a forward heelslip SRA value ≥ 0.40 and a forward flat slip SRA value ≥ 0.40, both according to EN 13287 (2020). Simultaneously, when used as a sole material, the thermoplastic elastomer composition (E) has a forward heelslip SRB value ≥ 0.15 and a forward flat slip SRB value ≥ 0.20, both according to EN 13287 (2020).

[0096] Furthermore, the thermoplastic elastomer composition (E) is easy to prepare and process. As described below, the thermoplastic elastomer composition (E) is preferably prepared by extrusion, dry mixing, and / or manual mixing. The thermoplastic elastomer composition (E) is preferably transparent, translucent, or opaque in the absence of additives (C) (additives (C), such as colorants, can affect transparency). The transparency of the final product further increases the design freedom in practical applications.

[0097] Another object of the present invention is to provide an article (T) formed from the thermoplastic elastomer composition (E) according to the invention. The article (T) can be obtained by molding, extrusion, thermoforming, lamination, calendering, and / or 3D printing. When improved slip resistance is required, the article (T) can advantageously be used as a material for a product, for example, as a shoe sole material. In a preferred embodiment, the article (T) is a shoe sole material, particularly as a sole material for safety shoes.

[0098] Aromatic thermoplastic polyurethane (component A)

[0099] The thermoplastic elastomer composition (E) comprises at least one aromatic thermoplastic polyurethane (A), wherein the at least one aromatic thermoplastic polyurethane (A) is at least one transparent, translucent, or opaque aromatic thermoplastic polyurethane (A), preferably having a Shore A value of <85 according to DIN ISO 7619-1, more preferably ≤75, and more preferably ≤70. Preferably, the at least one aromatic thermoplastic polyurethane (A) is selected from polyester-type aromatic thermoplastic polyurethane (A-1), polyether-type aromatic thermoplastic polyurethane (A-2), and / or polycarbonate-type aromatic thermoplastic polyurethane (A-3). Mixtures of the aforementioned aromatic thermoplastic polyurethanes are also included within the scope of this invention.

[0100] Aromatic thermoplastic polyurethane (A) can be obtained from a reaction (addition polymerization) comprising a reaction mixture containing at least one at least partially aromatic diisocyanate, at least one polyol selected from polyether polyols, polyester polyols and / or polycarbonate polyols, and optionally at least one chain extender.

[0101] Preferred aromatic diisocyanates suitable for the production of aromatic thermoplastic polyurethanes (A) may be selected from 2,4-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, p-phenylene diisocyanate (PDI), m-,p-xylene diisocyanate (XDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI), mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'- and / or 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanate diphenylethane (1,2) (EDI), and 1,5-naphthalene diisocyanate.

[0102] Suitable polyols are reactive to isocyanates, preferably including polyether polyols, polyester polyols, and / or polycarbonate polyols, more preferably polyether polyols and polyester polyols. The polyols mentioned can be used as individual components or in mixtures.

[0103] Preferably, the reaction mixture used to prepare the aromatic thermoplastic polyurethane (A) is primarily based on a difunctional polyol reactive to isocyanates. Therefore, the resulting aromatic thermoplastic polyurethane (A) is predominantly unbranched.

[0104] Suitable polyether polyols can be prepared according to known methods, for example by anionic or cationic polymerization from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene group and optional starting molecules. Specifically, the alkylene oxides can be ethylene oxide, 1,2-epoxypropane, tetrahydrofuran, and 1,2- and 2,3-epoxybutane. Suitable polyester polyols can, for example, be derived from dicarboxylic acids and polyols having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms. Suitable dicarboxylic acids include aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, octanoic acid, azelaic acid, sebacic acid, preferably adipic acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid.

[0105] Examples of polyols are alkanediols having 2 to 10, preferably 2 to 6, carbon atoms. The preparation of polycarbonate polyols can be carried out by reacting phosgene or a carbonate monomer (typically a dialkyl carbonate having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms) with an alkanediol or a mixture of alkanediols. In this regard, alkanediols mentioned above in the context of polyester polyols can be used. Particularly preferred chain extenders are alkanediols having 2 to 6 carbon atoms in the alkylene group, particularly 1,4-butanediol and / or dialkylene diols having 4 to 8 carbon atoms.

[0106] To adjust the hardness of aromatic thermoplastic polyurethane (A), the molar ratio of polyol to chain extender is typically 1:0.8 to 1:10, preferably 1:1 to 1:6.4. The hardness of aromatic thermoplastic polyurethane (A) increases with the increase of diol content.

[0107] The aromatic thermoplastic polyurethane (A) used in the thermoplastic elastomer composition (E) according to the invention is typically an aromatic thermoplastic polyurethane, which can be obtained by known methods from the reaction of an aromatic diisocyanate, a polyol, and optionally a chain extender (the reaction may be carried out in the presence of a catalyst and / or additives, if suitable). The ratio of the isocyanate groups of the diisocyanate to the total number of groups reacting therewith (including optional chain extenders) is typically from 1:0.9 to 1:1.1.

[0108] The at least one aromatic thermoplastic polyurethane (A) is preferably selected from:

[0109] (a-1) 0 to 100% by weight of at least one polyester-type aromatic thermoplastic polyurethane (A-1), having a Shore A value of <85, preferably ≤75, and more preferably ≤65 according to DIN ISO 7619-1.

[0110] (a-2) 0-100% by weight of at least one polyether-type aromatic thermoplastic polyurethane (A-2), having a Shore A value of 20 to Shore D value of 80 according to DIN ISO 7619-1; and

[0111] (a-3) 0 to 100% by weight of at least one polycarbonate-type aromatic thermoplastic polyurethane (A-3), having a Shore A value of 20 to Shore D value of 80 according to DIN ISO 7619-1.

[0112] Or a mixture of components (A-1), (A-2) and / or (A-3), wherein the total of components (A-1), (A-2) and (A-3) is 100% by weight of an aromatic thermoplastic polyurethane (A).

[0113] In a preferred embodiment, the at least one aromatic thermoplastic polyurethane (A) is a polyester-type aromatic thermoplastic polyurethane with a Shore A value of 50 to 80, preferably 55 to 75, and more preferably 55 to 65 according to DIN ISO 7619-1 Shore A hardness.

[0114] In an alternative preferred embodiment, the at least one aromatic thermoplastic polyurethane (A) is a polyether-type aromatic thermoplastic polyurethane with a Shore A hardness of 20 to 80 according to DIN ISO 7619-1, preferably 50 to 80 Shore A, more preferably 55 to 75 Shore A, and more preferably 55 to 65 Shore A.

[0115] In another alternative embodiment, the at least one aromatic thermoplastic polyurethane (A) is a polycarbonate-type aromatic thermoplastic polyurethane with a Shore A value between 20 and 80 according to DIN ISO 7619-1, preferably 50 to 80 Shore A, more preferably 55 to 75 Shore A, and more preferably 55 to 65 Shore A.

[0116] The preparation of aromatic thermoplastic polyurethanes (A) from at least one diisocyanate, at least one polyol and optionally one chain extender as starting materials is known in the art and has been described in the literature.

[0117] Optionally, additives are added during the production of the aromatic thermoplastic polyurethane (A) to improve performance and / or processability. Suitable preferred additives will be described below. The aromatic thermoplastic polyurethane (A) produced in a known manner can then be granulated or pelletized, or directly mixed with block copolymers (B) and optional other additives (C) to obtain a homogeneous thermoplastic elastomer composition (E) according to the invention.

[0118] Suitable aromatic thermoplastic polyurethanes are commercially available, for example, BASF SE's trade name. The products, especially the Elastollan 565A12P and / or Elastollan 1155A12P.

[0119] Block copolymer (component B)

[0120] According to the present invention, the thermoplastic elastomer composition (E) comprises at least one block copolymer (B), which includes:

[0121] (B-1) At least one polymer block (B-1), which is essentially composed of repeating units derived from at least one vinyl aromatic monomer (also known as a hard block or hard segment), and

[0122] (B-2) At least one polymer block (B-2) which is essentially composed of repeating units derived from isobutylene, isobutylene derivatives and / or mixtures thereof (also known as soft blocks or soft segments).

[0123] The at least one block copolymer (B) is preferably at least partially hydrogenated.

[0124] The present invention does not impose any particular limitation on the structure of the at least one block copolymer (B). For example, the block copolymer (B) may comprise a diblock copolymer comprising a polymer block (B-1) containing a repeating unit derived from at least one vinyl aromatic monomer and a polymer block (B-2) containing a repeating unit derived from isobutylene, isobutylene derivatives, and / or mixtures thereof. The block copolymer (B) may also comprise a triblock copolymer comprising at least one polymer block (B-1) and at least one polymer block (B-2), preferably comprising two polymer blocks (B-1) and one polymer block (B-2). Further embodiments include a multiblock copolymer comprising at least two polymer blocks (B-1) and at least one polymer block (B-2). Still further embodiments include a star-shaped block copolymer comprising arms having at least one polymer block (B-1) and at least one polymer block (B-2). In a preferred embodiment, the terminal polymer blocks of the at least one block copolymer (B) are composed of polymer blocks (B-1). In this invention, in order to obtain the desired physical properties and formability, the at least one block copolymer (B) having these structures can be used alone or in combination of two or more.

[0125] In the at least one block copolymer (B), the weight ratio of polymer block (B-1) to polymer block (B-2) is not particularly limited. However, it is preferred that the weight ratio of (B-1) to (B-2) is 95 / 5 to 5 / 95, and more preferably 15 / 85 to 30 / 70.

[0126] The block (B-1) is essentially composed of repeating units derived from at least one vinyl aromatic monomer, wherein the vinyl aromatic monomer is polymerized to become its main component. Preferably, the at least one vinyl aromatic monomer is selected from styrene, α-methylstyrene, and vinyltoluene, more preferably styrene, α-methylstyrene, or mixtures thereof. Preferably, the polymer block (B-1) comprises (preferably consists of): based on the total polymer block (B-1), 90 to 100% by weight, preferably 95 to 100% by weight, more preferably 98 to 100% by weight, repeating units derived from vinyl aromatic monomers, particularly styrene; and based on the total polymer block (B-1), 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0 to 2% by weight, repeating units derived from isobutylene, isobutylene derivatives, and / or mixtures thereof.

[0127] The at least one polymer block (B-2) is formed as its main component by polymerization of isobutylene, isobutylene derivatives, and / or mixtures thereof. In a preferred embodiment, the at least one polymer block (B-2) is formed by polymerization of a monomer selected from isobutylene. In one embodiment, the at least one polymer block (B-2) is formed by polymerization of isobutylene as its main component. In one embodiment, the at least one polymer block (B-2) is formed by polymerization of an isobutylene derivative as its main component. In one embodiment, the at least one polymer block (B-2) is formed by polymerization of a mixture of isobutylene and an isobutylene derivative as its main component. For the purposes of this invention, the isobutylene derivative preferably includes tetramethylethylene or trimethylethylene.

[0128] Preferably, the polymer block (B-2) comprises (preferably consists of): based on the total polymer block (B-2), 0 to 10% by weight, preferably 0 to 5% by weight, repeating units derived from vinyl aromatic monomers (especially styrene), and based on the total polymer block (B-2), 90 to 100% by weight, preferably 95 to 100% by weight, repeating units derived from isobutylene, isobutylene derivatives and / or mixtures thereof, particularly repeating units derived from isobutylene.

[0129] The present invention does not particularly limit the method for producing the block copolymer (B). Suitable methods are known in the art. For example, it can be prepared by polymerizing a vinyl aromatic monomer component in the presence of an initiator to form at least one polymer block (B-1), followed by the addition of repeating units derived from isobutylene, isobutylene derivatives, and / or mixtures thereof to form at least one polymer block (B-2). Preferably, the block copolymer (B) is prepared in a controlled manner, for example by cationic or anionic polymerization. Suitable methods and initiators are known in the art. WO2016 / 093091A1 discloses a particularly preferred method and initiator for cationic polymerization processes.

[0130] The at least one block copolymer (B) is preferably a block copolymer comprising at least two polymer blocks (B-1) containing ≥90% by weight of repeating units derived from styrene, and at least one polymer block (B-2) containing ≥90% by weight of repeating units derived from isobutylene, isobutylene derivatives and / or mixtures thereof.

[0131] In a further preferred embodiment, the at least one block copolymer (B) is a triblock copolymer (B-1 / B-2 / B-1), more preferably poly(styrene-b-isobutylene-b-styrene). In a preferred embodiment, the block copolymer (B) is at least partially hydrogenated.

[0132] In another preferred embodiment of the invention, the at least one block copolymer (B) is selected from poly(styrene-b-isobutylene-b-styrene), wherein at least 90 mol%, preferably at least 95 mol%, and particularly at least 98 mol% of the non-conjugated double bonds in the block copolymer (B) are hydrogenated. In yet another preferred embodiment, the at least one block copolymer (B) is selected from poly(styrene-b-isobutylene-b-styrene), wherein all the non-conjugated double bonds in the block copolymer (B) are hydrogenated.

[0133] Prior to hydrogenation, the non-conjugated double bonds of the at least one block copolymer (B) are typically present in the polymer block (B-2) (also referred to as the soft block), while the polymer block (B-1) (also referred to as the hard block) typically does not contain non-conjugated double bonds (that is, only conjugated double bonds are typically present in the polymer block (B-1)). This means that, in a preferred embodiment, the at least one block copolymer (B) is selected from poly(styrene-b-isobutylene-b-styrene), wherein at least 90 mol%, preferably at least 95 mol%, and particularly at least 98 mol% of the double bonds in the copolymer block (B-2) of the block copolymer (B) are hydrogenated. In yet another preferred embodiment, the at least one block copolymer (B) is selected from poly(styrene-b-isobutylene-b-styrene), wherein all double bonds in the polymer block (B-2) of the block copolymer (B) are hydrogenated. Suitable hydrogenation methods are known in the art.

[0134] In a particularly preferred embodiment of the invention, the at least one block copolymer (B) is poly(styrene-b-isobutylene-b-styrene), wherein at least 90 mol%, preferably at least 95 mol%, and particularly at least 98 mol% of the non-conjugated double bonds in the poly(styrene-b-isobutylene-b-styrene) are hydrogenated. In a further preferred embodiment, the at least one block copolymer (B) is selected from poly(styrene-b-isobutylene-b-styrene), wherein all (i.e., 100 mol%) of the non-conjugated double bonds are hydrogenated, i.e., the double bonds in the isobutylene block (soft block (B-2)) are hydrogenated.

[0135] Optionally, additives are added during the production of the block copolymer (B) to improve performance and / or processability. Suitable preferred additives will be described below. The block copolymer (B) produced in this manner can then be granulated or pelletized, or directly mixed with at least one thermoplastic polyurethane (A) and optional other additives (C) to obtain a homogeneous thermoplastic elastomer composition (E).

[0136] SIBSTAR (manufactured by Kaneka) is an example of a commercially available product that can be used as the block copolymer (B) of the present invention, particularly Sibstar 062T.

[0137] Optional additives (component C)

[0138] In addition to components (A) and (B), the thermoplastic elastomer composition (E) according to the invention may optionally contain an additive (C). In a preferred embodiment, in addition to components (A) and (B), the thermoplastic elastomer composition (E) according to the invention further contains at least one additive (C). Preferred additives (C) include, for example, plasticizers, lubricants, abrasion-resistant additives, propellants, surfactants, flame retardants, mold release agents, colorants, light, heat, or oxidative stabilizers, and / or reinforcing agents.

[0139] Preferably, the thermoplastic elastomer composition (E) comprises at least one additive (C) selected from lubricants, plasticizers, wear-modifying additives and / or mixtures thereof.

[0140] Suitable lubricants include any lubricants known in the art. Stearyl alcohol, alkyl stearate, and amides (preferably) may be mentioned herein. Types), and esters of pentaerythritol with long-chain fatty acids. Calcium, zinc, or aluminum salts of stearic acid and dialkyl ketones, such as distearate, can also be used. Furthermore, ethylene oxide-propylene oxide copolymers can be used as lubricants and mold release agents. In addition, natural and synthetic waxes can be used. These include polypropylene wax, polyethylene wax, polyamide wax, PO grafted wax, high-density polyethylene wax, poly(tetrafluoroethylene) wax, ethylene bis(stearamide) wax, mountain wax, carnauba wax, and beeswax.

[0141] Suitable plasticizers include benzoates, phthalates and phosphates.

[0142] Suitable wear-resistant additives include silicones, waxes, fluorinated polymers and oligomers, and ethylene polymers and oligomers. In addition, suitable lubricants can be used as wear-resistant additives.

[0143] Suitable antioxidants can be any antioxidant known in the art, such as phenolic antioxidants (e.g., alkylated monophenols, esters, and sterically hindered amides, such as 3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine, or benzotriazole). Exemplarily, antioxidants can be those listed in EP-A 0 698637 and / or EP-A 0 669 367.

[0144] Suitable propellants include both chemical and physical propellants.

[0145] The surfactant can be any emulsifier known in the art, such as basic salts of alkyl sulfonic acids or alkyl aryl sulfonic acids, alkyl sulfates or resin salts, especially basic salts of fatty acids with 8-30 carbon atoms.

[0146] Flame retardants can be halogenated or halogen-free compounds. Suitable halogenated compounds remain stable during the manufacture and processing of the thermoplastic elastomer composition (E). Brominated compounds are preferred over corresponding chlorinated compounds. Halogen-free compounds, such as phosphorus compounds, particularly phosphine oxides and acid derivatives of phosphorus, and their acid salts, are preferred. Particularly preferred phosphorus compounds comprise esters, alkyl groups, cycloalkyl groups, and / or aryl groups.

[0147] Suitable release agents can be selected from long-chain fatty acids, such as stearic acid or benzyl acid, salts of fatty acids (such as calcium stearate or zinc stearate), esters of fatty acids (such as stearate or pentaerythritol tetrastearate), and amide derivatives of fatty acids (such as ethylene bis-stearamide, erucamide, etc.). ), phosphates (e.g., tricalcium phosphate), hydrocarbon waxes (e.g., microcrystalline waxes and paraffin waxes (e.g.) ) and fumed silica (e.g. Fatty acids are typically carboxylic acids with straight or branched chains, saturated or unsaturated, and C5-C25 alkyl chains.

[0148] Suitable colorants include any known dyes and pigments suitable for coloring thermoplastics, see, for example, R. See H. Müller's "Pocket Book of Plastic Additives", Carl Hanser Verlag, 1983, pp. 494-510.

[0149] Available light stabilizers are all conventional light stabilizers, such as compounds of various substituted resorcinols, salicylates, benzophenones, benzotriazoles, cinnamic acid, organophosphites and phosphonites, as well as hindered amines.

[0150] An example of an oxidation inhibitor and heat stabilizer is sterically hindered phenol.

[0151] Stabilizers are preferred, especially oxygen free radical scavengers, such as 1010 (BASF SE) 1010 1076、 565 and its mixtures; carbon radical scavengers, such as GS GM and its mixtures, and / or secondary stabilizers, such as 168 (BASFSE). All of the stabilizers are commercially available.

[0152] Examples of reinforcing agents include particulate mineral fillers (e.g., amorphous silica, carbonates such as magnesium carbonate, calcium carbonate (chalk), quartz powder, mica, various silicates such as clay, muscovite, biotite, chalcopyrite, tin maleate, talc, chlorite, phlogopite, feldspar, calcium silicates such as wollastonite or kaolin, especially calcined kaolin) and / or fiber fillers (e.g., carbon fiber, glass fiber, aramid fiber).

[0153] More details about the above additives can be found in technical literature, such as the Handbook of Plastic Additives, 5th edition, edited by H. Zweifel, published by Hanser Publishers, Munich, 2001.

[0154] The at least one additive (C) may be added during the production of the thermoplastic elastomer composition (E). Alternatively, it may be added during the production of the at least one aromatic thermoplastic polyurethane (A) and / or during the production of the at least one block copolymer (B). Typically, the at least one additive (C) also has the effect of improving properties, particularly the stability and processability of the at least one aromatic thermoplastic polyurethane (A) and / or the at least one block copolymer (B), and therefore it is added at least partially to the at least one aromatic thermoplastic polyurethane (A) and / or the at least one block copolymer (B) prior to the preparation of the thermoplastic elastomer composition (E).

[0155] However, the remaining or total amount of the at least one additive (C) may be added to the blend components (A), (B) and (C) during the production of the thermoplastic elastomer composition (E).

[0156] Based on the total weight of the thermoplastic elastomer, the optional additive (C) is preferably added to the composition (E) in an amount of 0 to 10% by weight, more preferably 0.1 to 7% by weight, and particularly 0.1 to 5% by weight. Preferably, the thermoplastic elastomer composition (E) may contain at least one additive (C) in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 0.1 to 2.5% by weight.

[0157] Preferably, the additive used as an optional additive (C) in the polymer composition of the present invention does not scatter light, thereby maintaining the transparency of the polymer composition.

[0158] Preparation of thermoplastic elastomer composition (E)

[0159] The thermoplastic elastomer composition (E) is preferably prepared by extrusion, dry mixing and / or hand mixing.

[0160] When components (A) and (B) and optionally (C) are mixed, they are preferably in a flowable, softened, or molten state. The components are preferably mixed uniformly at a temperature higher than the melting temperature of components (A) and (B). Preferably, the mixing of components (A) and (B) and optionally (C) is carried out at 160 to 250°C, more preferably 175 to 240°C, and particularly preferably 190 to 230°C. The mixing of components (A) and (B) and optionally (C) into a homogeneous product can be achieved using conventional equipment, including equipment for heating and stirring, kneading, or rolling. The preparation of the thermoplastic elastomer composition can be carried out continuously or discontinuously, with or without degassing. Mixing is preferably carried out in a conventional extruder. The thermoplastic elastomer composition (E) obtained according to the invention can be granulated or pelletized by known methods. Alternatively, the thermoplastic elastomer composition (E) can be extruded and directly processed into the desired article (T), for example. Through molding processes, extrusion processes, thermoforming processes, lamination processes, calendering processes, and / or 3D printing processes.

[0161] The present invention will be further illustrated below through embodiments and claims. Example

[0162] Various thermoplastic elastomer compositions listed in Table 1 were prepared and homogenized in twin-screw and single-screw extruders at temperatures ranging from 190°C to 230°C. The resulting transparent samples were subjected to the following characterization tests.

[0163] SRA, SRB and SRC standards

[0164] Safety footwear testing according to EN ISO 13287 (2020) includes two sub-tests:

[0165] The SRA (Slip Resistance Assessment) evaluates the slip resistance of ceramic tiles using soapy water as a lubricant. A forward heel slip value ≥ 0.28 and a forward flat slip value ≥ 0.32 are considered passing the SRA standard. The SRB (Slip Resistance Assessment) evaluates the slip resistance of steel using glycerin as an oil. A forward heel slip value ≥ 0.13 and a forward flat slip value ≥ 0.18 are considered passing the SRB standard. If the same material passes both the SRA and SRB standards, it is considered to have passed the SRC (Slip Resistance Assessment) standard.

[0166] Glass transition temperature Tg(E)

[0167] The glass transition temperature Tg(E) was determined according to ISO 6721-2 by measuring the glass transition temperatures Tg of components A and B at 1 Hz using dynamic mechanical analysis (DMA).

[0168] The glass transition temperature Tg of composition (E) is calculated using the following equation as described above:

[0169]

[0170] Reference: “Prediction of glass transition temperature: binary blends and copolymers”; W. Brostow, R. Chiu, A. Vassilikou-Dova; Materials Communications 62 (2008); 3152-3155.

[0171] To determine the glass transition temperatures (Tg) of components A and B, a strip specimen (rectangular) is securely clamped vertically at its ends and subjected to sinusoidal torsion by a motor connected to the lower support. By default, this is performed at a frequency of 1 Hz and a material-dependent rotation angle (amplitude). A load cell connected to the upper strip support records the generated torque. Based on the torque, rotation angle, and phase shift between them, as well as data on the sample geometry, the shear modulus and loss factor can be determined. Measurements are typically performed within predefined temperature intervals while the sample is continuously heated in a temperature chamber; therefore, the result is a complex shear modulus measured as a function of temperature. Measurements are performed according to ISO 6721-2. In particular, the glass transition can be determined very precisely as a damping parameter (tan delta). Furthermore, these measurements are used to characterize damping and softening behavior as a function of temperature.

[0172] For the glass transition temperatures and weight proportions of components A, B, and PP (i.e., components with glass transition temperatures) in the table below, calculate Tg(E) using the following formula, which includes the necessary conversions (e.g., ℃ to K) for the data given in the table:

[0173]

[0174] and

[0175]

[0176] Shore hardness is determined according to DIN ISO 7619-1(3s).

[0177] The resilience is determined according to DIN 53512.

[0178] Components used

[0179] A1: Polyester-type aromatic thermoplastic polyurethane with a Shore A value of 65 according to DIN ISO 7619-1(3s), which also contains lubricant and plasticizer (Elastollan 565A12P, BASF).

[0180] A2: Polyether-type aromatic thermoplastic polyurethane with a Shore A value of 55 according to DIN ISO 7619-1(3s), which also contains lubricant and plasticizer (Elastollan 1155A12P, BASF).

[0181] A3: Polyether-type aromatic thermoplastic polyurethane with a Shore D value of 74 according to DIN ISO 7619-1(3s), which also contains lubricant and plasticizer (Elastollan 1174D11, BASF).

[0182] A4: Polyether-type aromatic thermoplastic polyurethane with a Shore A value of 80 according to DIN ISO 7619-1(3s) and also contains a lubricant (Elastollan 1180A10, BASF).

[0183] B1 Sibstar 062T: (Styrene / isobutylene / styrene) copolymer with saturated (i.e., hydrogenated) soft segments.

[0184] B2 Kraton G 1651: A transparent linear triblock copolymer (SE / BS) based on styrene and ethylene / butene, incorporating 31.5% by mass of styrene (Kraton).

[0185] B3 Novodur: Acrylonitrile-butadiene-styrene (ABS) copolymer (INEOS Styrolution)

[0186] B4 Kraton D-1161: Non-hydrogenated styrene / isoprene / styrene (SlS) block copolymer

[0187] B5 Kraton D 1171: A triblock copolymer (SIBS block copolymer) based on styrene, butadiene, and isoprene.

[0188] PP Bormed: Polypropylene from Borealis

[0189] Table 1. Examples 1 to 3: Composition and Properties

[0190]

[0191] Table 2. Comparative Examples 1 to 4: Composition and Properties

[0192]

[0193]

[0194] Table 3. Comparative Examples 5 to 10: Composition and Properties

[0195]

[0196]

[0197] Comparative Examples 1 and 2 (Table 2) show that pure aromatic thermoplastic polyurethane compounds failed the SRA, SRB, and SRC tests.

[0198] Although the anti-slip performance can be improved by replacing 20% ​​by weight of the at least one aromatic thermoplastic polyurethane with (SE / BS) block copolymer (Comparative Example 3), ABS block copolymer (Comparative Example 4), S1S block copolymer (Comparative Examples 5 and 6), or SIBS block copolymer (Comparative Examples 7 and 8), the SRB and SRC tests still cannot be passed.

[0199] Comparative Example 9 shows that the composition comprising the aromatic TPU and styrene / isobutylene / styrene block copolymer according to the present invention does not have a glass transition temperature Tg(E) below 10°C and fails the SRB and SRC tests.

[0200] Only Examples 1, 2, and 3 of the present invention can meet all the requirements of SRA, SRB, and SRC tests under otherwise unchanged conditions. Examples 1, 2, and 3 comprise at least one aromatic thermoplastic polyurethane (A) and at least one block copolymer (B) in 20 wt% and 40 wt% respectively, said block copolymer (B) comprising at least one polymer block (B-1) consisting essentially of repeating units derived from at least one vinyl aromatic monomer, and at least one polymer block (B-2) consisting essentially of repeating units derived from isobutylene, wherein said at least one block copolymer (B) is at least partially hydrogenated; and wherein the glass transition temperature Tg(E) of the thermoplastic elastomer composition (E), determined by dynamic mechanical analysis, is <0°C, and its resilience is between 25% and 60% according to DIN 53512, and wherein said at least one aromatic thermoplastic polyurethane (A) is a transparent, translucent, or opaque aromatic thermoplastic polyurethane (A).

[0201] Comparative Example 10 shows that the polypropylene-containing compositions taught in WO 2009 / 069666 A1 are inferior in performance.

Claims

1. A thermoplastic elastomer composition (E) comprising the following components: (a) 50 to 95% by weight of at least one aromatic thermoplastic polyurethane (A), wherein the at least one aromatic thermoplastic polyurethane (A) is selected from: (a-1) Polyester-type aromatic thermoplastic polyurethane (A-1) with a Shore A value of 55 to 75 according to DIN ISO 7619-1, and / or (a-2) Polyether-type aromatic thermoplastic polyurethane (A-2), with a Shore A hardness of 20 to 80 according to DIN ISO 7619-1. The total of components (A-1) and (A-2) is 100% by weight of aromatic thermoplastic polyurethane (A). (b) 5 to 50% by weight of at least one block copolymer (B), comprising: (B-1) At least one polymer block (B-1) comprising repeating units formed of at least one vinyl aromatic monomer, and (B-2) At least one polymer block (B-2) consisting of repeating units formed of isobutylene. The weight ratio of (B-1) / (B-2) is 95 / 5 to 5 / 95; and (c) 0 to 10% by weight of at least one optional additive (C), Components (A), (B), and (C) together constitute 100% by weight of the thermoplastic elastomer composition (E). The thermoplastic elastomer composition (E) has a glass transition temperature Tg(E) <0°C, calculated according to the following formula: in w(A) is the mass fraction of component A. w(B) is the mass fraction of component B. Tg(A) is the glass transition temperature of pure component A, expressed in Kelvin. Tg(B) is the glass transition temperature of pure component B, expressed in Kelvin. Tg(E) is the glass transition temperature of composition E, expressed in Kelvin. Tg(A) and Tg(B) were determined by dynamic mechanical analysis at 1 Hz according to ISO 6721-2. According to DIN 53512, the thermoplastic elastomer composition (E) has a resilience of 25% to 60%, and The aromatic thermoplastic polyurethane (A) therein is at least one transparent, translucent or opaque aromatic thermoplastic polyurethane (A).

2. The thermoplastic elastomer composition (E) according to claim 1, wherein the thermoplastic elastomer composition (E) comprises the following components: (a) 55 to 85% by weight of at least one aromatic thermoplastic polyurethane (A), (b) 5 to 50% by weight of at least one block copolymer (B), and (c) 0 to 10% by weight of at least one additive (C), The total of components (A), (B) and (C) is 100% by weight of a thermoplastic elastomer composition (E).

3. The thermoplastic elastomer composition (E) according to claim 1, wherein the Shore A value of the thermoplastic elastomer composition (E) is ≤85 according to DIN ISO 7619-1.

4. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the at least one aromatic thermoplastic polyurethane (A) is a reaction product of a reaction mixture, the reaction mixture comprising at least one aromatic diisocyanate, at least one polyol selected from polyether polyols and / or polyester polyols, and optionally at least one chain extender.

5. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the at least one block copolymer (B) is a block copolymer comprising at least two blocks of repeating units formed of styrene at ≥90% by weight, and at least one block of repeating units formed of isobutylene at ≥90% by weight.

6. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the at least one block copolymer (B) is a block copolymer selected from poly(styrene-b-isobutylene-b-styrene).

7. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the resilience of the thermoplastic elastomer composition (E) is 30 to 50% according to DIN 53512.

8. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the thermoplastic elastomer composition (E) is prepared by extrusion, dry mixing and / or manual mixing.

9. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the thermoplastic elastomer composition (E) comprises at least one additive (C) selected from lubricants, plasticizers, wear-resistant agents, and mixtures thereof.

10. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein the thermoplastic elastomer composition (E) is free from (styrene-ethylene-butene-styrene) block copolymer (SEBS), (styrene-ethylene-propylene-styrene) block copolymer (SEPS), (styrene-ethylene-ethylene-propylene-styrene) block copolymer (SEEPS), (styrene-butadiene-styrene) block copolymer (SBS) and / or (acrylonitrile-butadiene-styrene) copolymer (ABS).

11. The thermoplastic elastomer composition (E) according to claim 1 or 2, wherein at least one block copolymer (B) is at least partially hydrogenated.

12. Use of a thermoplastic elastomer composition (E) according to claim 1 or 2 for the production of outsole or outsole components.

13. An article (T) formed from a thermoplastic elastomer composition (E) according to claim 1 or 2.

14. The article (T) according to claim 13, wherein the article (T) is obtained by molding, extrusion, thermoforming, lamination, calendering and / or 3D printing.

15. The article (T) according to claim 13 or 14, wherein the article (T) is a sole material.

16. The article (T) according to claim 15, wherein the article (T) is a sole material for a safety shoe.

Images