TPU for in-mold forming assembly of the outer sole of eTPU

Abstract

The present invention relates to a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a molded article (M) comprising an expanded pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) that deviates from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) by 25°C or less, the softening temperature being determined by TMA in accordance with ISO 11359-3:2014. The present invention also relates to a method for producing the molded article according to the present invention, and to its use in the fields of sports, industry, medicine, sports medicine, safety, automotive and consumer goods, in particular in shoe soles, parts of shoe soles, bicycle saddles, cushioning, mattresses, underlays, handles, protective films or as components in the interior and exterior of automobiles.

Description

Technical Field

[0001] The present invention relates to a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a molded article (M) containing a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014, and relates to the molded article (M). The present invention further relates to a method for manufacturing a molded article according to the present invention, and to uses in the fields of sports, industry, medicine, sports medicine, safety, automotive and consumer goods, in particular as shoe soles, as part of a shoe sole, bicycle saddles, cushioning materials, mattresses, underlays, handles, protective films, or as components in automotive interiors and exteriors, and further relates to a method of use therefor.

Background Art

[0002] Foams, specifically foams including particulate foams, have long been known and have been described in the literature many times, for example, Ullmann's "Encyklopaedie der technischen Chemie" [Encyclopedia of Industrial Chemistry], 4th edition, volume 20, pages 416ff.

[0003] Highly elastic closed-cell foams, for example particulate foams made of thermoplastic polyurethane produced in an autoclave or by an extrusion process, exhibit good mechanical properties and, in some cases, good resilience. Hybrid foams consisting of particles of thermoplastic elastomers and system foams or binders are also known. Depending on the foam density, production method and matrix material, it is generally possible to produce a relatively wide range of hardness levels. Post-treatment of the foam, such as heat treatment, can also affect the properties of the foam.

[0004] The thermoplastic polyurethane-based particulate foam is also referred to as TPU in this document and is disclosed in WO94 / 20568 A1. The drawback of the TPU foam described in WO94 / 20568 is the high energy consumption in production and processing. A steam pressure of 4.5 bar to 7 bar is utilized at a temperature of 145 °C to 165 °C. In addition, WO94 / 20568 describes expanded, i.e., foamed, TPU particles that can be processed to produce a molded article. These TPU foam particles are produced at a temperature of 150 °C or higher and have a bulk density between 55 and 180 g / L, as shown by way of example, which is disadvantageous for the transport and storage of these particles due to the increased space requirement.

[0005] WO2007 / 082838 A1 discloses a thermoplastic polyurethane-based particulate foam having a Shore hardness between A44 and A84. The Shore hardness of the TPU is measured in the dense, i.e., unexpanded, TPU. Moreover, WO2007 / 082838 A1 discloses a method for producing an expandable, preferably particulate, foaming agent-containing thermoplastic polyurethane, a method for producing an expanded thermoplastic polyurethane, a method for producing a foam based on thermoplastic polyurethane, and a foam, or an expanded thermoplastic polyurethane, that can be obtained in this way.

[0006] However, while it is frequently possible to achieve good mechanical properties, it has been found that it is complex to achieve the processing of the particles, especially in combination with further components. As an example, depending on the processing method, it may be necessary to use additional materials, such as an additional adhesive. Also, in the case of processing by a method of fusing the foamed particles in the presence of components, there may be problems, for example, with respect to adhesion and shape retention of the contours of the components.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

[0008] [Non-Patent Document 1] Ullmann's "Encyklopaedie der technischen Chemie" [Encyclopedia of Industrial Chemistry], 4th Edition, Volume 20, pages 416ff [Summary of the Invention] [Problems to be Solved by the Invention]

[0009] Accordingly, an object of the present invention was to provide a method for manufacturing a molded article from a dense component and a foamed particle or foamed pellet material, in which the components can be easily combined with each other and a stable bond can be obtained. A further object of the present invention was to provide a corresponding molded article. [Means for Solving the Problems]

[0010] According to the present invention, this object is achieved by a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a molded article (M) containing a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25°C or less, and the softening temperature is determined by TMA in accordance with ISO11359-3:2014. [Brief Description of the Drawings]

[0011]

Figure 1

Mode for Carrying Out the Invention

[0012] In the context of the present invention, the softening temperature of the molded article (M-1) is determined by TMA in accordance with ISO 11359-3:2014. Unless otherwise stated, the softening temperature is usually determined on the surface of the molded article in this specification. The measurement is usually carried out on an unheat-treated sample.

[0013] In the context of the present invention, the processing temperature is understood to be the temperature or temperature range at which the foamed pellet material can be processed into a molded article, that is, a softening rate sufficient for the individual particles to bond to each other is present on the surface of the foamed pellet material, while at the same time it is understood to be a temperature that widely retains the cellular structure of the foamed pellet material.

[0014] Unless otherwise stated, the processing temperature of the foamed pellet material is determined by DSC measurement. In the context of the present invention, the processing temperature is the temperature range in which endothermic melting (s) of the hard phase is (are) present in the DSC measurement of the pre-dried sample. In the context of the present invention and unless otherwise stated, the DSC measurement is carried out on the pre-dried sample at a heating rate of 20 K / min in accordance with DIN 11357-3:2013. The pre-drying is usually carried out at 100 °C for 10 minutes. The pre-drying may be carried out directly in the DSC instrument, for example. In that case, the start of the endothermic (s) for 10 mg of the pre-dried TPU sample pre-dried directly in the DSC instrument at 100 °C for 10 minutes before the measurement is determined in accordance with DIN EN11357-1:2016 and DIN EN11357-3:2013.

[0015] Unless otherwise stated, TMA and DSC are measured at the same heating rate of 20 K / min.

[0016] It has surprisingly been found that the softening behavior at the surface of the component is decisive for good adhesion and must be similar to the softening behavior of the foamed pellet material used in order to sufficiently bond both components of the molded article there.

[0017] It has been found that the processing can be satisfactorily carried out in the processing temperature range TP of the thermoplastic elastomer TPE-2, where this temperature range exists within the range from a temperature 10% above the lowest temperature of endotherm determined by DSC to a temperature 10% below the maximum temperature of endotherm determined by DSC.

[0018] Particularly good results are achieved when the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2) and a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometry of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

[0019] According to a further embodiment, the invention also relates to a molded article as described above, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2) and a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometry of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

[0020] The processing temperature or temperature range may vary depending on the chemical properties of the thermoplastic elastomer. Typically, the processing temperature is within the range of 100 to 170 °C, preferably within the range of 110 to 160 °C, more preferably within the range of 120 to 150 °C.

[0021] According to a further embodiment, the present invention also relates to the molded article described above, wherein the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2) is within the range of 100 to 170 °C.

[0022] The molded article according to the present invention includes a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a foamed pellet material made of a thermoplastic elastomer (TPE-2). The thermoplastic elastomer (TPE-1) is preferably in a dense form.

[0023] Suitable thermoplastic elastomers are known per se to those skilled in the art. For example, the thermoplastic elastomer (TPE-1) may be a thermoplastic polyurethane, a thermoplastic polyether amide, a polyether ester, a polyester ester, a thermoplastic olefin-based elastomer, a crosslinked thermoplastic olefin-based elastomer or a thermoplastic vulcanizate, or a thermoplastic styrene-butadiene block copolymer. According to the present invention, the thermoplastic elastomer (TPE-1) may preferably be a thermoplastic polyurethane, a thermoplastic polyether amide, a polyether ester, a polyester ester or a thermoplastic styrene-butadiene block copolymer.

[0024] According to a further embodiment, thus, the invention also relates to the above-described particulate foam in which the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethane, thermoplastic polyetheramide, polyether ester, polyester ester or thermoplastic styrene-butadiene block copolymer. Irrespective of this, in the context of the invention, the thermoplastic elastomer (TPE-2) may also be selected from the group consisting of thermoplastic polyurethane, thermoplastic polyetheramide, polyether ester, polyester ester, thermoplastic olefinic elastomer, crosslinked thermoplastic olefinic elastomer or thermoplastic vulcanizate, or thermoplastic styrene-butadiene block copolymer, as long as the softening behavior of the thermoplastic elastomers used is ensured to be compatible with each other as specified. According to the invention, when the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic polyurethane, thermoplastic polyetheramide, polyether ester or polyester ester, it is preferred that the thermoplastic elastomer (TPE-2) is also selected from this group. When the thermoplastic elastomer (TPE-1) is selected from the group consisting of thermoplastic olefinic elastomer, crosslinked thermoplastic olefinic elastomer or thermoplastic vulcanizate, or thermoplastic styrene-butadiene block copolymer, in the context of the invention, it is preferred that the thermoplastic elastomer (TPE-2) is also selected from this group.

[0025] Suitable thermoplastic polyether esters and polyester esters can be produced by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms or their esters with suitable aliphatic and aromatic di- and polyols according to any standard method known from the literature (cf. "Polymer Chemistry", Interscience Publ., New York, 1961, pp. 111-127; Kunststoffhandbuch [Plastics Handbook], Volume VIII, C. Hanser Verlag, Munich 1973, and Journal of Polymer Science, Part A1, 4, 1851-1859 (1966)).

[0026] Examples of suitable aromatic dicarboxylic acids include phthalic acid, iso- and terephthalic acids and their esters. Suitable aliphatic dicarboxylic acids include, for example, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid as saturated dicarboxylic acids, and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids.

[0027] Examples of suitable diol components include diols of the general formula HO-(CH2)n-OH (where n = 2-20), such as ethylene glycol, propane-1,3-diol, butane-1,4-diol or hexane-1,6-diol, polyetherols of the general formula HO-(CH2)n-O-(CH2)m-OH (where n is equal to or not equal to m and n and m = 2-20), unsaturated diols and polyetherols, such as butene-1,4-diol; diols and polyetherols containing aromatic units; and polyesterols.

[0028] In addition to the carboxylic acids and their esters that are cited, and the alcohols that are cited, it is possible to provide polyether esters and polyester esters that are used according to the present invention using any other standard representatives of these compound classes.

[0029] Thermoplastic polyether amides can be obtained according to any standard method known from the literature by reaction of amines with carboxylic acids or their esters. The amines and / or carboxylic acids additionally contain, herein, ether units of the R-O-R type, where R = organic group (aliphatic and / or aromatic). Generally, monomers of the following compound classes are used: HOOC-R'-NH2, where R' may be aromatic and aliphatic, preferably containing ether units of the R-O-R type, where R = organic group (aliphatic and / or aromatic); aromatic dicarboxylic acids, including, for example, phthalic acid, iso- and terephthalic acid or their esters, and aromatic dicarboxylic acids containing ether units of the R-O-R type, where R = organic group (aliphatic and / or aromatic); aliphatic dicarboxylic acids, including, for example, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids, and maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids, and aliphatic dicarboxylic acids containing ether units of the R-O-R type, where R = organic group (aliphatic and / or aromatic); diamines of the general formula H2N-R''-NH2, where R'' may be aromatic and aliphatic, preferably containing ether units of the R-O-R type, where R = organic group (aliphatic and / or aromatic); lactams, such as ε-caprolactam, pyrrolidone or laurolactam; and amino acids.

[0030] In addition to the carboxylic acids and their esters, and the amines, lactams and amino acids cited, it is possible to provide polyetheramines for use according to the invention using any other standard representatives of these compound classes.

[0031] The thermoplastic elastomers having a block copolymer structure for use according to the invention preferably contain vinyl aromatic units, butadiene units and isoprene units, and polyolefin units and vinyl units, such as units of ethylene, propylene and vinyl acetate. Preferred is a styrene-butadiene copolymer.

[0032] The thermoplastic elastomers having a block copolymer structure for use according to the invention, polyetheramides, polyetheresters and polyesteresters are preferably selected such that their melting points are ≤ 300 °C, preferably ≤ 250 °C, in particular ≤ 220 °C.

[0033] The thermoplastic elastomers having a block copolymer structure for use according to the invention, polyetheramides, polyetheresters and polyesteresters may be semi-crystalline or amorphous.

[0034] In the context of the present invention, the thermoplastic elastomer (TPE-1) is particularly preferably a thermoplastic polyurethane.

[0035] The thermoplastic elastomer (TPE-2) may also be, according to the invention, a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester or a thermoplastic styrene-butadiene block copolymer. According to a further embodiment, the present invention therefore also relates to the molded article described above, wherein the thermoplastic elastomer (TPE-2) is selected from the group consisting of a thermoplastic polyurethane, a thermoplastic polyetheramide, a polyetherester, a polyesterester or a thermoplastic styrene-butadiene block copolymer.

[0036] The molded article according to the invention has a particularly advantageous property profile when the thermoplastic elastomer (TPE-2) is thermoplastic polyurethane. According to a further embodiment, the invention also relates to the molded article described above, wherein the thermoplastic elastomers (TPE-1) and (TPE-2) are independently selected from thermoplastic polyurethane, thermoplastic polyester and thermoplastic polyamide.

[0037] Good properties were observed especially when both the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) were selected from thermoplastic polyurethane. According to a further embodiment, the invention also relates to the molded article described above, wherein the thermoplastic elastomers (TPE-1) and (TPE-2) are selected from thermoplastic polyurethane.

[0038] Thermoplastic polyurethanes are known from the prior art. They are typically obtained by the reaction of a polyisocyanate composition with a polyol composition, which typically contains a polyol and a chain extender.

[0039] In the context of the present invention, thermoplastic polyurethanes obtained or obtainable by the reaction of a polyisocyanate composition with a polyol composition are typically used.

[0040] According to a further embodiment, the invention also relates to the molded article described above, wherein the thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane (TPU-1) obtained or obtainable by the reaction of components (i) to (iii): (i) a polyisocyanate composition (IC) and (ii) at least one chain extender (CE1) and (iii) a polyol composition (PC) and is the molded article described above. The component is reacted at an exponent within the range of 0.99 to 1.02, and the average molecular weight of the polyol present in the polyol composition (PC) is within the range of 1250 g / mol to 2500 g / mol. It also relates to a molded article.

[0041] Typically, the polyol composition contains at least one polyol. Polyols are basically known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane" [Plastics Handbook, volume 7, Polyurethane], Carl Hanser Verlag, 3rd edition 1993, chapter 3.1. Particularly preferred is the use of polyester polyols or polyether polyols as polyols. The use of polycarbonates is likewise possible. Copolymers may also be used in the context of the present invention. The number average molecular weight of the polyol used according to the present invention is preferably from 0.5×10 3 g / mol to 8×10 3 g / mol, preferably from 0.6×10 3 g / mol to 5×10 3 g / mol, specifically from 0.8×10 3 g / mol to 3×10 3 g / mol.

[0042] Polyether polyols but also hybrid polyols such as polyester polyols, block copolymers, and poly(ester / amide) are preferred according to the present invention. Preferred polyether polyols according to the present invention are polyethylene glycol, polypropylene glycol, polyadipate, polycarbonate, polycarbonate diol, and polycaprolactone.

[0043] According to a further embodiment, the present invention also relates to the thermoplastic polyurethane described above, wherein the polyol composition contains a polyol selected from the group consisting of polyether polyols, polyester polyols, polycaprolactone, and polycarbonate.

[0044] Suitable block copolymers are, for example, those having ether and ester blocks, such as polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, or polyethers having polycaprolactone end blocks. Preferred polyetherols according to the invention are polyethylene glycol and polypropylene glycol. Polycaprolactone is also preferred.

[0045] According to a particularly preferred embodiment, the polyol used has a number average molecular weight Mn in the range from 500 g / mol to 4000 g / mol, preferably in the range from 800 g / mol to 3000 g / mol.

[0046] According to a further embodiment, the invention thus relates to a thermoplastic polyurethane as described above, in which at least one polyol present in the polyol composition has a number average molecular weight Mn in the range from 500 g / mol to 4000 g / mol. According to the invention, the average molecular weight of the polyols present in the polyol composition (PC) is preferably in the range from 1250 g / mol to 2500 g / mol.

[0047] It is also possible according to the invention to use mixtures of different polyols. The polyol / polyol composition used preferably has an average functionality of between 1.8 and 2.3, preferably between 1.9 and 2.2, specifically 2. The polyols used according to the invention preferably have only primary hydroxyl groups.

[0048] According to one embodiment of the invention, at least one polyol composition comprising at least polytetrahydrofuran is used in the production of the thermoplastic polyurethane. The polyol composition also comprises, according to the invention, further polyols in addition to polytetrahydrofuran.

[0049] Further polyols suitable according to the invention are, for example, polyethers, but also polyesters, block copolymers, and also hybrid polyols such as poly(ester / amide). Suitable block copolymers are, for example, those having ether and ester blocks, such as polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, or polyethers having polycaprolactone end blocks. Preferred polyetherols according to the invention are polyethylene glycol and polypropylene glycol. Also preferred as a further polyol is polycaprolactone.

[0050] Suitable polyols are, for example, polyetherols, such as polytrimethylene oxide or polytetramethylene oxide. According to a further embodiment, the invention also relates to the molded article described above, wherein the polyol composition comprises a polyol selected from the group consisting of polyetherols, polyesterols, and polycaprolactone polyols.

[0051] According to a particularly preferred embodiment, polytetrahydrofuran has a number average molecular weight Mn in the range of 500 g / mol to 5000 g / mol, more preferably in the range of 750 to 3000 g / mol, and particularly preferably in the range of 1000 to 2500 g / mol. According to a further embodiment, the invention also relates to the molded article described above, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1400 g / mol to 2200 g / mol. Mixtures of various polytetrahydrofurans may also be used according to the invention, i.e., mixtures of polytetrahydrofurans having different molecular weights.

[0052] In the context of the present invention, the composition of the polyol composition may vary within a wide range. For example, the content of the first polyol, preferably the first polyol of polytetrahydrofuran, may be in the range of 15% to 85%, preferably in the range of 20% to 80%, more preferably in the range of 25% to 75%.

[0053] The polyol composition may also contain a solvent according to the present invention. Suitable solvents are known per se to those skilled in the art.

[0054] Examples of suitable chain extenders are compounds having at least two isocyanate-reactive functional groups, such as hydroxyl groups, amino groups or thiol groups.

[0055] Examples of suitable chain extenders are compounds selected from the group consisting of aliphatic and aromatic diols having a molecular weight of <500 g / mol, preferably <350 g / mol.

[0056] It is preferred according to the present invention that the chain extender used is a diol. In this case, it is preferred to use aliphatic, araliphatic, aromatic and / or alicyclic diols having a molecular weight of 50 g / mol to 220 g / mol. Preferred are alkanediols having 2 to 10 carbon atoms in the alkylene group, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols. Particularly preferred for the present invention are 1,2-ethylene glycol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol.

[0057] Also, suitable as a chain extender in the context of the present invention are branched compounds such as cyclohexyl-1,4-dimethanol, 2-butyl-2-ethylpropanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, pinacol, 2-ethylhexane-1,3-diol, cyclohexane-1,4-diol or N-phenyldiethanolamine. Similarly suitable are mixed compounds such as 4-aminobutanol.

[0058] According to a further embodiment, the present invention also relates to the molded article described above, wherein the chain extender (CE1) is selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol and hexane-1,6-diol.

[0059] According to the present invention, it is also possible to use further chain extenders. According to the present invention, it is also possible to use compounds having an amino group, such as diamines. Similarly, it is possible to use a mixture of diol and diamine.

[0060] In the context of the present invention, the amount of chain extender used and the amount of polyol used may vary within a wide range.

[0061] According to the present invention, the production of thermoplastic polyurethane uses a polyisocyanate composition containing at least one polyisocyanate.

[0062] In the context of the present invention, preferred polyisocyanates are diisocyanates, especially aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates. Suitable isocyanates are known per se to those skilled in the art.

[0063] According to the present invention, it is also possible that the isocyanate composition contains 4,4'-methylenediphenyl diisocyanate and at least one further methylenediphenyl diisocyanate. According to the present invention, the term "methylenediphenyl diisocyanate" is understood to mean diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate, or a mixture of two or three isomers. Therefore, further isocyanates that can be used according to the present invention are diphenylmethane 2,2'- or 2,4'-diisocyanate, or a mixture of two or three isomers. According to the present invention, the polyisocyanate composition may also contain a further polyisocyanate.

[0064] In addition, some of the OH components can use a prepolymer product that has been reacted with isocyanate in a previous reaction step as the isocyanate component. In the subsequent step, the actual polymer reaction, the resulting product is reacted with the remaining OH components to form a thermoplastic polyurethane in that way.

[0065] The aliphatic diisocyanates used are conventional aliphatic and / or cycloaliphatic diisocyanates, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, trimethylhexamethylene 1,6-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and / or 2,6-diisocyanate, methylenedicyclohexyl 4,4'-, 2,4'- and / or 2,2'-diisocyanate (H12MDI).

[0066] Preferred aliphatic polyisocyanates are hexamethylene 1,6 - diisocyanate (HDI), 1 - isocyanato - 3,3,5 - trimethyl - 5 - isocyanatomethylcyclohexane and methylenedicyclohexyl 4,4’ -, 2,4’ - and / or 2,2’ - diisocyanate (H12MDI).

[0067] Preferred aliphatic polyisocyanates are hexamethylene 1,6 - diisocyanate (HDI), 1 - isocyanato - 3,3,5 - trimethyl - 5 - isocyanatomethylcyclohexane and methylenedicyclohexyl 4,4’ -, 2,4’ - and / or 2,2’ - diisocyanate (H12MDI); particularly preferred are methylenedicyclohexyl 4,4’ -, 2,4’ - and / or 2,2’ - diisocyanate (H12MDI) and 1 - isocyanato - 3,3,5 - trimethyl - 5 - isocyanatomethylcyclohexane, or mixtures thereof.

[0068] Suitable aromatic diisocyanates are, in particular, naphthylene 1,5 - diisocyanate (NDI), tolylene 2,4 - and / or 2,6 - diisocyanate (TDI), 3,3’ - dimethyl - 4,4’ - diisocyanatobiphenyl (TODI), p - phenylene diisocyanate (PDI), diphenylethane 4,4’ - diisocyanate (EDI), diphenylmethane diisocyanate, dimethyldiphenyl 3,3’ - diisocyanate, diphenylethane 1,2 - diisocyanate and / or phenylene diisocyanate.

[0069] Particularly suitable in the context of the present invention are, for example, polyisocyanate compositions comprising 4,4’ - MDI and 2,4 - MDI, polyisocyanate compositions comprising 4,4’ - MDI and 3,3’ - dimethyl - 4,4’ - diisocyanatobiphenyl (TODI), or polyisocyanate compositions comprising 4,4’ - MDI and naphthylene 1,5 - diisocyanate (NDI).

[0070] Three or more isocyanates can also be used according to the present invention. The polyisocyanate composition typically contains 4,4'-MDI in an amount of 2% to 50% based on the total polyisocyanate composition, and further contains additional isocyanates in an amount of 3% to 20% based on the total polyisocyanate composition.

[0071] Preferred examples of higher functionality isocyanates are triisocyanates such as triphenylmethane 4,4',4''-triisocyanate, also the cyanurate of the diisocyanates described above, and also oligomers that can be obtained by the partial reaction of diisocyanates with water, such as the biuret of the diisocyanates described above, and additionally oligomers that can be obtained by the specific reaction of semi-blocked diisocyanates with polyols having on average more than two, preferably three or more hydroxy groups.

[0072] According to the present invention, the polyisocyanate composition may also contain one or more solvents. Suitable solvents are known to those skilled in the art. Suitable examples are non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.

[0073] Also, within the context of the present invention, even more usable are crosslinking agents, such as the higher functionality polyisocyanates or polyols described above, or other higher functionality molecules having a plurality of isocyanate-reactive functional groups. Similarly, within the context of the present invention, it is possible to achieve crosslinking of the product by having isocyanate groups in excess with respect to the hydroxyl groups utilized.

[0074] According to the present invention, the components are used in a ratio such that the molar ratio of the sum of the functionality of the polyol composition used to the sum of the functionality of the isocyanate composition used is in the range of 1:0.8 to 1:1.3. The ratio is preferably in the range of 1:0.9 to 1:1.2, more preferably in the range of 1:0.965 to 1:1.11, more preferably in the range of 1:0.97 to 1:1.11, more preferably in the range of 1:0.97 to 1:0.97, and particularly preferably in the range of 1:0.98 to 1:1.03.

[0075] A further parameter considered in the reaction of the components is the isocyanate index. As used herein, the index is defined through the ratio of all of the isocyanate groups used during the reaction to the isocyanate-reactive groups, specifically, the ratio of all of the reactive groups of the polyol component. When the index is 1000, there is one active hydrogen atom per isocyanate group. At indices above 1000, there are more isocyanate groups than isocyanate-reactive groups. The index in the reaction of the components is preferably in the range of 965 to 1110, for example, in the range of 970 to 1110, more preferably in the range of 970 to 1050, and particularly preferably in the range of 980 to 1030.

[0076] According to the present invention, further additives, such as catalysts or auxiliaries, and adducts may be added during the production of the thermoplastic polyurethane. The adducts and auxiliaries are known per se to those skilled in the art. It is also possible according to the present invention to use a combination of two or more additives. Suitable auxiliaries and adducts can be found, for example, in Kunststoffhandbuch [Plastics Handbook], Volume VII, edited by Vieweg and Hoechtlen, Carl Hanser Verlag, Munich 1966 (pages 103-113).

[0077] According to the present invention, the thermoplastic polyurethane used as (TPE-1) preferably has a hard segment content in the range of 10% to 20%, preferably in the range of 14% to 17%. The hard segment content herein is the proportion of the thermoplastic polyurethane formed by the isocyanate and the chain extender. In the context of the present invention, the hard segment content is determined by the formula disclosed in WO2007 / 118827 A1, where a value of 1.0 corresponds to 100%, and a hard segment content >50% corresponds to a value >0.50 according to the formula specified in WO2007 / 118827 A1.

[0078] According to the present invention, a foamed pellet material made of a thermoplastic elastomer (TPE-2) is used. The method for manufacturing the foamed pellet material from the thermoplastic elastomer is known per se to those skilled in the art. The bulk density of the foamed pellet material is typically in the range of 20 g / l to 200 g / l, preferably 50 g / l to 180 g / l, and particularly preferably 60 g / l to 150 g / l.

[0079] For example, the diameter of the foamed pellet material is between 0.5 and 20 mm, preferably between 1 and 15 mm, and more specifically between 3 and 12 mm. In the case of non-spherical, e.g., elongated or cylindrical, foamed pellet materials, the diameter means the longest dimension.

[0080] According to a further aspect, the present invention also relates to a method for manufacturing a molded article (M), the method comprising (a) providing a molded article (M-1) containing a thermoplastic elastomer (TPE-1) in a mold; (b) filling the mold with a foamed pellet material containing a thermoplastic elastomer (TPE-2) having a processing temperature TP(TPE-2); (c) manufacturing the molded article (M) by fusion at a temperature within the range of 100 to 170 °C and The molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014. It also relates to a method.

[0081] According to a further embodiment, the present invention also provides that the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2). The method described above, wherein the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, TPU sample geometry: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014. It also relates to a method.

[0082] Regarding the preferred embodiment, the above description is referred to.

[0083] According to the present invention, the molded article (M) is first produced by providing the molded article (M-1) in a suitable mold in step (a), and then filling the mold with a foamed pellet material containing the thermoplastic elastomer (TPE-2) in step (b). The amount of the foamed pellet material filled in the mold is adapted to the size of the mold and the desired density of the molded article. In the context of the present invention, the method may also include further steps, such as temperature adjustment. In the context of the present invention, the molded article (M) may also contain further components. Thus, in the production, further molded articles or foamed particles made of different materials may be used.

[0084] According to step (c), the molded article (M) is produced by fusion at a temperature within the range of 100 to 170 °C. The temperature during the fusion of the expanded particles is preferably between 100 °C and 140 °C.

[0085] According to process (c), the fusing may be effected, for example, by fusing the components together in a closed mold under the action of heat. In contrast, the components, i.e. at least the foamed pellet material and the molded article (M-1), are introduced into the mold, and after the mold is closed, steam or warm air is introduced, which causes further expansion of the particles of the foamed pellet material and fuses them together and to the molded article (M-1) to produce a foam, preferably a foam having a density in the range of 8 to 600 g / l. The foam may be a semi-finished product, such as a slab, profile or sheet, or a finished shaped article having a simple or complex geometry.

[0086] Specifically, the present invention relates to a method for producing the above-described molded article, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are independently selected from the group consisting of thermoplastic polyurethane, polyether ester, polyester ester and polyether amide. According to a further embodiment, the present invention also relates to the above-described method, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethane.

[0087] According to a further aspect, the present invention also relates to a molded article obtained or obtainable by the above-described method.

[0088] The method according to the present invention can easily process different materials, including, for example, bio-based thermoplastic elastomers or thermoplastic elastomers of different colors, and can very precisely adapt to the geometric shape of the surface. The method according to the present invention enables distribution to further layers, such as an adhesive layer.

[0089] It is also advantageous that the foam of the present invention can be reused as a thermoplastic without difficulty. In contrast, for example, the foamed material is extruded using an extruder having a ventilation device, and optionally, mechanical grinding may precede the extrusion. Thereafter, they can be reprocessed to produce a foam in the above-described method.

[0090] The present invention also relates to a method of using a molded article (M-1) made of a thermoplastic elastomer (TPE-1) for manufacturing the molded article in the presence of a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) on the surface where the deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) is 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014. According to a further embodiment, the present invention also relates to a method of using, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate in the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, TPU sample geometry: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

[0091] The molded article of the present invention can be used in various fields. According to a further aspect, the present invention also relates to a method of using the molded article according to the present invention, wherein the molded article is suitable for use in the fields of sports, industry, medicine, sports medicine, safety, automotive and consumer goods. The present invention also further relates to a method of using the molded article according to the present invention, wherein the molded article is a component in shoe soles, parts of shoe soles, bicycle saddles, cushioning materials, mattresses, underlays, handles, protective films, and automotive interiors and exteriors. The molded article according to the present invention is particularly suitable for use in external shoe soles.

[0092] Further embodiments of the present invention can be found in the "Claims" and the Examples. The features of the article / method / method of use according to the present invention, cited above and clarified hereinbelow, can be used not only in the specifically identified combinations but also in other combinations without departing from the scope of the present invention. Therefore, for example, combinations of preferred features, in particular with particularly preferred features, or further combinations of uncharacterized features with particularly preferred features, etc., are also implicitly included even if such combinations are not explicitly listed.

[0093] Exemplary embodiments of the present invention are detailed hereinbelow, but it is not intended to limit the present invention. Specifically, the present invention also includes embodiments resulting from dependent references and thus includes the combinations specified hereinbelow. More specifically, where the scope of an embodiment is listed in connection with an expression such as "any one of Embodiments 1 to 4", it is pointed out that each of the embodiments within that scope is explicitly disclosed. This phrase will be considered by those skilled in the art to be synonymous with the phrase "any one of Embodiments 1, 2, 3 and 4". The following embodiments do not constitute the "Claims", but it is explicitly stated that they are a structured part of the description of the general and preferred aspects of the present invention.

[0094] 1. A molded article (M) comprising a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25°C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014.

[0095] 2. The molded article according to Embodiment 1, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO11359-3:2014.

[0096] 3. The molded article according to Embodiment 1 or 2, wherein the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2) is within the range of 100 to 170 °C.

[0097] 4. The molded article according to any one of Embodiments 1 to 3, wherein the thermoplastic elastomers (TPE-1) and (TPE-2) are independently selected from thermoplastic polyurethane, thermoplastic polyester, and thermoplastic polyamide.

[0098] 5. The molded article according to any one of Embodiments 1 to 4, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethane.

[0099] 6. The thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane (TPU-1) obtained or obtainable by the reaction of components (i) to (iii): (i) a polyisocyanate composition (IC); (ii) at least one chain extender (CE1); (iii) a polyol composition (PC) and the components are reacted at an index within the range of 0.99 to 1.02, and the average molecular weight of the polyol present in the polyol composition (PC) is within the range of 1250 g / mol to 2500 g / mol. The molded article according to any one of Embodiments 1 to 5. The molded article according to any one of Embodiments 1 to 5.

[0100] 7. The molded article according to embodiment 6, wherein the chain extender (CE1) is selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol.

[0101] 8. The molded article according to embodiment 6 or 7, wherein the polyol composition contains a polyol selected from the group consisting of polyether polyols, polyester polyols, and polycaprolactone polyols.

[0102] 9. The molded article according to any one of embodiments 6 to 8, wherein the polyol composition contains a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1400 g / mol to 2200 g / mol.

[0103] 10. A method for producing a molded article (M), preferably the molded article according to any one of embodiments 1 to 9, the method comprising: (a) providing a molded article (M-1) containing a thermoplastic elastomer (TPE-1) in a mold; (b) filling the mold with a foamed pellet material containing a thermoplastic elastomer (TPE-2) having a processing temperature TP (TPE-2); and (c) producing the molded article (M) by fusion at a temperature within the range of 100 to 170°C. and the molded article (M-1) has a softening temperature TS (TPE-1) with a deviation from the processing temperature TP (TPE-2) of the thermoplastic elastomer (TPE-2) of 25°C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014. Method.

[0104] 11. The method according to embodiment 10, wherein the processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2) is within the range of 100 to 170°C.

[0105] 12. The method according to embodiment 10 or 11, wherein the thermoplastic elastomers (TPE-1) and (TPE-2) are independently selected from thermoplastic polyurethane, thermoplastic polyester, and thermoplastic polyamide.

[0106] 13. The method according to any one of embodiments 10 to 12, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate in the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometry of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

[0107] 14. The method according to any one of embodiments 10 to 13, wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethane.

[0108] 15. The thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane (TPU-1) obtained or obtainable by the reaction of (i) a polyisocyanate composition (IC), (ii) at least one chain extender (CE1), and (iii) a polyol composition (PC) wherein the components are reacted at an index in the range of 0.99 to 1.02, and the average molecular weight of the polyol present in the polyol composition (PC) is in the range of 1250 g / mol to 2500 g / mol. The method according to any one of embodiments 10 to 14.

[0109] 16. The method according to embodiment 15, wherein the chain extender (CE1) is selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol.

[0110] 17. The method according to embodiment 15 or 16, wherein the polyol composition comprises a polyol selected from the group consisting of polyether polyols, polyester polyols, and polycaprolactone polyols.

[0111] 18. The method according to any one of embodiments 10 to 17, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1400 g / mol to 2200 g / mol.

[0112] 19. A molded article obtained or obtainable by the method according to any one of embodiments 10 to 18, preferably the molded article according to any one of embodiments 1 to 9.

[0113] 20. A method of use for manufacturing a molded article (M-1) made of a thermoplastic elastomer (TPE-1) in the presence of a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014.

[0114] 21. The method according to embodiment 20, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO11359-3:2014.

[0115] 22. The method according to embodiment 20 or 21, wherein the molded article is suitable for use in the fields of sports, industry, medicine, sports medicine, safety, automotive and consumer goods.

[0116] 23. The method according to any one of embodiments 20 to 22, wherein the molded article is a component in a part of a shoe sole, a part of a shoe, a bicycle saddle, a cushioning material, a mattress, an underlay, a handle, a protective film, and the interior and exterior of an automobile.

[0117] 24. The method according to any one of embodiments 20 to 23, wherein the molded article is an external shoe sole.

[0118] 25. A molded article (M) comprising a molded article (M-1) made from a thermoplastic elastomer (TPE-1) and a foamed pellet material made from a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25°C or less, and the softening temperature is determined by TMA in accordance with ISO11359-3:2014, the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethanes, the molded article (M).

[0119] 26. The molded article according to embodiment 25, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

[0120] 27. The molded article according to embodiment 25 or 26, wherein the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2) is within the range of 100 to 170 °C.

[0121] 28. The thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane (TPU-1) obtained or obtainable by the reaction of components (i) to (iii): (i) a polyisocyanate composition (IC), and (ii) at least one chain extender (CE1), and (iii) a polyol composition (PC) and the components are reacted at an index within the range of 0.99 to 1.02, and the average molecular weight of the polyol present in the polyol composition (PC) is within the range of 1250 g / mol to 2500 g / mol. The molded article according to any one of embodiments 25 to 27.

[0122]

[0122] 29. The molded article according to embodiment 28, wherein the chain extender (CE1) is selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol.

[0123] 30. The molded article according to embodiment 28 or 29, wherein the polyol composition contains a polyol selected from the group consisting of polyether polyols, polyester polyols, and polycaprolactone polyols.

[0124] 31. The molded article according to any one of Embodiments 28 to 30, wherein the polyol composition contains a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1400 g / mol to 2200 g / mol.

[0125] 32. A method for manufacturing a molded article (M), preferably the molded article according to any one of Embodiments 25 to 31, the method comprising (a) providing a molded article (M-1) containing a thermoplastic elastomer (TPE-1) in a mold; (b) filling the mold with a foamed pellet material containing a thermoplastic elastomer (TPE-2) having a processing temperature TP(TPE-2); (c) manufacturing the molded article (M) by fusion at a temperature within the range of 100 to 170 °C and the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO11359-3:2014, the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethanes, method.

[0126] 33. The method according to Embodiment 32, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate in the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round ram 3 mm, geometry of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO11359-3:2014.

[0127] 34. A molded article obtained or obtainable by the method according to Embodiment 32 or 33, preferably the molded article according to any one of Embodiments 25 to 31.

[0128] 35. A method of using for manufacturing a molded article (M-1) made of a thermoplastic elastomer (TPE-1) in the presence of a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS(TPE-1) with a deviation from the processing temperature TP(TPE-2) of the thermoplastic elastomer (TPE-2) of 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014. The thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethanes. The method of using.

[0129] 36. The method according to Embodiment 35, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2) and a softening rate in the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

[0130] 37. The method according to Embodiment 35 or 36, wherein the molded article is suitable for use in the fields of sports, industry, medicine, sports medicine, safety, automotive and consumer goods.

[0131] 38. The method according to any one of Embodiments 35 to 37, wherein the molded article is a component in shoes, part of a shoe sole, a bicycle saddle, a cushioning material, a mattress, an underlay, a handle, a protective film, and the interior and exterior of an automobile.

[0132] 39. The method according to any one of embodiments 35 to 38, wherein the molded article is an external sole.

[0133] The following examples serve to illustrate the invention but in no way limit the subject matter of the invention.

Example

[0134] 1. Starting materials The following starting materials were used: Polyol 1: A polyether polyol having a number average molecular weight of 1 kg / mol and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) Polyol 2: A polyether polyol having a number average molecular weight of 2 kg / mol and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) Isocyanate 1: An aromatic isocyanate (4,4'-methylenediphenyl diisocyanate) CE1: Butane-1,4-diol Plasticizer 1: Acetyl tributyl citrate, abbreviated as ATBC, hereinafter also referred to as P1 in this specification Catalyst 1: Tin (II) isooctoate (50% in dioctyl adipate) Stabilizer 1: Hindered phenol Processing Auxiliary 1: Ethylene bis stearoyl amide, hereinafter also referred to as PA1 in this specification Crosslinking agent 1: TPU1, which is a 40% 2,4-functional prepolymer based on 4,4'-methylenediphenyl diisocyanate (MDI), polymeric MDI, and a polyether polyol having a number average molecular weight of 0.5 kg / mol and exclusively primary OH groups (based on tetramethylene oxide, functionality: 2) in separate extrusion steps, and the remaining NCO is 28.5 g / 100 g (ASTM D5155-96).

[0135] 1.1 Production of TPU1 A mixture of 5.72 mass% butane-1,4-diol and 62.72 mass% polytetrahydrofuran having a number average molecular weight Mn of 1000 g / mol was heated to 70 °C and vigorously mixed in a mixing head in the presence of 31.56 mass% diphenylmethane 4,4'-diisocyanate and 1.0 mass% Crodamide EBS wax based on the first three components. The resulting reaction mixture was applied to a circulating PTFE belt at a temperature of 90 °C. The reaction mixture solidified to form a solid slab at the end of the belt was continuously fed at about 80 °C via a take-up roll directly into a grinding and homogenizing apparatus. It was ground therein at a temperature of about 105 °C and conveyed to a single-shaft extruder connected thereto by a tangential flange. The temperature of the barrel was about 170 °C - 190 °C in the take-up region and 190 - 220 °C in the central zone. The melt excited at the die plate was treated by underwater pelletization to obtain homogeneous lens-shaped pellets having a mass of 32 mg and then dried.

[0136] 1.2 Production of eTPU In an impregnation container with 80% filling degree, TPU1 pellets were added to a mixture of calcium carbonate water and a surfactant such that the solid / liquid phase ratio was 0.32. The airtight container was first purged with nitrogen and then the blowing agent butane was injected in the amounts shown in the table based on the solid phase (TPU). The container was heated while stirring the solid / liquid phase and the container was pressurized to 8 bar with a specified amount of nitrogen at a temperature of 50 °C. Then the mixture was further heated to the desired impregnation temperature (IMT). When the impregnation temperature and pressure were reached, the pressure in the container was released via a valve after a specified holding time. The exact production parameters and bulk densities achieved in the experiments are listed in Table 1.

[0137]

Table 1

[0138] 2. Production of Comparative Examples + Examples (Dense TPU) 2.1 Manufacturing method 1 - (a two-step method including the following, a first step, a reactive extrusion method without a plasticizer with a polyol mixture, and a second step, incorporation of P1 in a twin-screw extruder), the continuous synthesis method of Comparative Example 1 On the other hand, a mixture of CE1, processing aid 1, stabilizer 1, polyol 1 and polyol 2 was weighed into the first barrel of a ZSK92 twin-screw extruder with a processing length of 56D, manufactured by Werner & Pfleiderer, Stuttgart, at a charging temperature of 150 °C, and separately, isocyanate 1 was weighed into the first barrel of this same extruder at a charging temperature of 65 °C. The speed of the twin-screw was 280 rpm. The set temperature value for the barrel in the downstream direction was 190 °C in the first one-third of the screw and 190 °C in the two-thirds and three-thirds of the screw. The output was 850 kg / h. In this way, thermoplastic polyurethane (TPU) was synthesized by a known reactive extrusion method. The pelletizable reaction melt thus obtained can be formed into lens-shaped pellets in a subsequent step known as underwater pelletization. The pellets are dried at approximately 80 - 90 °C by subsequent post-treatment and then packaged in transportable containers. The preliminary product 1 obtained therefrom is further processed as described below.

[0139] The preliminary product 1 is weighed into the first barrel of a ZE65 twin-screw extruder with a processing length of 42D made by Berstorff at a charging temperature of approximately 30°C. Separately, plasticizer 1 is weighed into the fourth barrel of the same extruder at a charging temperature of 40°C. The speed of the twin-screw is set at 160 rpm. The set temperature values for the barrels in the downstream direction are 190°C in the first third of the screw and 170°C in the two-thirds and three-thirds of the screw. The output is 300 kg / h. In this way, thermoplastic polyurethane (TPU) is synthesized by a known chemical method. The pelletizable polymer melt thus obtained can be formed into lens-shaped pellets in a subsequent process known as underwater pelletization. The pellets are dried at approximately 80°C by subsequent post-treatment and then packaged in transportable containers, in this case 25 kg PE bags.

[0140] The TPU pellets thus obtained are pre-dried at 80 - 100°C for 3 hours, then further processed and then formed into test specimens by injection molding. The zone temperature of the injection molding unit used for this is between 190°C and 220°C. S2 test bars are cut out from the specimen panels thus obtained and subjected to further mechanical tests. In addition, chemical values, for example, the molar mass of these test specimens are determined.

[0141] 2.2 Manufacturing method 2 - Dry blend, i.e., mixing of TPU pellets with crosslinking agent 1, continuous synthesis method of Comparative Example 2 98.5 parts by mass of TPU pellets manufactured under 2.1 are pre-dried at 80 - 100°C for 3 hours for further processing and then mixed with 1.5 parts by mass of crosslinking agent 1.

[0142] The TPU pellet mixture thus obtained is formed into test specimens by injection molding. The zone temperature of the injection molding unit used for this shall be between 190°C and 220°C. S2 test bars are cut out from the specimen panels thus obtained and subjected to further mechanical tests. In addition, chemical values, such as the molar mass of these test specimens, are determined.

[0143] The synthesis and properties of the obtained thermoplastic polyurethane are summarized in Tables 2 and 3. The samples manufactured using these methods serve as Comparative Examples 1+2.

[0144] [Table 2]

[0145] [Table 3]

[0146] 2.3 Manufacturing method 3 (one-step reaction extrusion method with P1 + polyol mixture), continuous synthesis methods for Comparative Example 3 and Example 3 On the one hand, a mixture of CE1, processing aid 1, stabilizer 1, polyol 1 and polyol 2 was weighed into the first barrel of a ZSK92 twin-screw extruder with a processing length of 56D, manufactured by Werner & Pfleiderer, Stuttgart, at a charging temperature of 150°C. Separately, isocyanate 1 was weighed into the first barrel of this same extruder at a charging temperature of 65°C. Separately, plasticizer 1 was weighed into the downstream barrel at a charging temperature of 40°C in the last third of this same extruder. The speed of the twin-screw was set at 280 rpm. The set temperature values for the barrels in the downstream direction were 190°C in the first third of the screw and 170°C in the two-thirds and three-thirds of the screw. The output was 600 kg / h. In this way, thermoplastic polyurethane (TPU) was synthesized by a known reactive extrusion process. The pelletizable reaction melt thus obtained can be formed into lens-shaped pellets in a subsequent process known as underwater pelletization. The pellets are dried at approximately 80 - 90°C by subsequent post-treatment and then packaged in transportable containers.

[0147] The TPU pellets thus obtained are pre-dried at 80 - 100°C for 3 hours, then further processed and then formed into test specimens by injection molding. The zone temperature of the injection molding unit used for this is between 190°C and 220°C. S2 test bars are cut out from the specimen panels thus obtained and subjected to further mechanical tests. In addition, chemical values, such as the molar mass of these test specimens, are determined.

[0148] 2.4 Manufacturing method 4 (one-step reactive extrusion method with P1 + polyol), comparative example 4 and continuous synthesis methods of examples 1, 2, 4, 5, 6 and 7 On the one hand, a mixture of CE1, processing aid 1, stabilizer 1, and polyol 2 was weighed into the first barrel of a ZSK92 twin-screw extruder with a processing length of 56D, manufactured by Werner & Pfleiderer, Stuttgart, at a feed temperature of 150 °C. Separately, isocyanate was weighed into the first barrel of the same extruder at a feed temperature of 65 °C. Separately, plasticizer 1 was weighed into the last third of the same extruder into the downstream barrel at a feed temperature of 40 °C. The speed of the twin-screw was set at 280 rpm. The set temperature values for the barrels in the downstream direction were 190 °C in the first third of the screw and 170 °C in the two-thirds and three-thirds of the screw. The output was 600 kg / h. In this way, thermoplastic polyurethane (TPU) was synthesized by a known reactive extrusion process. The pelletizable reaction melt thus obtained can be formed into lens-shaped pellets in a subsequent process known as underwater pelletization. The pellets are dried at approximately 80 - 90 °C by subsequent post-treatment and then packaged in transportable containers.

[0149] The TPU pellets thus obtained were pre-dried at 80 °C to 100 °C for 3 hours, then further processed and then formed into test specimens by injection molding. The zone temperature of the injection molding unit used for this is between 190 °C and 220 °C. S2 test bars are cut out from the specimen panels thus obtained and subjected to further mechanical tests. In addition, chemical values, for example, the molar mass of these test specimens, are determined.

[0150] The synthesis and properties of the obtained thermoplastic polyurethane are summarized in Tables 4, 5, 6, and 7. The samples manufactured using these methods serve as Comparative Examples 3 and 4 and Examples 1, 2, 4, 5, 6, and 7.

[0151]

Table 4

[0152]

Table 5

[0153]

Table 6

[0154]

Table 7

[0155] The molded product (M-1) was manufactured from the described TPU pellet materials (Examples and Comparative Examples) by an injection molding method. In contrast, the pellets were pre-dried at 80 to 100 °C for 3 hours and then formed into the molded product (M-1) by injection molding. The zone temperature of the injection molding unit used for this was between 190 °C and 220 °C. The obtained molded product (M-1) was optionally subjected to aging (annealing by heat treatment, 10 hours at 70 °C), as described in Table 8.

[0156] The final molded product (M) is manufactured in several sub-steps: a. A sub-step of inserting the molded product (M-1) having holes through which steam can pass into a steam molding machine manufactured by Kurtz (Boost Foamer), b. A sub-step of filling with the foamed pellet material eTPU1, c. A sub-step of exposing eTPU1 to steam and subjecting it, as well as the molded product M-1, to fusion at a temperature of 130 to 135 °C, d. A sub-step of annealing the final M at 70 °C for 4 hours.

[0157] The properties described in Table 8 were evaluated as follows: 1. After obtaining the molded product M, the shape retention in the molded product (M-1) was visually evaluated. The label "defective" means a change in the structure of M-1 that results in deterioration in the visual appearance of the surface, for example, sharpness of the edges, deformation, gloss, or flow of the structure.

[0158] 2. From the molded product M, 10-mm strips were cut out every 2 centimeters around it. After introducing the groove into the molded product M, the adhesiveness was determined by measuring the tensile strength. In contrast, the molded product M-1 and the fused pellet material were pulled apart in opposite directions at a speed of 100 mm / min in a tensile strength machine. "Good" means a sample having a tensile strength in this test exceeding 2.7 N / mm.

[0159] 3. Storage stability refers to the change in the TPU pellet material after synthesis but before processing. The label "bad" means an excessive change in the consistency of the sample.

[0160] 4. Processing stability refers to the consistency of the method for manufacturing M-1 and the aging change in M-1. The label "bad" means an excessive change in the consistency of the method.

[0161] 5. Thermomechanical analysis (TMA) was performed in accordance with ISO11359 (2014), heating rate 20 K / min, mass 15 g, diameter of the round drum 3 mm, geometry of the TPU sample: diameter 4 mm and thickness 2 mm.

[0162] In the case of the method of fusing the foamed particles in the presence of the component or in the case of the method of maintaining the shape of the contour of the component, it was possible to determine two regions (zone (1) and zone (2) shown in FIG. 1) that are characteristic for the evaluation of adhesiveness.

[0163]

Table 8

[0164] The results show that good products are obtained using thermoplastic polyurethanes based on PTHF having Mn > 1500 g / mol and the index does not exceed 1020 during production.

[0165] Specifically, as shown in Comparative Example 2, when using Crosslinking Agent 1, the high sensitivity of Crosslinking Agent 1 causes problems in production, which are reflected, for example, in the shrinkage of the shoe sole. This means that the shoe sole has to undergo additional heat treatment that is more expensive. The heat treatment of the shoe sole (M-1) was adapted for these samples when manufacturing the final molded product M so that the shoe sole would no longer exhibit any change in shape and the shrinkage of M-1 would be less obvious. In contrast, these samples were heat-treated at 70 °C for 10 hours.

[0166] 3. Measurement method / Standard: Shore A: DIN ISO 7619-1 (02 / 2012) Tensile strength: For Germany, DIN 53504 (03 / 2017), internationally, DIN EN ISO 527-2 (06 / 2012) Elongation at break: For Germany, DIN 53504 (03 / 2017), internationally, DIN EN ISO 527-2 (06 / 2012) Tear propagation resistance: (with notch) DIN ISO 34-1, B(b) (09 / 2016) Wear assessment: DIN ISO 4649 (03 / 2014) Gel permeation chromatography (GPC): DIN 55672-2 (2008), previously, the sample was completely dissolved in 0.5% amine-containing DMF at 80 °C. DMF was also used as the mobile phase. Thermomechanical analysis (TMA): ISO 11359 (2014), heating rate 20 K / min, mass 15 g, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm.

[0167] Cited references: Ullmann’s "Encyklopaedie der technischen Chemie” [Encyclopedia of Industrial Chemistry], 4th edition, volume 20, pp. 416 ff WO 94 / 20568 A1 WO 2007 / 082838 A1 “Polymer Chemistry”, Interscience Publ., New York, 1961, pp. 111-127 “Kunststoffhandbuch” [Plastics handbook], volume VIII, C. Hanser Verlag, Munich 1973 Journal of Polymer Science, Part A1, 4, pages 1851-1859 (1966) Kunststoffhandbuch, volume 7, “Polyurethane”, Carl Hanser Verlag, 3rd edition, 1993, chapter 3.1 Kunststoffhandbuch, volume VII, Vieweg and Hoechtlen, Carl Hanser Verlag, 1966, pp. 103-113 WO 2007 / 118827 A1

Claims

1. A method for manufacturing a molded article (M) comprising a molded article (M-1) made of a thermoplastic elastomer (TPE-1) and a foamed pellet material made of a thermoplastic elastomer (TPE-2), wherein the molded article (M-1) has a softening temperature TS (TPE-1) with a deviation from the processing temperature TP (TPE-2) of the thermoplastic elastomer (TPE-2) of 25 °C or less, and the softening temperature is determined by TMA in accordance with ISO 11359-3:2014, and the processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2) is within the range of 100 to 170 °C, wherein the thermoplastic elastomer (TPE-1) is in a dense form, and wherein the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethanes, a method.

2. The method according to claim 1, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate within the range of 3% to 12% within the processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

3. The thermoplastic elastomer (TPE-1) is a thermoplastic polyurethane (TPU-1) obtained or obtainable by the reaction of: (i) a polyisocyanate composition (IC), (ii) at least one chain extender (CE1), and (iii) a polyol composition (PC) , wherein the components are reacted at an index within the range of 0.99 to 1.02, and the average molecular weight of the polyol present in the polyol composition (PC) is within the range of 1250 g / mol to 2500 g / mol. The method according to claim 1 or 2.

4. The method according to claim 3, wherein the chain extender (CE1) is selected from the group consisting of ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, and hexane-1,6-diol.

5. ​ The method according to claim 3 or 4, wherein the polyol composition comprises a polyol selected from the group consisting of a polyether polyol, a polyester polyol, and a polycaprolactone polyol.

6. The method according to any one of claims 3 to 5, wherein the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofuran having a number average molecular weight Mn in the range of 1400 g / mol to 2200 g / mol.

7. A method comprising: providing a molded article (M-1) containing a thermoplastic elastomer (TPE-1) in a mold (a); filling the mold with a foamed pellet material containing the thermoplastic elastomer (TPE-2) having a processing temperature TP (TPE-2) (b); manufacturing the molded article (M) by fusion at a temperature within the range of 100 to 170°C (c) The method according to any one of claims 1 to 6.

8. A method of use for manufacturing a molded article in the presence of a foamed pellet material made of a thermoplastic elastomer (TPE-2) of a molded article (M-1) made of a thermoplastic elastomer (TPE-1), wherein the molded article (M-1) has a softening temperature TS (TPE-1) with a deviation from the processing temperature TP (TPE-2) of the thermoplastic elastomer (TPE-2) of 25°C or less, the softening temperature being determined by TMA in accordance with ISO 11359-3:2014, and the processing temperature range TP (TPE-2) of the thermoplastic elastomer (TPE-2) is within the range of 100 to 170°C, the thermoplastic elastomer (TPE-1) is in a dense form, and the thermoplastic elastomer (TPE-1) and the thermoplastic elastomer (TPE-2) are selected from thermoplastic polyurethanes. Method of use.

9. The method according to claim 8, wherein the thermoplastic elastomer (TPE-1) has a maximum softening rate of less than 10% at a temperature below the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and has a softening rate within the range of 3% to 12% within the processing temperature range TP(TPE-2) of the thermoplastic elastomer (TPE-2), and the softening rate is determined by TMA (mass 15 g, heating rate 20 K / min, diameter of the round drum 3 mm, geometric shape of the TPU sample: diameter 4 mm and thickness 2 mm) in accordance with ISO 11359-3:2014.

10. The method according to claim 8 or 9, wherein the molded article is suitable for use in the fields of sports, industry, medicine, sports medicine, safety, automobiles, and consumer goods.

11. The method according to any one of claims 8 to 10, wherein the molded article is a component in a shoe sole part, a bicycle saddle, a cushioning material, a mattress, an underlay, a handle, a protective film, an interior and exterior of an automobile.

12. The method according to any one of claims 8 to 11, wherein the molded article is an external shoe sole.

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