Use of poly(alkylphenol) resins in thermoplastic polyurethanes

Abstract

This invention relates to the use of poly(alkylphenol) resins for reducing the melt viscosity of thermoplastic polyurethane (TPU), and to a composition comprising thermoplastic polyurethane (TPU) and at least one poly(alkylphenol) resin. The invention also relates to a method for preparing a composition as defined herein, wherein the poly(alkylphenol) resin is incorporated into the TPU, particularly into molten TPU. Specifically, the poly(alkylphenol) resin comprises repeating units of formula (I), wherein iR 1 It is a straight-chain or branched alkylene group having 1 to 10 carbon atoms; ii.R 2 It is a straight-chain or branched alkyl group having up to 10, for example, 1 to 10 carbon atoms, especially 2 to 8 carbon atoms or 3 to 6 carbon atoms, especially 4 carbon atoms.

Description

Technical Field

[0001] This invention relates to the use of poly(alkylphenol) resins for reducing the melt viscosity of thermoplastic polyurethane (TPU), and to a composition comprising thermoplastic polyurethane (TPU) and at least one poly(alkylphenol) resin. The invention also relates to a method for preparing a composition as defined herein, wherein the poly(alkylphenol) resin is incorporated into the TPU, particularly into molten TPU. Background Technology

[0002] Thermoplastic polyurethane (TPU) is a type of polyurethane plastic that can be processed by heating at temperatures above its softening temperature, such as through thermoforming, injection molding, blow molding, melt blowing, melt coating, calendering, etc. TPU can also be used in 3D printing, including fused filament deposition (FFD) 3D printing, selective laser sintering (SSD) 3D printing, and 3D inkjet printing.

[0003] Generally, TPU refers to a thermoplastic polyurethane elastomer composed of rigid and flexible polyurethane segments covalently linked together, thus essentially forming a block copolymer. Typically, the rigid segments form a crystalline or quasi-crystalline phase within a matrix formed by the flexible segments. The flexible segments are typically responsible for the high elasticity of TPU, while imparting its elongation characteristics. The rigid segments of TPU are obtained by reacting diisocyanates with low-molecular-weight difunctional compounds (so-called chain extenders), while the flexible segments are obtained by reacting diisocyanates with high-molecular-weight difunctional or polyfunctional compounds, which typically have a molecular weight (number average) of at least 400 g / mol (e.g., from 400 to 10000 g / mol) and a functionality of at least 1.5 (e.g., from 1.5 to 3), including polyether polyols, polyester polyols, polyether ester polyols, polyacrylate polyols, etc.

[0004] Due to its structure, TPU possesses many beneficial properties, including good mechanical properties (such as high impact resistance, high flexibility at low temperatures, and high elasticity) and good chemical durability (such as high durability, especially resistance to chemical degradation, high solvent resistance, and high tolerance to oils or greases). In addition, TPU exhibits high transparency and high abrasion resistance.

[0005] Due to its excellent properties, TPU is used in many technical fields, including, for example, in the manufacture of mechanically elastic molded products such as automotive dashboards, casters, drive belts, power tools, footwear, sporting goods, inflatable rafts, fire hoses, and various extruded films, sheets, and profiles. TPU is also a common material found in the flexible housings of devices such as mobile phones and keypad protectors. TPU is well-known for its use in wire and cable sheathing, hoses and tubing, in adhesives and textile coatings, and as an impact modifier for other polymers. It is also used in high-performance films such as high-impact glass structures.

[0006] A key application of TPU is its use as a melt adhesive. Melt adhesives allow for bonding techniques using solvent-free, 100% solid adhesive systems. Melt adhesives are applied as a hot melt that rapidly solidifies upon cooling, thereby building their bond strength. For example, US 2011245449 A1 discloses a melt adhesive based on TPU obtained essentially from a symmetrical aliphatic diisocyanate and at least one isocyanate reactive compound containing hydroxyl and / or amino groups.

[0007] A general disadvantage of TPUs is their high melt viscosity and their sensitivity to shear in the molten state. In particular, TPUs tend to degrade under thermoplastic processing conditions because the temperatures required to achieve the acceptable low viscosity needed for thermal processing are quite high and approach or exceed the degradation temperature of TPUs. Furthermore, TPUs exhibit a large temperature dependence on melt viscosity and a high flow activation energy. Therefore, TPUs are more difficult to process compared to common thermoplastic polymers. For example, during extrusion or calendering, resin dripping or deformation may occur immediately after leaving the processing machine, and during blown film forming, bubble shapes may fluctuate. Because TPUs are thermoplastic, the corresponding bonded articles can primarily be debonded by heating. This allows for the reuse of components without complete decomposition. However, due to the high melt viscosity, high debonding temperatures are often required. Therefore, additives are needed to reduce the melt viscosity of TPUs and thus allow for lower processing temperatures.

[0008] Adding plasticizers to TPU can help reduce melt viscosity. However, the use of plasticizers may also lower the melting point and crystallization rate of the crystalline hard phase of TPU, thereby increasing cycle time in molding and hindering processing. Furthermore, tensile strength and modulus may be adversely affected by the addition of plasticizers. Finally, plasticizers may leach from the finished product, especially at high ambient temperatures.

[0009] US 5,977,268 proposes low molecular weight resins containing multiple (hydroxyl) groups, namely resins prepared from styrene and 4-hydroxystyrene, poly(vinylphenol) resins, resins based on copolymers of terpenes and phenols, such as vinyl aromatic / terpene / phenol terpolymers and copolymers or terpolymers prepared from dicyclopentadiene and phenol, as additives for TPU to reduce cycle time in molding processes. Summary of the Invention

[0010] There is still a need for a means to reduce the melt viscosity of TPU, particularly TPU suitable for adhesive applications, thereby allowing for a reduction in processing temperature and the adverse effects of shear and high temperature on the quality of the processed TPU.

[0011] Furthermore, when using TPU compositions as hot melt adhesives, melt adhesive bonding should be possible at low processing temperatures. Additionally, it is necessary that TPU-based hot melt adhesives rapidly build good bond strength and have a low bubble count to save energy and allow for high productivity, while also meeting stringent requirements for mechanical strength.

[0012] Surprisingly, it has now been found that the use of poly(alkylphenol) resins in TPU solves the aforementioned problems. Specifically, poly(alkylphenol) resins reduce the melt viscosity of TPU without affecting other chemical and / or physical properties of the TPU composition, such as melt temperature and / or mechanical properties. In particular, only a small amount of poly(alkylphenol) resin is required to achieve a significant reduction in melt viscosity. Therefore, compared to TPU compositions without poly(alkylphenol) resin, adding poly(alkylphenol) resin to TPU allows for a reduction in the melt viscosity of the TPU and thus enables processing of the TPU at lower processing temperatures. Furthermore, poly(alkylphenol) resin does not, or only minimally, affect the curing time of the molten TPU and does not significantly reduce the melt temperature, so that the mechanical properties of the TPU and the adhesive strength when the TPU is used as a hot melt adhesive are not significantly affected. In applications as hot melt adhesives, TPU compositions containing poly(alkylphenol) resin enable the melt adhesive to bond at lower bonding temperatures without affecting bond strength and / or delaying the development of bond strength.

[0013] Therefore, the present invention relates to the use of poly(alkylphenol) resins for reducing the melt viscosity of thermoplastic polyurethane (TPU).

[0014] Occasionally, poly(alkylphenol) resins have been suggested as tackifying additives for polymers, including polyurethanes, for example in CN 112536733 and JP 2000 / 230166.

[0015] The present invention also relates to a composition containing

[0016] A) Thermoplastic polyurethane (TPU), and

[0017] B) At least one poly(alkylphenol) resin as described herein, other than poly(alkylphenol) formaldehyde resin.

[0018] The present invention also relates to a method for preparing compositions as defined below, wherein a poly(alkylphenol) resin is incorporated into a TPU, particularly into a molten TPU. Detailed Implementation

[0019] As used herein, the term "thermoplastic polyurethane" refers to any polyurethane that becomes flexible or moldable at a certain elevated temperature and cures upon cooling.

[0020] The terms “wt%”, “wt.-%”, “wt.%”, “weight percentage”, and “by weight %” are used synonymously herein and throughout this specification.

[0021] "Molecular weight Mn" or "molar mass Mn" refers to the number-average molecular weight or molar mass. "Molecular weight Mw" or "molar mass Mw" refers to the mass-average molecular weight or molar mass. Unless otherwise specified, Mn and Mw are determined by GPC with an RI (refractive index) detector, using a mixture of hexafluoroisopropanol and 0.05% potassium trifluoroacetate as the eluent (temperature: 40°C, flow rate: 1 mL / min) and polymethyl methacrylate with a defined molecular weight as a calibration standard.

[0022] As used herein, the term "resin" refers to a solid or liquid synthetic organic polymer used as a base material for plastics, adhesives, varnishes, or other products.

[0023] As used herein, the term poly(alkylphenol) resin refers to a resin containing repeating alkylphenol units, such as C1-C1. 10 Resins containing alkylphenol repeating units, particularly C2-C8 or C3-C6 alkylphenol repeating units, especially C4-alkylphenol repeating units such as tert-butylphenol repeating units.

[0024] Here, the term alkyl refers to having, for example, 1 to 10 carbon atoms (C1-C1). 10Alkyl groups are straight-chain or branched saturated hydrocarbon groups, particularly those with 2 to 8 carbon atoms (C2-C8 alkyl) or 3 to 6 carbon atoms (C3-C6 alkyl), especially those with 4 carbon atoms (C4-alkyl). Examples of alkyl groups include methyl, ethyl, n-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (= tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, etc.

[0025] In poly(alkylphenol) resins, the amount of alkylphenol repeating units is preferably at least 50%, particularly at least 60%, and especially at least 70% by weight of the poly(alkylphenol) resin. In addition to the alkylphenol repeating units, poly(alkylphenol) resins typically also contain linking units that connect the alkylphenol repeating units. Typical linking units include divalent hydrocarbon groups that generally have 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, and especially 1 or 2 carbon atoms.

[0026] Examples of poly(alkylphenol) resins include methyl alkylphenol resins and linear alkylphenol resins, which are obtained by reacting alkylphenols with aliphatic aldehydes such as formaldehyde or acetaldehyde.

[0027] Specifically, the poly(alkylphenol) resin includes the repeating unit of formula (I).

[0028] (I)

[0029] in

[0030] iR 1 It is a straight-chain or branched alkylene group having 1 to 10 carbon atoms or 2 to 10 carbon atoms, particularly 1 to 4 carbon atoms or 2 to 4 carbon atoms and especially 1, 2 or 3 carbon atoms;

[0031] ii.R 2 It is a straight-chain or branched alkyl group having up to 10, for example, 1 to 10 carbon atoms, especially 2 to 8 carbon atoms or 3 to 6 carbon atoms, especially 4 carbon atoms.

[0032] The repeating unit of formula (I) preferably accounts for at least 50% by weight of the poly(alkylphenol) resin, particularly at least 60% by weight, and especially at least 70% by weight.

[0033] Preferably, R in formula (I) 1It is a straight-chain or branched alkylene group having 1 to 4 carbon atoms or 2 to 4 carbon atoms. In a particularly preferred set of embodiments of the invention, R in formula (I) 1 It is CH2, HC-CH3, or H2C-CH2. In another particularly preferred group of embodiments of the invention, R in formula (I) 1 Unlike CH2, where R 1 In particular, straight-chain or branched alkylene groups with 2 to 4 carbon atoms, especially HC-CH3 or H2C-CH2.

[0034] Specifically, R in equation (I) 2 It is a straight-chain or branched alkyl group having 2 to 8 carbon atoms, preferably a straight-chain or branched alkyl group having 2 to 6 carbon atoms or 3 to 6 carbon atoms, even more preferably a straight-chain or branched alkyl group having 4 to 6 carbon atoms, especially a straight-chain or branched alkyl group having 4 carbon atoms, particularly tert-butyl.

[0035] It has repeating units (I) (where R) 1 = CH2) resin can be made by making formula R 2 The phenyl compound with -C6H4-OH is reacted with formaldehyde to obtain the product. In this reaction, formaldehyde adds to R. 2 The carbon atom of -C6H4-OH (usually the carbon atom adjacent to the OH group), followed by the obtained hydroxymethyl group and another R 2 The reaction of -C6H4-OH with the elimination of water. The resulting resin may be cross-linked to some extent because additional formaldehyde may add to the less reactive meta position.

[0036] Preferably, the poly(alkylphenol) resin is a formaldehyde-free poly(alkylphenol) resin, meaning that the poly(alkylphenol) does not contain detectable amounts of formaldehyde or does not produce formaldehyde during storage or at elevated temperatures. In particular, the formaldehyde-free poly(alkylphenol) resin is that which has repeating units of formula (I), wherein R 1 Unlike CH2, especially R 1 It is HC-CH3 (ethane-1,1-diyl) or H2C-CH2 (ethane-1,2-diyl). In this respect, it has R 1 = HC-CH3 or R 1 = H2C-CH2 resin can be made by using formula R 2 The phenyl compound with -p-C6H4-OH is given by reacting it with acetylene. In this reaction, acetylene adds to R. 2 The carbon atom of -p-C6H4-OH (usually the carbon atom adjacent to the OH group), followed by the obtained vinyl group and another R 2The reaction of -C6H4-OH. The resulting resin may be cross-linked to some extent because additional acetylene may add to the less reactive meta position.

[0037] In this preferred embodiment group, the formaldehyde-free poly(alkylphenol) resin typically comprises units of formula (II):

[0038] (II)

[0039] In equation (II), R 2 As defined herein, and especially tert-butyl. In this preferred group of embodiments, the formaldehyde-free poly(alkylphenol) resin may further comprise units of formula (III) and / or (IV):

[0040]

[0041] In equations (III) and (IV), R 2 As defined in this article, and especially tert-butyl.

[0042] Typically, at least 50% by weight, and in particular at least 60% by weight, of the units forming the resin are units of formula (II), while the total amount of units of formula (III) and (IV) does not exceed 50% by weight, and in particular not exceed 40% by weight, based on the total weight of units (II), (III) and (IV).

[0043] The end groups of the polymer molecules of formaldehyde-free poly(alkylphenol) resins can be vinyl or tert-butyl-p-hydroxyphenyl, specifically produced by excess acetylene.

[0044] The resin may contain additional structural elements, which are incorporated by using monomers or reactive additives as additional starting materials in the reaction.

[0045] Preferably, apart from the catalyst, at least 80% by weight of the starting material used to prepare the resin is R. 2 -p-C6H4-OH (p- indicates R) 2 (and OH at the para position of phenylene C6H4) and formaldehyde (in R 1 (in the case of CH2) or R 2 -p-C6H4-OH or acetylene (in R) 1 = HC-CH3 or R 1 = H2C-CH2 or mixtures thereof). In particular, apart from the catalyst, at least 90%, especially at least 95%, of the starting material used to prepare the resin is R by weight. 2 -p-C6H4-OH and formaldehyde (in R)1 (in the case of CH2) or R 2 -C6H4-OH or acetylene (in R) 1 = HC-CH3 or R 1 = H2C-CH2 or a mixture thereof). In the most preferred embodiment, no catalyst other than R is used. 2 -p-C6H4-OH and formaldehyde (in R) 1 (in the case of CH2) or R 2 -p-C6H4-OH and acetylene (in R) 1 = HC-CH3 or R 1 Other starting materials besides H2C-CH2 or mixtures thereof are used to prepare poly(alkylphenol) resins.

[0046] The preferred poly(alkylphenol) resin is the one traded under the name Koresin. ® (The resin, sold by BASF and obtained by reacting acetylene with p-tert-butylphenol,) is commercially available. Koresin ® The unit containing equation (II) (where R) 1 = HC-CH3), and optionally, units of type (III) and / or (IV) (where R 1 = H2C-CH2 and R in equations (II), (III) and (IV) 2 It is tert-butyl.

[0047] Poly(alkylphenol) resins, especially those having repeating units of formula (I), typically have a number-average molecular weight in the range of 500 to 5000 g / mol, particularly in the range of 800 to 3000 g / mol, and particularly in the range of 1000 to 2500 g / mol, as determined by size exclusion chromatography (SEC) in tetrahydrofuran (THF) with a refractive index detector (RI) and polystyrene calibration.

[0048] Poly(alkylphenol) resins, particularly those having repeating units of formula (I), typically have an OH value in the range of 50 to 500 mg KOH / g, preferably in the range of 100 to 350 mg KOH / g, and more preferably in the range of 150 to 250 mg KOH / g, as determined by esterification with acetic anhydride, hydrolysis of excess reagent, titration with KOH, and correction with acid value (total acid). The OH value can be determined, for example, by the methods disclosed in DIN 53240-1:2013 or DIN 53240-2:2007.

[0049] Preferably, poly(alkylphenol) resins, especially those having repeating units of formula (I), typically have a softening point as determined by the ring and ball method according to DIN 52011:1986, in the range of 100°C to 200°C, particularly in the range of 110°C to 180°C, preferably in the range of 120°C to 170°C, more preferably in the range of 130°C to 160°C, and especially in the range of 135°C to 155°C.

[0050] Poly(alkylphenol) resins, especially those having repeating units of formula (I), typically have dropping points in the range of 110°C to 180°C, preferably in the range of 120°C to 170°C, and more preferably in the range of 140°C to 160°C, as determined by the Ubbel method according to DIN 51801:1980.

[0051] Typically, poly(alkylphenol) resin is used in an amount ranging from 0.5% to 30% by weight, preferably from 1% to 20% by weight, more preferably from 2% to 15% by weight, and even more preferably from 4% to 12% by weight, based on the total weight of TPU and poly(alkylphenol) resin.

[0052] Thermoplastic polyurethanes (TPUs) are well known and commercially available in the art. They are typically reaction products of at least the following monomer components.

[0053] • Isocyanate components (A) having a functionality of at least 2, also referred to below as diisocyanates and polyisocyanates;

[0054] • Isocyanate reactive component (B), and

[0055] • Optionally, a chain extender component (C) with a functionality of 2 or higher.

[0056] Typically, thermoplastic polyurethanes are obtained by reacting an organic isocyanate component (A) (typically a combination of at least one diisocyanate or at least one diisocyanate and at least one polyisocyanate having an isocyanate functionality greater than 2 (e.g., 2.1 to 4)) with an isocyanate reactive component (B) (preferably comprising a polymeric polyol having a functionality in the range of 1.8 to 3.0). The reaction is typically carried out in the presence of at least one catalyst that catalyzes the reaction of the isocyanate reactive groups of the compound of component (B) with the isocyanate groups of isocyanate component A.

[0057] In the context of TPU, the term "functionality" refers to the average number of isocyanate groups / molecules and the average number of isocyanate reactive functional groups / molecules in the respective components (A), (B), and (C). Isocyanate reactive functional groups are those that react with the isocyanate groups of component (A) in addition reactions by forming bonds. Isocyanate reactive functional groups typically have one or two Zerewitinoff active hydrogen atoms.

[0058] The organic isocyanate component (A), the isocyanate reactive component (B), and the chain extender (C) are also referred to individually or together as building components. Where applicable, building components including catalysts, optional auxiliaries, and / or additives are also referred to as input materials.

[0059] The terms “isocyanate” and “isocyanate component (A)” are used synonymously herein and throughout the specification.

[0060] The isocyanate component (A) is typically selected from organic isocyanates and preferably contains at least one diisocyanate compound. In particular, the isocyanate component (A) is selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aryliphatic isocyanates, aromatic isocyanates, and combinations thereof.

[0061] More preferably, the isocyanate component (A) is selected from the group consisting of aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates and combinations thereof.

[0062] Isocyanate component (A) typically comprises one or more diisocyanate compounds, i.e., isocyanates having an isocyanate functionality of 2. In addition to diisocyanates, isocyanate component A may also contain one or more isocyanates having an isocyanate functionality of >2 (e.g., in the range of 2.1 to 4).

[0063] Suitable diisocyanates include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, or combinations thereof. In some embodiments, isocyanate component A comprises one or more aromatic diisocyanates. In some embodiments, isocyanate component A is substantially free of, or even completely free of, aliphatic diisocyanates. In other embodiments, isocyanate component A comprises one or more aliphatic diisocyanates and / or alicyclic diisocyanates. In some embodiments, isocyanate component A is substantially free of, or even completely free of, aromatic diisocyanates. In some embodiments, mixtures of aliphatic and aromatic diisocyanates may be available.

[0064] Examples of available diisocyanates include aromatic diisocyanates such as 4,4'-methylenebis(phenyl isocyanate) (4,4'-MDI), 2,4-diphenylmethane diisocyanate (2,4-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), m-xylene diisocyanate (XDI), phenyl-1,4-diisocyanate (1,4-PDI), naphthalene-1,5-diisocyanate (NDI), 4,4'-diisocyanate-1,2-diphenylethane, and 3,3'-dimethyl-4,4'-biphenyl diisocyanate (…). TODI and toluene diisocyanate (TDI); and aliphatic diisocyanates, such as ethylene diisocyanate (EDI), 1,4-butane diisocyanate (BDI), 1,6-hexamethylene diisocyanate (HDI), decane-1,10-diisocyanate, 1,12-dodecane diisocyanate (DDI), lysine diisocyanate (LDI); and cycloaliphatic diisocyanates, such as isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), and dicyclohexylmethane-4,4'-diisocyanate (H12MDI). Isomers of these diisocyanates may also be available. Mixtures of two or more polyisocyanates may be used. In some embodiments, the diisocyanate is MDI and / or H12MDI. In some embodiments, the polyisocyanate consists essentially of MDI. In some embodiments, the polyisocyanate consists essentially of H12MDI.

[0065] According to another embodiment, the aromatic diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-diphenylmethane diisocyanate and / or 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanato-1,2-diphenylethane, 1,5-naphthalene diisocyanate, and combinations thereof. In another preferred embodiment, the aromatic diisocyanate is 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, or 4,4'-diphenylmethane diisocyanate (MDI), or mixtures thereof, with 4,4'-diphenylmethane diisocyanate being particularly preferred. In a more preferred embodiment, the aromatic diisocyanate is diphenylmethane diisocyanate (MDI). In a particularly preferred embodiment, the aromatic diisocyanate is 4,4'-diphenylmethane diisocyanate (4,4'-MDI).

[0066] Aliphatic isocyanates are preferred when the stability of TPU against electromagnetic waves (such as light) is important, while aromatic isocyanates are preferred when high mechanical strength of thermoplastic polyurethane is required. Another advantage of aliphatic isocyanates is that they can be produced based on biotechnology.

[0067] In the preferred group of embodiments, the aliphatic isocyanate is selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, and combinations thereof. In a more preferred group of embodiments, the aliphatic isocyanate is 1,6-hexamethylene diisocyanate (HDI). In yet another more preferred group of embodiments, the aliphatic isocyanate is 1,5-pentamethylene diisocyanate. This has the additional advantage that it can be produced based on biotechnology.

[0068] According to another group of embodiments, the alicyclic isocyanate is preferably selected from the group consisting of isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof with their corresponding isomers, 4,4'-, 2,4- and 2,2'-dicyclohexylmethane diisocyanate and mixtures thereof with their corresponding isomers, and combinations thereof. In this group of embodiments, the alicyclic isocyanate is more preferably 4,4'-dicyclohexylmethane diisocyanate (H12MDI).

[0069] According to the present invention, the isocyanate component (A) comprises at least one of the following: hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate and combinations thereof, especially 4,4'-MDI, dicyclohexylmethane diisocyanate (especially H12MDI), and combinations thereof.

[0070] The terms “isocyanate reactive component (B)” and “isocyanate reactive compound” are used synonymously herein and throughout the specification.

[0071] The isocyanate reactive component (B) typically comprises an oligomer or polymer and preferably has a content of at least 0.4 x 10⁻⁶. 3 g / mol, for example from 0.4 x 10 3 g / mol to 20 x 10 3 g / mol, preferably at 0.4 x 10 3 g / mol to 10 x 10 3 Within the range of g / mol, more preferably within 0.7 x 10 g / mol 3 g / mol up to 8.0 x 10 3Within the range of g / mol, or even more preferably within 0.8 x 10⁻⁶ g / mol. 3 g / mol up to 8.0 x 10 3 Number average molecular weight in the range of g / mol, or oligomers or polymers with lower molecular weights (e.g., in the range of 0.05 x 10⁻⁶ g / mol). 3 g / mol to 0.4 x 10 3 A mixture of low molecular weight isocyanate functional compounds (in the range of g / mol). Preferably, the isocyanate reactive component (B) has an average functionality of about 2, for example in the range of 1.8 to 2.3, preferably in the range of 1.9 to 2.2, and especially 2, with respect to the isocyanate reactive group. In particular, the isocyanate reactive group of the compound of component (B) is a hydroxyl group.

[0072] Chain extenders can be used in the production of TPU if desired. Preferably, the chain extender has a molecular weight lower than that of the isocyanate reactive component (B), for example, in the range of 0.05 x 10⁻⁶. 3 g / mol to 0.4 x 10 3 Within the range of g / mol.

[0073] Preferably, the isocyanate reactive component (B) has a statistical average of at least 1.8 and at most 3.0 Zelvidinov active hydrogen atoms. This value is also referred to as the functionality of the isocyanate reactive compound and indicates the amount of isocyanate reactive groups in a molecule theoretically calculated from a given amount of substance. Functional groups having Zelvidinov active hydrogen atoms include hydroxyl, amino, mercapto, and carboxylic acid groups. The preferred isocyanate reactive group of the compound of isocyanate reactive component (B) is hydroxyl. The functionality of the compound is preferably in the range of 1.8 to 2.6, more preferably in the range of 1.9 to 2.2, and particularly preferably 2.

[0074] In a preferred embodiment, the isocyanate reactive component (B) comprises an oligomer or polymeric polyol, hereinafter referred to as polyol, which particularly has a content of 0.4 x 10⁻⁶. 3 g / mol to 20 x 10 3 Within the range of g / mol, preferably within 0.4 x 10⁻⁶ g / mol. 3 g / mol to 10 x 10 3 Within the range of g / mol, more preferably within 0.7 x 10 g / mol 3 g / mol up to 8.0 x 10 3 Within the range of g / mol, or even more preferably within 0.8 x 10⁻⁶ g / mol. 3 g / mol up to 8.0 x 103 Number-average molecular weight in the range of g / mol. In this set of examples, the polymeric polyol typically constitutes at least 50% by weight of the total weight of component (B), particularly at least 70% by weight or up to 100% by weight.

[0075] Polyols preferably belonging to the group consisting of polyester alcohols, polyether alcohols, polyether ester alcohols, and polycarbonate alcohols are also commonly referred to as "polyols" or polyester polyols, polyether polyols, polyether ester polyols, and polycarbonate polyols. These polyols preferably have an average functionality in the range of 1.8 to 2.3, more preferably in the range of 1.9 to 2.2, and even more particularly in the range of 2. In this case, they may also be named polyester diols, polyether diols, polyether ester diols, and polycarbonate diols.

[0076] In a preferred embodiment, component (B) comprises a polyester polyol. Herein and throughout the specification, the terms "polyester" and "polyester polyol" are used synonymously. Preferably, the polyester is selected from the group consisting of reaction products of polyols, polymerization products of lactones, and polymerization products of dicarboxylic acids with polyols. The term "lactone" refers to a cyclic ester of a hydroxycarboxylic acid. Such polyester polyols include hydroxyl-terminated reaction products of polyols, polyester polyols obtained as polymerization products of lactones (e.g., caprolactone) combined with polyols, and polyester polyols obtained by polymerization of dicarboxylic acids (e.g., adipic acid) with polyols. Preferred polyester polyols include polymerization products of lactones or polycaprolactones and polymerization products obtained by polymerization of dicarboxylic acids with polyols.

[0077] Preferably, the polyester polyol is obtained by polymerizing a dicarboxylic acid with a polyol. The preferred dicarboxylic acid is C4-C. 12 At least one of the dicarboxylic acids, and C2-C 14 At least one of the diols is suitable as a polyol. Preferably, C4-C 12 Dicarboxylic acids are selected from the group consisting of: aliphatic dicarboxylic acids, preferably selected from succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, and sebacic acid, or mixtures thereof; and aromatic dicarboxylic acids, preferably selected from phthalic acid, isophthalic acid, and terephthalic acid, or mixtures thereof. More preferably, the dicarboxylic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, octanoic acid, phthalic acid, isophthalic acid, and terephthalic acid, or mixtures thereof. Most preferably, the dicarboxylic acid is selected from the group consisting of adipic acid, octanoic acid, and phthalic acid, or mixtures thereof.

[0078] Preferably, the C2-C used to obtain polyester polyols 14The diol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-propane-1,3-diol, 1,3-propanediol, 2-methyl-1,3-propanediol, and dipropylene glycol, or mixtures thereof. More preferably, the diol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, or mixtures thereof. Most preferably, it is selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol, or mixtures thereof.

[0079] Suitable diols for the production of polyester alcohols also include polyether diols as defined below, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-copoly-oxypropylene glycol, and polytetrahydrofuran. In this case, the polyester alcohol is also referred to as a polyether ester alcohol.

[0080] Polyester polyols have lower stability against hydrolysis and are preferred for applications requiring biodegradability.

[0081] In a preferred embodiment, the isocyanate reactive component (B) comprises or is a polyester alcohol, preferably having a number-average molecular weight (Mn) of not more than 12,000 g / mol, more preferably not more than 6,000 g / mol, and more particularly not more than 4,000 g / mol. In particular, the polyester alcohol is a polyester alcohol based on butanediol and adipic acid.

[0082] In another preferred embodiment, component (B) comprises a polyether diol, particularly a polyether diol selected from the group consisting of: polyethylene oxide (polyoxyethylene glycol), polypropylene oxide (poly-1,2-propanediol), polyethylene oxide-copolymer-propylene oxide, and polytetrahydrofuran (poly-1,4-butanediol). In a preferred embodiment, the polyether polyol, particularly the polytetrahydrofuran, has a content of 0.6 x 10⁻⁶. 3 g / mol up to 1.7 x 10 3 Number-average molecular weight in the range of g / mol, more preferably in the range of 0.8 x 10⁻⁶ g / mol. 3 g / mol up to 1.4 x 10 3 Number-average molecular weight in the range of g / mol, or even more preferably in the range of 0.9 x 10⁻⁶ g / mol. 3 g / mol to 1.1 x 10 3 The number-average molecular weight is in the range of g / mol, and most preferably 1.0 x 10⁻⁶ g / mol. 3Number-average molecular weight (NMR) in g / mol. Preferred polyether polyols include polytetramethylene ether glycol (also known as PTMEG), poly-1,3-propanediol, and poly-1,4-butanediol. Particularly preferred is PTHF, which preferably has a NMR range of 500 g / mol to 3.0 x 10⁻⁶ g / mol. 3 Within the range of g / mol, preferably within 0.6 x 10⁻⁶ g / mol. 3 g / mol up to 2.0 x 10 3 Within the range of g / mol, more preferably within 0.7 x 10 g / mol 3 g / mol to 1.8 x 10 3 Number-average molecular weights (Mn) in the range of g / mol. These are marketed under the trade name PolyTHF. ® Available for commercial purchase.

[0083] Polyether polyols have the advantage of being more stable to hydrolysis and will therefore be used in applications with such requirements.

[0084] In the preferred group of embodiments, the isocyanate reactive component (B) comprises or is a combination of polyester alcohol and polyether alcohol.

[0085] In another preferred embodiment, the polyol comprises or is a polycarbonate diol, preferably an aliphatic polycarbonate diol. The preferred polycarbonate diol is an alkane-based polycarbonate diol. The production of the polycarbonate diol can be carried out by the condensation polymerization of phosgene with the diol or by the ring-opening polymerization of a cyclic carbonate. As a preferred alternative to phosgene synthesis, transesterification with a carbonate diester is employed.

[0086] Preferred polycarbonate diols are strictly OH-bifunctional polycarbonate diols, preferably strictly OH-bifunctional aliphatic polycarbonate diols. Preferred polycarbonate diols are based on butanediol, pentanediol, or hexanediol. In particular, polycarbonate diols are based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane-(1,5)-diol, or mixtures thereof. More preferably, polycarbonate diols are based on 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or mixtures thereof. Even more preferably, polycarbonate diols are based on butanediol and hexanediol, pentanediol and hexanediol, hexanediol, or mixtures thereof.

[0087] Preferably, the polycarbonate diol has a content in the range of 0.5 x 10⁻⁶. 3 Up to 4.0 x 10 3 Within the range of g / mol, preferably from 0.65 x 10⁻⁶ g / mol. 3 g / mol up to 3.0 x 10 3 Within the range of g / mol, preferably from 0.8 x 10⁻⁶ g / mol.3 g / mol up to 2.5 x 10 3 The number-average molecular weight Mn is in the range of g / mol, more preferably in the range of 1.8 x 10 g / mol. 3 g / mol up to 2.2 x 10 3 Within the range of g / mol or 0.8 x 10 3 g / mol to 1.2 x 10 3 Within the range of g / mol.

[0088] Polycarbonate diol has better microwave permeability, less dirt absorption, and exhibits better flame retardancy.

[0089] In another preferred embodiment, the polyol comprises or is a polysiloxane diol. Preferably, the oligosiloxane or polysiloxane has formula (I):

[0090] HO-[Ak-O] q -Ak-Si(R2)-[O-Si(R2)] p -O-Si(R2)-Ak-[O-Ak] q’ -OH formula (I)

[0091] Wherein Ak preferably represents a C2-C4 alkylene group, R represents a C1-C4 alkyl group, and each of p, q, and q' is independently a number selected from the range of 0 to 50. In a more preferred part (B) of formula (I), p ranges from 1 to 50, especially from 2 to 50.

[0092] In one preferred embodiment, Ak represents the same alkylene unit in each residue (C1), and in yet another preferred embodiment, Ak represents different alkylene units in the same residue (C1). In one preferred embodiment, Ak is ethylene or propylene within the same residue (C1).

[0093] A preferred polydimethylsiloxane diol has formula (II).

[0094] Equation (II)

[0095] Where m is in the range of 5 to 80,

[0096] Or it may have formula (III)

[0097] Formula (III).

[0098] The molecular weight is preferably in the range of 0.500 x 10⁻⁶. 3 g / Mol to 15 x 10 3Within the range of g / Mol, more preferably within 1.0 x 10⁻⁶ g / Mol 3 g / Mol up to 3.0 x 10 3 Within the range of g / Mol.

[0099] In one preferred embodiment, the polyol is a single polyol; in another preferred embodiment, the polyol is a mixture of two or more polyols as preferred above. In one preferred embodiment, it is a mixture of at least one polyether polyol and at least one polycarbonate diol.

[0100] When using a mixture of polyether polyol and polycarbonate diol, the polycarbonate diol is preferably used in an amount of less than 50% by weight based on the total weight of the polyol mixture, preferably less than 35% by weight, more preferably less than 15% by weight, and most preferably less than 5% by weight.

[0101] Preferably, the TPU is obtained from an isocyanate component (A) and a polyol component (B) comprising at least one aliphatic polymer polyol.

[0102] In particular, the polyol component (B) comprises at least one aliphatic polymeric polyol, which is particularly selected from the group consisting of aliphatic polyester alcohols, aliphatic polyether alcohols, aliphatic polycarbonate polyols and combinations thereof, especially from the group consisting of aliphatic polyester diols, aliphatic polyether diols, aliphatic polycarbonate diols and combinations thereof.

[0103] In a particularly preferred group of embodiments, the TPU is obtained from an isocyanate component (A) comprising at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and combinations thereof, and a component (B) comprising at least one aliphatic polymeric polyol, particularly selected from aliphatic polyester alcohols, polyether alcohols, polycarbonate polyols, and combinations thereof, especially aliphatic polyester diols, polyether diols, polycarbonate diols, and combinations thereof. In this group of embodiments, the aliphatic polymeric polyol typically constitutes at least 50% by weight, particularly at least 70% by weight, or up to 100% by weight of the total weight of component (B).

[0104] In a particularly preferred group of embodiments, the TPU is obtained from an isocyanate component (A) comprising at least one selected from hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and combinations thereof, and a component (B) comprising at least one aliphatic polymeric polyol, particularly selected from aliphatic polyester alcohols, polyether alcohols, polycarbonate polyols, and combinations thereof, especially aliphatic polyester diols, polyether diols, polycarbonate diols, and combinations thereof. In this group of embodiments, the aliphatic polymeric polyol typically constitutes at least 50% by weight, particularly at least 70% by weight, or up to 100% by weight of the total weight of component (B).

[0105] Preferably, the chain extender component is selected from aliphatic diols and polyols having a number average molecular weight in the range of 50 to 400 g / mol. Examples include aliphatic diols, alicyclic diols, and aryliphatic diols, such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, neopentanediol, cyclohexanediol (CHDM), hydroquinone bis(2-hydroxyethyl) ether (HQEE), and mixtures thereof. In particular, the chain extender is butanediol, hexanediol, cyclohexanediol (CHDM), hydroquinone bis(2-hydroxyethyl) ether (HQEE), or mixtures thereof.

[0106] To adjust the hardness and melt flow index of TPU, the molar ratio of the building components and chain extender (water, if used) can be changed, thereby increasing the hardness and melt viscosity with increasing isocyanate content or with increasing isocyanate and chain extender content, while decreasing the melt flow index.

[0107] Thermoplastic polyurethanes typically have a Shore A hardness in the range of 50 to 150 Shore A, preferably in the range of 65 to 120 Shore A, more preferably in the range of 70 to 100 Shore A, and even more preferably in the range of 74 to 98 Shore A.

[0108] Thermoplastic polyurethanes typically have a melt flow index (2.16 kg, 150°C) in the range of 1 to 70 g / 10 min, preferably in the range of 1.5 to 65 g / 10 min, more preferably in the range of 2 to 60 g / 10 min, and even more preferably in the range of 5 to 55 g / 10 min, as determined by JIS K 7210 at 150°C with a load of 2.16 kg.

[0109] Thermoplastic polyurethane preferably has a density of at least 0.04 x 10⁻⁶. 6 g / mol, more preferably at least 0.06 x 10 g / mol 6 g / mol, more preferably at least 0.07 x 10 g / mol. 6g / mol and more preferably at least 0.08 x 10 g / mol. 6 The weight-average molecular weight (MAM) is measured in g / mol. The upper limit of the MAM of TPU is typically determined by processability and the desired property range. Preferably, the MAM does not exceed 0.5 x 10⁻⁶ g / mol. 6 g / mol, more preferably 0.4 x 10 g / mol 6 g / mol, more preferably 0.25 x 10 g / mol 6 g / mol and more preferably 0.2 x 10 g / mol 6 g / mol. The weight-average molecular weight as outlined herein is preferably determined by gel permeation chromatography, preferably according to DIN 55672-1, wherein dimethylformamide (DMF) is used as the solvent.

[0110] Typically, TPU has a flow initiation temperature (Tfb) in the range of 50°C to 160°C, preferably in the range of 50°C to 155°C, more preferably in the range of 50°C to 150°C, even more preferably in the range of 50°C to 140°C, and most preferably in the range of 50°C to 120°C, as determined by a capillary rheometer (e.g., a Shimadzu flow tester).

[0111] Typically, TPU has a melt temperature in the range of 50°C to 160°C, preferably in the range of 50°C to 160°C, and more preferably in the range of 50°C to 150°C, as determined by differential scanning calorimetry according to ASTM E 794-06 (2018) at a heating rate of 20 K / min.

[0112] In particular, TPU is suitable for hot melt welding.

[0113] Preferred TPUs for hot melt adhesive applications are commercially available under the brand name ELASTOLLAN HOTBOND, such as the following brands:

[0114] ELASTOLLAN HOTBOND AH-530, ELASTOLLAN HOTBOND AH-535, ELASTOLLAN HOTBOND AH-560, ELASTOLLAN HOTBOND AH-560XF, ELASTOLLAN HOTBOND AH-560F, ELASTOLLAN HOTBOND AH-560T, ELASTOLLAN HOTBOND AH-562, ELASTOLLAN HOTBOND AH-567, ELASTOLLAN HOTBOND AH-571, ELASTOLLAN HOTBOND AH-571E, ELASTOLLAN HOTBOND AH-573, ELASTOLLAN HOTBOND AH-576, ELASTOLLAN HOTBOND AH-579, ELASTOLLAN HOTBOND AH-580, ELASTOLLAN HOTBOND AH-582, ELASTOLLAN HOTBOND AH-583, ELASTOLLAN HOTBOND AH-588, ELASTOLLAN HOTBOND AH-591, ELASTOLLAN HOTBOND AH-620, ELASTOLLAN HOTBOND AH-650, ELASTOLLAN HOTBOND AH-652, ELASTOLLAN HOTBOND AH-660, ELASTOLLAN HOTBOND AH-661, ELASTOLLAN HOTBOND AH-670, ELASTOLLAN HOTBOND AH-780, ELASTOLLAN HOTBOND AH-781, ELASTOLLAN HOTBOND AH-782, ELASTOLLAN HOTBOND AH-810, ELASTOLLAN HOTBOND SP 100,

[0115] DESMOMELT grades, such as DESMOMELT U grades, such as DESMOMELT U 230 and DESMOMELT U 320, and

[0116] PEARLBOND TPU grades, such as PEARLBOND 100 TPU, PEARLBOND 103 TPU, PEARLBOND106 TPU, PEARLBOND 1160 TPU, PEARLBOND 120 TPU, PEARLBOND 121 TPU, PEARLBOND 122TPU, PEARLBOND 123 TPU, PEARLBOND 180 TPU, PEARLBOND 220 TPU, PEARLBOND 223 TPU, PEARLBOND 300 TPU, PEARLBOND 301 TPU, PEARLBOND 305 TPU, PEARLBOND 5708 F3 TPU, PEARLBOND 5713 TPU, PEARLBOND 5717 NT2 TPU, PEARLBOND 920 TPU, PEARLBOND 960TPU, PEARLBOND DIPP119 TPU, PEARLBOND 410a TPU and PEARLBOND 410b TPU.

[0117] A more preferred TPU is commercially available under the trade names ELASTOLLAN HOTBOND AH-560XF, ELASTOLLAN HOTBONDSP 100, and ELASTOLLAN HOTBOND AH-652.

[0118] Essentially, the bifunctional component B, typically an oligomer or polymeric diol, and the chain extender (C) (and water, if present) are used in a molar ratio of 1:1 to 1:5, preferably 1:1.5 to 1:4.5, such that the resulting mixture of component (B) and chain extender (C) has a hydroxyl equivalent weight greater than 200, and particularly from 230 to 450. For the production of more rigid thermoplastic polyurethanes, for example, having a Shore A hardness greater than 98, preferably in the range of 55 to 75 Shore D, the molar ratio of compound (B) to chain extender (C) is typically in the range of 1:5.5 to 1:15, preferably 1:6 to 1:12, such that the resulting mixture of compound (B) and chain extender (C) has a hydroxyl equivalent weight of 110 to 200, preferably 120 to 180.

[0119] In a preferred embodiment, TPU is obtained by reacting components (A) and (B) and optionally (C) in the presence of a catalyst. The catalyst may be a single catalyst or a mixture of several catalysts.

[0120] The catalyst preferably accelerates the reaction between the NCO group of the isocyanate and the isocyanate reactive groups of component (B) and the chain extender. In a preferred embodiment, the catalyst is selected from the group consisting of tertiary amines and organometallic compounds or mixtures thereof.

[0121] Preferred organometallic compounds are selected from the group consisting of titanates, iron compounds, tin compounds, and bismuth salts, or mixtures thereof. A preferred iron compound is ferric acetylacetonate (III). Preferred tin compounds are selected from the group consisting of tin diacetate, tin dioctanoate, tin dilaurate, tin neodecanoate (II), and dialkyltin salts of aliphatic carboxylic acids, or mixtures thereof. Preferably, the catalyst is tin dioctanoate, tin neodecanoate (II), or a mixture thereof. A preferred titanate is tetrabutyl orthotitanate. In preferred bismuth salts, bismuth is present in oxidation states 2 or 3, particularly 3, preferably a carboxylic acid, preferably a salt of a carboxylic acid having 6 to 14 carbon atoms, particularly preferably 8 to 12 carbon atoms. Very preferred bismuth salts are bismuth neodecanoate (III), bismuth 2-ethylhexanoate, or bismuth octanoate, or mixtures thereof.

[0122] The catalyst is preferably used in an amount from 0.0001 to 0.1 parts by weight per 100 parts by weight of polyol. Tin catalysts, especially tin dioctanoate, are preferred.

[0123] In a preferred embodiment, the composition comprises SDO (tin(II) 2-ethylhexanoate), tin(II) neodecanoate, or a mixture thereof, preferably used in an amount of 0.35-0.4 parts by weight relative to the whole composition.

[0124] In a preferred embodiment, the auxiliary agent or additive is included in the composition. In a preferred embodiment, the auxiliary agent or additive is selected from the group consisting of: surfactants, fillers, flame retardants, nucleating agents, oxidative stabilizers, lubricants, release agents, dyes, pigments, inorganic or organic fillers, reinforcing agents, plasticizers, antistatic agents, stabilizers, preferably stabilizers, inorganic fillers, organic fillers, reinforcing agents, plasticizers, or mixtures thereof that are hydrolytic, light, heat, or discoloration resistant.

[0125] In the context of this invention, a stabilizer is an additive that protects plastics or plastic compositions from harmful environmental effects. Preferred examples are primary or secondary antioxidants, hindered phenols, hindered amine light stabilizers, UV absorbers, phosphites, hydrolysis inhibitors, quenchers, and flame retardants. Examples of commercial stabilizers are given in Plastics Additives Handbook, 5th edition, edited by H. Zweifel, Hanser Publishers, Munich, 2001 ([1]), pp. 98-S136.

[0126] Preferably, the UV absorber has a density greater than 0.3 x 10⁻⁶. 3 g / mol, especially greater than 0.39 x 10 3 The number-average molecular weight is g / mol. Furthermore, the preferred UV absorber has a molecular weight not exceeding 5 x 10⁻⁶ g / mol. 3 g / mol, particularly preferably not exceeding 2 x 10 g / mol 3 Molecular weight in g / mol.

[0127] UV absorbers are preferably selected from the group consisting of cinnamic acid esters, oxaloyl aniline, benzophenone, and benzotriazole, or mixtures thereof, with benzotriazole being particularly suitable as a UV absorber. A particularly suitable example of a UV absorber is Tinuvin. ® 213, Tinuvin ® 234. Tinuvin ® 312, Tinuvin ® 571, Tinuvin ® 384 and Eversorb ® 82.

[0128] Preferably, the UV absorber is added in an amount of 0.01 wt.% to 5 wt.% based on the total weight of the composition, preferably 0.1 wt.% to 2.0 wt.%, particularly 0.2 wt.% to 0.5 wt.%.

[0129] Typically, UV stabilization based on antioxidants and UV absorbers as described above is insufficient to guarantee good stability of the composition against the harmful effects of UV rays. In such cases, hindered amine light stabilizers (HALS) are added to the composition, either in addition to antioxidants and / or UV absorbers, or as a single stabilizer.

[0130] Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanzel Publishers, Munich, 2001, pp. 123-136.

[0131] A particularly preferred hindered amine light stabilizer is bis-(1,2,2,6,6-pentamethylpiperidinyl) sebacate (Tinuvin). ® 765, Ciba Spezialitätenchemie AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin) ®622). In particular, if the titanium content of the finished product is less than 150 ppm by weight, preferably less than 50 ppm by weight, and especially less than 10 ppm by weight, based on the components used, then the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin) ® 622) is the preferred option.

[0132] HALS compounds are preferably used at concentrations from 0.01 wt.% to 5 wt.% based on the total weight of the composition, particularly preferably from 0.1 wt.% to 1 wt.%, and especially from 0.15 wt.% to 0.3 wt.%.

[0133] The particularly preferred UV stabilizer contains a mixture of phenolic stabilizers, benzotriazole and HALS compounds in preferred amounts as described above.

[0134] Further information on the aforementioned auxiliaries and additives can be found in technical literature such as Plastics Additives Handbook, 5th edition, edited by H. Zweifel, Hanser Publishers, Munich, 2001.

[0135] Compositions containing thermoplastic polyurethane can be produced discontinuously or continuously. Preferred methods include reactive extrusion, belt production line, and "one-shot injection" methods, preferably "one-shot injection" or reactive extrusion, with reactive extrusion being the most preferred method.

[0136] These methods are used by directly mixing the components or alternatively by applying prepolymer methods.

[0137] Polyisocyanate prepolymers can be obtained by reacting the above-mentioned polyisocyanate with an isocyanate reactive compound, preferably a polyol, in excess at a temperature of 30°C to 100°C.

[0138] In the "single injection" method, the building component diisocyanate and a compound reactive with the isocyanate, preferably a polyol, more preferably a polyol diol, and in other preferred embodiments a chain extender, and in other preferred embodiments a catalyst are mixed together. In a preferred embodiment, this is carried out sequentially or simultaneously in the presence of the catalyst. In the extrusion method, the building component diisocyanate and a compound reactive with the isocyanate, preferably a polyol, more preferably a diol, and in other preferred embodiments a chain extender, and in other preferred embodiments a catalyst are mixed together. The mixing in the reactive extrusion method is preferably carried out at a temperature in the range of 100°C to 280°C, preferably in the range of 140°C to 250°C.

[0139] To prepare thermoplastic polyurethane, in a preferred embodiment, the building components isocyanate, polyol, and chain extender are reacted in the presence of a catalyst and optionally auxiliaries and / or additives in amounts such that the equivalence ratio of the NCO groups of the isocyanate, preferably diisocyanate, to the sum of the hydroxyl groups of the isocyanate reactive component and the chain extender is 0.95:1 to 1.10:1, preferably 0.98:1 to 1.08:1, and particularly 1.0:1 to 1.05:1. In a very preferred embodiment, the equivalence ratio is 1.0:1.

[0140] The obtained thermoplastic polyurethane is preferably in the form of granules or powder. Additives and auxiliaries may be added during the synthesis of the thermoplastic polyurethane or incorporated into the thermoplastic polyurethane. The latter is preferred. This is especially true if the additives or auxiliaries are not inert to isocyanates, chain extenders, compounds reactive with isocyanates, or catalysts.

[0141] In a preferred embodiment, the synthesis of the thermoplastic polyurethane is carried out in an extruder, more preferably a twin-screw extruder. The twin-screw extruder operates in a forward conveying manner, and therefore allows for more precise setting of temperature and output on the extruder.

[0142] The compositions of the present invention are typically produced by incorporating a poly(alkylphenol) resin into TPU, particularly into molten TPU. Incorporation can be achieved by any method suitable for mixing thermoplastic polymers. Typically, the thermoplastic polyurethane is mixed with the poly(alkylphenol) resin and optionally other components of the composition in a mixing unit (such as a kneader or preferably an extruder, particularly a twin-screw extruder). In a preferred embodiment, the poly(alkylphenol) resin is introduced into the mixing unit in a molten state. Specifically, the poly(alkylphenol) resin is introduced into the extruder downstream of the fill point in the flow direction of the TPU within the extruder.

[0143] In one preferred embodiment, the composition according to the invention is produced by processing thermoplastic polyurethane, poly(alkylphenol) resin, and optionally other components of the composition. In another preferred embodiment, the composition is produced by a method comprising: providing TPU (preferably as granules), and then introducing poly(alkylphenol) resin and optionally other components of the composition therein in at least one or more additional steps. In another preferred embodiment, a masterbatch of TPU and poly(alkylphenol) resin is prepared, for example, by mixing thermoplastic polyurethane with poly(alkylphenol) resin, optionally with additional components such as flame retardants, UV stabilizers, or other auxiliaries, in a suitable mixing apparatus, preferably in a kneader or extruder. The masterbatch is then optionally incorporated into additional TPU along with other components of the composition.

[0144] The invention is further described by way of examples. These examples relate to practical, and in some cases preferred embodiments of the invention, without limiting the scope of the invention.

[0145] 1. Preparation of the composition of the present invention

[0146] Commercially available TPU hot melt adhesive (Elastollan) ® Hotbond was added once without any poly(alkylphenol) resin (Comparative Examples 1, 2, 3, and 4) and once with a corresponding amount of Koresin (which is a commercially available poly(alkylphenol) resin according to the invention) (Examples 1-1, 1-2, 2-1, 2-2, 3-1, and 3-2 of the invention) to a conical twin-screw micro-extruder (X-plore) under the conditions listed in Table 1. After recirculation in the extruder for 5 min, the blends were collected and allowed to cool to room temperature. Additionally, using the same method as used to prepare the other examples (Comparative Examples 4-1 and 4-2), the commercial hydrocarbon resin Piccotac was added. ® A commercially available TPU hot melt adhesive was prepared using 1095 N.

[0147] Table 1: Blending Conditions

[0148]

[0149] a: wt% refers to the total weight of TPU and poly(alkylphenol) resin.

[0150] b: Koresin ® The poly(alkylphenol) resin according to the present invention

[0151] c: Piccotac ® 1095N is a hydrocarbon resin based on C5 olefins (not according to the present invention).

[0152] Hot melt adhesive 1 to 3, Koresin ® and Piccotac ® The physical and chemical properties of 1095N are summarized below:

[0153] 1.1 Hot melt adhesive 1 (Elastollan Hotbond AH560 F)

[0154] - Hardness: 75 ± 20 Shore A, as determined by DIN ISO 7619

[0155] - Density at room temperature: 1.2 g / cm³ 3 As determined by DIN EN ISO 1138-1 A

[0156] -Tensive strength: 120 kg / cm 2 As defined by ASTM D 412

[0157] -Elongation at break: 600%, as determined by ASTM D 412.

[0158] - Melt flow index (2.16 kg, 150°C): 20 ± 50 g / 10 min, as determined by DIN EN ISO 1133.

[0159] - Flow initiation temperature: 95°C ± 10°C, as determined by a capillary rheometer (Shimadzu flow tester).

[0160] I

[0161] 1.2 Hot melt adhesive 2 (Elastollan Hotbond SP 100)

[0162] - Hardness: 75 Shore A, as determined by DIN ISO 7619

[0163] - Density at room temperature: 1.2 g / cm³ 3 As determined by DIN EN ISO 1138-1 A

[0164] -Tensile strength: 70 kg / cm² 2 As defined by ASTM D 412

[0165] - Elongation at break: 800%, as determined by ASTM D 412.

[0166] - Melt flow index (2.16 kg, 150°C): 50 g / 10 min, as determined by DIN EN ISO 1133; Flow onset temperature: 95°C, as determined by a capillary rheometer (Shimadzu flow tester).

[0167] 1.3 Hot melt adhesive 3 (Elastollan Hotbond AH 652)

[0168] - Hardness: 97 ± 2 Shore A, as determined by DIN ISO 7619

[0169] - Density at room temperature: 1.2 g / cm³ 3 As determined by DIN EN ISO 1138-1 A

[0170] - Melt flow index (2.16 kg, 150°C): 10 ± 3 g / 10 min, as determined by DIN EN ISO 1133.

[0171] - Flow initiation temperature: 60°C ± 10°C, as determined by a capillary rheometer (Shimadzu flow tester).

[0172] 1.4 The poly(alkylphenol) resin according to the present invention (BASF's Koresin) ® )

[0173] - Softening point using the ring and ball method: 135°C-150°C, as determined by DIN 52011.

[0174] - Ubbelohde dropping point: 140°C-160°C, as determined by DIN 51801.

[0175] - Density (20°C): 1.02-1.04 g / cm³ 3 As defined by DIN EN ISO 787-10

[0176] - Solubility: Soluble in hydrocarbons, for example, 10 g will completely dissolve in 90 g of toluene;

[0177] 1.5 Piccotac ® 1095N (Synthomer's conventional aliphatic polymer tackifier)

[0178] - Ring and ball softening point: 96°C, as determined by ASTM E 28.

[0179] -DACP cloud point: 47°C in a 1:1 mixture of xylene and diacetone alcohol.

[0180] - Molecular weight, Mn: 1100 g / mol, as determined by GPC using polystyrene standards eluted with THF (Mw: 1980 g / mol, Mz: 3510 g / mol).

[0181] 2. Measurement of melt viscosity

[0182] The viscosities of Examples 1 to 3 and the comparative examples of the present invention were measured as follows:

[0183] 2.1 Device:

[0184] The viscosity of IE1 to 3 and CE1 was measured using the following apparatus and tools:

[0185] - DV2T-HB Brinell viscometer with heating element

[0186] - PC with Rheocalc T software

[0187] -Disposable rotor SCA4-27

[0188] - Disposable sample tubes for use in a thermosel furnace

[0189] - Needle-nose pliers

[0190] -Precision balance

[0191] 2.2 Detailed description of the measurement:

[0192] Weigh 11 to 13 g of sample into a disposable sample tube and then place it in the furnace. During this process, ensure the tube is properly seated in the groove at the bottom. To do this, rotate the tube with needle-nose pliers until it slides into the groove. Afterward, manually heat the RHM sample in the furnace to 75°C and melt it during this process.

[0193] Then insert the SCA4-27 rotor into the rotor adapter of the disposable rotor and secure it in place. Once the sample has melted, guide the rotor into the melt by lowering the viscometer until the alignment guide of the viscometer contacts the groove of the heating furnace. It is necessary to ensure that the viscometer and the furnace are level during operation.

[0194] To homogenize the sample and improve temperature distribution, the rotor was manually turned on to rotate the viscometer. The rotation speed was adjusted so that the relative torque was within the range of 50% to 90%.

[0195] Select the "Standard Method - RHM Viscosity Curve" method for measurement.

[0196] The parameters of this method are as follows:

[0197] • Rotor SCA4-27

[0198] • Temperature step program with multi-point measurement

[0199] 75°C at 4 U / Min.

[0200] 90°C at 10 U / Min.

[0201] 110°C at 10 U / Min.

[0202] 130°C at 22 U / Min. and 10 U / Min.

[0203] 150°C at 22 U / Min. and 10 U / Min.

[0204]

[0205] 3. Differential Scanning Calorimetry (DSC)

[0206] Differential scanning calorimetry measurements were performed using Examples 1 to 3 of the present invention and comparative examples as follows:

[0207] Approximately 10 mg of TPU or blend was weighed into an aluminum pan and sealed. Heating, cooling, and a second heating run were performed using a differential scanning calorimeter (TA-Instruments) model Q 2000 at 20 K / min.

[0208] 4. Results

[0209] Viscosity and DSC measurement results of examples of the present invention and comparative examples are presented in the following table.

[0210] 4.1 Viscosity

[0211] 4.1.1 Examples featuring hot melt adhesive 1 (AH 560 XF) and Koresin.

[0212]

[0213] 4.1.2 Examples featuring hot melt adhesive 2 (SP100) and Koresin.

[0214]

[0215] 4.1.3 Examples featuring hot melt adhesive 3 (AH 652) and Koresin.

[0216]

[0217] 4.1.4 Examples featuring hot melt adhesive 1 (AH 560 XF) and Piccotac 1095N.

[0218]

[0219] 4.2 DSC

[0220] 4.2.1 Examples featuring hot melt adhesive 1 (AH 560 XF) and Koresin.

[0221]

[0222] 4.2.2 Examples featuring hot melt adhesive 2 (SP100) and Koresin.

[0223]

[0224] 4.2.3 Examples featuring hot melt adhesive 3 (AH 652) and Koresin.

[0225]

[0226] 4.2.4 Examples featuring hot melt adhesive 1 (AH 560 XF) and Piccotac 1095N.

[0227]

[0228] The viscosity and melt temperature results indicate that, compared to TPU hot melt adhesives without poly(alkylphenol) resins, the examples of the present invention exhibit lower viscosity while maintaining a similar melt temperature, representing a processing advantage over prior art resins.

Claims

1. Use of poly(alkylphenol) resins to reduce the melt viscosity of thermoplastic polyurethane (TPU).

2. The use according to claim 1, wherein, The poly(alkylphenol) resin has a softening point in the range of 100°C to 200°C, particularly in the range of 110°C to 180°C, preferably in the range of 120°C to 170°C, as determined by the ring and ball method according to DIN 52011:1986, and / or wherein the poly(alkylphenol) resin has a dropping point in the range of 110°C to 180°C, preferably in the range of 120°C to 170°C, more preferably in the range of 140°C to 160°C, as determined by the Ubbelohde method according to DIN 51801:1980.

3. The use according to any one of the preceding claims, wherein, The poly(alkylphenol) resin has a number-average molecular weight in the range of 500 to 5000 g / mol, particularly in the range of 800 to 3000 g / mol, and particularly in the range of 1000 to 2500 g / mol, as determined by size exclusion chromatography (SEC) in tetrahydrofuran (THF) with a refractive index detector (RI) and polystyrene calibration.

4. The use according to any one of the preceding claims, wherein, The poly(alkylphenol) resin has an OH value in the range of 50 to 500 mg KOH / g, preferably in the range of 100 to 350 mg KOH / g, and more preferably in the range of 150 to 250 mg KOH / g, as determined by esterification with acetic anhydride, hydrolysis of excess reagent, titration with KOH, and correction with acid value (total acid).

5. The use according to any one of the preceding claims, wherein, The poly(alkylphenol) resin contains repeating units of formula (I). (I) in iR 1 It is a straight-chain or branched alkylene group having 2 to 10 carbon atoms; ii.R 2 It is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon group with up to 10 carbon atoms.

6. The use or composition according to claim 5, wherein, R in equation (I) 2 It is an aliphatic hydrocarbon group having 2 to 8 carbon atoms, and R 2 In particular, tert-butyl.

7. The use according to claim 5 or 6, wherein, This poly(alkylphenol) resin is a formaldehyde-free poly(alkylphenol) resin.

8. The use according to any one of claims 5 to 7, wherein, This poly(alkylphenol) resin can be obtained by reacting p-tert-butylphenol with acetylene.

9. A composition comprising A) Thermoplastic polyurethane (TPU) as well as B) At least one poly(alkylphenol) resin other than the poly(alkylphenol) formaldehyde resin.

10. The composition according to claim 9, wherein, The poly(alkylphenol) resin is as defined in any one of claims 5 to 8.

11. The use according to any one of claims 1 to 8 or the composition according to any one of claims 9 or 10, wherein, Based on the total weight of the TPU and the poly(alkylphenol) resin, the amount of poly(alkylphenol) resin is in the range of 0.5% to 30% by weight, preferably 1% to 20% by weight, more preferably 2% to 15% by weight, and even more preferably 4% to 12% by weight.

12. The use or composition according to any one of the preceding claims, wherein, This TPU is suitable for hot melt.

13. The use or composition according to any one of the preceding claims, wherein, The TPU has a flow initiation temperature (Tfb) in the range of 50°C to 160°C as determined by capillary rheometer, and / or the TPU has a melt temperature in the range of 50°C to 160°C as determined by differential scanning calorimetry at a heating rate of 20 K / min according to ASTM.

14. The use or composition according to any one of the preceding claims, wherein, The TPU is obtained from an isocyanate component (A) and a polyol component (B) containing at least one aliphatic polymer polyol.

15. The use or composition according to claim 14, wherein, The aliphatic polymer polyol is selected from the group consisting of aliphatic polyester alcohols, aliphatic polyether alcohols, aliphatic polycarbonate polyols and combinations thereof, and wherein the isocyanate component (A) comprises at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and combinations thereof.

16. A method for preparing the composition according to claims 9 to 15, wherein, The poly(alkylphenol) resin is incorporated into the TPU, particularly into molten TPU, wherein the TPU and the poly(alkylphenol) resin are mixed in an extruder.

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