Waterborne polyurethane dispersion and application thereof

Abstract

The invention relates to a waterborne polyurethane dispersion and application thereof. The aqueous polyurethane dispersion comprises a polyurethane and / or a polyurethane-urea and an aliphatic alcohol ester. The waterborne polyurethane dispersion disclosed by the invention not only can maintain the stability of dispersion emulsion under the condition of relatively low air temperature, but also can provide good initial heat resistance, so that the requirements of downstream application are met.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane technology. Specifically, this invention relates to waterborne polyurethane dispersions and their applications. Background Technology

[0002] Compared to solvent-based adhesives, waterborne polyurethane adhesives offer advantages such as low VOC emissions, environmental friendliness, non-toxicity, and safe operation, meeting industry requirements for green and environmentally friendly practices. With increasing public awareness of environmental protection, waterborne polyurethane adhesives have found widespread application in fields such as automotive interiors and footwear materials.

[0003] However, waterborne polyurethane adhesives still face some challenges in application, such as storage stability at low temperatures. Many waterborne polyurethane dispersions exhibit a sharp increase in viscosity or even gelation after being stored at low temperatures (e.g., 5°C) for a period of time, which limits the use of adhesives prepared based on these waterborne polyurethane dispersions in colder climates or during colder periods.

[0004] In addition, typical waterborne polyurethane dispersions have poor initial heat resistance, and their bonding strength will drop significantly at temperatures of 80°C or even 60°C, causing quality problems such as delamination of freshly bonded parts.

[0005] Currently, those skilled in the art have explored various methods to improve the heat resistance of polyurethane dispersions. CN104004486A discloses a method for preparing a water-based adhesive with good heat resistance and no tackiness at 120°C by adding inorganic materials such as siloxane coupling agents, talc, titanium dioxide, and fumed silica to a polyurethane dispersion. However, while this method of adding inorganic components can improve initial heat resistance, it often reduces the initial bond strength of the polyurethane dispersion itself, making it unsuitable for applications requiring high initial bond strength. CN103435760A discloses a method for preparing a two-component water-based polyurethane adhesive by adding an isocyanate curing agent to a polyurethane dispersion, thereby increasing the crosslinking density of the adhesive after curing and giving it better heat resistance. However, this method requires the isocyanate curing agent to undergo crosslinking, typically requiring three days, to effectively improve heat resistance, offering little benefit to initial heat resistance.

[0006] Therefore, there is still a need in the art for an aqueous polyurethane dispersion that can maintain the relative stability of the dispersion emulsion at low temperatures (e.g., 5°C) while providing good initial heat resistance to meet the needs of downstream applications. Summary of the Invention

[0007] One object of the present invention is to provide an aqueous polyurethane dispersion that can maintain the relative stability of the dispersion emulsion under low temperature conditions (e.g., 5°C) and provide good initial heat resistance.

[0008] Therefore, according to a first aspect of the present invention, an aqueous polyurethane dispersion is provided, characterized in that it comprises:

[0009] (i) Polyurethanes and / or polyurethane-urea, which are prepared by reacting a system comprising components a)-c) and optional components d)-e):

[0010] a) At least one crystalline polyol,

[0011] b) At least one polyisocyanate,

[0012] c) At least one hydrophilic compound containing an NCO reactive functional group, wherein the hydrophilic group of the hydrophilic compound comprises one or more of ionic groups, potentially ionic groups, and nonionic groups.

[0013] d) Small molecule alcohols containing 1-4 NCO reactive functional groups, unlike components a) and c), have a molecular weight of 32-400 g / mol.

[0014] e) Other isocyanate reactive compounds, which are one or more of amine chain extenders and amine end-capping agents, and

[0015] (ii) at least one aliphatic alcohol ester, which is the product of the reaction of one or more aliphatic diols and one or more C2-C18 monocarboxylic acids.

[0016] The amount of the at least one aliphatic alcohol ester is 1-8% by weight of the solids portion of the aqueous polyurethane dispersion.

[0017] The polyurethane and / or polyurethane-urea have a weight-average molecular weight of 260,000 g / mol or higher.

[0018] According to a second aspect of the present invention, coatings, adhesives, sealants or inks prepared using the above-described aqueous polyurethane dispersion are provided.

[0019] According to a third aspect of the invention, the use of coatings, adhesives, sealants, or inks for preparing coated products, adhesive products, sealing products, or printed products is provided.

[0020] According to a fourth aspect of the invention, articles comprising a substrate coated, bonded, sealed, or printed with the aforementioned coatings, adhesives, sealants, or inks are provided.

[0021] The aqueous polyurethane dispersion of the present invention can maintain the stability of the dispersion emulsion at low temperatures (e.g., 5°C) and provide good initial heat resistance, thereby meeting the needs of downstream applications. Detailed Implementation

[0022] Some specific embodiments of the invention will now be described for illustrative purposes and not for limitation.

[0023] Waterborne polyurethane dispersion

[0024] According to a first aspect of the present invention, an aqueous polyurethane dispersion is provided, characterized in that it comprises:

[0025] (i) Polyurethanes and / or polyurethane-urea, which are prepared by reacting a system comprising components a)-c) and optional components d)-e):

[0026] a) At least one crystalline polyol,

[0027] b) At least one polyisocyanate,

[0028] c) At least one hydrophilic compound containing an NCO reactive functional group, wherein the hydrophilic group of the hydrophilic compound comprises one or more of ionic groups, potentially ionic groups, and nonionic groups.

[0029] d) Small molecule alcohols containing 1-4 NCO reactive functional groups, unlike components a) and c), with a molecular weight of 32-400 g / mol.

[0030] e) Other isocyanate reactive compounds, which are one or more of amine chain extenders and amine end-capping agents, and

[0031] (ii) at least one aliphatic alcohol ester, which is the product of the reaction of one or more aliphatic diols and one or more C2-C18 monocarboxylic acids or their derivatives.

[0032] The amount of the at least one aliphatic alcohol ester is 1-8% by weight of the solids portion of the aqueous polyurethane dispersion.

[0033] The polyurethane and / or polyurethane-urea have a weight-average molecular weight of 260,000 g / mol or higher.

[0034] The solids component of the waterborne polyurethane dispersion mentioned in this application refers to the non-volatile components in the waterborne polyurethane dispersion.

[0035] The weight-average molecular weight described in this application was determined by gel permeation chromatography. The chromatograph used was an Agilent Technologies liquid chromatograph with a polyester copolymer GPC column and an exclusion limit of 1,000,000 g / mol. The sample concentration was approximately 0.006 g / mL, the injection volume was 100 μL, and dimethylacetamide (DMAc) was used as the mobile phase. Analysis was performed at a column temperature of 60°C using a differential refractive index detector. The final weight-average molecular weight was calculated based on polystyrene standards, selecting components with a molecular weight of 200 or higher for calculation.

[0036] Preferably, the polyurethane and / or polyurethane-urea has a weight-average molecular weight of 260,000-1,000,000 g / mol, more preferably 260,000-500,000 g / mol, and even more preferably 260,000-400,000 g / mol.

[0037] The aqueous polyurethane dispersion contains water. Preferably, the aqueous polyurethane dispersion has a solid content of 15-70% by weight.

[0038] More preferably, the aqueous polyurethane dispersion has a solid content of 30-65% by weight.

[0039] More preferably, the aqueous polyurethane dispersion has a solid content of 40-60% by weight.

[0040] The solid content can be determined using a Mettler Toledo HS153 moisture analyzer according to DIN-EN ISO3251:2019, with a heating temperature of 120°C. The test endpoint is determined when the sample weight loss is less than 1 mg / 140 seconds.

[0041] Preferably, the pH value of the aqueous polyurethane dispersion is in the range of 4-11.

[0042] More preferably, the pH value of the aqueous polyurethane dispersion is in the range of 5-10.

[0043] pH values ​​can be measured at 23°C using a PB-10 pH meter from Sartorius, Germany.

[0044] Preferably, the average particle size of the aqueous polyurethane dispersion is in the range of 20-750 nm.

[0045] More preferably, the average particle size of the aqueous polyurethane dispersion is in the range of 50-450 nm.

[0046] More preferably, the average particle size of the aqueous polyurethane dispersion is in the range of 100-300 nm.

[0047] Most preferably, the average particle size of the aqueous polyurethane dispersion is in the range of 150-250 nm.

[0048] The average particle size was determined using a laser correlation (laser particle size analyzer) with a ZEN 1600 analyzer from Malvem, UK. One drop (approximately 0.05 g) of sample was added to 50 ml of ultrapure water according to ISO 13321:1996 test method. The diluted sample was tested at 23.0 ± 0.1 °C. RI: 1.590; Absorbance: 0.010; Dispersant: Water (Temperature: 23.0 °C; Viscosity: 0.9308 cP; RI: 0.330); Equilibrium time: 60 seconds; Disposable cuvette DTS0012 was used; Positioning method: Automatic attenuation selection; Optimal position search: Yes; Analysis model: General (normal resolution); Measurement angle: 173° backscatter (NIBS default value); Number of runs: 3; Run duration: 10 seconds; Number of measurements: 10.

[0049] Preferably, the viscosity of the aqueous polyurethane dispersion is in the range of 300-6000 mPa·s.

[0050] The viscosity was measured using a Brookfield DV-II+Pro rotational viscometer at 23°C according to ISO 2555:2018, rotor type: S62-64, rotational speed: 30 RPM, test temperature: 23°C.

[0051] Component a): Crystalline polyol

[0052] As used in this application, a polyol is an alcohol compound having at least two hydroxyl groups in its molecule.

[0053] As used in this application, the term "crystalline polyol" means that the polyol has a melting enthalpy of not less than 15 J / g.

[0054] The enthalpy of fusion was obtained by DSC from the first heating curve from 20°C to 100°C according to Method A in DIN 65467:1999, with a sample loading amount of 10-20 mg and a heating rate of 20 K / min.

[0055] Preferably, the enthalpy of melting of the crystalline polyol is in the range of 25 J / g to 100 J / g.

[0056] The crystalline polyol can be an aliphatic and / or aromatic polyester polyol.

[0057] Preferably, the crystalline polyol used to prepare polyurethane and / or polyurethane-urea is selected from one or more of the following: diols with a number average molecular weight of 62-15000 and triols with a number average molecular weight of 92-15000.

[0058] More preferably, the crystalline polyol is selected from one or more of the following: diols with a number average molecular weight of 62-5000 and triols with a number average molecular weight of 92-5000.

[0059] Most preferably, the crystalline polyol is selected from one or more of the following: polyester polyols containing 1.5-3 hydroxyl groups with a number average molecular weight of 500-2500, polycarbonate polyols containing 1.5-3 hydroxyl groups with a number average molecular weight of 400-2500, polyether polyols containing 1.5-3 hydroxyl groups with a number average molecular weight of 200-2500, and polylactone polyols containing 1.5-3 hydroxyl groups with a number average molecular weight of 250-2500.

[0060] The number-average molecular weight described in this application is determined by gel permeation chromatography, using tetrahydrofuran as the mobile phase, and the molecular weight is calculated based on polystyrene as a standard. Components with a molecular weight of 200 or higher are selected for calculation, and the molecular weight is measured using a differential refractive index detector.

[0061] Advantageously, the amount of the crystalline polyol is 50-97% by weight of the solids of the aqueous polyurethane dispersion, preferably 60-95% by weight, more preferably 70-93% by weight.

[0062] Component b): Polyisocyanate

[0063] The polyisocyanates used to prepare polyurethanes and / or polyurethane-urea can be organic compounds having at least two isocyanate groups.

[0064] Preferably, the polyisocyanate is selected from diisocyanates represented by the formula Y(NCO)2, wherein Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms, a divalent aromatic hydrocarbon group containing 6-15 carbon atoms, and a divalent aromatic aliphatic hydrocarbon group containing 7-15 carbon atoms.

[0065] Examples of the polyisocyanates mentioned above include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 4,4′-dicyclohexylpropane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate, and terephthalic diisocyanate.

[0066] More preferably, the polyisocyanate is selected from diisocyanates represented by the formula Y(NCO)2, wherein Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms and a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms.

[0067] More preferably, the polyisocyanate is selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 4,4′-dicyclohexylpropane diisocyanate.

[0068] Most preferably, the polyisocyanate is a mixture of hexamethylene diisocyanate and isophorone diisocyanate.

[0069] Advantageously, the amount of the polyisocyanate component is 2-80% by weight of the solids of the aqueous polyurethane dispersion, preferably 4-60% by weight, more preferably 5-40% by weight.

[0070] Component c): Hydrophilic compounds

[0071] The hydrophilic compound contains an NCO reactive functional group, and the hydrophilic group of the hydrophilic compound includes one or more of ionic groups, potentially ionic groups, and nonionic groups.

[0072] The hydrophilic compound used in this application is different from component a) crystalline polyol.

[0073] Specifically, the hydrophilic groups of the hydrophilic compound can be sulfonium, ammonium, phosphine, carboxylates, sulfonates or phosphonates, or groups that can be converted into the above groups through salt formation (potentially ionic groups), or polyether groups, and can be covalently linked to the polymer chain through isocyanate reactive groups.

[0074] Salt formation can be achieved by adding an organic base (such as a tertiary amine) or an inorganic base (such as an alkali metal hydroxide or ammonia). Preferably, an aqueous solution of N-(2-aminoethyl)-2-aminoethane sulfonate, dimethylolpropionate, or an aqueous solution of N-(2-aminoethyl)-2-aminoethane carboxylate (e.g., KV1386) is used.

[0075] The NCO reactive functional groups of the hydrophilic compound are preferably hydroxyl and / or amino groups.

[0076] In some embodiments, the hydrophilic compound is an ionic or potentially ionic compound.

[0077] Suitable ionic or potential ionic compounds include, for example, mono- and dihydroxycarboxylic acids, dihydroxydicarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, and mono- and dihydroxyphosphonic acids or mono- and diaminophosphonic acids and their salts, such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypentanoic acid, N-(2-aminoethyl)alanine, 2-(2-amino-ethylamino)ethanesulfonic acid, ethylenediaminepropyl- or butylsulfonic acid, 1,2- or -1,3-propanediamineethylsulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, and the addition product of IPDI and acrylic acid (EP-A). 0916647, Example 1) and its alkali metal salts and / or ammonium salts, sodium bisulfite adducts on butene-2-diol-1,4, polyether sulfonates, propoxylated adducts of 2-butenediol and NaHHSO3 (e.g., formulas I-III as described in DE-A 2 446440), and structural units that can be converted into cationic groups, such as N-methyl-diethanolamine. Furthermore, salts of cyclohexylaminopropanesulfonic acid (CAPS) from WO-A01 / 88006 can be used as anionic hydrophilic compounds.

[0078] Preferred ionic or potential ionic compounds are those having a carboxyl or carboxylate group and / or a sulfonate group and / or an amino group.

[0079] Preferably, the hydrophilic compound is selected from 6-aminohexanoate, lysine salt, N-(2-aminoethyl)-ββ-alanine salt, 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamine)-1-propanesulfonate.

[0080] More preferably, the hydrophilic compound is selected from 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamine)-1-propanesulfonate.

[0081] Most preferably, the hydrophilic compound is selected from sodium 2-[(2-aminoethyl)amino]ethanesulfonate and sodium 3-(cyclohexylamine)-1-propanesulfonate.

[0082] Advantageously, the amount of the hydrophilic compound is 0.1-45% by weight of the solids of the aqueous polyurethane dispersion, preferably 0.2-30% by weight, more preferably 0.3-10% by weight.

[0083] Component d): Small molecule alcohol

[0084] In some embodiments, the system used to prepare polyurethane and / or polyurethane-urea contains component d).

[0085] Examples of small molecule alcohols include ethanol, propanol, 2-propanol, n-butanol, sec-butanol, n-hexanol and its isomers, 2-ethylhexanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 1-octanol, 1-dodecyl alcohol, 1-hexadecyl alcohol, lauryl alcohol and stearyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, dipropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, di ... -Propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-dimethyl-1,3-propanediol, 1,4-dihydroxymethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, 1,4-dihydroxybenzene, or 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), tricyclodecanediethanol, trimethylolpropane, glycerol, pentaerythritol, dipentanetriol, or mixtures of at least two of the above.

[0086] Preferably, the small molecule alcohol is selected from 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

[0087] Advantageously, the amount of the small molecule alcohol is 0-5% by weight of the solids of the aqueous polyurethane dispersion, preferably 0-3% by weight, more preferably 0-1% by weight.

[0088] Component e): Other isocyanate reactive compounds

[0089] In some embodiments, the system used to prepare polyurethane and / or polyurethane-urea contains component e).

[0090] Other isocyanate reactive compounds described in this application refer to compounds other than components a), c), and d) that can react with isocyanate groups, selected from amine chain extenders and amine end capping agents.

[0091] For example, the other isocyanate reactive compounds may be water, hydrazine, acylhydrazine, aliphatic or alicyclic monoamine, diamine or triamine, or hydroxyl functional group monoamine or diamine.

[0092] Preferably, the other isocyanate reactive compounds are selected from ethylenediamine, isophorone diamine, diethylenetriamine, ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino-2-propanol, N-(2-hydroxyethyl)-ethylenediamine, N,N-bis(2-hydroxyethyl)-ethylenediamine and 2-propanolamine.

[0093] More preferably, the other isocyanate reactive compounds are selected from isophorone diamine, N-(2-hydroxyethyl)ethylenediamine and diethanolamine.

[0094] Advantageously, the amount of other isocyanate reactive compounds is 0.1-10% by weight of the solids of the aqueous polyurethane dispersion, preferably 0.3-8% by weight, more preferably 0.5-5% by weight.

[0095] Component (ii): Aliphatic alcohol esters

[0096] The aliphatic alcohol esters contained in the waterborne polyurethane dispersion are reaction products of one or more aliphatic diols and one or more C2-C18 monocarboxylic acids.

[0097] Examples of aliphatic diols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, 2-methylbutanediol, 2-methylpentanediol, and 2,2,4-trimethyl-1,3-pentanediol.

[0098] One or more hydrogen atoms on the aliphatic diol may be optionally replaced by amino, nitro, or halogen (e.g., fluorine, chlorine, bromine, or iodine).

[0099] The aliphatic diol is preferably selected from straight-chain or branched C2-C12 diols, more preferably from straight-chain or branched C4-C10 diols, and most preferably from branched C4-C10 diols.

[0100] Examples of C2-C18 monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, octanoic acid, isopropionic acid, isobutyric acid, and isovaleric acid.

[0101] The aliphatic monocarboxylic acid is preferably selected from straight-chain or branched C2-C14 monocarboxylic acids, more preferably from straight-chain or branched C3-C10 monocarboxylic acids, and most preferably from branched C3-C8 monocarboxylic acids. Preferably, the aliphatic alcohol ester is a reaction product of a fatty alcohol diol selected from branched C4-C10 diols and one or more monocarboxylic acids selected from branched C3-C8 monocarboxylic acids.

[0102] Most preferably, the aliphatic alcohol ester is selected from alcohol ester twelve and alcohol ester sixteen.

[0103] Advantageously, the amount of aliphatic alcohol ester is 1-8% by weight of the solids of the aqueous polyurethane dispersion, preferably 1-4% by weight, more preferably 1-2% by weight.

[0104] Other components

[0105] The aqueous polyurethane dispersion of the present invention may also contain one or more other components that are typically added to the aqueous polyurethane dispersion, such as solvents, preservatives, external emulsifiers, etc.

[0106] Those skilled in the art can adjust the amounts of these other components as needed so that the aqueous polyurethane dispersion of the present invention is not significantly adversely affected.

[0107] Preparation of waterborne polyurethane dispersions

[0108] The aqueous polyurethane dispersion of the present invention can be prepared using methods commonly used in the art, such as emulsification dispersion, prepolymer mixing, acetone method, melt emulsification, ketimine solid-phase dispersion and related derivative methods.

[0109] For example, the aqueous polyurethane dispersion of the present invention can be prepared by a method comprising the following steps:

[0110] (A) React components a), b) and d) at 60-120°C to form a prepolymer with terminal isocyanates, and dissolve it using acetone;

[0111] (B) React the prepolymer with components c) and optional e) at 20-60°C;

[0112] (C) Add distilled water to disperse and emulsify;

[0113] (D) The solvent acetone is removed by vacuuming, and then component (ii) and optional other components are added to obtain an aqueous polyurethane dispersion.

[0114] The aqueous polyurethane dispersion of the present invention can maintain the stability of the dispersion emulsion under low temperature conditions (e.g., 5°C). For example, the viscosity change rate is less than 300% after being stored at 5°C for 4 weeks, which greatly reduces the risk of quality problems during transportation, storage and use under low temperature climatic conditions.

[0115] Furthermore, the aqueous polyurethane dispersion of the present invention exhibits excellent initial heat resistance. In this application, the thermal stability of the aqueous polyurethane dispersion is characterized by the initial heat resistance of the adhesive containing the aqueous polyurethane dispersion. Excellent initial heat resistance ensures sufficient heat resistance even during bonding and lamination under high ambient temperatures, preventing problems such as peeling and popping.

[0116] Applications of waterborne polyurethane dispersions

[0117] The aqueous polyurethane dispersion of the present invention can be used to prepare coatings, adhesives, sealants and inks.

[0118] According to a second aspect of the present invention, coatings, adhesives, sealants or inks prepared using the above-described aqueous polyurethane dispersion are provided.

[0119] The coatings, adhesives, sealants, or inks may also contain one or more additives selected from the following: emulsifiers, light stabilizers, antioxidants, bactericides, fillers, antisettling agents, defoamers, wetting agents, flow modifiers, reactive diluents, plasticizers, neutralizers, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents, and tackifiers.

[0120] The content of the additive can be adjusted according to actual needs.

[0121] In some embodiments, the present invention provides an adhesive comprising the aqueous polyurethane dispersion and a thickener, wherein the thickener comprises 0.5-2.0% by weight of the total adhesive weight.

[0122] According to a third aspect of the invention, the above-described coatings, adhesives, sealants, or inks are provided for use in the preparation of coated products, adhesive products, sealing products, or printed products.

[0123] Preferably, the coating product, adhesive product, sealing product, or printing product is thermally activated.

[0124] According to a fourth aspect of the invention, articles comprising a substrate coated, bonded, sealed, or printed with the aforementioned coatings, adhesives, sealants, or inks are provided.

[0125] Preferably, the article is thermally activated.

[0126] The substrate can be, for example, rubber, plastic, paper, cardboard, wood, textiles, metal, alloy, fabric, fiber, artificial leather, leather, inorganic materials, human or animal hair, and human or animal skin.

[0127] The above-mentioned articles can be prepared by applying the above-mentioned waterborne polyurethane dispersion onto a substrate through brushing, dipping, spraying, roller coating, doctor blade coating, flow coating, casting, printing or transfer, preferably by brushing, dipping or spraying.

[0128] The descriptions of each feature in this application can be combined with each other as long as they do not contradict each other, and all of them fall within the scope of protection claimed in this application.

[0129] The word “and / or” as used in this application refers to one or all of the elements mentioned.

[0130] All percentages in this application are weight percentages unless otherwise stated.

[0131] All analytical measurements described in this application were performed at 23±2℃, unless otherwise stated.

[0132] The terms "comprising" and "including" as used in this application cover situations where other elements not explicitly mentioned are also included, as well as situations where the elements mentioned are constituted.

[0133] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the event of any discrepancy between the definitions of terms in this specification and their commonly understood meaning by one of ordinary skill in the art to which this invention pertains, the definitions set forth herein shall prevail.

[0134] Unless otherwise stated, all numerical values ​​for the amounts of expressed components, reaction conditions, etc., used in the specification and claims are to be understood as being modified by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth herein are approximate values ​​that can be varied to obtain the desired performance as needed.

[0135] Example

[0136] The following will further illustrate the concept, specific structure, and technical effects of the present invention with reference to embodiments, so as to enable those skilled in the art to fully understand the purpose, features, and effects of the present invention. It will be readily understood by those skilled in the art that the embodiments described herein are merely illustrative, and the scope of the present invention is not limited thereto.

[0137] Main raw materials

[0138] The main raw materials used in the following examples are as follows. Unless otherwise stated, all chemical reagents used are of analytical grade.

[0139] Polyester I: A difunctional polyester polyol based on adipic acid and 1,4-butanediol, with a number-average molecular weight Mn of 2250 g / mol, a hydroxyl value of 50 mg KOH / g, a glass transition temperature of -61℃, a melting temperature of 49℃, and a melting enthalpy of 80 J / g.

[0140] Isocyanate 1: Hexamethylene diisocyanate ( Covestro AG (Germany).

[0141] Isocyanate 2: Isophorone diisocyanate ( Covestro AG (Germany).

[0142] Hydrophilic chain extender: Sodium N-(2-aminoethyl)-2-aminoethanesulfonate aqueous solution, concentration 49.5% by weight. A 95 was purchased from Evonik Chemicals.

[0143] Texanol: Twelfth alcohol ester, purchased from Eastman Chemical Company.

[0144] TXIB: Hexadecyl alcohol ester, purchased from Eastman Chemical Company.

[0145] DINP: Diisononyl phthalate, purchased from Sinopharm Chemicals.

[0146] Benzoflex 50: a benzoate plasticizer, purchased from Eastman Chemical Company.

[0147] DMM: Dipropylene glycol dimethyl ether, purchased from Dow Chemical Company.

[0148] DPM: Dipropylene glycol monomethyl ether, purchased from Dow Chemical Company.

[0149] PMA: Propylene glycol methyl ether acetate, purchased from Dow Chemical Company.

[0150] Glycerol: Freeze-thaw stabilizer, purchased from Sinopharm Chemicals.

[0151] TERGITOL FT 893: Freeze-thaw stabilizer, purchased from Dow Chemical Company.

[0152] Borchigel L75N: Polyurethane associative thickener, purchased from Borchers.

[0153] Test methods used

[0154] The isocyanate group (NCO) content is determined by volume according to DIN-EN ISO 1 1909:2007.

[0155] The viscosity of the waterborne polyurethane polyurea dispersion was measured using a Brookfield DV-II+Pro rotational viscometer at 23°C according to ISO 2555:2018. Rotor type: S62-64, rotation speed: 30 RPM, test temperature: 23°C.

[0156] The initial heat resistance test was conducted as follows:

[0157] PVC leather (overall dimensions: 2.5cm*20cm; glued and bonded portion: 2.5cm*10cm) and ABS sheet (overall dimensions: 2.5cm*12.5cm; glued and bonded portion: 2.5cm*10cm) were used as test substrates. The ABS sheet was wiped with ethanol before bonding.

[0158] Apply the adhesive on the PVC leather and ABS surface with a 100-μm wire bar, then place it in an oven at 50 °C for drying for 10 min. After drying, let it stand at room temperature for 1 h, and then put it back into the oven at 60 °C for 10 min for reactivation. Take out the activated sample from the oven, after manual positioning, roll it with a 4.5-kg roller for one round trip for lamination. After good lamination, immediately put it into an oven at 80 °C, load a 100-g weight, with the weight and the sample at an angle close to 180 degrees, and record the peeling time of the sample. The longer the peeling time, the better the initial heat resistance of the adhesive. In this application, when the time required for the weight to fall off (peeling 10 cm) is greater than 60 minutes, it is considered qualified.

[0159] Other testing methods have been described in other parts of the specification or are common methods in the art.

[0160] Inventive Example 1 (1E1)

[0161] Dehydrate 450 g of polyester I at 110 °C and 100 mbar for 1 hour, then add 2.0 g of 1,4-butanediol and cool while stirring. Add 40.3 g of isocyanate 1 and 14.9 g of isocyanate 2 at 60 °C, and stir at 80 - 90 °C until the isocyanate content reaches 1.6%, obtaining a reactant containing a prepolymer. Then dissolve this reactant in 760 g of acetone and cool to 40 °C to obtain an acetone solution containing the prepolymer. Add a 30-g aqueous solution of 11.1 g of N-(2-aminoethyl) aminoethanesulfonic acid sodium salt, 1.1 g of diethanolamine, and 1.3 g of hydroxyethyl ethylenediamine to the acetone solution containing the prepolymer while stirring vigorously. After stirring for 30 min, then disperse this mixture by adding 489 g of water. After separating acetone by distillation (the material at this time is called Material A, with a solid content of 50 wt.%), then add aliphatic alcohol ester Texanol (the weight ratio of aliphatic alcohol ester Texanol to Material A is 0.8:100) to obtain an aqueous polyurethane dispersion with a pH of 7.0 and a particle size of 175 nm, where the amount of aliphatic alcohol ester Texanol is 1.6 wt.% of the solid content of the aqueous polyurethane dispersion.

[0162] It is found through testing that the obtained polyurethane and / or polyurethane-urea has a weight-average molecular weight of 291,000 g / mol and a melting enthalpy of 37.79 J / g.

[0163] Mix the obtained aqueous polyurethane-urea dispersion and Borchigel L75N with a concentration of 25 wt.% by stirring to obtain an adhesive, and adjust the amount of Borchigel L75N (within the range of 0.5 - 2.0 wt.% relative to the total amount of the adhesive) so that the viscosity of the adhesive is about 5000 mPa·s.

[0164] Embodiment 2 of the Invention (IE2)

[0165] Example 2 is based on Example 1 of the invention, except that the weight ratio of aliphatic alcohol ester Texanol to material A is 1:100, wherein the amount of aliphatic alcohol ester Texanol is 2 times the weight of the solids of the aqueous polyurethane dispersion.

[0166] Embodiment 3 of the Invention (IE3)

[0167] Example 3 of the invention is based on Example 1 of the invention, except that the weight ratio of aliphatic alcohol ester Texanol to material A is 1.5:100, wherein the amount of aliphatic alcohol ester Texanol is 3 by weight of the solids of the aqueous polyurethane dispersion.

[0168] Embodiment 4 of the Invention (IE4)

[0169] Example 4 of the invention is based on Example 1 of the invention, except that the weight ratio of aliphatic alcohol ester Texanol to material A is 2:100, wherein the amount of aliphatic alcohol ester Texanol is 4% by weight of the solids of the aqueous polyurethane dispersion.

[0170] Invention Embodiment 5 (IE5)

[0171] Example 5 of the invention is based on Example 1 of the invention, except that the weight ratio of aliphatic alcohol ester Texanol to material A is 4:100, wherein the amount of aliphatic alcohol ester Texanol is 8% by weight of the solids of the aqueous polyurethane dispersion.

[0172] Embodiment 6 of the Invention (IE6)

[0173] Example 6 of the invention is based on Example 1 of the invention, except that the aliphatic alcohol ester TXIB is used instead of the aliphatic alcohol ester Texanol, and the weight ratio of the aliphatic alcohol ester TXIB to material A is 0.5:100, wherein the amount of the aliphatic alcohol ester TXIB is 1% by weight of the solids of the aqueous polyurethane dispersion.

[0174] Embodiment 7 of the Invention (IE7)

[0175] Example 7 of the invention is carried out with reference to Example 1 of the invention, except that 1g of aliphatic alcohol ester TXIB is added instead of aliphatic alcohol ester Texanol, and the weight ratio of aliphatic alcohol ester TXIB to material A is 1:100, wherein the amount of aliphatic alcohol ester TXIB is 2 times the weight of the solids of the aqueous polyurethane dispersion.

[0176] Embodiment 8 of the Invention (IE8)

[0177] Example 8 is an example of the invention with reference to Example 1, except that 1.5g of aliphatic alcohol ester TXIB is added instead of aliphatic alcohol ester Texanol, and the weight ratio of aliphatic alcohol ester TXIB to material A is 1.5:100, wherein the amount of aliphatic alcohol ester TXIB is 3% by weight of the solids of the aqueous polyurethane dispersion.

[0178] Test Example 1

[0179] The initial viscosity of the aqueous polyurethane dispersions obtained in Examples 1-8 of the invention and the viscosity after storage at 5°C for 4 weeks were tested, and the viscosity change rate was calculated. The results are summarized in Table 1.

[0180] The initial heat resistance of the adhesive containing the obtained waterborne polyurethane dispersion was tested, and the results are summarized in Table 1.

[0181] Table 1

[0182]

[0183] Material A: The material before adding the aliphatic alcohol ester Texanol in Example 1.

[0184] As can be seen from Table 1, the waterborne polyurethane dispersions obtained in Examples 1-8 of the Invention have good low-temperature storage stability and initial heat resistance.

[0185] Comparative Example 1 (CE1)

[0186] Comparative Example 1 is given with Example 1 of the Invention, except that the aliphatic alcohol ester Texanol is not added.

[0187] Comparative Example 2 (CE2)

[0188] Comparative Example 2 is made with reference to Example 1 of the Invention, except that the weight ratio of aliphatic alcohol ester Texanol to material A is 0.4:100, wherein the amount of aliphatic alcohol ester Texanol is 0.8% by weight of the solids of the aqueous polyurethane dispersion.

[0189] Comparative Example 3 (CE3)

[0190] Comparative Example 3 is made with reference to Example 1 of the Invention, except that diisononyl phthalate (DINP) is added instead of aliphatic alcohol ester Texanol, and the weight ratio of diisononyl phthalate (DINP) to material A is 1:100, wherein the amount of diisononyl phthalate (DINP) is 2 by weight of the solids of the aqueous polyurethane dispersion.

[0191] Comparative Example 4 (CE4)

[0192] Comparative Example 4 is made with reference to Example 1 of the Invention, except that a benzoic acid ester plasticizer (Benzoflex 50) is added instead of an aliphatic alcohol ester Texanol, and the weight ratio of the benzoic acid ester plasticizer (Benzoflex 50) to material A is 1:100, wherein the amount of the benzoic acid ester plasticizer (Benzoflex 50) is 2% by weight of the solids of the aqueous polyurethane dispersion.

[0193] Comparative Example 5 (CE5)

[0194] Comparative Example 5 is made with reference to Example 1 of the Invention, except that dipropylene glycol dimethyl ether (DMM) is added instead of aliphatic alcohol ester Texanol, and the weight ratio of dipropylene glycol dimethyl ether (DMM) to material A is 1:100, wherein the amount of dipropylene glycol dimethyl ether (DMM) is 2 by weight of the solids of the aqueous polyurethane dispersion.

[0195] Comparative Example 6 (CE6)

[0196] Comparative Example 6 is made with reference to Example 1 of the Invention, except that dipropylene glycol monomethyl ether (DPM) is added instead of aliphatic alcohol ester Texanol, and the weight ratio of dipropylene glycol monomethyl ether (DPM) to material A is 1:100, wherein the amount of dipropylene glycol monomethyl ether (DPM) is 2 by weight of the solids of the aqueous polyurethane dispersion.

[0197] Comparative Example 7 (CE7)

[0198] Comparative Example 7 is made with reference to Example 1 of the Invention, except that propylene glycol methyl ether acetate (PMA) is added instead of aliphatic alcohol ester Texanol, and the weight ratio of propylene glycol methyl ether acetate (PMA) to material A is 1:100, wherein the amount of propylene glycol methyl ether acetate (PMA) is 2 by weight of the solids of the aqueous polyurethane dispersion.

[0199] Comparative Example 8 (CE8)

[0200] Comparative Example 8 is made with reference to Example 1 of the Invention, except that glycerol is added instead of aliphatic alcohol ester Texanol, and the weight ratio of glycerol to material A is 1:100, wherein the amount of glycerol is 2 by weight of the solids of the aqueous polyurethane dispersion.

[0201] Comparative Example 9 (CE9)

[0202] Comparative Example 8 is made with reference to Example 1 of the Invention, except that the freeze-thaw stabilizer TERGITOL FT893 is added instead of the aliphatic alcohol ester Texanol, and the weight ratio of freeze-thaw stabilizer TERGITOL FT893 to material A is 1:100, wherein the amount of TERGITOL FT893 is 2 times the weight of the solids of the aqueous polyurethane dispersion.

[0203] Comparative Example 10 (CE10)

[0204] 450g of polyester I was dehydrated at 110℃ and 100mbar for 1 hour, then 0.3g of 1,4-butanediol was added while cooling with stirring. 40.1g of isocyanate 1 and 10.1g of isocyanate 2 were added at 60℃, and the mixture was stirred at 80-90℃ until an isocyanate content of 1.6% was achieved, yielding a reactant containing the prepolymer. This reactant was then dissolved in 760g of acetone and cooled to 40℃ to obtain an acetone solution containing the dissolved prepolymer. 30g of an aqueous solution of 14.4g of N-(2-aminoethyl)aminoethanesulfonate and 2.4g of diethanolamine were added to the acetone solution containing the dissolved prepolymer while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 490g of water. After acetone is separated by distillation (the material at this point is called material B, with a solid content of 50 wt.%), aliphatic alcohol ester Texanol is added (the weight ratio of aliphatic alcohol ester Texanol to material B is 0.8:100) to obtain an aqueous polyurethane dispersion with a pH of 6.9 and a particle size of 190 nm. The amount of aliphatic alcohol ester Texanol is 1.6 wt% of the solid content of the aqueous polyurethane dispersion.

[0205] Tests revealed that the weight-average molecular weight of the obtained polyurethane and / or polyurethane-urea was 160,000 g / mol, and the enthalpy of fusion was 37.69 J / g.

[0206] The obtained aqueous polyurethane urea dispersion and Borchigel L75N at a concentration of 25% by weight were stirred and mixed to obtain an adhesive. The amount of Borchigel L75N was adjusted (relative to the total amount of adhesive, in the range of 0.5-2.0% by weight) so that the viscosity of the adhesive was about 5000 mPa·s.

[0207] Test Example 2

[0208] The initial viscosity and viscosity after 4 weeks of storage at 5°C of the aqueous polyurethane dispersions obtained in Comparative Examples 1-10 were tested, and the viscosity change rate was calculated. The results are summarized in Table 2.

[0209] The initial heat resistance of the adhesive containing the obtained waterborne polyurethane dispersion was tested, and the results are summarized in Table 2.

[0210] Table 2

[0211]

[0212] Material A: The material before adding the aliphatic alcohol ester Texanol in Example 1.

[0213] Material B: The material before the addition of aliphatic alcohol ester Texanol in Comparative Example 10.

[0214] na: Untested.

[0215] As can be seen from Table 2, the waterborne polyurethane dispersions obtained in Comparative Examples 1-10 cannot simultaneously possess both good low-temperature storage stability and initial heat resistance.

[0216] The foregoing descriptions are merely exemplary embodiments or examples of the present invention and are not intended to limit the invention. Those skilled in the art will recognize that the present invention can be modified and varied in many ways. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention are included within the scope of the claims of this application.

Claims

1. An aqueous polyurethane dispersion, characterized in that, comprising: (i) a polyurethane and / or polyurethane-urea prepared from a system comprising components a) - c) and optionally components d) - e): a) at least one crystalline polyol, b) at least one polyisocyanate, c) at least one hydrophilic compound containing NCO-reactive functional groups, the hydrophilic groups of the hydrophilic compound comprising one or more of ionic groups, latent ionic groups, non-ionic groups, d) a small molecule alcohol containing 1 - 4 NCO-reactive functional groups, different from components a) and c), having a molecular weight of 32 - 400 g / mol, e) a further isocyanate-reactive compound which is one or more of an amine-based chain extender and an amine-based blocking agent, and (ii) at least one fatty alcohol ester which is the reaction product of one or more fatty diols and one or more C2 - C18 mono carboxylic acids, the amount of the at least one fatty alcohol ester being 1 - 8 wt. % of the solids of the aqueous polyurethane dispersion, the weight average molecular weight of the polyurethane and / or polyurethane-urea being 260,000 g / mol or more, preferably 260,000 - 1,000,000 g / mol, more preferably 260,000 - 500,000 g / mol, still more preferably 260,000 - 400,000 g / mol.

2. The aqueous polyurethane dispersion according to claim 1, characterized in that, the aqueous polyurethane dispersion having a solids content of 15 - 70 wt. %, preferably 30 - 65 wt. %, more preferably 40 - 60 wt. %.

3. The aqueous polyurethane dispersion according to claim 1 or 2, characterized in that the crystalline polyol is selected from one or more of diols having a number average molecular weight of 62 - 15000 and triols having a number average molecular weight of 92 - 15000, preferably the crystalline polyol is selected from one or more of diols having a number average molecular weight of 62 - 5000 and triols having a number average molecular weight of 92 - 5000. more preferably the crystalline polyol is selected from one or more of polyester polyols containing 1.5 - 3 hydroxyl groups having a number average molecular weight of 500 - 2500, polycarbonate polyols containing 1.5 - 3 hydroxyl groups having a number average molecular weight of 400 - 2500, polyether polyols containing 1.5 - 3 hydroxyl groups having a number average molecular weight of 200 - 2500, polylactone polyols containing 1.5 - 3 hydroxyl groups having a number average molecular weight of 250 - 2500.

4. The aqueous polyurethane dispersion according to any one of claims 1 - 3, characterized in that the amount of the crystalline polyol is 50 - 97 wt. %, preferably 60 - 95 wt. %, more preferably 70 - 93 wt. % of the solids of the aqueous polyurethane dispersion.

5. The aqueous polyurethane dispersion according to any one of claims 1 - 4, characterized in that the polyisocyanate is selected from diisocyanates represented by the formula Y(NCO)2, wherein Y represents a divalent aliphatic hydrocarbon group containing 4 - 12 carbon atoms, a divalent cycloaliphatic hydrocarbon group containing 6 - 15 carbon atoms, a divalent aromatic hydrocarbon group containing 6 - 15 carbon atoms, and a divalent araliphatic hydrocarbon group containing 7 - 15 carbon atoms, Preferably, Y represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms and a divalent cycloaliphatic hydrocarbon group having 6 to 15 carbon atoms, More preferably, the polyisocyanate is selected from the group consisting of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 4,4'-dicyclohexylpropane diisocyanate.

6. The aqueous polyurethane dispersion according to any one of claims 1 to 5, characterized in that The amount of the polyisocyanate component is 2 to 80 wt.-%, preferably 4 to 60 wt.-%, more preferably 5 to 40 wt.-%, based on the solids of the aqueous polyurethane dispersion.

7. The aqueous polyurethane dispersion according to any one of claims 1 to 6, characterized in that, The NCO-reactive functional groups of the hydrophilic compound are hydroxyl groups and / or amino groups, preferably the hydrophilic compound is an ionic or potentially ionic compound, preferably an ionic or potentially ionic compound having a carboxyl group or carboxylate and / or sulfonate group and / or an amino group, more preferably selected from the group consisting of 6-aminohexanoate, lysine, N-(2-aminoethyl)-beta-alanine, 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamino)-1-propanesulfonate, still more preferably selected from the group consisting of 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamino)-1-propanesulfonate, most preferably selected from the group consisting of sodium 2-[(2-aminoethyl)amino]ethanesulfonate and sodium 3-(cyclohexylamino)-1-propanesulfonate.

8. The aqueous polyurethane dispersion according to any one of claims 1 to 7, characterized in that, The amount of the hydrophilic compound is 0.1 to 45 wt.-%, preferably 0.2 to 30 wt.-%, more preferably 0.3 to 10 wt.-%, based on the solids of the aqueous polyurethane dispersion.

9. The aqueous polyurethane dispersion according to any one of claims 1 to 8, characterized in that, The reaction system comprises component d) a small molecule alcohol, preferably the small molecule alcohol is selected from the group consisting of ethanol, propanol, 2-propanol, n-butanol, sec-butanol, n-hexanol and its isomers, 2-ethylhexanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 1-octanol, 1-dodecanol, 1-hexadecanol, lauryl alcohol and stearyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-dimethyl-1,3-propanediol, 1,4-dihydroxymethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-, 1,3-, 1,2-dihydroxybenzene or 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), tricyclodecane dimethylol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or a mixture of at least two thereof.

10. The aqueous polyurethane dispersion according to any one of claims 1 to 9, characterized in that, The amount of the small molecule alcohol is 0-5 wt.-%, preferably 0-3 wt.-%, more preferably 0-1 wt.-%, based on the solids of the aqueous polyurethane dispersion.

11. The aqueous polyurethane dispersion according to any one of claims 1 to 10, characterized in that, The reaction system comprises a component e) further isocyanate-reactive compound, preferably the further isocyanate-reactive compound is selected from the group consisting of ethylenediamine, isophorone diamine, diethylenetriamine, ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino-2-propanol, N-(2-hydroxyethyl)-ethylenediamine, N,N-bis(2-hydroxyethyl)-ethylenediamine and 2-propanolamine, more preferably the further isocyanate-reactive compound is selected from the group consisting of isophorone diamine, N-(2-hydroxyethyl)ethylenediamine and diethanolamine.

12. The aqueous polyurethane dispersion according to any one of claims 1 to 11, characterized in that, The amount of the further isocyanate-reactive compound is 0.1 -10 wt.-%, preferably 0.3-8 wt.-%, more preferably 0.5-5 wt.-%, based on the solids of the aqueous polyurethane dispersion.

13. The aqueous polyurethane dispersion according to any one of claims 1 to 12, characterized in that, The aliphatic diol used for the preparation of the aliphatic alcohol ester is selected from the group consisting of linear or branched C2-C12 diols, more preferably linear or branched C4-C10 diols, most preferably branched C4-C10 diols, the monocarboxylic acid used for the preparation of the aliphatic alcohol ester is selected from the group consisting of linear or branched C2-C14 monocarboxylic acids, more preferably selected from the group consisting of linear or branched C3-C10 monocarboxylic acids, most preferably selected from the group consisting of branched C3-C8 monocarboxylic acids, preferably the aliphatic alcohol ester is a reaction product of one or more aliphatic alcohol diols selected from the group consisting of branched C4-C10 diols and one or more monocarboxylic acids selected from the group consisting of branched C3-C8 monocarboxylic acids, more preferably selected from the group consisting of alcohol ester twelve and alcohol ester sixteen.

14. A coating material, an adhesive, a sealant or an ink, characterized by Prepared using the aqueous polyurethane dispersion according to any one of claims 1 -13.

15. An article of manufacture characterized by, An article comprising a substrate coated, bonded, sealed or printed with a coating, adhesive, sealant or ink according to claim 14.

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