Waterborne polyurethane dispersion and application thereof

Abstract

The invention relates to a waterborne polyurethane dispersion as well as a preparation method and application thereof. The aqueous polyurethane dispersion contains polyurethane and / or polyurethane urea. The waterborne polyurethane dispersion disclosed by the invention has excellent initial bonding strength and long adhesion time when being activated at low temperature.

Description

Technical Field

[0001] This invention relates to an aqueous polyurethane dispersion, its preparation method, and its applications. Background Technology

[0002] Waterborne polyurethane dispersions can be widely used in coatings, adhesives, sealants, and printing inks. Compared to traditional solvent-based polyurethanes, they offer advantages such as being environmentally friendly, non-flammable and non-explosive, safe to store, and having a high solids content. To achieve excellent initial tack, bond strength, and mechanical properties, they are typically synthesized from raw materials containing crystalline polyols. These materials have a regular molecular structure, crystallize rapidly, produce high-strength adhesive films, and exhibit good resistance to yellowing and heat. To obtain good initial tack and bond strength, these polyurethane or polyurethane urea adhesives need to be reactivated at a specific temperature. For example, Appendix A of GB / T 30779-2014 "Waterborne Polyurethane Adhesives for Shoes" recommends that waterborne polyurethane adhesives for shoes be dried and activated at 70±5℃ after application. Relatively high activation temperatures mean higher energy consumption during manufacturing. Conversely, lowering the activation temperature can lead to incomplete activation, resulting in adhesive failure.

[0003] CN1 12812727A describes a waterborne polyurethane adhesive with long-lasting tack and its preparation method. This application achieves long-lasting tack and adhesion by introducing hydroxyalkyl polysiloxanes into the ends of the polyurethane molecule and optimizing the molecular structure. However, as described in this application, the introduction of polysiloxanes inevitably requires a longer reaction time, which makes the waterborne polyurethane production process more complex and reduces the batch-to-batch stability of the product quality.

[0004] CN1 13234398A provides a cold-applied polyurethane adhesive that does not require heating activation and has high bonding strength. However, its preparation process and the product contain a large amount of organic solvents, which is not environmentally friendly.

[0005] CN103254867A discloses a method for preparing a sulfonic acid-based waterborne polyurethane adhesive, in which a sulfonate hydrophilic chain extender and a diamine chain extender are introduced during the preparation process. The minimum activation temperature of this adhesive is 30-40℃. However, since it uses polyoxypropylene glycol and crystalline polyester polyol, the initial tack performance of the product is poor.

[0006] In summary, there is currently no waterborne polyurethane dispersion and adhesive formulation in the industry that can simultaneously meet the requirements of low-temperature activation, excellent initial bond strength, and long holding time, and is suitable for efficient industrial production. Summary of the Invention

[0007] The purpose of this invention is to provide a waterborne polyurethane dispersion and its adhesive formulation that can be activated at low temperatures, has excellent initial bond strength and long holding time, and is suitable for efficient industrial production.

[0008] According to a first aspect of the present invention, an aqueous polyurethane dispersion comprising polyurethane and / or polyurethane urea is provided, wherein the polyurethane and / or polyurethane urea is obtained by reacting a system comprising the following components:

[0009] a) At least one aromatic polyester polyol component, which is a reaction product of at least one aromatic polyacid and / or aromatic anhydride with at least two polyols, wherein component a) is 5-75% by weight of the solids of the aqueous polyurethane dispersion.

[0010] b) At least one crystalline aliphatic polyol component, which is 10-83% by weight of the solids of the aqueous polyurethane dispersion.

[0011] c) At least one polyisocyanate component;

[0012] d) At least one hydrophilic compound component 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] e) Optional small molecule alcohol components, different from components a) and b), with a molecular weight of 32-400 g / mol;

[0014] f) Other isocyanate reactive compound components, said reactive compound including one or more of water, amine chain extenders, and amine end-capping agents.

[0015] The polyurethane and / or polyurethane urea have a weight-average molecular weight of 35,000-250,000 g / mol.

[0016] According to a second aspect of the present invention, coatings, adhesives, sealants or inks prepared using the above-described aqueous polyurethane dispersion are provided.

[0017] 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.

[0018] According to a fourth aspect of the present invention, an bonding method is provided, comprising the following steps:

[0019] i. Applying the adhesive according to the invention to at least one surface of a substrate;

[0020] ii. Heat and dry the surface of the substrate to which the adhesive has been applied at a temperature ranging from 30°C to 59°C; and

[0021] iii. Bring another substrate into contact with the surface of the substrate treated in step ii to obtain an adhesive product.

[0022] According to a fifth aspect of the invention, articles comprising a substrate coated, bonded, sealed, or printed with the aforementioned coatings, adhesives, sealants, or inks are provided.

[0023] The adhesive formulated with the waterborne polyurethane dispersion of the present invention exhibits excellent initial bond strength and a sufficiently long holding time even at a low activation temperature (e.g., 55°C), thus maintaining good initial bond strength and initial heat resistance during the holding time. Detailed Implementation

[0024] Some specific embodiments of the invention will now be described for illustrative purposes and not for limitation.

[0025] This invention provides an aqueous polyurethane dispersion comprising polyurethane and / or polyurethane urea, wherein the polyurethane and / or polyurethane urea are obtained by reacting a system comprising the following components:

[0026] a) At least one aromatic polyester polyol component, which is a reaction product of at least one aromatic polyacid and / or aromatic anhydride with at least two polyols, wherein component a) is 5-75% by weight of the solids of the aqueous polyurethane dispersion.

[0027] b) At least one crystalline aliphatic polyol component, which is 10-83% by weight of the solids of the aqueous polyurethane dispersion.

[0028] c) At least one polyisocyanate component;

[0029] d) At least one hydrophilic compound component 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;

[0030] e) Optional small molecule alcohol components, different from components a) and b), with a molecular weight of 32-400 g / mol;

[0031] f) Other isocyanate reactive compound components, said reactive compound including one or more of water, amine chain extenders, and amine end-capping agents.

[0032] The polyurethane and / or polyurethane urea have a weight-average molecular weight of 35,000-250,000 g / mol.

[0033] The present invention also provides a method for preparing the aqueous polyurethane dispersion and its applications, particularly in the fields of coatings, adhesives or inks, as well as products obtained by coating, bonding, sealing or printing using the aqueous polyurethane dispersion.

[0034] As used in this application, the term "adhesive" refers to a chemical substance that can be applied to the surface of an object using various construction techniques to form a coating on the object itself or on the surface of one object to another, and to bond the object itself or on the surface of one object to another. It is also used as a synonym for adhesive and / or sealant and / or bonding agent.

[0035] The term “polyurethane and / or polyurethane urea” as used in this application refers to polyurethane and / or polyurethane polyurea and / or polyurea and / or polysulfurethane.

[0036] The term "waterborne polyurethane dispersion" as used in this application refers to waterborne polyurethane dispersion and / or waterborne polyurethane polyurea dispersion and / or waterborne polyurea dispersion and / or waterborne polysulfuric acid ester dispersion.

[0037] The solids component of the waterborne polyurethane dispersion mentioned in this application refers to the non-volatile components in the waterborne polyurethane dispersion.

[0038] As used in this application, the term "polyol" refers to an alcohol compound having at least two hydroxyl groups in its molecule.

[0039] The term "isocyanate-reactive compound" as used in this application refers to a component containing a group that is reactive to an isocyanate group, i.e., a component containing a group with a zeravitinov-active hydrogen atom. The definition of zeravitinov-active hydrogen atom is found in Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th ed., Georg Thiem Verlag Stuttgart, 1996. Generally, groups containing zeravitinov-active hydrogen atom are understood in the art to refer to hydroxyl (OH), amino (NH4+), etc. x ) and thiol group (SH).

[0040] Waterborne polyurethane dispersion

[0041] The amount of organic solvent in the aqueous polyurethane dispersion is preferably less than 1% by weight, relative to the total weight of the aqueous polyurethane dispersion.

[0042] The aqueous polyurethane dispersion preferably meets at least one of the following characteristics:

[0043] Viscosities range from 10 to 6000 mPa·s, tested using a Brookfield DV-II+Pro viscometer according to ISO 2555:2018 standard.

[0044] Solid content is 15-70% by weight, tested according to DIN-EN ISO 3251:2019 using a Metteler Teredo Halogen Moisture Analyzer Excellence HS153.

[0045] The average particle size is 20-750 nm, and was determined by laser correlation (laser particle size analyzer) using a Malvem ZEN 1600 analyzer according to ISO 13321:1996.

[0046] The pH value is 4-10, measured at 23°C using a PB-10 pH meter from Sartorius, Germany.

[0047] The polyurethane and / or polyurethane urea had a weight-average molecular weight of 35,000-250,000 g / mol, determined by gel permeation chromatography. The chromatograph was an Agilent Technologies liquid chromatograph using a polyester copolymer GPC column with a size exclusion limit of 1,000,000 g / mol. The sample concentration was approximately 0.006 g / mL, with an injection volume of 100 μL. Dimethylacetamide (DMAc) was used as the mobile phase, and 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.

[0048] The solids content of the aqueous polyurethane dispersion is preferably 30-65% by weight, more preferably 40-60% by weight, relative to the total weight of the aqueous polyurethane dispersion.

[0049] The average particle size of the aqueous polyurethane dispersion is preferably 50-450 nm, and most preferably 100-350 nm.

[0050] The pH value of the aqueous polyurethane dispersion is preferably in the range of 5.0-10.0, and more preferably in the range of 6.0-9.0.

[0051] Component a): Aromatic polyester polyol

[0052] Component a) is preferably prepared by comprising: aromatic di- or polycarboxylic acids and / or anhydrides selected from terephthalic acid, isophthalic acid and phthalic acid, phthalic anhydride, trimellitic anhydride and succinic anhydride; at least two low molecular weight polyols selected from ethylene glycol, di-,tri-,tetra-ethylene glycol, 1,2-propanediol, di-,tri-,tetra-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol. Alcohols, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dihydroxymethylcyclohexane, 1,8-octanediol / 1,10-decanediol and 1,12-dodecanediol; and optionally, higher-functionality polyols such as trimethylolpropane, glycerol or pentaerythritol, alicyclic and / or aromatic di- and poly-hydroxy compounds.

[0053] Component a) is further preferably obtained by reacting a mixture comprising at least one of an aromatic diacid and an aromatic anhydride with at least two diols. The aromatic diacid is preferably one or more of the following: terephthalic acid, isophthalic acid, phthalic acid; the aromatic anhydride is preferably phthalic anhydride; and the diol is preferably two or more of the following: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, butanediol, neopentyl glycol, 3-methylpentyl glycol, hexanediol, heptahydrate, nonanediol, and decanediol. The most preferred diol is a mixture of neopentyl glycol and hexanediol. The molar ratio of neopentyl glycol to hexanediol is preferably 9 / 1 to 1 / 9, more preferably 6 / 1 to 1 / 6, and even more preferably 3 / 1 to 1 / 3.

[0054] The most preferred component a) is the product of phthalic anhydride, neopentyl glycol, and hexanediol.

[0055] The number average molecular weight of component a) is 100-20,000 g / mol, preferably 500-5,000 g / mol, more preferably 500-4,000 g / mol, and / or the functionality is 1.5-4.0, preferably 1.8-2.5, more preferably 2.

[0056] Component a) is 5-75% by weight of the solids of the aqueous polyurethane dispersion, preferably 7-70% by weight, more preferably 15-60% by weight;

[0057] Component b): Crystalline aliphatic polyols

[0058] Suitable crystalline aliphatic polyol components are aliphatic and crystalline polyester polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, and polyester polycarbonate polyols. Particularly preferred are at least one or more of aliphatic and crystalline polyester polyols, polyether polyols, polycarbonate polyols, and polycaprolactone polyols. More preferably are at least one or more of aliphatic and crystalline polyester polyols, polycaprolactone polyols, and polycarbonate polyols. Most preferably are crystalline aliphatic polyester polyols.

[0059] Preferred polyester polyols are known condensation polymers of di- and optionally tri- and tetra-ols with di- and optionally tri- and tetra-carboxylic acids or hydroxycarboxylic acids or lactones. Instead of free polycarboxylic acids, polyesters can also be prepared using the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols. Examples of suitable diols are ethylene glycol, butanediol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, and 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and its isomers, neopentyl glycol or neopentyl glycol hydroxypentanoate, with the three compounds mentioned later being preferred. To achieve a functionality ≥2, polyols with a functionality of 3 can optionally be used in proportion, such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene, or trihydroxyethyl isocyanurate.

[0060] Suitable hydroxycarboxylic acids as reaction participants in the preparation of polyester polyols with terminal hydroxyl groups include, for example, hydroxyhexanoic acid, hydroxybutyric acid, hydroxydecanoic acid, and hydroxystearic acid. Suitable lactones are especially v-caprolactone, butyrolactone, and their homologues.

[0061] Preferred polyester polyols are typically constructed from one or more aliphatic and / or alicyclic dicarboxylic acids and one or more aliphatic and / or alicyclic diols, and prepared by polycondensation.

[0062] Preferred dicarboxylic acids are saturated aliphatic acids, such as hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, itaconic acid, malonic acid, octanoic acid, 2-methylsuccinic acid, succinic acid, 3,3-diethylglutaric acid, and 2,2-dimethylsuccinic acid. Anhydrides of these acids are also acceptable, provided they are present. Therefore, for the purposes of this invention, anhydrides are referred to as "acids".

[0063] Polyester polyols based on butanediol and / or neopentyl glycol and / or hexanediol and / or ethylene glycol and / or diethylene glycol with adipic acid are preferred. Polyester polyols based on butanediol and / or neopentyl glycol and / or hexanediol with adipic acid are particularly preferred.

[0064] Preferably, the enthalpy of melting of component b) is greater than 10 J / g, more preferably greater than 20 J / g, even more preferably 30-130 J / g, and most preferably 40-100 J / g.

[0065] Preferably, the melting temperature of component b) is greater than 15°C and less than 100°C, more preferably greater than 40°C and less than 70°C.

[0066] Melting temperature and enthalpy of fusion were measured using a Perkin-Elmer DSC-7 according to DIN 65467:1999 from -85°C to 150°C, taken from the first heating profile. The sample loading was approximately 5 mg, and the heating rate was 20 K / min.

[0067] The number average molecular weight of component b) is 100-20,000 g / mol, preferably 500-5,000 g / mol, more preferably 500-4,000 g / mol, and / or the functionality is 1.5-4.0, preferably 1.8-2.5, more preferably 2.

[0068] The component b) is 10-83% by weight of the solids of the aqueous polyurethane dispersion, preferably 15-81% by weight, and most preferably 20-80% by weight.

[0069] Preferably, the weight ratio of component a) to component b) is 6 / 1-1 / 15, more preferably 5 / 1-1 / 11, more preferably 2 / 1-1 / 9, and most preferably 1 / 1-1 / 6.

[0070] Component c): Polyisocyanate

[0071] The isocyanate functionality of the polyisocyanate component is preferably not less than 2, and most preferably 2-4.

[0072] The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their derivatives having iminooxadiazine dione, isocyanurate, urea dione, carbamate, urethane, biuret, urea, oxadiazine trione, oxazolidinone, acylurea and / or carbodiimide groups.

[0073] The aliphatic polyisocyanate is preferably one or more of the following: hexamethylene diisocyanate, 1,5-pentanediisocyanate, 2,2-dimethylpentanediisocyanate, 2,2,4-trimethylhexanediisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethyl-1,6-hexanediisocyanate, 1,6,11-undecane triisocyanate, and 1,3,6-hexamethylene triisocyanate. 1,8-Diisocyanate-4-methyl isocyanate octane, bis(ethyl isocyanate) carbonate, bis(ethyl isocyanate) ether, lysine methyl ester diisocyanate, lysine triisocyanate, bis(methyl isocyanate) sulfide, bis(ethyl isocyanate) sulfide, bis(propyl isocyanate) sulfide, bis(hexyl isocyanate) sulfide, bis(methyl isocyanate) sulfone, bis(methyl isocyanate) disulfide, bis(ethyl isocyanate) disulfide Ethers, bis(propyl isocyanate)disulfide, bis(isocyanate methylthio)methane, bis(isocyanate ethylthio)methane, bis(isocyanate methylthio)ethane, bis(isocyanate ethylthio)ethane, 1,5-diisocyanate-2-methyl isocyanate-3-thiapentane, 1,2,3-tris(isocyanate methylthio)propane, 1,2,3-tris(isocyanate ethylthio)propane, 3,5-dithia-1,2, 6,7-Heptanetetraisocyanate, 2,6-methyl diisocyanate-3,5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanate-methylthiophene, isocyanate-ethylthio-2,6-dithia-1,8-octane diisocyanate, thiobis(3-isothiocyanate-propane), thiobis(2-isothiocyanate-ethane), and dithiobis(2-isothiocyanate-ethane), with hexamethylene diisocyanate being the most preferred.

[0074] The alicyclic polyisocyanate is preferably one or more of the following: 2,5-bis(methyl isocyanate)-bicyclo[2.2.1]heptane, 2,6-bis(methyl isocyanate)-bicyclo[2.2.1]heptane, bis(methyl isocyanate)cyclohexane, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,5-diisocyanate-tetrahydrothiophene, 2,5-diisocyanate-tetrahydrothiophene, 3,4-diisocyanate-tetrahydrothiophene, 2,5-diisocyanate-1,4-dithiane, 2,5-diisocyanate-1,4-dithiane, 4,5-diisocyanate- 1,3-Dithiocyclopentane, 4,5-bis(methyl isocyanate)-1,3-dithiocyclopentane, 4,5-methyl diisocyanate-2-methyl-1,3-dithiocyclopentane, norbornene diisocyanate (NBDI), phenylenediamine diisocyanate (XDI), hydrogenated phenylenediamine diisocyanate (H6XDI), 1,4-cyclohexyl diisocyanate (H6PPDI), m-tetramethylphenylenediamine diisocyanate (m-TMXDI), and cyclohexane diisothiocyanate, most preferably one or more of the following: isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

[0075] The aromatic polyisocyanate is preferably one or more of the following: 1,2-diisocyanate-based benzene, 1,3-diisocyanate-based benzene, 1,4-diisocyanate-based benzene, 2,4-diisocyanate-based toluene, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, toluene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 4,4'-methylenebis(2-methylphenyl isocyanate), bibenzyl-4,4'-diisocyanate, bis(phenyl isocyanate)ethylene, bis(methyl isocyanate)benzene, bis(ethyl isocyanate)benzene, bis(propyl isocyanate)benzene, α,α,α',α'-tetramethylphenyl dimethylene diisocyanate, bis(butyl isocyanate)benzene, bis(methyl isocyanate)naphthalene, bis(methyl isocyanate phenyl) ether, bis(ethyl isocyanate)phthalate, 2,6-bis(methyl isocyanate)furan, 2-phenyl isocyanate-4-phenyl isocyanate sulfide, bis(4-phenyl isocyanate) sulfide, bis(4-methyl isocyanate phenyl) sulfide, bis(4-phenyl isocyanate) disulfide, bis(2-methyl-5-phenyl isocyanate) disulfide, bis(3-methyl-5- Phenyl isocyanate disulfide, bis(3-methyl-6-phenyl isocyanate) disulfide, bis(4-methyl-5-phenyl isocyanate) disulfide, bis(4-methoxy-3-phenyl isocyanate) disulfide, 1,2-diisothiocyanate-benzene, 1,3-diisothiocyanate-benzene, 1,4-diisothiocyanate-benzene, 2,4-diisothiocyanate-toluene, 2,5-diisothiocyanate-m-xylene, 4,4'-methylenebis(phenyl isothiocyanate), 4,4'-methylenebis(2-methylphenyl isothiocyanate), 4,4'-methylenebis(3-methylphenyl isothiocyanate), 4,4'-diisothiocyanate The preferred phenoxybenzene is 4,4'-diisothiocyanate-3,3'-dimethylbenzophenone, bis(4-isothiocyanate phenyl) ether, 1-isothiocyanate-4-[(2-isothiocyanate)sulfonyl]benzene, thiobis(4-isothiocyanate benzene), sulfonyl(4-isothiocyanate benzene), hydrogenated toluene diisocyanate (H6TDI), diphenylmethane diisocyanate, and dithiobis(4-isothiocyanate benzene), with one or more of the following being most preferred: 1,2-diisocyanate benzene, 1,3-diisocyanate benzene, 1,4-diisocyanate benzene, diphenylmethane diisocyanate, and 2,4-diisocyanate toluene.

[0076] The other isocyanates may also have isocyanate and isothiocyanate groups, such as 1-isocyanate-6-isothiocyanate hexane, 1-isocyanate-4-isothiocyanate cyclohexane, 1-isocyanate-4-isothiocyanate benzene, 4-methyl-3-isocyanate-1-isothiocyanate benzene, 2-isocyanate-4,6-diisothiocyanate-1,3,5-triazine, 4-phenylisocyanate-4-phenylisothiocyanate sulfide, and 2-ethylisocyanate-2-ethylisothiocyanate disulfide.

[0077] The other isocyanates may also be halogenated derivatives of the above polyisocyanates, such as chlorinated derivatives, bromine derivatives, alkyl derivatives, alkoxy derivatives, nitro derivatives, or silane derivatives such as propyltriethoxysilane or propyltrimethoxysilane.

[0078] The isocyanate is preferably one or more of aliphatic and alicyclic diisocyanates. More preferably, one or more of the following: 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0079] The polyisocyanate is further preferably a mixture of aliphatic diisocyanate and alicyclic diisocyanate, preferably hexamethylene diisocyanate and isophorone diisocyanate, or a mixture of hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

[0080] The amount of component c) is 5-80% by weight of the solids of the aqueous polyurethane dispersion, preferably 5-70% by weight, more preferably 5-50% by weight.

[0081] Component d): Hydrophilic compound

[0082] The hydrophilic group of the hydrophilic compound includes one or more of ionic groups, latent ionic groups, and nonionic groups, and the hydrophilic compound contains at least one NCO reactive functional group.

[0083] Suitable nonionic hydrophilic compounds are, for example, monovalent polyoxyethylene ether alcohols with a statistical average of 5-70, preferably 7-55 ethylene oxide units per molecule, as they can be obtained by alkoxylation with a suitable initiator molecule in a manner known per se. Suitable initiator molecules are, for example, saturated monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, isomeric pentanol, hexanol, octanol and nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, isomeric methylcyclohexanol or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleyl alcohol, and aromatic alcohols.

[0084] Examples of starting agents include phenol, isomeric cresol or methoxyphenol, aromatic aliphatic alcohols such as benzyl alcohol, anisyl alcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis-(2-ethylhexyl)-amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine, and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starting agent molecules are saturated monohydric alcohols. Diethylene glycol monobutyl ether is particularly preferred as a starting agent molecule. Suitable alkoxylated alkenes, especially ethylene oxide and propylene oxide, can be used in any order or in mixtures for alkoxylation reactions.

[0085] 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 with acrylic acid (EP-A). 0916647, Example 1) and its alkali metal salts and / or ammonium salts; adducts of sodium bisulfite on buten-2-diol-1,4, polyether sulfonates, propoxylated adducts of 2-butenyldiol and NaHSO3, such as those described in DE-A 2446440 (pages 5-9, formulas I-III), and structural units that can be converted into cationic groups, such as N-methyl-diethanolamine, as hydrophilic building blocks. Furthermore, salts of cyclohexylaminopropanesulfonic acid (CAPS) from WO-A 01 / 88006 can be used as anionic hydrophilizing agents. Preferred ionic or potential ionic compounds are those having carboxyl or carboxylate groups and / or sulfonate groups and / or amino groups.

[0086] The amino-containing compound is preferably selected from: 6-aminohexanoate, lysine salt, N-(2-aminoethyl)-β-alanine monosodium salt, 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamine)-1-propanesulfonate.

[0087] The amino-containing sulfonate is preferably selected from: sodium 2-[(2-aminoethyl)amino]ethanesulfonate and sodium 3-(cyclohexylamine)-1-propanesulfonate.

[0088] Preferably, the amount of component d) is 0.1-5% by weight, more preferably 0.3-3% by weight, and even more preferably 0.5-1.5% by weight, based on the solids content of the aqueous polyurethane dispersion.

[0089] Component e): A small molecule alcohol component that differs from components a) and b).

[0090] Suitable small molecule alcohol components are compounds having at least one active hydrogen atom with a molecular weight of 32-400 g / mol that is reactive to isocyanates, and can be selected from 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, 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, Neopentylenediol, 1,4-Cyclohexanediol, 1,4-Cyclohexanediol, 1,4-, 1,3-, 1,2-Dihydroxybenzene or 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), tricyclodecanediethanol, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, dipentanetriol or a mixture of at least two thereof, preferably selected from 1,4-Butanediol, 1,6-Hexanediol, and neopentylenediol.

[0091] The amount of component e) is preferably 0-3% by weight, more preferably 0-2% by weight, and most preferably 0-1% by weight, based on the solids content of the aqueous polyurethane dispersion.

[0092] Component f): Other isocyanate group reactive compounds

[0093] The other isocyanate reactive compounds refer to compounds other than components a), b), e), and d) that can react with isocyanate groups, selected from water, amine chain extenders, and amine end-capping agents. Preferably, they are isocyanate reactive compounds with a molecular weight of 62-399 g / mol.

[0094] Organic diamines or polyamines can be used as component f), such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophorone diamine, a mixture of isomers of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 4,4-diaminodicyclohexylmethane, hydrazine hydrate and / or dimethylethylenediamine.

[0095] In addition, compounds that have a secondary amino group in addition to a primary amino group, or compounds that have an OH group in addition to an amino group (primary or secondary), can also be used. Examples include diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, and alkanolamines such as N-aminoethyl-ethanolamine, ethanolamine, 3-aminopropanol, and neopentyl alcoholamine.

[0096] In addition, monofunctional isocyanate reactive amine compounds such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononoxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl(methyl)aminopropylamine, morpholine, piperidine or suitable substituted derivatives thereof, amide amines formed from primary amines and monocarboxylic acids, monoketimines of primary amines, and primary / tertiary amines such as N,N-dimethylaminopropylamine can also be used.

[0097] It can also be a dihydrazide, such as adipic acid dihydrazide, oxalate dihydrazide, carbamate dihydrazide, and succinate dihydrazide. Or long-chain amino functional compounds, such as polyetheramine (Jeffamine).

[0098] The component f) is preferably selected from 1,2-ethylenediamine, bis(4-aminocyclohexyl)methane, N-(2-hydroxyethyl)ethylenediamine, 1,4-diaminobutane, isophorone diamine, monoethanolamine, diethanolamine and diethylenetriamine.

[0099] The component f) is most preferably selected from isophorone diamine, N-(2-hydroxyethyl)ethylenediamine, diethanolamine and 1,2-ethylenediamine.

[0100] The dosage of component f) is known and easily determined by those skilled in the art, for example, preferably 0-3% by weight, most preferably 0.1-2.5% by weight, based on the solids content of the aqueous polyurethane dispersion.

[0101] system

[0102] The system may further include one or more of the following: external emulsifiers, solvents, reactive diluents, and stabilizers, in amounts commonly used by those skilled in the art.

[0103] Method for preparing aqueous polyurethane dispersions containing polyurethane and / or polyurethane urea

[0104] The preparation process of the aqueous polyurethane dispersion of the present invention is simple and suitable for efficient industrial production. All known processes can be used to prepare the aqueous polyurethane dispersion of the present invention, such as the emulsifier / shear force method, acetone method, prepolymer mixing method, melt emulsification method, ketimide method, and solid spontaneous dispersion method or derivatives thereof, with melt emulsification or acetone method being preferred, and acetone method being the most preferred. These methods are summarized in Method of Organischen Chemie.

[0105] (Houben-Weyl, Erweitenmgs-und zur4. Auflage, Volume E20, H Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, p. 1671-1682).

[0106] The mixing order of the components in the system for preparing the aqueous polyurethane dispersion can be followed in a conventional manner.

[0107] The polyisocyanate, or the compound containing isocyanate reactive groups of polyester polyol, can be added at once or in multiple additions, and can be the same or different from the previously added components.

[0108] Organic solvents present in the aqueous polyurethane dispersion can be removed by distillation. These organic solvents can be removed during or after the polyurethane formation process.

[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), c) and e) at 60-120°C to form a prepolymer with terminal isocyanates, and dissolve it using a solvent;

[0111] (B) React the prepolymer with components d) and f) at 20-60°C;

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

[0113] (D) The solvent is removed by vacuum to obtain an aqueous dispersion of polyurethane or polyurethane-urea.

[0114] Component d) may also be added in step (A).

[0115] The organic solvent is preferably a water-miscible solvent that is inert to isocyanate groups, and more preferably one or more of the following: acetone, methyl ethyl ketone, propylene glycol dimethyl ether, other ethers and esters without hydroxyl functional groups; most preferably one or more of the following: acetone and butanone.

[0116] The organic solvent preferably does not contain pyrrolidone compounds.

[0117] The organic solvent can be removed by distillation.

[0118] The amount of residual organic solvent in the aqueous polyurethane dispersion is preferably less than 1.0% by weight, relative to the total weight of the aqueous polyurethane dispersion.

[0119] To accelerate the reaction rate of step (A), catalysts commonly used in prepolymer preparation can be used, such as triethylamine, 1,4-diazabicyclo-[2,2,2]octane, tin dioctanoate or dibutyltin dilaurate, or other organometallic catalysts, such as organic or inorganic salts of titanium, bismuth, zirconium, zinc, and lead.

[0120] The catalyst can be placed in the reactor simultaneously with the components of step (A), or it can be added later.

[0121] The degree of conversion of the component in step (A) can be obtained by testing the NCO content in the component. For this purpose, the extracted sample can be subjected to spectral measurements, such as infrared or near-infrared spectroscopy, as well as refractive index determination or chemical analysis, such as titration.

[0122] The prepolymer can be in a solid or liquid state at room temperature.

[0123] Paints, adhesives or inks

[0124] The coating, adhesive, or ink preferably further comprises an additive. The additive is preferably one or more of the following: co-adhesive, lubricant, emulsifier, light stabilizer, antioxidant, filler, antisettling agent, defoamer, wetting agent, flow conditioner, antistatic agent, film-forming aid, reactive diluent, plasticizer, catalyst, thickener, pigment, dye, tackifier, and matting agent.

[0125] The selection and dosage of the additives mentioned are, in principle, known to those skilled in the art and easily measurable.

[0126] The aqueous polyurethane dispersions of the present invention can also be mixed and used with other aqueous or solvent-containing oligomers or polymers, such as aqueous or solvent-containing polyesters, polyurethanes, polyurethane-polyacrylates, polyacrylates, polyethers, polyester-polyacrylates, alkyd resins, addition polymers, polyamides / imides, or polyepoxides. The compatibility of such mixtures must be tested using simple preliminary tests in each case.

[0127] The aqueous polyurethane dispersion of the present invention can also be mixed with and used with other compounds containing functional groups such as carboxyl, hydroxyl and / or blocked isocyanate groups.

[0128] The coatings, adhesives, or inks of the present invention are obtained by processing according to methods known to those skilled in the art.

[0129] Coating methods, adhesive products or printed products

[0130] The substrate is preferably one or more of the following: wood, metal, glass, fiber, textile, artificial leather, genuine leather, paper, plastic, rubber, foam, ceramic and various polymer coatings, and most preferably one or more of the following: textile, plastic, ceramic, metal, genuine leather, artificial leather and various polymer coatings.

[0131] The coating may be applied to the entire surface of the substrate or only to one or more portions of the surface of the substrate.

[0132] The coating can be applied by brushing, dipping, spraying, roller coating, doctor blade coating, flow coating, pouring, or printing.

[0133] bonding method

[0134] The bonding method preferably includes the following steps:

[0135] i. Applying the adhesive according to the invention to at least one surface of a substrate;

[0136] ii. Heat and dry the surface of the substrate to which the adhesive has been applied at a temperature ranging from 30°C to 59°C; and

[0137] iii. Bring another substrate into contact with the surface of the substrate treated in step ii to obtain an adhesive product.

[0138] The substrate is preferably one or more of the following: rubber, plastic, paper, cardboard, wood, textile, metal, alloy, fabric, fiber, artificial leather, leather, inorganic material, human or animal hair and human or animal skin, and most preferably one or more of the following: rubber and plastic.

[0139] The application may be to apply the adhesive to the entire surface of the substrate or to one or more portions of the surface of the substrate.

[0140] The application can be by brushing, dipping, spraying, roller coating, doctor blade coating, flow coating, pouring, printing or transfer, preferably by brushing, dipping or spraying.

[0141] The heating and drying of the substrate surface to which the adhesive has been applied can refer to heating and drying only the substrate surface, or heating and drying part or all of the substrate, including the substrate surface to which the adhesive has been applied.

[0142] The heating and drying process removes volatile components. These volatile components may be water.

[0143] The heating and drying process preferably uses one or more of the following: infrared thermal radiation, near-infrared thermal radiation, microwave, and convection oven or spray dryer under elevated temperature conditions.

[0144] The heating temperature is preferably 40°C to 59°C, more preferably 50°C to 59°C.

[0145] The adhesive product is obtained by the substrate surface treated in step ii coming into contact with the substrate itself or another substrate within one hour, more preferably within 30 minutes, even more preferably within 10 minutes, and most preferably within 5 minutes.

[0146] The other substrate can be any substrate that needs to be bonded.

[0147] The other substrate may be the same as or different from the substrate.

[0148] The other substrate is preferably coated and heat-treated in the same way as the substrate.

[0149] After the substrate surface treated in step ii comes into contact with the other substrate, it can be further heat-treated.

[0150] After the substrate surface treated in step ii comes into contact with the other substrate, a further cooling process can be performed to reduce the temperature of the bonded product to room temperature.

[0151] The preferred method for introducing heat is one or more of the following: heat transfer under elevated temperature conditions using a convection oven or spray dryer, infrared thermal radiation, near-infrared thermal radiation, microwaves, and objects in contact with the substrate coated with the adhesive of the present invention.

[0152] It is preferable that heat is not introduced to the substrate surface before the substrate surface is brought into contact with another substrate after being treated in step ii.

[0153] Unless otherwise specified, all technical and scientific terms used in this application 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.

[0154] 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.

[0155] The word “and / or” as used in this application refers to one or all of the elements mentioned.

[0156] The terms “comprising” and “including” as used in this application cover situations where only the mentioned elements are present, as well as situations where other unmentioned elements exist in addition to the mentioned elements.

[0157] Unless otherwise stated, the terms “a,” “an,” “an,” and “the” as used in this application are intended to include “at least one” or “one or more.” For example, “a component” refers to one or more components, and therefore more than one component may be considered and may be employed or used in the implementation of the described embodiments.

[0158] All percentages in this application are weight percentages unless otherwise stated.

[0159] All analytical measurements in this application were performed at 23±2℃, unless otherwise stated.

[0160] The number-average molecular weight of the polymeric polyols was determined by gel permeation chromatography with tetrahydrofuran as the mobile phase and polystyrene standard at 40°C.

[0161] Example

[0162] The following will further illustrate the concept, specific structure, and technical effects of the present invention with reference to embodiments, so that those skilled in the art can 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.

[0163] Raw materials and reagents

[0164] Polyester I: Poly(1,4-butanediol adipate), OH value 50 mg KOH / g, number average molecular weight 2250 g / mol, melting temperature approximately 50°C, melting enthalpy 60 J / g (Covestro AG, Germany)

[0165] Polyester II: An aromatic polyester diol composed of 1,6-hexanediol, neopentyl glycol, and phthalic anhydride, HDPOL-320NH, with an OH value of 56 mg KOH / g and a number-average molecular weight of 2000 g / mol. The molar ratio of 1,6-hexanediol to neopentyl glycol is approximately 1:1. Purchased from Shanghai Huide Technology Co., Ltd.

[0166] Polyester III: An aliphatic polyester diol composed of 1,6-hexanediol, neopentyl glycol, and adipic acid, with an OH value of 66 mg KOH / g, a number-average molecular weight of 1700 g / mol, a melting temperature of approximately 24°C, and a melting enthalpy of 30 J / g. Purchased from Covestro AG, Germany.

[0167] Polyester IV: An aromatic polyester diol composed of 1,6-hexanediol and phthalic anhydride, with an OH value of 56 mg KOH / g and a number-average molecular weight of 2000 g / mol, purchased from Covestro AG, Germany.

[0168] Isocyanate I: Hexamethylene diisocyanate, purchased from Covestro AG, Germany

[0169] Isocyanate II: Isophorone diisocyanate, purchased from Covestro AG, Germany.

[0170] A 95 (AAS): 51% by weight aqueous solution of sodium N-(2-aminoethyl)aminoethanesulfonate, purchased from Evonik Chemicals.

[0171] Emulsifier: Lucramul 1820, fatty alcohol poly(ethylene glycol / propylene glycol) ether, purchased from Levaco GmbH, Germany.

[0172] Fungicide: Preventol D7, purchased from Lanxess.

[0173] Thickener: Borchigel Gel L75N, clear liquid, 25% concentration, purchased from Borchers.

[0174] The chemical reagents used in the following examples are analytical grade. All percentages in this invention are weight percentages unless otherwise stated.

[0175] Test methods

[0176] Isocyanate group (NCO) content

[0177] Determined by volume according to DIN-EN ISO 11909:2007.

[0178] Viscosity of waterborne polyurethane dispersion

[0179] Viscosity was tested using a Brookfield DV-II+Pro viscometer according to ISO 3219:1994. 150g of the aqueous polyurethane dispersion was weighed into a glass bottle, and the viscosity was tested at 30 rpm using an S62 rotor at room temperature (20-25°C).

[0180] Solids content of waterborne polyurethane dispersion

[0181] The test was performed using a Mettler Teredo Halogen Moisture Analyzer Excellence HS153. A glass fiber filter paper was placed on a standard aluminum weighing pan, and 1 gram of aqueous polyurethane dispersion was dropped onto the filter paper. A standard drying procedure was used at 120°C, with a stop time of standard grade 5 (1 mg / 140 seconds). That is, the sample was kept heated at 120°C and continuously weighed; if the sample lost less than 1 mg of weight within 140 seconds, the test was stopped, and the percentage of remaining weight was recorded as the solids content.

[0182] Test method for initial adhesive strength under different bonding times

[0183] PVC leather (overall dimensions, 2.5cm*12.5cm; glued and bonded parts, 2.5cm*10cm) and ABS sheet (overall dimensions, 2.5cm*12.5cm; glued and bonded parts, 2.5cm*10cm) were used as test substrates. The ABS surface was cleaned with fibers containing ethanol and then exposed in a fume hood until it was dry.

[0184] Using a 100μm wire rod, apply adhesive to the surfaces of PVC and ABS, then dry at 50℃ for 10 min to remove moisture, and leave at room temperature for 1 hour. Place the sample in a 55℃ oven for 10 min to activate the adhesive film. After removing the activated sample from the oven, leave it at room temperature and then roll it back and forth with a 4.5Kg roller after 0, 3, and 8 min. Test the peel strength (T0, T3, T8) within 1 min. Test the bond strength of the samples using a ZWICK BZ2.5 / TN1 S tensile testing machine. The unbonded parts of the ABS and PVC leather are clamped in the upper and lower jigs of the tensile testing machine and stretched at a 180° peel rate of 300 mm / min. Record the tensile force used at this point as the bond strength. A higher bond strength indicates a stronger bond between the substrates and a more secure adhesion. In this application, the adhesion strength of T0, T3, and T8 is greater than or equal to 0.4 N / mm, 0.3 N / mm, and 0.2 N / mm, respectively, to be considered qualified.

[0185] Heat resistance test method

[0186] PVC leather (overall dimensions, 2.5cm*12.5cm; glued and bonded parts, 2.5cm*10cm) and ABS sheet (overall dimensions, 2.5cm*12.5cm; glued and bonded parts, 2.5cm*10cm) were used as test substrates. The ABS surface was cleaned with fibers containing ethanol and then exposed in a fume hood until it was dry.

[0187] Using a 100μm wire rod, adhesive was applied to the surfaces of PVC and ABS, then dried at 50℃ for 10 min to remove moisture, and left at room temperature for 1 hour. Before testing, the sample was placed at 55℃ for 10 min to heat-activate the adhesive film. After activation, the sample was removed from the oven and placed at room temperature, then immediately rolled back and forth with a 4.5Kg roller for 20 seconds to bond the sample. After bonding, a 100g weight was immediately loaded into an 80℃ oven, suspended at a 90-degree angle to the sample, and the time for complete peeling was recorded. The longer the time, the better the heat resistance. In this application, a peeling time of 2 minutes or more for 100mm is considered acceptable.

[0188] Other test methods have been described in other parts of the specification or are commonly used in the field.

[0189] Preparation of waterborne polyurethane dispersions

[0190] Example 1 (E1)

[0191] 54.64 g of polyester I and 30.91 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, followed by the addition of 0.40 g of 1,4-butanediol, and cooled while stirring. 6.68 g of isocyanate I and 4.42 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.66 g of AAS and 0.69 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating acetone by distillation, 7g of aqueous solution containing 0.74g of external emulsifier and 0.20g of bactericide was added to obtain aqueous polyurethane dispersion 1 with a solid content of 50.1%, a viscosity of 277mPa·s, a pH of 6.3, and a weight-average molecular weight of 55,900g / mol.

[0192] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0193] Example 2 (E2)

[0194] 67.36 g of polyester I and 19.96 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour while cooling with stirring. 6.04 g of isocyanate I and 3.99 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.2% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.12 g of AAS and 0.53 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.20 g of bactericide was added. Aqueous polyurethane dispersion 2 was obtained with a solids content of 50.6%, a pH of 6.6, a viscosity of 56 mPa·s, and a weight-average molecular weight of 72,100 g / mol.

[0195] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0196] Example 3 (E3) )

[0197] 50.46 g of polyester I and 36.70 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 6.17 g of isocyanate I and 4.08 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.2% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.26 g of AAS and 0.40 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.20 g of bactericide was added. Aqueous polyurethane dispersion 3 was obtained with a solids content of 50.3%, a viscosity of 39 mPa·s, a pH of 6.6, and a weight-average molecular weight of 61,000 g / mol.

[0198] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0199] Example 4 (E4)

[0200] 79.43 g of polyester I and 7.85 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 5.93 g of isocyanate I and 3.92 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.15% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.16 g of AAS and 0.72 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.2 g of bactericide was added. Aqueous polyurethane dispersion 4 was obtained, with a solids content of 50.7%, a viscosity of 1880 mPa·s, a pH of 6.7, and a weight-average molecular weight of 69,300 g / mol.

[0201] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0202] Example 5 (E5) )

[0203] 18.96 g of polyester I and 67.41 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 6.37 g of isocyanate I and 4.21 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.25% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.8 g of AAS and 0.6 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.2 g of bactericide was added. Aqueous dispersion 5 was obtained with a solids content of 50.9%, a viscosity of 480 mPa·s, a pH of 6.5, and a weight-average molecular weight of 40,600 g / mol.

[0204] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0205] Example 6 (E6)

[0206] 54.74 g of polyester I and 30.96 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, followed by the addition of 0.40 g of 1,4-butanediol, and cooled while stirring. 6.69 g of isocyanate I and 4.42 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.44 g of AAS and 0.63 g of diethanolamine was added to the acetone solution containing the prepolymer, and the mixture was stirred vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.74 g of external emulsifier and 0.2 g of bactericide was added. A waterborne polyurethane dispersion 6 was obtained, with a solid content of 49.7%, a pH value of 6.6, a viscosity of 218 mPa·s, and a weight-average molecular weight of 40,700 g / mol.

[0207] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0208] Example 7 (E7)

[0209] 79.70 g of polyester I and 7.87 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 5.95 g of isocyanate I and 3.94 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.15% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.18 g of AAS and 0.39 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.20 g of bactericide was added. Aqueous polyurethane dispersion 7 was obtained with a solids content of 50.6%, a viscosity of 400 mPa·s, a pH of 6.6, and a weight-average molecular weight of 104,300 g / mol.

[0210] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0211] Example 8 (E8)

[0212] 79.72 g of polyester I and 7.91 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour while cooling with stirring. 6.05 g of isocyanate I and 3.97 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.2% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.30 g of AAS and 0.2 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.8 g of external emulsifier and 0.2 g of bactericide was added. Aqueous polyurethane dispersion 8 was obtained with a solids content of 50.2%, a viscosity of 175 mPa·s, a pH of 6.4, and a weight-average molecular weight of 205,500 g / mol.

[0213] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0214] Comparative Example 1 (CE1)

[0215] 53.03 g of polyester I and 32.05 g of polyester III were dehydrated at 110 °C and 100 mbar for 1 hour, followed by the addition of 0.42 g of 1,4-butanediol, and cooled while stirring. 7.13 g of isocyanate I and 4.71 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.4% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.26 g of AAS and 0.69 g of diethanolamine was added to the acetone solution containing the prepolymer, and the mixture was stirred vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.64 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 1 was obtained, with a solids content of 50.5%, a viscosity of 77 mPa·s, a pH of 6.3, and a weight-average molecular weight of 65,800 g / mol.

[0216] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0217] Comparative Example 2 (CE2)

[0218] 87.49 g of polyester I was dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 5.88 g of isocyanate I and 3.89 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.18% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 1.94 g AAS and 0.72 g diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g external emulsifier and 0.2 g bactericide was added. A comparative aqueous polyurethane dispersion 2 was obtained, with a solids content of 50.6%, a viscosity of 42 mPa·s, a pH of 6.5, and a weight-average molecular weight of 72,300 g / mol.

[0219] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0220] Comparative Example 3 (CE3)

[0221] 83.57 g of polyester I and 3.91 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 5.91 g of isocyanate I and 3.91 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.15% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.16 g of AAS and 0.55 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 3 was obtained, with a solids content of 49.6%, a viscosity of 105 mPa·s, a pH of 6.2, and a weight-average molecular weight of 76,500 g / mol.

[0222] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0223] Comparative Example 4 (CE4) )

[0224] 9.58 g of polyester I and 76.65 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 6.44 g of isocyanate I and 4.26 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.82 g of AAS and 0.60 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 4 was obtained, with a solids content of 50.3%, a viscosity of 55 mPa·s, a pH of 6.3, and a weight-average molecular weight of 43,300 g / mol.

[0225] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0226] Comparative Example 5 (CE5)

[0227] 86.19 g of polyester II was dehydrated at 110 °C and 100 mbar for 1 hour, while cooling with stirring. 6.52 g of isocyanate I and 4.31 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.62 g of AAS and 0.61 g of diethanolamine was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.86 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 5 was obtained, with a solids content of 50.4%, a viscosity of 48 mPa·s, a pH of 6.5, and a weight-average molecular weight of 40,000 g / mol.

[0228] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0229] Comparative Example 6 (CE6) )

[0230] 73.44 g of polyester I and 13.06 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, followed by the addition of 0.39 g of 1,4-butanediol, and cooled while stirring. 6.58 g of isocyanate I and 4.35 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.48 g of AAS was added to the acetone solution containing the prepolymer while stirring vigorously for 30 min, and then the mixture was dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.73 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 6 was obtained, with a solid content of 50.7%, a viscosity of 95 mPa·s, a pH of 6.4, and a weight-average molecular weight of 304,200 g / mol.

[0231] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0232] Comparative Example 7 (CE7)

[0233] 54.33 g of polyester I and 30.73 g of polyester II were dehydrated at 110 °C and 100 mbar for 1 hour, followed by the addition of 0.40 g of 1,4-butanediol, and cooled while stirring. 6.64 g of isocyanate I and 4.39 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.42 g of AAS and 1.25 g of diethanolamine was added to the acetone solution containing the prepolymer, and the mixture was stirred vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.85 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 7 was obtained, with a solids content of 50.5%, a viscosity of 5840 mPa·s, a pH value of 7.6, and a weight-average molecular weight of 33,800 g / mol.

[0234] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0235] Comparative Example 8 (CE8)

[0236] 70.25 g of polyester I and 15.72 g of polyester IV were dehydrated at 110 °C and 100 mbar for 1 hour, followed by the addition of 0.40 g of 1,4-butanediol, and cooled while stirring. 6.60 g of isocyanate I and 4.36 g of isocyanate II were added at 60 °C, and the mixture was stirred at 80-90 °C until an isocyanate content of 1.3% was achieved. The mixture was then dissolved in 150 g of acetone and cooled to 40 °C to obtain a prepolymer solution. A 10 g aqueous solution of 2.36 g of AAS and 0.44 g of diethanolamine was added to the acetone solution containing the prepolymer, and the mixture was stirred vigorously for 30 min. The mixture was then dispersed by adding 83 g of water. After separating the acetone by distillation, a 7 g aqueous solution of 0.85 g of external emulsifier and 0.2 g of bactericide was added. A comparative aqueous polyurethane dispersion 8 was obtained, with a solid content of 50.1%, a viscosity of 36 mPa·s, a pH value of 6.4, and a weight-average molecular weight of 75,360 g / mol.

[0237] The obtained aqueous polyurethane 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 approximately 5000 mPa·s.

[0238] Performance testing

[0239] The obtained samples were subjected to initial adhesion and heat resistance tests at different bonding times according to the test method, and the results are as follows.

[0240] Table 1 shows the test results of initial adhesion and heat resistance of Examples 1-8 (E1-E8) at different bonding times.

[0241] Table 1

[0242]

[0243] The samples obtained by bonding with the adhesives of Examples 1-8 of this invention exhibited good initial adhesion, holding time, and heat resistance at an activation temperature of 55°C. This indicates that the adhesives formulated with the waterborne polyurethane dispersions of Examples 1-8 have good initial adhesion, holding time, and heat resistance.

[0244] Table 2 shows the test results of initial adhesion and heat resistance of Comparative Examples 1-8 (CE1-CE8) at different bonding times.

[0245] Table 2

[0246]

[0247] Comparative Example CE1 demonstrates that the adhesive prepared from an aqueous polyurethane dispersion containing only aliphatic polyester polyols cannot achieve satisfactory initial adhesion and holding time at the same activation temperature.

[0248] Comparative example CE2-5 shows that if the proportion of aromatic polyester polyols and crystalline aliphatic polyester polyols in the waterborne polyurethane dispersion exceeds a certain range, the adhesive prepared from it cannot obtain qualified initial adhesion and holding time at the same activation temperature.

[0249] Comparative Example CE6-7 illustrates that when the molecular weight of polyurethane and / or polyurethane urea in the waterborne polyurethane dispersion is too high or too low, the resulting adhesive cannot obtain qualified initial adhesion and holding time at the same activation temperature.

[0250] Comparative example CE8 shows that when the waterborne polyurethane dispersion contains a diaromatic polyester polyol, a product with sufficient holding time cannot be obtained, and the initial bond strength at T8 does not meet the requirements.

[0251] It will be readily apparent to those skilled in the art that this invention is not limited to the specific details described above, and that it may be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments described should be considered illustrative rather than restrictive in any way, and the scope of the invention is determined by the claims rather than the foregoing description; and thus any modifications that fall within the meaning and scope of the equivalents of the claims should be considered part of this invention.

Claims

1. An aqueous polyurethane dispersion, characterized in that, The product comprises polyurethane and / or polyurethane urea, wherein the polyurethane and / or polyurethane urea are obtained by reacting a system comprising the following components: a) At least one aromatic polyester polyol component, which is a reaction product of at least one aromatic polyacid and / or aromatic anhydride with at least two polyols, wherein component a) is 5-75% by weight of the solids of the aqueous polyurethane dispersion. b) At least one crystalline aliphatic polyol component, which is 10-83% by weight of the solids of the aqueous polyurethane dispersion. c) At least one polyisocyanate component; d) At least one hydrophilic compound component 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; e) Optional small molecule alcohol components, different from components a) and b), with a molecular weight of 32-400 g / mol; f) Other isocyanate reactive compound components, said reactive compound including one or more of water, amine chain extenders, and amine end-capping agents. The polyurethane and / or polyurethane urea have a weight-average molecular weight of 35,000-250,000 g / mol.

2. The aqueous polyurethane dispersion according to claim 1, characterized in that, The aqueous polyurethane dispersion has a solid content of 15-70% by weight, preferably 30-65% by weight, and more preferably 40-60% by weight.

3. The aqueous polyurethane dispersion according to claim 1 or 2, characterized in that, The weight-average molecular weight of the aqueous polyurethane dispersion is 35,000-210,000 g / mol.

4. The aqueous polyurethane dispersion according to any one of claims 1-3, characterized in that, The aromatic polyacids and / or aromatic anhydrides used to prepare component a) are independently selected from phthalic anhydride, phthalic acid, isophthalic acid and terephthalic acid; The polyol used to prepare component a) is selected from ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, butanediol, neopentyl glycol, hexanediol, heptahydrate, nonanediol, and decanediol, preferably a mixture of neopentyl glycol and hexanediol, with the molar ratio of neopentyl glycol to hexanediol preferably being 9 / 1 to 1 / 9, more preferably 6 / 1 to 1 / 6, and most preferably 3 / 1 to 1 / 3. The preferred component a) is 7-70% by weight of the solids of the aqueous polyurethane dispersion, preferably 15-60% by weight.

5. The aqueous polyurethane dispersion according to any one of claims 1-4, characterized in that, The number average molecular weight of component a) is 100-20,000 g / mol, preferably 500-5,000 g / mol, more preferably 500-4,000 g / mol, and / or the functionality is 1.5-4.0, preferably 1.8-2.5, more preferably 2.

6. The aqueous polyurethane dispersion according to any one of claims 1-5, characterized in that, Component b) is selected from polyester polyols, polycaprolactone polyols, and polycarbonate polyols. The enthalpy of fusion of component b) is greater than 10 J / g, preferably greater than 20 J / g, more preferably 30-130 J / g, and most preferably 40-100 J / g. Preferably, component b) is 15-81% by weight of the solids of the aqueous polyurethane dispersion, preferably 20-80% by weight.

7. The aqueous polyurethane dispersion according to any one of claims 1-6, characterized in that, The number average molecular weight of component b) is 100-20,000 g / mol, preferably 500-5000 g / mol, more preferably 500-4000 g / mol, and / or the functionality is 1.5-4.0, preferably 1.8-2.5, more preferably 2.

8. The aqueous polyurethane dispersion according to any one of claims 1-7, characterized in that, The weight ratio of component a) to component b) is 6 / 1-1 / 15, preferably 5 / 1-1 / 11, more preferably 2 / 1-1 / 9, and most preferably 1 / 1-1 / 6.

9. The aqueous polyurethane dispersion according to any one of claims 1-8, characterized in that, Component c) is selected from diisocyanates represented by 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. Preferably, Y represents a divalent aliphatic hydrocarbon group containing 4-12 carbon atoms and a divalent alicyclic hydrocarbon group containing 6-15 carbon atoms. 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. Preferably, the amount of component c) is 5-80% by weight of the solids of the aqueous polyurethane dispersion, preferably 5-70% by weight, and more preferably 5-50% by weight.

10. The aqueous polyurethane dispersion according to any one of claims 1-9, characterized in that, Component d) The NCO reactive functional group of the hydrophilic compound is hydroxyl and / or amino. Preferably, the hydrophilic compound is an ionic or potential ionic compound, preferably having a carboxyl or carboxylate group and / or sulfonate group and / or amino group, more preferably selected from 6-aminohexanoate, lysine, N-(2-aminoethyl)-β-alanine, 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamine)-1-propanesulfonate, even more preferably selected from 2-[(2-aminoethyl)amino]ethanesulfonate and 3-(cyclohexylamine)-1-propanesulfonate, most preferably selected from sodium 2-[(2-aminoethyl)amino]ethanesulfonate and sodium 3-(cyclohexylamine)-1-propanesulfonate. Preferably, the amount of component d) is 0.1-5% by weight of the solids of the aqueous polyurethane dispersion, preferably 0.3-3% by weight, more preferably 0.5-1.5% by weight.

11. The aqueous polyurethane dispersion according to any one of claims 1-10, characterized in that, Component e) is selected from 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, 1,4-Butanediol, 1,3-Butanediol, 2,3-Butanediol, 1,5-Pentanediol, 1,6-Hexanediol, 2-Dimethyl-1,3-Propanediol, 1,4-Dimethylolcyclohexane, 1,8-Octanediol, 1,10-Decanediol, 1,12-Dodecanediol, Neopentylene glycol, 1,4-Cyclohexanediol, 1,4-Cyclohexanediol, 1,4-,1,3-,1,2-Dihydroxybenzene, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), tricyclodecanediethanol, trimethylolpropane, glycerol, pentaerythritol, and dipentanetriol. Preferably, the amount of component e) is 0-3% by weight of the solids of the aqueous polyurethane dispersion, preferably 0-2% by weight, and more preferably 0-1% by weight.

12. The aqueous polyurethane dispersion according to any one of claims 1-11, characterized in that, Component f) is selected from water, hydrazine, acylhydrazine, aliphatic or alicyclic monoamine, diamine or triamine or hydroxyl functional group monoamine or diamine, with preferred amines being 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.

13. A coating, adhesive, sealant, or ink, characterized in that, Prepared using the aqueous polyurethane dispersion according to any one of claims 1-12.

14. An bonding method comprising the following steps: i. Applying the adhesive according to claim 13 to at least one surface of the substrate; ii. Heat and dry the surface of the substrate to which the adhesive has been applied at a temperature ranging from 30°C to 59°C; and iii. Bring another substrate into contact with the surface of the substrate treated in step ii to obtain an adhesive product.

15. An article characterized in that, Articles including those with a substrate coated, bonded, sealed or printed with an aqueous polyurethane dispersion according to any one of claims 1-13.

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