Aqueous polyurethane-polyurea dispersions

Abstract

The invention relates to aqueous polyurethane-polyurea dispersions comprising polyurethane-polyurea, to a method for the production thereof, and to the use thereof, in particular in the field of coatings, adhesives or inks, and to objects or articles obtained by coating, bonding, sealing or printing with said aqueous polyurethane-polyurea dispersions. The polyurethane-polyurea of the water-based polyurethane-polyurea dispersion containing the polyurethane-polyurea is characterized by comprising two kinds of polyisocyanates; a polymer; a polyol; the present invention is obtained by reacting a system of a silane compound and a hydrophilic compound comprising 2 to 3 isocyanate-reactive groups. The waterborne polyurethane-polyurea dispersion disclosed by the invention has good adhesive force and hydrolysis resistance.

Description

Technical Field

[0001] The present invention relates to aqueous polyurethane-polyurea dispersions and their preparation methods and uses, especially in the fields of coatings, adhesives or inks, and to objects or articles obtained by coating, bonding, sealing or printing with said aqueous polyurethane-polyurea dispersions. Prior Art

[0002] Aqueous polyurethane-polyurea dispersions can be widely used in coatings, adhesives, sealants and printing inks. Compared with traditional solvent-based polyurethanes, they have the advantages of environmental protection performance, non-flammable and non-explosive properties, safe storage and high solid content. However, compared with solvent-based polyurethanes, aqueous polyurethane-polyurea dispersions contain hydrolyzable groups, which are prone to hydrolysis when stored under environmental conditions. At the same time, metal ions present in the system (such as those introduced in the catalyst) can also promote the hydrolysis of the hydrolyzable groups in the aqueous polyurethane-polyurea dispersion, which will reduce their application performance. Specifically, it may affect their adhesion, stain resistance, scratch resistance, impact resistance, elongation at break and wash resistance in the field of coating products, and may affect the paintable properties, heat resistance and hydrolysis resistance of sealant and adhesive products in the field of sealant and adhesive products.

[0003] In patents such as DE 19954500, DE 4410557 or EP 792908, it is proposed to introduce carboxylates into the polyurethane-polyurea dispersion and then blend it with carbodiimide to improve adhesion, where the carboxylate is obtained by adding dimethylolpropionic acid to the polyurethane-polyurea. The reactivity of the carboxyl group with carbodiimide in the above reaction is low.

[0004] US5066705 describes the preparation of a weather-resistant aqueous paint for plastic substrates by using a carboxyl group-containing polymer, a carboxyl group-containing polyurethane and polycarbodiimide.

[0005] CN 108250390 B describes the preparation of a self-crosslinkable aqueous polyurethane dispersion by adding a non-hindered bifunctional silane and introducing a terminal polyethoxy chain segment as a hydrophile.

[0006] CN 109081897 A describes the preparation of a self-crosslinkable aqueous polyurethane dispersion by adding a non-hindered bifunctional, monofunctional silane and introducing a terminal polyethoxy chain segment as a hydrophile.

[0007] EP 3026071 A1 describes a method for preparing an aqueous polyurethane dispersion, which is obtained from a mixture comprising at least one easily crystallizable polyester polyol and at least one polyether polyol, wherein the polyether polyol is a polyalkylene glycol homopolymer or copolymer containing ethylene oxide units.

[0008] WO 2016135162 A1 describes a method for preparing an aqueous peptide-functionalized polyurethane dispersion (PUD) that can be used as an adhesive, especially for metal surfaces, by reacting a maleimide-capped polyurethane prepolymer with one or more peptides. The adsorption quality of the peptide on the substrate surface is enhanced by the coupling reaction between the amino acid side chains in the peptide and the maleimide groups. The reaction mixture contains at least a polyether polyol and a polyester polyol, where the polyether polyol can be a polyalkylene glycol homopolymer or copolymer, and the polyester polyol can be a crystalline / semicrystalline polyol.

[0009] US10640702 B describes a method for preparing coated particles and their use as proppants in hydraulic fracturing to optimize capital and equipment costs and improve production efficiency. The coated particles consist of matrix particles with a particle size not greater than 3 mesh and a coating containing a crystalline or semicrystalline polyester / polyurethane with a melting temperature of at least 35 °C and modified with an aminosilane. The crystalline or semicrystalline polyester / polyurethane may contain a mono-functional or di-functional polyether polyol obtained by the polymerization of ethylene oxide or the copolymerization of ethylene oxide and propylene oxide. Summary of the Invention

[0011] The object of the present invention is to provide an aqueous polyurethane-polyurea dispersion, a method for preparing the same and its uses, especially in the fields of coatings, adhesives or inks, and objects or articles obtained by coating, bonding, sealing or printing with the aqueous polyurethane-polyurea dispersion.

[0012] In the aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to the present invention, the polyurethane-polyurea is obtained by the reaction of a system containing the following components:

[0013] a. At least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, where the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, where the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate is from 10:1 to 20:1;

[0014] b. A polymer having the structure of formula I:

[0015]

[0016] where n is from 10 to 75, R1 is an alkyl group containing 1 to 10 carbon atoms, and R2 is a moiety containing at least two isocyanate-reactive groups;

[0017] c. A polyol different from component b), which has a hydroxyl functionality of 1.5 to 4;

[0018] d. A silane compound containing an isocyanate-reactive group and at least two methoxy and / or ethoxy groups attached to a silicon atom;

[0019] e. A hydrophilic compound different from polymer b), which contains 2 to 3 isocyanate-reactive groups, wherein the hydrophilic group of the hydrophilic compound contains one or more of an ionic group, a latent ionic group, and a non-ionic group; and

[0020] Optionally,

[0021] f. A compound containing 1 to 3 amino groups and / or hydroxyl groups, preferably 1 to 3 amino groups.

[0022] According to one aspect of the present invention, there is provided a method for preparing an aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to the present invention, which comprises the following steps:

[0023] i. Reacting some or all of component a), a polymer of component b) having the structure of formula I, and a polyol of component c) different from component b) to obtain a prepolymer, wherein component a) is at least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, and the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, and the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate is from 10:1 to 20:1;

[0024] ii. Reacting the prepolymer, component d) the silane compound, component e) a hydrophilic compound different from polymer b) containing 2 to 3 isocyanate-reactive groups, and optionally component f) a compound containing 1 to 3 amino groups and / or hydroxyl groups, preferably 1 to 3 amino groups, to obtain the polyurethane-polyurea; and

[0025] iii. Introducing water before, during, or after step ii to obtain the aqueous polyurethane-polyurea dispersion.

[0026] According to another aspect of the present invention, there is provided a coating, adhesive, or ink, which contains an aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to the present invention.

[0027] According to still another aspect of the present invention, there is provided the use of an aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to the present invention for preparing a coated product, an adhered product, or a printed product.

[0028] According to another aspect of the present invention, there is provided an object or article comprising a substrate prepared, coated, adhered, sealed or printed with an aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea according to the present invention.

[0029] According to still another aspect of the present invention, there is provided a printing method comprising applying an aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea according to the present invention to the surface of a substrate and then curing.

[0030] According to still another aspect of the present invention, there is provided a printed product comprising a substrate and a coating formed by applying an aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea according to the present invention to the substrate.

[0031] The aqueous polyurethane-polyurea dispersion of the present invention has good adhesion and hydrolysis resistance and is suitable for coatings, adhesives or inks, especially in adhesives, particularly in shoe adhesives.

[0032] Embodiments

[0033] The present invention provides an aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea obtained by the reaction of a system comprising the following components:

[0034] a. At least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, wherein the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, wherein the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate is from 10:1 to 20:1;

[0035] b. A polymer having the structure of formula I:

[0036]

[0037] wherein n is from 10 to 75, R1 is an alkyl group containing 1 to 10 carbon atoms, and R2 is a moiety containing at least two isocyanate-reactive groups;

[0038] c. A polyol different from component b) having a hydroxyl functionality of 1.5 to 4;

[0039] d. A silane compound containing one isocyanate-reactive group and at least two methoxy and / or ethoxy groups attached to a silicon atom;

[0040] e. A hydrophilic compound different from polymer b) containing 2 to 3 isocyanate-reactive groups, wherein the hydrophilic group of the hydrophilic compound comprises one or more of an ionic group, a latent ionic group and a non-ionic group; and

[0041] Optionally,

[0042] f. A compound containing 1 to 3 amino groups and / or hydroxyl groups, preferably 1 to 3 amino groups.

[0043] The present invention further provides a method for preparing an aqueous polyurethane-polyurea dispersion, and its uses, especially in the fields of coatings, adhesives or inks, and objects or articles obtained by coating, bonding, sealing or printing with the aqueous polyurethane-polyurea dispersion.

[0044] The term "curing" as used herein refers to the process of a liquid material changing from a liquid state to a cured state.

[0045] The term "coating" as used herein refers to a material that can be applied to the surface of an object by various methods to form a continuous solid coating with strong adhesion and certain strength.

[0046] The term "adhesive" as used herein refers to a chemical material that can be applied to the surface of an object by various methods to form a coating on the object itself or on the surface of one object and the surface of another object, and bond the object itself or bond the surface of one object to the surface of another object, and is also used as a synonym for binder and / or sealant and / or adhesive.

[0047] The term "polyurethane-polyurea" as used herein refers to polyurethane and / or polyurethane urea and / or polyurea.

[0048] The term "aqueous polyurethane-polyurea dispersion" as used herein refers to an aqueous polyurethane dispersion and / or an aqueous polyurethane urea dispersion and / or an aqueous polyurea dispersion.

[0049] The content of polyurethane-polyurea in the aqueous polyurethane-polyurea dispersion described herein is equivalent to the content of the solid components in the aqueous polyurethane-polyurea dispersion.

[0050] The term "solid components" as used herein refers to the solid content or the active ingredient.

[0051] The term "isocyanate-reactive compound" as used herein refers to a component containing a group reactive to an isocyanate group, that is, a component containing a group having Zerewitinoff active hydrogen, where the definition of Zerewitinoff active hydrogen refers to Chemical Dictionary( Chemie Lexikon), 10th Edition, Georg Thieme Verlag Stuttgart, 1996. Generally, a group having Zerewitinoff active hydrogen is understood in the art to mean a hydroxyl group (OH), an amino group (NH x ) and a mercapto group (SH).

[0052] As used herein, the term "isocyanate-reactive group" refers to a group that is reactive with an isocyanate group, i.e., a group having Zerewitinoff active hydrogen, wherein the definition of Zerewitinoff active hydrogen is referenced Chemical Dictionary( Chemie Lexikon), 10th Edition, Georg Thieme Verlag Stuttgart, 1996. Generally, a group having Zerewitinoff active hydrogen is understood in the art to mean a hydroxyl group (OH), an amino group (NH x ) and a mercapto group (SH).

[0053] Waterborne polyurethane-polyurea dispersion

[0054] Based on the total weight of the aqueous polyurethane-polyurea dispersion, the amount of organic solvent in the aqueous polyurethane-polyurea dispersion is preferably less than 1% by weight.

[0055] Based on the total weight of the aqueous polyurethane-polyurea dispersion, the content of the solid component of the aqueous polyurethane-polyurea dispersion is preferably 15% to 70% by weight, most preferably 30% to 60% by weight, which is measured using an HS153 moisture analyzer from Mettler Toledo according to DIN-EN ISO 3251:2019, wherein the heating temperature is 120 °C, and the test end point is determined when the weight loss of the sample is less than 1 mg / 140 s.

[0056] The pH value of the aqueous polyurethane-polyurea dispersion is from 4 to 11, preferably from 5 to 9, most preferably from 6.0 to 7.5, which is measured at 23 °C using a PB-10 pH meter from Sartorius, Germany according to DIN ISO 976:2016-12.

[0057] The average particle size of the aqueous polyurethane-polyurea dispersion is preferably from 20 nm to 750 nm, more preferably from 50 nm to 450 nm, and most preferably from 100 nm to 250 nm. It is determined by laser correlation (laser particle size analyzer) using a ZEN 1600 tester from Malvern, UK according to the test method of ISO 13321:1996. One drop (about 0.05 g) of the sample is added to 50 ml of ultrapure water, and the diluted sample is tested at 23.0 ± 0.1 °C. Material: polystyrene latex (RI: 1.590; absorption rate: 0.010), dispersant: water (temperature: 23.0 °C; viscosity: 0.9308 cP; RI: 0.330), equilibration time: 60 seconds, using disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: yes, analysis model: general (normal resolution), measurement angle: 173° backscattering (NIBS default), runs: 3, run duration: 10 seconds, measurements: 10.

[0058] The viscosity of the aqueous polyurethane-polyurea dispersion is preferably from 30 mPa·s to 6000 mPa·s, more preferably from 1000 mPa·s to 3500 mPa·s. It is measured at 23 °C using a DV-II+Pro. rotational viscometer from Brookfield according to ISO2555:2018. Rotor type: s 62-64, speed: 30 RPM, test temperature: 23 °C.

[0059] Component a) Polyisocyanate

[0060] The isocyanate functionality of the polyisocyanate is preferably not less than 2, more preferably from 2 to 4, and most preferably 2.

[0061] Component a) the at least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, wherein the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, wherein the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably a mixture of hexamethylene diisocyanate and isophorone diisocyanate.

[0062] The weight ratio of the aliphatic polyisocyanate to the cycloaliphatic polyisocyanate is preferably from 10:1 to 20:1.

[0063] The aliphatic polyisocyanates are preferably one or more of hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2,2-dimethylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl) ether, lysine methyl ester diisocyanate, lysine triisocyanate, bis(isocyanatomethyl) sulfide, bis(isocyanatoethyl) sulfide, bis(isocyanatopropyl) sulfide, bis(isocyanatohexyl) sulfide, bis(isocyanatomethyl) sulfone, bis(isocyanatomethyl) disulfide, bis(isocyanatoethyl) disulfide, bis(isocyanatopropyl) disulfide, bis(isocyanatomethylthio)methane, bis(isocyanatoethylthio)methane, bis(isocyanatomethylthio)ethane, bis(isocyanatoethylthio)ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris(isocyanatomethylthio)propane, 1,2,3-tris(isocyanatoethylthio)propane, 3,5-dithia-1,2,6,7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithia-1,7-heptanediisocyanate, 2,5-diisocyanatomethylthiophene and isocyanatoethylthio-2,6-dithia-1,8-octanediisocyanate; most preferably hexamethylene diisocyanate.

[0064] The alicyclic polyisocyanates are preferably one or more of 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis(isocyanatomethyl)-1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane, norbornane diisocyanate (NBDI), hydrogenated xylylene diisocyanate (H6XDI) and 1,4-cyclohexylene diisocyanate (H6PPDI); most preferably isophorone diisocyanate.

[0065] The aliphatic polyisocyanate and the alicyclic polyisocyanate are most preferably hexamethylene diisocyanate and isophorone diisocyanate.

[0066] The weight ratio of hexamethylene diisocyanate to isophorone diisocyanate is preferably from 10:1 to 20:1.

[0067] Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component a) is preferably in an amount of 9% to 18% by weight, most preferably 10% to 12% by weight.

[0068] Component b) Polymer having the structure of formula I

[0069] In formula I, n is from 10 to 75 and may or may not be an integer, preferably from 10 to 40, more preferably from 10 to 30.

[0070] The at least two isocyanate-reactive groups are selected from at least two amino groups, at least two hydroxyl groups, or at least one amino group and at least one hydroxyl group.

[0071] In the case where the polymer of component b) having the structure of formula I contains three or more isocyanate-reactive groups, the isocyanate-reactive groups can be two amino groups and one or more amino groups or other isocyanate-reactive groups, or can be two hydroxyl groups and one or more hydroxyl groups or other isocyanate-reactive groups, or can also be one amino group, one hydroxyl group and one or more amino groups, hydroxyl groups or other isocyanate-reactive groups.

[0072] The polymer having the structure of formula I is most preferably one or more of the polymer having the structure of formula II and the polymer having the structure of formula III.

[0073]

[0074] Wherein in formula II, a is from 10 to 75 and may or may not be an integer, b is from 0 to 50 and may or may not be an integer; in formula III, x is from 10 to 75 and may or may not be an integer, y is from 1 to 50 and may or may not be an integer.

[0075] The polymer of component b) having the structure of formula I has a number average molecular weight preferably from 500 g / mol to 4000 g / mol, most preferably from 600 g / mol to 1500 g / mol, which is measured by gel permeation chromatography, wherein tetrahydrofuran is used as the mobile phase, and the molecular weight is calculated based on polystyrene having a molecular weight of 200 or higher as the standard, and measured with a differential refractive index detector (RI detector).

[0076] The polymer of component b) having the structure of formula I preferably has a functionality of 2.

[0077] Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, the polymer of component b) having the structure of formula I is preferably in an amount of 0.9% to 4% by weight, most preferably 1% to 2% by weight.

[0078] Component c) Polyol different from component b

[0079] The polyol different from component b) is preferably one or more of a diol having a number average molecular weight of 62 to 15,000 and a polyol having a number average molecular weight of 62 to 15,000, more preferably one or more of a diol having a number average molecular weight of 62 to 5,000 and a triol having a number average molecular weight of 92 to 5,000, and most preferably one or more of a polyester polyol having 2 to 3 hydroxyl groups with a number average molecular weight of 500 to 2,500, a polycarbonate polyol having 2 to 3 hydroxyl groups with a number average molecular weight of 400 to 2,500, a polyether polyol having 2 to 3 hydroxyl groups with a number average molecular weight of 200 to 2,500, a polylactone polyol having 2 to 3 hydroxyl groups with a number average molecular weight of 250 to 2,500, and a low molecular weight alcohol, wherein the number average molecular weight is measured by gel permeation chromatography, wherein tetrahydrofuran is used as the mobile phase, and the molecular weight is calculated based on polystyrene having a molecular weight of 200 or higher as the standard, and measured with a differential refractive index detector (RI detector).

[0080] The polyether polyol having 2 to 3 hydroxyl groups with a number average molecular weight of 200 to 2,500 is preferably a polytetrahydrofuran polyol having 2 to 3 hydroxyl groups with a number average molecular weight of 200 to 2,500.

[0081] The polyol different from component b) has a melting enthalpy preferably not less than 15 J / g, most preferably 25 J / g to 100 J / g, which is obtained from the first heating curve from 20 °C to 100 °C by DSC according to DIN 65467, method A, wherein the loading volume is 10 - 20 mg, and the heating rate is 20 K / min.

[0082] Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component c) is preferably in an amount of 5% to 94% by weight, most preferably 70% to 90% by weight.

[0083] Component d) Silane compound

[0084] The silane compound contains one isocyanate-reactive group and at least two methoxy groups attached to the silicon atom; or the silane contains one isocyanate-reactive group and at least two ethoxy groups attached to the silicon atom; or the silane contains one isocyanate-reactive group and at least one methoxy group attached to the silicon atom and one ethoxy group attached to the silicon atom.

[0085] This silane compound most preferably contains only one isocyanate-reactive group and at least two methoxy and / or ethoxy groups attached to the silicon atom.

[0086] Component d) The silane compound is preferably one or more of bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-aminopropyl(diethoxy)methylsilane, and 3-aminopropylmethyldimethoxysilane, and most preferably one or more of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, and 3-aminopropylmethyldimethoxysilane.

[0087] In addition, the corresponding aspartate esters (Formula IV) synthesized from the above amino-functional silanes and esters of unsaturated dicarboxylic acids such as maleic acid can be used.

[0088]

[0089] Wherein X is the same or different methoxy-, ethoxy-, methyl-, or ethyl-, provided that at least two groups are methoxy- and / or ethoxy-; wherein Q is an alkyl group, preferably n-propyl-, and Z is an alkoxy group, preferably methoxy- or ethoxy-.

[0090] Further preferred compounds are diethyl N-(3-triethoxysilylpropyl)aspartate, diethyl N-(3-trimethoxysilylpropyl)aspartate, and diethyl N-(3-dimethoxymethylsilylpropyl)aspartate.

[0091] Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component d) the silane compound is preferably in an amount of 0.12% to 0.7% by weight, and most preferably 0.18% to 0.4% by weight.

[0092] Component e) Hydrophilic compound containing 2 to 3 isocyanate-reactive groups

[0093] The hydrophilic group of this hydrophilic compound preferably contains one or more of ionic groups, latent ionic groups, and non-ionic groups.

[0094] Component e) The hydrophilic compound containing 2 to 3 isocyanate-reactive groups is preferably one or more of N-(2-aminoethyl)-2-aminoethanesulfonate, dimethylolpropionate, and N-(2-aminoethyl)-2-aminoethanecarboxylate.

[0095] Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component e) is preferably in an amount of 0.2% to 50% by weight, and most preferably 1% to 5% by weight.

[0096] Component f) Compound containing 1 to 3 amino groups and / or hydroxyl groups, preferably 1 to 3 amino groups

[0097] Component f) compounds containing 1 to 3 amino groups and / or hydroxyl groups preferably contain at least one amino group; further preferably, it is one or more aliphatic monoamines, cycloaliphatic monoamines, aliphatic primary and / or secondary diamines, aliphatic primary and / or secondary triamines, aliphatic primary and / or secondary amino alcohols, cycloaliphatic primary and / or secondary diamines, cycloaliphatic primary and / or secondary triamines, cycloaliphatic primary and / or secondary amino alcohols; most preferably, it is one or more of isophorone diamine, N-(2-hydroxyethyl)ethylenediamine, and diethanolamine.

[0098] Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component f) is preferably in an amount not greater than 10% by weight, and most preferably in the range of 0.5% to 3% by weight.

[0099] Method for preparing a waterborne polyurethane-polyurea dispersion comprising polyurethane-polyurea

[0100] The preparation method may further include step iv.: introducing an organic solvent that is miscible with water but inert to isocyanate groups during or after step i, and removing the organic solvent from the aqueous polyurethane-polyurea dispersion.

[0101] The organic solvent is preferably a solvent that is miscible with water but inert to isocyanate groups, and further preferably is one or more of acetone, methyl ethyl ketone, propylene glycol dimethyl ether, other ethers without hydroxyl functional groups, and esters without hydroxyl functional groups; most preferably, it is one or more of acetone and methyl ethyl ketone.

[0102] The organic solvent preferably does not contain N-methyl or N-ethyl pyrrolidone compounds.

[0103] The organic solvent is preferably removed partially or completely by distillation, where the distillation temperature is 10°C to 100°C and the distillation time is 1 hour to 12 hours.

[0104] The most preferred distillation temperature is 25°C to 60°C.

[0105] The most preferred distillation time is 2 hours to 7 hours.

[0106] The rectification pressure is preferably 500 mbar to 50 mbar, and most preferably 200 mbar to 60 mbar.

[0107] Based on the total weight of the aqueous polyurethane-polyurea dispersion, the amount of the organic solvent remaining in the aqueous polyurethane-polyurea dispersion is preferably less than 1.0% by weight.

[0108] To accelerate the reaction of step i, catalysts commonly used for preparing prepolymers can be used, such as triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, bismuth sebacate or bismuth neodecanoate, tin dioctoate, tin(II) chloride or dibutyltin dilaurate, with tin(II) chloride and bismuth neodecanoate being most preferred.

[0109] The catalyst can be placed in the reactor simultaneously with the components of step i or added later.

[0110] The conversion degree of the components of step i can be obtained by measuring the NCO content in the components. For this purpose, spectral measurements such as infrared or near-infrared spectroscopy, as well as refractive index determination or chemical analysis such as titration, can be carried out on the extracted samples simultaneously.

[0111] The prepolymer can be solid or liquid at room temperature.

[0112] The neutralization degree of the prepolymer can be 50 mol% to 125 mol%, preferably 65 mol% to 105 mol%.

[0113] Coating, adhesive or ink

[0114] The coating, adhesive or ink preferably further contains additives. The additives are preferably one or more of emulsifiers, light stabilizers, antioxidants, sterilizing agents, fillers, anti-settling agents, defoamers, wetting agents, flow regulators, reactive diluents, plasticizers, neutralizing agents, catalysts, co-solvents, thickeners, pigments, dyes, matting agents and tackifiers. The additives can be added during and / or after the preparation of the polyurethane-polyurea dispersion.

[0115] The selection and dosage of the additives are in principle known to those skilled in the art and can be easily determined.

[0116] The aqueous polyurethane-polyurea dispersion of the present invention can also be mixed with other water-containing or solvent-containing oligomers or polymers and used together, such as water-containing or solvent-containing polyesters, polyurethanes, polyurethane-polyacrylates, polyacrylates, polyethers, polyester-polyacrylates, alkyd resins, addition polymers, polyamides / imides or polyepoxides. In each case, the compatibility of such mixtures should be tested by means of simple preliminary tests.

[0117] The aqueous polyurethane-polyurea dispersion of the present invention can also be mixed with other compounds containing functional groups such as carboxyl groups, hydroxyl groups and / or blocked isocyanate groups and used together.

[0118] The coatings, adhesives or inks of the present invention are obtained by methods known to those skilled in the art.

[0119] Coated product, bonded product or printed product

[0120] The substrate is preferably one or more of 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 textile, plastic, ceramic, metal, genuine leather, artificial leather, and various polymer coatings.

[0121] Coating can be carried out by applying a coating, an adhesive, or an ink to the entire surface of the substrate or only to one or more parts of the substrate surface.

[0122] Coating can be carried out by brushing, dipping, spraying, roll coating, knife coating, flow coating, casting, or printing.

[0123] Description of the Drawings

[0124] The present invention will be illustrated in more detail below with reference to the accompanying drawings, in which:

[0125] Figure 1 is a schematic diagram for bonding a sample strip.

[0126] Figure 2 is a schematic diagram of the hydrolysis resistance test of the sample strip.

[0127] Figure 3 is a schematic diagram of the adhesion test of the sample strip, where Figure 3a is a schematic diagram of coating, Figure 3b is a schematic diagram of folding and bonding of the substrate. Examples

[0128] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. When the definitions of the terms in this specification conflict with the meanings commonly understood by those skilled in the art, the definitions described herein shall prevail.

[0129] Unless otherwise specified, all numerical values representing component amounts, reaction conditions, etc. used in the specification and claims should be understood to be modified by the term "about". Therefore, unless otherwise indicated, the numerical parameters given herein are approximate values that can vary depending on the desired properties to be obtained.

[0130] The phrase "and / or" used herein refers to one or all of the recited elements.

[0131] The phrases "comprising" and "including" used herein cover the recited elements existing alone and also the presence of other unrecited elements in addition to the recited elements.

[0132] Unless otherwise specified, the terms "a", "one kind", and "the" as used herein are intended to include "at least one kind" or "one kind or more". For example, the term "one component" refers to one or more components, so that more than one component can be considered, and can be adopted or used in the implementation of the embodiments.

[0133] Unless otherwise specified, all percentages in the present invention are weight percentages.

[0134] Unless otherwise specified, the analysis and measurement in the present invention are carried out at 23 ± 2 °C.

[0135] The content of the solid component (solid content) of the aqueous polyurethane-polyurea dispersion is measured using an HS153 moisture analyzer from Mettler Toledo according to DIN-EN ISO 3251:2019, where the heating temperature is 120 °C, and the test end point is determined when the weight loss of the sample is less than 1 mg / 140 s.

[0136] The average particle size of the aqueous polyurethane-polyurea dispersion is determined by laser correlation (laser particle size analyzer) using a ZEN 1600 tester from Malvern, UK according to the test method of ISO 13321:1996. One drop (about 0.05 g) of the sample is added to 50 ml of ultrapure water, and the diluted sample is tested at 23.0 ± 0.1 °C. Material: polystyrene latex (RI: 1.590; absorption rate: 0.010), dispersant: water (temperature: 23.0 °C; viscosity: 0.9308 cP; RI: 0.330), equilibration time: 60 s, using a disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: yes, analysis model: general (normal resolution), measurement angle: 173° backscattering (NIBS default), runs: 3, run duration: 10 s, measurements: 10.

[0137] The pH value of the aqueous polyurethane-polyurea dispersion is measured at 23 °C using a PB-10 pH meter from Sartorius, Germany according to DIN ISO 976:2016-12.

[0138] The viscosity of the aqueous polyurethane-polyurea dispersion is measured at 23 °C using a DV-II+Pro. rotational viscometer from Brookfield according to ISO 2555:2018. Rotor type: s 62-64, speed: 30 RPM, test temperature: 23 °C.

[0139] The content of isocyanate groups (NCO) is determined by volume according to DIN-EN ISO 11909:2007.

[0140] Raw materials and reagents

[0141] Polyester I: A semi-crystalline form based on adipic acid and 1,4-butanediol, a difunctional polyester polyol 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 °C, a melting temperature of 49 °C, and a melting enthalpy of 80 J / g.

[0142] Polyester II: A semi-crystalline form based on adipic acid, 1,6-hexanediol and neopentyl glycol (molar ratio of 1,6-hexanediol to neopentyl glycol is 3:2), a difunctional polyester polyol with a number average molecular weight Mn of 1700 g / mol, a hydroxyl value of 66 mg KOH / g, a glass transition temperature of -63 °C, a melting temperature of 26 °C, and a melting enthalpy of 55 J / g.

[0143] Polyether I: Ymer N120, a difunctional polyether containing methoxy poly(ethylene oxide) side chains with a number average molecular weight of 1000 g / mol, available from Perstorp Chemitec AB (SE).

[0144] Polyether II: Ymer N90, a difunctional polyether containing methoxy poly(ethylene oxide) side chains with a number average molecular weight of 1200 g / mol, available from Perstorp Chemitec AB (SE).

[0145] Polyether III: MPEG750, a monofunctional poly(ethoxy) ether with a number average molecular weight of 750 g / mol, available from Shanghai Dongda Chemical Co., Ltd.

[0146] Isocyanate I: H, hexamethylene diisocyanate, available from Covestro, Germany.

[0147] Isocyanate II: I, isophorone diisocyanate, available from Covestro, Germany.

[0148] Silane I: PC1110, (3-aminopropyl)trimethoxysilane, available from Sisbo Silicones.

[0149] Silane II: PC1100, (3-aminopropyl)triethoxysilane, available from Sisbo Silicones.

[0150] Silane III: PC1200, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, available from Sisbo Silicones.

[0151] Lucramul 1820 Liquid: An emulsifier, fatty alcohol poly(ethylene glycol / propylene glycol) ether, supplied as a 15% to 20% aqueous solution, available from Levaco GmbH, Germany.

[0152] Sodium N-(2-aminoethyl)-2-aminoethanesulfonate: Vestamin A 95, 49% in water, available from Evonik, Germany.

[0153] Diethanolamine: Analytical grade, available from Sinopharm Chemical Reagent Co., Ltd.

[0154] Hydroxyethyl ethylenediamine: Analytical grade, available from Sinopharm Chemical Reagent Co., Ltd.

[0155] Isophorone diamine: Analytical grade, available from Sinopharm Chemical Reagent Co., Ltd.

[0156] Borchigel Gel L75N: A thickener, as a clear liquid, with a concentration of 25%, available from Borchers Company.

[0157] Preparation of waterborne polyurethane-polyurea dispersion

[0158] If the raw materials in the following examples are aqueous emulsions or aqueous solutions, the weights are the weights including water.

[0159] Waterborne polyurethane-polyurea dispersion 1

[0160] 510.82 g of polyester I, 20.32 g of polyester II and 6.27 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 h. Then, 2.3 g of 1,4-butanediol was added and cooled with stirring. At 60 °C, 64.16 g of isocyanate I and 3.56 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 1.7% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 14.02 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 1.03 g of diethanolamine, 3.38 g of hydroxyethyl ethylenediamine in 51.57 g of water and 1.26 g of silane I in 12.6 g of acetone were added to the acetone solution in which the prepolymer was dissolved, respectively, while stirring vigorously. After stirring for 30 min, the mixture was dispersed by adding 560 g of water. Acetone was separated by distillation for 5 h. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid content of 49.7 wt%, an average particle size in the dispersed phase of 135 nm, a pH value of 6.8 and a viscosity of 2567 mPa·s was obtained.

[0161] Waterborne polyurethane-polyurea dispersion 2

[0162] 542.81 g of polyester I and 7.5 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 h. Then, 2.3 g of 1,4-butanediol was added and cooled with stirring. At 60 °C, 59.49 g of isocyanate I and 3.77 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 1.3% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 11.47 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 1.21 g of isophorone diamine, 2.30 g of hydroxyethyl ethylenediamine in 50 g of water and 1.26 g of silane II in 12.6 g of acetone were added to the acetone solution in which the prepolymer was dissolved, respectively, while stirring vigorously. After stirring for 30 min, the mixture was dispersed by adding 570 g of water. Acetone was separated by distillation for 4.5 h. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid content of 49.7 wt%, an average particle size in the dispersed phase of 166 nm, a pH value of 6.8 and a viscosity of 1692 mPa·s was obtained.

[0163] Waterborne polyurethane-polyurea dispersion 3

[0164] 531.56 g of polyester I and 12.5 g of polyether II were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and cooled while stirring. At 60 °C, 69.17 g of isocyanate I and 5.83 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 2.2% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 14.98 g of N-(2-aminoethyl)-2-aminoethanesulfonic acid sodium salt, 5.23 g of isophoronediamine, 3.1 g of hydroxyethyl ethylenediamine in 50 g of water, and 1.26 g of silane I in 12.6 g of acetone were added separately to the acetone solution in which the prepolymer was dissolved, while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 580 g of water. Acetone was separated by distillation for 5 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid content of 49.2 wt%, an average particle size in the dispersed phase of 210 nm, a pH value of 6.8, and a viscosity of 3012 mPa·s was obtained.

[0165] Comparative waterborne polyurethane-polyurea dispersion 1

[0166] 542.81 g of polyester I and 7.5 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and cooled while stirring. At 60 °C, 62.35 g of isocyanate I was added and stirred at 80 to 90 °C until an isocyanate content of 1.3% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 11.47 g of N-(2-aminoethyl)-2-aminoethanesulfonic acid sodium salt, 1.21 g of isophoronediamine, 2.30 g of hydroxyethyl ethylenediamine in 50 g of water, and 1.26 g of silane I in 12.6 g of acetone were added separately to the acetone solution in which the prepolymer was dissolved, while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 570 g of water. Acetone was separated by distillation for 4 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid content of 49.8 wt%, an average particle size in the dispersed phase of 170 nm, a pH value of 7.0, and a viscosity of 1680 mPa·s was obtained.

[0167] Comparative waterborne polyurethane-polyurea dispersion 2

[0168] 542.81 g of polyester I and 7.5 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and cooled while stirring. At 60 °C, 53.82 g of isocyanate I and 10.69 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 1.3% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 11.47 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 1.21 g of isophoronediamine, 2.30 g of hydroxyethyl ethylenediamine in 50 g of water and 1.26 g of silane I in 12.6 g of acetone were added separately to the acetone solution in which the prepolymer was dissolved while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 570 g of water. Acetone was separated by distillation for 5 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid content of 50.2 wt%, an average particle size in the dispersed phase of 148 nm, a pH value of 6.6 and a viscosity of 2347 mPa·s was obtained.

[0169] Comparative waterborne polyurethane-polyurea dispersion 3

[0170] 542.81 g of polyester I and 7.5 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and cooled while stirring. At 60 °C, 44.02 g of isocyanate I and 24.21 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 1.3% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 11.47 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, 1.21 g of isophoronediamine, 2.30 g of hydroxyethyl ethylenediamine in 50 g of water and 1.26 g of silane I in 12.6 g of acetone were added separately to the acetone solution in which the prepolymer was dissolved while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 570 g of water. Acetone was separated by distillation for 4 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid content of 50.7 wt%, an average particle size in the dispersed phase of 204 nm, a pH value of 6.8 and a viscosity of 1472 mPa·s was obtained.

[0171] Comparative waterborne polyurethane-polyurea dispersion 4

[0172] 542.81 g of polyester I and 7.5 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and cooled while stirring. At 60 °C, 67.30 g of isocyanate I and 8.1 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 2.2% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 14.98 g of N-(2-aminoethyl)-2-aminoethanesulfonic acid sodium salt, 5.23 g of isophoronediamine, 3.1 g of hydroxyethyl ethylenediamine in 50 g of water, and 1.26 g of silane I in 12.6 g of acetone were respectively added to the acetone solution in which the prepolymer was dissolved while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 580 g of water. Acetone was separated by distillation for 5 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid component content of 50.0 wt%, an average particle size in the dispersed phase of 159 nm, a pH value of 6.7, and a viscosity of 2612 mPa·s was obtained.

[0173] Comparative waterborne polyurethane-polyurea dispersion 5

[0174] 548.4 g of polyester I and 5 g of polyether I were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and cooled while stirring. At 60 °C, 59.49 g of isocyanate I and 3.77 g of isocyanate II were added and stirred at 80 to 90 °C until an isocyanate content of 1.3% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. Solutions of 11.47 g of N-(2-aminoethyl)-2-aminoethanesulfonic acid sodium salt, 1.87 g of hydroxyethyl ethylenediamine, 1.26 g of diethanolamine in 50 g of water, and 1.26 g of silane III in 12.6 g of acetone were respectively added to the acetone solution in which the prepolymer was dissolved while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 570 g of water. Acetone was separated by distillation for 4 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid component content of 49.7 wt%, an average particle size in the dispersed phase of 152 nm, a pH value of 6.9, and a viscosity of 1392 mPa·s was obtained.

[0175] Comparative waterborne polyurethane-polyurea dispersion 6

[0176] 542.8 g of polyester I and 12.6 g of polyether III were dehydrated at 110 °C and 80 mbar for 1 hour. Then, 2.3 g of 1,4-butanediol was added and the mixture was cooled while stirring. At 60 °C, 59.49 g of isocyanate I and 3.77 g of isocyanate II were added and the mixture was stirred at 80 to 90 °C until an isocyanate content of 1.3% was reached. Then it was dissolved in 930 g of acetone and cooled to 50 °C to obtain a reaction solution. 11.47 g of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, a solution of 2.81 g of hydroxyethyl ethylenediamine in 50 g of water, and a solution of 1.26 g of silane I in 12.6 g of acetone were respectively added to the acetone solution in which the prepolymer was dissolved while stirring vigorously. After stirring for 30 minutes, the mixture was dispersed by adding 570 g of water. Acetone was separated by distillation for 6 hours. When the acetone content was less than 1.0 wt%, 40 g of Lucramul 1820 liquid was added. Thus, an aqueous polyurethane-polyurea dispersion with a solid component content of 50.5 wt%, an average particle size in the dispersed phase of 134 nm, a pH value of 6.7, and a viscosity of 5403 mPa·s was obtained.

[0177] Method for preparing adhesives for examples and comparative examples

[0178] According to the components shown in Table 1, 0.7 g of BorchiL Gel L75N was added to 100 g of the aqueous polyurethane-polyurea dispersion (which was allowed to cure by standing at room temperature for 7 days) while stirring at a speed of 600 rpm, and then stirred at a high speed of 1200 rpm for 10 to 15 minutes to mix well. The viscosity was adjusted to 5000 mPa·s to 10000 mPa·s for later use.

[0179] Hydrolysis resistance test

[0180] Substrates 1 (black rubber) and 2 (black rubber) with a length of 120 mm and a width of 20 mm were mechanically polished and then coated with a rubber treatment agent (which was obtained by dissolving trichloroisocyanuric acid (Powder B) in ethyl acetate). After drying, the adhesive of the present invention was applied to substrates 1 and 2 using a brush, and the brushing area was 100 mm * 20 mm. The adhesive was dried and thermally activated by heating substrates 1 and 2 at 60 °C for 3 minutes. Then, substrates 1 and 2 were bonded at a pressure of 4 bar for 10 seconds to obtain a test sample strip as shown in Figure 1 After storing the test sample strip at room temperature (22 ± 2 °C, 50 ± 5% RH) for 72 hours, as shown in Figure 2As shown in the figure, a 1 kg heavy object is loaded on one end of the base. It is placed in an oven at a temperature of 70 °C and a humidity of 95%. The time taken for the test sample strip to completely come apart is measured. When the time taken for the test sample strip to completely come apart is greater than 8 hours, it is considered qualified.

[0181] Adhesion test

[0182] As Figure 3a shown in the figure, a black rubber with a length of 60 mm and a width of 20 mm is mechanically polished and then coated with a rubber treatment agent (obtained by dissolving trichloroisocyanuric acid (Powder B) in ethyl acetate). After drying, the adhesive of the present invention is applied to both ends of the base in an area of 25 mm in length and 20 mm in width using a brush. The test base is heated at 60 °C for 3 minutes to dry and thermally activate the adhesive. Then, it is taken out and placed at room temperature (22 ± 2 °C, 50 ± 5% RH) for 0 minutes, 2 minutes, 4 minutes, 6 minutes, 8 minutes, and 10 minutes respectively, and then manually folded and bonded (as Figure 3b shown in the figure). The speed and distance at which the sample strip comes apart are recorded. The test results are scored from 1 to 5. A score of 5 is the best, a score of 1 is the worst, and a score of 4 or above is considered qualified. If the two ends of the base bounce back within 5 seconds after bonding (or cannot be bonded at all), the score is 1. If the two ends of the base bounce back more than 5 seconds but less than 120 seconds after bonding, the score is 2. If the two ends of the base do not bounce back after at least 120 seconds and the separation distance is 16 mm to 25 mm, the score is 3. If the two ends of the base do not bounce back after at least 120 seconds and the separation distance is not less than 6 mm but less than 16 mm, the score is 4. If the two ends of the base do not bounce back at all after at least 120 seconds, or the separation distance is less than 6 mm, the score is 5.

[0183] Table 1 shows the evaluation results of the adhesion and hydrolysis resistance of the adhesives of Examples 1 - 3 and Comparative Examples 1 - 6 of the present invention.

[0184] Table 1 Evaluation of the Adhesives of Examples 1 - 3 and Comparative Examples 1 - 6

[0185]

[0186] Note: The amount of all aqueous polyurethane - polyurea dispersions in Table 1 for Examples and Comparative Examples is 100 grams

[0187] The aqueous polyurethane - polyurea dispersions of the examples of the present invention have good adhesion and hydrolysis resistance.

[0188] By comparing Example 2 and Comparative Example 1, it can be seen that when the system for preparing the aqueous polyurethane-polyurea dispersion contains only one polyisocyanate, such as hexamethylene diisocyanate, the adhesion of the aqueous polyurethane-polyurea dispersion is poor.

[0189] As can be seen from Comparative Examples 2-4, when the weight ratio of the aliphatic polyisocyanate to the alicyclic polyisocyanate contained in the system for preparing the aqueous polyurethane-polyurea dispersion is less than 10:1, the aqueous polyurethane-polyurea dispersion does not achieve both adhesion and hydrolysis resistance simultaneously.

[0190] As can be seen from Comparative Example 5, when the system for preparing the aqueous polyurethane-polyurea dispersion contains a silane compound having two isocyanate-reactive groups but does not contain a silane compound having one isocyanate-reactive group, the hydrolysis resistance of the aqueous polyurethane-polyurea dispersion is poor.

[0191] As can be seen from Comparative Example 6, when the system for preparing the aqueous polyurethane-polyurea dispersion contains a polyether polyol having one isocyanate-reactive group but does not contain a polymer having the structure of Formula I, the hydrolysis resistance of the aqueous polyurethane-polyurea dispersion is poor.

[0192] It is readily understood by those skilled in the art that the present invention is not limited to the foregoing details and can be implemented in other specific forms without departing from the spirit or main features of the present invention. Therefore, from any perspective, the embodiments should be considered exemplary rather than restrictive, so that the scope of the present invention is given by the claims rather than the foregoing description. Accordingly, any change that falls within the meaning and scope of the equivalents of the claims should be considered to belong to the present invention.

Claims

1. An aqueous polyurethane-polyurea dispersion comprising a polyurethane-polyurea, wherein the polyurethane-polyurea is obtained by the reaction of a system comprising the following components: a. At least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, wherein the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, wherein the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate is from 10:1 to 20:1; b. A polymer having the structure of formula I: wherein n is from 10 to 75, R1 is an alkyl group containing 1 to 10 carbon atoms, and R2 is a moiety containing at least two isocyanate-reactive groups; c. A polyol different from component b), which has a hydroxyl functionality of 1.5 to 4; d. A silane compound containing one isocyanate-reactive group and at least two methoxy and / or ethoxy groups attached to a silicon atom; e. A hydrophilic compound different from polymer b), which contains 2 to 3 isocyanate-reactive groups; and Optionally, f. A compound containing 1 to 3 amino groups and / or hydroxyl groups, preferably 1 to 3 amino groups.

2. The aqueous polyurethane-polyurea dispersion according to claim 1, characterized in that Component a) is a mixture of hexamethylene diisocyanate and isophorone diisocyanate.

3. The aqueous polyurethane-polyurea dispersion according to claim 2, characterized in that The weight ratio of hexamethylene diisocyanate to isophorone diisocyanate is from 10:1 to 20:

1.

4. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 3, characterized in that The polyisocyanate of component a) has an isocyanate functionality of not less than 2, more preferably from 2 to 4, and most preferably 2.

5. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 4, characterized in that The at least two isocyanate-reactive groups are selected from at least two amino groups, at least two hydroxyl groups, or at least one amino group and at least one hydroxyl group.

6. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 5, characterized in that The polymer having the structure of formula I is one or more of the polymer having the structure of formula II and the polymer having the structure of formula III, wherein in formula II, a is from 10 to 75 and b is from 0 to 50; in formula III, x is from 10 to 75 and y is from 1 to 50.

7. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 6, characterized in that The polymer having the structure of formula I of component b) has a number average molecular weight of from 500 g / mol to 4000 g / mol, which is measured by gel permeation chromatography, wherein tetrahydrofuran is used as the mobile phase, and the molecular weight is calculated based on polystyrene having a selected molecular weight of 200 or higher as the standard, and is measured with a differential refractive index detector (RI detector).

8. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 7, characterized in that The silane compound of component d) is one or more of bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, 3-aminopropyl(diethoxy)methylsilane, and 3-aminopropylmethyldimethoxysilane, and most preferably one or more of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, and 3-aminopropylmethyldimethoxysilane.

9. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 8, characterized in that The polyol different from component b) is one or more of a diol having a number average molecular weight of from 62 to 15000 and a polyol having a number average molecular weight of from 62 to 15000, more preferably one or more of a diol having a number average molecular weight of from 62 to 5000 and a triol having a number average molecular weight of from 92 to 5000, and most preferably one or more of a polyester polyol having 2 to 3 hydroxyl groups and a number average molecular weight of from 500 to 2500, a polycarbonate polyol having 2 to 3 hydroxyl groups and a number average molecular weight of from 400 to 2500, a polyether polyol having 2 to 3 hydroxyl groups and a number average molecular weight of from 200 to 2500, a polylactone polyol having 2 to 3 hydroxyl groups and a number average molecular weight of from 250 to 5000, and a low molecular weight alcohol, wherein the number average molecular weight is measured by gel permeation chromatography, wherein tetrahydrofuran is used as the mobile phase, and the molecular weight is calculated based on polystyrene having a selected molecular weight of 200 or higher as the standard, and is measured with a differential refractive index detector (RI detector).

10. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 9, characterized in that The polyol different from component b) has a melting enthalpy of not less than 15 J / g, and most preferably from 25 J / g to 100 J / g, which is obtained from the first heating curve from 20 °C to 100 °C by DSC according to DIN 65467, method A, wherein the loading volume is 10 - 20 mg and the heating rate is 20 K / min.

11. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 10, characterized in that The hydrophilic compound different from polymer b containing 2 to 3 isocyanate-reactive groups in component e) is one or more of N-(2-aminoethyl)-2-aminoethanesulfonate, dimethylolpropionate, and N-(2-aminoethyl)-2-aminoethanecarboxylate.

12. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 11, characterized in that The compound containing 1 to 3 amino groups and / or hydroxyl groups in component f) is one or more of aliphatic and / or alicyclic primary and / or secondary monoamines or diamines or triamines or amino alcohols, most preferably one or more of isophorone diamine, N-(2-hydroxyethyl)ethylenediamine, and diethanolamine.

13. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 12, characterized in that Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component a) is in an amount of 9% to 18% by weight, most preferably 10% to 12% by weight.

14. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 13, characterized in that Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component b) is in an amount of 0.9% to 4% by weight, most preferably 1% to 2% by weight.

15. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 14, characterized in that Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component c) is in an amount of 5% to 94% by weight, most preferably 70% to 90% by weight.

16. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 15, characterized in that Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component d) is in an amount of 0.12% to 0.7% by weight, most preferably 0.18% to 0.4% by weight.

17. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 16, characterized in that Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component e) is in an amount of 0.2% to 50% by weight, most preferably 1% to 5% by weight.

18. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 17, characterized in that Based on the total weight of the solid components of the aqueous polyurethane-polyurea dispersion, component f) is in an amount of not more than 10% by weight, most preferably 0.5% to 3% by weight.

19. The aqueous polyurethane-polyurea dispersion according to any one of claims 1 to 18, characterized in that The aqueous polyurethane-polyurea dispersion has at least one of the following characteristics: Based on the total weight of the aqueous polyurethane-polyurea dispersion, the content of the solid components is 15% to 70% by weight, most preferably 30% to 60% by weight, which is measured using an HS153 moisture analyzer from Mettler Toledo according to DIN-EN ISO 3251:2019, where the heating temperature is 120 °C, and the test end point is determined when the weight loss of the sample is less than 1 mg / 140 s; The pH value is 4 to 11, most preferably 5 to 10, which is measured using a PB-10 pH meter from Sartorius, Germany at 23 °C; The average particle size is 20 nm to 750 nm, more preferably 50 nm to 450 nm, most preferably 100 nm to 250 nm, which is determined by laser correlation (laser particle size analyzer) using a ZEN 1600 tester from Malvern, UK according to the test method of ISO 13321:1996, where 1 drop (about 0.05 g) of the sample is added to 50 ml of ultrapure water, and the diluted sample is tested at 23.0 ± 0.1 °C, material: polystyrene latex (RI: 1.590; Absorptivity: 0.010), dispersant: water (temperature: 23.0 °C; Viscosity: 0.9308 cP; RI: 0.330), Equilibration time: 60 seconds, Using disposable cuvette DTS0012, Positioning method: Auto attenuation selection, Best position found: Yes, Analysis model: General (Normal resolution), Measurement angle: 173° backscattering (NIBS default), Runs: 3, Run duration: 10 seconds, Measurements: 10; and Viscosity is from 1000 mPa·s to 3500 mPa·s, measured at 23 °C using a DV-II+Pro. rotational viscometer from Brookfield, Rotor type: s 62 - 64, Speed: 30 RPM, Test temperature: 23 °C.

20. A method for preparing an aqueous polyurethane-polyurea dispersion comprising polyurethane-polyurea according to any one of claims 1 to 19, which comprises the following steps: i. React some or all of component a), a polymer having the structure of formula I for component b), and component c), a polyol different from component b), to obtain a prepolymer, wherein component a) is at least one aliphatic polyisocyanate and at least one cycloaliphatic polyisocyanate, and the weight ratio of the at least one aliphatic polyisocyanate to the at least one cycloaliphatic polyisocyanate is from 10:1 to 20:1, preferably one aliphatic polyisocyanate and one cycloaliphatic polyisocyanate, and the weight ratio of the one aliphatic polyisocyanate to the one cycloaliphatic polyisocyanate is from 10:1 to 20:1; ii. React the prepolymer, component d), a silane compound, component e), a hydrophilic compound different from polymer b) containing 2 to 3 isocyanate-reactive groups, and optionally component f), a compound containing 1 to 3 amino groups and / or hydroxyl groups, preferably 1 to 3 amino groups, to obtain the polyurethane-polyurea; and iii. Introduce water before, during, or after step ii to obtain the aqueous polyurethane-polyurea dispersion.

21. The production method according to claim 20, further comprising step iv. During or after step i, introducing an organic solvent miscible with water but inert to isocyanate groups, and removing the organic solvent from the aqueous polyurethane-polyurea dispersion.

22. The production method according to claim 21, characterized in that The organic solvent is removed partially or completely by distillation, wherein the distillation temperature is from 10 °C to 100 °C, most preferably from 25 °C to 60 °C, the distillation time is from 1 hour to 12 hours, most preferably from 2 hours to 7 hours, and the rectification pressure is preferably from 500 mbar to 50 mbar, most preferably from 200 mbar to 60 mbar.

23. A coating, adhesive or ink, comprising the aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to any one of claims 1 to 19.

24. The coating, adhesive or ink according to claim 23, further comprising an additive selected from one or more of an emulsifier, a light stabilizer, an antioxidant, a sterilizing agent, a filler, an anti-settling agent, a defoaming agent, a wetting agent, a flow regulator, a reactive diluent, a plasticizer, a neutralizing agent, a catalyst, a co-solvent, a thickening agent, a pigment, a dye, a matting agent and a tackifier.

25. Use of the aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to any one of claims 1 to 19 for preparing a coated product, a bonded product or a printed product.

26. An object or article, comprising a substrate prepared, coated, bonded, sealed or printed with the aqueous polyurethane-polyurea dispersion containing polyurethane-polyurea according to any one of claims 1 to 19.

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