Water-based polyurethane-urea dispersion

Abstract

The present invention relates to an aqueous polyurethane-urea dispersion containing polyurethane-urea, and a method for its preparation, as well as its use, in particular in the field of coating compositions, binders or inks, and to products obtained by coating, gluing, sealing or printing with the aqueous polyurethane-urea dispersion. The polyurethane-urea of ​​the aqueous polyurethane-urea dispersion containing polyurethane-urea is obtained by reaction of a system containing the following components: polyisocyanate, polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1, polyester polyol having a hydroxyl functionality of 1.9 to 2.1, amino-containing compound, hydroxyl-containing carboxylic acid and neutralizing agent, where the weight ratio of polycarbonate polyol to polyester polyol is 6:1 to 20:1. The aqueous polyurethane-urea dispersion of the present invention has a small particle size, a narrow particle size distribution, good color rendering, hydrolysis resistance, color fastness to rubbing, and can be used as a binder for inkjet inks.

Description

[Technical field]

[0001] Technical Field The present invention relates to an aqueous polyurethane-urea dispersion, to a process for its preparation and to its use, in particular in the field of coating compositions, binders or inks, as well as to objects obtained by coating, gluing, sealing or printing with the aqueous polyurethane-urea dispersion. [Background technology]

[0002] prior art In order to fix the pigment of the ink to the substrate such as the textile or leather, the ink used for textile or leather printing usually contains a water-based resin. Currently, one of the main problems in the formulation for inkjet ink is how to find a water-based resin with good binding performance.

[0003] First, the water-based resin usually plays a decisive role in the color fastness to rubbing of the ink. The water-based resin usually has a milky appearance due to the large particle size and large polydispersity index, which has a negative effect on the good color rendering of the ink. Therefore, inks with higher color levels on the market usually contain less water-based resin binder, resulting in lower fastness of the ink. Conversely, to ensure that the ink has good color fastness to rubbing, it is necessary for the ink to contain a certain amount of water-based resin, which causes the ink to not meet the requirements for color rendering. In addition, the fine nozzles of the inkjet printhead are usually only a few microns in size, and the water-based resin has a large particle size, which tends to block the inkjet printhead.

[0004] Secondly, inks, especially inkjet inks, have requirements on the viscosity of the water-based resin binder: if the resin has a high viscosity, the inkjet ink will have a high viscosity and may be difficult to jet from the inkjet printhead.

[0005] Finally, the hydrolysis resistance of the aqueous resin itself also has a significant effect on the color fastness of printed matter during long-term use: objects printed with aqueous resins that have poor hydrolysis resistance may lose their color after several washing operations.

[0006] Therefore, there is a need in the industry for aqueous resins suitable for inkjet inks that have color rendering, color fastness to rubbing, and hydrolysis resistance. Summary of the Invention [Problem to be solved by the invention]

[0007] Summary of the Invention The object of the present invention is to provide an aqueous polyurethane-urea dispersion, a process for its preparation and its use, in particular in the field of coating compositions, binders or inks, as well as objects obtained by coating, gluing, sealing or printing with the aqueous polyurethane-urea dispersion. [Means for solving the problem]

[0008] In the aqueous polyurethane-urea dispersion comprising the polyurethane-urea according to the invention, the polyurethane-urea comprises the following components: a. at least one polyisocyanate; b. at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1; c. at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, said polyester polyol being obtained by reaction of a mixture comprising at least one of an aromatic diacid and an aromatic anhydride with a dihydric alcohol; d. at least one amino-containing compound which is one or more of an amino-containing carboxylic acid, an amino-containing carboxylate, an amino-containing sulfonic acid, and an amino-containing sulfonate; e. at least one hydroxyl-containing carboxylic acid; f. at least one neutralizing agent; and g. optionally, a compound reactive with isocyanate groups, different from components b) to e), having a molecular weight of 32 g / mol to 400 g / mol; (Here, the weight ratio of polycarbonate polyol to polyester polyol is 6:1 to 20:1.) It is obtained by reaction of a system containing

[0009] One aspect of the present invention is a method for preparing an aqueous polyurethane-urea dispersion comprising a polyurethane-urea according to the present invention, comprising the following steps: i. reacting component a) at least one polyisocyanate, component b) at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1, component c) at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, component e) at least one hydroxyl-containing carboxylic acid, and component g) optionally some or all of the compounds different from components b) to e) that are reactive towards isocyanate groups to obtain a prepolymer; ii. reacting the prepolymer with component d) at least one amino-containing compound and component g) optionally a compound that is reactive towards isocyanate groups and different from components b) to e) to obtain a polyurethane-urea; iii. adding component f) at least one neutralizing agent before or after step ii; and iv. introducing water before, during or after step ii to obtain an aqueous polyurethane-urea dispersion. The object of the present invention is to provide a method comprising the steps of:

[0010] Another aspect of the present invention is to provide a coating composition, binder or ink comprising an aqueous polyurethane-urea dispersion comprising a polyurethane-urea according to the present invention.

[0011] Yet another aspect of the present invention provides the use of an aqueous polyurethane-urea dispersion comprising a polyurethane-urea according to the present invention for preparing a coated, glued or printed object.

[0012] Yet another aspect of the present invention is to provide an object or article, including a substrate, prepared, coated, glued, sealed or printed with an aqueous polyurethane-urea dispersion comprising a polyurethane-urea according to the present invention.

[0013] Yet another aspect of the present invention is to provide a printing method comprising the steps of: applying an aqueous polyurethane-urea dispersion comprising a polyurethane-urea according to the present invention onto a surface of a substrate and then curing.

[0014] Yet another aspect of the present invention is to provide a printed article comprising a substrate and a coating formed by applying an aqueous polyurethane-urea dispersion comprising a polyurethane-urea according to the present invention onto the substrate.

[0015] The aqueous polyurethane-urea dispersion of the present invention has low viscosity and is very suitable as a binder for ink, especially inkjet ink.The aqueous polyurethane-urea dispersion of the present invention is also characterized by small particle size (Z-average particle size less than 75 nm), narrow particle size distribution (PDI less than 0.3), and translucent appearance.The wet film formed by this has a bright color.After drying the wet film, the dry film has high fastness to wet rubbing and long jungle test time (more than 2 weeks).The dry film formed by the aqueous polyurethane-urea dispersion of the present invention has good color rendering, color fastness to rubbing and hydrolysis resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Embodiment The present invention relates to a method for producing a composition comprising the following components: a. at least one polyisocyanate; b. at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1; c. at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, said polyester polyol being obtained by reaction of a mixture comprising at least one of an aromatic diacid and an aromatic anhydride with a dihydric alcohol; d. at least one amino-containing compound which is one or more of an amino-containing carboxylic acid, an amino-containing carboxylate, an amino-containing sulfonic acid, and an amino-containing sulfonate; e. at least one hydroxyl-containing carboxylic acid; f. at least one neutralizing agent; and g. Optionally, a compound different from components b) to e) and reactive with an isocyanate group, having a molecular weight of 32 g / mol to 400 g / mol. (Here, the weight ratio of polycarbonate polyol to polyester polyol is 6:1 to 20:1.) The present invention provides an aqueous polyurethane-urea dispersion comprising a polyurethane-urea obtained by reacting a system comprising:

[0017] The invention further provides a process for the preparation of the aqueous polyurethane-urea dispersion and its use, in particular in the field of coating compositions, binders or inks, as well as products obtained by coating, gluing, sealing or printing with the aqueous polyurethane-urea dispersion.

[0018] As used herein, the term "curing" refers to the process of a liquid substance going from a liquid state to a hardened state.

[0019] The term "coating composition" as used herein refers to a material that can be applied onto the surface of an object by various application processes to form a continuous solid coating layer having strong adhesion and specific strength.

[0020] The term "binder" as used herein refers to a chemical substance that can be applied to the surface of an object by various application processes such that a coating layer is formed on the surface of the object itself or on the surface of one object and another object, and the surfaces of the object itself or one object and another object are bonded together. It is also used as a synonym for adhesive and / or sealant and / or bonder.

[0021] As used herein, the term "polyurethane-urea" refers to polyurethanes and / or polyurethane polyureas and / or polyureas and / or polythiourethanes.

[0022] As used herein, the term "aqueous polyurethane-urea dispersion" refers to an aqueous polyurethane dispersion and / or an aqueous polyurethanepolyurea dispersion and / or an aqueous polyurea dispersion and / or an aqueous polythiourethane dispersion.

[0023] The content of polyurethane-urea in the aqueous polyurethane-urea dispersion described herein is equivalent to the content of the solid component in the aqueous polyurethane-urea dispersion.

[0024] As used herein, the term "solid ingredient" refers to a solid constituent or active ingredient.

[0025] In this specification, the term "compound reactive to an isocyanate group" refers to a component containing a group reactive to an isocyanate group, i.e., a component containing a group having a zerewitinoff active hydrogen. The definition of zerewitinoff active hydrogen refers to Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th edition, Georg Thieme Verlag Stuttgart, 1996. In general, a group having a zerewitinoff active hydrogen is defined in the art as a hydroxyl group (OH), an amino group (NH x) and thiol groups (SH).

[0026] Water-based polyurethane-urea dispersion The amount of organic solvent in the aqueous polyurethane-urea dispersion is preferably less than 1 wt %, based on the total weight of the aqueous polyurethane-urea dispersion.

[0027] The aqueous polyurethane-urea dispersion preferably has at least one of the following properties: Viscosity from 10 mPa·s to 1000 mPa·s (tested according to standard ISO3219:1994 using a viscometer from Brookfield (Brookfield DV-II+ Pro)); solids content of 30-40% by weight (tested with a halogen moisture analyzer from Mettler Toledo (Mettler Toledo Halogen Moisture Analyzer Excellence HS153)); Z-average particle size of 30 nm to 75 nm (tested with a Zetasizer Nano from Malvern (Malvern Zetasizer Nano ZS)); and Polydispersity index of 0-0.3 (tested with a Zetasizer Nano from Malvern (Malvern Zetasizer Nano ZS)).

[0028] The content of the aqueous polyurethane-urea is most preferably 33 to 40% by weight, based on the total weight of the aqueous polyurethane-urea dispersion.

[0029] The color fastness to wet rubbing of the aqueous polyurethane-urea dispersion is preferably 4-5.

[0030] Jungle test results for aqueous polyurethane-urea dispersions preferably exceed two weeks.

[0031] Component a) Polyisocyanate The isocyanate functionality of the polyisocyanate is preferably 2 or more, most preferably 2-4.

[0032] The polyisocyanate is preferably one or more of aliphatic, cycloaliphatic, aromatic polyisocyanates, and derivatives thereof having iminooxadiazinedione, isocyanurate, uretdione, carbamate, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and / or carbodiimide groups.

[0033] The aliphatic polyisocyanate is preferably 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-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, nate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, methyl lysinate 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, Preferably, the isocyanatoalkyl group is one or more of 2,6,7-heptane tetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanatomethylthiophene, isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate, thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane) and dithiobis(2-isothiocyanatoethane); most preferably, hexamethylene diisocyanate.

[0034] The alicyclic polyisocyanate is preferably 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-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanatomethyl-1,4-dithiane, Preferably, the diisocyanate is one or more of isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, and more preferably, the diisocyanate is one or more of isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

[0035] The aromatic polyisocyanate is preferably 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, toluene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenyl)diisocyanate, nyl isocyanate), 4,4'-methylenebis(2-methylphenyl isocyanate), bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, bis(isocyanatomethyl)benzene, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, α,α,α',α'-tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethylphenyl)ether, bis(isocyanatoethyl)phthalate, 2, 6-bis(isocyanatomethyl)furan, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis(4-isocyanatophenyl) sulfide, bis(4-isocyanatomethylphenyl) sulfide, bis(4-isocyanatophenyl) disulfide, bis(2-methyl-5-isocyanatophenyl) disulfide, bis(3-methyl-5-isocyanatophenyl) disulfide, bis(3-methyl-6-isocyanatophenyl) disulfide, bis(4-methyl-5-isocyanatophenyl) disulfide, bis(4-methoxy 4,4'-methylenebis(phenylisothiocyanate), 4,4'-methylenebis(2-methylphenylisothiocyanate), 4,4'-methylenebis(3-methylphenylisothiocyanate), 4,4'-diisothiocyanatobenzophenone, 4,4'-diisothiocyanato-3,3'-dimethylbenzophenone, bis(4-isothiocyanatophenyl)ether, 1-isothiocyanato-4-[(2-isothiocyanato)sulfonyl]benzene, thiobis(4-isothiocyanatobenzene), sulfonyl(4-isothiocyanatobenzene), hydrogenated toluene diisocyanate (H6TDI), diphenylmethane diisocyanate and dithiobis(4-isothiocyanatobenzene), most preferably one or more of 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, diphenylmethane diisocyanate and 2,4-diisocyanatotoluene.

[0036] Other isocyanates may contain isocyanate and isothiocyanate groups, such as 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanatophenyl sulfide, and 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide.

[0037] The other isocyanates may also be halogen substituted, for example chlorine substituted, bromine substituted, alkyl substituted, alkoxy substituted, nitro substituted or silane substituted, for example, isocyanatopropyltriethoxysilane or isocyanatopropyltrimethoxysilane, of the above polyisocyanates.

[0038] The polyisocyanate is more preferably one or more of hexamethylene diisocyanate and isophorone diisocyanate, most preferably a combination of hexamethylene diisocyanate and isophorone diisocyanate. The molar ratio of hexamethylene diisocyanate to isophorone diisocyanate is preferably 1:2 to 2:1.

[0039] The amount of component a) polyisocyanate is preferably 10-50% by weight, most preferably 15-30% by weight, based on the total weight of the polyurethane-urea.

[0040] Component b) Polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1 The polycarbonate polyol is preferably one or more of hexanediol polycarbonate, butanediol polycarbonate, neopentyl glycol polycarbonate, 3-methylpentanediol polycarbonate, and copolymers of the above polycarbonates.

[0041] The number average molecular weight of the polycarbonate polyol is preferably 800 g / mol to 4000 g / mol.

[0042] The polycarbonate polyol is preferably present in an amount of from 60% to 80% by weight, most preferably from 65% to 75% by weight, based on the total weight of the polyurethane-urea.

[0043] Component c) polyester polyol having a hydroxyl functionality of 1.9 to 2.1 The polyester polyol is preferably one or more of a linear polyester diol and a slightly branched polyester polyol.

[0044] The polyester polyol is more preferably one or more of polyhexylene phthalate, polybutylene phthalate, polyneopentyl glycol phthalate, poly(diethylene glycol) phthalate, poly(3-methylpentanediol) phthalate, polyhexylene isophthalate, polybutylene isophthalate, polyneopentyl glycol isophthalate, poly(diethylene glycol) isophthalate, poly(3-methylpentanediol) isophthalate, polyhexylene terephthalate, polybutylene terephthalate, polyneopentyl glycol terephthalate, poly(diethylene glycol) terephthalate and poly(3-methylpentanediol) terephthalate; most preferably one or more of polyhexylene phthalate, polybutylene phthalate, polyneopentyl glycol phthalate, poly(diethylene glycol) phthalate, and poly(3-methylpentanediol) phthalate.

[0045] The polyester polyols are preferably prepared from the following components: aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid; anhydrides, such as phthalic anhydride, trimellitic anhydride or mixtures thereof; low molecular weight polyols, such as ethylene glycol, di-, tri-, tetra-ethylene glycol, 1,2-propylene glycol, di-, tri-, tetra-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or mixtures thereof; and optionally higher functionality polyols, such as trimethylolpropane, glycerol or pentaerythritol, alicyclic and / or aromatic dihydroxy and polyhydroxy compounds.

[0046] The polyester polyol is more preferably obtained by reacting a mixture containing at least one of an aromatic dibasic acid and an aromatic acid anhydride with a dihydric alcohol. The aromatic dibasic acid is preferably one or more of terephthalic acid, isophthalic acid, and phthalic acid. The aromatic acid anhydride is preferably phthalic anhydride. The dihydric alcohol is preferably one or more of 1,6-hexanediol, 1,4-butanediol, neopentyl alcohol, 3-methylpentanediol, and diethylene glycol.

[0047] The number average molecular weight of the polyester polyol is preferably 800 g / mol to 4000 g / mol.

[0048] The polyester polyol is preferably present in an amount of from 2% to 12% by weight, based on the total weight of the polyurethane-urea.

[0049] Component d) Amino-containing compounds The amino-containing carboxylate salt is one or more of 6-aminocaproate, lysinate, and N-(2-aminoethyl)-β-alanine monosodium salt.

[0050] The amino-containing sulfonate salt is one or more of sodium 2-[(2-aminoethyl)amino]ethanesulfonate and sodium 3-(cyclohexylamine)-1-propanesulfonate.

[0051] The amino-containing compound is one or more of 6-aminocaproate, lysinate, N-(2-aminoethyl)-β-alanine monosodium salt, sodium 2-[(2-aminoethyl)amino]ethanesulfonate, and sodium 3-(cyclohexylamine)-1-propanesulfonate.

[0052] Component d), the amino-containing compound, is preferably present in an amount of from 0.5 to 2 weight percent, and most preferably from 0.5 to 1.0 weight percent, based on the total weight of the polyurethane-urea.

[0053] Component e) Hydroxyl-Containing Carboxylic Acid The hydroxyl-containing carboxylic acid is preferably one or more of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid.

[0054] The hydroxyl-containing carboxylic acid is preferably in an amount of from 1% to 5% by weight, most preferably from 2% to 3% by weight, based on the total weight of the polyurethane-urea.

[0055] Component f) Neutralizer The neutralizing agent is preferably one or more of an organic tertiary amine and an inorganic base; most preferably one or more of triethylamine, triethanolamine, dimethylethanolamine, methyldiethanolamine, ethyldiisopropylamine, ammonia, sodium hydroxide, and potassium hydroxide.

[0056] The neutralizing agent is preferably present in an amount of 65 to 105 mol % based on the total moles of carboxyl groups of component e) hydroxyl-containing carboxylic acid.

[0057] The hydroxyl-containing carboxylic acid and the neutralizing agent may be directly present in the system in the form of a salt of the hydroxyl-containing carboxylic acid.

[0058] Ingredient g) It is reactive towards isocyanate groups, Component b) ~ Component e) Compounds different from Component g) a compound reactive towards any isocyanate group and different from components b) to e) may be one or more of a polyol having a hydroxyl functionality of 2 to 3 and an amino compound having an amino functionality of 2 to 3.

[0059] The polyol having a hydroxyl functionality of 2 to 3 is preferably one or more of diethylene glycol, propanediol, butanediol, hexanediol, pentanediol, trimethylolpropane and glycerin.

[0060] The amino compound having an amino functionality of 2 to 3 is preferably one or more of ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine, N-(2-hydroxyethyl)-ethylenediamine, isophoronediamine, hydrazine hydrate and diethylenetriamine.

[0061] Component g) is preferably present in an amount of 0.5 to 2.5 wt. %, most preferably 0.5 to 1 wt. %, based on the total weight of the polyurethane-urea.

[0062] system The system may further include one or more of an external emulsifier, a solvent, a reactive diluent, and a stabilizer, added in amounts commonly used by those skilled in the art.

[0063] Method for producing aqueous polyurethane-urea dispersions containing polyurethane-ureas Preferably, when step iv is performed before step ii, step iii is performed before step iv.

[0064] The steps of this method are preferably carried out in succession in the order of steps i, iii, ii and iv.

[0065] The preparation method preferably further comprises step v, introducing an organic solvent during or after step i.

[0066] The organic solvent is preferably a solvent that is miscible with water but inert towards isocyanate groups, more preferably one or more of acetone, methyl ethyl ketone, propylene glycol dimethyl ether, other ethers without hydroxyl functionality, and esters without hydroxyl functionality; most preferably one or more of acetone and butanone.

[0067] The organic solvent preferably does not contain pyrrolidone compounds.

[0068] The preparation process preferably further comprises a step vi of removing the organic solvent introduced in step v from the aqueous polyurethane-urea dispersion.

[0069] The organic solvent can be removed by distillation. The solvent can be removed during or after step iv.

[0070] The amount of organic solvent remaining in the aqueous polyurethane-urea dispersion is preferably less than 1.0 wt %, based on the total weight of the aqueous polyurethane-urea dispersion.

[0071] To promote the reaction of step i, a catalyst commonly used to prepare prepolymers, such as triethylamine, 1,4-diazabicyclo[2,2,2]-octane, tin dioctanoate or dibutyltin dilaurate, most preferably dibutyltin dilaurate, can be used.

[0072] The catalyst may be charged to the reactor simultaneously with the ingredients of step i, or may be added at a later time.

[0073] The degree of conversion of the components of step i can be obtained by testing the NCO content in the components. For this purpose, spectroscopic measurements, such as infrared or near infrared spectroscopy, as well as chemical analyses, such as refractive index determination or titration, can be carried out simultaneously on the extracted samples.

[0074] The prepolymer may be in a solid or liquid state at ambient temperature.

[0075] The degree of neutralization of the prepolymer may be from 50 mol % to 125 mol %, preferably from 65 mol % to 105 mol %.

[0076] Coating composition, binder or ink The coating composition, binder or ink preferably further comprises an additive, which is preferably one or more of adhesion promoters, lubricants, emulsifiers, light stabilizers, antioxidants, fillers, anti-settling agents, defoamers, wetting agents, flow control agents, antistatic agents, film forming aids, reactive diluents, plasticizers, catalysts, thickeners, pigments, dyes, tackifiers and matting agents.

[0077] In principle, the choice of additives and dosage amounts are known to those skilled in the art and can be easily determined.

[0078] The aqueous polyurethane-urea dispersions of the present invention can also be mixed and used with other water- or solvent-containing oligomers or polymers, such as water- or solvent-containing polyesters, polyurethanes, polyurethane-polyacrylates, polyacrylates, polyethers, polyester-polyacrylates, alkyd resins, addition polymers, polyamide / -imides or polyepoxides. To test the suitability of such mixtures, simple preliminary tests should be used in each case.

[0079] The aqueous polyurethane-urea dispersions of the present invention may be mixed and used together with other compounds that contain functional groups such as carboxyl groups, hydroxyl groups and / or blocked isocyanate groups.

[0080] The coating composition, binder or ink of the present invention is obtained by processing according to methods known to those skilled in the art.

[0081] Painting methods, adhesives or printing The substrate is preferably one or more of wood, metal, glass, fiber, textile, artificial leather, real leather, paper, plastic, rubber, foam, ceramic and various polymer coatings, and most preferably one or more of textile, plastic, ceramic, metal, real leather, artificial leather and various polymer coatings.

[0082] Coating can be accomplished by applying a coating composition, binder, or ink to the entire surface of the substrate, or to only one or more portions of the surface of the substrate.

[0083] The coating may be brush coating, dip coating, spray coating, roller coating, knife coating, flow coating, casting, or printing.

[0084] Printing method and printed matter Application can be accomplished by applying the coating composition, binder, or ink over the entire surface of the substrate, or only over one or more portions of the surface of the substrate.

[0085] Application can be by means of knife coating or printing, which is preferably inkjet printing. EXAMPLES

[0086] Working Example Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. If the definition of a term herein conflicts with the meaning commonly understood by those skilled in the art, the definition set forth herein shall prevail.

[0087] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are understood to be modified by the term "about." Accordingly, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained, unless indicated to the contrary.

[0088] As used herein, the term "and / or" refers to one or all of the cited elements.

[0089] As used herein, the words "include" and "comprise" encompass the cases where only the stated elements are present, and the cases where the stated elements plus other unstated elements are present.

[0090] Unless otherwise indicated, the terms "a," "an," and "the" as used herein are intended to include "at least one" or "one or more." For example, the term "a component" means one or more components, such that a plurality of components is contemplated and may be employed or used in the practice of an embodiment.

[0091] All percentages in this invention are by weight unless otherwise specified.

[0092] Analyses and measurements herein are performed at 23±2° C. unless otherwise specified.

[0093] The number average molecular weight of the polymer polyols is measured at 40° C. using gel permeation chromatography with tetrahydrofuran as the mobile phase against polystyrene standards.

[0094] Raw materials and chemicals Desmophen C2202: Polycarbonate diol available from Covestro, Germany, with a hydroxyl functionality of 2.0, number average molecular weight of 2000 g / mol. P200H / DS: Polyhexylene phthalate diol available from Covestro, Germany, with a hydroxyl functionality of 2.0, number average molecular weight of 2000 g / mol. Desmophen C1200: Polycarbonate polycaprolactone diol available from Covestro, Germany, with a polycarbonate:polycaprolactone ratio of 1.2:1 (by weight), a hydroxyl functionality of 2.0, and a number average molecular weight of 2000 g / mol. Desmodur® H: 1,6-hexamethylene diisocyanate, available from Covestro, Germany. Desmodur® I: Isophorone diisocyanate, available from Covestro, Germany. Desmodur® W: Dicyclohexylmethane diisocyanate, available from Covestro, Germany. AAS: an aqueous solution of sodium N-(2-aminoethyl)aminoethanesulfonate NH2-CH2CH2-NH-CH2CH2-SO3Na, available from Covestro, Germany, with a concentration of 49%. Dimethylolpropionic acid: A hydroxyl-containing carboxylic acid available from Sigma Aldrich. SP-9111: Available from Shanghai Xude Fine Chemicals Co., Ltd., a red viscous liquid and a bright red paste. BYK349: A silicone surfactant available from BYK. 1,2-Propylene glycol: co-solvent available from Shanghai Gaoxin Chemical Glass Instrument Co., Ltd. Tego825: Defoamer available from Evonik Specialty Chemicals (Shanghai) Co., Ltd. Borchigel L 75N: A rheology additive available from Borchers USA. Borchigel ALA: A rheology additive available from Borchers USA. Imprafix IO 3025: An isocyanate crosslinker available from Covestro.

[0095] Test Method Z-Average particle size and polydispersity index PDI study of waterborne polyurethane-urea dispersions One drop of the aqueous polyurethane-urea dispersion was added to 50 ml of ultrapure water and gently stirred for dilution. After dilution, it was tested on a Zetasizer Nano manufactured by Malvern (Malvern Zetasizer Nano ZS). The test temperature was 23.0±0.1°C. Test material settings: polystyrene latex (refractive index 1.590, absorption value 0.010); dispersant settings: water (temperature 23.0°C, viscosity 0.9308 cps, refractive index 1.330); and equilibration time 60 seconds. Sample cell type: disposable sample cell DTS0012. Positioning method: auto attenuation, auto optimization of positioning. Analysis mode: generic (normal resolution). Test angle: 173° backscatter (NIBS default). Each sample was tested for 3 rounds with 10 rounds per round, and the duration of each test was 10 seconds. The Z-average particle size and polydispersity index were the average of all tests, respectively. The Z-average particle size was defined according to standard ISO 13321 as the average particle size measured according to the principle of dynamic light scattering. The polydispersity index describes the distribution of particle sizes. The closer the PDI is to 0, the narrower the particle size distribution.

[0096] A Z-average particle size of less than 75 nm is considered to be acceptable. A polydispersity index PDI (narrow particle size distribution) of less than 0.3 is considered to be acceptable.

[0097] Viscosity of Water-Based Polyurethane-Urea Dispersions The viscosity was tested with a Brookfield Viscometer DV-II+ Pro according to standard ISO 3219:1994. 150 g of aqueous polyurethane-urea dispersion was weighed into a glass bottle. The viscosity was measured at room temperature (20-25 °C) using a spindle with a number of S62 at a rotation speed of 30 rpm.

[0098] Aqueous polyurethane-urea dispersions having a viscosity of less than 1000 mPa·s are considered to be suitable.

[0099] Solid content of aqueous polyurethane-urea dispersion (solid content) This was tested using a halogen moisture analyzer from Mettler Toledo (Mettler Toledo Halogen Moisture Analyzer Excellence HS153). A piece of glass fiber filter paper was placed on a standard aluminum weighing dish and 1 gram of the aqueous polyurethane-urea dispersion was dropped onto the glass fiber filter paper. A standard drying procedure was used with a drying temperature of 120°C and a stop standard level of 5 (1 mg / 140 seconds). That is, the sample was heated to 120°C and weighed continuously. If the weight loss of the sample was less than 1 mg within 140 seconds, the test was stopped and the remaining weight percentage was recorded as the solid content.

[0100] Method for Evaluating the Appearance of Water-Based Polyurethane-Urea Dispersions 50g of the aqueous polyurethane-urea dispersion was placed in a 3cm diameter transparent glass bottle and visually observed in front of a paper card with a black / white grid pattern. If the grid pattern behind the glass was clearly visible through the glass bottle and there was no obvious change in the color of the grid pattern, it was transparent. If the grid pattern behind the glass was clearly visible through the glass bottle, but on the other hand, the color of the grid pattern changed, it was translucent. If the grid pattern behind the glass bottle was not clearly visible, it was opaque.

[0101] If the aqueous polyurethane-urea dispersion was translucent or transparent in appearance it was considered to be qualified. If it was opaque in appearance it was disqualified.

[0102] Jungle testing of dried films of water-based polyurethane-urea dispersions Step 1: Preparation of the film 99% by weight of the aqueous polyurethane-urea dispersion or the comparative aqueous polyurethane-urea dispersion was added to a batching tank. Then 1% by weight of Borchigel ALA was added. This was thoroughly stirred and the viscosity was adjusted to about 5000 cps. A glossy release paper of A4 size was placed on a glass table and smoothly fixed on the table with adhesive tape. A 500 μm film applicator was placed on the top end of the release paper. The film applicator was held by hand at both ends and pulled down to the bottom at a constant speed without stopping. After completion, the film applicator was washed. The resulting sample was removed, placed on a heat-resistant plate, and dried in a 50°C oven for 30 minutes. After the sample was dried, it was placed in a 150°C oven for 3 minutes. The sample was removed and the front side of the film was covered with talc powder in a fume hood. The film was removed from the release paper, talc powder was applied to the back side, and left at room temperature for 24 hours. The film preparation was completed.

[0103] The films were cut into dumbbell-shaped test strips using a standard cutter according to S2 of standard DIN 53504. The initial 100% modulus, initial tensile elongation at break and initial tensile strength of the samples were tested according to test standard DIN 53504 in a tensile tester from GOTECH.

[0104] Step 2: Jungle aging test The prepared films were placed in a thermo-hygrostatic chamber at a temperature of 70° C. and a relative humidity of 95%. At least three parallel samples were prepared for each example or comparative example.

[0105] After 7 days the films were removed and cut into dumbbell-shaped test specimens according to S2 of standard DIN 53504 with a standard cutter and tested after 24 hours at 23 °C and 55% relative humidity. The 100% modulus, tensile elongation at break and tensile strength after aging were tested according to test standard DIN 53504 on a tensile tester from GOTECH.

[0106] If the aged 100% modulus, tensile elongation at break, and tensile strength decreased by 50% or less from the initial 100% modulus, tensile elongation at break, and tensile strength, the sample was considered to have passed the test. The sample was again placed in a constant temperature and humidity chamber at a temperature of 70° C. and a relative humidity of 95%. After 7 days, the sample was again removed for testing for aged 100% modulus, tensile elongation at break, and tensile strength. If the morphology of the sample was significantly aged (e.g., sticky, deformed, or had holes, etc.), or if the aged 100% modulus, tensile elongation at break, and tensile strength decreased by more than 50% from the initial 100% modulus, tensile elongation at break, and tensile strength, the sample was considered to have failed the test. The aging test was completed, and the time (in weeks) that the sample film was stored in the chamber at constant temperature and humidity was recorded as the result of the jungle aging test of the sample. A sample was considered to have passed the test if the 100% modulus, tensile elongation at break, and tensile strength after aging were reduced by 50% or less from the initial 100% modulus, tensile elongation at break, and tensile strength. The sample was again placed in a constant temperature and humidity chamber at 70°C and 95% relative humidity. The sample was removed again for analysis after 7 days, and so on.

[0107] Longer storage times indicate better hydrolysis resistance of the samples. Jungle aging test times of more than 2 weeks were considered qualified.

[0108] Equipment used in the test Tensile Tester from GOTECH: Model GOTECH / AI-3000, available from GOTECH Testing Machines Inc. Film applicator: ISO-500μm model available from Shanghai Modern Environmental Engineering Technology Co., Ltd. Temperature and humidity chamber: GWS EW0440, available from Guangzhou Wusuo Environmental Instrument Co., Ltd. Film Thickness Gauge: Model SM-114 available from TECLOCK Co., Ltd.

[0109] Color fastness test to wet rubbing Step 1: A print paste was prepared by mixing the following components: 82 wt. % aqueous polyurethane-urea dispersion or comparative aqueous polyurethane-urea dispersion, 10 wt. % SP9111, 3 wt. % 1,2-propylene glycol, 0.5 wt. % Tego825, 0.5 wt. % BYK349, 1 wt. % Borchigel L75N and 3 wt. % Imprafix IO 3025.

[0110] Step 2: Preparation and testing of printed materials 1. The printing paste prepared above was printed using a 120 mesh nylon screen printing plate, and the substrate was white leather prepared with water-based polyurethane, and applied six times with a spatula. 2. The printed sample was left to dry naturally at 25°C and 50% relative humidity for 72 hours. 3. Color fastness to wet rubbing was tested with a crock meter (GT-7034-A, GOTECH Testing Machines Inc.) according to standard AATCC-8-2016. Dyeing was evaluated according to standard CTA, using a gray scale with a total of 1-5 levels of scoring. The higher the score, the better the color fastness to wet rubbing. Color fastness to wet rubbing with a score of 4 or more is considered qualified.

[0111] Equipment used in the test Disperser: Model SFJ400, available from Shanghai Modern Environmental Engineering Technology Co., Ltd. Electronic balance: Model BSA4202S Max 4200g, d=0.01g available from Sartorius Group.

[0112] Preparation of aqueous polyurethane-urea dispersions Water-based polyurethane-urea dispersion 1 225.14 g of Desmophen C2202 and 34.11 g of P200H / DS were dehydrated at 100° C. and 100 mbar for 1 hour. After the mixture was cooled to 70° C., 9.03 g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 5.99 g of Desmodur® H and 61.01 g of Desmodur® I were added at 65° C. and reacted at 100° C. until the isocyanate content was 2.84%. Then, it was dissolved in 596 g of acetone and cooled to 40° C. to obtain a reaction solution. Then, 6.68 g of triethylamine was added and stirred vigorously for 10 minutes. A solution of 5.26 g of sodium N-(2-aminoethyl)aminoethanesulfonate and 2.9 g of ethylenediamine in 33.32 g of water was added and stirred vigorously for 10 minutes. Then, 597 g of water was added to disperse the mixture. Subsequently, the acetone was separated by distillation to obtain an aqueous polyurethane-urea dispersion 1 having a solid content of 35.8 wt.%.

[0113] Water-based polyurethane-urea dispersion 2 246.37g of Desmophen C2202 and 12.88g of P200H / DS were dehydrated at 100°C and 100mbar for 1 hour. After the mixture was cooled to 70°C, 9.03g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 5.99g of Desmodur® H and 61.01g of Desmodur® I were added at 65°C and reacted at 100°C until the isocyanate content was 2.84%. Then, it was dissolved in 596g of acetone and cooled to 40°C to obtain a reaction solution. Then, 6.68g of triethylamine was added and stirred vigorously for 10 minutes. A solution of 5.26g of sodium N-(2-aminoethyl)aminoethanesulfonate and a solution of 2.9g of ethylenediamine in 33.32g of water were added and stirred vigorously for 10 minutes. Then, 596g of water was added to disperse the mixture. Subsequently, the acetone was separated by distillation to obtain an aqueous polyurethane-urea dispersion 2 having a solid content of 36.5 wt.%.

[0114] Comparative Water-Based Polyurethane-Urea Dispersion 1 259.26 g of Desmophen C2202 was dehydrated at 100° C. and 100 mbar for 1 hour. After cooling to 70° C., 9.03 g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 5.99 g of Desmodur® H and 61.01 g of Desmodur® I were added at 65° C. and reacted at 100° C. until the isocyanate content was 2.84%. Then, it was dissolved in 596 g of acetone and cooled to 40° C. to obtain a reaction solution. Then, 6.68 g of triethylamine was added and stirred vigorously for 10 minutes. A solution of 5.26 g of sodium N-(2-aminoethyl)aminoethanesulfonate and a solution of 7.06 g of n-butylamine in 60.67 g of water were added and stirred vigorously for 10 minutes. Then, 577 g of water was added to disperse the mixture. Subsequently, the acetone was separated by distillation to obtain Comparative Aqueous Polyurethane-urea Dispersion 1 having a solid content of 36.4 wt.%.

[0115] Comparative Water-Based Polyurethane-Urea Dispersion 2 259.26 g of Desmophen C2202 was dehydrated at 100° C. and 100 mbar for 1 hour. After cooling to 70° C., 9.03 g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 68.93 g of Desmodur® I was added at 65° C. and reacted at 100° C. until an isocyanate content of 2.83% was reached. Then, it was dissolved in 599 g of acetone and cooled to 40° C. to obtain a reaction solution. Then, 6.68 g of triethylamine was added and stirred vigorously for 10 minutes. A solution of 5.26 g of sodium N-(2-aminoethyl)aminoethanesulfonate and 2.9 g of ethylenediamine in 33.32 g of water was added and stirred vigorously for 10 minutes. Then, 600 g of water was added to disperse the mixture. The acetone was then separated by distillation to obtain comparative aqueous polyurethane-urea dispersion 2 having a solids content of 36.8 wt. %.

[0116] Comparative Water-Based Polyurethane-Urea Dispersion 3 216.05 g of Desmophen C2202 and 43.21 g of P200H / DS were dehydrated at 100° C. and 100 mbar for 1 hour. After cooling the mixture to 70° C., 9.03 g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 5.99 g of Desmodur® H and 61.01 g of Desmodur® I were added at 65° C. and reacted at 100° C. until the isocyanate content was 2.84%. This was then dissolved in 596 g of acetone and cooled to 40° C. to obtain a reaction solution. 6.68 g of triethylamine was then added and stirred vigorously for 10 minutes. A solution of 5.26 g of sodium N-(2-aminoethyl)aminoethanesulfonate and 2.9 g of ethylenediamine in 33.32 g of water was added and stirred vigorously for 10 minutes. 596 g of water was then added to disperse the mixture. Subsequently, the acetone was separated by distillation to obtain comparative aqueous polyurethane-urea dispersion 3 having a solids content of 35.5 wt. %.

[0117] Comparative Water-Based Polyurethane-Urea Dispersion 4 420 g of Desmophen C1200 was dehydrated at 100° C. and 100 mbar for 1 hour. After cooling to 70° C., 20.54 g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 25.74 g of Desmodur® W and 108.22 g of Desmodur® I were added at 65° C. and reacted at 100° C. until the isocyanate content was 3.24%. Then, it was dissolved in 1021 g of acetone and cooled to 40° C. to obtain a reaction solution. Then, 15.21 g of triethylamine was added and stirred vigorously for 10 minutes. A solution of 13.81 g of sodium N-(2-aminoethyl)aminoethanesulfonate and 9.6 g of ethylenediamine in 103.83 g of water was added and stirred vigorously for 10 minutes. Then, 968 g of water was added to disperse the mixture. The acetone was then separated by distillation to obtain comparative aqueous polyurethane-urea dispersion 4 having a solids content of 30.7% by weight.

[0118] Comparative Water-Based Polyurethane-Urea Dispersion 5 225.14 g of Desmophen C2202 and 34.11 g of P200H / DS were dehydrated at 100° C. and 100 mbar for 1 hour. After cooling the mixture to 70° C., 9.03 g of dimethylolpropionic acid was added and stirred until uniformly dispersed. 5.99 g of Desmodur® H and 61.01 g of Desmodur® I were added at 65° C. and reacted at 100° C. until the isocyanate content was 2.84%. Then, it was dissolved in 596 g of acetone and cooled to 40° C. to obtain a reaction solution. Then, 6.68 g of triethylamine was added and stirred vigorously for 10 minutes. A solution of 3.72 g of ethylenediamine in 24.43 g of water was added and stirred vigorously for 10 minutes. Then, 605 g of water was added to disperse the mixture. Subsequently, the acetone was separated by distillation to obtain comparative aqueous polyurethane-urea dispersion 5 having a solid content of 35.2 wt.%.

[0119] Comparative Water-Based Polyurethane-Urea Dispersion 6 225.14 g of Desmophen C2202 and 34.11 g of P200H / DS were dehydrated at 100° C. and 100 mbar for 1 hour. 4.96 g of Desmodur® H and 50.51 g of Desmodur® I were added at 65° C. and reacted at 100° C. until the isocyanate content was 3.40%. Then, it was dissolved in 559 g of acetone and cooled to 40° C. to obtain a reaction liquid. Then, 17.34 g of a solution of sodium N-(2-aminoethyl)aminoethanesulfonate and a solution of 2.4 g of ethylenediamine in 62.76 g of water were added and stirred vigorously for 10 minutes. Then, 533 g of water was added to disperse the mixture. Then, the acetone was separated by distillation to obtain a comparative aqueous polyurethane-urea dispersion 6 with a solids content of 34.9% by weight.

[0120] Table 1 shows the evaluation results of the viscosity, Z-average particle size, polydispersity index (PDI), color fastness to wet rubbing, jungle test and appearance of the aqueous polyurethane-urea dispersions of the examples of the present invention and the comparative examples.

[0121] [Table 1]

[0122] remarks: *Color fastness to wet rubbing was not tested due to unsatisfactory results in the Jungle test; ** Jungle testing not performed due to unsatisfactory test results for color fastness to wet rubbing; ***Due to inadequate Z-average particle size of the aqueous polyurethane-urea dispersion, color fastness to wet rub and jungle tests were not performed.

[0123] The aqueous polyurethane-urea dispersions of the examples of this patent application had the properties of small particle size, narrow particle size distribution and translucency. Therefore, the wet films formed by the aqueous polyurethane-urea dispersions of the present invention had bright colors. The paint films of the aqueous polyurethane-urea dispersions of this patent application had high color fastness to wet rubbing and long test times in the jungle test of dry films. Therefore, the dry films formed thereby had good color fastness to rubbing and hydrolysis resistance. The aqueous polyurethane-urea dispersions of this patent application had low viscosity and were particularly suitable as resin binder components for ink formulations for inkjet printing.

[0124] The aqueous polyurethane-urea dispersion system of Comparative Examples 1 and 2 does not contain aromatic polyester polyol, and the aqueous polyurethane-urea dispersion cannot have both good jungle test time and good color fastness to wet rubbing.In addition, the appearance of the aqueous polyurethane-urea dispersion of Comparative Example 1 is opaque.That is, the film formed thereby has poor color rendering and is not bright in color.

[0125] The weight ratio of polycarbonate polyol to aromatic polyester polyol in the aqueous polyurethane-urea dispersion system of Comparative Example 3 was less than 6:1, and the jungle test time of the aqueous polyurethane-urea dispersion was short.

[0126] The weight ratio of polycarbonate polyol to aliphatic polyester polyol in the system of the aqueous polyurethane-urea dispersion of Comparative Example 4 was greater than 20:1, and the aqueous polyurethane-urea dispersion had a high viscosity and a short jungle test time.

[0127] The aqueous polyurethane-urea dispersion system of Comparative Example 5 did not contain an amino group-containing compound, and the aqueous polyurethane-urea dispersion had a large Z-average particle size, low color fastness to wet rubbing, and an opaque appearance.

[0128] The aqueous polyurethane-urea dispersion system of Comparative Example 6 did not contain a hydroxyl-containing carboxylic acid, and the aqueous polyurethane-urea dispersion had a large Z-average particle size, a large polydispersity index, and an opaque appearance.

[0129] Those skilled in the art will readily understand that the present invention is not limited to the above details, and may be embodied in other specific forms without departing from the spirit or main characteristics of the present invention. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, and the scope of the present invention is thus exemplified by the claims, not the above description. Any modifications should therefore be considered as belonging to the present invention insofar as they come within the meaning and scope of the claims.

Claims

1. 1. An aqueous polyurethane-urea dispersion comprising a polyurethane-urea, the polyurethane-urea comprising the following components: a. at least one polyisocyanate; b. at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1; c. at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, said polyester polyol being obtained by reacting a mixture comprising at least one of an aromatic diacid and an aromatic acid anhydride with a dihydric alcohol; d. at least one amino-containing compound, which is one or more of an amino-containing carboxylic acid, an amino-containing carboxylate, an amino-containing sulfonic acid, and an amino-containing sulfonate; e. at least one hydroxyl-containing carboxylic acid; f. at least one neutralizing agent; and g. Optionally, a compound reactive with isocyanate groups, different from components b) to e), having a molecular weight of 32 g / mol to 400 g / mol. (Here, the weight ratio of polycarbonate polyol to polyester polyol is 6:1 to 20:1.) An aqueous polyurethane-urea dispersion obtained by reaction of a system comprising:

2. 2. The aqueous polyurethane-urea dispersion of claim 1, wherein the amount of organic solvent in the aqueous polyurethane-urea dispersion is less than 1% by weight, based on the total weight of the aqueous polyurethane-urea dispersion.

3. The aqueous polyurethane-urea dispersion has the following properties: a viscosity of 10 mPa·s to 1000 mPa·s (tested according to standard ISO 3219:1994 using a viscometer from Brookfield); a solids content of 30-40% by weight (tested with a halogen moisture meter from Mettler Toledo); Z-average particle size of 30 nm to 75 nm (tested with a Zetasizer Nano from Malvern); and Polydispersity index of 0-0.3 (tested with a Zetasizer Nano from Malvern) 2. The aqueous polyurethane-urea dispersion of claim 1, wherein the dispersion comprises at least one of the following:

4. A method for producing an aqueous polyurethane-urea dispersion comprising the polyurethane-urea of ​​any one of claims 1 to 3, comprising the steps of: i. reacting some or all of component a) at least one polyisocyanate, component b) at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1, component c) at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, component e) at least one hydroxyl-containing carboxylic acid, and component g) optionally a compound reactive with isocyanate groups different from components b) to e) to obtain a prepolymer; ii. Reacting the prepolymer with component d) at least one amino-containing compound and component g) optionally a compound reactive with isocyanate groups different from components b) to e) to obtain a polyurethane-urea; iii. adding component f) at least one neutralizing agent before or after step ii; and iv. before, during, or after step ii), introducing water to obtain an aqueous polyurethane-urea dispersion. A method comprising:

5. A coating composition, binder or ink comprising an aqueous polyurethane-urea dispersion comprising the polyurethane-urea of ​​any one of claims 1 to 3.

6. Use of an aqueous polyurethane-urea dispersion comprising the polyurethane-urea according to any one of claims 1 to 3 for preparing coated, glued or printed objects.

7. An object or article comprising a substrate that has been treated, coated, glued, sealed or printed with an aqueous polyurethane-urea dispersion comprising the polyurethane-urea of ​​any one of claims 1 to 3.

8. A printing method comprising the steps of: applying an aqueous polyurethane-urea dispersion comprising the polyurethane-urea of ​​any one of claims 1 to 3 to the surface of a substrate, and then curing.

9. A printed article comprising a substrate and a coating formed by applying an aqueous polyurethane-urea dispersion comprising the polyurethane-urea of ​​any one of claims 1 to 3 onto the substrate.