Urea-urethane composition and their use as rheology control additives

Abstract

The present invention relates to a urea-urethane composition comprising (a) at least one urea-urethane compound with a least one terminal group of formula (I) wherein R1 is a radical selected from the group consisting of C4 to C32 alkyl, C4 to C22 alkenyl, C5 to C12 cycloalkyl, C7 to C24 aralkyl, C6 to C24 aryl, a radical of formula R6-(O-CxH2x]y -, a radical of formula R6-[O-C(=O)-CwH2w]z - and a radical of formula R6-(O-CxH2x)y- [O-C(=O)-CwH2w]z -; R3 is a divalent group selected from the group consisting of an aromatic group and an araliphatic group; R6 is C1 to C32 alkyl; x is an integer from 2 to 4; w is an integer from 2 to 12; y and z is an integer from 1 to 20; (b) at least one aprotic solvent and (c) at least one alkyl ammonium salt, whose alkyl radicals independently of another is unsubstituted or hydroxy-substituted, a process for preparing the composition and the use of said composition in coating compositions as a thixotropic agent for coating formulations.

Description

[0001] 240554 1 Urea-urethane composition and their use as rheology control additives Description The present invention relates to a urea-urethane composition comprising at least one urea- urethane terminal group. The present invention further relates to a process for preparing the composition according to the present invention and the use of said composition in coating compositions as a thixotropic agent for coating formulations. Said composition is advantageous as rheology modifier additive in PVC, plastisol and cement formulations or coating formulations like paints, lacquers, adhesives and inks. It is state of the art to use urea-urethane compounds as rheology modifier additives in paints and coating formulations. They make it possible to obtain, for example, a thixotropic or pseudoplastic effect. Thixotropic agents in the liquid form are particularly valued since they can be easily incorporated in a formulation, in particular coating formulation. The method of action of the urea-urethanes to modify the rheology in a coating system involves the formation of reversible hydrogen bonds. Once the urea-urethane additive is mixed into the coating, the hydrogen bonds form between the additives and the coating forms a gel. Upon the addition of shear (mixing, shaking, etc.) the hydrogen bonds break up and the coating becomes flowable. After the shear force is removed, the hydrogen bonds build up again and the coating forms a gel again. The urea-urethane compound is generally prepared by a two-step procedure wherein in the first step a monoalkohol reacts with a diisocyanate. An almost equimolar amount of diisocyanate to monoalcohol leads to a monoadduct and thus to a monoisocyanate-urethan. In the second step, this monoisocyanate-urethan reacts with a diamine to a urea-urethane compound. The first step does not provide access to pure monoadduct, but instead forms mixtures of monoadducts and diadduct. Due to this side reaction, there is a small rest of diisocyanate. Unless isolation or purification steps are taken, this rest of diisocyanate leads to the formation of longer-chain polyurea-urethanes as by-products. Since polyurea-urethanes tend to precipitate and are difficult to keep in solution, one approach to solving the problem is to avoid their formation. US 6,420,466 describes a process for preparing a thixotropic agent which contains urea-urethanes wherein monohydroxyl compounds are reacted with an excess of toluene diisocyanate, whereby the unreacted portion of the toluene diisocyanate is removed from the reaction mixture and the monoisocyanate adduct 240554 2 obtained is further reacted with diamines in the presence of lithium salts. The disadvantage of this process is that the subsequent removal stoichiometric excess of diisocyanate by vacuum distillation is a complex and expensive process. There is still an ongoing need to provide storage stable urea-urethane compounds. It has been a challenge for the researchers to reduce the free diisocyanate in the first step such that the monoisocyanate adduct, i.e. without free diisocyanates, is formed which when reacts with the diamine in the second step results into a more definite structure of urea-urethane. US 4,314,924 disclose polyurea rheology modifiers comprising a solution of diurea-diurethane in DMSO or N-methyl-2-pyrrolidone as an aprotic solvent and from 0.1 to 2 mol of lithium chloride (LiCl) per urea group. WO 2019 / 096611 proposes feeding a mixture of lithium salt, diamine, and aprotic solvents to the urea-urethane. The older EP application No 24153711.7 proposes to improve the stability of the polyurea- urethane with a caprolactone caprolactam mixtures as an aprotic solvent. Furthermore, the earlier EP application No 24153708.3 proposes to improve the storage stability of the polyurea- urethane with dimethyl isosorbite or dihydrolevoglucosenone as an aprotic solvent. In both cases, lithium chloride is used as a salt. In a few examples, dioctyl sulfosuccinate sodium salt is alternatively added. In the wake of the high global demand for lithium, there is a desire to find alternatives to lithium compounds. It was an object of the present invention to provide a storage stable urea-urethane composition which can be prepared in a simple and economical process, and providing a urea- urethane composition which has rheological performance qualities equivalent to, or preferably even better than, those of the comparable additives of the prior art. According to the present invention, this object has been solved by a urea-urethane composition comprising (a) at least one urea-urethane compound with at least one terminal group of formula (I) wherein R1 is a radical selected from the group consisting of C4to C32alkyl, C4to C22alkenyl, C5to C12cycloalkyl, C7to C24aralkyl, C6to C24aryl, a radical of formula R6-(O-CxH2x]y̶ , 240554 3 a radical of formula R6-[O-C(=O)-CwH2w]z̶ and a radical of formula R6-y̶ [O-C(=O)-CwH2w]z̶ ; R3 is a divalent group selected from the group consisting of an aromatic group and an araliphatic group; R6 is C1 to C32 alkyl; x is an integer from 2 to 4; w is an integer from 2 to 12; y and z is an integer from 1 to 20; (b) at least one aprotic solvent and (c) at least one alkyl ammonium salt, whose alkyl radicals independently of another is unsubstituted or hydroxy-substituted. The present invention further relates to a process for preparing the urea-urethane, coating composition comprising it and the use of the urea-urethane composition as a thixotropic agent. In the present patent application, the terms "comprises a" and "comprises an" mean "comprises one or more". The term “thixotropic effect” as used herein means a property exhibited by a viscous or a gel like product turning more liquid as it is deformed for longer time and more rigorously (e.g. by stirring). The term ‶alkyl″, as used herein, refers to an acylic saturated aliphatic group, including linear or branched alkyl groups. A C1-C32alkyl means an alkyl having from 1 to 32 carbon atoms. The term ‶alkenyl″, as used herein, refers to acyclic unsaturated aliphatic group, including linear or branched aliphatic group, and comprise at least one double bond, preferably 1, 2, or 3 double bonds. A C4-22alkenyl means an alkenyl having from 4 to 22 carbon atoms. Within the context of the present invention and as used herein, the term “cycloalkyl” refers to a saturated cyclic hydrocarbon residue including 6, 7, 8, 9, 10, 11 or 12 atoms, as ring members. Cycloalkyl is preferably C5to C7cyclohexyl, especially cyclopentyl and cyclohexyl. The term “aryl” refers to aromatic carbocyclic group of 6 to 24 ring members, including both mono, bi-, and tri-cyclic ring systems. Non-limiting examples of aryl include indenyl, phenyl and naphthyl. 240554 4 The term "arylalkyl" means an alkyl group by an aryl group. Representative examples of aralkyl include, but are not limited to, benzyl, o-tolyl, m-tolyl, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl and mesityl. The term "solvent" means a liquid having the property of dissolving, diluting or lowering the viscosity of other substances without chemically modifying them and without itself being modified. The term "aprotic solvent" means a solvent which does not have an acidic hydrogen atom. In particular, an aprotic solvent does not comprise a hydrogen atom bonded to a heteroatom (O, N or S). The term “theoretical NCO content” refers to the content of NCO which is theoretically calculated based on only half amount of the NCO groups from diisocyanate reacted with R1- OH. The urea-urethane composition according to the invention comprises a at least one urea- urethane compound with at least one terminal group of formula (I) preferably with two terminal groups of formula (I) independent of one another. Preferred is an urea-urethane composition comprising (a) at least one urea-urethane compound of formula II, (II) wherein R1 and R2 independently of one another are a radical selected from the group consisting of C4to C32alkyl, C4to C22alkenyl, C5to C12cycloalkyl, C7to C24aralkyl, C6 to C24 aryl, a radical of formula R6-(O-CxH2x]y̶ , a radical of formula R6-[O-C(=O)-CwH2w]z̶ and a radical of formula R6-(O-CxH2x)y̶ [O-C(=O)-CwH2w]z̶ ; R3 and R4 independently of one another are a divalent group selected from the group consisting of an aromatic group and an araliphatic group 240554 5 R5 is a divalent group selected from the group consisting of an aliphatic group, a cycloaliphatic group, an group, an araliphatic group and a heterocyclic group R6 is C1to C32-alkyl x is an integer from 2 to 4; w is an integer from 2 to 12; y and z is an integer from 1 to 20; (b) at least one aprotic solvent and (c) at least one alkyl ammonium salt, whose alkyl radicals independently of another is unsubstituted or hydroxy-substituted. In one embodiment according to the present invention, R1, R2 and R6 independently of one another is linear or a branched alkyl selected from the group consisting of n-butyl, n-pentyl, n- hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n- pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n- docosyl, 2-ethylhexyl, 2-propyl-heptyl, 2-butyl-1-octyl, 2-pentyl-1-nonyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoeicosyl, isoheneicosyl and isodocosyl. In an embodiment according to the present invention, R1 and R2 independently of one another linear or a branched alkenyl selected from the group consisting 1-hexenyl, 2-hexenyl, 1- heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, 1-nonenyl, 2-nonenyl, 1-decenyl, 2-decenyl, 1- undecenyl, 2-undecenyl, 1-dodecenyl, 2-dodecenyl, 1-tridecenyl, 2-tridecenyl, 1-tetradecenyl, 2- tetradecenyl, 1-pentadecenyl, 2-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 1-nonadecenyl, 2-nonadecenyl, 1-eicosenyl, 2- eicosenyl, cis-7-decenyl, cis-9-octadecenyl (oleyl), cis-8,11-heptadecadienyl, cis-9,12- octadecadienyl (linoleyl), cis-10,13-nonadecadienyl and cis-6,9,12-octadecatrienyl. In an embodiment according to the present invention, R1 and R2 independently of one another is a cycloalkyl selected from the group consisting of cyclohexyl, cycloheptyl, cycloctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl. In an embodiment according to the present invention, R1 and R2 independently of one another is an aralkyl selected from the group consisting of benzyl, o-tolyl, m-tolyl, p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl and mesityl. 240554 6 In an embodiment according to the present R3 and R4 independently of one another are a divalent group selected from the group consisting of an aromatic group and an araliphatic group. Preferably these groups are derived from a diisocyanate especially these groups are derived from the group consisting of toluene diisocyanates and methylene diphenyl diisocyanate. In an embodiment according to the present invention, R5 is divalent group selected from the group consisting of an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group. Preferably these groups are derived from a diamine. The composition according to the present invention comprises the at least one urea-urethane compound, at least one at least one aprotic solvent and at least one alkyl ammonium salt, whose alkyl radicals independently of another is unsubstituted or hydroxy-substituted. According to one preferred embodiment, the aprotic solvent is chosen from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N- ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl- phosphoric acid triamide, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, γ- valerolactone, α-angelica lactone, α-methylene-γ-butyrolactone, α-hxdroxy-γ- butyrolactone, caprolactone, caprolactam, dimethyl isosorbide (DMI) and dihydrolevoglucosenone (DHGS). In particular, the aprotic solvent is chosen from dimethyl sulfoxide, N-butylpyrrolidone, γ-valerolactone, α-angelica lactone, α-methylene-γ- butyrolactone, α-hxdroxy-γ-butyrolactone, caprolactone, caproplactam, dimethyl isosorbide and dihydrolevoglucosenone and their mixtures. The urea-urethane composition can in particular comprise from 20% to 80% by weight, in particular from 40% to 80% by weight and more particularly from 50% to 70% by weight of aprotic solvent, with respect to the weight of the urea-urethane composition. Surprisingly, it has been found that the presence of an alkyl ammonium salt leads to the formation of a urea-urethane composition with advantageous properties. The urea-urethane compositions according to the invention are good storage stable. They further have good thickening properties in formulations. which upon use as an additive in paint and coating formulations imparts thixotropic properties to the formulations. 240554 7 Suitable alkyl ammonium salts are mono-, di- and trialkylated ammonium salts as well as quaternary ammonium salts. In quaternary salts, the nitrogen atom carries four alkyl residues. Since the alkyl ammonium salt and the urea-urethane are diluted in the aprotic solvent, the mono-, di- and trialkylated ammonium salts also have a stable cation. Preference is given to trialkyl ammonium salts and / or quaternary alkyl ammonium salts as part of the composition. According to one preferred embodiment of the present invention the alkyl ammonium salt is an unsubstituted alkyl ammonium salt or a hydroxylalkyl ammonium salts. Preferred are alkyl ammonium salts are compounds of the formula III An(III) R7 is a hydrogen atom or C1to C18alkyl; R8, R9 and R10 independently of one another are selected from the group consisting of C1to C18alkyl and C1to C18hydroxyalkyl; AnΘis an anionic radical. In connection with the alkyl ammonium salts alkyl is preferably straight-chain or branched C1to C18alkyl radicals, especially C1to C6and with particular preference C1to C4, alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2- ethylhexyl, n-dodecyl or n-stearyl. Preferred alkyl radicals are ethyl, n-propyl and / or iso-propyl. In connection with the alkyl ammonium salts C1to C18hydroxyalkyl, in which the alkyl radicals may be straight-chain or branched, and in particular is C1-C4-alkyl, preferably selected from the group consisting of 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-methyl-2-hydroxypropyl, and 4- hydroxybutyl. According one preferred embodiment the alkyl ammonium salts is a compound of the formula III 240554 8 wherein R7 is a hydrogen atom or C1to alkyl; R8 and R9 independently of one another are C1to C18alkyl or C1to C18hydroxyalkyl, preferably independently of one another are C1to C14alkyl or C1to C14hydroxyalkyl; R10 is C1to C18hydroxyalkyl, preferably C1to C4hydroxyalkyl; AnΘis an anionic radical. Suitable trialkyl ammonium salts, in which R7 stands for hydrogen, are known and are for example obtainable by reacting a tertiary amine with a protic acid such as hydrochloric acid, sulfuric acid, methyl sulfonic acid or p-toluene sulfonic. Suitable quaternary ammonium salts are known and can be prepared for example by a quaternization of tertiary amines. Suitable quaternization agents are, for example, dimethyl sulphate, diethyl sulphate, methyl chloride, ethyl chloride or benzyl chloride or methyl iodide. Both the trialkyl ammonium salts and the quaternary ammonium salts are based on a trialkylamine or a hydroxysubstituted trialkylamine. Preferably the alkylammonium salt is based on a tri(C1-C18)-alkylamine or a hydroxyl tri(C1-C18)-alkylamine, preferably a tri(C1-C4)-alkylamine or a hydroxyl tri(C1-C4)-alkylamine. Suitable trialkylamine are unsubstituted tri(C1-C18)-alkylamines. Preferred tri(C1-C4)-alkylamines from which the alkyl ammonium salt derives are selected from the group consisting of trimethylamine and triethylamine. Preferred hydroxyl tri(C1-C4)-alkylamines from which the alkyl ammonium salt derives are selected from the group consisting of triethanolamine, triisopropanolamine, methyldiethanolamine, butyldiethanolamine and methyldiisopropanolamine. Preferred anionic radicals of the alkyl ammonium salt (III) are anions of a protic acid where the protic acid has a pKa of ≤5, preferably ≤3, especially ≤0 in water at 20°C. Suitable protic acids from which the anion derives are hydrochloric acid, nitric acid, sulfuric acid, hydrogen-sulfuric acid and p-toluene sulfonic acid. Preferred anions are selected from the group consisting of halogenide anions like chloride, bromide, fluoride and iodide, sulfate, hydrogen sulfate, nitrate and p-toluene sulfonate. 240554 9 Especially preferred alkylammonium salts are cholinchloride (= 2-Hydroxy-N,N,N-trimethylethan- 1-aminium chloride, CAS No 67-48-1), chloride, triethylamine chloride and triethanolamine p-toluone sulfonate. In an embodiment according to the present invention, the alkyl ammonium salt (III) is present in the range of ≥ 0.03 to ≤ 0.5 mol, preferably in the range of ≥ 0.1 to ≤ 0.4 mol, relative to the mol equivalent of the diisocyanate. The urea-urethane composition according to the invention can be prepared according to the process described below. The preparation process according to the invention comprises a step (i), a step (ii), a step (iii) and optionally one or more additional steps which can take place before stage (i), between step (i) and step (ii), between step (ii) and step (iii), and / or after step iii). Preferred is a process for preparing the urea-urethane composition comprising the steps (i) providing the at least one diisocyanate of the formula NCO-R3-OCN; wherein R3 is a divalent group selected from the group consisting of an aromatic group and an araliphatic group; (ii) adding to the diisocyanate at least one monohydroxy compound R1-OH to obtain a monoisocyanate-urethan, wherein in step (ii) the molar ratio of the monohydroxyl compound to the diisocyanate is in the range of ≥1 : 1 to ≤ 1.5 : 1; (iii) adding to the monoisocyanate-urethan the aprotic solvent and the alkyl ammonium salt and at least one diamine of the formula H2N-R5-NH2in form of a composition or the diamine following the aprotic solvent and the alkyl ammonium salt, wherein R5 is a divalent group selected from the group consisting of an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group. The present invention further relates to urea-urethane composition obtainable by this process. The conditions applied in steps (i) to (iii) of the process according to the present invention might vary in broad ranges. Preferably, in step (iii) the temperature is in the range of ≥ 30°C to ≤ 100°C, preferably in the range of ≥ 40°C to ≤ 80°C, and more in the range of ≥ 40°C to ≤ 60°C. In context of the present invention the term “monoisocyanate urethane” refers to an addition product of the monohydroxyl compound and the diisocyanate. The monoisocyanate adduct has one free reactive isocyanate groups. 240554 10 The R1, R2, R3, R4 and R5 groups, the of formula OCN-R3-NCO and / or OCN-R4- NCO, the alcohol of formula R1 -OH and / or R2-OH and the diamine of formula H2N-R5-NH2can in particular be as defined above for the compound of formula (I) und formula (II). According to step (i), the diisocyanate of the formula NCO-R3-OCN is provided. The diisocyanate can be used both in substance or in the form of a solution. Preferred diisocyanates are toluene diisocyanates and methylene diphenyl diisocyanate. Preferably, the diisocyanate is selected from either 2,4-toluene diisocyanate or an isomeric mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, preferably an isomeric mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. Therefore, according to a further embodiment, the present invention is also directed to the composition as disclosed above, wherein the diisocyanate is selected from 2, 4-toluene diisocyanate and a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate. In an embodiment according to the present invention, the 2,4- toluene diisocyanate is present in the isomeric mixture in an amount in the range of ≥ 85.0 wt.-% to ≤ 99.9 wt.-%, related to the total weight of the isomeric mixture, preferably range of ≥ 90.0 wt.-% to ≤ 99.9 wt.-% of the 2,4-isomer, and most preferably in the range of ≥ 95.0 % to ≤ 99.9 wt.-% of the 2,4- isomer. According to step (ii), at least one monohydroxy compound of the formula R1-OH is added. Preferably the monohydroxy compounds of formula R1-OH is selected from the group consisting of butyltriglycol, butyldiglycol, butyltetraglycol, butanol, isotridecyl alcohol, oleyl alcohol, Guerbet alcohols containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol and ethoxylated 4-dodecylphenol, especially from the group consisting of butyltriglycol, 2- ethylhexanol and methoxy polyethylene glycol. 240554 11 Guerbet alcohols are represented by the general formula (X), p (X), wherein p is 1, 2, 3 or 4. The trivial name of Guerbet alcohol is used for 2-alkyl-substituted 1-alkanols whose industrial synthesis is described inter alia in H. Machemer, Angewandte Chemie, Vol.64, pages 213-220 (1952) and in G. Dieckelmann and H.J. Heinz in "The Basics of Industrial Oleochemistry", pages 145-145 (1988). In an embodiment the Guerbet alcohol is selected from 2-ethylhexanol, 2- propyl-heptanol, 2-butyl-1-octanol and 2-pentyl-1-nonanol. In an embodiment according to the present invention, the molar ratio of the at least one monohydroxyl compound to the diisocyanate is in the range of ≥1.0: 1.0 to ≤ 1.5: 1.0, preferably in the range of ≥ 1.005: 1.0 to ≤ 1.25: 1.0, more preferably in the range of ≥ 1.02: 1.0 to ≤ 1.1: 1.0. In one embodiment according to the present invention, in step (ii) optionally a diluent is added. The diluent used should be essentially inert to the reaction. While it may not be necessary to employ the diluent during formation of the urethane prepolymer, the use of a diluent may be desirable to maintain the reactants in the liquid state as well as permit better temperature control during the reaction by serving as a heat sink and, if desired, as a refluxing medium. Exemplary of diluents are esters, ethers, ketoesters, ketones, glycol-ether-esters, chlorinated hydrocarbons, aliphatic and alicyclic hydrocarbons, pyrrolidones, hydrogenated furans, and the like and mixtures thereof. If the diluent is a preferred solvent mentioned above, it is possible to add a part of the amount of solvent in step (ii). In a preferred embodiment according to the present invention, the diluent is selected from the group consisting of acetone, benzene, ethyl acetate, butyl acetate, diethylether, carbon tetrachloride and chlorobenzene. 240554 12 In a further preferred embodiment according to the present invention, the diluent is selected from the group consisting of caprolactone. In a preferred embodiment, the weight ratio of diisocyanate to the diluent is in the range of ≥ 0.5: 1 to ≤ 5.0: 1. According to one embodiment the monohydroxyl compound in step (ii) is added during a time period in the range of ≥ 3 hours to ≤ 50 hours, preferably in the range of ≥ 3 hours to ≤ 30 hours, and more preferably in the range of ≥ 3 hours to ≤ 20 hours. According to one embodiment in step ii) temperature is in the range of ≥ 20°C to ≤ 60° C, preferably in the range of ≥ 25°C to ≤ 55°C, and more preferably in the range of ≥ 30° C to ≤ 50°C. According to step (iii), the aprotic solvent, the alkyl ammonium salt and the diamine of the formula H2N-R5-NH2are added to the monoisocyanate-urethane. The aprotic solvent, the alkyl ammonium salt and the diamine can be added in form of a composition or the diamine following the aprotic solvent and the alkyl ammonium salt. Suitable diamines which may be used according to the present invention are in principle known. Preferably, the at least one diamine is selected from the group consisting of C2to C24aliphatic diamines, C6to C18cycloaliphatic diamines, C6to C24aromatic diamine, C7to C26araliphatic diamines and heterocyclic diamine. A C2to C24aliphatic diamine is a diamine of formula H2N-R5-NH2in which R5 is a divalent aliphatic group comprising from 2 to 24 carbon atoms. An aliphatic diamine can be linear or branched, preferably linear. An aliphatic diamine can be a polyetheramine, that is to say a diamine of formula H2N-R5-NH2in which R5 comprises ether (-O-) bonds, more particularly ethylene oxide (-O-CH2-CH2) and / or propylene oxide (-O-CH2-CHCH3-) units. An aliphatic diamine can be a polyalkyleneimine, that is to say a diamine of formula H2N-R5-NH2in which R5 is interrupted by one or more tertiary amines (-NX- with X a C1to C6alkyl). An aliphatic diamine can be interrupted by one or more tertiary amine groups. Examples of linear aliphatic diamines which are suitable are 1,2-ethylenediamine, 1,3- propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6- hexamethylenediamine, 1, 8-octamethylenediamine, 1,12-dodecamethylenediamine and their 240554 13 mixtures; preferably 1,2- ethylenediamine, 1,5-pentamethylenediamine and 1,6- hexamethylenediamine. Examples of aliphatic diamines which are suitable are 1,2- propylenediamine, 2,2- dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine and their mixtures. Examples of polyetheramines are the compounds sold by Huntsman under the Jeffamine®reference, in particular the Jeffamine®D, ED and EDR series (diamines). These series include in particular the following references: Jeffamine®D-230, Jeffamine®D-400, Jeffamine®D-2000, Jeffamine®D-4000, Jeffamine®ED-600, Jeffamine®ED-900, Jeffamine®ED-2003, Jeffamine®EDR-148 and Jeffamine®EDR-176. An example of polyalkyleneimine is 3,3'-diamino-N-methyldipropylamine. A C6to C18cycloaliphatic diamine is a diamine of formula H2N-R5-NH2in which R5 is a divalent cycloaliphatic group comprising from 6 to 18 carbon atoms. Examples of cycloaliphatic diamines which are suitable are 1,2-, 1,3- or 1,4- diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane- 1,3 -diamine, isophoronediamine, 1,2-, 1,3- or 1 ,4-bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'- diaminodicyclohexylmethane, bis(aminomethyl)norbomane and their mixtures; preferably, 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine and 4,4'-diaminodicyclohexylmethane. A C6to C24aromatic diamine is a diamine of formula H2N-R5-NH2in which R5 is an aromatic group comprising from 6 to 24 carbon atoms. Examples of aromatic diamines which are suitable are ortho-, meta- and para-phenylenediamine, ortho-, meta- and para-tolylenediamine, 3,4'- diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and their mixtures; preferably, ortho-, meta- and paraphenylenediamine. A C7to C26araliphatic diamine is a diamine of formula H2N-R5-NH2in which R5 is an araliphatic group comprising from 7 to 26 carbon atoms. Examples of araliphatic diamines which are suitable are ortho-, meta- and para-xylylenediamine, 4,4'-diaminodiphenylmethane and their mixtures; preferably, ortho-, meta- and para-xylylenediamine. A C3 to C18 heterocyclic diamine is a diamine of formula H2N-R5-NH2 in which R5 is a heterocyclic group comprising from 3 to 18 carbon atoms. Examples of heterocyclic diamines which are suitable are 1,2-diaminopiperazine, 1,4-diaminopiperazine, 1,4-bis(3- aminopropyl)piperazine, 2,3-, 2,6- and 3,4-diaminopyridine, 2,4-diamino-1, 3,5-triazine and their mixtures. 240554 14 Preferably, the at least one diamine is selected from the group consisting of 4,4-diamino- diphenylmethane, 3,3-dimethyl-4,4-diamino- 2,2-bis(4-aminocyclohexyl)- propane, N,N-dimethyl-4,4-diaminodiphenylmethane, (3-methyl-4-aminocylcohexyl)-(3-methyl-4- aminophenyl)-methane, 4,4-diaminodicyclohexylmethane, isomeric xylylenediamine, ethylenediamine, hexamethylenediamine, 4,4-methylenebis(cyclohexylamine), 1,12- diaminododecane, neopentanediamine, 1,2– and 1,3- propanediamine, 1,8- octamethylenediamine and 1,12-dodecamethylenediamine. Therefore, according to a preferred embodiment, the present invention is also directed to the composition as disclosed above, wherein the urea-urethane compound has a weight average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol, determined according to DIN 55672-2, preferably in the range of ≥ 700 g / mol to ≤ 4000 g / mol and more preferably in the range of ≥ 1000 g / mol to ≤ 3500 g / mol. Preferred are composition comprising (a) 20 to 80 wt% based on the weight of the urea-urethane composition of the at least one urea-urethane compound, (b) 20 to 80 wt% based on the weight of the urea-urethane composition of the aprotic solvent (c) of at least one alkyl ammonium salt wherein the sum of the components adds up to 100 wt%, with the proviso that the ratio of mol alkyl ammonium salt to the of molequivalent of diisocyanate is in the range from 0.03 / 1 to 0.5 / 1, preferably is in the range from 0.1 / 1 to 0.4 / 1. Especially preferred are urea-urethane composition comprising (a) 25 to 55 wt% based on the weight of the urea-urethane composition of the at least one urea-urethane compound, (b) 44.9 to 74.9 wt% based on the weight of the urea-urethane composition of the aprotic solvent (c) 0.1 to 5 wt% of at least one alkyl ammonium salt, preferably cholinchloride wherein the sum of the components adds up to 100 wt%, with the proviso that the ratio of mol alkyl ammonium salt to the of molequivalent of diisocyanate is in the range from 0.03 / 1 to 0.5 / 1, preferably is in the range from 0.1 / 1 to 0.4 / 1. The urea-urethane composition of the present invention shows very good behavior as rheology modifier in water-based formulation and in solvent-based formulations. 240554 15 The urea-urethane composition according to the invention is advantageously introduced into a binder formulation, cosmetic formulation or formulation in order to modify its rheology, in particular in order to confer a thixotropic or pseudoplastic effect on it. The binder formulation according to the invention comprises a binder and the urea-urethane composition as described above. In particular, the urea-urethane composition according the present invention can be used as rheology modifier in coating formulations, including masonry paints, interior paints, paints for wood coating and wood stains, and coating compositions for concrete and cement fiber board, as rheology modifier in paper coating formulations, as modifiers in hydraulically binding construction materials, such as concrete, plaster, and mortar, as rheology modifier in waterproofing membranes, as rheology modifier in flexible roofing, as rheology modifier for fiber bonding, and in adhesives, including e. g. pressure sensitive adhesives, construction adhesives and laminating adhesives. Furthermore, the present invention provides a liquid formulation comprising ≥ 0.01 wt.-% to ≤ 10.0 wt.-%, based on the total weight of the liquid formulation, of the urea- urethane composition, preferably in the range from ≥ 0.1 wt.-% to 7.0 ≤ wt.-%, more preferably in the range from ≥ 0.1 wt.-% to ≤ 5.0 wt.-%, even more preferably in the range from ≥ 0.1 wt.-% to ≤ 3.0 wt.-%; and ≥ 15.0 wt.-% to 99.9 ≤ wt.-%, preferably ≥ 25.0 wt.-% to 90.0 ≤ wt.-%, more preferably ≥ 35.0 wt.-% to 85.0 ≤ wt.-%, even more preferably ≥ 50.0 wt.-% to ≤ 80.0 wt.-%, and most preferably ≥ 55.0 wt.-% to ≤ 75.0 wt.-% based on the total weight of the liquid composition of at least one of the components, selected from the group consisting of pigments, binders, fillers, defoamers, neutralising agent, wetting agent, dispersants, preservatives and water. Suitable fillers are, for example, organic or inorganic particulate materials such as, for example, calcium carbonates and silicates, and also inorganic fiber materials such as glass fibers, for example. Organic fillers as well, such as carbon fibers, and mixtures of organic and inorganic fillers, such as mixtures of glass fibers and carbon fibers or mixtures of carbon fibers and inorganic fillers, for example, may find application. Suitable binders are the ones customarily used, for example the ones described in 30 Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.368-426, VCH, Weinheim 1991, Germany. In general, the film-forming binder is based on a thermoplastic or thermosetting resin. Examples thereof are alkyd, acrylic, unsaturated or saturated polyester resin, acrylate and methacrylate resins, nitrocellulose, cellulose acetobutyrate, alkyd-amino resins, alkyd resins, 240554 16 melamine resins, urea resins, silicone resins, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof. Also resins by radiation or air-drying 35 resins can be used. Binders may also be derived from polyvinylalcohol and polyvinylbutyral. Binders include latex polymers made by emulsion polymerization. For architectural coatings especially preferred latex polymers are based on acrylic emulsion polymers, styrene-acrylic emulsion polymers, vinyl acetate–acrylic emulsion polymers or emulsion polymers based on ethylene and vinyl acetate. Organic or inorganic pigments are suitable as additives. Examples of organic pigments are color pigments and mother-of-pearl-like pigments such as azo, disazo, naphthol, benzimidazolone, azo condensation, metal complex, isoindolinone, quinophthalone, and dioxazine pigments, polycyclic pigments such as indigo, thioindigo, quinacridones, phthalocyanines, perylenes, perinones, anthraquinones, e.g., aminoanthraquinones or hydroxyanthraquinones, anthrapyrimidines, indanthrones, flavanthrones, pyranthrones, anthanthrones, isoviolanthrones, diketopyrrolopyrroles, and also carbazoles, e.g., carbazole violet, and the like. Other examples of organic pigments can be found in the following monograph: W. Herbst, K. Hunger, “ Industrielle Organische Pigmente”, 2nd edition, 1995, VCH Verlagsgesellschaft, ISBN: 3527 287442. Examples of inorganic pigments are titanium dioxide, metallic flakes, such as aluminum and also aluminum oxide, iron (III) oxide, chromium (III) oxide, titanium (IV) oxide, zirconium(IV)oxide, zinc oxide, zinc sulfide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulfide, cadmium sulfide, graphite, vanadates such as bismuth vanadate, chromates, such as lead(IV) chromates, molybdates such as lead(IV) molybdate, and mixtures thereof. Suitable neutralizing agents are inorganic bases, organic bases, and combinations thereof. Examples of inorganic bases include but are not limited to the alkali metal hydroxides (especially lithium, sodium, potassium, magnesium, and ammonium), and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like; and mixtures thereof. Examples of organic bases include but are not limited to triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol (2- Amino-2-methyl-1 -propanol), dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis(hydroxypropyl)ethylenediamine, L-arginine, methyl glucamine, isopropylamine, aminomethyl propanol, tromethamine (2-amino 2-hydroxymethyl-1 ,3- propanediol), and PEG-15 cocamine. Alternatively, other alkaline materials can be used alone or in combination with the above-mentioned inorganic and organic bases. 240554 17 Suitable defoamers are selected from the wide range of defoamer used such as silicone based defoamers, emulsion defoamers, star defoamers, powder defoamers, oil based defoamers. The present invention is also directed to the use of urea-urethane composition or the composition obtained or obtainable according to the inventive process in formulations especially coating formulations, as a thixotropic agent. The urea-urethane composition used as a thickening additive in liquid formulations especially coating formulations, imparts thixotropic effects to said formulations. Further embodiments of the present invention can be found in the claims and the examples. It will be appreciated that the features of the subject matter / processes / uses according to the invention that are mentioned above and elucidated below are usable not only in the combination specified in each case but also in other combinations without departing from the scope of the invention. For example, the combination of a preferred feature with a particularly preferred feature or of a feature not characterized further with a particularly preferred feature etc. is thus also encompassed implicitly even if this combination is not mentioned explicitly. The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. Illustrative examples of the present invention are listed below, but these do not restrict the present invention. Examples Compounds TDI T100: 2,4-toluene diisocyanate (TDI) from Covestro TDI T80: isomer mixture of 2,4- and 2,6- toluene diisocyanate (TDI) from BASF. TDI T98, T97, T96, T95 and others are a blends of TDI T100 and TDI T80. For example, T98 is a blend of TDI T100 and TDI T80 with the ratio of 90:10, and T90 is a blend of TDI T100 and TDI T80 with the ratio of 50:50. DMSO: Dimethyl sulfoxide m-XDA: m-xylenediamine MPEG350: methoxyl polyethyleneglycol monoether, Mw of 350g / mol (from BASF) MPEG500: methoxyl polyethyleneglycol monoether, Mw of 500g / mol (from BASF) 240554 18 NMP: 1-Methyl-2-pyrrolidone NBP: 1-butyl-2-pyrrolidone BTG: Butyl triglycol TEA: Triethylamine TEA*HCl: triethylamine hydrochlorid TEOA: Triethanolamine TEOA*HCl: Triethanolamine hydrochlorid TEOA*pTSA: mixture of TEOA with p-toluene sulfonate with 1 to 1 mol / mol CHCl: cholin chloride LiNO3Lithium nitrate Jeffamine®D230 Polyoxypropylendiamine EpikoteTM1001-x-75 epoxy resin produced from bisphenol A and epichlorohydrin

[0002] 240554 19 Methods Viscosity The viscosity of a sample was determined either by a rheometer in accordance to DIN 53019 or calculated from values of a brabender plastograph. Theoretical NCO content Theoretical NCO content is calculated as follows: Theoretical NCO content = 0.2411*MTDI / (MTDI+MR-OH+Mdiluent)*100% MTDI: weight of TDI charged in MR-OH: weight of R-OH charged in Mdiluent: weight of diluent (optional) charged in Molecular Weight (Mw) and Polydispersity Index (PDI) The weight average molecular weight and polydispersity index were determined in accordance to and DIN 55672-2, with N,N-dimethylacetamide as mobile phase, 1mL / min, PMMA standard used for calibration). Example 1 Preparation of the urea-urethane composition In a 5-necked 200 ml Sulfier flask with an overhead stirrer, thermometer, reflux condenser and septum, 17.4 g TDI T100 (100 mmol ‘Isocyanate’) and 10 g of ethyl acetate was purged with nitrogen.52.5 g methoxyl polyethyleneglycol monoether (MPEG500) (105 mmol ‘Alcohol’) mixed with 0.1 g p-toluene sulfonic acid was fed to the reactor over a time period of 10 hours at a temperature 45°C. After the completion of the feed, the reaction was continued until the NCO value (NCO%) reaching to the theoretical calculated value (theoretically, half amount of NCO groups from TDI was consumed in this step). 5.6 g cholin chloride (0,4eq ‘Salt’ per TDI), 6.2 g m-xylylene diamine (46 mmol ‘Diamine’), and 123 g DMSO (‘Solvent’) were pre-mixed at 60°C. The resulting mixture was fed into the monoisocyanate adduct obtained at a temperature at 60°C. The reaction was exothermic, and the internal temperature was kept lower than 80°C. The resulting mixture was heated to a temperature of 80°C and held until the NCO value is 0%. Then ethyl acetate was distilled out under vacuum. The resulting urea-urethane composition (product) was a yellowish transparent liquid and was free flowing at room temperature. The product remained stable (no precipitation or gel formation) upon storage (>3 months) under ambient conditions. 240554 20 The weight average molecular weight of the urea-urethane compound was 2370 g / mol and its PDI was 1.1. Examples 2 to 20 and comparative examples CE1 and CE2 Examples 2 to 20, CE1 and CE2 were prepared in a manner according to Example 1 with variations in amounts and type of ‘Isocyanate’, ‘Alcohol’, ‘Salt’, ‘Diamine’ and ‘Solvent’. Table 1 provides details of the examples according to the presently claimed invention. Table 1: Educts for the preparation of the respective urea-urethane composition Ex Isocyan Alcohol Salt Salt Diamin Solvent Storage- GPC ate eq e stability TDI per diiso- cyanat e 2 T97 BTG CHCl 0.4 m-XDA DMSO >3 months Mw: 2080 17.4g 21.6g 5,6 g 6.2g 76g PDI: 1.1 3 T95 BTG CHCl 0.2 m-XDA NMP >3 months Mw: 2050 17.4g 21.6g 2.8 g 6.2g 72g PDI: 1.2 4 T95 BTG CHCl 0.1 m-XDA DMSO >3 months Mw: 2100 17.4g 21.6g 1.4g 6.2g 70g PDI: 1.3 5 T97 BTG CHCl 0.07 m-XDA DMSO = 3 months Mw: 2090 17.4g 21.6g 1.0g 6.2g 69g PDI: 1.3 6 T97 BTG TEOA*HCl 0.4 m-XDA DMSO >3 months Mw: 1950 17.4g 21.6g 7.4g 6.2g 80g PDI: 1.2 7 T95 BTG TEOA*HCl 0.2 m-XDA NMP >3 months Mw: 2060 17.4g 21.6g 3.7g 6.2g 74g PDI: 1.1 8 T95 BTG TEOA*pTS 0.1 m-XDA DMSO >2 months Mw: 2020 17.4g 21.6g A 6.2g 74g PDI: 1.2 3.2g 9 T95 BTG TEOA*HCl 0.07 m-XDA NMP = 3 months Mw: 2120 17.4g 21.6g 1.2g 6.2g 71g PDI: 1.2 10 T97 BTG TEA*HCl 0.4 m-XDA DMSO >3 months Mw: 2050 17.4g 21.6g 5.5g 6.2g 76g PDI: 1.2 11 T95 BTG TEA*HCl 0.2 m-XDA NBP = 3 months Mw: 2040 17.4g 21.6g 2.7g 6.2g 72g PDI: 1.2 12 T97 BTG, 7.2g CHCl 0.4 m-XDA DMSO >3 months Mw: 2250 17.4g MPEG350 5.6 g 6.2g 92g PDI: 1.2 24.5g 13 T95 BTG 4.3g CHCl 0.2 m-XDA DMSO >3 months Mw: 2850 17.4g MPEG350 2.8 g 6.2g 100g PDI: 1.3 14.7g MPEG500 21g 14 T95 BTG 6.8g CHCl 0.1 m-XDA DMSO >3 months Mw: 2700 17.4g MPEG350 1.4g 6.2g 97g PDI: 1.3 13.8g MPEG500 240554 21 Ex Isocyan Alcohol Salt Salt Diamin Solvent Storage- GPC ate e stability TDI diiso- cyanat e 15 T97 BTG 6,8g CHCl 0.07 m-XDA DMSO = 3 months Mw: 2780 17.4g MPEG350 1.0g 6.2g 97g PDI: 1.3 13.8g MPEG500 19.7g 16 T97 BTG 7.2g TEOA*HCl 0.2 m-XDA NBP >3months Mw: 2350 17.4g MPEG350 3.7g 6.2g 90g PDI: 1.3 24.5g 17 T95 BTG 4.3g TEOA*pTS 0.1 m-XDA DMSO >3months Mw: 2800 17.4g MPEG350 A 6.2g 100g PDI: 1.3 14.7g 3.2g MPEG500 21g 18 T97 BTG 6.8g TEOA*HCl 0.07 m-XDA DMSO >3 months Mw: 2750 17.4g MPEG350 1.3g 6.2g 97g PDI: 1.3 13.8g MPEG500 19.7g 19 T95 BTG 4.3g TEA*HCl 0.4 m-XDA NMP >3 months Mw: 2900 17.4g MPEG350 5.5g 6.2g 103g PDI: 1.4 14.7g MPEG500 21g 20 T97 BTG 6.8g TEOA*HCl 0.03 m-XDA DMSO =3 months Mw: 2780 17.4g MPEG350 0.6g 6.2g 98 g PDI: 1.3 13.8g MPEG500 19.7g 21 T97 BTG 7.2g CHCl0.41,6-DMSO>3 monthsMw: 223017.4g MPEG350 5.6 g hexamet 90g PDI: 1.2 24.5g hylenedi amine 5.3g 22 T97 BTG 7.2g CHCl0.4JeffaminDMSO>3 monthsMw: 235017.4g MPEG350 5.6 g eD-230 100g PDI: 1.2 24.5g 10.9g CE T97 BTG LiNO3 0.4 m-XDA DMSO >3 months Mw: 2050 1 17.4 21.6g 2.7g 6.2g 72 g PDI: 1.1 CE T100 BTG 6.8g LiNO30.4 m-XDA DMSO >3 months Mw: 2900 2 17.4 MPEG350 2.7g 6.2g 97 g PDI: 1.3 13.8g MPEG500 19.7g CE: comparative example Example 23: Preparation of the urea-urethane composition 240554 22 In a 5-necked 200 ml Sulfier flask with an overhead stirrer, thermometer, reflux condenser and septum, 17.4 g TDI T95 (100 mmol and 15 g of ε-Caprolactone was purged with nitrogen.21,6g butyltriglycol (105 mmol ‘Alcohol’) mixed with 0.1 g p-toluene sulfonic acid was fed to the reactor over a time period of 10 hours at a temperature 45°C. After the completion of the feed, the reaction was continued until the NCO value (NCO%) reaching to the theoretical calculated value (theoretically, half amount of NCO groups from TDI was consumed in this step). 2,8 g cholin chloride (0,2eq ‘Salt’ per TDI) and 20g ε-Caprolactam was added into the reactor, 6.2 g m-xylylene diamine (46 mmol ‘Diamine’) and 26 g NBP (‘Solvent’) were pre-mixed at 60°C and the resulting mixture was fed into the monoisocyanate adduct obtained at a temperature at 60°C. The reaction was exothermic, and the internal temperature was kept lower than 80°C. The resulting mixture was heated to a temperature of 80°C and held until the NCO value is 0%. The resulting urea-urethane composition (product) was a yellowish transparent liquid and was free flowing at room temperature. The product remained stable (no precipitation or gel formation) upon storage (>3 months) under ambient conditions. The weight average molecular weight of the urea-urethane compound was 2090 g / mol and its PDI was 1.1. Example 24: Preparation of the urea-urethane composition In a 5-necked 200 ml Sulfier flask with an overhead stirrer, thermometer, reflux condenser and septum, 17.4 g TDI T95 (100 mmol ‘Isocyanate’) and 15 g of ε-Caprolactone was purged with nitrogen.4,3g butyltriglycol, 14,7g MPEG350 and 21g MPEG500 (105 mmol ‘Alcohol’) mixed with 0.1 g p-toluene sulfonic acid was fed to the reactor over a time period of 10 hours at a temperature 45°C. After the completion of the feed, the reaction was continued until the NCO value (NCO%) reaching to the theoretical calculated value (theoretically, half amount of NCO groups from TDI was consumed in this step). 2,8 g cholin chloride (0,2eq ‘Salt’ per TDI) and 40g ε-Caprolactam was added into the reactor, 6.2 g m-xylylene diamine (46 mmol ‘Diamine’) and 35 g NBP (‘Solvent’) were pre-mixed at 60°C and the resulting mixture was fed into the monoisocyanate adduct obtained at a temperature at 60°C. The reaction was exothermic, and the internal temperature was kept lower than 80°C. The resulting mixture was heated to a temperature of 80°C and held until the NCO value is 0%. The resulting urea-urethane composition (product) was a yellowish transparent liquid and was free flowing at room temperature. The product remained stable (no precipitation or gel formation) upon storage (>3 months) under ambient conditions. 240554 23 The weight average molecular weight of the urea-urethane compound was 2380 g / mol and its PDI was 1.1. Example 25: Preparation of the urea-urethane composition In a 5-necked 200 ml Sulfier flask with an overhead stirrer, thermometer, reflux condenser and septum, 17.4 g TDI T95 (100 mmol ‘Isocyanate’) was purged with nitrogen.4,3g butyltriglycol, 14,7g MPEG350 and 21g MPEG500 (105 mmol ‘Alcohol’) mixed with 0.1 g p-toluene sulfonic acid was fed to the reactor over a time period of 10 hours at a temperature 45°C. After the completion of the feed, the reaction was continued until the NCO value (NCO%) reaching to the theoretical calculated value (theoretically, half amount of NCO groups from TDI was consumed in this step). 2,8 g cholin chloride (0,2eq ‘Salt’ per TDI) and 45g ε-Caprolactam was added into the reactor, 6.2 g m-xylylene diamine (46 mmol ‘Diamine’) and 45 g NBP (‘Solvent’) were pre-mixed at 60°C and the resulting mixture was fed into the monoisocyanate adduct obtained at a temperature at 60°C. The reaction was exothermic, and the internal temperature was kept lower than 80°C. The resulting mixture was heated to a temperature of 80°C and held until the NCO value is 0%. The resulting urea-urethane composition (product) was a yellowish transparent liquid and was free flowing at room temperature. The product remained stable (no precipitation or gel formation) upon storage (>3 months) under ambient conditions. The weight average molecular weight of the urea-urethane compound was 2370 g / mol and its PDI was 1.1. Storage stability: A 100 ml sample of the respective urea-urethane compositions was filled into a glass container measuring 5 cm x 5 cm x 5 cm and sealed. The sample was then stored at a temperature of 25 °C and visually assessed after a period of 1 months, 2 months, 3 months and >3 months: Assessment after 3 months ≥ 3 months: the product does not form precipitation or gel, and the product form is a clear liquid. = 3 months: the product does not form precipitation or gel, but the product form is slightly becoming a turbid liquid. The results show that the urea-urethane compositions according to the invention have comparably good storage stability in comparison to the compositions with lithium salts of the prior art. Thixotropy Measurement The thixotropy for the formulations was via shear jump measurement. The shear jumping measurement starts with the shear rate of 0.05 s-1for 200 seconds, and then immediately apply a high shear rate of 250 s-1for 60 seconds, and immediately thereafter, the shear rate was reduced to 0.05 s-1for 200 seconds. To study the thixotropic effect of the Examples, the viscosity was measured at the following intervals: i) Viscosity at t = 199 sec, just before the high shear is applied ii) Viscosity at t = 201 sec, just after high shear is applied iii) Viscosity at t = 259 sec, just after high shear is removed iv) Viscosity at t = 450 sec, well after high shear is removed. The viscosity measurements at different time intervals are provided in Table 4 and 5. Solvent based formulation (SBF) For solvent based application, the coating composition (Formulation 1, Table 2) was stirred via Dispermat for 5 min at 2000 rpm, and then kept at standby overnight at room temperature before measuring the viscosity. Table 2: composition of solvent based formulation 1 component wt% EpikoteTM1001-x-75 75 Methylisobutylketon 16.9 isobutanol 7 Urea-urethane compound of the Example 1.1 Total 100 Solvent based comparative formulation For solvent based application, a comparative coating composition (comparative formulation, Table 3) was stirred via Dispermat for 5 min at 2000 rpm, and then kept at standby overnight at room temperature before measuring the viscosity. 25 Table 3: Composition of the comparative formulation (no additive) component wt% Epikote 1001-x-75 75 Methylisobutylketon 18 Isobutanol 7 Total 100 Table 4: Thixotropy Measurement of solvent based formulations (SBF) Formulation Example Urea-urethane Viscosity (mPa.s) compound t=199 t=201 t=259 t=450 of example No. SBF1 No additive 200 190 200 200 SBF2 CE1 5050 230 230 990 SBF3 2 5650 220 220 980 SBF4 4 5950 230 230 1020 SBF5 6 6350 200 220 1100 SBF6 8 6150 210 220 1030 SBF7 10 6050 210 220 1010 As is evident from the results provided in above table 4, the viscosity of the respective formulation dropped significantly immediately after high shear forces were (i.e.250 s-1for 60 seconds) started to be applied. After the application of high shear forces was stopped, an increase in viscosity of the formulation was observed. This means formulation with the urea- urethane compositions according the invention exhibited a significant recovery of the viscosity. Thus, the Examples prepared according to the process of the present invention upon addition to formulation imparted thixotropic effect to said formulation which is demonstrated by the drop in viscosity immediately after applying shear stress and gradual recovery of viscosity as a function of time upon removal of shear stress. The comparison of the formulations of the invention containing the urea-urethane compound of examples 2, 4, 6, 6 and 10 shows a much better thickened rheology in t=199 and has not negative effects on its stability as the formulation of the Compartive example 1. Water based formulations (WBF) For water-based application, a formulation for the viscosity measurement was prepared by adding 0.6 wt% of urea urethane compound from the corresponding example into water. The mixture was shaken by hand for 30 seconds and then allowed to standby overnight at room 240554 26 temperature before measuring the viscosity (shear jumping test as above). The viscosity measurements at different time intervals are in Table 5. Table 5: Thixotropy Measurement of water-based formulations (WBF) Formulation Urea urethane compound Viscosity (mPa.s) Example of example No. t=199 t=201 t=259 t=450WBF1 No additive 5 5 5 5 WBF2 CE-2 50000 25 5000 6000 WBF3 12 56000 25 6850 8250 WBF4 14 56500 30 8500 9250 WBF5 16 65000 25 7500 8500 WBF6 17 75500 25 10500 11900 WBF7 18 71000 30 9500 10500 WBF8 24 74500 30 10500 11000 The comparison of the formulations of the invention containing the urea-urethane compound of examples 12, 14, 16, 17, 18 and 24 shows a much better thickened rheology in t=199 and have no negative effects on its stability as the formulation of the comparative examples 2.

Claims

1. 240554 27 CLAIMS 1. Urea-urethane composition comprising (a) at least one urea-urethane compound with a least one terminal group of formula I (I) wherein R1 is a radical selected from the group consisting of C4to C32alkyl, C4to C22alkenyl, C5to C12cycloalkyl, C7to C24aralkyl, C6to C24aryl, a radical of formula R6-(O-CxH2x]y̶ , a radical of formula R6-[O-C(=O)-CwH2w]z̶ and a radical of formula R6-(O-CxH2x)y̶ [O-C(=O)-CwH2w]z̶ ; R3 is a divalent group selected from the group consisting of an aromatic group and an araliphatic group; R6 is C1to C32alkyl; x is an integer from 2 to 4; w is an integer from 2 to 12; y and z is an integer from 1 to 20; (b) at least one aprotic solvent and (c) at least one alkyl ammonium salt, whose alkyl radicals independently of another is unsubstituted or hydroxy-substituted.

2. Urea-urethane composition according to claim 1 comprising (a) at least one urea-urethane compound of formula II, (II)wherein R1 and R2 independently of one another are a radical selected from the group consisting of C4to C32alkyl, C4to C22alkenyl, C5to C12cycloalkyl, C7to C24aralkyl, C6to C24aryl, a radical of formula R6-(O-CxH2x]y̶ , a radical of formula R6-[O-C(=O)-CwH2w]z̶ and a radical of formula R6-(O-CxH2x)y̶ [O-C(=O)-CwH2w]z̶ ;240554 28 R3 and R4 independently of one another are a divalent group selected from the group consisting of an aromatic and an araliphatic group R5 is a divalent group selected from the group consisting of an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group R6 is C1to C32-alkyl x is an integer from 2 to 4; w is an integer from 2 to 12; y and z is an integer from 1 to 20; (b) at least one aprotic solvent and (c) at least one alkyl ammonium salt, whose alkyl radicals independently of another is unsubstituted or hydroxy-substituted.

3. The urea-urethane composition according to claim 1 or 2, wherein the at least one aprotic solvent, is selected from the group consisting of dimethyl sulfoxide, N,N- dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N- propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea, hexamethyl-phosphoric acid triamide, and methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate γ-valerolactone, α-angelica lactone, α-methylene-γ-butyrolactone, α-hxdroxy-γ-butyrolactone, caprolactone, caproplactam, dimethyl isosorbide (DMI) and dihydrolevoglucosenone.

4. Urea urethane composition according to any of claims 1 to 3, wherein the alkyl ammonium salt is a compound of the formula IIIR7 is a hydrogen atom or C1to C18alkyl; R8, R9 and R10 independently of one another are selected from the group consisting of C1to C18alkyl and C1to C18hydroxyalkyl; AnΘis an anionic radical.

5. Urea urethane composition according to any of claims 1 to 4, wherein the cation of the alkyl ammonium salt is based on a tri(C1-C18)-alkylamine or a hydroxyl tri(C1-C18)- alkylamine.240554 29 6. Urea urethane composition according of claims 1 to 5, wherein the anionic radical of the alkyl ammonium salt (III) is the anion of a protic acid wherein the protic acid has a pKa value of ≤5 in water at 20°C.

7. Urea urethane composition according to any of claims 1 to 6, wherein the anionic radical of alkyl ammonium salt (III) is selected from the group consisting of halogenide, sulfate, hydrogen sulfate, nitrate and p-toluene sulfonate.

8. The urea-urethane composition according to any of claim 1 to 7, wherein the composition is obtained by a process comprising (i) providing the at least one diisocyanate of the formula NCO-R3-OCN; wherein R3 is a divalent group selected from the group consisting of an aromatic group and an araliphatic group; (ii) adding to the diisocyanate at least one monohydroxy compound R1-OH to obtain a monoisocyanate-urethan, wherein in step (ii) the molar ratio of the monohydroxyl compound to the diisocyanate is in the range of ≥1 : 1 to ≤ 1.5 : 1; (iii) adding to the monoisocyanate-urethan the aprotic solvent and the alkyl ammonium salt and at least one diamine of the formula H2N-R5-NH2in form of a composition or the diamine following the aprotic solvent and the alkyl ammonium salt, wherein R5 is a divalent group selected from the group consisting of an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group.

9. The urea-urethane composition according to claim 1 to 8, wherein the diisocyanate is selected from the group consisting of toluene diisocyanates and methylene diphenyl diisocyanate.

10. The urea-urethane composition according to claim 8 or 9, wherein the at least one monohydroxy compound is selected from the group consisting of butyltriglycol, butyldiglycol, butyltetraglycol, butanol, isotridecyl alcohol, oleyl alcohol, Guerbet alcohols containing 8 to 20 carbon atoms, linoleyl alcohol, lauryl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, 4-dodecylphenol, ethoxylated triphenylmethanol, ethoxylated 4-dodecylphenol and methoxy polyethylene glycol.240554 30 11. The urea-urethane composition according to any of claims 8 to 10, wherein the at least one diamine is selected from the group of 4,4-diamino-diphenylmethane, 3,3- dimethyl-4,4-diamino-diphenylmethane, 2,2-bis(4-aminocyclohexyl)-propane, N,N- dimethyl-4,4-diaminodiphenylmethane,(3-methyl-4-aminocylcohexyl)-(3-methyl-4- aminophenyl)-methane, 4,4-diaminodicyclohexylmethane, isomeric xylylenediamine, ethylenediamine, hexamethylenediamine, 4,4-methylenebis(cyclohexylamine), 1,12- diaminododecane, neopentanediamine, 1,2- and 1,3-propanediamine, 1,8- octamethylenediamine and 1,12-dodecamethylenediamine.

12. Urea-urethane composition according to any of claim 1 to 11 comprising (a) 20 to 80 wt% based on the weight of the urea-urethane composition of the at least one urea-urethane compound, (b) 20 to 80 wt% based on the weight of the urea-urethane composition of the aprotic solvent (c) of at least one alkyl ammonium salt wherein the sum of the components adds up to 100 wt%, with the proviso that the ratio of mol alkyl ammonium salt to the of molequivalent of diisocyanate is in the range from 0.03 / 1 to 0.5 / 1.

13. The urea-urethane composition according to any of claims 1 to 12, wherein the urea- urethane compound has a weight average molecular weight in the range of ≥ 300 g / mol to ≤ 5000 g / mol, determined according to DIN 55672-2.

14. A process for preparing the urea-urethane composition according to any of claim 1 to 13, comprising the steps (i) providing at least one diisocyanate of the formula NCO-R3-OCN; wherein R3 is a divalent group selected from the group consisting of an aromatic group and an araliphatic group; (ii) adding to the diisocyanate at least one monohydroxy compound R1-OH to obtain a monoisocyanate-urethan, wherein in step (ii) the molar ratio of the monohydroxy compound to the diisocyanate is in the range of ≥1 : 1 to ≤ 1.5 : 1; (iii) adding to the monoisocyanate-urethan the aprotic solvent and the alkyl ammonium salt and at least one diamine of the formula H2N-R5-NH2in form of a composition or the diamine following the aprotic solvent and the alkyl ammonium salt,240554 31 wherein R5 is a divalent group selected from the group consisting of an aliphatic group, a cycloaliphatic group, an group, an araliphatic group and a heterocyclic group.

15. A liquid composition comprising ≥ 0.01 wt.-% to ≤10.0 wt.-%, based on the total weight of the liquid composition, of the urea-urethane composition according to any of claims 1 to 13, and ≥ 15.0 wt.-% to ≤99.9 wt.-%, based on the total weight of the liquid composition of at least one of the components, selected from the group consisting of pigments, binders, fillers, defoamers, neutralising agent, wetting agent, dispersing agents, preservatives and water.

16. Use of the urea-urethane composition according to any of claims 1 to 13 in formulations as a thixotropic agent.

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