Liquid Rheology Control Agents

Abstract

The present invention relates to a composition comprising: a liquid carrier that is liquid at a temperature of 20°C; a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in the liquid carrier; and a urea compound having a molecular weight of less than 350 g / mol, dissolved in the liquid carrier.

Description

[Technical Field]

[0001] The present invention relates to a composition comprising a liquid carrier that is liquid at a temperature of 20° C., a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group dissolved in the liquid carrier, and a urea compound having a molecular weight of less than 350 g / mol dissolved in the liquid carrier. The present invention further relates to use of the composition for controlling the rheology of a liquid composition, the liquid composition, and a coated article. [Background technology]

[0002] In the fields of coating materials, adhesives, sealants, molding compounds, and even oil well drilling fluids, it is necessary to optimize the rheological properties of such liquid systems, primarily by adjusting their viscosity. This can be achieved, for example, by selecting binders and solvents, as well as by selecting pigment and filler concentrations. These types of liquids often require the addition of so-called rheological additives, which have the function of adjusting the rheological properties of the system, such as viscosity and viscoelasticity. This usually results in improved system properties in terms of sag resistance, storage stability (by inhibiting the settling of solid particles), or a general increase in viscosity, often referred to as "thickening."

[0003] The rheology of liquid systems is often controlled using organically modified clays, such as bentonite and silica, hydrogenated castor oil, and even polyamide waxes, as needed. These rheology control aids have drawbacks: they are generally dry solids that must be processed into semi-finished products using solvents and shear forces, and they must be introduced into the liquid system while controlling the target temperature. Failure to observe these temperatures and proper introduction conditions can not only result in poor rheological properties, but can also adversely affect the properties of the product. When the liquid system is a coating composition, these rheology control aids often cause cloudiness or haze in clear, transparent coatings. Furthermore, handling dry powder products that generate dust during processing can be technically undesirable.

[0004] An alternative to the liquid application of these rheology control aids is offered by solutions of certain urea components, as described, for example, in EP-A-1 188 779. It is also possible to use ionic liquids, as described in DE-A-10 2008 059 702, instead of conventional organic diluents.

[0005] Another aspect to consider with rheology control aids provided in liquid form is their storage stability. For example, if the storage period is extended or storage stress increases, for example, during storage accompanied by temperature fluctuations, the storage stability may decrease, thereby reducing the effectiveness in the target system. Therefore, it is desirable for the rheology control aid to have good storage stability and not easily precipitate or gel during storage. To prevent early precipitation during storage, a small amount of salt, particularly a halide such as LiCl, is usually added to act as a stabilizer. However, salts, especially halides such as LiCl, also cause many problems in terms of application performance, as these ionic compounds adversely affect properties such as corrosion caused by the coating system, resistance of the coated material to environmental effects, discoloration, whitening, staining, or conductivity.

[0006] All of these factors limit the selection of an appropriate formulation. Therefore, selecting a suitable rheology control aid is not easy, because the rheology control aid must satisfy many requirements, particularly while exhibiting compatibility with the subsequent application system. The rheology control aid must not only improve the rheological activity in the application system, but also exhibit broad compatibility in the formulations involved in the application. There is still a need to provide improved rheology additives. The use of improved rheology additives can provide highly reliable and increased thickening effects in various formulations, but at the same time, the storage stability of such rheology control additives must be favorable. Furthermore, it is desirable for the rheology additive to exhibit reduced impact on discoloration of the application system when added to, for example, a clearcoat. Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, a specific object of the present invention is to provide a high-quality rheology control agent that exhibits good effectiveness and can be used in a wide variety of application systems. More specifically, the present invention aimed to find a rheology control agent that provides outstanding anti-sag behavior. Another object of the present invention was to provide a rheology control agent that improves storage stability. A further object of the present invention was to provide a rheology control agent that is substantially salt-free. Another object of the present invention was to provide a rheology control agent that causes less discoloration when introduced into an application system. [Means for solving the problem]

[0008] Surprisingly, it has been found that these objects can be achieved by a composition comprising a liquid carrier that is liquid at a temperature of 20°C, a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in the liquid carrier, and a urea compound having a molecular weight of less than 350 g / mol, dissolved in the liquid carrier.

[0009] In one embodiment, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and at least one urea group comprises a urea-urethane compound. In another embodiment, the component comprises a molecule comprising at least one urea group and at least one urethane group. In another embodiment, the component comprises a molecule comprising at least one urea group and at least two urethane groups. In another embodiment, the component comprises a molecule comprising at least two urea groups; in a different embodiment, the component comprises two urea groups and two urethane groups; in yet another embodiment, the component comprises a molecule comprising at least four urea groups or more than four urea groups. In a different embodiment, the component comprises a molecule comprising at least two urea groups and at least two urethane groups. In different embodiments of the present invention, urethane groups may be absent.

[0010] Suitably, urea-based compounds as defined in WO 2015 / 158407, claim 11, WO 2015 / 158407, claim 13, WO 2015 / 158407, claim 16 and EP 1 396 510 A1 are used.

[0011] A preferred class of components having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is represented by the following general formula (U-1): [ka] where: R31 and R32, independently of each other and independently in each occurrence, represent a branched or unbranched, saturated or unsaturated organic group containing 1 to 100 carbon atoms and each having up to one urea group and up to one urethane group; R33 and R34, independently of one another and independently in each occurrence, represent a branched or unbranched polyester group containing 1 to 300 carbon atoms and optionally containing an ether group, a branched or unbranched polyether group containing 2 to 300 carbon atoms, a branched or unbranched polyamide group containing 1 to 300 carbon atoms, a polysiloxane group containing 3 to 100 silicon atoms, a C2 to C22 branched or unbranched alkylene group, a C2 to C22 branched or unbranched cycloalkylene group, a C2 to C18 branched or unbranched alkenylene group, a C6 to C12 arylene group, and / or a C7 to C22 branched or unbranched arylalkylene group; Z and W, independently of each other and independently when occurring multiple times, represent NH—CO—O and / or NH—CO—NH; n represents an integer of 1 to 150, preferably 2 to 150, and when n appears multiple times, n independently represents an integer of 1 to 150, preferably 2 to 150.

[0012] In another preferred embodiment, the component is represented by the general formula (U-2a), (U-2b), (U-2c), (U-2d), and (U-2e): [ka] is selected from, where: AM is selected from a linear or branched, saturated or unsaturated, aliphatic, alicyclic, aromatic or aliphatic-aromatic organic group having 2 to 50 C atoms, and if AM occurs several times, AM is independently selected from a linear or branched, saturated or unsaturated, aliphatic, alicyclic, aromatic or aliphatic-aromatic organic group having 2 to 50 C atoms, AM1 and AM2, independently of one another and independently in the case of multiple occurrences, represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 1 to 50 C atoms, IC1 and IC2, independently of one another and independently when occurring multiple times, represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon organic group having 2 to 40 C atoms, IC3 represents a linear or branched, saturated or unsaturated, aliphatic, aromatic, or aliphatic-aromatic hydrocarbon organic group having 2 to 24 carbon atoms, and when IC3 occurs multiple times, IC3 independently represents a linear or branched, saturated or unsaturated, aliphatic, aromatic, or aliphatic-aromatic hydrocarbon organic group having 2 to 24 carbon atoms; IC4 is a group as described for IC1 and IC2, or [ka] wherein RP3 is selected from urethane group-containing segments having a structure of: represents a group, and when R P3 occurs several times, R P3 independently represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 2 to 24 C atoms, and / or a (poly)ether group having 1 to 120 ether oxygen atoms, and / or a polyamide group having 1 to 100 amide groups, and / or a polysiloxane group having 3 to 100 silicon atoms, and / or a polyester group having 1 to 100 ester groups and optionally containing ether groups, RP1 and RP2 independently of one another, and independently when occurring several times, represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 1 to 24 C atoms, and / or a polyether group having 1 to 120 ether oxygen atoms, and / or a polyester group having 1 to 100 ester groups and optionally containing ether groups, and / or a polyamide group having 1 to 100 amide groups, and / or a polysiloxane group having 3 to 100 silicon atoms, R P3 represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 2 to 24 C atoms, and / or a (poly)ether group having 1 to 120 ether oxygen atoms, and / or a polyamide group having 1 to 100 amide groups, and / or a polysiloxane group having 3 to 100 silicon atoms, and / or a polyester group having 1 to 100 ester groups and optionally containing ether groups; when R P3 occurs multiple times, R P3 independently represents the above group, m is an integer of 0 to 20, preferably 1 to 20, and more preferably 1 to 5. p represents 0 and / or 1. q is an integer of 0 to 20.

[0013] Preferably, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group has a structure according to formula (U-2a), wherein: RP1 is a hydrocarbon group having 4 to 24 carbon atoms or a polyether segment having up to 50 alkylene oxide repeating units, preferably Q-(O-AO) r wherein Q is a C1-C18 alkyl or alkenyl group, AO is a C2H4 or C3H6 group, and r is an integer from 2 to 35; IC1 and IC2 are as follows: [ka] (wherein "*" indicates the position of attachment), AM is C2H4, C3H6, C4H8, C5H 10、 C6H 12 , C6H 10 , -CH2-C6H4-CH2-, or [ka] wherein: R x and R y represents H or CH3.

[0014] In one highly preferred embodiment of (U-2a), IC1 and / or IC2 are [ka] is selected from.

[0015] Even more preferably, IC1 and IC2 are [ka] is selected from.

[0016] In one highly preferred embodiment of (U-2a), AM is selected from C2H4 and -CH2-C6H4-CH2-.

[0017] In one highly preferred embodiment of (U-2a), m is an integer from 0 to 10. In one particular embodiment, m is an integer from 1 to 5. In another embodiment, m is 0.

[0018] In another preferred embodiment, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group has a structure according to formula (U-2b), wherein: Preferred embodiments of IC1 and IC2 are as described for (U-2a), in particular the radical C7H6 or the radical -C6H4-CH2-C6H4-, AM1 and AM2 are selected from linear or branched, saturated or unsaturated C1-C24 alkyl or alkenyl groups, or C6H5-CH2- groups; RP3 is selected from hydrocarbon groups having 2 to 20 carbon atoms or polyether segments having 1 to 40 ether oxygen atoms, preferably polyether segments containing 1 to 30 ethylene oxide and / or propylene oxide based repeat units.

[0019] In a further preferred embodiment, the moiety has a structure according to formula (U-2c), wherein: Preferred embodiments of AM1 and AM2 are as described for (U-2b), Preferred embodiments of AM are as described for (U-2a), IC4 is a group as described for IC1 and IC2, or [ka] wherein the urethane group-containing segment has the structure: IC2 is defined as described for (U-2a) and RP3 is defined as described for (U-2b).

[0020] With respect to (U-2c), IC4 is a C7H6 group, a -C6H4-CH2-C6H4- group, and [ka] wherein: It is particularly preferred that IC2 represents a C7H6 group or a -C6H4-CH2-C6H4- group and RP3 represents a polyether segment comprising 1 to 30 ethylene oxide and / or propylene oxide based repeat units.

[0021] In one preferred embodiment of (U-2c), q is an integer of 0 to 15, even more preferably 0 to 7, most preferably 0 to 4, for example 1 to 4.

[0022] In a preferred embodiment, at least 50% by weight of the components having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group have a structure according to formula (U-2a) or (U-2c).

[0023] In one highly preferred embodiment, at least 50% by weight of all components having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group have a structure according to formula (U-2a), where m is 0 or m is 1 to 5; highly preferably, m is 0.

[0024] In a preferred embodiment, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is a urea urethane, and 95 to 100% by weight of the component is represented by the general formula (U-3a): [ka] wherein: Y1 represents a saturated or unsaturated, branched or unbranched hydrocarbon group containing 6 to 20 carbon atoms, and when Y1 occurs multiple times, Y1 independently represents a saturated or unsaturated, branched or unbranched hydrocarbon group containing 6 to 20 carbon atoms; and in each case, the general formula (U-3b) [ka] wherein: Y2 represents a saturated or unsaturated, branched or unbranched hydrocarbon group containing 6 to 20 carbon atoms. When Y2 occurs multiple times, Y2 independently represents a saturated or unsaturated, branched or unbranched hydrocarbon group containing 6 to 20 carbon atoms.

[0025] The synthesis of a component having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group can be carried out directly in the presence of a liquid carrier and a urea compound having a molecular weight of less than 350 g / mol. In another embodiment, a component having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is synthesized in the presence of a liquid carrier, and a urea compound having a molecular weight of less than 350 g / mol is added later. In yet another embodiment, the component is synthesized in the presence of a urea compound having a molecular weight of less than 350 g / mol, and a liquid carrier is added later. In a further embodiment, a component having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is synthesized in the presence of a urea compound having a molecular weight of less than 350 g / mol and a liquid carrier, and a second liquid carrier different from the first one is added later.

[0026] The component having at least one urea group has a number average molecular weight of 400 g / mol to 30,000 g / mol. Preferably, the component has a number average molecular weight (Mn) of at least 400 g / mol, preferably at least 500 g / mol. More preferably, the number average molecular weight is greater than 600 g / mol, even more preferably greater than 650 g / mol, and most preferably greater than 800 g / mol. Furthermore, the number average molecular weight (Mn) of the component is preferably less than 20,000 g / mol, more preferably less than 10,000 g / mol, and most preferably less than 8,000 g / mol. Preferably, the number average molecular weight (Mn) is in the range of 650 g / mol to 20,000 g / mol, more preferably in the range of 800 g / mol to 8,000 g / mol, and even more preferably in the range of 800 g / mol to 5,000 g / mol.

[0027] In a further preferred embodiment, the number average molecular weight is at least 800 g / mol, preferably 1000 g / mol, preferably at least 1500 g / mol, preferably in the range of 1500 g / mol to 20000 g / mol, more preferably in the range of 1500 g / mol to 8000 g / mol, even more preferably in the range of 1500 to 5000 g / mol.

[0028] The number-average and weight-average molecular weights can be determined by gel permeation chromatography (eluent: lithium bromide (5 g / l) in dimethylacetamide, standard: polymethyl methacrylate, column temperature: 50 °C) in accordance with DIN EN ISO 13885-2 (November 2021). The number-average molecular weight can also be calculated. Furthermore, the number-average molecular weight of small molecules up to 1000 g / mol can be determined by other methods, such as mass spectrometry or nuclear magnetic resonance spectroscopy.

[0029] Preferably, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group dissolved in the liquid carrier is not crosslinked. A typical example of a crosslinked component is an elastomer. Preferably, the component having at least one urea group does not contain any crosslinked sections, and more preferably, the component is not or does not contain an elastomer.

[0030] The composition according to the invention comprises a liquid carrier that is liquid at a temperature of 20° C. and 1013 mbar.

[0031] Preferably, the liquid carrier comprises at least one of 1-(2-hydroxyethyl)-2-pyrrolidone, N,N-dimethyllactamide (2-hydroxy-N,N-dimethylpropanamide), or a polar aprotic solvent.

[0032] More preferably, the liquid carrier is a polar aprotic solvent.

[0033] Suitably, the liquid carrier comprises a compound having at least one of an N-substituted amide group and a sulfoxide group.

[0034] Preferably, the liquid carrier comprises at least one of an amide group and a sulfoxide group, wherein the amide nitrogen of the amide group has two substituents, and these substituents are selected from an aliphatic group and an aromatic group. Suitably, the amide nitrogen of the amide group has two substituents, and in this case, the amide group cannot be an NH amide group.

[0035] The liquid carrier suitably comprises at least one of N-substituted cyclic amides, acyclic dialkylamides of mono- and difunctional carboxylic acids, N-acylmorpholines, and sulfoxides.

[0036] Suitable liquid carriers include, for example, N-substituted cyclic amides, such as N-alkyl lactams, preferably N-alkyl butyrolactams, N-alkyl valerolactams, and N-alkyl caprolactams, where the alkyl group suitably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms, as well as hydroxyalkyl lactams (e.g., hydroxyethylpyrrolidone) and N-cycloalkyl lactams. Cyclic amide refers to an amide in which the amide nitrogen and amide carbonyl carbon are part of a cyclic structure.

[0037] Suitable examples of N-alkylbutyrolactams include N-methylbutyrolactam, N-ethylbutyrolactam, N-butylbutyrolactam, N-octylbutyrolactam, and N-hydroxyethylbutyrolactam. Another suitable example is N-cyclohexylbutyrolactam. Suitable examples of N-substituted caprolactams include N-ethylcaprolactam, N-methylcaprolactam, N-butylcaprolactam, and N-propylcaprolactam.

[0038] Further suitable liquid carriers are acyclic dialkylamides of monofunctional and difunctional carboxylic acids, such as N,N-dialkylamides of C1-C18 monocarboxylic acids and bis(N,N-dialkyl)amides of C1-C18 dicarboxylic acids, where these carboxylic acids optionally contain a hydroxyl group, an ether group, or an ester group, such as N,N-dialkylamidoalkyl esters, N,N-dialkylamidoalkyl ethers, and N,N-dialkyllactamides. Sulfoxides are also suitable, preferably dimethyl sulfoxide. Acyclic amides refer to amides in which the amide nitrogen and the amide carbonyl carbon are not both part of a ring structure. Under this definition, for example, N-formylmorpholine is considered to be an acyclic amide.

[0039] Further suitable liquid carriers are acyclic amides obtained from the reaction of diamines with monocarboxylic acids. Suitable examples are the reaction products of C1-C18 monocarboxylic acids with C2-C12 alkylenediamines.

[0040] Suitable liquid carriers are further linear amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylamides of C3 to C18 monocarboxylic acids (preferably N,N-dimethylamides of C6 to C10 monocarboxylic acids), N,N-dialkylamidoalkyl esters, N,N-dialkylamidoalkyl ethers, and acylmorpholines.

[0041] Further preferred examples of these are N,N-dimethylamidoalkyl esters, N,N-dimethylamidoalkyl ethers, N-formylmorpholine, and N-acetylmorpholine.

[0042] Further suitable liquid carriers are N-acetylcaprolactam, epsilon caprolactam, and 2-pyrrolidone, preferably these liquid carriers are combined with at least one further carrier containing at least one of an amide group and a sulfoxide group.

[0043] The composition according to the present invention comprises a urea compound having a molecular weight of less than 350 g / mol dissolved in a liquid carrier.

[0044] Preferably, the composition contains a urea compound having a molecular weight of less than 350 g / mol in an amount ranging from 0.05 to 15.00 wt.%, calculated relative to the total weight of the composition. More preferably, the composition contains a urea compound in an amount ranging from 0.1 to 10.0 wt.%, even more preferably from 0.2 to 8.0 wt.%, and most preferably from 0.25 to 7.00 wt.%, for example, from 0.3 to 6.0 wt.%, or from 0.4 to 5.0 wt.%. In another embodiment, the composition contains a urea compound having a molecular weight of less than 350 g / mol in an amount less than 40 wt.%, calculated relative to the total weight of the composition.

[0045] The urea compound having a molecular weight of less than 350 g / mol is represented by the formula (I) [ka] wherein R1, R2, and R3 independently represent an organic group or hydrogen, or R1 and R2 are bonded to each other. Preferably, R1, R2, and R3 independently represent an organic group or hydrogen, provided that at least one of R1, R2, and R3 is an organic group. In a different embodiment, R1, R2, and R3 independently represent an organic group or hydrogen, provided that R1 and R2 are bonded to each other. In a further embodiment, R1, R2, and R3 independently represent an organic group. In a preferred embodiment, two of the R1, R2, and R3 groups independently represent an organic group, and the third group represents hydrogen. In a preferred embodiment, R1 and R2 independently represent an organic group, and R3 represents hydrogen. In another preferred embodiment, R2 and R3 independently represent an organic group, and R1 represents hydrogen. In a further preferred embodiment, R1 represents an organic group, and R2 and R3 represent hydrogen. Preferably, the urea compound having a molecular weight of less than 350 g / mol contains one urea group. Suitably, the organic group can contain 1 to 8 carbon atoms. More suitably, the organic group can contain 1 to 4 carbon atoms, and most suitably, 1 to 2 carbon atoms. In other embodiments, the organic group can further contain a hydroxyl group, an amine group, or a combination of the foregoing.

[0046] The urea compound having a molecular weight of less than 350 g / mol is represented by the formula (I) [ka] It is also preferred to have a structure according to the formula: R1, R2, and R3 are independently an organic group having 1 to 8 carbon atoms and consisting of carbon and hydrogen, or hydrogen. In a preferred embodiment, two of the groups R1, R2, and R3 independently represent organic groups, and the third group represents hydrogen. In a preferred embodiment, R1 and R2 independently represent organic groups, and R3 represents hydrogen. In another preferred embodiment, R2 and R3 independently represent organic groups, and R1 represents hydrogen. In a further preferred embodiment, R1 represents an organic group, and R2 and R3 represent hydrogen. In one embodiment, R1, R2, and R3 are independently an organic group having 1 to 8 carbon atoms and consisting of carbon and hydrogen, or hydrogen, provided that at least one of R1, R2, and R3 is an organic group. Preferably, R1, R2, and R3 are independently an organic group having 1 to 8 carbon atoms and consisting of carbon and hydrogen. Suitably, the organic group consisting of carbon and hydrogen atoms consists of 1 to 4 carbon atoms, most suitably 1 to 2 carbon atoms.

[0047] Preferably, the urea compound having a molecular weight of less than 350 g / mol comprises at least one of 2-imidazolidinone, 1,3-dimethylurea, 1-(2-hydroxyethyl)imidazolidin-2-one, 1-methylurea, urea, biuret, N,N'-diethylurea, 1,1-dimethylurea, N-ethylurea, 1,3-diphenylurea, N-phenylurea, N-butylurea, 1,1-diethylurea, N-tert-butylurea, 3-methyl-1,1-diphenylurea, 1,1-dimethyl-3-phenylurea, N,N'-dicyclohexylurea, benzoyleneurea, N,N'-trimethyleneurea, or glycoluril.

[0048] Preferably, the urea compound having a molecular weight of less than 350 g / mol comprises at least one of 2-imidazolidinone, 1,3-dimethylurea, 1-(2-hydroxyethyl)imidazolidin-2-one, 1-methylurea, urea, or biuret.

[0049] The urea compound preferably has a molecular weight of 55 to 349 g / mol, more preferably 55 to 310 g / mol, and most preferably 55 to 280 g / mol, for example, 55 to 250 g / mol.

[0050] In another embodiment, the urea compound preferably has a molecular weight of 72 to 349 g / mol, more preferably 72 to 310 g / mol, and most preferably 72 to 280 g / mol, for example 72 to 250 g / mol.

[0051] In another embodiment, the urea compound preferably has a molecular weight of 84 to 349 g / mol. More preferably, the urea compound has a molecular weight of 84 to 310 g / mol. Most preferably, the urea compound has a molecular weight of 84 to 280 g / mol, for example, 84 to 250 g / mol. In a preferred embodiment, the urea compound has a molecular weight of 84 to 200 g / mol or 84 to 150 g / mol.

[0052] Preferably, the urea compound having a molecular weight of less than 350 g / mol and the liquid carrier are present in the composition in a weight ratio of 1:5 to 1:200, more preferably 1:7 to 1:150, even more preferably 1:8 to 1:140, such as 1:10 to 1:120, for example 1:12 to 1:80, or 1:12 to 1:50.

[0053] Preferably, the amount of the urea compound having a molecular weight of less than 350 g / mol relative to the total weight of the urea compound having a molecular weight of less than 350 g / mol and the liquid carrier is at least 0.5 wt%, preferably at least 0.6 wt%, more preferably at least 0.7 wt%, even more preferably at least 0.8 wt%, for example at least 1.2 wt%, or at least 1.5 wt%. Also preferably, the amount of the urea compound having a molecular weight of less than 350 g / mol relative to the total weight of the urea compound having a molecular weight of less than 350 g / mol and the liquid carrier is at most 20.0 wt%, preferably at most 14 wt%, more preferably at most 12 wt%, at most 10 wt%, for example at most 8 wt%.

[0054] Suitably, the amount of the urea compound having a molecular weight of less than 350 g / mol relative to the total weight of the urea compound having a molecular weight of less than 350 g / mol and the liquid carrier is in the range of 0.5% to 20% by weight, more suitably in the range of 0.7% to 14% by weight, even more suitably in the range of 0.8% to 12% by weight, and most suitably in the range of 1.2% to 10% by weight. In another suitable embodiment, the amount of the urea compound having a molecular weight of less than 350 g / mol relative to the total weight of the urea compound having a molecular weight of less than 350 g / mol and the liquid carrier is in the range of 1.5% to 8% by weight.

[0055] The weight ratio of the urea compound having a molecular weight of less than 350 g / mol to the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is suitably 1:2 to 1:100, more suitably 1:3 to 1:80, most suitably 1:4 to 1:60, for example 1:5 to 1:40.

[0056] Overall, the composition is liquid at 23° C. and 1013 mbar.

[0057] In general, the composition may contain one or more salts. The salts according to the present invention suitably contain cations of main group elements (alkali and alkaline earth metals) of Groups 1 and 2 of the Periodic Table of the Elements, or ammonium ions and mixtures thereof. Preferred salts contain lithium, calcium, or magnesium cations, particularly preferably lithium and calcium cations, preferably in the form of chloride, acetate, and / or nitrate. In some embodiments, the salts preferably contain monovalent anions as anions, particularly preferably halides, pseudohalides, formates, acetates, and / or nitrates, most particularly preferably chlorides, acetates, and / or nitrates. The salts described herein generally do not have surfactant properties. Salts with surfactant properties fall within the definition of surfactants, as explained below.

[0058] Particularly preferred salts are inorganic lithium salts, such as lithium chloride or lithium nitrate, and ammonium salts.

[0059] The composition suitably comprises 0.01 to 15.00 wt. % of the salt, said 0.01 to 15.00 wt. % being calculated relative to the total weight of the liquid carrier, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, the urea compound, and the salt. Preferably, the composition comprises the salt in an amount of 0.1 to 10.0 wt. %, more preferably 0.1 to 8.0 wt. %, even more preferably 0.1 to 5.0 wt. %, and most preferably 0.1 to 3.0 wt. %.

[0060] In one preferred embodiment, the composition is free of salts selected from lithium salts and halide salts or contains such salts in low amounts, where low amounts are amounts of salts that do not exceed 1.0% by weight calculated relative to the weight of the composition, more preferably this amount does not exceed 0.5% by weight, more preferably this amount does not exceed 0.3% by weight, and preferably this amount does not exceed 0.1% by weight.

[0061] In a further preferred embodiment, the composition does not contain salt. When the composition does not contain salt, the salt content, calculated relative to the weight of the composition, is preferably not more than 0.50 wt%, more preferably not more than 0.30 wt%, preferably not more than 0.10 wt%, for example not more than 0.05 wt%. In another preferred embodiment, the composition does not contain salt and contains a surfactant. In yet another preferred embodiment, the composition does not contain salt and contains at least one of a surfactant and an ionic liquid.

[0062] In some embodiments, the composition further comprises a surfactant. Preferably, the salt in the composition can be replaced with a surfactant. Preferably, the salt can be completely replaced with a surfactant, but it is also possible to add a surfactant together with the salt. In the latter case, the salt can be partially replaced with a surfactant, thereby reducing the salt content, or it is also possible to add a surfactant together with the salt, in which case the salt content remains the same without being reduced. Suitable surfactants include anionic surfactants such as sulfosuccinates, alk(en)yl sulfates, alk(en)yl ether sulfates, ester sulfonates, soaps, and ether carboxylic acids; nonionic surfactants such as alcohol alkoxylates, alkyl glycosides, fatty acid ester alkoxylates, amine oxides, and gemini surfactants; cationic surfactants such as alkylammonium salts, for example, tetraalkylammonium salts, quaternary ammonium salts, and ester quats; and amphoteric or zwitterionic surfactants such as betaines, alkylamido betaines, and imidazolines. Particularly preferred are quaternary ammonium salts and sulfosuccinates. Suitably, the surfactant is used in an amount of 0.1 to 15.0% by weight, preferably 0.2 to 14.0% by weight, more preferably 0.4 to 13.0% by weight, even more preferably 0.5 to 12.0% by weight, and most preferably 0.8 to 11.0% by weight, for example 1.0 to 10.0% by weight, calculated relative to the total weight of the composition.

[0063] In other embodiments, the composition further comprises an ionic liquid. Ionic liquids have a relatively high molecular weight and are ionic in nature, so they can generally be considered to be substantially or completely non-volatile and therefore free of volatile organic compounds. The term "ionic liquid" herein should be understood to mean an organic salt or mixture of organic salts that is liquid at room temperature (23°C) and 1013 mbar, where the organic salt and salt in general is solid at 23°C and 1013 mbar and has a crystalline structure.

[0064] The cations of the ionic liquids used are preferably based on ammonium, pyridinium, pyrrolidinium, pyrrolium, oxazolium, oxazolinium, imidazolium, thiazolium or phosphonium ions, and also mixtures thereof, with particular preference given to cations based on imidazolium and oxazolium ions.

[0065] The anion is preferably selected from alkyl sulfates, aryl sulfates, sulfates, hydrogen sulfates, phosphates, alkyl phosphates, aryl phosphates, tosylates, alkyl borates, haloborates such as tetrafluoroborates, haloaluminates such as tetrachloroaluminates, carboxylates such as acetates and trifluoroacetates, perchlorates, and also mixtures thereof, with alkyl sulfates, tosylates, and acetates being particularly preferred.

[0066] Suitably, the composition comprises at least one ionic liquid having a cation selected from imidazolium and oxazolium and an anion selected from alkyl sulfate, tosylate, tetrafluoroborate and acetate.

[0067] Preferably, the composition comprises, calculated on the total weight of the urea compound having a molecular weight of less than 350 g / mol, the liquid carrier and the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group: 0.05 to 40.00 wt. % of a urea compound having a molecular weight of less than 350 g / mol; 5.00 to 90.00 wt. % of a liquid carrier; 5.00 to 60.00 wt. % of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0068] In a particularly preferred embodiment, the composition comprises, calculated on the total weight of the urea compound having a molecular weight of less than 350 g / mol, the liquid carrier and the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group: 0.1 to 15.0 wt. % of a urea compound having a molecular weight of less than 350 g / mol; 10.0 to 90.0 wt % of a liquid carrier; 5.0 to 60.0% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0069] In a more preferred embodiment, the composition comprises a urea compound having a molecular weight of less than 350 g / mol, a liquid carrier, and a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, calculated on the total weight of the component: 0.2 to 12.0 wt. % of a urea compound having a molecular weight of less than 350 g / mol; 20.0 to 90.0 wt % of a liquid carrier; 7.0 to 55.0% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0070] In another preferred embodiment, the composition comprises a urea compound having a molecular weight of less than 350 g / mol, a liquid carrier, and a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, calculated on the total weight of the component: 0.3 to 10.0 wt % of a urea compound having a molecular weight of less than 350 g / mol; 25.0 to 90.0 wt. % of a liquid carrier; 9.7 to 50.0% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0071] In another preferred embodiment, the composition comprises a urea compound having a molecular weight of less than 350 g / mol, a liquid carrier, and a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, calculated on the total weight of the component: 0.4 to 9.0 wt. % of a urea compound having a molecular weight of less than 350 g / mol; 30.0 to 85.0 wt. % of a liquid carrier; 14.6 to 45.0% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0072] In another preferred embodiment, the composition comprises a urea compound having a molecular weight of less than 350 g / mol, a liquid carrier, and a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, calculated on the total weight of the component: 0.5 to 8.0 wt. % of a urea compound having a molecular weight of less than 350 g / mol; 35.0 to 84.5 wt. % of a liquid carrier; 15.0 to 40.0% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0073] In another preferred embodiment, the composition comprises a urea compound having a molecular weight of less than 350 g / mol, a liquid carrier, and a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, calculated on the total weight of the component: 0.7 to 7.5 wt. % of a urea compound having a molecular weight of less than 350 g / mol; 50.0 to 80.0 wt % of a liquid carrier; 15.0 to 40.0% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in a liquid carrier; Includes:

[0074] In a particular embodiment, the composition comprises at least two different liquid carriers, provided that one of these liquid carriers is dimethyl sulfoxide (DMSO), and the second liquid carrier is a liquid carrier that comprises at least one aliphatic disubstituted amide group.Preferably, the weight of DMSO relative to the total weight of DMSO and the second liquid carrier that comprises at least one aliphatic disubstituted amide group is at least 1%, preferably at least 2%, more preferably at least 5%, even more preferably at least 7%, and most preferably at least 10%.Also preferably, the weight of DMSO relative to the total weight of DMSO and the second liquid carrier that comprises at least one aliphatic disubstituted amide group is at most 60%, preferably at most 50%, more preferably at most 45%, even more preferably at most 40%, most preferably at most 35%, for example at most 30%.

[0075] Furthermore, the present invention relates to the use of said composition for controlling the rheology of a liquid composition.The term "liquid composition" according to the present invention refers to a composition that is liquid at 23°C and 1013 mbar.

[0076] The composition of the present invention can be used to control the rheology of a wide variety of liquid compositions. Thus, in one embodiment, the liquid composition can be an aqueous composition. The main, or even the only, liquid diluent in a liquid aqueous composition is water. Furthermore, the liquid aqueous composition can contain a certain amount of organic diluent. The organic diluent is the same as or different from at least one liquid carrier. Preferably, the liquid aqueous composition contains less than 35 wt. %, preferably less than 25 wt. %, more preferably less than 20 wt. %, most preferably less than 10 wt. %, or even less than 5 wt. % of organic diluent, calculated based on the total weight of the liquid composition. In a particular embodiment, the liquid aqueous composition does not contain any organic diluent.

[0077] Generally, liquid aqueous compositions contain at least 10% by weight of water, preferably at least 15% by weight, and more preferably at least 20% by weight. In certain cases, liquid aqueous compositions can contain at least 25% by weight of water, more preferably at least 30% by weight of water. Generally, liquid aqueous compositions contain up to 90% by weight of water, for example up to 80% by weight or up to 70% by weight of water. In particular embodiments, liquid aqueous compositions contain up to 95% by weight, or even up to 97%, 98%, or 99% by weight of water.

[0078] In another embodiment, the liquid composition may be a non-aqueous composition. A non-aqueous liquid composition is substantially free of water. This means that the liquid composition contains water in an amount suitably in the range of 0.0 to 10.0 wt. % and preferably in the range of 0.0 to 7.0 wt. % based on the total weight of the liquid composition. More preferably, the non-aqueous liquid composition contains less than 5.0 wt. % of water. For example, the liquid composition contains less than 3.0 wt. % or less than 1.0 wt. % of water calculated based on the total weight of the liquid composition.

[0079] Suitably, the liquid compositions are selected from coating compositions, clear coat compositions, lacquers, varnishes, plastic formulations, pigment pastes, effect pigment pastes, polymer formulations, sealant formulations, cosmetic formulations, household or industrial care formulations (including perfume and fragrance formulations), ceramic formulations, adhesive formulations, liquid formulations used in gas and oil production, compositions for the manufacture of electrical components and circuits, liquid formulations used in energy storage media, cleaning agents, potting compounds, building material formulations, lubricants, filling compounds, wax emulsions, metalworking fluids, metalworking supplies, liquid compositions in the form of sprays, so-called adhesion aids (for example for plant protection applications or for general applications with the aim of reducing splashing), inks, printing inks and inkjet inks, or compositions that can be used for anticorrosion purposes in the field of marine and protective coatings, and mixtures thereof.

[0080] Other liquid compositions in which the compositions according to the invention can be used include solvent-based or solvent-free paints, printing inks, and inks and lacquers, such as lacquers for varnishing plastics, wire enamels, floor coverings, coating compositions for coating food and seeds, and so-called color resists, which are used, for example, in color filters for flat panel displays such as liquid crystal displays. Lacquer applications generally include paste-like materials containing a very high proportion of solids and a small amount of liquid components, such as so-called pigment pastes, or even pastes based on effect pigments, such as pastes based on metal effect pigments, such as aluminum pigments, silver pigments, brass pigments, zinc pigments, copper pigments, bronze pigments, such as gold bronze, flame-colored bronzes, or iron-aluminum oxide pigments. Effect pigments also include, for example, interference pigments or pearlescent pigments, such as metal oxide mica pigments, fish silver, bismuth oxide chloride, or basic lead carbonate.

[0081] Plastic formulations may be liquid or non-liquid starting materials that result in plastic materials that are preferably converted into duromers by a chemical crosslinking process ("curing"). Preferred plastic formulations are unsaturated polyester resins, vinyl ester resins, acrylate resins, epoxy resins, polyurethane resins, formaldehyde resins (e.g., melamine formaldehyde or urea formaldehyde). They can be cured under a wide variety of conditions, for example, at room temperature (cold-cure systems) or at elevated temperatures (thermosetting systems), optionally under pressure ("closed mold" applications, sheet molding compounds or bulk molding compounds). Plastic formulations also include PVC plastisols.

[0082] Cosmetic formulations may be various liquid compositions used in the so-called personal care or health care field, including, for example, lotions, creams, pastes such as toothpaste, foams such as shaving foams, gels such as shaving gels, shower gels or active ingredients in gel formulations, hair shampoos, liquid soaps, nail varnishes, lipsticks, hair dyes, etc.

[0083] So-called wax emulsions are preferably dispersions of solid waxes in particulate form at room temperature in water or an organic medium.

[0084] Building material formulations may be liquid or paste-like materials used in the construction field that harden after curing. Examples include hydraulic binders such as concrete, cement, mortar, tile adhesives, and plasters.

[0085] Metalworking fluids may be cutting fluids, drilling fluids (e.g., those used in metal machining), or forging fluids, or lubricants in general. Other areas of application include mold release agents (often in the form of aqueous emulsions, e.g., for aluminum die-casting and foundry applications), mold washes (mold washes), and liquids for the surface treatment of metals (e.g., "surface finishing", surface treatments and plating).

[0086] Lubricants are means used to lubricate, i.e., reduce friction and wear, as well as provide power, cooling, vibration damping, sealing, and corrosion protection, with liquid lubricants being preferred herein.

[0087] Detergents are used to clean a wide range of objects, for example in the fields of household or industrial care. Detergents remove or assist in the removal of impurities, residues and deposits. Detergents also include detergents (mainly for cleaning textiles, their precursors, leather and dishwashing) and personal care products. Formulations containing perfumes and other fragrances (as liquid ingredients or in encapsulated form), for example as perfume gels, also belong to this field of application.

[0088] Liquid formulations used in gas and oil production are formulations used in the development and exploitation of mineral deposits. Drilling fluids or "drilling muds" are preferred examples. Another application example is the liquids used in the preparation or execution of hydraulic fracturing processes, as well as liquids that support the gas and oil production process.

[0089] The adhesive can be any adhesive material that is liquid under processing conditions and is capable of bonding parts together with surface adhesion and internal strength.

[0090] The liquid composition of the present invention may further contain conventional additives. Examples of additives include antiblocking agents, stabilizers, antioxidants, pigments, wetting agents, dispersants, emulsifiers, additional rheological additives, UV absorbers, free radical scavengers, slip additives, defoamers, adhesion promoters, leveling agents, waxes, nanoparticles, film-forming aids, and flame retardants. Preferred additives are wetting agents, dispersants, and / or emulsifiers, as well as rheological additives different from those of the composition of the present invention, such as clay-based thickeners (including organoclays), (poly)amides, polysaccharides (cellulose derivatives, guar, xanthan, etc.), polyacrylates, or associative thickeners. In one example, the composition of the present invention can be used in combination with other thickeners that affect the low-, medium-, and / or high-shear performance of the liquid composition in need of modification in terms of rheological behavior.

[0091] In a further embodiment, the present invention also relates to a method for controlling the rheology of a liquid composition, comprising the steps of providing a composition according to the present invention, providing a liquid composition, and mixing the composition according to the present invention with the liquid composition. Suitable liquid compositions include those described above. The step of mixing the components can be carried out by current processes known to those skilled in the art. This can include, inter alia, mixing by manual or electrical means. Mixing refers to combining the compositions and applying shear forces to the combined composition.

[0092] The present invention further relates to a liquid composition comprising the composition of the present invention and a binder. Suitable binders include at least one of alkyd resins (e.g., short-, medium-, or long-oil alkyds), ​​unsaturated polyester resins, vinyl ester resins, acrylate resins, epoxy resins, polyurethane resins, polyaspartic resins, phenolic binders, silicones, chlorinated rubbers, vinyl binders, polyvinyl alcohol, polyvinyl acetate, saturated polyester binders, polyacrylates and acrylate copolymers, urea and melamine resins, silicate binders, cellulose-based binders, and silyl-modified polymers. Preferred binders include at least one of alkyd resins (e.g., short-, medium-, or long-oil alkyds), ​​unsaturated polyester resins, vinyl ester resins, acrylate resins, epoxy resins, polyurethane resins, polyacrylates and acrylate copolymers, polyaspartic resins, and silyl-modified polymers.

[0093] These binders may be solvent-based, solventless, or water-based. Both solvent-based and water-based binders may be supplied as solutions, emulsions, or dispersions. Thus, the binders mentioned above include water-based binder systems such as styrene-acrylic dispersions, urethane-acrylic dispersions, and alkyd emulsions. Binders also include non-aqueous dispersion (NAD) systems.

[0094] Another subject of the present invention is an article, at least a portion of whose surface is coated with a liquid composition. In a different embodiment, the coated article is obtained by the steps of providing an article, providing a liquid composition according to the present invention, and coating at least a portion of the surface of the article with the liquid composition.

[0095] Furthermore, in yet another embodiment, the present invention relates to a coated article, at least a portion of the surface of which is coated with a liquid composition according to the present invention, and the liquid composition has solidified. In another embodiment, the coated article can be obtained by the steps of providing an article, providing a liquid composition according to the present invention, coating at least a portion of the surface of the article with the liquid composition, and allowing the liquid composition to solidify.

[0096] Suitable articles are all three-dimensional objects, regardless of size and volume, whether movable or immovable. Illustrative, but non-limiting, examples include interior and exterior constructions, flooring, furniture, vehicles used for transportation (such as automobiles, motorcycles, boats, aircraft, agricultural machinery, and all types of freight vehicles), bridges and tunnels, machinery and production equipment, electrical equipment, cans, metal coils, wires, containers, household goods and hardware, pulp and paper, and all types of articles made of wood, metal, plastic, or glass (e.g., functional or decorative). The meaning of the term "coating" is well known to those skilled in the art. In this context, this term relates to the application of a liquid composition to a surface or other area of ​​an article to at least partially cover or even completely encase the article. In this case, the liquid composition toughens or solidifies after application to the article. Solidification means that the liquid composition is transformed into a solid state. This solidification can be achieved by evaporation of the liquid diluent (physical drying) or by a chemical crosslinking reaction (hardening), and combinations thereof.

[0097] The present invention will be further described with reference to the following examples, in which the selection of reaction conditions, such as reaction temperature, reaction time, and feed rate, is known to those skilled in the art and is described in more detail.

[0098] Experimental section Preparation of intermediates

[0099] [Table 1]

[0100] Preparation of Intermediates I1-I3: [Table 2]

[0101] Intermediates I1-I3: 2 mol of TDI T65, TDI T80, or TDI T100 and 200 ppm of benzoyl chloride were weighed into a glass flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet, and heated to 40°C. Next, 1 mol of a monoalcohol (listed in Table 2 above) was added portionwise to the reaction mixture over 30 minutes. The reaction mixture was stirred at 60°C for an additional 5 hours. A clear, pale yellow liquid crude intermediate containing excess diisocyanate was obtained. The excess diisocyanate contained in the resulting crude reaction product was removed by distillation to obtain intermediates I1 to I3.

[0102] Intermediate I4: 3.5 mol of TDI T100 and 200 ppm of benzoyl chloride were weighed into a glass flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet, and heated to 40°C. 1 mol of a monoalcohol (listed in Table 2 above) was then added portionwise to the reaction mixture over 30 minutes. The reaction mixture was stirred at 60°C for an additional 5 hours. A clear, pale yellow liquid, intermediate I4, was obtained.

[0103] Example General synthesis protocol (C1–C6, C9–C11, E1–E28, E30–E38): In a four-necked flask equipped with a stirrer, the liquid carrier and stabilizer (a urea compound having a molecular weight of less than 350 g / mol or lithium chloride) were heated to 80°C with stirring under a nitrogen atmosphere. m-Xylylenediamine was added and the mixture was homogenized. Intermediate I1, Intermediate I3, or a mixture of Intermediate I1 and Intermediate I2 was added in small portions within 30 minutes with stirring so that the temperature did not exceed 85°C. The mixture was then stirred at 80°C for 3 hours. As a result, a transparent yellowish product was obtained. The exact amounts are shown in Table 3. The liquid carrier and stabilizer are shown in Table 4.

[0104] [Table 3]

[0105] [Table 4]

[0106] Comparative Rheological Additive C7: In a four-necked flask equipped with a stirrer, 80.0 g of DMSO was heated to 80°C under a nitrogen atmosphere. 1.68 g (28.0 mmol) of ethane-1,2-diamine was added and the mixture was homogenized. 18.3 g of intermediate I4 was added in small portions within 30 minutes with stirring, so that the temperature did not exceed 85°C. The mixture was then stirred at 80°C for 3 hours. This resulted in a clear, yellowish product.

[0107] Comparative Rheological Additive C8: In a four-necked flask equipped with a mechanical stirrer, 1.22 g of lithium chloride was added to 78.8 g of DMSO while stirring. The mixture was heated to 80°C under a nitrogen atmosphere. The lithium chloride was dissolved within 30 minutes while stirring. 1.68 g (28.0 mmol) of ethane-1,2-diamine was added, and the mixture was homogenized. 18.3 g of intermediate I4 was added in small portions within 30 minutes while stirring, so that the temperature did not exceed 85°C. The mixture was then stirred at 80°C for 3 hours. This resulted in a transparent, yellowish product.

[0108] Rheological additive E29 according to the invention: In a four-necked flask equipped with a mechanical stirrer, 6.00 g of 1,3-dimethylurea was added to 74 g of DMSO while stirring. The mixture was heated to 80°C under a nitrogen atmosphere. The 1,3-dimethylurea was dissolved within 30 minutes with stirring. 1.68 g (28.0 mmol) of ethane-1,2-diamine was added, and the mixture was homogenized. 18.3 g of intermediate I4 was added in small portions within 30 minutes with stirring, ensuring that the temperature did not exceed 85°C. The mixture was then stirred at 80°C for 3 hours. This resulted in a clear, yellowish product.

[0109] Storage stability 100 g of the inventive and non-inventive examples were stored in sealed glass bottles at room temperature (23° C.) until an optical change became noticeable, which may include gelling of the material and / or the formation of a precipitate.

[0110] [Table 5]

[0111] From Table 5a it can be seen that Examples E1-26, E29 and E32-38 according to the invention show a significant improvement in storage stability compared to the corresponding examples not according to the invention.

[0112] The Hazen and Gardner color indices of Examples C9, E30, and E31 were measured using a spectrophotometer LCS IV (BYK-Gardner GmbH). The Hazen scale is a color standard in accordance with DIN EN ISO 6271 for assessing the intensity of transparent, pale yellow samples by comparison with color reference standards, and ranges from 0 (colorless) to 500 (pale yellow). The Gardner scale is a color standard in accordance with DIN EN ISO 6271 for assessing the intensity of transparent, darker samples by comparison with color reference standards, and ranges from 1 (pale yellow) to 18 (dark brown).

[0113] [Table 6]

[0114] From Table 5b it can be seen that Examples E30 and E31 according to the invention have significantly lower Gardner color numbers than Comparative Example C9, which is not according to the invention, which means that Examples E30 and E31 according to the invention exhibit significantly less yellowing than Comparative Example C9.

[0115] The Hazen color number of Comparative Example 9, not according to the invention, was too high and off scale and therefore could not be measured, whereas Examples E30 and E31 according to the invention fall within the Hazen color scale and are therefore significantly less yellow than Comparative Example C9.

[0116] Applicable Test [Table 7-1]

[0117] [Table 7-2]

[0118] Test 1: Whitening of a water-based two-component PU clear coat A waterborne two-component PU clearcoat was prepared using the formulation in Table 7. All components of component A were added to a PE beaker under stirring conditions and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a 4 cm diameter toothed plate at room temperature (23°C) for 10 minutes. The pH of component A was then adjusted to 8.2-8.5 with a DMEA solution (10% in water). Component B was prepared under the same stirring conditions. Component A was divided into small portions (50 g in a 175 ml PE beaker) and stirred in a Dispermat LC3 (VMA Getzmann) equipped with a 2.5 cm diameter toothed plate at 1500 rpm for 5 minutes at room temperature (23°C). The compositions according to the present invention and the non-inventive compositions were then introduced into the mixture, with the components having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group being added in an amount of 0.5 wt. % (calculated based on the total clearcoat).

[0119] After overnight storage at room temperature, the hardener solution was added in the specified mixing ratio and homogenized by stirring with a spatula. The samples were applied to glass with a 120 μm wet film thickness using a frame film applicator (BYK Gardner GmbH) and allowed to dry at room temperature for one week. For the whitening test, a water-soaked household sponge (2 cm × 2 cm) was placed on the lacquer film for 24 hours. Immediately after removing the sponge and drying, the lacquer film was visually evaluated for whitening on a scale of 1 to 5, ranging from no whitening (a rating of "1") to significant whitening (a rating of "5").

[0120] [Table 8]

[0121] [Table 9]

[0122] While the control without rheological additive exhibits low viscosity, the samples containing rheological additives C4, E14, E16, E19, E22, and E25 exhibit significantly higher viscosity. Table 8 surprisingly reveals that the rheological additives of the present invention, E14, E16, E19, E22, and E25, do not affect the whitening of the waterborne clearcoat, while the comparative rheological additive C4 exhibits significantly worse whitening.

[0123] Test 2: Whitening of solvent-based two-component PU clear coats A solvent-based two-component PU clearcoat was prepared using the formulation in Table 9. All components of component A were added to a PE beaker under stirring and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a 4 cm diameter toothed plate for 5 minutes at room temperature (23°C). Component A was divided into small portions (50 g in a 100 ml glass bottle) and stirred in a Dispermat LC3 (VMA Getzmann) equipped with a 2.5 cm diameter toothed plate at 1500 rpm for 5 minutes at room temperature (23°C). Inventive and non-inventive compositions were introduced into the mixture, with the components having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group at a dosage of 0.5 wt. % (calculated based on the total clearcoat).

[0124] After overnight storage at room temperature, the hardener was added in the specified mixing ratio and homogenized by stirring with a spatula. Samples were applied to glass with a 120 μm wet film thickness using a frame film applicator (BYK Gardner GmbH) and allowed to dry at room temperature for one week. For whitening, a water immersion test was performed in which the drawdown was placed in a water bath (Gesellschaft für Labortechnik mbH) at 60 °C for one week. Immediately after removing the sample from the bath and drying, the lacquer film was visually evaluated for whitening on a scale of 1 to 5, ranging from no whitening (a rating of "1") to significant whitening (a rating of "5").

[0125] [Table 10]

[0126] [Table 11]

[0127] While the control without rheological additive exhibits low viscosity, the samples containing rheological additives C2, E2, E4, E6, E9, E11, and E25 exhibit significantly higher viscosity. Table 10 surprisingly reveals that the rheological additives E2, E4, E6, E9, and E11 of the present invention do not affect the whitening of the solvent-based clearcoat, while the comparative rheological additive C2 exhibits significantly worse whitening.

[0128] Test 3: Sag Resistance of Thermoplastic Acrylic Clearcoats A thermoplastic acrylic clearcoat was prepared using the formulation in Table 11. All components were added to a PE beaker under stirring and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a 4 cm diameter toothed plate for 15 minutes at room temperature (23°C). The clearcoat was divided into small portions (50 g in a 100 ml glass bottle) and stirred in a Dispermat LC3 (VMA Getzmann) equipped with a 2.5 cm diameter toothed plate at 1500 rpm for 5 minutes at room temperature (23°C). The compositions according to the invention and the compositions not according to the invention were introduced at a dosage of 0.75 wt. % (column I of Table 12) and 1.0 wt. % (column II of Table 12) of the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group (calculated based on the total clearcoat). After overnight storage at room temperature, the samples were subjected to sag resistance tests by coating them with a stepped doctor blade, model 421 / S (Erichsen GmbH & Co. KG), at wet film thicknesses of 50–500 and 550–1000 μm, respectively. The coatings were performed on a contrast card 2801 (BYK-Gardner GmbH) using an automatic applicator, byko-drive XL (BYK-Gardner GmbH), at a coating speed of 50 mm / s. Immediately after coating, the drawdowns were suspended vertically at room temperature until they dried. After drying, sag resistance was evaluated visually. Therefore, wet film thicknesses were considered where, after drying, the drawdown boundary between the coatings was clearly defined and no flow marks or blistering were observed.

[0129] [Table 12]

[0130] [Table 13]

[0131] Table 12 surprisingly reveals that the rheological additives E2, E4, E6, E9, and E11 of the present invention exhibit better sag resistance in thermoplastic acrylic clearcoats than the comparative rheological additive C2.

[0132] Test 4: Rheological effects and compatibility in various solvents 50 g of each solvent was filled into a 100 ml glass bottle. While stirring for 5 minutes at room temperature (23 °C) at 1500 rpm using a Dispermat LC3 (VMA Getzmann) equipped with a 2.5 cm diameter toothed plate, the compositions according to the invention and the compositions not according to the invention were introduced so that the amount of the component having a number-average molecular weight Mn ranging from 400 g / mol to 30,000 g / mol and at least one urea group (calculated relative to the amount of solvent) reached 1.0 wt. %. After overnight storage at room temperature, the samples were evaluated for gel level (rheological effect) and turbidity (compatibility). The visual assessment of gel level ranged from significant gel (gel level rating of "1") to no gel (gel level rating of "5"), and the visual assessment of turbidity ranged from clear (turbidity rating of "1") to significant turbidity (turbidity rating of "5").

[0133] [Table 14]

[0134] [Table 15]

[0135] Table 14a surprisingly reveals that the inventive rheological additives E2, E4, E6, E9, and E11 exhibit better gel degrees in each solvent than the comparative rheological additive C2.

[0136] [Table 16]

[0137] Table 14b surprisingly reveals that in each solvent, the rheological additives E2, E4, E6, E9, and E11 of the present invention have less of an effect on turbidity than the comparative rheological additive C2.

[0138] Test 5: Sag Resistance in Long Oil Alkyd Clearcoats A solvent-borne long-oil alkyd clear coat was prepared using the formulation in Table 15. All components of this formulation were added to a PE beaker under stirring and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a 4 cm diameter toothed plate for 10 minutes at room temperature (23°C). The clear coat was divided into small portions (50 g in a 100 ml glass bottle) and stirred in a Dispermat LC3 (VMA Getzmann) equipped with a 2.5 cm diameter toothed plate at 1500 rpm for 5 minutes at room temperature (23°C). While stirring, compositions according to the invention and compositions not according to the invention were introduced so that the amount of the component having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group was 1.0 wt. % (calculated based on the total clear coat).

[0139] After overnight storage at room temperature, the samples were subjected to sag resistance testing by applying a wet film thickness of 30 to 300 μm using a stepped doctor blade, model 421 / S (Erichsen GmbH & Co. KG). The application was performed using an automatic applicator, byko-drive XL (BYK-Gardner GmbH), on a Contrast Card 2801 (BYK-Gardner GmbH) at a coating speed of 50 mm / s. Immediately after application, the drawdowns were hung vertically at room temperature until they dried. After drying, sag resistance was evaluated visually. Therefore, the wet film thickness at which the drawdown boundary was clearly defined and no flow marks or blistering were observed was considered. Furthermore, after drying for 2 days at room temperature, the gloss of the drawdowns was measured at a wet film thickness of 60 μm using a Micro-Tri-gloss (BYK-Gardner GmbH).

[0140] [Table 17]

[0141] [Table 18]

[0142] Table 16 surprisingly reveals that the rheological additives E27 and E28 of the present invention exhibit better sag resistance and higher gloss than the comparative rheological additive C6 in long oil alkyd clearcoats.

[0143] Test 6: Whitening of solvent-borne long oil alkyd clear coats A solvent-borne long-oil alkyd clear coat was prepared using the formulation in Table 17. All components of the formulation were added to a PE beaker under stirring conditions and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a 4 cm diameter toothed plate for 10 minutes at room temperature (23°C). The clear coat was divided into small portions (50 g in a 100 ml glass bottle) and stirred in a Dispermat LC3 (VMA Getzmann) equipped with a 2.5 cm diameter toothed plate at 1500 rpm for 5 minutes at room temperature (23°C). Inventive and non-inventive compositions were introduced into the clear coat in such a way that the component having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group was added in an amount of 1.0 wt. % (calculated based on the total clear coat).

[0144] After overnight storage at room temperature, the samples were applied to glass with a 120 μm wet film thickness using a frame film applicator (BYK Gardner GmbH) and allowed to dry at room temperature for one week. For the whitening test, a water-soaked household sponge (2 cm × 2 cm) was placed on the lacquer film for 24 hours. Immediately after removing the sponge and drying, the lacquer film was visually evaluated for whitening on a scale of 1 to 5, ranging from no whitening (a rating of 1) to significant whitening (a rating of 5).

[0145] [Table 19]

[0146] [Table 20]

[0147] The control without rheological additive exhibits low viscosity, while the samples containing rheological additives C6, E27, and E28 exhibit significantly higher viscosity. Table 18 also shows that rheological additives E27 and E28 of the present invention have less of an effect on whitening of long oil alkyd clearcoats than comparative rheological additive C6.

[0148] Test 7: Yellowing in Solvent-Based Clearcoats A solvent-based two-component PU clear coat was prepared using the formulation in Table 19. All components of component A were added to a PE beaker under stirring and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a toothed plate having a diameter of 4 cm at room temperature (23°C) for 5 minutes. A small amount of component A (50 g in a 100 ml glass bottle) was added to a Dispermat LC3 (VMA Getzmann) equipped with a toothed plate having a diameter of 2.5 cm at 1500 rpm for 5 minutes at room temperature (23°C). A composition according to the present invention was introduced into the mixture, with a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group, at a dosage of 1.0 wt. % (calculated based on the total lacquer).

[0149] After overnight storage at room temperature, the hardener was added at the specified mixing ratio and homogenized by stirring with a spatula. The samples were applied to DIN A4 white-primed aluminum panels (Novelis Deutschland GmbH) at a wet film thickness of 200 μm using a wire bar (BYK Gardner GmbH) and allowed to dry at room temperature for one day. The degree of yellowing was measured one day after application using a color spectrometer, Color Guide 45 / 0 (BYK-Gardner GmbH). The YE 98 values ​​were measured and compared. DYE 98 was calculated as the difference between the degree of yellowing of the sample without rheological additive (control) and the degree of yellowing of each sample containing rheological additive.

[0150] [Table 21]

[0151] [Table 22]

[0152] Table 20 surprisingly reveals that the rheology additives E30 and E31 of the present invention have less of an effect on yellowing of two-component PU clearcoats than the comparative rheology additive C9.

[0153] Test 8: Rheological Effects and Compatibility in Two-Component PU Clearcoats A solvent-based two-component PU clear coat was prepared using the formulation in Table 21. All components of component A were added to a PE beaker under stirring and homogenized in a Dispermat LC3 (VMA Getzmann) at 1000 rpm with a toothed plate having a diameter of 4 cm at room temperature (23°C) for 5 minutes. While stirring in a Dispermat LC3 (VMA Getzmann) equipped with a toothed plate having a diameter of 2.5 cm at 1500 rpm at room temperature (23°C) for 5 minutes, a composition according to the invention was introduced such that the amount of the component having a number-average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and containing at least one urea group was 0.55 wt. % (calculated based on the total lacquer).

[0154] After two days of storage at room temperature, the degree of gelation and turbidity were visually assessed on a scale of 1 to 5 for gelation (no gelation to significant gelation) and turbidity (clear to significant turbidity). The curing agent was added in the specified mixing ratio and homogenized with a spatula until the clearcoat composition was optically homogenous. The flow time of the clearcoat composition was then measured using a DIN 4 mm flow cup (BYK-Gardner GmbH). The clearcoat composition was diluted with a solvent mixture (n-butyl acetate / Dowanol PMA; 40:60 w / w) to adjust the DIN 4 flow time upon application to 21 seconds (+ / - 1 second). The clearcoat compositions were applied to vertically suspended primed perforated steel panels (N / 16300500L cold-rolled sheet steel (gray / white, gray coated side, 300 mm x 500 mm x 0.60-0.70 mm) with a protective coating containing 16 10 mm holes, using an air-powered spray applicator from Eisenmann LaTec ​​GmbH (spray gun AGMD Pro (De Vilbiss), 1.2 mm nozzle De Vilbiss GTI PRO High Efficiency TE 40 C, air flow rate 0.6 m / s). The clearcoat was applied in three spray passes to determine the sag limit of the clearcoat composition. After spray application, the coated panels were ventilated vertically at room temperature for 10 minutes and then reflowed in a VTL 60 / 90 reflow oven (Votsch Industrietechnik GmbH). The plates were dried vertically at 60°C for 60 minutes in a BYK-Gardner GmbH (Byko-Test GmbH). After 24 hours, the sag limit was determined by optically checking the position below the hole on the plate where there was no accumulation of clearcoat (no obvious blister or flow marks). Furthermore, the dry film thickness above and below the determined hole was measured using a Byko-Test 1500 dry film thickness measuring device (BYK-Gardner GmbH) by performing three measurements and then averaging the values.

[0155] [Table 23]

[0156] [Table 24]

[0157] Table 22 surprisingly reveals that the inventive rheology additive E29 exhibits better rheological effects (degree of gel) in liquid clearcoats, as well as better rheological effects (sag limit) after application, and, in contrast to comparative rheology additive C8, does not affect the turbidity of the two-component PU clearcoats.

Claims

1. 1. A composition comprising: a liquid carrier that is liquid at a temperature of 20°C; a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in the liquid carrier; a urea compound having a molecular weight of less than 350 g / mol dissolved in the liquid carrier; A composition comprising:

2. 2. The composition of claim 1, wherein the composition comprises the urea compound having a molecular weight of less than 350 g / mol in an amount ranging from 0.05 to 15.00% by weight, calculated relative to the total weight of the composition.

3. The urea compound having a molecular weight of less than 350 g / mol is represented by the formula (I) 【Chemistry 1】 3. The composition of claim 1, comprising a structure according to the formula: wherein R1, R2, and R3 independently represent an organic group or hydrogen, or R1 and R2 are bonded to each other.

4. The urea compound having a molecular weight of less than 350 g / mol is represented by the formula (I) 【Chemistry 2】 wherein: The composition according to any one of claims 1 to 3, wherein R1, R2, and R3 are independently an organic group having 1 to 8 carbon atoms and consisting of carbon and hydrogen elements, or hydrogen.

5. 5. The composition of any one of claims 1 to 4, wherein the urea compound comprises at least one of 2-imidazolidinone, 1,3-dimethylurea, 1-(2-hydroxyethyl)imidazolidin-2-one, 1-methylurea, urea, biuret, N,N'-diethylurea, 1,1-dimethylurea, N-ethylurea, 1,3-diphenylurea, N-phenylurea, N-butylurea, 1,1-diethylurea, N-tert-butylurea, 3-methyl-1,1-diphenylurea, 1,1-dimethyl-3-phenylurea, N,N'-dicyclohexylurea, benzoyleneurea, N,N'-trimethyleneurea, or glycoluril.

6. 6. The composition of any one of claims 1 to 5, wherein the liquid carrier comprises at least one of 1-(2-hydroxyethyl)-2-pyrrolidone, 2-hydroxy-N,N-dimethylpropanamide, or a polar aprotic solvent.

7. The composition according to any one of claims 1 to 6, wherein the liquid carrier comprises a compound having at least one of an N-substituted amide group and a sulfoxide group.

8. The composition according to any one of claims 1 to 7, wherein the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group dissolved in the liquid carrier comprises at least two urea groups and at least two urethane groups.

9. The component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is represented by the formulae U-2a, U-2b, U-2c, U-2d, and U-2e 【Transformation 3】 wherein: AM is selected from a linear or branched, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic organic group having 2 to 50 C atoms, and if AM occurs several times, AM is independently selected from a linear or branched, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or aliphatic-aromatic organic group having 2 to 50 C atoms, AM1 and AM2, independently of one another and independently in the case of several occurrences, represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic radical having 1 to 50 C atoms, IC1 and IC2, independently of one another and independently in the case of several occurrences, represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 2 to 40 C atoms, IC3 represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon group having 2 to 24 carbon atoms, and when IC3 occurs multiple times, IC3 independently represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic hydrocarbon group having 2 to 24 carbon atoms; IC4 is a group as described for IC1 and IC2, or 【Chemistry 4】 wherein RP3 is a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 2 to 24 C atoms, and / or a (poly)ether group having 1 to 120 ether oxygen atoms, and / or a polyamide group having 1 to 100 amide groups, and / or a polysiloxane group having 3 to 100 silicon atoms, and / or a polyester having 1 to 100 ester groups and optionally containing ether groups. if RP3 occurs several times, RP3 independently represents a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 2 to 24 C atoms, and / or a (poly)ether group having 1 to 120 ether oxygen atoms, and / or a polyamide group having 1 to 100 amide groups, and / or a polysiloxane group having 3 to 100 silicon atoms, and / or a polyester group having 1 to 100 ester groups and optionally containing ether groups, RP1 and RP2, independently of one another and independently in the case of several occurrences, represent a linear or branched, saturated or unsaturated, aliphatic, aromatic or aliphatic-aromatic organic group having 1 to 24 C atoms, and / or a polyether group having 1 to 120 ether oxygen atoms, and / or a polyester group having 1 to 100 ester groups and optionally comprising ether groups, and / or a polyamide group having 1 to 100 amide groups, and / or a polysiloxane group having 3 to 100 silicon atoms, The composition according to any one of claims 1 to 8, wherein m is an integer from 0 to 20, p represents 0 and / or 1, and q is an integer from 0 to 20.

10. 10. The composition according to claim 1, wherein a weight ratio of the urea compound having a molecular weight of less than 350 g / mol to the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group is 1:2 to 1:

100.

11. The composition according to any one of claims 1 to 10, wherein the composition comprises 0.01 to 15.00 wt% of a salt, the 0.01 to 15.00 wt% being calculated relative to the total weight of the urea compound having a molecular weight of less than 350 g / mol, the liquid carrier, the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, and the salt.

12. The composition comprises, calculated based on the total weight of the urea compound having a molecular weight of less than 350 g / mol, the liquid carrier, and the component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group: 0.05 to 40.00 wt. % of the urea compound having a molecular weight of less than 350 g / mol; 5.00 to 90.00% by weight of the liquid carrier; 5.00 to 60.00% by weight of a component having a number average molecular weight Mn in the range of 400 g / mol to 30,000 g / mol and having at least one urea group, dissolved in the liquid carrier; The composition of any one of claims 1 to 11, comprising:

13. Use of a composition according to any one of claims 1 to 12 for controlling the rheology of a liquid composition.

14. A liquid composition comprising the composition according to any one of claims 1 to 12 and a binder.

15. A coated article, wherein at least a portion of a surface of the article is coated with the liquid composition of claim 14.

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