Rheology control agents

Abstract

This invention relates to a composition comprising a mixture of compounds according to formula (I) wherein IC1 and IC2 independently represent a hydrocarbon group each time they appear, AM independently represents a hydrocarbon group each time it appears, m is the average number of repeating units from 0 to 20, RP1 and RP2 independently represent an organic group selected from RP3, RP4, and RP5 each time they appear, wherein RP3 represents a hydrocarbon group, and RP4 represents an organic group according to formula (II) RP41-(AO). n - Wherein RP41 represents a hydrocarbon group having 1 to 24 carbon atoms, AO represents an alkylene oxide repeating unit and n is the average number of repeating units from 6 to 30, and RP5 represents an organic group according to formula (III) RP51-(AO) p - Wherein RP51 represents a hydrocarbon group having 1 to 24 carbon atoms, AO represents an alkylene oxide repeating unit and p is an average number of repeating units of 1 to 5, wherein the mixture comprises a compound of formula (I), wherein (A) RP1 is RP3 and RP2 is RP4, (B) RP1 is RP4 and RP2 is RP5, and (C) RP1 is RP3 and RP2 is RP5.

Description

[0001] This invention relates to a composition comprising a mixture of compounds according to formula (I) and its use in controlling the rheology of the liquid composition. The invention further relates to a liquid composition comprising a mixture of compounds according to formula (I) and articles coated with said liquid composition.

[0002] Rheology control auxiliaries typically use optionally organically modified clays, such as bentonite and / or silica, hydrogenated castor oil, and polyamide waxes, to control the rheology of liquid systems. A drawback of these rheology control auxiliaries is that they are mostly dry solids that must be processed into semi-finished forms using solvents and shear forces, and / or introduced into liquid systems with targeted temperature control. Failure to adhere to these temperature and / or appropriate incorporation conditions not only leads to poor rheological properties but also to undesirable properties of the product.

[0003] In the case of liquid systems that are coating compositions, these rheology control additives often cause turbidity and haze in clear, transparent coatings. Furthermore, handling them with dry, powdered products that generate dust during processing may be technically disadvantageous.

[0004] Liquid applications of these rheology control aids are provided by solutions of specific urea components, such as those described in EP 1 188 779 A. The solvent and / or carrier medium is typically a polar / aprotic solvent. Alternatively, ionic liquids may be used instead of classic organic diluents, as described in DE 102008059702 A.

[0005] These liquid rheology control agents need to meet many requirements. They must not only exhibit improved rheological activity, but also demonstrate broad compatibility in the relevant formulations.

[0006] Another aspect to note regarding rheology control additives supplied in liquid form is the potential for certain undesirable effects. For example, the incorporation of urea-carbamate rheology control additives into the liquid phase of the application system can lead to pronounced elastic behavior. This effect, also known as the jelly effect, results in an undesirable visual appearance and surface defects in the applied coating. Another drawback relates to the more complex incorporation of rheology additives. All these parameters mentioned above limit the selection of suitable products. The selection of suitable rheology control additives is therefore difficult because they must be compatible with the subsequent application system and also meet further requirements.

[0007] Therefore, improved rheological control agents are needed to improve rheological performance and other parameters mentioned above.

[0008] Therefore, a specific object of the present invention is to provide a high-quality rheology control agent that is effective and easily incorporated, applicable to a wide range of systems and does not exhibit significant elastic behavior, while retaining the advantageous properties of prior art rheology control agents. Such advantageous properties include, for example, the anti-sagging properties, leveling properties, and orange peel effect that the rheology control agent provides in the application system.

[0009] Surprisingly, it has been found that these objectives can be achieved by providing a composition comprising a mixture of compounds according to formula (I).

[0010]

[0011] IC1 and IC2 represent hydrocarbon groups independently of each other and independently in each occurrence.

[0012] AM independently represents a hydrocarbon group each time it appears.

[0013] m is the average number of repeating units between 0 and 20.

[0014] RP1 and RP2 independently represent organic groups selected from RP3, RP4, and RP5 each time they appear.

[0015] RP3 represents a hydrocarbon group.

[0016] RP4 represents an organic group according to formula (II).

[0017] (II)RP41-(AO) n -

[0018] RP41 represents a hydrocarbon group having 1 to 24 carbon atoms.

[0019] AO represents a repeating unit of alkyl oxide and

[0020] n is the average number of repeating units between 6 and 30.

[0021] RP5 represents an organic group according to formula (III).

[0022] (III)RP51-(AO) p -

[0023] RP51 represents a hydrocarbon group having 1 to 24 carbon atoms.

[0024] AO represents a repeating unit of alkyl oxide and

[0025] p is the average number of repeating units from 1 to 5.

[0026] The mixture said mixture comprises a compound of formula (I), wherein

[0027] (A) RP1 is RP3 and RP2 is RP4.

[0028] (B) RP1 is RP4 and RP2 is RP5.

[0029] (C) RP1 is RP3 and RP2 is RP5.

[0030] Preferably, AM is selected from straight-chain or branched, saturated or unsaturated, aliphatic, alicyclic, aromatic or aliphatic-aromatic hydrocarbon groups having 2 to 50 C atoms; in the case where AM appears multiple times, AM is independently selected from straight-chain or branched, saturated or unsaturated, aliphatic, alicyclic, aromatic or aliphatic-aromatic hydrocarbon groups having 2 to 50 C atoms.

[0031] Preferably, IC1 and IC2 independently represent straight-chain, branched, or cyclic, saturated or unsaturated, aliphatic, aromatic, or aliphatic-aromatic hydrocarbon groups having 2 to 40 C atoms; when IC1 and IC2 appear multiple times, IC1 and IC2 independently represent the aforementioned groups, and m is 0 to 20, preferably 0 to 10, more preferably 0 to 7, even more preferably 0 to 5, such as an average repeating unit number of 0 to 3. m is most preferably 0.

[0032] In another embodiment, m is 1 to 20, preferably 1 to 10, more preferably 1 to 7, such as 1 to 5, the average number of repeating units.

[0033] In a preferred embodiment, IC1 and IC2 are preferably selected from one of the following divalent groups (where "*" indicates the linkage site).

[0034]

[0035] Furthermore, AM is selected from the groups C2H4, C3H6, C4H8, and C5H. 10 C6H 12 C6H 10 CH2-C6H4-CH2 or related groups

[0036]

[0037] Where R x and R y It represents H or CH3.

[0038] In a highly preferred embodiment, IC1 is selected from...

[0039]

[0040] More preferably, IC1 and IC2 are selected from

[0041]

[0042] In a highly preferred embodiment, AM is selected from C2H4, C3H6, and CH2-C6H4-CH2. More preferably, AM is selected from C2H4 and CH2-C6H4-CH2.

[0043] Urea-based compounds can be prepared in known ways by reacting the corresponding isocyanate with an amine, such as the amine or isocyanate described in claim 14 of WO2015 158 407. Methods for preparing this type of urea compound are described in more detail in, for example, US 7250487 B2, US 7348397 B2, EP 13 96 510A1, and EP 2 292 675A1.

[0044] In urea-based compounds, the terminal groups RP1 and RP2 independently represent organic groups selected from RP3, RP4, and RP5 each time they appear.

[0045] RP3 represents a hydrocarbon group. Suitably, RP3 represents a hydrocarbon group having 6 to 24 carbon atoms. More suitably, RP3 represents a hydrocarbon group having 8 to 20 carbon atoms, and most suitably, having 9 to 18 carbon atoms. RP3 may represent a saturated or unsaturated, aromatic or aryl aliphatic hydrocarbon group, preferably alkyl or alkenyl. Most preferably, RP3 represents an alkyl group. In a suitable embodiment, RP3 is a branched or straight-chain hydrocarbon group.

[0046] RP4 represents an organic group according to formula (II).

[0047] (II)RP41-(AO) n -

[0048] RP41 represents a hydrocarbon group having 1 to 24 carbon atoms. In one embodiment, RP41 represents a hydrocarbon group having 1 to 5 carbon atoms, while in another embodiment, RP41 represents a hydrocarbon group having 6 to 24 carbon atoms.

[0049] AO represents an alkylene oxide repeating unit. The alkylene oxide repeating unit may be based on ethylene oxide, propylene oxide, butane oxide, and mixtures thereof. Preferably, the n AO repeating units in RP4 comprise 70 to 100 mol% of ethylene oxide repeating units, calculated based on the number of AO repeating units in RP4. More preferably, the n AO repeating units in RP4 comprise 90 to 100 mol% of ethylene oxide repeating units, calculated based on the number of AO repeating units in RP4. Most preferably, the n AO repeating units in RP4 comprise 100 mol% of ethylene oxide repeating units.

[0050] n is the average number of repeating units from 6 to 30. Preferably, n is the average number of repeating units from 6 to 25, more preferably from 6 to 20, even more preferably from 6 to 17, such as from 6 to 14.

[0051] RP5 represents an organic group according to formula (III).

[0052] (III)RP51-(AO) p -

[0053] RP51 represents a hydrocarbon group having 1 to 24 carbon atoms. Preferably, RP51 represents a hydrocarbon group having 1 to 8 carbon atoms, more preferably, RP51 represents a hydrocarbon group having 1 to 4 carbon atoms. In a preferred embodiment, RP51 represents a straight-chain hydrocarbon group; very preferably, RP51 represents a straight-chain alkyl group.

[0054] AO represents an alkyl oxide repeating unit. The alkyl oxide repeating unit of RP5 may be based on ethylene oxide, propylene oxide, butane oxide, and mixtures thereof. Suitably, p AO repeating units in RP5 comprise 95 to 100 mol% of ethylene oxide repeating units calculated based on the number of AO repeating units in RP5. More suitably, RP5 comprises 100 mol% of ethylene oxide repeating units.

[0055] p is the average number of repeating units from 1 to 5. In another embodiment, p is 1 to 4, more preferably 2 to 4, such as 2.5 to 3.5.

[0056] The composition according to the invention comprises a mixture of compounds according to formula (I), wherein

[0057] (A) RP1 is RP3 and RP2 is RP4.

[0058] (B) RP1 is RP4 and RP2 is RP5.

[0059] (C) RP1 is RP3 and RP2 is RP5.

[0060] A mixture of compounds according to formula (I) may additionally contain additional compounds. For example, it may contain compounds as follows, wherein

[0061] (D) RP1 is RP3 and RP2 is RP3

[0062] (E) RP1 is RP4 and RP2 is RP4

[0063] (F)RP1 is RP5 and RP2 is RP5.

[0064] The present invention further relates to a method for preparing a mixture of compounds according to formula (I). The method comprises the steps of...

[0065] 1.) Reaction of at least three monohydroxy compounds selected from RP3-OH, RP4-OH, and RP5-OH with at least one diisocyanate of the formula OCN-IC1-NCO and optionally with at least one diisocyanate of the formula OCN-IC2-NCO to produce monoisocyanate urethane adducts and

[0066] 2.) React the monoisocyanate-carbamate adduct with at least one diamine of the formula NH2-AM-NH2.

[0067] Monoisocyanate-carbamate adducts are molecules containing one urethane group and one isocyanate group.

[0068] AM, IC1, IC2, RP3, RP4, and RP5 have the meanings described above.

[0069] Regarding the preparation of the mixture of compounds according to formula (I) in the first step, three different monohydroxy compounds are reacted with one or more diisocyanates to produce monoisocyanate-carbamate adducts, which are therefore different in alcohol composition. In the second step, these monoisocyanate-carbamate adducts are reacted with diamines to form six different urea urethanes, which differ at their two end groups (RP1 and RP2) and can be described as follows:

[0070] (A) RP1 is RP3 and RP2 is RP4.

[0071] (B) RP1 is RP4 and RP2 is RP5.

[0072] (C) RP1 is RP3 and RP2 is RP5.

[0073] (D) RP1 is RP3 and RP2 is RP3.

[0074] (E) RP1 is RP4 and RP2 is RP4.

[0075] (F)RP1 is RP5 and RP2 is RP5.

[0076] Combination (A) originates from the reaction of diisocyanate with two different monohydroxy compounds, namely those described above for RP3 and RP4, in the first step. Correspondingly, combination (B) is the product of the reaction of diisocyanate with two different monohydroxy compounds, as described above for RP4 and RP5, in the first step, and compound (C) originates from the reaction with two monohydroxy compounds, as described above for RP3 and RP5, in the first step. Therefore, the compounds according to combinations (A), (B), and (C) each have two different terminal groups RP1 and RP2 in the manner described above.

[0077] On the other hand, combinations (D), (E), and (F) are each reaction products of diisocyanates with only one type of monohydroxy compound. Thus, combination (D) has two end groups as described for RP3, combination (E) has two end groups as described for RP4, and combination (F) has two end groups as described for RP5.

[0078] The composition suitably contains

[0079] At least 12% by weight of compound (A)

[0080] At least 9% by weight of compound (B)

[0081] At least 10% by weight of compound (C),

[0082] Calculated based on the total weight of the compound according to formula (I).

[0083] More preferably, the composition comprises

[0084] At least 13% by weight of compound (A)

[0085] At least 10% by weight of compound (B)

[0086] At least 13% by weight of compound (C)

[0087] Calculated based on the total weight of the compound according to formula (I).

[0088] Most preferably, the composition comprises

[0089] At least 14% by weight of compound (A)

[0090] At least 12% by weight of compound (B)

[0091] At least 17% by weight of compound (C)

[0092] Calculated based on the total weight of the compound according to formula (I).

[0093] The composition preferably contains

[0094] 12 to 33% by weight of compound (A)

[0095] 9 to 35% by weight of compound (B)

[0096] 10 to 30% by weight of compound (C),

[0097] Calculated based on the total weight of the compound according to formula (I).

[0098] More preferably, the composition comprises

[0099] 12 to 31% by weight of compound (A)

[0100] 9 to 34% by weight of compound (B)

[0101] 10 to 28% by weight of compound (C),

[0102] Calculated based on the total weight of the compound according to formula (I).

[0103] More preferably, the composition comprises

[0104] 12 to 29% by weight of compound (A)

[0105] 9 to 33% by weight of compound (B)

[0106] 10 to 27% by weight of compound (C),

[0107] Calculated based on the total weight of the compound according to formula (I).

[0108] Most preferably, the composition comprises

[0109] 12 to 27% by weight of compound (A)

[0110] 9 to 32% by weight of compound (B)

[0111] 10 to 25% by weight of compound (C),

[0112] Calculated based on the total weight of the compound according to formula (I).

[0113] Preferably, the composition comprises

[0114] At least 4% by weight of compound (D)

[0115] At least 6% by weight of compound (E)

[0116] At least 4% by weight of compound (F),

[0117] Calculated based on the total weight of the compound according to formula (I).

[0118] More preferably, the composition comprises

[0119] At least 5% by weight of compound (D)

[0120] At least 7% by weight of compound (E)

[0121] At least 5% by weight of compound (F)

[0122] Calculated based on the total weight of the compound according to formula (I).

[0123] Most preferably, the composition comprises

[0124] At least 6% by weight of compound (D)

[0125] At least 8% by weight of compound (E)

[0126] At least 6% by weight of compound (F),

[0127] Calculated based on the total weight of the compound according to formula (I).

[0128] In one different embodiment, the composition comprises

[0129] 4 to 30% by weight of compound (D)

[0130] 6 to 22% by weight of compound (E)

[0131] 4 to 30% by weight of compound (F),

[0132] Calculated based on the total weight of the compound according to formula (I).

[0133] 4 to 28% by weight of compound (D)

[0134] 6 to 20% by weight of compound (E)

[0135] 4 to 28% by weight of compound (F),

[0136] Calculated based on the total weight of the compound according to formula (I).

[0137] 4 to 27% by weight of compound (D)

[0138] 6 to 18% by weight of compound (E)

[0139] 4 to 26% by weight of compound (F),

[0140] Calculated based on the total weight of the compound according to formula (I).

[0141] 4 to 25% by weight of compound (D)

[0142] 6 to 16% by weight of compound (E)

[0143] 4 to 24% by weight of compound (F),

[0144] Calculated based on the total weight of the compound according to formula (I).

[0145] In a further embodiment, the composition comprises less than 40% by weight of each of (A), (B), (C), (D), (E), and (F) based on the total weight of the compounds according to formula (I). In another embodiment, the composition comprises no more than 35% by weight of each of (A), (B), (C), (D), (E), and (F).

[0146] Preferably, the composition comprises

[0147] 26 to 55 mol% RP3

[0148] 22 to 35 mol% RP4

[0149] 22 to 45 mol% RP5

[0150] Calculated based on the sum of RP3, RP4, and RP5.

[0151] In addition, the composition may contain one or more salts. Generally, any salt having a melting point above 80°C and different from an ionic liquid is suitable.

[0152] The salts according to the invention contain cations of elements (alkali metals and alkaline earth metals) belonging to Group I and II of the periodic table, or ammonium ions (including substituted ammonium ions, such as alkylammonium ions) and mixtures thereof. Preferred salts are those containing lithium, calcium, or magnesium, with lithium and calcium cations being particularly preferred. In some embodiments, the salt contains preferably monovalent anions, particularly halide ions, pseudohalides, formate, acetate, and / or nitrate ions, and most particularly preferably chloride, acetate, and / or nitrate ions as anions.

[0153] Inorganic lithium salts, such as lithium chloride or lithium nitrate, and ammonium salts, such as alkylammonium salts, especially quaternary ammonium salts, such as tetraalkylammonium halides, are particularly preferred as salts.

[0154] In this composition, the one or more salts are preferably present in an amount of 0.0 to 10.0% by weight, more preferably 0.0 to 6.0% by weight, even more preferably 0.0 to 4.0% by weight, and most preferably 0.0 to 2.0% by weight, calculated based on the weight of the mixture of compounds according to formula (I) and the salts.

[0155] Furthermore, the composition suitably comprises one or more diluents. These diluents may be organic or inorganic. They are preferably organic diluents. These diluents do not contain urea groups and typically comprise aprotic polar diluents. Organic diluents include volatile organic solvents as well as non-volatile organic solvents.

[0156] Examples of suitable diluents include amides, preferably cyclic amides (i.e., lactams), acyclic dialkylamides of monofunctional and difunctional carboxylic acids, sulfoxides, preferably dimethyl sulfoxides, and / or ionic liquids. Particularly suitable are diluents selected from N-alkyl-lactams, preferably N-alkylbutyrolactams, wherein the alkyl group is selected from C1 to C2. 12 alkyl.

[0157] Examples of N-alkylbutyrolactams are N-methylbutyrolactam, N-ethylbutyrolactam, N-butylbutyrolactam, N-octylbutyrolactam, and N-hydroxyethylbutyrolactam. Suitable examples of N-substituted caprolactams are N-vinylcaprolactam, N-ethylcaprolactam, N-methylcaprolactam, N-acetylcaprolactam, N-butylcaprolactam, and N-propylcaprolactam. Examples of linear amides are N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dialkylamide alkyl esters, N,N-dialkylamide alkyl ethers, hexamethylphosphoric triamine, and acylmorpholine. Preferred examples of these include N,N-dimethylamide alkyl esters, N,N-dimethylamide alkyl ethers, N-formylmorpholine, and N-acetylmorpholine.

[0158] In another preferred embodiment, the one or more organic diluents in the composition are ionic liquids. In this invention, the so-called ionic liquid is an organic salt with a melting point of 80°C or lower.

[0159] Examples of ionic liquids are substituted imidazolium salts, such as 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-butyl-3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium thiocyanate, and 1-butyl-3-methylimidazolium thiocyanate. Ionic liquids can be combined with the nonionic organic diluents mentioned above.

[0160] In this composition, the one or more diluents are preferably present in an amount of 35.0 to 95.0% by weight, more preferably 40.0 to 94.0% by weight, and even more preferably 45.0 to 90.0% by weight, calculated based on the weight of the mixture of compounds according to formula (I) and the diluent.

[0161] In a preferred embodiment, the composition comprises

[0162] A mixture of 5 to 65% by weight of compounds according to formula (I)

[0163] 35 to 95% by weight of the one or more diluents and

[0164] 0 to 10% by weight of the one or more salts

[0165] Calculated based on the total weight of the composition.

[0166] In a more preferred embodiment, the composition comprises

[0167] A mixture of 6 to 60% by weight of compounds according to formula (I)

[0168] 40 to 94% by weight of the one or more diluents and

[0169] 0 to 8% by weight of the one or more salts

[0170] Calculated based on the total weight of the composition.

[0171] In a further preferred embodiment, the composition comprises

[0172] A mixture of 7 to 58% by weight of compounds according to formula (I)

[0173] 42 to 93% by weight of the one or more diluents and

[0174] 0 to 6% by weight of the one or more salts

[0175] Calculated based on the total weight of the composition.

[0176] In a further preferred embodiment, the composition comprises

[0177] A mixture of 10 to 55% by weight of the compound according to formula (I)

[0178] 45 to 90% by weight of the one or more diluents and

[0179] 0 to 4% by weight of the one or more salts

[0180] Calculated based on the total weight of the composition.

[0181] The compositions of the present invention can be used to control the rheology of various types of liquid compositions. In a preferred embodiment, the liquid composition may be an aqueous composition. The main or even sole liquid diluent of the aqueous liquid composition is water. Additionally, the aqueous liquid composition may contain a certain amount of an organic diluent. This organic diluent may be the same as or different from one or more organic diluents described above. Preferably, the aqueous liquid composition contains less than 50% by weight, preferably less than 40% by weight, more preferably less than 30% by weight, even more preferably less than 20% by weight, and most preferably less than 10% or even less than 5% by weight of organic diluent based on the total weight of the aqueous liquid composition. In a particular embodiment, the aqueous liquid composition is completely free of organic diluent.

[0182] Generally, the aqueous liquid composition contains at least 10% by weight, preferably at least 15% by weight, and more preferably at least 20% by weight of water, calculated based on the total weight of the aqueous liquid composition. In some cases, the aqueous liquid composition may contain at least 25% by weight, and more preferably at least 30% by weight of water. Generally, the aqueous liquid composition contains up to 90% by weight of water, such as up to 80% by weight or up to 70% by weight. In a particular embodiment, the aqueous liquid composition contains up to 95% by weight or even up to 97, 98, or 99% by weight of water.

[0183] 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 non-aqueous liquid composition suitably contains 0.0 to less than 10.0% by weight of water, preferably 0.0 to 7.0% by weight, based on the total weight of the non-aqueous liquid composition. More preferably, the non-aqueous liquid composition contains less than 5.0% by weight of water. For example, the liquid composition contains less than 3.0% by weight or less than 1.0% by weight of water based on the total weight of the liquid composition.

[0184] Suitablely, the liquid composition is selected from coating compositions, clear coating compositions, varnishes, varnishes, plastic formulations, pigment pastes, effect pigment pastes, polymer formulations, sealant formulations, cosmetic formulations, household or industrial care formulations (including fragrance and perfume formulations), ceramic formulations, adhesive formulations, liquid formulations for oil and gas extraction (including drilling and exploration), compositions for the manufacture of electrical components and circuits, liquid formulations for energy storage media, cleaning agents, potting compounds, building material formulations, lubricants, filler compounds, wax emulsions, metalworking fluids, metalworking products, liquid compositions in the form of sprays, so-called deposition aids (e.g., for plant protection agents or for general purposes of reducing drift), inks, printing inks and inkjet inks, or compositions that can be used for corrosion protection in the fields of marine and protective coatings, and mixtures thereof.

[0185] The liquid compositions of the present invention may further comprise conventional additives. Examples of additives include antiblocking agents, stabilizers, antioxidants, pigments, wetting agents, dispersants, emulsifiers, additional rheology modifiers, ultraviolet absorbers, free radical scavengers, slip additives, defoamers, adhesion promoters, leveling agents, waxes, nanoparticles, film-forming aids, and flame retardants.

[0186] The present invention also relates to a liquid composition comprising the composition according to the invention. The term liquid composition refers to a composition that is liquid at 23°C and 100 kPa. Preferably, the liquid composition comprises a binder. Very preferably, the liquid composition comprising the composition is an aqueous composition.

[0187] All conventional adhesives known to those skilled in the art are suitable as adhesive components. In one embodiment, the adhesive used according to the invention has crosslinkable functional groups. Any conventional crosslinkable functional groups known to those skilled in the art are contemplated herein.

[0188] In addition, suitable examples of film-forming adhesives may include synthetic or natural resins, such as alkyd resins; acrylic resins in combination with aliphatic polyisocyanates, such as self-crosslinking multiphase acrylic dispersions, thermosetting acrylic resins, styrene-acrylate dispersions, water-dilutable hydroxyl-functionalized polyacrylic dispersions; vinyl acrylate resins; vinyl acetate / ethylene copolymers; polyurethanes, polyesters; melamine resins; epoxy resins, optionally in combination with amine curing agents; silanes; siloxanes; silicate adhesives, natural oils; polyurethanes (one-component and two-component systems); polyvinyl acetate; polyaspartic acid esters; PVC plastisols, PVC organosols; thermoplastics; unsaturated polyester resins; and hybrids thereof and combinations thereof.

[0189] Liquid compositions containing adhesives may be provided as a one-component system or as a two-component system.

[0190] The liquid composition preferably contains an amount of 3 to 90% by weight, more preferably 5 to 80% by weight, and more preferably 10 to 75% by weight, of an adhesive based on the total weight of the composition.

[0191] The liquid composition suitably comprises 0.01 to 15.00% by weight of a mixture of compounds according to the invention, wherein the weight percentage is calculated based on the weight of the liquid composition. Preferably, the liquid composition comprises 0.10 to 10.00% by weight of a mixture of compounds according to formula (I), more preferably 0.12 to 7.50% by weight, such as 0.15 to 5.00% by weight or 0.15 to 3.00% by weight.

[0192] In a further embodiment, the invention also relates to a method for controlling the rheology of a liquid composition, comprising the steps of providing a composition according to the invention, providing a liquid composition, and mixing the composition according to the invention with the liquid composition. Suitable liquid compositions are those mentioned above. The mixing step can be performed according to existing methods known to those skilled in the art. This may involve mixing, particularly by manual or power tools.

[0193] In another embodiment, the present invention relates to a coated article wherein at least a portion of its surface is coated with a liquid composition according to the invention. Furthermore, in a different embodiment, the present invention relates to a coated article wherein at least a portion of its surface is coated with a liquid composition according to the invention and wherein the liquid composition is hardened.

[0194] Suitable articles are all three-dimensional objects, regardless of their size and volume and whether they are movable or stationary. Exemplary but non-limiting examples include building interiors and exteriors, floors, furniture, vehicles for transport (such as automobiles, bicycles, ships, airplanes, agricultural machinery, and all kinds of delivery trucks), bridges and tunnels, machinery and production equipment, electrical equipment, cans, metal coils, wires, containers, household goods and hardware, pulp and paper, and all kinds of articles made of wood, metal, plastic, or glass (e.g., for functional or ornamental purposes). The meaning of the term "coating" is well known to those skilled in the art. Herein, it refers to applying a liquid composition to the surface or other areas of the article to at least partially cover or even completely encapsulate it. In this case, the liquid composition toughens or hardens after being applied to the article. Hardening refers to converting the liquid composition into a solid state. This can be achieved by evaporation of the liquid diluent (physical drying) or by a chemical cross-linking reaction (curing) and by a combination thereof.

[0195] Preparation of Examples

[0196] Preparation of monoisocyanate-carbamate adducts

[0197] All monoadducts according to Table 1 were prepared in two steps, including the following synthesis and removal of excess diisocyanate by thin-film evaporation:

[0198] Use an isocyanate group in 4 molar excess relative to the alcohol group. Heat TDI to 50-60°C and add the alcohol dropwise. As an example, to synthesize MA1, heat 139.3 g (0.8 mol) of TDI to 50-60°C and add 179.52 g (0.4 mol) of polyethylene glycol monomethyl ether with a hydroxyl value of 125 mg KOH / g as the alcohol component. Stir the reaction mixture for 2-6 hours and control the reaction conversion by measuring the isocyanate value.

[0199] Subsequently, excess TDI was distilled using a thin-film evaporator at a temperature of 100°C to 150°C (under a vacuum of <1 mbar). After this step, the resulting monoisocyanate-carbamate adduct contained less than 0.5% by weight of residual diisocyanate.

[0200] Table 1:

[0201]

[0202] Preparation of urea-carbamate

[0203] Load the solvents according to Table 2 and the respective amounts of lithium chloride into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser, and heat to 80°C under a nitrogen atmosphere.

[0204] After 30 minutes, m-phenylenediamine (m-XDA) was added to the mixture. Within 30 minutes of adding m-phenylenediamine, a mixture of monoisocyanate-carbamate adducts or monoisocyanate-carbamate adducts according to Table 1 was added and the mixture was stirred at 80°C for 2 hours.

[0205] Table 2: Preparation of Examples 1-16

[0206]

[0207]

[0208] Table 3 Non-volatile content of Examples 1-16

[0209]

[0210]

[0211] Comparative examples are marked with *.

[0212] Non-volatile matter content is expressed as a percentage by weight of the sample. The values ​​shown are theoretical values, calculated based on the amounts of urea-carbamate and LiCl present in the sample.

[0213] Table 4: Determination of the contents of components A, B, C, D, E, and F by coupled high performance liquid chromatography and mass spectrometry

[0214] Example A B C D E F weight% weight% weight% weight% weight% weight% U1 16.1 27.2 20.1 7.4 10.1 19.1 U2 20.4 24.7 9.6 5.4 33.3 6.6 U3 23.0 14.2 23.0 21.9 10.0 7.9 U4 15.0 26.8 19.3 6.8 10.7 21.4 U5 25.1 14.2 20.7 22.9 9.0 8.1 U6 15.0 31.0 19.3 4.8 13.9 16.0 U7 17.2 25.4 21.3 8.8 9.0 18.3 U8* 0 0 0 0 100 0 U9* 0 0 0 0 0 100 U10* 0 0 0 100 0 0 U11* 45.0 0 0 21.0 34.0 0 U12* 0 43.3 0 0 46.4 10.3 U13* 0 47.5 0 0 27.3 25.2 U14* 0 0 47.3 19.4 0 33.3 U15* 0 32.6 0 29.2 20.2 18.0 U16* 0 0 29.5 13.7 35.8 21.0

[0215] The content of each component was determined by high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The eluent was a mixture of water and 0.9 mM / L sodium chloride and methanol in the following gradient: starting with 30% methanol, reaching 90% methanol within 20 minutes, reaching 100% methanol within 5 minutes, holding for 9 minutes, returning to the initial mixture within 1 minute and holding until the measurement was completed after 40 minutes. The flow rate was 0.5 mL / min. The column used was a Phenomenex Kinetex 2.6u XBridge-C18 100A 50 mm column. The temperature was 50 °C. Detection and quantification were performed at 213 nm using a UV detector.

[0216] Application Trial

[0217] Table 5: Raw Materials

[0218]

[0219] The formulation of the test system: white paint based on Alberdingk AC2025.

[0220] Table 6: Preparation of lacquer formulations

[0221]

[0222] Production method of paint paste:

[0223] The test system of white paint based on the Alberdingk AC 2025 composition was produced using the formulations in Table 6. Components 1 to 4 were mixed with Dispermat:LC-220-6VMA Getzmann at 1 m / s for 5 minutes. Component 5 was ground with a serrated disc VMA Getzmann at room temperature (23°C) at 12 m / s for 20 minutes and added to the mixture of components 1 to 4. The mixture containing components 1 to 5 was then ground at 12 m / s for 20 minutes.

[0224] Production method of let-down:

[0225] Components 6 through 12 in Table 6 were homogenized at room temperature with stirring at 2 m / s for 10 minutes. The resulting mill base was then added to the mixture of components 6 through 12. The completed system (based on white paint from Alberdingk AC 2025) was homogenized for 10 minutes using a sawtooth disc VMA Getzmann at 2 m / s.

[0226] Additives included:

[0227] 50 g of white paint based on Albertingk AC 2025 was placed in a 175 mL plastic cup. 0.30 wt% of a synthetic urea-carbamate (U1-U16*) based on its non-volatile content was added and stirred for 5 minutes at 4 m / s using a Dispermat CV (VMAGetzmann) with a 4 cm diameter sawtooth disc. The mixture was then stored at 23 °C for 24 hours.

[0228] Evaluation of experimental applications

[0229] Anti-sagging properties:

[0230] For this coating, the sample was stirred with a doctor blade to homogenize it, and then applied with a stepped doctor blade from BYK-Chemie GmbH at wet film thicknesses of 75-300 μm. The coating was performed on a contrast card 2851 (BYK-Gardner GmbH) using an automated coater, byko-drive XL (BYK-Gardner GmbH), at a coating speed of 50 mm / s. After coating, the drawdown was hung vertically at room temperature until dry, with the thinnest film streak at the top. Sagging resistance was visually evaluated after drying. The wet film thicknesses exhibiting clear separation of the drawdown after drying, without sagging, and without the formation of bulges / edges between applied film thicknesses were considered.

[0231] Leveling:

[0232] For this coating, the sample was stirred with a spatula to homogenize it, and then applied using a stripes blade from the Leneta Leveling Bar LTB-2. The coating was applied using an automated applicator, the byko-drive XL (BYK-Gardner GmbH), at a speed of 50 mm / s on a contrast card 2811 (BYK-Gardner GmbH). The drawdown was dried directly at room temperature after application. Leveling was visually evaluated after drying. A smooth surface without stripes was rated 1 and showed very good leveling. Very noticeable stripes did not show sufficient leveling and were rated 5.

[0233] Assessment: 1 = Very good leveling, 2 = Good leveling, 3 = Moderate leveling, 4 = Poor leveling, 5 = Insufficient leveling

[0234] Elastic behavior (viscosity):

[0235] The elastic behavior of the white paint based on Albertingk AC 2025 was evaluated after 24 hours. The sample was slowly stirred with a spatula to visually assess the elastic behavior. Special attention was paid to whether the sample exhibited a creamy viscosity or an unacceptable jelly effect. Extremely thin viscosity was also unacceptable.

[0236] Assessment: 0 = Very low viscosity (no rheological effect at all), 1 = Creamy viscosity, 5 = Jelly effect (exhibits obvious elastic behavior)

[0237] Orange peel:

[0238] Twenty-four hours after preparation, the sample was stirred with a spatula to homogenize it, and then applied to a 10cm x 20cm glass panel using a Model 360 96314 spatula from ERICHSEN GmbH and CoKG. The wet film thickness was 150μm. After drying, a visual evaluation of orange peel was performed. The surface should not be uneven, rugged, or have any dents.

[0239] Assessment: 1 = No orange peel, 2 = Minimal orange peel, 3 = Medium orange peel, 4 = Poor orange peel, 5 = Unacceptable surface (lots of orange peel)

[0240] spot:

[0241] Twenty-four hours after preparation, the sample was stirred with a spatula to homogenize it, and then applied to a 10cm x 20cm glass panel with a wet film thickness of 150μm using a Model 360 96314 spatula from ERICHSEN GmbH and CoKG. After drying, the specks were visually evaluated. Values ​​higher than 3 were unacceptable.

[0242] Assessment: 1 = No spots, 2 = Minimal spots, 3 = Moderate spots, 4 = Numerous spots, 5 = Unacceptable surface (the entire surface is composed of spots).

[0243] Table 7: Results of the Application Trial

[0244]

[0245] As is evident from Table 7, the embodiments of the present invention exhibit reduced elastic behavior and fewer specks compared to the non-inventory embodiments (the additive-free embodiments and the embodiments marked with *). Furthermore, the embodiments of the present invention retain other advantageous properties such as high anti-sagging properties, less orange peel, and better leveling.

Claims

1. A composition comprising a mixture of compounds according to formula (I). IC1 and IC2 represent hydrocarbon groups independently of each other and independently in each occurrence. AM independently represents a hydrocarbon group each time it appears. m is the average number of repeating units between 0 and 20. RP1 and RP2 independently represent organic groups selected from RP3, RP4, and RP5 each time they appear. RP3 represents a hydrocarbon group. RP4 represents an organic group according to formula (II). (II) RP41-(AO) n - RP41 represents a hydrocarbon group having 1 to 24 carbon atoms. AO represents a repeating unit of alkyl oxide and n is the average number of repeating units between 6 and 30. RP5 represents an organic group according to formula (III). (III) RP51-(AO) p - RP51 represents a hydrocarbon group having 1 to 24 carbon atoms. AO represents a repeating unit of alkyl oxide and p is the average number of repeating units from 1 to 5. The mixture said mixture comprises a compound of formula (I), wherein (A) RP1 is RP3 and RP2 is RP4. (B) RP1 is RP4 and RP2 is RP5. (C) RP1 is RP3 and RP2 is RP5.

2. The composition according to claim 1, wherein m is the average number of repeating units from 0 to 5.

3. The composition according to claim 1 or 2, wherein RP3 represents a hydrocarbon group having 6 to 24 carbon atoms.

4. The composition according to claim 1 or 2, wherein the n AO repeating units in RP4 comprise 70 to 100 mol% of ethylene oxide repeating units calculated based on the number of AO repeating units in RP4.

5. The composition according to claim 1 or 2, wherein RP51 represents a hydrocarbon group having 1 to 8 carbon atoms.

6. The composition according to claim 1 or 2, wherein the p AO repeating units in RP5 comprise 95 to 100 mol% of ethylene oxide repeating units calculated based on the number of AO repeating units in RP5.

7. The composition according to claim 1 or 2, wherein the mixture of compounds of formula (I) further comprises the following compound, wherein (D) RP1 is RP3 and RP2 is RP3 (E) RP1 is RP4 and RP2 is RP4 (F) RP1 is RP5 and RP2 is RP5.

8. The composition according to claim 1 or 2, comprising At least 12% by weight of compound (A) At least 9% by weight of compound (B) At least 10% by weight of compound (C), Calculated based on the total weight of the compound according to formula (I).

9. The composition according to claim 1 or 2, comprising 12 to 33% by weight of compound (A) 9 to 35% by weight of compound (B) 10 to 30% by weight of compound (C), Calculated based on the total weight of the compound according to formula (I).

10. The composition according to claim 1 or 2, comprising At least 4% by weight of compound (D) At least 6% by weight of compound (E) At least 4% by weight of compound (F), Calculated based on the total weight of the compound according to formula (I).

11. The composition according to claim 1 or 2, comprising 26 to 55 mol% RP3 22 to 35 mol% RP4 22 to 45 mol% RP5, Calculated based on the sum of RP3, RP4, and RP5.

12. The composition according to claim 1 or 2, wherein the composition comprises one or more salts.

13. The composition according to claim 1 or 2, wherein the composition comprises one or more diluents.

14. A liquid composition comprising the composition according to any one of the preceding claims.

15. The liquid composition of claim 14, wherein it comprises a binder.

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

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

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