Composition Based on Congruent Components and Thixotropic Additives

Abstract

The present invention relates to a composition based on a polymerizable component and a thixotropic additive, and a two-component system comprising said composition, and a method for preparing a crosslinked product from said composition. The present invention also relates to the use of an additive for increasing the viscosity of a polymerizable component and / or imparting thixotropic properties to a polymerizable component.

Description

Technical Field

[0001] The present invention relates to a composition based on a polymerizable component and a thixotropic additive, a two-component system comprising said composition, and a method for preparing a crosslinked product from said composition. The present invention also relates to the use of an additive for increasing the viscosity of a polymerizable component and / or imparting thixotropic properties to a polymerizable component. Prior Art

[0002] (Meth)acrylate-functionalized compound-based compositions are widely used in many fields such as coatings, adhesives, and composite materials. By using a rheology additive to increase the viscosity of a (meth)acrylate-functionalized compound-based composition, it becomes possible to facilitate the storage, handling, and use of these compositions. Furthermore, the sedimentation phenomenon of the filler in a (meth)acrylate-functionalized compound-based composition results in non-uniformity in the properties of the resulting material; to suppress this phenomenon, it is desirable to impart anti-sedimentation properties.

[0003] However, special care is required for the use of (meth)acrylate-functionalized compound-based compositions because these compounds, especially (meth)acrylate-functionalized monomers, have a high saturated vapor pressure and evaporate easily. This causes a change in the concentration of the composition and requires the installation of special equipment to capture the released vapor.

[0004] Technologies exist for rheology additives, especially fatty acid diamides and silica, and these are suitable for solving this problem, but require activation by high shear that causes heating and / or self-heating.

[0005] Rheology modifiers based on diurea-diurethane are liquids and do not require a high-temperature activation step, so they are excellent alternatives to these rheology additives. Therefore, they can be easily and directly included in compositions that thicken at ambient temperature (20 - 25°C).

[0006] Patent application EP3381961A1 describes a molding composition prepared from a monomer composition containing a thixotropic additive based on diurea-diurethane. However, the thixotropic additives described in this application contain salts such as lithium chloride or surfactants. Lithium salts may cause corrosion problems when the composition is applied to a metal substrate and may produce uncontrollable species due to their Lewis acidity. Furthermore, lithium salts, especially LiCl, are toxic compounds, and formulations containing them are subject to current regulations regarding the classification, labeling, and packaging of chemicals.

[0007] Therefore, there is a need for a new composition based on a thixotropic agent containing a (meth)acrylate-functionalized compound and a diurea-diurethane compound containing no salts or surfactants. The thixotropic additive is stable, can be easily prepared without a distillation step for residual diisocyanates, and has rheological properties at least equivalent to, or better than, those of equivalent additives in the prior art.

[0008] After numerous research investigations, the applicant has developed a composition that meets this need.

SUMMARY OF THE INVENTION

[0009] The present invention relates to a) a polymerizable component containing a (meth)acrylate-functionalized compound; b) a thixotropic additive containing a diurea-diurethane compound and relates to a composition, wherein component b) contains less than 0.1 mol of salt per urea group in component b).

[0010] The present invention also relates to - a first cartridge containing a radical initiator; - a second cartridge containing the composition according to the invention and optionally an activator for the radical initiator and relates to a two-component system, wherein the first cartridge is held separately from the second cartridge.

[0011] The present invention also relates to - A step of mixing the composition according to the present invention with a radical initiator and optionally an activator of the radical initiator; - A step of applying the obtained mixture onto a substrate relates to a method for preparing a crosslinked product comprising.

[0012] The present invention also relates to the use of an additive comprising a diurea-diurethane compound for increasing the viscosity of a polymerizable component containing a (meth)acrylate functionalized compound and / or imparting thixotropic properties to the polymerizable component, the additive containing less than 0.1 mole of salt per urea group.

Embodiments for Carrying Out the Invention

[0013] [Definitions] In this patent application, the terms "comprising one (a)" and "comprising one (an)" mean "comprising one or more".

[0014] Unless otherwise specified, the weight percentages in a compound or composition are expressed relative to the weight of the compound or composition.

[0015] The term "diurea-diurethane compound" means a compound having two urea functional groups and two urethane functional groups.

[0016] The term "diurethane compound" means a compound having two urethane functional groups and no urea functional groups.

[0017] The term "polyurea-diurethane compound" means a compound having two urethane functional groups and at least four urea functional groups.

[0018] The term "urea functional group" or "urea group" means the -NH-C(=O)-NH- sequence.

[0019] The term "urethane functional group" or "urethane group" means the -NH-C(=O)-O- or -O-C(=O)-NH- sequence.

[0020] The term "solvent" means a liquid that has the property of dissolving, diluting, or reducing the viscosity of other substances without chemically modifying those other substances and without itself being modified.

[0021] "Aprotic solvent" means a solvent that does not have acidic hydrogen atoms. In particular, an aprotic solvent does not contain hydrogen atoms bonded to heteroatoms (O, N, or S).

[0022] The term "salt" means an ionic compound. The salt may be an inorganic salt or an organic salt, but inorganic salts are preferred. In the context of the present invention, the term "salt" does not include ionic surfactants.

[0023] The term "surfactant" means a compound that can change the surface tension between two surfaces. A surfactant can in particular be an amphiphilic compound, i.e., it has two parts of different polarities, where the lipophilic part (which holds fatty substances) is nonpolar and the other hydrophilic (water-miscible) part is polar.

[0024] The term "alkyl" means a saturated monovalent acyclic group of the formula -C n H 2n+1 An alkyl may be linear or branched. C1-C 30 alkyl means an alkyl having from 1 to 30 carbon atoms.

[0025] The term "alkenyl" means a monovalent acyclic hydrocarbon group having one or more C=C double bonds. An alkenyl may be linear or branched. C2-C 30 alkenyl means an alkenyl having from 2 to 30 carbon atoms.

[0026] The term "cycloalkyl" means a monovalent cyclic hydrocarbon group. A cycloalkyl may be saturated or unsaturated. A cycloalkyl is non-aromatic. C5-C 12 cycloalkyl means a cycloalkyl having from 5 to 12 carbon atoms.

[0027] The term "aryl" means a monovalent aromatic hydrocarbon group. C6-C 12 Aryl means aryl having 6 to 12 carbon atoms.

[0028] The term "arylalkyl" means an alkyl group substituted with an aryl group.

[0029] The term "aliphatic" means a non-aromatic acyclic compound or group. It can be linear or branched, saturated or unsaturated, and substituted or unsubstituted. It can contain one or more bonds / functional groups selected from, for example, ethers, esters, amines, and mixtures thereof.

[0030] The term "alicyclic" means a non-aromatic compound or group containing a ring having only carbon atoms as ring atoms. It may be substituted or unsubstituted.

[0031] The term "aromatic" means a compound or group containing an aromatic ring, i.e., a compound or group that follows Hückel's rule of aromaticity, particularly a compound containing a phenyl group. It may be substituted or unsubstituted. It can contain one or more bonds / functional groups defined for the term "aliphatic".

[0032] The term "araliphatic" means a compound or group containing an aliphatic part and an aromatic part.

[0033] The term "heterocyclic" means a compound or group containing a ring having at least one heteroatom selected from N, O, and / or S as ring atoms. It may be substituted or unsubstituted. It may be aromatic or non-aromatic.

[0034] [Component a)-(Meth)acrylate functionalized compound] The composition according to the invention comprises a polymerizable component, also referred to as component a). Component a) can in particular comprise all of the polymerizable compounds of the composition according to the invention. In particular, component a) can in particular comprise all of the ethylenically unsaturated compounds of the composition according to the invention. These compounds can in particular be intended to be polymerized, in particular by a radical polymerization reaction.

[0035] For the purposes of the present invention, the term "ethylenically unsaturated compound" means a compound containing a polymerizable carbon-carbon double bond. The polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. The polymerizable carbon-carbon double bond is generally included in groups selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrene, maleates, fumarates, itaconates, allyl, propenyl, vinyl and corresponding combinations, preferably selected from acrylates, methacrylates and vinyl, more preferably selected from acrylates and methacrylates. The carbon-carbon double bond of the phenyl ring is not considered a polymerizable carbon-carbon double bond.

[0036] Component a) comprises (meth)acrylate-functionalized compounds. Component a) can comprise a mixture of (meth)acrylate-functionalized compounds.

[0037] As used herein, the term "(meth)acrylate-functionalized compound" means a compound containing at least one (meth)acryloyloxy group, in particular an acryloyloxy group. The term "(meth)acryloyloxy group" encompasses the acryloyloxy (-O-CO-CH=CH2) group and the methacryloyloxy (-O-CO-C(CH3)=CH2) group.

[0038] The total amount of the (meth)acrylate-functionalized compound in component a) can be 20% to 100% by weight, particularly 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% to 100%, 80% to 100%, 90% to 100% based on the weight of component a). According to one embodiment, component a) does not contain a polymerizable compound other than the (meth)acrylate-functionalized compound.

[0039] Component a) can particularly contain a (meth)acrylate-functionalized compound selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof. In particular, component a) can contain a (meth)acrylate-functionalized monomer and optionally a (meth)acrylate-functionalized oligomer.

[0040] Component a) can particularly contain a (meth)acrylate-functionalized monomer. Component a) can contain a mixture of (meth)acrylate-functionalized monomers.

[0041] The (meth)acrylate-functionalized monomer can have a molecular weight of less than 600 g / mol, particularly less than 70 to 550 g / mol, more particularly 80 to 450 g / mol, more particularly 90 to 350 g / mol.

[0042] The (meth)acrylate-functionalized monomer can have 1 to 6 (meth)acryloyloxy groups, particularly 1 to 4 (meth)acryloyloxy groups.

[0043] (Meth)acrylate-functionalized monomers can include a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, the (meth)acrylate-functionalized monomer can include a (meth)acrylate-functionalized monomer containing a single acryloyloxy or methacryloyloxy group per molecule (hereinafter referred to as "mono(meth)acrylate-functionalized monomer") and a (meth)acrylate-functionalized monomer containing two or more, preferably two to six acryloyloxy groups and / or methacryloyloxy groups per molecule (hereinafter referred to as "poly(meth)acrylate-functionalized monomer").

[0044] Component a) can particularly include mono(meth)acrylate-functionalized monomers. Component a) can particularly include a mixture of mono(meth)acrylate-functionalized monomers. The mono(meth)acrylate-functionalized monomer can advantageously function as a reactive diluent and can reduce the viscosity of the composition according to the present invention.

[0045] Examples of suitable mono(meth)acrylate-functionalized monomers include, but are not limited to, (meth)acrylic acid; mono(meth)acrylic acid esters of aliphatic alcohols (wherein the alcohol may be linear or branched, and may be a monoalcohol, dialcohol or polyalcohol, provided that only one hydroxyl group is esterified with (meth)acrylic acid); mono(meth)acrylic acid esters of cycloaliphatic alcohols or heterocyclic alcohols; mono(meth)acrylic acid esters of aromatic alcohols (e.g., phenols including alkylated phenols); mono(meth)acrylic acid esters of alkylaryl alcohols (e.g., benzyl alcohol); mono(meth)acrylic acid esters of oligomeric glycols and polymeric glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylic acid esters of monoalkyl ethers of glycols and oligoglycols; caprolactone mono(meth)acrylate; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and mixtures thereof.

[0046] Component a) includes, in particular, (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; isodecyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-ethoxypropyl (meth)acrylate; 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; benzyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; phenol (meth)acrylate; nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexyl (meth)acrylate; trimethylcyclohexyl (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; polyethylene glycol monomethyl ether (meth)acrylate; hydroxyethyl-butylurethane (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate;(2-Ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl)methyl (meth)acrylate; glycerol carbonate (meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof, may contain a mono(meth)acrylate functionalized monomer selected therefrom.;

[0047] In particular, component a) may especially contain (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; n-dodecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; cyclohexyl (meth)acrylate; trimethylcyclohexyl (meth)acrylate; glycidyl (meth)acrylate; benzyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate; (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl)methyl (meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and mixtures thereof, a mono(meth)acrylate functionalized monomer selected therefrom.;

[0048] More specifically, component a) may especially contain methyl methacrylate, optionally as a mixture with at least one other (meth)acrylate functionalized compound.;

[0049] Component a) may in particular contain poly(meth)acrylate-functionalized monomers.

[0050] Examples of poly(meth)acrylate-functionalized monomers include acrylate esters and methacrylate esters of polyols (organic compounds containing two or more hydroxyl groups such as 2 to 6 per molecule). Specific examples of suitable polyols are ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornenedimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, hydrogenated bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(ethylene glycol-co-propylene glycol), alditols (i.e., erythritol, threitol, arabinitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol or iditol), dianhydrohexitols (i.e., isosorbide, isomannide or isoidide), tris(2-hydroxyethyl) isocyanurate, polybutadiene polyol, and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives, and derivatives obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) initiated with one of the above polyols.Such a polyol may be completely or partially esterified (by (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.) as long as it contains at least two (meth)acryloyloxy functional groups per molecule.

[0051] In particular, component a) is bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-decanediol di(meth)acrylate; 1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; di(trimethylolpropane) di(meth)acrylate; di(trimethylolpropane) tri(meth)acrylate; di(trimethylolpropane) tetra(meth)acrylate; sorbitol penta(meth)acrylate; di(pentaerythritol) tetra(meth)acrylate;Di(pentaerythritol) penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; and their alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives; and poly(meth)acrylate-functionalized monomers selected from mixtures thereof may be particularly included.;

[0052] More specifically, component a) may particularly include poly(meth)acrylate-functionalized monomers selected from 1,6-hexanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; and mixtures thereof.;

[0053] Component a) may include (meth)acrylate-functionalized monomers in an amount of 0% to 100%, particularly 5% to 100%, 10% to 100%, 15% to 100%, 20% to 95%, 25% to 95%, 30% to 95%, 35% to 90%, 40% to 90%, or 50% to 90% by weight based on the weight of component a). Component a) may include (meth)acrylate-functionalized monomers in an amount of 0% to 60%, 5% to 60%, 10% to 60%, 15% to 60%, 20% to 60%, 25% to 60%, 30% to 60%, 35% to 60%, 40% to 60%, or 45% to 60% by weight based on the weight of component a). As a variant, component a) may include (meth)acrylate-functionalized monomers in an amount of 60% to 100%, 65% to 100%, 70% to 100%, 75% to 100%, 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100% by weight based on the weight of component a).;

[0054] Component a) may particularly include (meth)acrylate-functionalized oligomers. Component a) may include a mixture of (meth)acrylate-functionalized oligomers.;

[0055] (Meth)acrylate-functionalized oligomers can be selected to enhance in particular the flexibility, strength, and / or modulus of elasticity among some properties of the products obtained by the polymerization of the compositions according to the present invention.

[0056] (Meth)acrylate-functionalized oligomers can have from 1 to 18 (meth)acryloyloxy groups, in particular from 2 to 6 (meth)acryloyloxy groups, more specifically from 2 to 6 acryloyloxy groups.

[0057] (Meth)acrylate-functionalized monomers can have a number average molecular weight of 600 g / mol or more, in particular from 800 to 15000 g / mol, more specifically from 1000 to 5000 g / mol.

[0058] In particular, component a) can particularly include (meth)acrylate-functionalized oligomers selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized polycarbonate oligomers, (meth)acrylate-functionalized polyester oligomers; (meth)acrylate-functionalized acrylic oligomers; and mixtures thereof.

[0059] (Meth)acrylate-functionalized urethane oligomers (often also referred to as "polyurethane (meth)acrylate oligomers") suitable for use in the polymerizable compositions of the present invention include urethanes based on at least one polyol, at least one polyisocyanate, and at least one hydroxyl-functionalized and (meth)acrylate-functionalized compound (also known as a hydroxyl-functionalized (meth)acrylate).

[0060] (Meth)acrylate-functionalized urethane oligomers can be prepared by reacting a polyisocyanate (e.g., a diisocyanate or triisocyanate that is aliphatic, alicyclic, heterocyclic, or aromatic) with a polyol (in particular, a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol, or a polydiene polyol such as a polybutadiene polyol, all corresponding combinations) to form an isocyanate-terminated oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate (e.g., hydroxyethyl (meth)acrylate) to obtain terminal (meth)acrylate groups. For example, (meth)acrylate-functionalized urethane oligomers may contain two, three, four or more (meth)acrylate functional groups per molecule. Other addition sequences can also be used to prepare (meth)acrylate-functionalized urethane oligomers. For example, a hydroxyl-functionalized (meth)acrylate can first be reacted with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which can then be reacted with a polyol. As a variant, all components can also be combined and reacted simultaneously.

[0061] Examples of suitable (meth)acrylate-functionalized epoxy oligomers include reaction products of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters or anhydrides) with an epoxy resin containing at least one epoxide group, in particular at least one group selected from glycidyl ethers, glycidyl esters and combinations thereof.Epoxy resins can be selected from, in particular, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3’,4’-epoxy-6’-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butylphenol or polyether alcohol obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutyl stearate, epoxyoctyl stearate, epoxidized linseed oil, epoxidized polybutadiene, etc.

[0062] Suitable (meth)acrylate-functionalized polyether oligomers include, but are not limited to, the reaction products of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters or anhydrides) and at least one polyetherol corresponding to a polyether polyol (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers thereof). Suitable polyetherols can be linear or branched substances containing ether bonds and terminal hydroxyl groups. The polyetherol can be prepared by ring-opening polymerization of a cyclic ether such as tetrahydrofuran or an alkylene oxide (such as ethylene oxide and / or propylene oxide) with a starting molecule. Suitable starting molecules include water, polyhydroxyl-functionalized materials, polyester polyols and amines.

[0063] Examples of (meth)acrylate-functionalized polydiene oligomers include the reaction products of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters or anhydrides) and hydroxyl-terminated polydiene polyols, particularly hydroxyl-terminated polybutadiene polyols.

[0064] Examples of (meth)acrylate-functionalized polycarbonate oligomers include the reaction products of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters or anhydrides) and hydroxyl-terminated polycarbonate polyols.

[0065] Examples of (meth)acrylate-functionalized polyene oligomers include reaction products of (meth)acrylic acid (or corresponding synthetic equivalents such as acid chlorides, alkyl esters or anhydrides) and hydroxyl-terminated polyester polyols. In particular, when the polyester polyol is difunctional, the reaction process can be carried out such that all or essentially all of the hydroxyl groups of the polyester polyol are (meth)acrylated. The polyester polyol can be prepared by polycondensation reaction of a polyhydroxyl-functionalized component (especially a diol) and a poly(carboxylic acid)-functionalized compound (especially a dicarboxylic acid and an anhydride). The polyhydroxyl-functionalized component and the poly(carboxylic acid)-functionalized component each have a linear, branched, alicyclic or aromatic structure and can be used individually or as a mixture.

[0066] Suitable (meth)acrylate-functionalized acrylic oligomers (often also known in the prior art as "acrylic oligomers") include oligomers that can be described as substances having an acrylic backbone functionalized with one or more (meth)acrylate groups (either at the ends of the oligomer or pendant from the acrylic backbone). The acrylic backbone can be a homopolymer, random copolymer or block copolymer consisting of repeating units of acrylic-type monomers. The acrylic-type monomers can be any monomer (meth)acrylate such as C1-C6 alkyl (meth)acrylate, as well as functionalized (meth)acrylates having hydroxyl, carboxylic acid and / or epoxy groups. The acrylic (meth)acrylate oligomers can be prepared using any procedure known in the prior art, such as oligomerizing monomers (e.g., hydroxyalkyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate) that are at least partially functionalized with hydroxyl, carboxylic acid and / or epoxy groups to obtain a functionalized oligomeric intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0067] In particular, component a) may especially comprise (meth)acrylate-functionalized oligomers selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized acrylic oligomers; and mixtures thereof.

[0068] Component a) may comprise, based on the weight of component a), 0% to 100%, in particular 5% to 100%, 10% to 100%, 15% to 100%, 20% to 95%, 25% to 95%, 30% to 95%, 35% to 90%, 40% to 90%, or 50% to 90% by weight of (meth)acrylate-functionalized oligomers. Component a) may comprise, based on component a), 0% to 60%, 5% to 60%, 10% to 60%, 15% to 60%, 20% to 60%, 25% to 60%, 30% to 60%, 35% to 60%, 40% to 60%, or 45% to 60% by weight of (meth)acrylate-functionalized oligomers. As a variant, component a) may comprise, based on the weight of component a), 60% to 100%, 65% to 100%, 70% to 100%, 75% to 100%, 80% to 100%, 85% to 100%, 90% to 100%, or 95% to 100% by weight of (meth)acrylate-functionalized oligomers.

[0069] According to a particular embodiment, component a) - 10% to 100%, 20% to 100%, 30% to 100%, 40% to 95%, or 50% to 90% by weight of (meth)acrylate-functionalized monomers; and - 0% to 90%, 0% to 80%, 0% to 70%, 5% to 60%, or 10% to 50% by weight of (meth)acrylate-functionalized oligomers comprises.

[0070] [Component b) - Thixotropic additive] The composition according to the present invention contains a thixotropy additive, also referred to as component b). The thixotropy additive is used, in particular, to increase the viscosity of the composition according to the present invention and / or to impart thixotropic properties to the composition. For the purposes of the present invention, the term "impart thixotropic properties to the composition" means increasing the viscosity of the composition when it is at rest (when no shear stress is applied) and decreasing the viscosity of the composition when the composition is subjected to shear stress in a reversible or time-dependent manner with memory of the history. The increase and decrease in viscosity can be determined in comparison with a control composition that does not contain the thixotropy additive.

[0071] Component b) contains a diurea-diurethane compound. Component b) may contain a mixture of polyurea-diurethane compounds. Component b) may further contain an aprotic solvent.

[0072] Component b) contains little or no salt but is stable. Component b) contains less than 0.1 mole of salt per urea group in component b) (excluding the aprotic solvent). The number of urea groups is determined for all the compounds contained in component b) (excluding the aprotic solvent). The diurea-diurethane compound contains two urea groups. If component b) contains 1 mole of the diurea-diurethane compound and there are no other compounds in component b) having at least one urea group, component b) contains less than 0.2 mole of salt.

[0073] In particular, component b) may contain from 0 to less than 0.1 mole, or from 0 to 0.09 mole, or from 0 to 0.07 mole, or from 0 to 0.05 mole, or from 0 to 0.03 mole, or from 0 to 0.01 mole, or from 0 to 0.001 mole of salt per urea group in component b) (excluding the aprotic solvent).

[0074] More specifically, component b) may contain LiCl in an amount of less than 1% by weight, or from 0% to 0.9%, or from 0% to 0.7%, or from 0% to 0.5%, or from 0% to 0.25%, or from 0% to 0.2%, or from 0% to 0.15%, or from 0% to 0.09%, or from 0% to 0.03%, based on the weight of component b) (excluding aprotic solvents).

[0075] More specifically, component b) may contain LiNO3 in an amount of less than 1.6% by weight, or from 0% to 1.4%, or from 0% to 1.1%, or from 0% to 0.8%, or from 0% to 0.4%, or from 0% to 0.3%, or from 0% to 0.25%, or from 0% to 0.15%, or from 0% to 0.05%, based on the weight of component b) (excluding aprotic solvents).

[0076] The salt can be particularly selected from metal salts, ionic liquids and ammonium salts. In particular, the salt can be a metal salt selected from halides, acetates, formates, or nitrates. More specifically, the salt can be a lithium salt. Even more specifically, the salt can be a lithium salt selected from LiCl, LiNO3, LiBr and mixtures thereof.

[0077] Component b) can be particularly stable without adding a stabilizer such as a surfactant. According to a specific embodiment, component b) according to the present invention contains less than 0.1 mole of surfactant per urea group in component b).

[0078] In particular, component b) may contain from 0 to 0.1 mole, or from 0 to 0.08 mole, or from 0 to 0.06 mole, or from 0 to 0.04 mole, or from 0 to 0.02 mole, or from 0 to 0.01 mole, or from 0 to 0.001 mole of surfactant per urea group in component b) (excluding aprotic solvents).

[0079] More specifically, component b) may contain, by weight, less than 3%, or from 0% to 2.8%, or from 0% to 2.4%, or from 0% to 2%, or from 0% to 1.6%, or from 0% to 1.2%, or from 0% to 1%, or from 0% to 0.5%, or from 0% to 0.1%, or from 0% to 0.01% of a surfactant, based on the weight of component b) (excluding aprotic solvents).

[0080] The surfactant may in particular be selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof. The surfactant may in particular have an HLB of from 8 to 12.

[0081] Examples of anionic surfactants are sulfonates, sulfates, sulfosuccinates, phosphates and carboxylates. Examples of cationic surfactants are quaternary ammonium salts (in particular tetraalkylammonium salts and quaternary ammonium esters or esterquats). Examples of nonionic surfactants are alkoxylated (in particular ethoxylated and / or propoxylated) fatty alcohols, alkyl glycosides, fatty acid esters (in particular glycol esters, glycerol esters, sorbitan esters or sucrose esters of fatty acids) and alkoxylated (in particular ethoxylated and / or propoxylated) fatty acid esters. Examples of zwitterionic surfactants are betaines, imidazolines, sultaines, phospholipids and amine oxides.

[0082] Component b) may have an NCO value of less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more specifically less than 0.1 mg KOH / g, and even more specifically 0 mg KOH / g. The NCO value can be measured according to the method described below.

[0083] [Diurea-diurethane compound] Component b) contains a diurea-diurethane compound. Component b) may contain a mixture of diurea-diurethane compounds.

[0084] The diurea-diurethane compound has the formula (I): TIFF2025521194000001.tif20170 (In the above formula, the R', R2, and R3 groups are as described below) may correspond to the compound of

[0085] Preferably, the compound of formula (I) does not contain a tertiary amine functional group or a quaternary ammonium functional group.

[0086] The compound of formula (I) may in particular correspond to the reaction product of at least one alcohol of formula R'-OH, at least one diisocyanate of formula OCN-R2-NCO and at least one diamine of formula H2N-R3-NH2.

[0087] Component b) may contain, in particular, from 5 to 80 mol%, in particular from 15 to 75 mol%, more particularly from 25 to 65 mol% of the compound of formula (I) relative to the total molar amount of the compound(s) having one or more functional groups selected from urea, urethane and mixtures thereof (excluding aprotic solvents).

[0088] [R' group] The compound of formula (I) contains two R' groups. The R' groups of one and the same compound of formula (I) may be the same or different. Component b) may contain a mixture of compounds of formula (I) having the same R' group. Component b) may contain a mixture of compounds of formula (I) having different R' groups. For example, some compounds of the mixture may have the same R' group and some compounds of the mixture may have different R' groups.

[0089] Each R' group may result from the use of an alcohol of formula R'-OH for the formation of the diurea-durethane compound of formula (I). The R' group may correspond to the residue of an alcohol of formula R'-OH without an OH group. The alcohol of formula R'-OH corresponding to the R' group described below is also applicable to the method for the preparation of the diurea-durethane compound described below.

[0090] Each R' is alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, ·-[(CRa R b ) n -O] m -Y and ·-[(CR c R d ) p -C(=O)O] q is independently selected from; The symbol · represents the point of attachment to the urethane group of formula (I); Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl; R a , R b , R c and R d are independently selected from H and methyl, especially H; Each n is independently equal to 2, 3 or 4, especially n is 2; m ranges from 1 to 30, especially m ranges from 2 to 25; p ranges from 3 to 5, especially p is 5; q ranges from 1 to 20, especially q ranges from 2 to 10.

[0091] The R' group can be alkyl, especially C1 to C 30 alkyl. Examples of suitable alkyl groups are methyl, propyl, 1-methylethyl, butyl, X 1-2 -methylpropyl, pentyl, X 1-3 -methylbutyl, hexyl, X 1-4 -methylpentyl, heptyl, X 1-5 -methylhexyl, octyl, X 1-6 -methylheptyl, 2-ethylhexyl, nonyl, X 1-7 -methyloctyl, decyl, X 1-8 -methylnonyl, undecyl, X 1-9 -methyldecyl, dodecyl, X 1-10 -methylundecyl, tridecyl, X 1-11 -methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, X 1-12 -methyltridecyl, pentadecyl, X 1-13 -methyltetradecyl, hexadecyl, X 1-14-Methylpentadecyl, heptadecyl, X 1-15 -Methylhexadecyl, octadecyl, X 1-16 -Methylheptadecyl, nonadecyl, X 1-17 -Methyloctadecyl, icosyl, X 1-18 -Methylnonadecyl, henicosyl, X 1-19 -Methylicosyl, docosyl, X 1-20 -Methylhenicosyl, 2-propylheptyl, 2-propylnonyl, 2-pentylnonyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 6-methyldodecyl and their isomers, where X a-b represents an integer that can take any value in the range from a to b, and X a-b indicates the position of the substituent in the alkyl group. X 1-11 -Methyldodecyl group is a dodecyl group substituted at the 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 position with a methyl group, for example 11-methyldodecyl or 2-methyldodecyl. The term "isomer" is understood to mean an alkyl group containing the same number of carbon atoms but having a different substitution scheme, for example an alkyl group having an ethyl substituent instead of a methyl substituent or more methyl substituents. Thus, 2,5,9-trimethyldecyl group is an isomer of 11-methyldodecyl group or 2-methyldodecyl group. The above alkyl groups can be bonded to the urethane group especially at the 1 position. Thus, 2,5,9-trimethyldecyl group can be represented by the following formula: TIFF2025521194000002.tif26170 (In the above formula, the wavy line represents the bonding point to the urethane group of the compound of formula (I))

[0092] The R' group is alkenyl, especially C2 to C 30 Alkenyl can be. Examples of suitable alkenyl groups are hexa-Y 2-5 -enyl, hepta-Y 2-6 -enyl, octa-Y 2-7 -enyl, nona-Y 2-8 -enyl, deca-Y 2-9 -enyl, undeca-Y2-10 -enyl, dodeca-Y 2-11 -enyl, trideca-Y 2-12 -enyl, tetradeca-Y 2-13 -enyl, hexadeca-Y 2-15 -enyl, octadeca-Y 2-17 -enyl, icos-Y 2-19 -enyl, docos-Y 2-21 -enyl, heptadeca-8,11-dienyl, octadeca-9,12-dienyl, nonadeca-10,13-dienyl, icos-11,14-dienyl, docosa-13,16-dienyl, octadeca-5,9,12-trienyl, octadeca-6,9,12-trienyl, octadeca-9,12,15-trienyl, octadeca-9,11,13-trienyl, icos-8,11,14-trienyl and icos-11,14,17-trienyl, wherein Y a-b represents an integer that can take any value in the range from a to b, and Y a-b indicates the position of the double bond of the alkenyl group. Hexa-Y 2-5 -enyl group is a hexenyl group in which the double bond can be at the 2, 3, 4 or 5 position, which corresponds to hex-2-enyl, hex-3-enyl, hex-4-enyl and hex-5-enyl groups. The above alkenyl groups can be bonded to the urethane group, especially at the 1 position. Thus, the hex-2-enyl group can be represented by the following formula: TIFF2025521194000003.tif14170 (In the above formula, the wavy line represents the bonding point to the urethane group of the compound of formula (I))

[0093] The R' group is cycloalkyl, especially C5 to C 12 It can be cycloalkyl. Examples of suitable cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.

[0094] The R' group is aryl, especially C6 to C 12It may be aryl. Examples of suitable aryl groups are phenyl, naphthyl, biphenyl, ortho-, meta- or para-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-xylenyl and mesityl.

[0095] The R' group is arylalkyl, especially C7 to C 12 It may be arylalkyl. Examples of suitable arylalkyl groups are benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and 2-phenylbutyl.

[0096] The R' group is ·-[(CR a R b ) n -O] m -Y group, where Y is selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl; R a and R b are independently selected from H and methyl, especially H; each n is independently equal to 2, 3 or 4, especially n is 2; m ranges from 1 to 30, especially m ranges from 2 to 25.

[0097] ·-[(CR a R b ) n -O] m Examples of -Y groups are alkoxylated derivatives of the above alkyl, alkenyl, cycloalkyl, aryl and alkylaryl groups. Polyethylene glycol, polypropylene glycol, copoly(ethylene glycol / propylene glycol) and polytetramethylene glycol containing end groups selected from the above alkyl, alkenyl, cycloalkyl, aryl and arylalkyl groups are particularly suitable. These groups can be obtained in particular by reacting an alcohol R'OH having the above R' group with a cyclic compound selected from ethylene oxide, propylene oxide, tetrahydrofuran and mixtures thereof.

[0098] The R' group is ·-[(CR c R d ) p -C(=O)O] q and can be a -Z group, where Z is selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl; R c and R d are independently selected from H and methyl, especially H; p ranges from 3 to 5, especially p is 5; q ranges from 1 to 20, especially q ranges from 2 to 10.

[0099] ·-[(CR c R d ) p -C(=O)O] q Examples of the -Z group are esterified derivatives of the above alkyl, alkenyl, cycloalkyl, aryl and arylalkyl groups. Polyester containing a terminal group selected from the above alkyl, alkenyl, cycloalkyl, aryl and arylalkyl groups is particularly suitable. These groups can be obtained in particular by reacting an alcohol R'OH having the above R' group with a lactone selected from γ-butyrolactone, δ-valerolactone, ε-caprolactone and mixtures thereof.

[0100] According to one embodiment, each R' is independently selected from alkyl and ·-[(CR a R b ) n -O] m -Y groups. In particular, each R' is independently selected from linear or branched C1-C 30 alkyl and ·-[CH2-CH2-O] m -Y, where Y is C1-C 24 alkyl and m ranges from 1 to 25. More specifically, each R' is independently selected from branched C8-C 20 alkyl and ·-[CH2-CH2-O] m -Y, where Y is C1-C6 alkyl and m ranges from 2 to 20.

[0101] More specifically, each R' is octyl, X 1-6 -methylheptyl, 2-ethylhexyl, nonyl, X 1-7 -methyloctyl, decyl, X 1-8 -methylnonyl, undecyl, X 1-9 -methyldecyl, dodecyl, X 1-10 -methylundecyl, tridecyl, X 1-11 -methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, X 1-12 -methyltridecyl, pentadecyl, X 1-13 -methyltetradecyl, hexadecyl, X 1-14 -methylpentadecyl, heptadecyl, X 1-15 -methylhexadecyl, octadecyl, X 1-16 -methylheptadecyl, nonadecyl, X 1-17 -methyloctadecyl, icosyl, X 1-18 -methylnonadecyl, henicosyl, X 1-19 -methylicosyl, docosyl, X 1-20 -methylhenicosyl, 2-propylheptyl, 2-propylnonyl, 2-pentylnonyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 6-methyldodecyl and their isomers, ·-[CH2-CH2-O]3-(CH2)3-CH3 and ·-[CH2-CH2-O] m -CH3 (where m = 2 to 20) and is independently selected from.

[0102] The compounds of formula (I) may have the same or different R' groups. The compounds of formula (I) may have R' groups with different molecular weights. The compounds of formula (I) may have R' groups with different chemical properties, especially hydrophilicity.

[0103] Component b) may include compounds of formula (I) in which the R' groups are the same. Component b) may include compounds of formula (I) in which the R' groups are different. Component b) may include compounds of formula (I) in which the R' groups are the same and compounds of formula (I) in which the R' groups are different.

[0104] Component b) may in particular include compounds of formula (I) in which the R' groups are the same. The R' groups are the same and may correspond to R1, and R1, as described above, is a linear or branched C1-C 30 alkyl, in particular a linear or branched C8-C 20 alkyl, more particularly a branched C8-C 20 alkyl.

[0105] Component b) may in particular include a mixture of compounds of formula (I), which mixture includes at least one compound of formula (I) in which the R' groups are different. The mixture may include at least one compound of formula (I) having different molecular weights where the R' groups are different. The mixture may include at least one compound of formula (I) having different chemical properties, in particular hydrophilicity, where the R' groups are different.

[0106] A thixotropic additive including compounds of formula (I) in which the R' groups are different can be obtained in particular by forming the compounds of formula (I) using a mixture of at least two different alcohols R'-OH (in particular corresponding to R4-OH and R5-OH).

[0107] In particular, the mixture of compounds of formula (I) may - at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4 and the other R' group corresponding to R5; - optionally, a compound of formula (I) in which the R' groups are the same and correspond to R4; - optionally, a compound of formula (I) in which the R' groups are the same and correspond to R5 and R4 and R5 are as defined above for R'.

[0108] The mixture of the compounds of formula (I) can in particular comprise the compound of formula (Ia), optionally as a mixture with the compound of formula (Ib) and / or the compound of formula (Ic): TIFF2025521194000004.tif63170(wherein all R4 groups are identical and as defined above for R'; all R5 groups are identical and as defined above for R'; the R4 groups are different from R5)

[0109] The R4 groups can be more hydrophobic than the R5 groups; and / or the R5 groups can have a higher molecular weight than the R4 groups.

[0110] The molecular weights of the R4 groups and the R5 groups may be different. In particular, the R4 groups can have a lower molecular weight than the R5 groups. More specifically, the difference in molecular weight between the R4 groups and the R5 groups can be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0111] The chemical properties of the R4 groups and the R5 groups may be different. In particular, the R4 groups can be more hydrophobic than the R5 groups.

[0112] The R4 groups and the R5 groups are groups of the formula -[(CR a R b ) n -O] m -Y where Y, R a R b n and m are as defined above. Alternatively, the R4 groups are linear or branched C1-C 30 alkyl and the R5 groups are groups of the formula -[(CR a R b ) n -O] m -Y where Y, R a R b n and m are as defined above.

[0113] The total molar amount of the R5 group, especially the least hydrophobic group and / or the largest molecular weight group, can account for more than 20%, especially 25% to 95%, 30% to 90%, 35% to 85%, or 40% to 80% of the total molar amount of the R4 and R5 groups of all products having one or more functional groups selected from urea, urethane, and mixtures thereof in component b) (excluding aprotic solvents).

[0114] Component b) can especially contain a mixture of compounds of formula (I), and the mixture contains at least two different compounds of formula (I) with different R' groups. The mixture can contain at least two different compounds of formula (I) with different molecular weights of the R' groups. The mixture can contain at least two different compounds of formula (I) with different chemical properties, especially hydrophilicity, of the R' groups.

[0115] A thixotropic additive containing at least two compounds of formula (I) with different R' groups can be obtained, especially by using a mixture of at least three different alcohols R'-OH corresponding to R4-OH, R5-OH, and R6-OH to form a diurea-diurethane compound of formula (I).

[0116] The mixture of compounds of formula (I) is - at least one compound of formula (I) with different R' groups, one of the R' groups corresponding to R4 and the other R' group corresponding to R5; and - at least one compound of formula (I) with different R' groups, one of the R' groups corresponding to R4 and the other R' group corresponding to R6; - optionally, a compound of formula (I) with different R' groups, one of the R' groups corresponding to R5 and the other R' group corresponding to R6; - optionally, a compound of formula (I) with the same R' group corresponding to R4; - optionally, a compound of formula (I) with the same R' group corresponding to R5; - optionally, a compound of formula (I) with the same R' group corresponding to R6 can be included, and R4, R5, and R6 are as defined above for R'.

[0117] The mixture of compounds of formula (I) can in particular comprise a compound of formula (Ia), a compound of formula (Id), and optionally one or more compounds of formula (Ib), (Ic), (Ie) or (If), as represented below: TIFF2025521194000005.tif63170TIFF2025521194000006.tif61170(In the above formula, all R4 groups are identical and are as defined above for R'; all R5 groups are identical and are as defined above for R'; all R6 groups are identical and are as defined above for R'; the R4 group is different from R5; the R4 group is different from R6; the R5 group is different from R6)

[0118] The R4 group can be more hydrophobic than the R5 group and / or the R6 group; and / or the R4 group can have a lower molecular weight than the R5 group and / or the R6 group.

[0119] The molecular weights of the R4 group, the R5 group, and the R6 group may be different. In particular, the R4 group can have a lower molecular weight than the R5 group; and / or the R4 group can have a lower molecular weight than the R6 group; and / or the R5 group can have a lower molecular weight than the R6 group. More specifically, the R4 group has a lower molecular weight than the R5 group and the R6 group. Even more specifically, the difference between the molecular weight of the R4 group and the molecular weight of the R5 group; and / or the difference between the molecular weight of the R4 group and the molecular weight of the R6 group; and / or the difference between the molecular weight of the R5 group and the molecular weight of the R6 group can be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0120] The R4 group, the R5 group, and the R6 group can have different chemical properties. In particular, the R4 group can be more hydrophobic than the R5 group; and / or the R4 group can be more hydrophobic than the R6 group, and / or the R5 group can be more hydrophobic than the R6 group. More specifically, the R4 group is more hydrophobic than the R5 group and the R6 group.

[0121] The R4 group can be a linear or branched C1-C 30 alkyl, and the R5 group and the R6 group can be groups of the formula -[(CR a R b ) n -O] m -Y where Y, R a , R b , n and m are as described above.

[0122] The total molar amount of the R5 group and the R6 group, in particular the total molar amount of the least hydrophobic group and / or the group with the highest molecular weight, can in particular account for more than 20%, in particular from 25% to 95%, from 30% to 90%, from 35% to 85%, or from 40% to 80% of the total molar amount of the R4, R5 and R6 groups of all products having one or more functional groups selected from urea, urethane and their mixtures in component b) (excluding aprotic solvents).

[0123] According to a preferred embodiment, more than 20 mol%, in particular from 25 to 95 mol%, from 30 to 90 mol%, from 35 to 85 mol%, or from 40 to 80 mol% of all the R' groups contained in the compound of formula (I) are hydrophilic groups, in particular -[(CR a R b ) n -O] m -Y groups.

[0124] The R' group can in particular be the residue of one or more alcohols of the formula R'-OH without an OH group. The alcohol R'-OH is in particular an alkane substituted with an OH group from C1 to C 30 alkane, an alkene substituted with an OH group from C2 to C 30 alkene, a cycloalkane substituted with an OH group from C5 to C 12 cycloalkane, a cycloalkane substituted with an OH group from C6 to C 12An arene, C7 to C substituted with an OH group 12 An arylalkane, HO-[(CR a R b ) n -O] m -Y and HO-[(CR c R d ) p -C(=O)O] q -Z can be selected from.

[0125] Y and Z are independently selected from C1 to C 30 alkyl, C2 to C 30 alkenyl, C5 to C 12 cycloalkyl, C6 to C 12 aryl, and C7 to C 12 arylalkyl; R a R b R c and R d are independently selected from H and methyl, especially H; Each n is independently equal to 2, 3 or 4, especially n is 2; m ranges from 1 to 30, especially m ranges from 2 to 25; p ranges from 3 to 5, especially p is 5; q ranges from 1 to 20, especially q ranges from 2 to 10.

[0126] An alkane substituted with an OH group from C1 to C 30 is especially octan-1-ol, octan-2-ol, X 1-6 -methylheptan-1-ol, 2-ethylhexan-1-ol, nonan-1-ol, X 1-7 -methyloctan-1-ol, decan-1-ol, X 1-8 -methylnonan-1-ol, undecan-1-ol, X 1-9 -methyldecan-1-ol, dodecan-1-ol, X 1-10 -methylundecan-1-ol, tridecan-1-ol, X 1-11-Methyldodecan-1-ol, 2,5,9-trimethyldecan-1-ol, tetradecan-1-ol, X 1-12 -Methyltridecan-1-ol, pentadecan-1-ol, X 1-13 -Methyltetradecan-1-ol, hexadecan-1-ol, X 1-14 -Methylpentadecan-1-ol, heptadecan-1-ol, X 1-15 -Methylhexadecan-1-ol, octadecan-1-ol, X 1-16 -Methylheptadecan-1-ol, nonadecan-1-ol, X 1-17 -Methyloctadecan-1-ol, icosan-1-ol, X 1-18 -Methylnonadecan-1-ol, henicosan-1-ol, X 1-19 -Methylicosan-1-ol, docosan-1-ol, X 1-20 -Methylhenicosan-1-ol, 2-propylheptan-1-ol, 2-propylnonan-1-ol, 2-pentylnonan-1-ol, 2-butyloctan-1-ol, 2-butyldecan-1-ol, 2-hexyloctan-1-ol, 2-hexyldecan-1-ol, 2-octyldecan-1-ol, 2-hexyldodecan-1-ol, 2-octyldodecan-1-ol, 2-decyltetradecan-1-ol, 6-methyldodecan-1-ol and their isomers can be selected, where X a-b represents an integer that can take any value in the range from a to b, and X a-b indicates the position of the alkyl substituent on the alkane. X 1-11-Methyldodecan-1-ol is a dodecane with an OH group at the 1-position and a methyl group substituted at the 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11-position, for example, 2-methyldodecan-1-ol or 11-methyldodecan-1-ol. The term "isomer" is understood to mean an alkane that contains the same number of carbon atoms but has a different substitution scheme, for example, an alkane that has an ethyl substituent instead of a methyl substituent or more methyl substituents. Thus, 2,5,9-trimethyldecan-1-ol is an isomer of 2-methyldodecan-1-ol and 11-methyldodecan-1-ol. Preferably, the C1 to C 30 alkane is selected from 11-methyldodecan-1-ol and 2,5,9-trimethyldecan-1-ol.

[0127] The C2 to C alkane substituted with an OH group 30 alkene is, in particular, Y 2-5 -hexen-1-ol, Y 2- 6-hepten-1-ol, Y2 -7 -octen-1-ol, Y 2-8 -nonen-1-ol, Y 2-9 -decen-1-ol, Y 2-10 -undecen-1-ol, Y 2-11 -dodecen-1-ol, Y 2-12 -tridecen-1-ol, Y 2-13 -tetradecen-1-ol, Y 2-15 -hexadecene-1-ol, Y 2-17 -octadecene-1-ol, Y 2-19 -icosen-1-ol, Y 2-21-Docosen-1-ol, heptadeca-8,11-dien-1-ol, octadeca-9,12-dien-1-ol, nonadeca-10,13-dien-1-ol, icos-11,14-dien-1-ol, docosa-13,16-dien-1-ol, octadeca-5,9,12-trien-1-ol, octadeca-6,9,12-trien-1-ol, octadeca-9,12,15-trien-1-ol, octadeca-9,11,13-trien-1-ol, icos-8,11,14-trien-1-ol, icos-11,14,17-trien-1-ol may be selected, where Y a-b represents an integer that can take any value in the range from a to b, and Y a-b indicates the position of the double bond of the alkene. Y 2-5 -Hexen-1-ol is hexene substituted with OH at the 1-position, and the double bond can be at the 2-position, 3-position, 4-position or 5-position.

[0128] C5 to C substituted with an OH group 12 The cycloalkane can be selected particularly from cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol and cyclododecanol, preferably from cyclopentanol and cyclohexanol.

[0129] C6 to C substituted with an OH group 12 The arene can be selected particularly from phenol, 1- or 2-naphthol, 2-, 3- or 4-phenylphenol, 2-, 3- or 4-methylphenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenol, and 2,4,6-, 2,3,5- or 2,3,6-trimethylphenol.

[0130] C7 to C substituted with an OH group 12Aryl alkanes can be selected, in particular, from benzyl alcohol, 2-phenylethan-1-ol, 3-phenylpropan-1-ol, 4-phenylbutan-1-ol, and 2-phenylbutan-1-ol, preferably from benzyl alcohol and 2-phenylethan-1-ol.

[0131] Alcohol HO-[(CR a R b ) n -O] m -Y is, in particular, an alkoxylation derivative of a C1 to C 30 alkane substituted with the OH group defined above, an alkoxylation derivative of a C2 to C 30 alkene substituted with the OH group defined above, an alkoxylation derivative of a C5 to C 12 cycloalkane substituted with the OH group defined above, an alkoxylation derivative of a C6 to C 12 arene substituted with the OH group defined above, an alkoxylation derivative of a C7 to C 12 aryl alkane. The alkoxylation derivative can be selected, in particular, from ethoxylation, propoxylation, and / or butoxylation derivatives, preferably an ethoxylation derivative. Preferably, the alcohol HO-[(CR a R b ) n -O] m -Y is selected from polyethylene glycol monomethyl ether (MPEG), polyethylene glycol monoethyl ether, and polyethylene glycol monobutyl ether; more preferably, MPEG having a number average molecular weight of 200 to 1000 g / mol (in particular MPEG-250, MPEG-350, MPEG-400, MPEG-450, MPEG-500, MPEG-550, MPEG-650, or MPEG-750), or triethylene glycol monobutyl ether (also known as butyl triglycol (BTG)).

[0132] Alcohol HO-[(CR c R d ) p -C(=O)O]q -Z is, in particular, C1 to C substituted with the OH group defined above 30 A polyester derivative of an alkane, C2 to C substituted with the OH group defined above 30 A polyester derivative of an alkene, C5 to C substituted with the OH group defined above 12 A polyester derivative of a cycloalkane, C6 to C substituted with the OH group defined above 12 A polyester derivative of an arene, C7 to C substituted with the OH group defined above 12 It may be a polyester derivative of an arylalkane. The polyester derivative may particularly preferably contain a polyester moiety obtained by ring-opening polymerization of a lactone selected from γ-butyrolactone, δ-valerolactone, ε-caprolactone and mixtures thereof.

[0133] [R2 group] The compound of formula (I) contains two R2 groups. The R2 groups of one and the same compound of formula (I) may be the same or different. Component b) may be a mixture of compounds of formula (I) having the same R2 group. Component b) may include a mixture of compounds of formula (I) having different R2 groups. For example, some compounds of the mixture may have the same R2 group and some compounds of the mixture may have different R2 groups.

[0134] Each R2 group can result from using a diisocyanate of the formula OCN-R2-NCO to form the diurea-diurethane compound of formula (I). The R2 group can correspond to the residue of a diisocyanate of the formula OCN-R2-NCO without an NCO group. The R2 group and the corresponding diisocyanate of the formula OCN-R2-NCO described below are also applicable to the method according to the present invention.

[0135] Each R2 is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group and an araliphatic group.

[0136] According to one embodiment, each R2 is independently an aromatic group.

[0137] In particular, each R2 is independently of the following formula: TIFF2025521194000007.tif31170(In the above formula, the symbol · represents the bonding point to the urea or urethane group of formula (I)) and is an aromatic group having

[0138] More specifically, each R2 is independently of the following formula: TIFF2025521194000008.tif42170(In the above formula, the symbol · represents the bonding point to the urea or urethane group of formula (I)) and is an aromatic group having one of

[0139] Component b) can in particular have more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% of all the R2 groups comprised in the compounds of formula (I) which are aromatic groups of the following formula: TIFF2025521194000009.tif39170(In the above formula, the symbol · represents the bonding point to the urea or urethane group of formula (I))

[0140] In particular, component b) can have from 86 to 100 mol%, from 90 to 100 mol%, from 95 to 100 mol%, from 97 to 100 mol%, from 98 to 100 mol%, from 99 to 100 mol%, or 100 mol% of all the R2 groups comprised in the compounds of formula (I) which are aromatic groups of the following formula: TIFF2025521194000010.tif39170(In the above formula, the symbol · represents the bonding point to the urea or urethane group of formula (I))

[0141]

[0142] The R2 group is bonded on the one hand to a urethane group (resulting from the reaction between the isocyanate group of the diisocyanate OCN-R2-NCO and the OH group of the alcohol R'OH) and on the other hand to a urea group (resulting from the reaction between the other isocyanate group of the diisocyanate OCN-R2-NCO and the NH2 group of the diamine H2N-R3-NH2). ​​Even more specifically, each R2 is independently of the following formula: It is an aromatic group of TIFF2025521194000011.tif62170.

[0143] When the R2 group is asymmetric, preferably one side of the R2 group bonded to the urethane group and preferably the other side bonded to the urea group may exist. Without wishing to be bound by any theory, the applicant company assumes that the least hindered side of the R2 group is preferably bonded to the urethane group.

[0144] Component b) in particular has the following formula: It may have more than 60 mol%, more than 65 mol%, more than 70 mol%, more than 75 mol%, more than 80 mol%, more than 85 mol%, or more than 90 mol% of all of the R2 groups contained in the compound of formula (I) which is an aromatic group of TIFF2025521194000012.tif57170.

[0145] In particular, component b) has the following formula: It may have from 61 to 100 mol%, from 65 to 100 mol%, from 70 to 100 mol%, from 75 to 100 mol%, from 80 to 100 mol%, from 85 to 100 mol%, or from 90 to 100 mol% of all of the R2 groups contained in the compound of formula (I) which is an aromatic group of TIFF2025521194000013.tif57170.

[0146] The R2 group may in particular be the residue of one or more diisocyanates of the formula OCN-R2-NCO without an NCO group. The diisocyanate of the formula OCN-R2-NCO may be toluene diisocyanate (TDI). TDI may be in the form of one or more isomers selected from toluene-2,4-diisocyanate and toluene-2,6-diisocyanate.

[0147] In the context of the present invention, it is advantageous to use TDI containing a high proportion of toluene-2,4-diisocyanate, even TDI containing only toluene-2,4-diisocyanate in practice. The applicant company assumes that due to the asymmetry of this compound, the amount of by-products in component b), in particular the amount of the compound of formula (II), can be reduced. Thereby, the following formula: TIFF2025521194000014.tif57170 allows for a high proportion of the R2 group and actually makes it possible to obtain a compound of formula (I) consisting exclusively of the R2 group.

[0148] In particular, the diisocyanate of the formula OCN-R2-NCO is a TDI containing more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% of toluene-2,4-diisocyanate relative to the total amount of toluene diisocyanate isomers. More specifically, the diisocyanate of the formula OCN-R2-NCO is a TDI containing 86 to 100 mol%, 90 to 100 mol%, 95 to 100 mol%, 97 to 100 mol%, 98 to 100 mol%, 99 to 100 mol%, or 100 mol% of toluene-2,4-diisocyanate relative to the total amount of toluene diisocyanate isomers. Preferably, the diisocyanate of the formula OCN-R2-NCO is a TDI containing 100 mol% of toluene-2,4-diisocyanate relative to the total amount of toluene diisocyanate isomers.

[0149] [R3 group] The compound of formula (I) contains an R3 group. Component b) can include a mixture of compounds of formula (I) having the same R3 group. Component b) can include a mixture of compounds of formula (I) having different R3 groups.

[0150] Each R3 group can result from the use of a diamine of the formula H2N-R3-NH2 to form a diurea-diurethane compound of formula (I). The R3 group can correspond to the residue of a diamine of the formula H2N-R3-NH2 without an NH2 group. The R3 group and the corresponding diamine of the formula H2N-R3-NH2 described below are also applicable to the process according to the invention.

[0151] Each R3 is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, an araliphatic group, and a heterocyclic group.

[0152] According to a specific embodiment, each R3 is independently a C2-C 24 alkylene, -(CR h R i ) s -[A-(CR j R k ) t u -, -(CR l R m ) v -CY-(CR n R o ) w - and -(CR p R q ) x -CY-(CH2) y -CY-(CR r R s ) z -selected groups; where A is O or NX; R h , R i , R j , R k , R l , R m , R n , R o , R p , R q , R r and R s are independently selected from H and methyl, especially H; X is C1 to C6 alkyl, especially methyl or ethyl; CY is a ring selected from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl, and pyridinyl, and the ring is unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups; s ranges from 2 to 4, especially s is 2; t ranges from 2 to 4, especially t is 2; u ranges from 1 to 30; ​v, w, x, y, and z are independently in the range from 0 to 4.

[0153] Each R3 can in particular be a group selected from C2-C 24 alkylene and -(CR l R m ) v -CY-(CR n R o ) w - and can be a group selected from; in particular, C2-C 18 alkylene and -(CH2) v -CY-(CH2) w -, where CY is a cyclohexyl or phenyl ring which is unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups, and v and w are in the range from 0 to 1.

[0154] More specifically, each R3 can be a group selected from C2-C6 alkylene and a group having the following formula: TIFF2025521194000015.tif41170 (in the above formula, the symbol · represents the point of attachment to the urea group of the compound of formula (I)).

[0155] Component b) can in particular have more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% of all of the R3 groups contained in the compound of formula (I) which is a group of the following formula: TIFF2025521194000016.tif23170.

[0156] In particular, component b) can have from 86 to 100 mol%, from 90 to 100 mol%, from 95 to 100 mol%, from 97 to 100 mol%, from 98 to 100 mol%, from 99 to 100 mol%, or 100 mol% of all of the R3 groups contained in the compound of formula (I) which is a group of the following formula: TIFF2025521194000017.tif23170.

[0157] The R3 group can in particular be the residue of (one or more) diamines of the formula H2N-R3-NH2 that do not have an NH2 group. The diamine of the formula H2N-R3-NH2 is from C2 to C 24 an aliphatic diamine, from C6 to C 18 a cycloaliphatic diamine, from C6 to C 24 an aromatic diamine, from C7 to C 26 an araliphatic diamine and from C3 to C 18 a heterocyclic diamine.

[0158] From C2 to C 24An aliphatic diamine is a diamine of the formula H2N-R3-NH2, where R3 is an aliphatic group containing from 2 to 24 carbon atoms. The aliphatic diamine can be linear or branched, preferably linear. The aliphatic diamine is a polyetheramine, i.e., a diamine of the formula H2N-R3-NH2, where R3 contains ether (-O-) bonds, more specifically ethylene oxide (-O-CH2-CH2) and / or propylene oxide (-O-CH2-CHCH3-) units. The aliphatic diamine can be a polyalkyleneimine, i.e., a diamine of the formula H2N-R3-NH2, where R3 is interrupted by one or more tertiary amines (-NX-, X is C1 to C6 alkyl). The aliphatic diamine may be interrupted by one or more tertiary amine groups. Examples of suitable linear aliphatic diamines are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, and mixtures thereof; preferably 1,2-ethylenediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine. Examples of suitable branched aliphatic diamines are 1,2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, and mixtures thereof. Examples of polyetheramines are compounds sold under the reference name Jeffamine® from Huntsman, in particular the Jeffamine® D, ED, and EDR series (diamines). These series include, in particular, the following references: Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, and Jeffamine® EDR-176. An example of a polyalkyleneimine is 3,3'-diamino-N-methyldipropylamine.

[0159] From C6 to C 18 The alicyclic diamine is a diamine of the formula H2N-R3-NH2, where R3 is an alicyclic group containing 6 to 18 carbon atoms. Examples of suitable alicyclic diamines are 1,2-, 1,3-, or 1,4-diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, isophoronediamine, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, bis(aminomethyl)norbornane and mixtures thereof; preferably, 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine and 4,4'-diaminodicyclohexylmethane.

[0160] From C6 to C 24 The aromatic diamine is a diamine of the formula H2N-R3-NH2, where R3 is an aromatic group containing 6 to 24 carbon atoms. Examples of suitable aromatic diamines are ortho-, meta- and para-phenylenediamine, ortho-, meta- and para-tolylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and mixtures thereof; preferably, ortho-, meta- and para-phenylenediamine.

[0161] From C7 to C 26 The aromatic aliphatic diamine is a diamine of the formula H2N-R3-NH2, where R3 is an aromatic aliphatic group containing 7 to 26 carbon atoms. Examples of suitable aromatic aliphatic diamines are ortho-, meta- and para-xylylenediamine, 4,4'-diaminodiphenylmethane and mixtures thereof; preferably, ortho-, meta- and para-xylylenediamine.

[0162] From C3 to C 18The complex cyclic diamine is a diamine of the formula H2N-R3-NH2, where R3 is a complex cyclic group containing 3 to 18 carbon atoms. Examples of suitable complex cyclic diamines are 1,2-diaminopiperazine, 1,4-diaminopiperazine, 1,4-bis(3-aminopropyl)piperazine, 2,3-, 2,6- and 3,4-diaminopyridine, 2,4-diamino-1,3,5-triazine and mixtures thereof.

[0163] [Aprotic solvent] Component b) may further contain an aprotic solvent. Component b) may contain a mixture of aprotic solvents.

[0164] According to one embodiment, the aprotic solvent is selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N’,N’-tetramethylurea, and mixtures thereof. In particular, the aprotic solvent is selected from dimethyl sulfoxide, N-butylpyrrolidone, and mixtures thereof.

[0165] Component b) may in particular contain from 20% to 95% by weight, in particular from 40% to 80% by weight, more particularly from 50% to 70% by weight of an aprotic solvent, based on the weight of component b).

[0166] [Diurethane compound] Component b) may further contain a diurethane compound. Component b) may contain a mixture of diurethane compounds.

[0167] The diurethane compound can be a by-product resulting from the preparation method of component b) described below. This is because when the alcohol is stoichiometrically in excess with respect to the diisocyanate, a diurethane can also be formed by the reaction of a diisocyanate of the formula OCN-R2-NCO with an alcohol of the formula R'-OH to form a monoisocyanate adduct of the formula R'-O-C(=O)-NH-R2-NCO.

[0168] While not intending to be bound by any theory, the Applicant company believes that the diurethane can stabilize component b) and reduce the number of by-products obtained during its preparation. The presence of diurethane in component b) makes it possible to eliminate or significantly reduce the amount of salts, especially lithium salts, or surfactants compared to prior art thixotropic additives.

[0169] The diurethane compound is in particular of formula (II): TIFF2025521194000018.tif20170(wherein R' and R2 are as described above for the compound of formula (I)) may correspond to the compounds of.

[0170] According to a particular embodiment, component b) comprises from 20 to 95 mol%, in particular from 25 to 85 mol%, more particularly from 35 to 75 mol% of the compound of formula (II) with respect to the total molar amount of the compound having one or more functional groups selected from urea, urethane and mixtures thereof (excluding aprotic solvents).

[0171] [Polyurea-diurethane compound] Component b) may further comprise a polyurea-diurethane compound. Component b) may comprise a mixture of polyurea-diurethane compounds.

[0172] The polyurea-diurethane compound can in particular be a by-product resulting from the method for preparing component b) described below. This is because when the reaction medium contains a diisocyanate of formula OCN-R2-NCO, a polyurea-diurethane can also be formed by the reaction between a monoisocyanate adduct of formula R'-O-C(=O)-NH-R2-NCO and a diamine of formula H2N-R3-NH2. The diisocyanate can in particular be the residual diisocyanate resulting from the reaction between a diisocyanate of formula OCN-R2-NCO and an alcohol of formula R'-OH for forming a monoisocyanate adduct of R'-O-C(=O)-NH-R2-NCO.

[0173] The polyurea-diu rethane compound corresponds in particular to the compound of formula (III): TIFF2025521194000019.tif30170(wherein R', R2 and R3 are as described above for the compound of formula (I); z is from 1 to 10).

[0174] Since polyurea-diu rethane compounds are generally solids, it is advantageous to limit their amount in component b). It is possible to reduce the content of residual diisocyanate by carrying out a distillation step before the reaction of the monoisocyanate adduct with the diamine, but this is quite costly and requires a specific plant. Component b) has a low content of polyurea-diu rethane compounds despite the fact that its preparation method does not require a distillation step for residual diisocyanate. This is made possible in particular by adjusting the molar ratio of the reactants used in the preparation method of component b) described below.

[0175] According to a particular embodiment, component b) contains less than 4 mol%, in particular from 3.0 to 1.5 mol%, from 2.0 to 1.0 mol%, or from 1.0 to 0 mol% of the compound of formula (III) with respect to the total molar amount of the compound(s) having one or more functional groups selected from urea, urethane and mixtures thereof (excluding aprotic solvents).

[0176] [Method for preparing a thixotropy additive] Component b) can be prepared according to the method described below.

[0177] The method for preparing component b) comprises step a), step b), and optionally one or more additional steps that can be carried out before step a), between step a) and step b), and / or after step b).

[0178] Step a) is a step in which at least one diisocyanate of the formula OCN-R2-NCO reacts with at least one alcohol of the formula R'-OH to form at least one monoisocyanate adduct of the formula R'-O-C(=O)-NH-R2-NCO.

[0179] Step b) is a step in which at least one monoisocyanate adduct obtained in step a) reacts with at least one diamine of the formula (I): TIFF2025521194000020.tif20170(wherein each R' is independently selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, ·-[(CR a R b ) n -O] m -Y and ·-[(CR c R d ) p -C(=O)O] q -Z; the symbol · represents the point of attachment to the urethane group of formula (I); each R2 is independently a divalent group selected from aliphatic, alicyclic, aromatic and araliphatic groups; each R3 is independently a divalent group selected from aliphatic, alicyclic, aromatic, araliphatic and heterocyclic groups; Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl; R a R b R c and R d are independently selected from H and methyl, especially H; each n is independently equal to 2, 3 or 4, especially n is 2; m ranges from 1 to 30, especially m ranges from 2 to 25; p ranges from 3 to 5, especially p is 5; q ranges from 1 to 20, especially q ranges from 2 to 10) to form at least one compound of formula (I).

[0180] The R', R2 and R3 groups, the diisocyanate of the formula OCN-R2-NCO, the alcohol of the formula R'-OH, and the diamine of the formula H2N-R3-NH2 can be as described above, in particular for the compounds of formula (I). The specific embodiments described for the compounds of formula (I) also apply to the method for preparing component b).

[0181] Step a) can be carried out, in particular, by gradually adding at least one alcohol to a reactor containing at least one diisocyanate. The at least one diisocyanate can in particular be in a molten state. The addition rate of the at least one alcohol can be controlled in order to limit the exotherm. In particular, the addition rate of the at least one alcohol can be controlled in order to maintain the temperature of the reaction medium at 60 °C or below, in particular from 20 to 60 °C, from 25 to 55 °C or from 30 to 40 °C.

[0182] Step a) is carried out with a molar ratio of the total amount of alcohol to the total amount of diisocyanate in the range from 1.10 to 1.80. In particular, the molar ratio of the total amount of alcohol to the total amount of diisocyanate in step a) is in the range from 1.20 to 1.60, more particularly from 1.25 to 1.45, even more particularly from 1.30 to 1.40.

[0183] Depending on the ratio of alcohol to diisocyanate in step a), it becomes possible to limit the amount of residual diisocyanate at the end of step a). The amount of residual diisocyanate at the end of step a) corresponds to the amount of diisocyanate introduced in step a) that did not react with at least one kind of alcohol. By controlling the amount of residual diisocyanate at the end of step a), it is advantageously possible to limit the formation of insoluble species during step b), particularly the formation of the compound of formula (III) above. According to a specific embodiment, the amount of residual diisocyanate in the reaction mixture at the end of step a) is less than 6 mol%, particularly 0 to 5 mol%, 0.01 to 4.5 mol% or 0.05 to 4 mol% with respect to the total molar amount of the compound having one or more functional groups selected from urethane, isocyanate and mixtures thereof.

[0184] The ratio of alcohol to diisocyanate in step a) advantageously makes it possible to avoid carrying out the step of removing residual diisocyanate. This is because the amount of residual diisocyanate at the end of step a) is sufficiently small and does not cause excessive formation of insoluble species, particularly the compound of formula (III) above, during step b). According to a specific embodiment, the method for preparing component b) does not include a step of distilling residual diisocyanate, particularly does not include a step of distilling residual diisocyanate between step a) and step b).

[0185] One or more kinds of diurethane compounds as described above can be formed depending on the ratio of alcohol to diisocyanate in step a). The diurethane compound can particularly result from the reaction of an alcohol of formula R'-OH and a monoisocyanate adduct of formula R'-O-C(=O)-NH-R2-NCO. Therefore, the reaction mixture obtained in step a) can contain a monoisocyanate adduct of formula R'-O-C(=O)-NH-R2-NCO and a compound of formula (II): TIFF2025521194000021.tif20170 (wherein R' and R2 are as described above).

[0186] Although not intending to adhere to any theory, the Applicant company believes that the presence of the diurethane compound in component b) can stabilize the urea bonds formed during step b). Therefore, compared to the methods of the prior art, the amount of stabilizers (especially salts, such as lithium salts, or surfactants) added in step b) can be significantly reduced and can actually even be eliminated.

[0187] Once the addition of at least one alcohol is complete, step a) can be continued until the NCO value of the reaction mixture reaches the theoretical NCO value. The NCO value at the end of step a) can in particular be less than 200 mg KOH / g. In particular, the NCO value at the end of step a) can be from 5 to 150 mg KOH / g, from 25 to 125 mg KOH / g, from 50 to 100 mg KOH / g, or from 60 to 80 mg KOH / g. The NCO value at the end of step a) can in particular be measured according to the method described below. The theoretical NCO value at the end of step a) can in particular be calculated according to the method described below.

[0188] Step b) can in particular be carried out by gradually adding the mixture obtained in step a) to a reactor containing at least one diamine and optionally an aprotic solvent and / or a salt. In order to limit the exotherm, the addition rate of the mixture obtained in step a) can be controlled. In particular, the addition rate of the mixture obtained in step a) can be controlled in order to maintain the temperature of the reaction medium at 80°C or below, in particular from 20°C to 80°C, from 30°C to 70°C or from 40°C to 60°C.

[0189] Once the addition of at least one monoisocyanate adduct is complete, step b) can be continued until the NCO value of the reaction mixture reaches the desired value. The NCO value of the thixotropy additive obtained by the method for preparing component b) can be less than 0.5 mg KOH / g, particularly less than 0.2 mg KOH / g, more specifically less than 0.1 mg KOH / g, and even more specifically 0 mg KOH / g. The NCO value of the thixotropy additive can be determined, in particular, according to the method described in the patent application filed under the number PCT / EP2021 / 084323.

[0190] Step b) is carried out in the presence of less than 0.2 moles of salt per mole of diamine used. In particular, step b) is carried out in the presence of 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01 or 0 moles of salt per mole of diamine used. The salt can be, in particular, as described above for component b).

[0191] Step b) can be carried out in the presence of less than 0.2 moles of surfactant per mole of diamine used. In particular, step b) is carried out in the presence of 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01 or 0 moles of surfactant per mole of diamine used. The surfactant can be, in particular, as described above for component b).

[0192] The molar ratio of the total amount of monoisocyanate adduct to the total amount of diamine in step b) can be in the range of 1.8 to 2.2. In particular, the molar ratio of the total amount of monoisocyanate adduct to the total amount of diamine in step b) is in the range of 1.9 to 2.1, more specifically 1.95 to 2.05, and even more specifically 1.98 to 2.02.

[0193] A solvent can be added during step a) and / or step b) and / or between step a) and step b) in order to reduce the viscosity of the composition and dissolve the resulting compound. In particular, step a) and / or step b) can be carried out in the presence of an aprotic solvent. The viscosity of the reaction medium obtained at the end of step a) can be reduced by adding an aprotic solvent. The aprotic solvent can in particular be as described above for component b).

[0194] The method for preparing component b) can be carried out using an alcohol or a mixture of alcohols in step a).

[0195] According to a first embodiment, in step a), at least one diisocyanate reacts with a single alcohol of the formula R1-OH to form at least one monoisocyanate adduct of the formula R1-O-C(=O)-NH-R2-NCO, In step b), the product obtained in step a) reacts with at least one diamine of the formula H2N-R3-NH2 to form at least one compound of the formula (I’): TIFF2025521194000022.tif20170(wherein, the R1 groups are identical and R' is as described above; R2 and R3 are as described above)

[0196] The alcohol R1-OH of the first embodiment can in particular be a linear or branched C1-C alkyl substituted with OH. 30 alkyl.

[0197] According to a second embodiment, in step a), at least one diisocyanate reacts with at least two different alcohols of the formula R4-OH and R5-OH to form a mixture of at least two monoisocyanate adducts of the formula R4-O-C(=O)-NH-R2-NCO and R5-O-C(=O)-NH-R2-NCO, In step b), the mixture obtained in step a) reacts with at least one diamine of the formula H2N-R3-NH2, optionally as a mixture with a compound of formula (Ib) and / or a compound of formula (Ic), to form at least one compound of formula (Ia): TIFF2025521194000023.tif63170(In the above formula, all R4 groups are the same and are as described above for R'; all R5 groups are the same and are as described above for R'; the R4 groups are different from R5).

[0198] The R4 and R5 groups, and the alcohols of the formulas R4-OH and R5-OH can be, in particular, as described above for the compounds of formula (I).

[0199] In a second embodiment, the alcohol R4-OH can be more hydrophobic than the alcohol R5-OH; and / or the alcohol R5-OH can have a higher molecular weight than the molecular weight of the alcohol R4-OH.

[0200] In a second embodiment, the molecular weights of the alcohols R4-OH and R5-OH can be different. In particular, R4-OH can have a lower molecular weight than R5-OH. More specifically, the difference between the molecular weight of R4-OH and the molecular weight of R5-OH can be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0201] In a second embodiment, the chemical properties of the alcohols R4-OH and R5-OH can be different. In particular, the alcohol R4-OH can be more hydrophobic than the alcohol R5-OH.

[0202] In a second embodiment, the alcohols R4-OH and R5-OH can be alcohols of the formula HO-[(CR a R b ) n -O] m -Y having different molecular weights, where Y, R a , Rb , n, and m are as described above. Alternatively, the alcohol R4-OH may be a linear or branched C1-C alkyl substituted with OH, and the alcohol R5-OH may be Y, R 30 , R a , R b , n, and m are as described above, and the alcohol of the formula HO-[(CR a R b ) n -O] m -Y may be possible.

[0203] In a second embodiment, the total molar amount of the alcohol R5-OH, particularly the alcohol with the lowest hydrophobicity and / or the highest molecular weight, may particularly account for more than 20%, particularly from 25% to 95%, 30% to 90%, 35% to 85%, or 40% to 80% of the total molar amount of the alcohols R4-OH and R5-OH introduced in step a).

[0204] In a second embodiment, the alcohol R5-OH, particularly the alcohol with the lowest hydrophobicity and / or the highest molecular weight, can particularly react with the diisocyanate before the alcohol R4-OH, particularly the alcohol with the highest hydrophobicity and / or the lowest molecular weight, is introduced into the reaction mixture in step a).

[0205] According to a third embodiment, in step a), the diisocyanate reacts with a mixture of at least three different alcohols of the formulas R4-OH, R5-OH, and R6-OH to form a mixture of at least three kinds of monoisocyanate adducts of the formulas R4-O-C(=O)-NH-R2-NCO, R5-O-C(=O)-NH-R2-NCO, and R6-O-C(=O)-NH-R2-NCO. In step b), the mixture obtained in step a) reacts with at least one diamine of the formula H2N-R3-NH2 to form the compounds of formula (Ia), the compounds of formula (Id), and optionally one or more compounds of formula (Ib), (Ic), (Ie), or (If) represented below: TIFF2025521194000024.tif63170TIFF2025521194000025.tif61170(In the above formula, all R4 groups are the same and are as described above for R'; all R5 groups are the same and are as described above for R'; all R6 groups are the same and are as described above for R'; the R4 group is different from R5; the R4 group is different from R6; the R5 group is different from R6).

[0206] The R4, R5, and R6 groups, and the alcohols of the formulas R4-OH, R5-OH, and R6-OH can, in particular, be as described above for the compounds of formula (I).

[0207] In a third embodiment, the alcohol R4-OH can be more hydrophobic than the alcohol R5-OH and / or the alcohol R6-OH; and / or the alcohol R4-OH can have a lower molecular weight than the molecular weight of the alcohol R5-OH and / or the molecular weight of the alcohol R6-OH.

[0208] In a third embodiment, the molecular weights of the alcohols R4-OH, R5-OH, and R6-OH can be different. In particular, R4-OH can have a lower molecular weight than R5-OH; and / or R4-OH can have a lower molecular weight than R6-OH; and / or R5-OH can have a lower molecular weight than R6-OH. More specifically, the alcohol R4-OH has a lower molecular weight than the molecular weights of the alcohols R5-OH and R6-OH. Even more specifically, the difference between the molecular weight of R4-OH and the molecular weight of R5-OH; and / or the difference between the molecular weight of R4-OH and the molecular weight of R6-OH; and / or the difference between the molecular weight of R5-OH and the molecular weight of R6-OH can be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0209] The alcohols R4-OH, R5-OH, and R6-OH may have different chemical properties. In particular, R4-OH may be more hydrophobic than R5-OH; and / or R4-OH may be more hydrophobic than R6-OH; and / or R5-OH may be more hydrophobic than R6-OH. More specifically, the alcohol R4-OH may be more hydrophobic than the alcohols R5-OH and R6-OH.

[0210] In a third embodiment, the alcohol R4-OH may be a linear or branched C1-C alkyl substituted with OH, and the alcohols R5-OH and R6-OH may be alcohols of the formula HO-[(CRaR) -O][ -Y where Y, R, R, n, and m are as described above and have different molecular weights. 30 The total molar amount of the alcohols R5-OH and R6-OH, particularly the total molar amount of the least hydrophobic alcohol and / or the alcohol with the highest molecular weight, may in particular account for more than 20%, particularly 25% to 95%, 30% to 90%, 35% to 85%, or 40% to 80% of the total molar amount of the alcohols R4-OH, R5-OH, and R6-OH introduced in step a). a R b The alcohols R5-OH and R6-OH, particularly the least hydrophobic alcohol and / or the alcohol with the highest molecular weight, can in particular be reacted with the diisocyanate before the alcohol R4-OH, particularly the most hydrophobic alcohol and / or the alcohol with the lowest molecular weight, is introduced into the reaction mixture of step a). b ) n -O] m -Y.

[0211]

[0212]

[0213] [Composition] The composition according to the invention comprises a polymerizable component and a thixotropy additive as described above.

[0214] The composition may, in particular, contain component a) in an amount of from 50% to 99.95% by weight, in particular from 70% to 99.9% by weight, more particularly from 80% to 99.8% by weight, and even more particularly from 90% to 99.75% by weight, based on the weight of the composition.

[0215] The thixotropy additive may be added in an amount sufficient to, in particular, increase the viscosity of the composition according to the invention and / or impart thixotropic properties to the composition.

[0216] The composition may, in particular, contain component b) in an amount of from 0.05% to 50% by weight, in particular from 0.1% to 30% by weight, more particularly from 0.2% to 20% by weight, and even more particularly from 0.25% to 10% by weight, based on the weight of the composition.

[0217] The composition may, in particular, have a higher viscosity than that of a composition that does not contain component b) or contains an insufficient amount of component b), and the viscosity is measured at low shear (0.01 s -1 ) at 25°C.

[0218] According to a particular embodiment, the composition is a coating composition, a molding composition, a mastic composition, an adhesive composition, a liquid waterproof composition, a composite material composition, a chemical sealing composition, or a dental material composition.

[0219] The composition according to the invention may further contain one or more additional components selected from fillers, plasticizers, wetting agents, pigments, antioxidants, radical inhibitors, UV absorbers, light stabilizers, and mixtures thereof.

[0220] The composition according to the present invention may include a filler, particularly a filler selected from mineral fillers, organic fillers, or mixtures thereof. In particular, the composition may include mineral fillers particularly selected from gravel, marble, granite, quartz, diatomaceous earth, feldspar, mica, gypsum, glass beads, rock powder, limestone, ceramic, clay, loam, carbon black, graphite, sand, silica, alumina, titanium dioxide, magnesium oxide, zirconium dioxide, talc, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zirconium hydroxide, calcium phosphate, calcium carbonate, calcium sulfate, barium sulfate, and mixtures thereof.

[0221] The composition may include polymer particles such as polyolefin particles (particularly polyethylene, polytetrafluoroethylene, or polypropylene particles), polyester particles, polyether particles, (meth)acrylic polymer particles (particularly polymethyl methacrylate particles), polyurethane particles, polyamide particles (particularly Orgasol® type), styrene-maleic acid copolymer particles; natural or synthetic waxes such as paraffin, microcrystalline wax, ceresin, montan wax, beeswax, candelilla wax, carnauba wax, rice bran wax, wood rosin, soybean wax, rapeseed wax, palm wax, whale oil, shea butter, cocoa butter, tristearin, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated rapeseed oil, hydrogenated soybean oil, hydrogenated palm oil; gums such as guar gum and xanthan gum; and organic fillers particularly selected from mixtures thereof.

[0222] In particular, the composition may include fillers in an amount of 0% to 70% by weight, particularly 10% to 60% by weight, more particularly 20% to 50% by weight, based on the weight of the composition.

[0223] The composition according to the present invention may include a reinforcing material, more particularly a reinforcing material selected from plant fibers, glass fibers, carbon fibers, carbon nanotubes, polyester fibers, aramid fibers, and mixtures thereof.

[0224] The composition may contain, in particular, from 0% to 70% by weight, in particular from 10% to 60% by weight, more particularly from 20% to 50% by weight of a reinforcing material, based on the weight of the composition.

[0225] The composition according to the invention may contain a tackifying resin, in particular a rosin which may also be modified.

[0226] The composition according to the invention may further contain a radical initiator. The radical initiator is particularly capable of initiating the polymerization of component a).

[0227] The radical initiator may in particular be a peroxide compound or an azo compound, in particular a peroxide.

[0228] An azo compound is a compound containing an azo group of the formula -N=N-. An example of a suitable azo compound is azobisisobutyronitrile (AIBN).

[0229] A peroxide compound is a compound containing a peroxide group of the formula -O-O-. The peroxide compound may in particular be selected from hydrogen peroxide, hydroperoxides (R-O-O-H), dialkyl or alkylaryl peroxides (R-O-O-R'), peracids (RC(=O)-O-O-H), peroxyesters (RC(=O)-O-O-R'), diacyl peroxides (RC(=O)-O-O-C(=O)-R'), peroxicarbonates (R-O-C(=O)-O-O-C(=O)-O-R'), peroxyketals (resulting from the reaction of a ketone with hydrogen peroxide or a hydroperoxide), and mixtures thereof, where R and R' are independently aliphatic, alicyclic or aromatic groups. It is advantageous for the peroxide compound to be in a stabilized form, in particular in an aqueous phase, a plasticizer or an organic solvent.

[0230] Examples of suitable peroxide compounds are dibenzoyl peroxide, dilauroyl peroxide, diisopropyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, tert-butyl peroxy octoate, tert-butyl peroxy benzoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxy maleate, and mixtures thereof.

[0231] In particular, the radical initiator can be benzoyl peroxide.

[0232] The composition can particularly contain an amount of radical initiator sufficient to achieve complete polymerization of component a). In particular, the composition can contain 0.05% to 10%, 0.1% to 5%, 0.5% to 5%, or 0.5% to 3% by weight of radical initiator, based on the weight of component a).

[0233] The composition according to the invention can further contain an activator of the radical initiator. The radical initiator activator can in particular activate the radical initiator at ambient temperature (20 - 25 °C) in order to initiate the polymerization of component a). The radical initiator activator can in particular contain a tertiary amine or a redox pair.

[0234] In order to prevent premature polymerization of the composition according to the invention, the radical initiator may be brought into contact with component a) immediately before the end user applies the composition.

[0235] Accordingly, the invention also relates to - a first cartridge containing a radical initiator; - a second cartridge containing the composition according to the invention and optionally an activator of the radical initiator which can relate to a two-component system, in which the first cartridge is held separately from the second cartridge.

[0236] The containers of the first and second cartridges are intended to be brought into contact shortly before applying the composition to the substrate.

[0237] The present invention also relates to - a step of mixing the composition according to the invention with a radical initiator and optionally an activator of the radical initiator to form a mixture; - a step of applying the resulting mixture onto a substrate and may relate to a method for preparing a crosslinked product comprising the steps.

[0238] The crosslinked product can be, in particular, a coating, a molding, a mastic, an adhesive, a liquid waterproofing system, a composite material, a chemical sealing system, or a dental material.

[0239] The mixture can be applied, in particular, to the surface of a substrate to be coated or waterproofed. Alternatively, the mixture can be applied to the surface of a substrate intended to be adhered to another substrate. Alternatively, the mixture can be applied so as to fill a gap between two adjacent substrates or to fill a hole in the surface of a substrate. Alternatively, the mixture can be applied onto a substrate containing reinforcing fibers to form a composite material. Alternatively, the mixture can be applied to a substrate in the form of a mold.

[0240] The present invention also relates to the use of an additive containing a diurea-diurethane compound and containing less than 0.1 mol of salt per urea group in the additive (excluding aprotic solvents) for increasing the viscosity of a polymerizable component containing a (meth)acrylate functionalized compound and / or imparting thixotropic properties to the polymerizable component. The additive can in particular correspond to component b) described above for the composition according to the invention. The polymerizable component can in particular correspond to component a) described above for the composition according to the invention.

[0241] The present invention is illustrated by the following non-limiting examples.

Example

[0242] [Starting materials] TIFF2025521194000026.tif106170

[0243] [Thixotropic additive 1 (TA1) according to the present invention] The thixotropic additive 1 according to the present invention is prepared as described in Example 8 of the patent application filed under number PCT / EP2021 / 084323 (an additive based on diurea - diurethane without LiCl).

[0244] [Thixotropic additive 2 (TA2) according to the present invention] The thixotropic additive 2 according to the present invention corresponds to the commercially available product Crayvallac® LA - 377 (an additive based on diurea - diurethane without LiCl) available from Arkema.

[0245] [Comparative thixotropic additive C1 (TA C1)] The comparative thixotropic additive C1 corresponds to the commercially available product Crayvallac® LA - 350 (an additive based on diurea - diurethane containing more than 0.1 mol% LiCl per urea group) available from Arkema.

[0246] [Comparative thixotropic additive C2 (TA C2)] The comparative thixotropic additive C2 corresponds to the commercially available product RHEOBYK® D - 420 (an additive based on diurea - diurethane containing more than 0.1 mol% LiCl per urea group) available from BYK.

[0247] [Preparation of the composition] [Composition based on (meth)acrylate - functionalized monomers] Using a high - speed disperser equipped with a peptizing device, the composition was prepared in a 50 ml flask. The components, namely 1 g of the thixotropic additive and 19 g of the (meth)acrylate - functionalized monomer, were placed in the flask. Next, the mixture was homogenized while stirring at 1000 rpm for 1 minute at 20°C. After this dispersion step, the mixture was left without stirring for at least 10 minutes at 20°C.

[0248] List the components used to prepare the composition in the following table (thixotropic additive at 1 wt% based on the weight of the composition). TIFF2025521194000027.tif167170

[0249] [Composition based on (meth)acrylate-functionalized monomers and (meth)acrylate-functionalized oligomers] Using a high-speed disperser equipped with a peptizing device, the composition was prepared in a 250 ml flask. 97.7 g of MMA and 2.3 g of CN981, which are (meth)acrylate-functionalized compounds, were put in and stirred at 20 °C until a homogeneous mixture was obtained. Next, the desired amount of the thixotropic additive TA2 was added to the flask. Then, using a high-speed disperser equipped with a peptizing device, the mixture was homogenized while stirring at 1500 rpm for 5 minutes at 20 °C. After this dispersion step, the mixture was left standing without stirring at 20 °C for at least 10 minutes.

[0250] List the amount of the thixotropic additive used to prepare the composition in the following table (weight% of the thixotropic additive based on the weight of the composition). TIFF2025521194000028.tif53170

[0251] [Composition based on (meth)acrylate-functionalized compounds] This series of compositions based on (meth)acrylate-functionalized compounds was prepared in a 50 ml flask according to a protocol similar to that described in Examples 1a - C2e. The desired amount of the thixotropic additive TA2 and the resin Elium® 190 were put into the flask. Then, using a high-speed disperser equipped with a peptizing device, the mixture was homogenized while stirring at 800 rpm for 30 seconds at 20 °C. After this dispersion step, the mixture was left standing without stirring at 20 °C for at least 10 minutes.

[0252] List the amount of the thixotropic additive used to prepare the composition in the following table (weight% of the thixotropic additive based on the weight of the composition). TIFF2025521194000029.tif58170

[0253] [Composition based on (meth)acrylate-functionalized monomers and (meth)acrylate-functionalized oligomers and fillers] For these compositions, a mixture of (meth)acrylate-functionalized compounds was prepared beforehand as follows: 97.7 g of MMA and 2.3 g of CN981 were placed in a 250 ml flask and stirred at 20 °C using a high-speed disperser equipped with a peptizing device until a homogeneous mixture was obtained. Next, the desired amount of Omyacarb® 10AV filler was added and dispersed at 2000 rpm for 10 minutes using the same high-speed disperser equipped with a peptizing device. Next, in a 50 ml flask, the desired amount of thixotropy additive TA2 and the previously prepared MMA / CN981 / filler were placed in the flask. Next, the mixture was homogenized while stirring at 1500 rpm for 5 minutes at 20 °C using a high-speed disperser equipped with a peptizing device. After this dispersion step, the mixture was left to stand at 20 °C for at least 10 minutes without stirring.

[0254] The amounts of the components used to prepare the compositions are listed in the following table (weight % based on the weight of the composition). TIFF2025521194000030.tif49170

[0255] [Evaluation of the properties of the composition] [Evaluation of visual properties] The performance of the thixotropy additive is evaluated by the visual property evaluation of the composition after standing at 20 °C (without stirring) for 1 hour, 24 hours, or 1 week.

[0256] To enable comparison of the samples, the evaluation scale is defined as follows. TIFF2025521194000031.tif116170

[0257] The visual evaluation of the compositions of Examples 1a to 11 is described in detail in the following table: TIFF2025521194000032.tif255170

[0258] The visual evaluation of the compositions of Examples 12 to 15 is described in detail in the following table: TIFF2025521194000033.tif58170

[0259] [Viscosity measurement] The viscosity measurement was carried out at 22 °C in accordance with the NF EN ISO 2555 standard using a Brookfield® viscometer (spindle: S63). The cylindrical spindle rotates at a constant rotational speed about its axis within the product under inspection. The resistance exerted by the fluid on the spindle depends on the viscosity of the product. This resistance causes the torsion of the helical spring, which is reflected in the viscosity value.

[0260] The viscosities of the compositions of Examples 7 to 11 measured 24 hours after at 22 °C are described in detail in the following table. TIFF2025521194000034.tif71170

[0261] The viscosities of the compositions of Examples 12 and 14 measured 1 week after at 22 °C are described in detail in the following table. TIFF2025521194000035.tif42170

Claims

1. a) Polymerizable components containing (meth)acrylate-functionalized compounds; b) Thixotropic additives containing diurea-diurethane compounds A composition comprising the above, characterized in that component b) contains less than 0.1 moles of salt per urea group in component b) (excluding aprotic solvents).

2. Component a) is (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; isodecyl (meth)acrylate; n-dodecyl (meth) Acrylate; Tridecyl (meth)acrylate; Tetradecyl (meth)acrylate; Hexadecyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate; 2-Hydroxypropyl (meth)acrylate; 3-Hydroxypropyl (meth)acrylate; 4-Hydroxybutyl (meth)acrylate; 2-Methoxyethyl (meth)acrylate; 2-Ethoxyethyl (meth)acrylate; 2-Ethoxypropyl (meth)acrylate; 3-Ethoxypropyl (meth)acrylate; Tetrahydrofurfuryl (meth)acrylate Acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; benzyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; phenol (meth)acrylate; nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecane methanol (meth)acrylate; tert-butylcyclohexyl (meth)acrylate; trimethyl ethyl Chlohexyl (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; polyethylene glycol monomethyl ether (meth)acrylate; hydroxyethyl-butyl urethane (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate;The composition according to claim 1, characterized by comprising (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl)methyl (meth)acrylate; glycerol carbonate (meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and mono(meth)acrylate-functionalized monomers selected from mixtures thereof.

3. The composition according to claim 1, characterized in that component a) optionally comprises methyl methacrylate as a mixture with at least one other (meth)acrylate functionalized compound.

4. Component a) is bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate Acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediool di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10- Decanediol di(meth)acrylate; 1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecanediethanol di(meth)acrylate; glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate Relate; Trimethylolpropane tri(meth)acrylate; Trimethylolpropane di(meth)acrylate; Pentaerythritol di(meth)acrylate; Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Di(trimethylolpropane) di(meth)acrylate; Di(trimethylolpropane) tri(meth)acrylate; Di(trimethylolpropane) tetra(meth)acrylate; Sorbitol penta(meth)acrylate; Di(pentaerythritol) tetra(meth)acrylate;The composition according to claim 1, characterized by comprising di(pentaerythritol)penta(meth)acrylate; di(pentaerythritol)hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and poly(meth)acrylate functionalized monomers selected from mixtures thereof.

5. The composition according to claim 1, characterized in that component a) comprises a (meth)acrylate-functionalized oligomer selected from (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized polycarbonate oligomers, (meth)acrylate-functionalized polyester oligomers; (meth)acrylate-functionalized acrylic oligomers; and mixtures thereof.

6. Component a) is, - (meth)acrylate-functionalized monomers in amounts of 10% to 100%, 20% to 100%, 30% to 100%, 40% to 95%, or 50% to 90% by weight; and - (meth)acrylate-functionalized oligomers in amounts of 0% to 90%, 0% to 80%, 0% to 70%, 5% to 60%, or 10% to 50% by weight. The composition according to claim 1, characterized by containing the following:

7. Component b) is given by formula (I): (In the above formula, Each R' is alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, and -[(CR ａ R ｂ ) ｎ -O] ｍ -Y and -[(CR ｃ R ｄ ) ｐ -C(=O)O] ｑ - Selected independently from Z; The symbol ・ represents the bond point to the urethane group in formula (I); Each R ２ is independently a divalent group selected from an aliphatic group, an alicyclic group, an aromatic group, and an aromatic aliphatic group; Each R ３ These are independently divalent groups selected from aliphatic groups, alicyclic groups, aromatic groups, aromatic aliphatic groups, and heterocyclic groups; Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl, and arylalkyl groups; R ａ , R ｂ , R ｃ and R ｄ is independently selected from H and methyl, and is particularly H; Each n is independently equal to 2, 3, or 4, in particular when n is 2; m is in the range of 1 to 30, and in particular m is in the range of 2 to 25; p is in the range of 3 to 5, and in particular p is 5; q is in the range of 1 to 20, and in particular, q is in the range of 2 to 10. The composition according to claim 1, characterized by comprising a diurea-diurethane compound or a mixture of diurea-diurethane compounds of formula (I).

8. The composition according to claim 1, characterized in that component b) contains 0 to less than 0.1 moles, or 0 to 0.09 moles, or 0 to 0.07 moles, or 0 to 0.05 moles, or 0 to 0.03 moles, or 0 to 0.02 moles, or 0 to 0.001 moles of salt per urea group in component b).

9. The composition according to claim 1, characterized in that component b) contains less than 0.1 moles of surfactant per urea group in component b).

10. The composition according to claim 1, characterized in that component b) contains 5 to 80 mol%, particularly 15 to 75 mol%, and more specifically 25 to 65 mol%, of a diurea-diurethane compound, based on the total molar amount of a compound having one or more functional groups selected from urea, urethane, and mixtures thereof.

11. Component b) is given by formula (II): (In the above formula, R' and R ２ (This is as described in claim 7.) The composition according to claim 1, further comprising at least one diurethane compound.

12. The composition according to claim 11, characterized in that component b) contains, excluding the aprotic solvent, 20 to 95 mol%, particularly 25 to 85 mol%, and more specifically 35 to 75 mol%, of a diurethane compound of formula (II) based on the total molar amount of a compound having one or more functional groups selected from ureas, urethanes and mixtures thereof.

13. Each R' is alkyl and -[(CR ａ R ｂ ) ｎ -O] ｍ - Selected independently from Y; in particular, each R' is linear or branched C １ -C ３０ Alkyl and -[CH ２ -CH ２ -O] ｍ -Y (where Y is C) １ -C ２４ It is an alkyl group, and m is in the range of 1 to 25, independently selected from; more specifically, each R' is a branched C ８ -C ２０ Alkyl and -[CH ２ -CH ２ -O] ｍ -Y (where Y is C) １ -C ６ The composition according to claim 7, characterized in that it is alkyl and m is independently selected from 2 to 20.

14. Component b) a) Formula R'-O-C(=O)-NH-R ２ -Formula OCN-R to form at least one monoisocyanate adduct of NCO ２ A step of reacting at least one diisocyanate of NCO with at least one alcohol of formula R'-OH, wherein the molar ratio of the total amount of alcohol to the total amount of diisocyanate is in the range of 1.10 to 1.80, particularly 1.20 to 1.60, more specifically 1.25 to 1.45, and even more specifically 1.30 to 1.40; b) Formula (I): (In the above formula, R', R ２ and R ３ To form at least one diurea-diurethane compound of formula H (as described in claim 7), at least one monoisocyanate adduct obtained in step a) is formed in the presence of less than 0.2 moles of a metal salt per mole of the diamine used. ２ N-R ３ -NH ２ A step of reacting with at least one diamine. The composition according to claim 7, characterized in that it can be obtained by a method comprising the following.

15. The composition according to claim 14, characterized in that step b) is carried out in the presence of 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01 or 0 moles of salt per mole of diamine used.

16. The composition according to claim 14, characterized in that step b) is carried out in the presence of less than 0.2 moles of surfactant per mole of diamine used, particularly 0 to 0.19, 0 to 0.15, 0 to 0.1, 0 to 0.05, 0 to 0.02, 0 to 0.01, or 0 moles of surfactant.

17. The composition according to claim 1, characterized by containing component b) in an amount of 0.05% to 50% by weight, particularly 0.1% to 30% by weight, more specifically 0.2% to 20% by weight, and even more specifically 0.25% to 10% by weight, based on the weight of the composition.

18. The composition according to claim 1, further comprising a reinforcing material, particularly a reinforcing material selected from plant fibers, glass fibers, carbon fibers, carbon nanotubes, polyester fibers, aramid fibers, and mixtures thereof.

19. The composition according to claim 1, further comprising a tackifying resin; a rosin resin which may be particularly modified.

20. The composition according to claim 1, further comprising a radical initiator, particularly an azo compound or a peroxide compound.

21. - A step of mixing the composition according to claim 1 with a radical initiator and optionally an activator of the radical initiator; - Step of applying the obtained mixture onto a substrate. A method for preparing a crosslinking product, including [a specific compound / component].

22. Use of an additive containing a diurea-diurethane compound and less than 0.1 mole of salt per urea group in the additive to increase the viscosity of a polymerizable component containing a (meth)acrylate functionalized compound, and / or to impart thixotropic properties to the polymerizable component.

Images