Composition based on a polymerizable component and a thixotropic additive

Abstract

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

Description

[0001] Composition based on a polymerizable component and a thixotropic additive

[0002] TECHNICAL FIELD

[0003] The present invention relates to a composition based on a polymerizable component and a thixotropic additive as well as a two-component system containing said composition and a process for preparing a crosslinked product from said composition.

[0004] The invention also relates to the use of an additive for increasing the viscosity and / or imparting thixotropic properties to a polymerizable component.

[0005] PRIOR ART

[0006] Compositions based on (meth)acrylate functionalized compounds are widely used in many fields, such as coatings, adhesives and composite materials. Increasing the viscosity of a composition based on a (meth)acrylate functionalized compound using a rheology additive advantageously facilitates the storage, handling and use of these compositions. Furthermore, the phenomenon of sedimentation of fillers in a composition based on (meth)acrylate functionalized compounds leads to inhomogeneities in the properties of the resulting material; it is advisable to provide anti-sedimentation properties to limit this phenomenon.

[0007] However, the implementation of compositions based on compounds functionalized by (meth)acrylate requires special precautions since these compounds, in particular monomers functionalized by (meth)acrylate, can have a high saturated vapor pressure and evaporate easily. This results in a modification of the concentration of the composition and the need to set up specific installations to trap the released vapors.

[0008] There are rheology additive technologies, including fatty acid diamides and silicas, which are suitable for addressing this issue but require activation by heating and / or high shear causing self-heating.

[0009] Diurea-diurethane rheology modifiers are a good alternative to these rheology additives since they are liquid and do not require hot activation steps. Thus, they can be easily and directly incorporated into the composition to be thickened at room temperature (20-25°C). Patent application EP 3 381 961 A1 describes molding compositions prepared from a monomer composition comprising a diurea-diurethane thixotropic additive. However, the thixotropic additive described in this application contains salts such as lithium chloride or a surfactant. Lithium salts can cause corrosion problems when the composition is applied to metal substrates and generate uncontrolled species due to its Lewis acidity.Furthermore, lithium salts, particularly LiCl, are toxic compounds and formulations containing them are subject to current regulations on the classification, labelling and packaging of chemical products.

[0010] There is therefore a need for new compositions based on (meth)acrylate functionalized compounds and a thixotropic agent comprising a diurea-diurethane compound not containing salt or surfactant. Said thixotropic additive is stable, easily prepared without a residual diisocyanate distillation step and has rheological performances at least equivalent, or even better, than comparable additives of the prior art.

[0011] After extensive research, the Applicant has developed a composition that meets this need.

[0012] SUMMARY OF THE INVENTION

[0013] The invention relates to a composition comprising: a) a polymerizable component comprising a (meth)acrylate functionalized compound; b) a thixotropic additive comprising a diurea-diurethane compound; component b) containing less than 0.1 moles of salt per urea group in component b).

[0014] The invention also relates to a two-component system comprising:

[0015] - a first cartridge comprising a radical initiator;

[0016] - a second cartridge comprising the composition according to the invention and optionally an activator of the radical initiator; the first cartridge being kept separate from the second cartridge.

[0017] The invention also relates to a process for preparing a crosslinked product comprising the following steps:

[0018] - mixing the composition according to the invention with a radical initiator and optionally an activator of the radical initiator;

[0019] - apply the mixture obtained on a substrate.

[0020] The invention also relates to the use of an additive comprising a diurea-diurethane compound and containing less than 0.1 moles of salt per urea group in the additive for increasing the viscosity and / or imparting thixotropic properties to a polymerizable component comprising a (meth)acrylate functionalized compound.

[0021] DETAILED DESCRIPTION

[0022] Definitions

[0023] In this application, the terms "includes a" and "includes a" mean respectively "includes one or more" and "includes one or more".

[0024] Unless otherwise stated, percentages by weight in a compound or composition are expressed relative to the weight of the compound or composition.

[0025] The term "diurea-diurethane compound" means a compound having two urea functions and two urethane functions.

[0026] The term "diurethane compound" means a compound having two urethane functions and no urea functions.

[0027] The term "polyurea-diurethane compound" means a compound having two urethane functions and at least four urea functions.

[0028] The term "urea function" or "urea group" means a -NH-C(=O)-NH- chain,

[0029] The term "urethane function" or "urethane group" means a -NH-C(=O)-O- or -OC(=O)-NH- chain,

[0030] The term "solvent" means a liquid having the property of dissolving, diluting or lowering the viscosity of other substances without chemically modifying them and without modifying itself.

[0031] The term "aprotic solvent" means a solvent that does not have an acidic hydrogen atom. In particular, an aprotic solvent does not comprise a hydrogen atom bonded to a heteroatom (O, N or S). The term "salt" means an ionic compound. A salt may be inorganic or organic, preferably inorganic. For the purposes of the present invention, the term "salt" does not include ionic surfactants.

[0032] The term "surfactant" means a compound capable of modifying the surface tension between two surfaces. A surfactant can notably be an amphiphilic compound, that is to say that it has two parts of different polarity, one lipophilic (which retains fatty substances) is apolar, the other hydrophilic (miscible in water) is polar.

[0033] The term "alkyl" means a monovalent saturated acyclic group of the formula -CnEhn+i. An alkyl can be straight or branched. A C1-C30 alkyl means an alkyl having 1 to 30 carbon atoms.

[0034] The term "alkenyl" means a monovalent acyclic hydrocarbon group having one or more C=C double bonds. Alkenyl can be straight or branched. C2-C30 alkenyl means alkenyl having 2 to 30 carbon atoms.

[0035] The term "cycloalkyl" means a monovalent cyclic hydrocarbon group. A cycloalkyl can be saturated or unsaturated. A cycloalkyl is non-aromatic. A C5-C12 cycloalkyl means a cycloalkyl having 5 to 12 carbon atoms

[0036] The term "aryl" means a monovalent aromatic hydrocarbon group. C6-C12 aryl means an aryl having 6 to 12 carbon atoms.

[0037] The term "alkylaryl" means an alkyl group substituted with an aryl group.

[0038] The term "aliphatic" means a non-aromatic acyclic compound or group. It may be linear or branched, saturated or unsaturated, substituted or unsubstituted. It may include one or more bonds / functions, for example chosen from ether, ester, amine and mixtures thereof.

[0039] The term "cycloaliphatic" means a non-aromatic compound or group comprising a ring having only carbon atoms as ring atoms. It may be substituted or unsubstituted.

[0040] The term "aromatic" means a compound or group comprising an aromatic ring, i.e., complying with Hückel's rule of aromaticity, in particular a compound comprising a phenyl group. It may be substituted or unsubstituted. It may comprise one or more bonds / functions as defined for the term "aliphatic".

[0041] The term "araliphatic" means a compound or group comprising an aliphatic part and an aromatic part.

[0042] The term "heterocyclic" means a compound or group comprising a ring having at least one heteroatom selected from N, O and / or S as a ring atom. It may be substituted or unsubstituted. It may be aromatic or non-aromatic.

[0043] The composition according to the invention comprises a polymerizable component, also called component a). Component a) may in particular comprise all of the polymerizable compounds of the composition according to the invention. In particular, component a) may in particular comprise all of the ethylenically unsaturated compounds of the composition according to the invention. These compounds may in particular be intended to be polymerized, in particular by radical polymerization reaction.

[0044] For the purposes of the invention, an "ethylenically unsaturated compound" means a compound that comprises a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. A polymerizable carbon-carbon double bond is generally comprised in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, preferably selected from acrylate, methacrylate and vinyl, more preferably selected from acrylate and methacrylate. Carbon-carbon double bonds of a phenyl ring are not considered to be polymerizable carbon-carbon double bonds.

[0045] Component a) comprises a (meth)acrylate functionalized compound. Component a) may comprise a mixture of (meth)acrylate functionalized compounds.

[0046] As used herein, the term "(meth)acrylate-functionalized compound" means a compound comprising at least one (meth)acryloyloxy group, in particular an acryloyloxy group. The term "(meth)acryloyloxy group" encompasses acryloyloxy groups (-O-CO-CH=CH2) and methacryloyloxy groups (-O-CO-C(CH3)=CH2). The total amount of (meth)acrylate-functionalized compound in component a) may be 20 to 100%, in particular 30 to 100%, 40 to 100%, 50 to 100%, 60 to 100%, 70 to 100%, 80 to 100%, or 90 to 100%, by weight based on the weight of component a). According to one embodiment, component a) does not comprise polymerizable compounds other than compounds functionalized by (meth)acrylate.

[0047] Component a) may in particular comprise a (meth)acrylate functionalized compound chosen from a (meth)acrylate functionalized monomer, a (meth)acrylate functionalized oligomer, and mixtures thereof. In particular, component a) may comprise a (meth)acrylate functionalized monomer and optionally a (meth)acrylate functionalized oligomer.

[0048] Component a) may in particular comprise a monomer functionalized with (meth)acrylate. Component a) may comprise a mixture of monomers functionalized with (meth)acrylate.

[0049] The (meth)acrylate functionalized monomer may have a molecular weight of less than 600 g / mol, in particular from 70 to less than 550 g / mol, more particularly from 80 to 450 g / mol, more particularly from 90 to 350 g / mol.

[0050] The (meth)acrylate functionalized monomer may have 1 to 6 (meth)acryloyloxy groups, in particular 1 to 4 (meth)acryloyloxy groups.

[0051] The (meth)acrylate functionalized monomer may comprise a mixture of (meth)acrylate functionalized monomers having different functionalities. For example, the (meth)acrylate functionalized monomer may comprise a mixture of a (meth)acrylate functionalized monomer containing a single acryloyloxy or methacryloyloxy group per molecule (referred to herein as a "mono(meth)acrylate functionalized monomer") and a (meth)acrylate functionalized monomer containing 2 or more, preferably 2 to 6, acryloyloxy and / or methacryloyloxy groups per molecule (referred to herein as a "poly(meth)acrylate functionalized monomer").

[0052] Component a) may in particular comprise a mono(meth)acrylate functionalized monomer. Component a) may in particular comprise a mixture of mono(meth)acrylate functionalized monomers. A mono(meth)acrylate functionalized monomer may advantageously function as a reactive diluent and reduce the viscosity of the composition according to the invention. Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, (meth)acrylic acid, mono(meth)acrylate esters of aliphatic alcohols (the alcohol may be straight or branched chain and may be a monoalcohol, a dialcohol or a polyalcohol, provided that only one hydroxyl group is esterified by a (meth)acrylic acid); mono(meth)acrylate esters of cycloaliphatic or heterocyclic alcohols; mono(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols);mono(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylate esters of oligomeric and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; caprolactone mono(meth)acrylates; as well as alkoxylated (eg, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.;

[0053] Component a) may in particular comprise a monomer functionalized by mono(meth)acrylate chosen from (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;

[0054] 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; trimethylolpropane formalin cyclic (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;Hydroxyl ethyl-butyl urethane (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; as well as alkoxylated (eg, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.;

[0055] In particular, component a) may in particular comprise a monomer functionalized by mono(meth)acrylate chosen from (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; (meth)acrylate of trimethylolpropane cyclic formai; (meth)acrylate of isocarboxylic acid; (meth)acrylate of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl; (meth)acrylate of (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl;1,3-Dioxan-5-yl (meth)acrylate; (1,3-Dioxan-4-yl)methyl (meth)acrylate; as well as alkoxylated (eg, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.;

[0056] More particularly, component a) may in particular comprise methyl methacrylate optionally in a mixture with at least one other compound functionalized by (meth)acrylate.

[0057] Component a) may in particular comprise a monomer functionalized by poly(meth)acrylate.

[0058] Examples of poly(meth)acrylate functionalized monomers include acrylate and methacrylate esters of polyols (organic compounds containing two or more hydroxyl groups per molecule, e.g., 2 to 6). 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, norbornene dimethanol, norbornene dimethanol, tricyclodecanediol, tricyclodecane dimethanol, 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, a polyethylene glycol, a polypropylene glycol, a polytetramethylene glycol, a poly(ethylene glycol-co-propylene glycol), an alditol (i.e. erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, glactitol, fucitol or iditol), a dianhydrohexitol (i.e. isosorbide, isomannide or isoidide), tris(2-hydroxyethyl)isocyanurate, a polybutadiene polyol, as well as alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof, and derivatives obtained by ring-opening polymerization of a lactone (e.g. s-caprolactone) initiated with one of the aforementioned polyols. Such polyols may be totally or partially esterified (with an acid (meth)acrylic, (meth)acrylic anhydride, (meth)acryloyl chloride or the like), provided that they contain at least two (meth)acryloyloxy functional groups per molecule.,

[0059] In particular, component a) may in particular comprise a poly(meth)acrylate functionalized monomer chosen from 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-denanediol 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;as well as alkoxylated (eg, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.;

[0060] More particularly, component a) may in particular comprise a monomer functionalized by poly(meth)acrylate chosen from 1,6-hexanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, and mixtures thereof.

[0061] Component a) may comprise from 0 to 100%, in particular from 5 to 100%, from 10 to 100%, from 15 to 100%, from 20 to 95%, from 25 to 95%, from 30 to 95%, from 35 to 90%, from 40 to 90%, or from 50 to 90%, by weight of (meth)acrylate functionalized monomer based on the weight of component a). Component a) may comprise from 0 to 60%, from 5 to 60%, from 10 to 60%, from 15 to 60%, from 20 to 60%, from 25 to 60%, from 30 to 60%, from 35 to 60%, from 40 to 60% or from 45 to 60% by weight of (meth)acrylate functionalized monomer based on the weight of component a). Alternatively, component a) may comprise from 60 to 100%, from 65 to 100%, from 70 to 100%, from 75 to 100%, from 80 to 100%, from 85 to 100%, from 90 to 100%, or from 95 to 100%, by weight of (meth)acrylate functionalized monomer based on the weight of component a).

[0062] Component a) may in particular comprise an oligomer functionalized with (meth)acrylate. Component a) may comprise a mixture of oligomers functionalized with (meth)acrylate.

[0063] The (meth)acrylate functionalized oligomer may be selected to increase the flexibility, strength and / or modulus, among other attributes, of a product obtained by polymerization of the composition according to the present invention.

[0064] The (meth)acrylate functionalized oligomer may have 1 to 18 (meth)acryloyloxy groups, in particular 2 to 6 (meth)acryloyloxy groups, more particularly 2 to 6 acryloyloxy groups. The (meth)acrylate functionalized oligomer may have a number average molecular weight greater than or equal to 600 g / mol, in particular 800 to 15,000 g / mol, more particularly 1,000 to 5,000 g / mol.

[0065] In particular, component a) may in particular comprise an oligomer functionalized by (meth)acrylate chosen from urethane oligomers functionalized by (meth)acrylate, epoxy oligomers functionalized by (meth)acrylate, polyether oligomers functionalized by (meth)acrylate, polydiene oligomers functionalized by (meth)acrylate, polycarbonate oligomers functionalized by (meth)acrylate, polyester oligomers functionalized by (meth)acrylate; acrylic oligomers functionalized by (meth)acrylate; and mixtures thereof.

[0066] (Meth)acrylate functionalized urethane oligomers (sometimes also referred to as "polyurethane (meth)acrylate oligomers") suitable for use in the polymerizable compositions of the present invention include methanes based on at least one polyol, at least one polyisocyanate, and at least one (meth)acrylate and hydroxyl functionalized compound (also referred to as hydroxyl functionalized (meth)acrylate).

[0067] The (meth)acrylate-functionalized urethane oligomers may be prepared by reacting a polyisocyanate (e.g., aliphatic, cycloaliphatic, heterocyclic, or aromatic diisocyanate or triisocyanate) with a polyol (including a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol, or a polydiene polyol such as a polybutadiene polyol, or combinations thereof), to form isocyanate-terminated oligomers which are then reacted with a hydroxyl-functionalized (meth)acrylate (such as hydroxyethyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, the (meth)acrylate-functionalized urethane oligomers may contain two, three,four or more (meth)acrylate functional groups per molecule. Other orders of addition may also be practiced to prepare the (meth)acrylate-functionalized urethane oligomer. For example, a hydroxyl-functionalized (meth)acrylate may first be reacted with a polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which may then be reacted with a polyol. Alternatively, all components may be combined and reacted at the same time. Examples of suitable (meth)acrylate-functionalized epoxy oligomers include the reaction products of (meth)acrylic acid (or a synthetic equivalent thereof, such as acid chloride, alkyl ester, or anhydride) with an epoxy resin comprising at least one epoxide group (particularly at least one group selected from glycidyl ether, glycidyl ester, or combinations thereof). The epoxy resin may, in particular,be selected from 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, oxide of vinylcyclohexene, 4- vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxy cyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylenebis(3,4-epoxy cyclohexanecarboxylate),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 a polyether polyol obtained by the addition of one or more alkylene oxides to an aliphatic polyhydric alcohol, such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of long-chain aliphatic dibasic acids, monoglycidyl ethers of higher aliphatic alcohols, monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by the addition of alkylene oxide to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutylstearic acid, epoxyoctylstearic acid, epoxidized linseed oil, epoxidized polybutadiene, and the like.,

[0068] Suitable (meth)acrylate functionalized polyether oligomers include, but are not limited to, the reaction products of reacting (meth)acrylic acid (or a corresponding synthetic equivalent, such as acid chloride, alkyl ester, or anhydride) with at least one polyetherol that corresponds to a polyether polyol (such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or a copolymer thereof). Suitable polyetherols may be linear or branched substances containing ether linkages and terminal hydroxyl groups. Polyetherols may be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with a starting molecule. Suitable starting molecules include water, polyhydroxyl-functionalized materials, polyester polyols, and amines.

[0069] Exemplary (meth)acrylate-functionalized polydiene oligomers include the reaction products of (meth)acrylic acid (or a corresponding synthetic equivalent, such as acid chloride, alkyl ester, or anhydride) with hydroxyl-terminated polydiene polyols, including a hydroxyl-terminated polybutadiene polyol.

[0070] Exemplary (meth)acrylate functionalized polycarbonate oligomers include the reaction products of (meth)acrylic acid (or a corresponding synthetic equivalent, such as acid chloride, alkyl ester, or anhydride) with hydroxyl-terminated polycarbonate polyols.

[0071] Exemplary (meth)acrylate-functionalized polyester oligomers include the reaction products of (meth)acrylic acid (or a corresponding synthetic equivalent, such as acid chloride, alkyl ester, or anhydride) with hydroxyl-terminated polyester polyols. The reaction process may be conducted such that all, or essentially all, of the hydroxyl groups of the polyester polyol have been (meth)acrylated, particularly in cases where the polyester polyol is difunctional. The polyester polyols may be prepared by polycondensation reactions of polyhydroxyl-functionalized components (particularly, diols) and poly(carboxylic acid)-functionalized compounds (particularly, dicarboxylic acids and anhydrides).The polyhydroxyl-functionalized and poly(carboxylic acid)-functionalized components may each have linear, branched, cycloaliphatic, or aromatic structures and may be used individually or as mixtures.

[0072] Suitable (meth)acrylate-functionalized acrylic oligomers (sometimes also referred to in the prior art as "acrylic oligomers") include oligomers that can be described as substances having an acrylic backbone that is functionalized with one or more (meth)acrylate groups (which may be at a terminus of the oligomer or pendant to the acrylic backbone). The acrylic backbone may be a homopolymer, a random copolymer, or a block copolymer composed of repeating units of acrylic-type monomers. The acrylic-type monomers may be any monomeric (meth)acrylate such as C1-C6 alkyl (meth)acrylates as well as functionalized (meth)acrylates such as (meth)acrylates bearing hydroxyl, carboxylic acid, and / or epoxy groups.The acrylic (meth)acrylate oligomers may be prepared using any procedure known in the state of the art, such as oligomerization of monomers, at least a portion of which is functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylate) to obtain a functionalized oligomer intermediate, which is then reacted with one or more (meth)acrylate-containing reactants to introduce the desired (meth)acrylate functional groups.

[0073] In particular, component a) may in particular comprise an oligomer functionalized with (meth)acrylate chosen from urethane oligomers functionalized with (meth)acrylate, polydiene oligomers functionalized with (meth)acrylate, acrylic oligomers functionalized with (meth)acrylate, and mixtures thereof.

[0074] Component a) may comprise from 0 to 100%, in particular from 5 to 100%, from 10 to 100%, from 15 to 100%, from 20 to 95%, from 25 to 95%, from 30 to 95%, from 35 to 90%, from 40 to 90%, or from 50 to 90%, by weight of (meth)acrylate functionalized oligomer based on the weight of component a). Component a) may comprise 0-60%, 5-60%, 10-60%, 15-60%, 20-60%, 25-60%, 30-60%, 35-60%, 40-60% or 45-60% by weight of (meth)acrylate functionalized oligomer based on the weight of component a). Alternatively, component a) may comprise from 60 to 100%, from 65 to 100%, from 70 to 100%, from 75 to 100%, from 80 to 100%, from 85 to 100%, from 90 to 100%, or from 95 to 100%, by weight of (meth)acrylate functionalized oligomer based on the weight of component a).

[0075] According to a particular embodiment, component a) comprises

[0076] - from 10 to 100%, from 20 to 100%, from 30 to 100%, from 40 to 95%, or from 50 to 90%, by weight of monomer functionalized by (meth)acrylate; and - from 0 to 90%, from 0 to 80%, from 0 to 70%, from 5 to 60%, or from 10 to 50%, by weight of oligomer functionalized by (meth)acrylate.

[0077] The composition according to the invention comprises a thixotropic additive, also called component b). The thixotropic additive is in particular used to increase the viscosity and / or confer thixotropic properties to the composition according to the invention. For the purposes of the invention, the term "confer thixotropic properties on a composition" means increasing the viscosity of a composition when the composition is at rest (no shear stress is applied) and lowering the viscosity of a composition when the composition is subjected to shear stress in a reversible manner with a memory of the history or time dependence. The increase and decrease in viscosity can be determined relative to a control composition not comprising a thixotropic additive.

[0078] Component b) comprises a diurea-diurethane compound. Component b) may comprise a mixture of diurea-diurethane compounds. Component b) may further comprise an aprotic solvent.

[0079] Component b) is stable despite containing little or no salt. Component b) contains less than 0.1 moles of salt per urea group in component b) (excluding any aprotic solvent). The number of urea groups is determined over all the compounds contained in component b) (excluding any aprotic solvent). The diurea-diurethane compound(s) contains(s) 2 urea groups. If component b) contains 1 mole of diurea-diurethane compound(s) and there is no other compound with at least one urea group in component b), then component b) contains less than 0.2 moles of salt.

[0080] In particular, component b) may contain from 0 to less than 0.1 moles, or from 0 to 0.09 moles, or from 0 to 0.07 moles, or from 0 to 0.05 moles, or from 0 to 0.03 moles, or from 0 to 0.01 moles, or from 0 to 0.001 moles, of salt per urea group in component b) (excluding any aprotic solvent).

[0081] More particularly, component b) may contain less than 1%, 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%, by weight of LiCl relative to the weight of component b) (excluding any aprotic solvent). More particularly, component b) may contain less than 1.6%, 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%, by weight of LiNOs relative to the weight of component b) (excluding any aprotic solvent).

[0082] The salt may in particular be chosen from a metal salt, an ionic liquid and an ammonium salt. In particular, the salt may be a metal salt chosen from a halide, an acetate, a formate, a nitrate. More particularly, the salt may be a lithium salt. Even more particularly, the salt may be a lithium salt chosen from LiCl, LiNCh, LiBr and mixtures thereof.

[0083] Component b) may in particular be stable without the addition of a stabilizer, such as in particular a surfactant. According to a particular embodiment, component b) according to the invention contains less than 0.1 moles of surfactant per urea group in component b).

[0084] In particular, component b) may contain from 0 to 0.1 moles, or from 0 to 0.08 moles, or from 0 to 0.06 moles, or from 0 to 0.04 moles, or from 0 to 0.02 moles, or from 0 to 0.01 moles, or from 0 to 0.001 moles, of surfactant per urea group in component b) (excluding any aprotic solvent).

[0085] More particularly, component b) may contain 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%, by weight of surfactant relative to the weight of component b) (excluding any aprotic solvent).

[0086] The surfactant may in particular be chosen from an anionic surfactant, a cationic surfactant, a non-ionic surfactant, a zwitterionic surfactant and mixtures thereof. The surfactant may in particular have an HLB of 8 to 12.

[0087] Examples of anionic surfactants are sulfonates, sulfates, sulfosuccinates, phosphates and carboxylates. Examples of cationic surfactants are quaternary ammonium salts (including tetraalkylammonium salts and quaternary ammonium esters or esterquats). Examples of non-ionic surfactants are alkoxylated (including ethoxylated and / or propoxylated) fatty alcohols, alkyl glycosides, fatty acid esters (including glycol esters, glycerol esters, sorbitan esters or sucrose esters of fatty acids) and alkoxylated (including ethoxylated and / or propoxylated) fatty acid esters. Examples of zwitterionic surfactants are betaines, imidazolines, sultaines, phospholipids, and amine oxides.

[0088] 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 particularly less than 0.1 mg KOH / g, more particularly still 0 mg KOH / g. The NCO value may be measured according to the method described below.

[0089] Diurea-diurethane compound

[0090] Component b) comprises a diurea-diurethane compound. Component b) may comprise a mixture of diurea-diurethane compounds.

[0091] The diurea-diurethane compound may correspond to a compound of formula (I): in which the groups R', R2 and R3 are as defined below.

[0092] Preferably, the compounds of formula (I) do not contain a tertiary amine function or a quaternary ammonium function.

[0093] The compound(s) of formula (I) may in particular correspond to the reaction product(s) of at least one alcohol of formula R' -OH, of at least one diisocyanate of formula OCN-R2-NCO and of at least one diamine of formula H2N-R3-NH2.

[0094] Component b) may in particular comprise 5% to 80%, in particular 15% to 75%, more particularly 25% to 65%, in moles of compound of formula (I) relative to the total molar quantity of compounds having one or more functions chosen from urea, urethane, and their mixtures (excluding any aprotic solvent).

[0095] Group R'

[0096] A compound of formula (I) contains two R' groups. The R' groups in a single compound of formula (I) may be the same or different. Component b) may comprise a mixture of compounds of formula (I) having identical R' groups. Component b) may comprise a mixture of compounds of formula (I) that are distinguished by their R' groups. For example, some compounds in the mixture may have identical R' groups and some compounds in the mixture may have different R' groups.

[0097] Each R' group may originate from the use of an alcohol of formula R'-OH to form the diurea-diurethane compound(s) of formula (I). The R' group may correspond to the residue of an alcohol of formula R'-OH without the OH group. The R' groups and the corresponding alcohols of formula R'-OH described below are also applicable to the process for preparing the diurea-diurethane compound described below.

[0098] Each R' is independently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, •-[(CR a Rb)nO] m -Y and •-[(CR c Rd) P -C(=O)O] q -Z; the symbol • represents a point of attachment to a urethane group of formula (I);

[0099] Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and alkylaryl;

[0100] R a , Rb, Rc and Rd are independently selected from H and methyl, in particular H; each n is independently 2, 3 or 4, in particular n is 2; m ranges from 1 to 30, in particular m ranges from 2 to 25; p ranges from 3 to 5, in particular p is 5; q ranges from 1 to 20, in particular q ranges from 2 to 10.

[0101] An R' group may be an alkyl, in particular a C1 to C30 alkyl.Examples of suitable alkyl groups are methyl, propyl, 1-methylethyl, butyl, Xi-2-methylpropyl, pentyl, Xi-3-methylbutyl, hexyl, Xi-4-methylpentyl, heptyl, Xi-s-methylhexyl, octyl, Xi-6-methylheptyl, 2-ethylhexyl, nonyl, Xi-7-methyloctyl, decyl, Xi-s-methylnonyl, undecyl, Xi-9-methyldecyl, dodecyl, Xi-10-methylundecyl, tridecyl, Xi-11-methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, Xi-12-methyltridecyl, pentadecyl, Xi-13-methyltetradecyl, hexadecyl, Xi-14-methylpentadecyl, heptadecyl, Xi-15-methylhexadecyl, octadecyl, Xi-16-methylheptadecyl, nonadecyl, Xi-17-methyloctadecyl, icosyl, Xins-methylnonadecyl, henicosyl, Xi-19-methylicosyl, docosyl, Xi-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 isomers thereof, wherein X. a-b represents an integer that can take any value from a to b, X a -b indicating the position of the substituent in the alkyl group. The Xi-11-methyldodecyl group is a dodecyl group substituted by a methyl group in the 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 position, e.g. 11-methyldodecyl, 2-methyldodecyl. Isomers are alkyl groups with the same number of carbon atoms but a different substitution pattern, e.g. an ethyl substituent instead of a methyl substituent or a greater number of methyl substituents. Thus, the 2,5,9-trimethyldecyl group is an isomer of the 11-methyldodecyl or 2-methyldodecyl group. The above-mentioned alkyl groups can in particular be linked to the urethane group in position 1. Thus, the 2,5,9-trimethyldecyl group can be represented by the following formula: in which the broken line represents a point of attachment to a urethane group of the compound of formula (I).

[0102] An R' group may be alkenyl, especially C2 to C30 alkenyl. Examples of suitable alkenyl groups are hex-Y2-5-enyl, hept-Y2-6-enyl, oct-Y2-7-enyl, non-Y2-8-enyl, dec-Y2-9-enyl, undec-Y2-io-enyl, dodec-Y2-n-enyl, tridec-Y2-i2-enyl, tetradec-Y2-i3-enyl, hexadec-Y2-is-enyl, octadec-Y2-i7-enyl, icos-Y2-i9-enyl, docos-Y2-2i-enyl, heptadeca-8,l l-dienyl, octadeca-9,12-dienyl, nonadeca-10,13-dienyl, icosa-l l,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, icosa-8,11,14-trienyl, and icosa-1,14,17-trienyl, in which Y a -b represents an integer that can take any value from a to b, Y a-b indicating the position of the double bond in the alkenyl group. The hex-Y2-5-enyl group is a hexenyl group in which the double bond can be in position 2, 3, 4 or 5, which corresponds to the hex-2-enyl, hex-3-enyl, hex-4-enyl and hex-5-enyl groups. The above-mentioned alkenyl groups can in particular be linked to the urethane group in position 1. Thus, the hex-2-enyl group can be represented by the following formula: in which the broken line represents a point of attachment to a urethane group of the compound of formula (I).

[0103] An R' group may be cycloalkyl, especially C5-C12 cycloalkyl. Examples of suitable cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, cycloctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl. An R' group may be aryl, especially C6-C12 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-xylyl and mesityl.

[0104] An R' group may be alkylaryl, especially C7-C12 alkylaryl. Examples of suitable alkylaryl groups are benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 2-phenylbutyl.

[0105] A group R' can be a group •-[(CR a Rb)ii-O] m -Y in which

[0106] Y is selected from alkyl, alkenyl, cycloalkyl, aryl and alkylaryl;

[0107] R aand Rb are independently selected from H and methyl, especially H; each n is independently 2, 3 or 4, especially n is 2; m ranges from 1 to 30, especially m ranges from 2 to 25.

[0108] Examples of groups •-[(CR a Rb)ii-O] m -Y are the alkoxylated derivatives of the alkyl, alkenyl, cycloalkyl, aryl and alkylaryl groups described above. Particularly suitable are polyethylene glycols, polypropylene glycols, co-poly (ethylene glycol / propylene glycol) and polytetramethylene glycols comprising a terminal group chosen from an alkyl, alkenyl, cycloalkyl, aryl and alkylaryl group as described above. These groups can in particular be obtained by reacting an alcohol R' OH having a group R' as described above with a cyclic compound chosen from ethylene oxide, propylene oxide, tetrahydrofuran and mixtures thereof.

[0109] A group R' may be a group *-[(CRcRd)pC(=O)O]qZ in which Z is selected from alkyl, alkenyl, cycloalkyl, aryl and alkylaryl;

[0110] R c and Rd are independently selected from H and methyl, in particular H; p ranges from 3 to 5 in particular p is 5; q ranges from 1 to 20, in particular q ranges from 2 to 10.

[0111] Examples of *-[(CRcRd)pC(=O)O]qZ groups are the esterified derivatives of the alkyl, alkenyl, cycloalkyl, aryl and alkylaryl groups described above. Particularly suitable are polyesters comprising a terminal group selected from an alkyl, alkenyl, cycloalkyl, aryl and alkylaryl group as described above. These groups can in particular be obtained by reacting an alcohol R' OH having a group R' as described above with a lactone selected from gamma-butyrolactone, delta-valerolactone, epsilon-caprolactone and mixtures thereof. According to one embodiment, each R' is independently selected from alkyl and •-[(CR a Rb)ii-O]mY as defined above. In particular, each R' is independently selected from linear or branched C1-C30 alkyl and •-[CH2-CH2-O] m -Y with Y being C1-C24 alkyl and m is from 1 to 25. More particularly, each R' is independently selected from C8-C20 branched alkyl and •-[CH2-CH2-O]m -Y with Y being a C1-C6 alkyl and m ranging from 2 to 20.

[0112] More particularly, each R' is independently selected from octyl, Xi-6-methylheptyl, 2-ethylhexyl, nonyl, Xi-7-methyloctyl, decyl, Xi-s-methylnonyl, undecyl, Xi-9-methyldecyl, dodecyl, Xi-10-methylundecyl, tridecyl, Xi-11-methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, Xi-12-methyltridecyl, pentadecyl, Xi-13-methyltetradecyl, hexadecyl, Xi-14-methylpentadecyl, heptadecyl, Xi-15-methylhexadecyl, octadecyl, Xi-16-methylheptadecyl, nonadecyl, Xi-17-methyloctadecyl, icosyl, Xis-methylnonadecyl, henicosyl, Xi-19-methylicosyl, docosyl, Xi-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-CH3and •-[CH2-CH2-O] m -CH3 with m = 2 to 20.

[0113] A compound of formula (I) may have the same or different R' groups. A compound of formula (I) may have R' groups having a different molecular mass. A compound of formula (I) may have R' groups having a different chemical nature, in particular hydrophilicity.

[0114] Component b) may comprise a compound of formula (I) in which the R' groups are the same. Component b) may comprise a compound of formula (I) in which the R' groups are different. Component b) may comprise a compound of formula (I) in which the R' groups are the same and a compound of formula (I) in which the R' groups are different.

[0115] Component b) may in particular comprise a compound of formula (I) in which the R' groups are identical. The R' groups may be identical and correspond to Ri, Ri being a linear or branched C1-C30 alkyl, in particular a linear or branched C8-C20 alkyl, more particularly a branched C8-C20 alkyl as described above. Component b) may in particular comprise a mixture of compounds of formula (I), said mixture containing at least one compound of formula (I) in which the R' groups are different. The mixture may contain at least one compound of formula (I) in which the R' groups have a different molecular mass. The mixture may contain at least one compound of formula (I) in which the R' groups have a different chemical nature, in particular a different hydrophilicity.

[0116] A thixotropic additive comprising a compound of formula (I) in which the R' groups are different can in particular be obtained by using a mixture of at least 2 different R'-OH alcohols, corresponding in particular to R4-OH and R5-OH, to form the compound(s) of formula (I).

[0117] In particular, the mixture of compounds of formula (I) may contain:

[0118] - at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4, the other R' group corresponding to R5;

[0119] - optionally a compound of formula (I) in which the R' groups are identical and correspond to R4;

[0120] - optionally a compound of formula (I) in which the R' groups are identical and correspond to R5;

[0121] R4 and R5 being as previously defined for R'.

[0122] The mixture of compounds of formula (I) may in particular comprise a compound of formula (Ia), optionally in a mixture with a compound of formula (Ib) and / or a compound of formula (Ic): in which all R4 groups are the same and as previously defined for R'; all R5 groups are the same and as previously defined for R'; the R4 groups are different from R5.

[0123] The R4 group may be more hydrophobic than the R5 group; and / or the R5 group may have a higher molecular weight than the R4 group.

[0124] The molecular masses of the R4 and R5 groups may be different. In particular, the R4 group may have a lower molecular mass than that of the R5 group. More particularly, the difference between the molecular mass of the R4 group and that of the R5 group may be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0125] The chemical natures of the R4 and R5 groups can be different. In particular, the R4 group can be more hydrophobic than the R5 group.

[0126] The groups R4 and R5 can be groups of formula •-[(CR a Rb)ii-O] m -Y having different molecular masses, Y, R a , Rb, n and m being as defined above. Alternatively, the group R4 may be a linear or branched C1-C30 alkyl and the group R5 may be a group of formula •-[(CR a Rb)nO] m -Y in which Y, R a , Rb, n and m are as defined previously.

[0127] The total molar quantity of group R5, in particular of the least hydrophobic group and / or of the group having the highest molecular mass, may in particular represent more than 20%, in particular 25 to 95%, 30 to 90%, 35 to 85%, or 40 to 80%, of the total molar quantity of groups R4 and R5 of all the products having one or more functions chosen from urea, urethane, and their mixtures in component b) (excluding any aprotic solvent).

[0128] Component b) may in particular comprise a mixture of compounds of formula (I), said mixture containing at least two different compounds of formula (I) in which the R' groups are different. The mixture may contain at least two different compounds of formula (I) in which the R' groups have a different molecular mass. The mixture may contain at least two different compounds of formula (I) in which the R' groups have a different chemical nature, in particular hydrophilicity.

[0129] A thixotropic additive comprising at least two compounds of formula (I) in which the R' groups are different can in particular be obtained by using a mixture of at least 3 different R'-OH alcohols, corresponding in particular to R4-OH, R5-OH and RÔ-OH, to form the diurea-diurethane compound(s) of formula (I).

[0130] The mixture of compounds of formula (I) may contain:

[0131] - at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4, the other R' group corresponding to R5; and

[0132] - at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4, the other R' group corresponding to RÔ;

[0133] - optionally a compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R5, the other R' group corresponding to RÔ; - optionally a compound of formula (I) in which the R' groups are identical and correspond to R4;

[0134] - optionally a compound of formula (I) in which the R' groups are identical and correspond to R5;

[0135] - optionally a compound of formula (I) in which the R' groups are identical and correspond to RÔ;

[0136] R4, R5 and RÔ being as previously defined for R'.

[0137] The mixture of compounds of formula (I) may 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) represented below:

[0138] in which all R4 groups are identical and as previously defined for R'; all R5 groups are identical and as previously defined for R'; all RÔ groups are identical and as previously defined for R'; the R4 groups are different from R5; the R4 groups are different from RÔ; the R5 groups are different from RÔ.

[0139] The R4 group may be more hydrophobic than the R5 group and / or the RÔ group; and / or the R4 group may have a lower molecular weight than the R5 group and / or the RÔ group.

[0140] The molecular masses of the R4, R5 and RÔ groups may be different. In particular, the R4 group may have a lower molecular mass than that of the R5 group; and / or the R4 group may have a lower molecular mass than that of the RÔ group; and / or the R5 group may have a lower molecular mass than that of the RÔ group. More particularly, the R4 group has a lower molecular mass than those of the R5 and RÔ groups. Even more particularly, the difference between the molecular mass of the R4 group and that of the R5 group; and / or the difference between the molecular mass of the R4 group and that of the RÔ group; and / or the difference between the molecular mass of the R5 group and that of the RÔ group may be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0141] The R4, R5 and RÔ groups may have different chemical natures. In particular, the R4 group may be more hydrophobic than the R5 group; and / or the R4 group may be more hydrophobic than the RÔ group; and / or the R5 group may be more hydrophobic than the RÔ group. More particularly, the R4 group is more hydrophobic than the R5 and RÔ groups.

[0142] The R4 group may be a linear or branched C1-C30 alkyl and the R5 and R6 groups may be groups of formula •-[(CR a Rb)ii-O] m -Y having different molecular masses, Y, R a , Rb, n and m being as defined previously.

[0143] The total molar quantity of the R5 and RÔ groups, in particular the total molar quantity of the least hydrophobic groups and / or of the groups having the highest molecular masses, may in particular represent more than 20%, in particular 25 to 95%, 30 to 90%, 35 to 85%, or 40 to 80%, of the total molar quantity of the R4, R5 and RÔ groups in all the products having one or more functions chosen from urea, urethane, and their mixtures in component b) (excluding any aprotic solvent).

[0144] According to a preferred embodiment, more than 20 mol%, in particular 25 to 95 mol%, 30 to 90 mol%, 35 to 85 mol%, or 40 to 80 mol%, of all the R' groups contained in the compound(s) of formula (I) are hydrophilic groups, in particular •-[(CR a R b )nO] m -Y.

[0145] The R' groups may in particular be the residues of one or more alcohols of formula R' -OH without the OH group. An alcohol R' -OH may in particular be chosen from a C1 to C30 alkane substituted by an OH group, a C2 to C30 alkene substituted by an OH group, a C5 to C12 cycloalkane substituted by an OH group, a C6 to C12 arene substituted by an OH group, a C7 to C12 alkylarene substituted by an OH group, HO-[(CR a Rb)nO]mY and HO-[(CR c Rd) P -C(=O)O] q -Z

[0146] Y and Z are independently selected from C1-C30 alkyl, C2-C30 alkenyl, C5-C12 cycloalkyl, C6-C12 aryl and C7-C12 alkylaryl;

[0147] R a, Rb, Rc and Rd are independently selected from H and methyl, in particular H; each n is independently 2, 3 or 4, in particular n is 2; m is from 1 to 30, in particular m is from 2 to 25; p is from 3 to 5, in particular p is 5; q is from 1 to 20, in particular q is from 2 to 10

[0148] A C1 to C30 alkane substituted by an OH group may in particular be chosen from octan-l-ol, octan-2-ol, Xi-6-methylheptan-l-ol, 2-ethylhexan-l-ol, nonan-l-ol, Xi-7-methyloctan-l-ol, decan-l-ol, Xi-s-methylnonan-l-ol, undecan-l-ol, Xi-9-methyldecan-l-ol, dodecan-l-ol, Xi-io-methylundecan-l-ol, tridecan-l-ol, Xi-n-methyldodecan-l-ol, 2,5,9-trimethyldecan-l-ol, tetradecan-l-ol, Xi-i2-methyltridecan-l-ol, pentadecan-l-ol, Xi-i3-methyltetradecan-l-ol, hexadecan-l-ol, Xi-i4-methylpentadecan-l-ol, heptadecan-l-ol, Xi-i9-methylicosan-l-ol, docosan-l-ol, Xi-20-methylhenicosan-l-ol, 2-propylheptan-l-ol, 2-propylnonan-l-ol, 2-pentylnonan-l-ol, 2-butyloctan-l-ol, 2-butyldecan-l-ol, 2-hexyloctan-l-ol, 2-hexyldecan-l-ol, 2-octyldecan-l-ol, 2-hexyldodecan-l-ol, 2-octyldodecan-l-ol, 2-decyltetradecan-l-ol,6-methyldodecan-l-ol and their isomers, in which X, a -b represents an integer that can take any value from a to b, X a -b indicating the position of an alkyl substituent on the alkane. Xi-n-methyldodecan-1-ol is a dodecane substituted with an OH group in the 1-position and a methyl group in 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. Isomers are alkanes with the same number of carbon atoms but a different substitution pattern, for example, an ethyl substituent instead of a methyl substituent or a greater number of methyl substituents. Thus, 2,5,9-trimethyldecan-1-ol is an isomer of 2-methyldodecan-1-ol and 11-methyldodecan-1-ol. Preferably, the OH-substituted C1-C30 alkane is selected from 11-methyldodecan-1-ol and 2,5,9-trimethyldecan-1-ol.

[0149] An alkene at C2 to C30 substituted by an OH group can be selected from Y2-5-hexene-l-ol, Y2-6-heptene-l-ol, Y2-7-octene-l-ol, Y2-8-nonene-l-ol, Y2-9-decene-ol, Y2-iol-one, Y2-n-dodecene-l-ol, Y2-i2-tridecene-l-ol, Y2-i3-tetradecene-l-ol, Y2 i5-hexadecene-l-ol, Y2 i7-octadecene-l-ol, Y2-i9-icocene-l-ol, Y2-2i-docosyl-ol, heptal-8, l-dien-l-ol, octadeca-9,12-dien-l-ol, nonadeca-10,13-dien-l-ol, icosa-l l,14-dien-l-ol, docosa- 13, 16-dien-l-ol, octadeca-5,9,12-trien-l-ol, octadeca-6,9,12-trien-l-ol, octadeca-9,12,15-trien-l-ol, octadeca-9,ll,13-trien-l-ol, icosa-8,ll,14-trien-l-ol, icosa-l,14,17-trien-l-ol, in which Y a -b represents an integer that can take any value from a to b, Y a -b indicating the position of the double bond in the alkene. The Y2-5-hexene-l-ol is a hexene substituted with an OH in position 1 in which the double bond can be in position 2, 3, 4 or 5.

[0150] A C5 to C12 cycloalkane substituted by an OH group may in particular be chosen from cyclopentanol, cyclohexanol, cycloheptanol, cycloctanol, cyclononanol, cyclodecanol, cycloundecanol, and cyclododecanol; preferably cyclopentanol and cyclohexanol.

[0151] A C6 to C12 arene substituted by an OH group may in particular be chosen 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.

[0152] A C7 to C12 alkylarene substituted by an OH group may in particular be chosen from benzyl alcohol, 2-phenylethan-1-ol, 3-phenylpropan-1-ol, 4-phenylbutan-1-ol, 2-phenylbutan-1-ol; preferably benzyl alcohol and 2-phenylethan-1-ol.

[0153] An alcohol HO-[(CR a Rb)nO] m-Y may in particular be chosen from an alkoxylated derivative of a C1 to C30 alkane substituted by an OH group as defined above, an alkoxylated derivative of a C2 to C30 alkene substituted by an OH group as defined above, an alkoxylated derivative of a C5 to C12 cycloalkane substituted by an OH group as defined above, an alkoxylated derivative of a C6 to C12 arene substituted by an OH group as defined above, an alkoxylated derivative of a C7 to C12 alkylarene substituted by an OH group as defined above. An alkoxylated derivative may in particular be an ethoxylated, propoxylated and / or butoxylated derivative, preferably ethoxylated. Preferably, the alcohol HO-[(CR a Rb)nO] m-Y is selected from a polyethylene glycol monomethyl ether (MPEG), a polyethylene glycol monoethyl ether and a polyethylene glycol monobutyl ether; more preferably an 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 MPEG-750) or triethylene glycol monobutyl ether (also called butyltriglycol (BTG)).

[0154] An alcohol HO-[(CR c Rd)pC(=O)O] q-Z may in particular be a polyester derivative of a C1 to C30 alkane substituted by an OH group as defined above, a polyester derivative of a C2 to C30 alkene substituted by an OH group as defined above, a polyester derivative of a C5 to C12 cycloalkane substituted by an OH group as defined above, a polyester derivative of a C6 to C12 arene substituted by an OH group as defined above, a polyester derivative of a C7 to C12 alkylarene substituted by an OH group as defined above. A polyester derivative may in particular comprise a polyester part obtained by ring-opening polymerization of a lactone, preferably chosen from gamma-butyrolactone, delta-valerolactone, epsilon-caprolactone and mixtures thereof.

[0155] Group R2

[0156] A compound of formula (I) contains two R2 groups. The R2 groups in a single compound of formula (I) may be the same or different. Component b) may comprise a mixture of compounds of formula (I) having identical R2 groups. Component b) may comprise a mixture of compounds of formula (I) that are distinguished by their R2 groups. For example, some compounds in the mixture may have identical R2 groups and some compounds in the mixture may have different R2 groups.

[0157] Each R2 group may originate from the use of a diisocyanate of formula OCN-R2-NCO to form the diurea-diurethane compound(s) of formula (I). The R2 group may correspond to the residue of a diisocyanate of formula OCN-R2-NCO without the NCO groups. The R2 groups and the corresponding diisocyanates of formula OCN-R2-NCO described below also apply to the process according to the invention.

[0158] Each R2 is independently a divalent group selected from an aliphatic group, a cycloaliphatic group, an aromatic group and an araliphatic group.

[0159] According to one embodiment, each R2 is independently an aromatic group.

[0160] In particular, each R2 is independently an aromatic group having the following formula: wherein the symbol • represents a point of attachment to a urea or urethane group of formula (I). More particularly, each R2 is independently an aromatic group having one of the following formulas: in which the symbol • represents a point of attachment to a urea or urethane group of formula (I).

[0161] Component b) may 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 contained in the compound(s) of formula (I) which are aromatic groups of the following formula: in which the symbol • represents a point of attachment to a urea or urethane group of formula (I).

[0162] In particular, component b) may 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 contained in the compound(s) of formula (I) which are aromatic groups of the following formula: in which the symbol • represents a point of attachment to a urea or urethane group of formula (I). The R2 group is linked on one side to a urethane group (arising from the reaction between an isocyanate group of the diisocyanate OCN-R2-NCO and the OH group of the alcohol R'OH) and on the other side to a urea group (arising from the reaction between the other isocyanate group of the diisocyanate OCN-R2-NCO and an NH2 group of the diamine H2N-R3-NH2).

[0163] More particularly, each R2 is independently an aromatic group of the following formula: in which the symbol ★ represents a point of attachment to a urethane group of formula (I) and the symbol =|= represents a point of attachment to a urea group of formula (I).

[0164] When the R2 group is asymmetric, there may be one side of the R2 group that is preferentially bonded to the urethane group and the other side that is preferentially bonded to the urea group. Without wishing to be bound by any theory, Applicant assumes that the less hindered side of the R2 group is preferentially bonded to the urethane group.

[0165] Component b) may in particular 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 the R2 groups contained in the compound(s) of formula (I) which are aromatic groups of the following formula: the symbol ★ represents a point of attachment to a urethane group of formula (I) and the symbol =|= represents a point of attachment to a urea group of formula (I). In particular, component b) 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 the R2 groups contained in the compound(s) of formula (I) which are aromatic groups of the following formula: in which the symbol ★ represents a point of attachment to a urethane group of formula (I) and the symbol =|= represents a point of attachment to a urea group of formula (I).

[0166] The R2 groups may in particular be the residues of one or more diisocyanates of formula OCN-R2-NCO without the NCO groups. A diisocyanate of formula OCN-R2-NCO may be a toluene diisocyanate (TDI). A TDI may be in the form of one or more isomers selected from toluene 2,4-diisocyanate and toluene 2,6-diisocyanate.

[0167] In the context of the present invention, it is advantageous to use a TDI which comprises a high proportion of toluene 2,4-diisocyanate, or even a TDI which comprises only toluene 2,4-diisocyanate. The Applicant assumes that the asymmetry of this compound makes it possible to reduce the quantity of secondary products, in particular of the compound of formula (II), in component b). This makes it possible to obtain compounds of formula (I) having a high proportion, or even all, of R2 groups according to the formula in which the symbol ★ represents a point of attachment to a urethane group of formula (I) and the symbol =|= represents a point of attachment to a urea group of formula (I). In particular, a diisocyanate of 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

[0168] 99 mol% or 100 mol%, of 2,4-toluene diisocyanate relative to the total amount of toluene diisocyanate isomers. More particularly, a diisocyanate of formula OCN-R2-NCO is a TDI containing from 86 to 100 mol%, from 90 to 100 mol%, from 95 to

[0169] 100 mol%, from 97 to 100 mol%, from 98 to 100 mol%, from 99 to 100 mol%, or 100 mol%, of toluene 2,4-diisocyanate relative to the total amount of toluene diisocyanate isomers. Preferably, a diisocyanate of formula OCN-R2-NCO is a TDI containing 100 mol%, of toluene 2,4-diisocyanate relative to the total amount of toluene diisocyanate isomers.

[0170] Group R3

[0171] A compound of formula (I) contains an R3 group. Component b) may comprise a mixture of compounds of formula (I) having identical R3 groups. Component b) may comprise a mixture of compounds of formula (I) distinguished by their R3 groups.

[0172] Each R3 group may originate from the use of a diamine of formula H2N-R3-NH2 to form the diurea-diurethane compound(s) of formula (I). The R3 group may correspond to the residue of a diamine of formula H2N-R3-NH2 without the NH2 groups. The R3 groups and the corresponding diamines of formula H2N-R3-NH2 described below also apply to the process according to the invention.

[0173] Each R3 is independently a divalent group selected from an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group.

[0174] According to a particular embodiment, each R3 is independently a group selected from C2-C24 alkylene, -(CRhRi)s-[A-(CRjRk)t]u- -(CRiR m ) v -CY-(CR n Ro)w-, and -(CR P R q ) x -CY-(CH2) y -CY-(CRrRs)z- ; in which

[0175] A is O or NX;

[0176] Rh, Ri, Rj, Rk Ri, Rm, R11, Ro, Rp, Rq, Rr and R s are independently selected from H and methyl, in particular H;

[0177] X is C1 to C6 alkyl, in particular methyl or ethyl;

[0178] CY is a ring selected from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl and pyridinyl, the ring being unsubstituted or substituted by 1 to 3 C1-C4 alkyl groups; s is from 2 to 4, in particular s is 2; t is from 2 to 4, in particular t is 2; u is from 1 to 30; v, w, xy and z are independently from 0 to 4.

[0179] Each R3 may in particular be a group chosen from C2-C24 alkylene and -(CRiR m )v-CY-(CR n Ro)w- ; in particular a group selected from C2-C18 alkylene and -(CH2)v-CY-(CH2)w- with CY a cyclohexyl or phenyl ring, the ring being unsubstituted or substituted by 1 to 3 C1-C4 alkyl groups, v and w ranging from 0 to 1.

[0180] More particularly, each R3 may be a group selected from C2-C6 alkylene and a group having the following formula: in which the symbol • represents a point of attachment to a urea group of the compound of formula (I).

[0181] Component b) may 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 R3 groups contained in the compound(s) of formula (I) which are groups of the following formula:

[0182] In particular, component b) may 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 the total of the R3 groups contained in the compound(s) of formula (I) which are groups of the following formula:

[0183] The R3 group(s) may in particular be the residue(s) of one or more diamines of formula H2N-R3-NH2 without the NH2 groups. A diamine of formula H2N-R3-NH2 may be chosen from a C2 to C24 aliphatic diamine, a C6 to C18 cycloaliphatic diamine, a C6 to C24 aromatic diamine, a C7-C26 araliphatic diamine, a C3 to C18 heterocyclic diamine.

[0184] A C2-C24 aliphatic diamine is a diamine of the formula H2N-R3-NH2 in which R3 is an aliphatic group comprising 2 to 24 carbon atoms. An aliphatic diamine may be linear or branched, preferably linear. An aliphatic diamine may be a polyetheramine, i.e. a diamine of the formula H2N-R3-NH2 in which R3 comprises ether linkages (-O-), more particularly ethylene oxide (-O-CH2-CH2) and / or propylene oxide (-O-CH2-CHCH3-) units. An aliphatic diamine may be a polyalkyleneimine, i.e. a diamine of the formula H2N-R3-NH2 in which R3 is interrupted by one or more tertiary amines (-NX- with X being a C1-C6 alkyl). An aliphatic diamine may be interrupted by one or more tertiary amine groups. Examples of suitable linear aliphatic amines are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine,

[0185] 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine and mixtures thereof; preferably 1,2-ethylenediamine,

[0186] 1,5-pentamethylenediamine and 1,6-hexamethylenediamine. Examples of suitable branched aliphatic amines are 1,2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine and mixtures thereof. Examples of polyetheramines are the compounds marketed by Hunstmann under the reference Jeffamine®, 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, Jeffamine® EDR-176. An example of a polyalkyleneimine is 3,3'-diamino-N-methyldipropylamine.

[0187] A C6-C18 cycloaliphatic diamine is a diamine of the formula H2N-R3-NH2 in which R3 is a cycloaliphatic group comprising 6 to 18 carbon atoms. Examples of suitable cycloaliphatic diamines are

[0188] 1,2-, 1,3- or 1,4-diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, isophoronediamine,

[0189] 1,2-, 1,3- or l,4-bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, bis(aminomethyl)norbornane and mixtures thereof; preferably 1,3- or l,4-bis(aminomethyl)cyclohexane,

[0190] 1,2-, 1,3- or l,4-bis(aminomethyl)cyclohexane, isophorone diamine and 4,4'- diaminodicy clohexy Imethane.

[0191] A C6-C24 aromatic diamine is a diamine of the formula H2N-R3-NH2 in which R3 is an aromatic group comprising 6 to 24 carbon atoms. Examples of suitable aromatic diamines are ortho-, meta- and para-phenylenediamine, ortho-, meta- and para-toluylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and mixtures thereof; preferably ortho-, meta- and para-phenylenediamine.

[0192] A C7-C26 araliphatic diamine is a diamine of the formula H2N-R3-NH2 in which R3 is an araliphatic group comprising 7 to 26 carbon atoms. Examples of suitable araliphatic diamines are ortho-, meta- and para-xylylenediamine, 4,4'-diaminodiphenylmethane and mixtures thereof; preferably ortho-, meta- and para-xylylenediamine.

[0193] A C3-C18 heterocyclic diamine is a diamine of the formula H2N-R3-NH2 in which R3 is a heterocyclic group comprising 3 to 18 carbon atoms. Examples of suitable heterocyclic 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.

[0194] Aprotic solvent

[0195] Component b) may further comprise an aprotic solvent. Component b) may comprise a mixture of aprotic solvents.

[0196] According to one embodiment, the aprotic solvent is chosen 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 chosen from dimethyl sulfoxide, N-butylpyrrolidone and mixtures thereof.

[0197] Component b) may in particular comprise 20 to 95% by weight, in particular 40 to 80%, more particularly 50 to 70%, by weight of aprotic solvent relative to the weight of component b).

[0198] Diurethane compound

[0199] Component b) may further comprise a diurethane compound. Component b) may comprise a mixture of diurethane compounds.

[0200] The diurethane compound may be a by-product from the process for preparing component b) as described below. Indeed, the reaction between a diisocyanate of formula OCN-R2-NCO and an alcohol of formula R'-OH to form a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO may also generate a diurethane when the alcohol is in stoichiometric excess relative to the diisocyanate.

[0201] Without wishing to be bound by any theory, the Applicant assumes that the diurethane makes it possible to 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 quantity of salt, in particular lithium salt, or surfactant compared to the thixotropic additives of the prior art.

[0202] A diurethane compound may in particular correspond to a compound of formula (II): in which R' and R2 are as defined above for the compound of formula (I).

[0203] According to a particular embodiment, component b) comprises 20% to 95%, in particular 25% to 85%, more particularly 35% to 75%, in moles of compound of formula (II) relative to the total molar quantity of compounds having one or more functions chosen from urea, urethane, and their mixtures (excluding any aprotic solvent).

[0204] Polyurea-diurethane compound

[0205] Component b) may further comprise a polyurea-diurethane compound. Component b) may comprise a mixture of polyurea-diurethane compounds. The polyurea-diurethane compound may in particular be a by-product resulting from the process for preparing component b) as described below. Indeed, the reaction between a monoisocyanate adduct of formula R'-O-C(=O)-NH-R2-NC0 and a diamine of formula H2N-R3-NH2 may also generate a polyurea-diurethane when the reaction medium contains diisocyanate of formula OCN-R2-NCO. The diisocyanate may in particular be residual diisocyanate resulting from the reaction between a diisocyanate of formula OCN-R2-NCO and an alcohol of formula R'-OH to form a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO.

[0206] A polyurea-diurethane compound may in particular correspond to a compound of formula (III): wherein R', R2 and R3 are as defined above for the compound of formula (I); z is 1 to 10.

[0207] Since polyurea-diurethane compounds are generally solid, it is advantageous to limit their quantity in component b). Although it is possible to reduce the residual diisocyanate content by implementing a distillation step before the reaction between the monoisocyanate adduct and the diamine, this represents a significant cost and requires specific installations. Component b) has a low content of polyurea-diurethane compound although its preparation process does not require a residual diisocyanate distillation step. This is made possible in particular by adjusting the molar ratio of the reactants used in the preparation process of component b) as described below.

[0208] According to a particular embodiment, component b) less than 4%, in particular from 3.0 to 1.5%, from 2.0 to 1.0% or from 1.0 to 0% by mole of compound of formula (III) relative to the total molar quantity of compounds having one or more functions chosen from urea, urethane, and their mixtures (excluding any aprotic solvent).

[0209] Process for the preparation of thixotropic additive

[0210] Component b) may be prepared according to the process described below. The process for preparing component b) comprises a step a), a step b) and optionally one or more additional steps which may take place before step a), between step a) and step b) and / or after step b).

[0211] Step a) is a step during which at least one diisocyanate of formula OCN-R2-NCO reacts with at least one alcohol of formula R'-OH to form at least one monoisocyanate adduct of formula R'-O-C(=O)-NH-R2-NC0.

[0212] Step b) is a step during which the at least one monoisocyanate adduct obtained in step a) reacts with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula (I) wherein each R' is independently selected from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, •-[(CR a Rb)nO] m -Y and •-[(CR c Rd) P -C(=O)O] q -Z; the symbol • represents a point of attachment to a urethane group of formula (I); each R2 is independently a divalent group selected from an aliphatic group, a cycloaliphatic group, an aromatic group and an araliphatic group; each R3 is independently a divalent group selected from an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group;

[0213] Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and alkylaryl;

[0214] R a , Rb, Rc and Rd are independently selected from H and methyl, in particular H; each n is independently 2, 3 or 4, in particular n is 2; m ranges from 1 to 30, in particular m ranges from 2 to 25; p ranges from 3 to 5, in particular p is 5; q ranges from 1 to 20, in particular q ranges from 2 to 10.

[0215] The groups R', R2 and R3, the diisocyanate of formula OCN-R2-NCO, the alcohol of formula R'-OH and the diamine of formula H2N-R3-NH2 may in particular be as defined previously for the compound of formula I. The particular embodiments described for the compound of formula (I) also apply to the process for preparing component b).

[0216] Step a) may in particular be carried out by gradually adding F at least one alcohol to a reactor containing F at least one diisocyanate. The at least one diisocyanate may in particular be in the molten state. The rate of addition of the at least one alcohol may be controlled in order to limit the exothermicity. In particular, the rate of addition of the at least one alcohol may be controlled in order to maintain the temperature of the reaction medium less than or equal to 60°C, in particular from 20 to 60°C, from 25 to 55°C or from 30 to 40°C.

[0217] Step a) is carried out with a molar ratio between the total amount of alcohol and the total amount of diisocyanate of 1.10 to 1.80. In particular, the molar ratio between the total amount of alcohol and the total amount of diisocyanate in step a) ranges from 1.20 to 1.60, more particularly from 1.25 to 1.45, more particularly still 1.30 to 1.40.

[0218] The ratio of alcohol to diisocyanate in step a) makes it 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) which has not reacted with the at least one alcohol. Controlling the amount of residual diisocyanate at the end of step a) advantageously makes it possible to limit the formation of insoluble species, in particular of the compound of formula (III) as described above, during step b). According to a particular embodiment, the quantity of residual diisocyanate in the reaction mixture at the end of step a) is less than 6%, in particular from 0 to 5%, from 0.01 to 4.5% or from 0.05 to 4% mol relative to the molar quantity of all the compounds having one or more functions chosen from urethane, isocyanate and their mixtures.

[0219] The ratio of alcohol to diisocyanate in step a) advantageously makes it possible to avoid the implementation of a step of removing residual diisocyanate. Indeed, the quantity of residual diisocyanate at the end of step a) is sufficiently low and will not cause excessive formation of insoluble species, in particular of the compound of formula (III) as described above, during step b). According to a particular embodiment, the process for preparing component b) does not comprise a step of distilling residual diisocyanate, in particular no step of distilling residual diisocyanate between step a) and step b). The ratio of alcohol to diisocyanate in step a) can lead to the formation of one or more diurethane compound(s) as described above. A diurethane compound may in particular result from the reaction between an alcohol of formula R' -OH and the monoisocyanate adduct of formula R'-0-C(=0)-NH-R2-NC0.Thus, the reaction mixture obtained in step a) may comprise the monoisocyanate adduct of formula R'-O-C(=O)-NH-R2-NC0 and a compound of formula (II):. in which R' and R2 are as defined previously.

[0220] Without wishing to be bound by any theory, the Applicant assumes that the presence of diurethane compound in component b) makes it possible to stabilize the urea bonds formed during step b). Thus, it is possible to significantly reduce, or even eliminate, the quantity of stabilizer (in particular salt, for example lithium salt, or surfactant) added in step b) compared to the methods of the prior art.

[0221] Once the addition of the at least one alcohol is complete, step a) may be continued until the NCO number of the reaction mixture reaches the theoretical NCO number. The NCO number at the end of step a) may in particular be less than 200 mg KOH / g. In particular, the NCO number at the end of step a) may be 5 to 150 mg KOH / g, 25 to 125 mg KOH / g, 50 to 100 mg KOH / g or 60 to 80 mg KOH / g. The NCO number at the end of step a) may in particular be measured according to the method described below. The theoretical NCO number at the end of step a) may in particular be calculated according to the method described below.

[0222] Step b) may in particular be carried out by gradually adding the mixture obtained in step a) to a reactor containing the at least one diamine and optionally aprotic solvent and / or salt. The rate of addition of the mixture obtained in step a) may be controlled in order to limit the exothermicity. In particular, the rate of addition of the mixture obtained in step a) may be controlled in order to maintain the temperature of the reaction medium less than or equal to 80°C, in particular from 20 to 80°C, from 30 to 70°C, or from 40 to 60°C.

[0223] Once the addition of the at least one monoisocyanate adduct is complete, step b) can be continued until the NCO index of the reaction mixture reaches the desired value. The NCO index of the thixotropic additive obtained by the process for preparing component b) may in particular be less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, more particularly still 0 mg KOH / g. The NCO index of the thixotropic additive may in particular be determined according to the method described in the patent application filed under No. PCT / EP2021 / 084323.

[0224] 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 may in particular be as defined above for component b).

[0225] Step b) may 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 may in particular be as defined above for component b).

[0226] The molar ratio between the total amount of monoisocyanate adduct and the total amount of diamine in step b) can range from 1.8 to 2.2. In particular, the molar ratio between the total amount of monoisocyanate adduct and the total amount of diamine in step b) ranges from 1.9 to 2.1, more particularly from 1.95 to 2.05, even more particularly from 1.98 to 2.02.

[0227] A solvent may be added in step a) and / or in step b) and / or between step a) and step b) in order to reduce the viscosity of the composition and solubilize the compounds obtained. In particular, step a) and / or step b) may be carried out in the presence of an aprotic solvent. The viscosity of the reaction medium obtained at the end of step a) may be lowered by adding aprotic solvent. The aprotic solvent may in particular be as defined previously for component b).

[0228] The process for preparing component b) may be carried out using an alcohol or a mixture of alcohols in step a).

[0229] According to a first embodiment, in step a) F at least one diisocyanate reacts with a single alcohol of formula Ri-OH to form at least one monoisocyanate adduct of formula RI-OC(=O)-NH-R2-NCO, and in step b), the product obtained in step a) reacts with at least one diamine of formula

[0230] H2N-R3-NH2 to form at least one compound of formula (!) in which the groups Ri are identical and as previously defined for R';

[0231] R2 and R3 are as defined previously.

[0232] The alcohol R1-0H of the first embodiment may in particular be a linear or branched C1-C30 alkyl substituted by OH.

[0233] According to a second embodiment, in step a), the at least one diisocyanate reacts with at least two different alcohols of formula R4-OH and R5-OH to form a mixture of at least two monoisocyanate adducts of formula R4-OC(=O)-NH-R2-NCO and R5-OC(=O)-NH-R2-NCO, and in step b), the mixture obtained in step a) reacts with at least one diamine of formula H2N-R3-NH2 to form a compound of formula (Ia), optionally in admixture with a compound of formula (Ib) and / or a compound of formula (Ic): in which all R4 groups are the same and as previously defined for R'; all R5 groups are the same and as previously defined for R'; the R4 groups are different from R5.

[0234] The groups R4 and R5, as well as the alcohols of formula R4-OH and R5-OH may in particular be as defined previously for the compound of formula I. In the second embodiment, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH; and / or the alcohol R5-OH may have a higher molecular mass than that of the alcohol R4-OH.

[0235] In the second embodiment, the molecular masses of the alcohols R4-OH and R5-OH may be different. In particular, R4-OH may have a lower molecular mass than that of R5-OH. More particularly, the difference between the molecular mass of R4-OH and that of R5-OH may be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0236] In the second embodiment, the chemical natures of the alcohols R4-OH and R5-OH may be different. In particular, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH.

[0237] In the second embodiment, the alcohols R4-OH and R5-OH may be alcohols of formula HO-[(CR a Rb)ii-O] m -Y having different molecular masses, Y, R a, Rb, n and m being as defined above. Alternatively, the alcohol R4-OH may be a linear or branched C1-C30 alkyl substituted with OH and the alcohol R5-OH may be an alcohol of formula HO-[(CR a Rb)nO] m -Y in which Y, R a , Rb, n and m are as defined previously.

[0238] In the second embodiment, the total molar quantity of the alcohol R5-OH, in particular of the least hydrophobic alcohol and / or of the alcohol having the highest molecular mass, may in particular represent more than 20%, in particular 25 to 95%, 30 to 90%, 35 to 85%, or 40 to 80%, of the total molar quantity of the alcohols R4-OH and R5-OH introduced in step a).

[0239] In the second embodiment, the alcohol R5-OH, in particular the least hydrophobic alcohol and / or the alcohol having the highest molecular mass, may in particular be reacted with the diisocyanate before the alcohol R4-OH, in particular the most hydrophobic alcohol and / or the alcohol having the lowest molecular mass, is introduced into the reaction mixture of step a).

[0240] According to a third embodiment, in step a), the diisocyanate reacts with a mixture of at least three different alcohols of formula R4-OH, R5-OH and R6-OH to form a mixture of at least three monoisocyanate adducts of formula R4-OC(=O)-NH-R2-NCO, R5-OC(=O)-NH-R2-NCO and R6-OC(=O)-NH-R2-NCO, and in step b) the mixture obtained in step a) reacts with at least one diamine of formula H2N-RS-NH2 to form a compound of formula (Ia), a compound of formula (Id) and optionally one or more compounds of formula (Ib) (Ic) (Ic) or (If) represented below: (If) in which all R4 groups are identical and as previously defined for R'; all R5 groups are identical and as previously defined for R'; all RÔ groups are identical and as previously defined for R'; the R4 groups are different from R5; the R4 groups are different from RÔ; the R5 groups are different from RÔ.

[0241] The groups R4, R5 and RÔ, as well as the alcohols of formula R4-OH, R5-OH and RÔ-OH may in particular be as defined previously for the compound of formula I. In the third embodiment, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH and / or than the alcohol RÔ-OH; and / or the alcohol R4-OH may have a lower molecular mass than that of the alcohol R5-OH and / or than that of the alcohol RÔ-OH.

[0242] In the third embodiment, the molecular masses of the alcohols R4-OH, R5-OH and RÔ-OH may be different. In particular, R4-OH may have a lower molecular mass than that of R5-OH; and / or R4-OH may have a lower molecular mass than that of RÔ-OH; and / or R5-OH may have a lower molecular mass than that of RÔ-OH. More particularly, the alcohol R4-OH has a lower molecular mass than those of the alcohols R5-OH and RÔ-OH. Even more particularly, the difference between the molecular mass of R4-OH and that of R5-OH; and / or the difference between the molecular mass of R4-OH and that of RÔ-OH; and / or the difference between the molecular mass of R5-OH and that of RÔ-OH may be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0243] The alcohols R4-OH, R5-OH and RÔ-OH can have different chemical natures. In particular, R4-OH can be more hydrophobic than R5-OH; and / or R4-OH can be more hydrophobic than RÔ-OH; and / or R5-OH can be more hydrophobic than RÔ-OH. More particularly, the alcohol R4-OH is more hydrophobic than the alcohols R5-OH and RÔ-OH.

[0244] In the third embodiment, the alcohol R4-OH may be a linear or branched C1-C30 alkyl substituted with OH and the alcohols R5-OH and R6-OH may be alcohols of formula HO-[(CR a Rb)ii-O] m -Y having different molecular masses, Y, R a , Rb, n and m being as defined previously.

[0245] The total molar quantity of alcohols R5-OH and RÔ-OH, in particular the total molar quantity of the least hydrophobic alcohols and / or of the alcohols having the highest molecular masses, may in particular represent more than 20%, in particular 25 to 95%, 30 to 90%, 35 to 85%, or 40 to 80%, of the total molar quantity of alcohols R4-OH, R5-OH and RÔ-OH introduced in step a).

[0246] The alcohols R5-OH and RÔ-OH, in particular the less hydrophobic alcohols and / or the alcohols having the highest molecular masses, may in particular be reacted with the diisocyanate before the alcohol R4-OH, in particular the more hydrophobic alcohol and / or the alcohol having the lowest molecular mass, is introduced into the reaction mixture of step a).

[0247] The composition according to the invention comprises a polymerizable component and a thixotropic additive as described above.

[0248] The composition may in particular comprise from 50 to 99.95%, in particular from 70 to 99.9%, more particularly from 80 to 99.8%, more particularly still 90 to 99.75% by weight of component a) relative to the weight of the composition.

[0249] The thixotropic additive may in particular be added in a quantity sufficient to increase the viscosity and / or confer thixotropic properties to the composition according to the invention.

[0250] The composition may in particular comprise from 0.05 to 50%, in particular from 0.1 to 30%, more particularly from 0.2 to 20%, more particularly still 0.25 to 10% by weight of component b) relative to the weight of the composition.

[0251] The composition may in particular have a viscosity greater than the viscosity of a composition which does not comprise component b) or which comprises an insufficient quantity of component b), the viscosity being measured at 25°C at low shear (0.01 s' 1 )-

[0252] According to a particular embodiment, the composition is a coating, molding, sealant, adhesive, liquid sealing system, composite material, chemical sealing system or dental material composition.

[0253] The composition according to the invention may further comprise one or more additional components chosen from fillers, plasticizers, wetting agents, pigments, antioxidants, radical inhibitors, UV absorbers, light stabilizers and mixtures thereof.

[0254] The composition according to the invention may comprise a filler, in particular a filler chosen from a mineral filler, an organic filler or mixtures thereof. In particular, the composition may comprise a mineral filler, in particular chosen from gravel, marble, granite, quartz, diatomaceous earth, feldspar, mica, gypsum, glass beads, stone 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.

[0255] The composition may comprise an organic filler, in particular chosen from polymer particles such as polyolefin particles (in particular polyethylene, polytetrafluoroethylene or polypropylene particles), polyester particles, polyether particles, (meth)acrylic polymer particles (in particular polymethyl methacrylate particles), polyurethane particles, polyamide particles (in particular of the Orgasol® type), styrene-maleic copolymer particles; natural or synthetic waxes such as paraffin, microcrystalline wax, ceresin, montanic wax, beeswax, candelilla wax, carnauba wax, rice bran wax, Japanese wax, soybean wax, rapeseed wax, palm wax, spermaceti, 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 mixtures thereof.;

[0256] The composition may in particular comprise from 0 to 70%, in particular from 10 to 60%, more particularly from 20 to 50%, by weight of filler relative to the weight of the composition.

[0257] The composition according to the invention may comprise a reinforcement, more particularly a reinforcement chosen from plant fibers, glass fibers, carbon fibers, carbon nanotubes, polyester fibers, aramid fibers and mixtures thereof.

[0258] The composition may in particular comprise from 0 to 70%, in particular from 10 to 60%, more particularly from 20 to 50%, by weight of reinforcement relative to the weight of the composition.

[0259] The composition according to the invention may comprise a tackifying resin; in particular an optionally modified rosin resin.

[0260] The composition according to the invention may further comprise a radical initiator. The radical initiator may in particular make it possible to initiate the polymerization of component a).

[0261] The radical initiator may in particular be a peroxide compound or an azo compound, in particular a peroxide. An azo compound is a compound comprising an azo group of formula -N=N-. An example of a suitable azo compound is azobisisobutyronitrile (AIBN).

[0262] A peroxide compound is a compound comprising a peroxide group of formula -OO-. A peroxide compound may in particular be chosen from hydrogen peroxide, a hydroperoxide (ROOH), a dialkyl or alkylaryl peroxide (ROO-R'), a peracid (RC(=O)-O-O-H), a peroxyester (RC(=O)-O-O-R'), a diacyl peroxide (RC(=O)-OOC(=O)-R'), a peroxycarbonate (ROC(=O)-OOC(=O)-O-R'), a peroxy ketal (originating from the reaction between a ketone and hydrogen peroxide or a hydroperoxide), as well as mixtures thereof, R and R' being independently aliphatic, cycloaliphatic or aromatic groups. A peroxide compound may advantageously be in a stabilized form, in particular in an aqueous phase, in a plasticizer or in an organic solvent.

[0263] 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 peroxyoctoate, tert-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxymaleate and mixtures thereof.

[0264] In particular, the radical initiator can be benzoyl peroxide.

[0265] The composition may in particular comprise a quantity of radical initiator sufficient to obtain complete polymerization of component a). In particular, the composition may comprise from 0.05 to 10%, from 0.1 to 5%, from 0.5 to 5% or from 0.5 to 3% by weight of radical initiator relative to the weight of component a).

[0266] The composition according to the invention may further comprise an activator of the radical initiator. An activator of the radical initiator may in particular enable the radical initiator to be activated at room temperature (20-25°C) in order to initiate the polymerization of component a). The activator of the radical initiator may in particular comprise a tertiary amine or a redox couple.

[0267] In order to avoid any premature polymerization of the composition according to the invention, the radical initiator may be placed in the presence of component a) just before the application of the composition by the end user. Thus, the present invention may also relate to a two-component system comprising:

[0268] - a first cartridge comprising a radical initiator;

[0269] - a second cartridge comprising the composition according to the invention and optionally an activator of the radical initiator; the first cartridge being kept separate from the second cartridge.

[0270] The containers of the first cartridge and the second cartridge are intended to be brought into contact shortly before the application of the composition to a substrate.

[0271] The invention may also relate to a process for preparing a crosslinked product comprising the following steps:

[0272] - mixing the composition according to the invention with a radical initiator and optionally an activator of the radical initiator to form a mixture;

[0273] - apply the mixture obtained on a substrate.

[0274] The crosslinked product may include, but is not limited to, a coating, a molding, a sealant, an adhesive, a liquid sealing system, a composite material, a chemical sealing system, or a dental material.

[0275] The mixture may in particular be applied to the surface of a substrate to be coated or sealed. Alternatively, the mixture may be applied to the surface of a substrate intended to be adhered to another substrate. Alternatively, the mixture may be applied so as to fill the void between two adjacent substrates or to fill holes in the surface of a substrate. Alternatively, the mixture may be applied to a substrate comprising reinforcing fibers to form a composite material. Alternatively, the mixture may be applied in a mold-shaped substrate.

[0276] The invention also relates to the use of an additive comprising a diurea-diurethane compound and containing less than 0.1 moles of salt per urea group in the additive (excluding any aprotic solvent) to increase the viscosity and / or confer thixotropic properties to a polymerizable component comprising a compound functionalized by (meth)acrylate. Said additive may in particular correspond to component b) as described above for the composition according to the invention. The polymerizable component may in particular correspond to component a) as described above for the composition according to the invention. The invention is illustrated by the following non-limiting examples.

[0277] EXAMPLES

[0278] Raw materials

[0279] [Table 1] Thixotropic additive 1 (AT 1) according to the invention

[0280] The thixotropic additive 1 according to the invention is prepared as described in example 8 of the patent application filed under No. PCT / EP2021 / 084323 (additive based on diurea-diurethane without LiCl).

[0281] Thixotropic additive 2 (AT 2) according to the invention Thixotropic additive 2 according to the invention corresponds to the commercial product Crayvallac®

[0282] LA-377 available from Arkema (LiCl-free diurea-diurethane additive) Comparative thixotropic additive Cl (AT Cl)

[0283] Comparative thixotropic additive C1 corresponds to the commercial product Crayvallac® LA-350 available from Arkema (diurea-diurethane based additive containing more than 0.1% mol of LiCl per urea group). Comparative thixotropic additive C2 (AT C2)

[0284] Comparative thixotropic additive C2 corresponds to the commercial product RHEOBYK® D-420 available from B YK (diurea-diurethane based additive containing more than 0.1 mol% LiCl per urea group)

[0285] Preparation of compositions Compositions based on monomer functionalized by (meth)acrylate

[0286] The compositions were prepared in a 50 mL flask, using a high-speed disperser equipped with a deflocculator. The components, namely 1 g of thixotropic additive and 19 g of (meth)acrylate-functionalized monomer, were introduced into the flask. Then the mixture was homogenized under stirring for 1 minute at 1000 rpm at 20°C. After this dispersion phase, the mixture was left at 20°C without stirring for at least 10 min.

[0287] The components used to prepare the compositions are described in the table below (1% by weight of thixotropic additive relative to the weight of the composition):

[0288] [Table 2]

[0289] Compositions based on monomer and oligomer functionalized with (meth)acrylate

[0290] The compositions were prepared in a 250 mL flask using a high-speed disperser equipped with a deflocculator. The (meth)acrylate-functionalized compounds, namely

[0291] 97.7 g of MAM and 2.3 g of CN981 were introduced and stirred at 20°C until a homogeneous mixture was reached. Then the desired amount of thixotropic additive AT 2 was added to the flask. The mixture was then homogenized under stirring, using a high-speed disperser equipped with a deflocculator for 5 minutes at 1500 rpm at 20°C. After this dispersion phase, the mixture was left at 20°C without stirring for a minimum of 10 min. The amounts of thixotropic additive used to prepare the compositions are described in the table below (% by weight of thixotropic additive relative to the weight of the composition):

[0292] [Table 3]

[0293] Compositions based on a compound functionalized by (meth)acrylate

[0294] This series of compositions based on a (meth)acrylate-functionalized compound was prepared in a 50 mL bottle according to a protocol similar to that described for examples 1a to 2e. The desired quantities of thixotropic additive AT2 and Elium® 190 resin were introduced into the bottle. Then the mixture was homogenized under stirring, using a high-speed disperser equipped with a deflocculator, for 30 seconds at 800 rpm at 20°C. After this dispersion phase, the mixture was left at 20°C without stirring for at least 10 min.

[0295] The amounts of thixotropic additive used to prepare the compositions are described in the table below (% by weight of thixotropic additive relative to the weight of the composition):

[0296] [Table 4] Compositions based on monomer and oligomer functionalized with (meth)acrylate and filler

[0297] For these compositions, the mixture of (meth)acrylate functionalized compounds was previously prepared as follows: In a 250 mL flask, 97.7 g of MAM and 2.3 g of CN981 were introduced and stirred at 20°C, using a high-speed disperser equipped with a deflocculator, until a homogeneous mixture was reached. Then the desired amount of Omyacarb® 10 AV filler was added and dispersed using the same high-speed disperser equipped with a deflocculator for 10 minutes at 2000 rpm. Then, in a 50 mL flask, the desired amounts of thixotropic additive AT 2 and the previously prepared MAM / CN981 / filler mixture were introduced into the flask. The mixture was then homogenized with stirring, using a high-speed disperser equipped with a deflocculator, for 5 minutes at 1500 rpm at 20°C. After this dispersion phase, the mixture was left at 20°C without stirring for at least 10 min.

[0298] The quantities of components used to prepare the compositions are described in the table below (% by weight relative to the weight of the composition):

[0299] [Table 5]

[0300] Characterization of compositions

[0301] Visual characterization

[0302] The performance of the thixotropic additive is evaluated by visual characterization of the compositions, after being left at 20°C (without stirring) for 1 h, 24 h or 1 week. An evaluation scale is defined as follows to allow comparison of samples. [Table 6]

[0303] The visual evaluation of the compositions of examples 1a to 11 is detailed in the table below:

[0304] [Table 7] The visual evaluation of the compositions of examples 12 to 15 is detailed in the table below:

[0305] [Table 8]

[0306] 5 Viscosity measurement

[0307] Viscosity measurements were carried out in accordance with NF EN ISO 2555 using a Brookfield® viscometer at 22°C (rotary: S63). A cylindrical rotor rotates at a constant speed around its axis in the product to be tested. The resistance exerted by the fluid on the rotor depends on the viscosity of the product. This resistance causes the spiral spring to twist, which is translated into a viscosity value.

[0308] The viscosity of the compositions of examples 7 to 11 measured at 22°C, after 24 hours is detailed in the table below:

[0309] [Table 9]

[0310] 15 * The thixo index 5 / 50 corresponds to the ratio between viscosity at 5 rpm and viscosity at 50 rpm. The viscosity of the compositions of examples 12 and 14 measured at 22°C, after one week is detailed in the table below:

[0311] [Table 10]

Claims

DEMANDS

1. Composition comprising: a) a polymerizable component comprising a (meth)acrylate functionalized compound; b) a thixotropic additive comprising a diurea-diurethane compound; characterized in that component b) contains less than 0.1 moles of salt per urea group in component b) (excluding any aprotic solvent).

2. Composition according to claim 1, characterized in that component a) comprises a (meth)acrylate functionalized compound selected from a (meth)acrylate functionalized monomer, a (meth)acrylate functionalized oligomer, and mixtures thereof; in particular component a) comprises a (meth)acrylate functionalized monomer and optionally a (meth)acrylate functionalized oligomer.

3. Composition according to claim 1 or 2, characterized in that component a) comprises a monomer functionalized by mono(meth)acrylate selected from (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; Trimethylolpropane (meth)acrylate (cyclic form); Isosomal (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; ethyl-butyl hydroxy(meth)acrylate urethane; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; (2,2-dimethyl-l,3-dioxolan-4-yl)methyl (meth)acrylate; (2-ethyl-2-methyl-l,3-dioxolan-4-yl)methyl (meth)acrylate; l,3-dioxan-5-yl (meth)acrylate; (l,3-dioxolan-4-yl)methyl (meth)acrylate; glycerol carbonate (meth)acrylate; and alkoxylated derivatives (e.g., ethoxylated and / or propoxylated) thereof; and mixtures thereof.

4. Composition according to any one of claims 1 to 3, characterized in that component a) comprises a monomer functionalized with mono(meth)acrylate selected from (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 (meth)acrylate; isobomyl (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate;(Meth)acrylate of (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl; (Meth)acrylate of 1,3-dioxan-5-yl; (Meth)acrylate of (1,3-dioxolan-4-yl)methyl; as well as alkoxylated derivatives (e.g., ethoxylated and / or propoxylated) thereof; and mixtures thereof.

5. Composition according to any one of claims 1 to 4, characterized in that component a) comprises methyl methacrylate optionally mixed with at least one other (meth)acrylate functionalized compound.

6. Composition according to any one of claims 1 to 5, characterized in that component a) comprises a poly(meth)acrylate functionalized monomer selected from 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-denanediol 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 di(meth)acrylate dimethanol; 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; as well as alkoxylated derivatives (e.g., ethoxylated and / or propoxylated) thereof; and mixtures thereof.

7. Composition according to any one of claims 1 to 6, characterized in that component a) comprises a poly(meth)acrylate functionalized monomer selected from 1,6-hexanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, and mixtures thereof.

8. Composition according to any one of claims 1 to 7, characterized in that component a) comprises an oligomer functionalized with (meth)acrylate 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.

9. Composition according to any one of claims 1 to 8, characterized in that component a) comprises an oligomer functionalized with (meth)acrylate selected from urethane oligomers functionalized with (meth)acrylate, polydiene oligomers functionalized with (meth)acrylate, acrylic oligomers functionalized with (meth)acrylate, and mixtures thereof.

10. Composition according to any one of claims 1 to 9, characterized in that component a) comprises - from 10 to 100%, from 20 to 100%, from 30 to 100%, from 40 to 95%, or from 50 to 90%, by weight of monomer functionalized with (meth)acrylate; and - from 0 to 90%, from 0 to 80%, from 0 to 70%, from 5 to 60%, or from 10 to 50%, by weight of oligomer functionalized by (meth) acrylate.

11. Composition according to any one of claims 1 to 10, characterized in that component b) comprises a diurea-diurethane compound of formula (I) or a mixture of diurea-diurethane compounds of formula (I): in which each R' is independently chosen from alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, •-[(CR a Rb)nO] m -Y and •-[(CRc Rd) P -C(=O)O] q -Z; the symbol • represents an attachment point to a urethane group of formula (I); each R2 is independently a divalent group chosen from an aliphatic group, a cycloaliphatic group, an aromatic group and an araliphatic group; each R3 is independently a divalent group chosen from an aliphatic group, a cycloaliphatic group, an aromatic group, an araliphatic group and a heterocyclic group; Y and Z are independently chosen from alkyl, alkenyl, cycloalkyl, aryl and alkylaryl; R a , Rb, Rc and Rd are independently chosen from H and methyl, in particular H; each n is independently equal to 2, 3 or 4, in particular n is 2; m goes from 1 to 30, in particular m goes from 2 to 25; p goes from 3 to 5, in particular p is 5; q goes from 1 to 20, in particular q goes from 2 to 10.

12. Composition according to any one of claims 1 to 11, characterized in that component b) contains from 0 to less than 0.1 moles, or from 0 to 0.09 moles, or from 0 to 0.07 moles, or from 0 to 0.05 moles, or from 0 to 0.03 moles, or from 0 to 0.02 moles, or from 0 to 0.01 moles, of salt per urea group in component b).

13. Composition according to any one of claims 1 to 12, characterized in that the salt of component b) is selected from a metallic salt, an ionic liquid and an ammonium salt; in particular the salt is a metallic salt selected from a halide, an acetate, a formate, a nitrate; more particularly the salt is a lithium salt; more particularly still the salt is a lithium salt selected from LiCl, LiNCh, LiBr and mixtures thereof.

14. Composition according to any one of claims 1 to 13, characterized in that component b) contains less than 0.1 moles of surfactant per urea group in component b).

15. Composition according to any one of claims 1 to 14, characterized in that the NCO index of component b) is less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, more particularly still 0 mg KOH / g.

16. Composition according to any one of claims 1 to 15, characterized in that component b) comprises 5% to 80%, in particular 15% to 75%, more particularly 25% to 65%, by moles of diurea-diurethane compound relative to the total molar amount of compounds having one or more functions selected from urea, urethane, and mixtures thereof.

17. Composition according to any one of claims 1 to 16, characterized in that component b) further comprises at least one diurethane compound of formula (II): in which R' and R2 are as defined in claim 11.

18. Composition according to claim 17, characterized in that component b) comprises 20% to 95%, in particular 25% to 85%, more particularly 35% at 75%, in moles of diurethane compound of formula (II) relative to the total molar quantity of compounds having one or more functions selected from urea, urethane, and their mixtures, excluding possible aprotic solvent.

19. Composition according to any one of claims 11 to 18, characterized in that each R' is independently chosen from alkyl and "-[(CRaRb)!!- O]mY; in particular each R' is independently chosen from linear or C1-C30 branched alkyl and •-[CH2-CH2-O] m -Y with Y a C1-C24 alkyl group and m ranges from 1 to 25; more particularly, each R' is independently selected from C8-C20 branched alkyl groups and •-[CH2-CH2-O]mY with Y a C1-C6 alkyl group and m ranges from 2 to 20.

20. Composition according to any one of claims 11 to 19, characterized in that each R2 is independently an aromatic group; in particular, an aromatic group having the following formula: more specifically an aromatic group according to one of the following formulas: ; in which the symbol • represents an attachment point to a urea or urethane group of formula (I); more particularly, an aromatic group according to one of the following formulas: in which the symbol ★ represents an attachment point to a urethane group of formula (I) and the symbol =|= represents an attachment point to a urea group of formula (I).

21. Composition according to any one of claims 11 to 20, characterized in that 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 contained in the diurea-diurethane compound(s) of formula (I) are aromatic groups of the following formula: in which the symbol • represents an attachment point to a urea or urethane group of formula (I); in particular, 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 the R2 groups contained in the diurea-diurethane compound(s) of formula (I) are aromatic groups of the following formula: in which the symbol ★ represents an attachment point to a urethane group of formula (I) and the symbol =|= represents an attachment point to a urea group of formula (I).

22. Composition according to any one of claims 11 to 21, characterized in that each R3 is independently a group selected from C2-C24 alkylene, -(CRhRi)s-[A-(CRjR k )t]u- and -(CRiR m )v-CY-(CR n Ro)w-,-(CRpR q ) x -CY-(CH2) y -CY-(CRrRs)z- ; in which A is O or NX; Rh, Ri, Rj, Rk Ri, Rm, Rn, Ro, Rp, Rq, Rr and R s are independently chosen from H and methyl, in particular H; X is a Cl- to C6 alkyl, in particular methyl or ethyl; CY is a ring chosen from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl and pyridinyl, the ring being unsubstituted or substituted by 1 to 3 alkyl groups at C1-C4; s goes from 2 to 4, in particular s is 2; t goes from 2 to 4, in particular t is 2; u goes from 1 to 30; v, w, xy and z go independently from 0 to 4.

23. Composition according to any one of claims 11 to 22, characterized in that each R3 is independently a group selected from C2-C24 alkylene and -(CRiR m )v-CY-(CR nRo)w- ; in particular a group selected from alkylene in C2-C18 and -(CH2)v-CY-(CH2)w- with CY a cyclohexyl or phenyl ring, the ring being unsubstituted or substituted by 1 to 3 alkyl groups in C1-C4, v and w ranging from 0 to 1; more particularly a group selected from alkylene in C2-C6 and a group having the following formula: in which the symbol • represents an attachment point to a urea group of formula (I).

24. A composition according to any one of claims 11 to 23, characterized in that component b) is capable of being obtained by a process comprising the following steps: a) reacting at least one diisocyanate of formula OCN-R2-NCO with at least one alcohol of formula R'-OH to form at least one monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO, the molar ratio between the total amount of alcohol and the total amount of diisocyanate ranging from 1.10 to 1.80, in particular from 1.20 to 1.60, plus particularly from 1.25 to 1.45, more particularly 1.30 to 1.40; b) react F at least one monoisocyanate adduct obtained in step a) with at least one diamine of formula H2N-R3-NH2 in the presence of less than 0.2 mole of salt per mole of diamine used, to form at least one diurea-diurethane compound of formula (I) in which R', R2, and R3 are as defined in claim 11.

25. Composition according to claim 24, 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.

26. Composition according to claim 24 or 25, characterized in that step b) is carried out in the presence of less than 0.2, in particular 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.

27. ​​Composition according to any one of claims 24 to 26, characterized in that it does not comprise a residual diisocyanate distillation step, in particular no residual diisocyanate distillation step between step a) and step b).

28. Composition according to any one of claims 24 to 27, characterized in that the amount of residual diisocyanate in the reaction mixture at the end of step a) is less than 6%, in particular 0 to 5%, 0.01 to 4.5% or 0.05 to 4%, molar relative to the molar amount of all the compounds having one or more functions selected from urethane and isocyanate.

29. Composition according to any one of claims 24 to 28, characterized in that step a) and / or step b) is carried out in the presence of an aprotic solvent.

30. Composition according to any one of claims 1 to 29, characterized in that component b) further comprises an aprotic solvent; in particular an aprotic solvent 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, more particularly an aprotic solvent selected from dimethyl sulfoxide or N-butylpyrrolidone.

31. Composition according to any one of claims 1 to 30, characterized in that component b) comprises 20 to 95% by weight, in particular 40 to 80%, more particularly 50 to 70%, by weight of aprotic solvent relative to the weight of component b).

32. Composition according to any one of claims 1 to 31, characterized in that said composition comprises from 0.05 to 50%, in particular from 0.1 to 30%, more particularly from 0.2 to 20%, more particularly still from 0.25 to 10% by weight of component b) relative to the weight of the composition.

33. Composition according to any one of claims 1 to 32, characterized in that said composition is a composition of coating, molding, sealant, adhesive, liquid sealing system, composite material, chemical sealing system or dental material.

34. Composition according to any one of claims 1 to 33, characterized in that said composition further comprises a filler, in particular a filler selected from a mineral filler, an organic filler and mixtures thereof.

35. Composition according to any one of claims 1 to 34, characterized in that said composition further comprises a reinforcement, in particular a reinforcement selected from vegetable fibers, glass fibers, carbon fibers, carbon nanotubes, polyester fibers, aramid fibers and mixtures thereof.

36. Composition according to any one of claims 1 to 35, characterized in that said composition further comprises a tackifying resin; in particular a rosin resin possibly modified.

37. Composition according to any one of claims 1 to 36, characterized in that said composition further comprises a radical initiator, in particular an azo compound or a peroxide compound.

38. Composition according to claim 37, characterized in that said composition further comprises a radical initiator activator, in particular a tertiary amine or a redox couple.

39. Two-component system characterized in that it comprises: - a first cartridge comprising a radical initiator; - a second cartridge comprising the composition according to any one of claims 1 to 38 and optionally an activator of the radical initiator; the first cartridge being kept separate from the second cartridge.

40. A process for preparing a crosslinked product comprising the following steps: - mixing the composition according to any one of claims 1 to 38 with a radical initiator and optionally an activator of the radical initiator; - apply the resulting mixture onto a substrate.

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

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