CROSSLINKABLE COMPOSITION BY MICHAEL ADDITION

Abstract

The present invention relates to a real Michael addition (RMA) crosslinkable composition, more particularly to a solvent-free crosslinkable composition, usable for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical sealant, an adhesive, a polymeric concrete or a composite. The present invention relates in particular to a catalyst system suitable for use in solvent-free RMA crosslinking, as well as to a method for preparing a crosslinked product by applying and crosslinking the composition to at least one substrate.

Description

Title of the invention: Michael addition crosslinkable composition Field of invention

[0001] The present invention relates to a real Michael addition (RMA) crosslinkable composition, more particularly a solvent-free crosslinkable composition, usable for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite. The present invention relates in particular to a catalytic system which can be used in solvent-free RMA crosslinking, as well as to a method for preparing a crosslinked product by applying and crosslinking the composition to at least one substrate. Technical background

[0002] Durable and highly crosslinked coatings can be obtained using true Michael addition (RMA) chemistry. RMA crosslinkable compositions typically comprise a Michael donor component A and a Michael acceptor component B that react and crosslink with each other in the presence of a basic catalyst component. The catalyst component must be strong enough to abstract a proton from component A to form the carbanion donor component B.

[0003] EP 0326723 A1 (Rohm and Haas Company) describes crosslinkable compositions based on the Michael reaction comprising a catalyst component derived from the reaction of an epoxide with a tertiary amine. The catalyst components are brought into contact before use, which then activates the crosslinking of the donor and acceptor components. All the disclosed formulations further comprise organic solvents indicated as being capable of improving the pot life and gloss of the coatings, and which are also used to lower the viscosity of the formulations before use.

[0004] WO 2011 / 124665 A1 and WO 2013 / 050622 A1 (Nuplex Resins BV) describe the use of a catalyst comprising a latent strong base for the Michael addition based on substituted carbonate salts. When the composition is applied to a substrate, the carbonate salts release carbon dioxide, thus generating a strong base which is capable of catalyzing (or initiating) the Michael reaction between components A and B. The base is either a hydroxide or an alkoxide. The crosslinkable compositions described in these documents also all comprise an organic solvent whose role is to adjust the viscosity of the formulations before use. lization so that they can be easily applied to the substrates by the formulator.

[0005] A major drawback of the systems described in the prior art is that they contain organic solvents and thus generate volatile organic compounds (VOCs). Eliminating the presence of solvents in crosslinkable compositions, or even reducing their quantity, is nevertheless not easy, because high solids content systems have reduced pot lives and extended curing speeds, which does not correspond to market expectations.

[0006] The present invention aims in particular to solve these problems by proposing solvent-free crosslinkable compositions, easily applicable to the surface of substrates, and which have a suitable appearance and satisfactory hardness properties after crosslinking.

[0007] Another object of the present invention is to provide a crosslinkable composition such that it can be stored before use without its viscosity changing significantly over time (storage stability, pot life).

[0008] Another object of the present invention is to provide crosslinkable compositions which exhibit a rapid drying time. Summary of the invention

[0009] A first subject of the present invention relates to a crosslinkable composition, in particular a composition crosslinkable by adding a catalyst component C.

[0010] The crosslinkable composition according to the invention comprises: a. a Michael A donor component; b. a Michael B acceptor component; c. a catalyst component C comprising: - an epoxy component Cl; and - an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1.

[0011] A second subject of the present invention relates to a process for preparing a crosslinked product, characterized in that the process comprises the following steps: a. the preparation of a component C2 by reaction between a component C2a and a component C2b with a molar ratio of the (meth)acrylate groups of the compound C2a to the NH bonds of the compound C2b greater than 1; b. the preparation of a composition by bringing components A, B and C into contact; c. applying the composition to at least a portion of a surface of a substrate; and d. crosslinking the composition, preferably at a temperature ranging from 0 to 60°C,

[0012] wherein components A, B, Cl, C2, C2a and C2b are as defined in the present description.

[0013] A third object of the present invention relates to a catalytic system comprising: - an epoxy component Cl; and - an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1.

[0014] A fourth object of the present invention relates to the use of the catalytic system according to the invention for catalyzing a real Michael addition crosslinking (RMA).

[0015] A fifth subject of the present invention relates to the use of the crosslinkable composition according to the invention for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite. Detailed description

[0016] In the context of the present invention:

[0017] - the expression “between ... and ...” (for example, a range of values) must be understood to include the limits (e.g., the limit values ​​of that range of values);

[0018] - the expression “includes a / an” must be understood as meaning “includes at minus one / one”;

[0019] - any description relating to an embodiment is applicable and inter interchangeable with all other embodiments of the invention; and

[0020] - when an element or component is included in and / or chosen and / or selected in a list of elements or components, it is to be understood that that individual element or component may be chosen / selected and combined with other individual elements, or may be chosen / selected to constitute a subgroup of two or more explicitly listed elements or components; also, any element or component cited in a list of elements or components may be omitted from that list. Crosslinkable composition

[0021] A first subject of the present invention relates to a crosslinkable composition, in particular a composition crosslinkable by adding a catalyst component C.

[0022] The crosslinkable composition according to the invention comprises:

[0023] a) a Michael A donor component;

[0024] b) a Michael B acceptor component;

[0025] c) a catalyst component C comprising:

[0026] - an epoxy component Cl; and

[0027] - an amino-(meth)acrylate component C2 having a group functionality (meth)acrylate greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1; and

[0028] d) optionally a neutralizing component D.

[0029] The crosslinkable composition according to the invention may in particular be a solvent-free composition.

[0030] In the context of the present invention, the term "solvent-free composition" means a composition comprising less than 2% by weight, less than 1% by weight, less than 500 ppm, less than 200 ppm, less than 50 ppm or less than 1 ppm of non-reactive organic solvent relative to the total weight of the composition. The solvent content can in particular be determined according to the method described below.

[0031] In the context of the present invention, the term "solvent" means an organic compound which is liquid at 0°C and which has a boiling point, measured at 101.325 kPa, of less than 250°C.

[0032] In the context of the present invention, the term “organic solvent” means a solvent having carbon atoms.

[0033] In the context of the present invention, the term "non-reactive organic solvent" means an organic solvent which remains unchanged during the crosslinking process, i.e. it is non-reactive with respect to the components of the crosslinkable composition. Consequently, components A and B of the crosslinkable composition according to the invention do not fall within the definition of "non-reactive organic solvent" mentioned above.Examples of non-reactive organic solvents are alkanes, halogenated hydrocarbons, alcohols, glycols, esters, ethers, glycol ethers, aldehydes, ketones, and aromatic hydrocarbons, including hexane, heptane, dichloromethane, methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, diethyl ether, ethylene glycol n-butyl ether, formaldehyde, acetaldehyde, acetone, 2-butanone (MEK), butyl acetate, ethyl acetate, benzene, toluene, xylene, or ethylbenzene. Michael A donor component

[0034] The crosslinkable composition according to the present invention comprises a Michael A donor component (component A hereinafter).

[0035] Component A is such that it comprises at least one Michael donor compound A. Compound A may in particular be in the form of a monomer comprising at least one Michael donor group, or a polymer comprising at least one Michael donor group. When compound A is a polymer, said polymer may for example be a polyester, a polyurethane, a poly(meth)acrylate, an epoxy polymer, a polyamide, a polyesteramide, a polyvinyl polymer, or a mixture of these polymers. Preferably, when compound A is a polymer, it is a polyester.

[0036] The crosslinkable composition according to the present invention may comprise a component A comprising several distinct Mickaël donor compounds A, for example two, three or four distinct compounds A.

[0037] Each compound A comprises at least one Michael donor group. A Michael donor group is a group having a labile proton alpha to a carbonyl function. Each compound A may comprise several Michael donor groups, for example two, three or four Michael donor groups. These groups may be the same or different. Examples of Michael donor groups are a malonate group and an acetoacetate group.

[0038] Preferably, component A comprises at least one compound with a malonate group and is referred to in the context of the present invention as component AL. Component A may comprise several Al compounds, for example 2, 3 or 4 distinct Al compounds.

[0039] According to one embodiment, the component Al comprises a polymer having at least one malonate group, said polymer being chosen from a polyester, a polyurethane, a poly(meth)acrylate, an epoxy polymer, a polyamide, a polyesteramide, a polyvinyl polymer, and mixtures thereof.

[0040] The malonate group may in particular be a dialkyl malonate group chosen from a dimethyl malonate, a diethyl malonate, a di-n-propyl malonate, a diisopropyl malonate, a di-n-butyl malonate, a diisobutyl malonate, a di-tert-butyl malonate, a dilauryl malonate, a di-2-ethylhexyl malonate, and mixtures thereof.

[0041] According to one embodiment, component Al comprises a compound selected from a dialkyl malonate, a polymer having at least one malonate group, and mixtures thereof.

[0042] Preferably, component Al comprises a polyester having at least one malonate group.

[0043] According to one embodiment, the component Al has a malonate index (MI) greater than 260 mgKOH / g, in particular greater than 270 mgKOH / g or greater than 280 mgKOH / g. The malonate index can in particular be calculated according to the following equation (Math 1):

[0044] [Math.l] Imalo- MT F (g)

[0045] in which

[0046] Nmalo: number of moles of malonate functions introduced into the reactor

[0047] MTF: final theoretical mass, calculated according to the following equation (Math 2):

[0048] [Math.2] MTF — MI-2 *MA *Nmalo

[0049] in which

[0050] MI: initial mass of the reactor contents before heating

[0051] MA: molar mass of the distilled alcohol

[0052] According to one embodiment, the component Al has an average malonate functionality (fM) greater than 4. The malonate functionality can in particular be calculated according to the following equation (Math 3):

[0053] [Math.3] Fmalo = Nmglo-- (L, ^n^-Nmalo

[0054] in which

[0055] n represents the number of different polyols introduced during the synthesis and

[0056] n; represents the number of moles of each of the polyols introduced.

[0057] According to one embodiment, component A has a residual content of non-reactive organic solvent of less than 2% by weight, less than 1% by weight, less than 500 ppm, less than 200 ppm, less than 50 ppm or less than 1 ppm, relative to the total weight of component A. The solvent content can in particular be determined according to the method described below.

[0058] When component A comprises a polymer, the latter is preferably prepared according to a solvent-free process (in other words a process not using a non-reactive organic solvent as defined above), i.e. no compound having the following three cumulative properties: 1 / being present from the start to the end of the reaction, possibly added during the process, 2 / unchanged during the process, i.e. non-reactive with respect to the reagents involved, and 3 / having to be eliminated at the end of the process in the case where the product of the reaction must be in its pure form. Michael B acceptor component

[0059] The crosslinkable composition according to the present invention comprises a Michael B acceptor component (component B hereinafter).

[0060] Component B may in particular comprise a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2, and / or a component Michael acceptor B2 having a group functionality α,[3-unsaturated greater than or equal to 3.

[0061] For the purposes of the present invention, an α,[3-unsaturated group is a group comprising a carbon-carbon double bond in the α,[3 position of a carbonyl function, in particular in the α,[3 position of a group of formula -C(=O)-R in which R is H, halogen, alkyl, aryl, OH, O-alkyl, -O-aryl, NRaRb, -OC(=O)-alkyl and Ra and Rb are independently H, alkyl or aryl.

[0062] According to one embodiment, component B comprises only component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 or only Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3.

[0063] According to another embodiment, component B comprises component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 and component B2 having an α,[3-unsaturated group functionality greater than or equal to 3.

[0064] According to one embodiment of the present invention, component B1 has a viscosity of less than 100 mPa.s, as measured at 23°C according to the method described below. For example, according to this embodiment, component B1 has a viscosity of less than 50 mPa.s, preferably less than 30 mPa.s, more preferably less than 15 mPa.s.

[0065] Component B1 of the present invention may comprise one or more distinct Michael donor compounds, each having an α,[3-unsaturated group functionality ranging from 1 to 2.

[0066] Component B1 of the present invention may in particular comprise one or more compounds having at least one (meth)acrylate group (preferably at least one acrylate group), one or more compounds having at least one (meth)acrylamide group, one or more vinyl ketones, one or more maleates, one or more fumarates, one or more mesaconates and / or one or more itaconates. Compound B1 may comprise several distinct compounds, for example a mixture of compounds comprising 1 or 2 (meth)acrylate groups and compounds comprising 1 or 2 other unsaturations.

[0067] According to one embodiment, component B1 comprises a compound selected from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, a maleate, an itaconate, a fumarate and mixtures thereof. Preferably, component B1 comprises a compound selected from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, and mixtures thereof. More preferably, component B1 comprises a monomer having 2 (meth)acrylate groups.

[0068] According to one embodiment, component B1 comprises a compound chosen from a monomer having 1 acrylate group, a monomer having 2 acrylate groups, a maleate, an itaconate, a fumarate and mixtures thereof. Preferably, component B1 comprises a compound selected from a monomer having 1 acrylate group, a monomer having 2 acrylate groups, and mixtures thereof. More preferably, component B1 comprises a monomer having 2 acrylate groups.

[0069] According to one embodiment, component B1 comprises a monomer having 1 (meth)acrylate group selected from 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, 2-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-octadecyl (meth)acrylate, oleyl (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 formalin cyclic (meth)acrylate, isobutyl (meth)acrylate, tricyclodecanemethanol (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, (poly)caprolactone (meth)acrylate, n-butyl acryloyloxy ethyl carbamate,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 (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the aforementioned compounds are particularly preferred.

[0070] According to one embodiment, component B1 comprises a monomer having 2 (meth)acrylate groups chosen from bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, di-, tri-, tetra- or polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, di-, tri-, tetra- or polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 2,3-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, di(meth)acrylate 3-methyl-1,5-pentanediol, 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; as well as alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the aforementioned compounds are particularly preferred.

[0071] According to one embodiment, component B1 comprises a maleate chosen from dimethyl maleate, diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-n-butyl maleate, diisobutyl maleate, di-tert-butyl maleate, and mixtures thereof.

[0072] According to one embodiment, component B1 comprises an itaconate selected from dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, diisopropyl itaconate, di-n-butyl itaconate, diisobutyl itaconate, di-tert-butyl itaconate, and mixtures thereof.

[0073] According to one embodiment, component B1 comprises a fumarate chosen from dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-tert-butyl fumarate, and mixtures thereof.

[0074] Preferably, component B1 comprises at least one monomer having 2 acrylate groups chosen from di-, tri-, tetra- or polyethylene glycol diacrylate, di-, tri-, tetra- or polypropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, neopentyl glycol diacrylate, cyclohexane-1,4-dimethanol diacrylate and mixtures thereof.

[0075] Component B2 of the present invention may comprise one or more distinct Michael donor compounds, each having an α,[3-unsaturated group functionality greater than or equal to 3.

[0076] According to one embodiment, component B2 comprises a compound chosen from a monomer having at least 3 (meth)acrylate groups, an oligomer having at least 3 (meth)acrylate groups, and mixtures thereof; preferably, a monomer having at least least 3 (meth)acrylate groups. In particular, component B2 may comprise a compound selected from a monomer having at least 3 acrylate groups, an oligomer having at least 3 acrylate groups, and mixtures thereof; preferably, a monomer having at least 3 acrylate groups.

[0077] According to one embodiment, component B2 comprises at least one compound having 3, 4, 5 or 6 (meth)acrylate groups; preferably, at least one compound having 3 or 4 (meth)acrylate groups. In particular, component B2 may comprise at least one compound having 3, 4, 5 or 6 acrylate groups; preferably, at least one compound having 3 or 4 acrylate groups.

[0078] According to one embodiment, component B2 comprises at least one monomer having at least 3 (meth)acrylate groups chosen from glycerol tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, sorbitol penta(meth)acrylate, di(pentaerythritol) hexa(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; as well as alkoxylated (for example, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the compounds cited above are particularly preferred.

[0079] According to one embodiment, component B2 comprises an oligomer having at least 3 (meth)acrylate groups chosen from urethane oligomers functionalized with a (meth)acrylate, epoxy oligomers functionalized with a (meth)acrylate, polyether oligomers functionalized with a (meth)acrylate, polyester oligomers functionalized with a (meth)acrylate, (meth)acrylic oligomers functionalized with a (meth)acrylate, polydiene oligomers functionalized with a (meth)acrylate, polycarbonate oligomers functionalized with a (meth)acrylate, polyamide oligomers functionalized with a (meth)acrylate, and mixtures thereof.

[0080] Preferably, component B2 comprises at least one monomer having 3 or 4 acrylate groups chosen from glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate and mixtures thereof.

[0081] When the crosslinkable composition according to the invention comprises a component B1 and a component B2, the mass ratio between the component B1 and the component B2 may in particular be between 1:0.1 and 1:100, preferably from 1:0.2 to 1:20, more preferably from 1:1 to 1:10.

[0082] According to one embodiment, the average functionality in the α,[3-unsaturated group of component B varies between 1.5 and 6, preferably between 2 and 4. Catalyst component C

[0083] The present invention uses a catalyst component particularly suitable for solvent-free crosslinkable compositions. More specifically, the composition re- crosslinkable according to the present invention comprises a catalyst component C comprising: - an epoxy component Cl; and - an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1.

[0084] Catalyst component C is a catalytic system capable of generating a strong base in order to catalyze (or initiate) the Michael reaction between components A and B. The strong base is generated by bringing components C1 and C2 into contact. Thus, components C1 and C2 are intended to be brought into contact shortly before application of the crosslinkable composition by an end user.

[0085] As demonstrated in the experimental part of the present patent application, the catalyst component of the present invention comprising an epoxy component C1 and an amino-(meth)acrylate component C2, is particularly suitable for solvent-free formulations. The compositions which incorporate it have satisfactory hardnesses and appearance after crosslinking, whereas the prior art catalytic system is not efficient for solvent-free RMA crosslinking.

[0086] The epoxy component Cl (or component Cl hereinafter) is such that it comprises at least one compound having at least 1 epoxy group. This compound may comprise several epoxy groups, for example two, three or four epoxy groups. The epoxy component Cl may, itself, comprise several distinct epoxy compounds, each comprising one or more epoxy groups. Preferably, the component Cl is liquid at 25°C.

[0087] The component Cl may in particular comprise at least one compound selected from a glycidyl ether, a glycidyl ester, a cycloaliphatic epoxy (in particular a compound having an epoxy group fused with an aliphatic ring such as cyclohexyl) and combinations thereof. The component Cl may comprise several of these compounds, for example 2, 3 or 4 distinct Cl compounds.

[0088] The component Cl may in particular comprise a compound chosen from 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxycyclohexane, a glycidyl ether of a C4-C26 aliphatic or aromatic monoalcohol (in particular ethanol glycidyl ether, isopropanol glycidyl ether, butan-1-ol glycidyl ether, tert-butanol glycidyl ether, 2-ethylhexanol, dodecan-1-ol glycidyl ether, phenol glycidyl ether, cresol glycidyl ether, 2-methoxyphenol glycidyl ether, p-nonylphenol glycidyl ether, 4-tert-butylphenol glycidyl ether, benzyl alcohol glycidyl ether, cardanol glycidyl ether such as Cardolite Ultra LITE 513 marketed by Cardolite), a glycidyl ester of a C4-C26 aliphatic or aromatic monoacid (in particular 4-tert-butylbenzoic acid glycidyl ester, oleic acid glycidyl ester, linolenic acid glycidyl ester, palmitic acid glycidyl ester, stearic acid glycidyl ester, neodecanoic acid glycidyl ester or versatic acid glycidyl ester such as Cardura El OP marketed by Hexion), methyl 9,10-epoxystearate, ethyl 9,10-epoxystearate, butyl 9,10-epoxystearate, 2-ethylhexyl, n-octyl 9,10-epoxystearate, diglycidyl ether, 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, 1,2,9,10-diepoxydecane, 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, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, novolac epoxy resin (obtained by epoxidation of condensation products of phenolic derivatives, in particular m- / p-cresol, 2,5-dimethylphenol, bisphenol A or cardanol, with formaldehyde), glycidyl (meth)acrylate functionalized (meth)acrylic resin, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy )cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ethylene glycol ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), ethylene glycol diglycidyl ether, 1,2- or 1,3-propylene glycol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propane diol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, ether 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly-glycidyl 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), glycerol triglycidyl ether, tri- triglycidyl ether, methylolmethane, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexane-1,2 or 1,4-dicarboxylate diglycidyl ester, 4-cyclohexene-1,2-dicarboxylate diglycidyl ester, cyclohexane-1,2 or 1,4-diol diglycidyl ether, cyclohexane-1,2 or 1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, pyrocatechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl esters of long-chain aliphatic dibasic acids, diglycidyl esters of ortho-, iso- or terephthalic acid,tetrahydrophthalic acid diglycidyl esters, hexahydrophthalic acid diglycidyl esters, epoxidized vegetable oil (especially epoxidized soybean oil, epoxidized linseed oil), epoxidized polybutadiene, triglycidyl isocyanurate, as well as alkoxylated (especially ethoxylated and / or propoxylated) derivatives thereof, and mixtures thereof.

[0089] Preferably, component C1 comprises a compound selected from versatic acid glycidyl ester, cardanol glycidyl ether, bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, isosorbide diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, novolac epoxy resin and mixtures thereof.

[0090] In addition to the epoxy component C1, the catalyst component C also comprises an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1. Preferably, the amino-(meth)acrylate component C2 has an NH bond functionality less than 1, or even zero NH bond functionality.

[0091] For the purposes of the present invention, an “amino-(meth)acrylate” is a compound resulting from the reaction between a (meth)acrylate (i.e. a compound functionalized by at least one acrylate or methacrylate group) and a primary or secondary amine (aza-Michael reaction).

[0092] The amino-(meth)acrylate component C2 (or component C2 hereinafter) may in particular comprise an amino-(meth)acrylate having at least 2 (meth)acrylate groups and at least one latent catalyst group, preferably an amino-acrylate having at least 2 acrylate groups and at least one latent catalyst group. The component C2 may also comprise a mixture of amino-(meth)acrylates as defined above. In this case, the (meth)acrylate group functionality of the component C2 corresponds to the average (meth)acrylate group functionality of the mixture. The average (meth)acrylate group functionality may in particular correspond to the sum (meth)acrylate group functionalities of each constituent of the mixture weighted by the mole fraction of each constituent in the mixture.

[0093] For the purposes of the present invention, a "latent catalyst group" is a group capable of generating a strong base after reaction with the Cl component in order to catalyze (or initiate) the Michael reaction between the donor A and acceptor B components.

[0094] In particular, the latent catalyst group may be chosen from an imidazole function or a tertiary amine function having a pka > 9, preferably a pKa > 10.

[0095] The tertiary amine function may in particular correspond to the formula -NRaRb (1) in which Ra and Rb, identical or different, represent a C1-C4 alkyl or a cycloalkyl, or else Ra and Rb form a C2-C6 heterocycle.

[0096] The imidazole function can in particular correspond to the following formula (2):

[0097] [Chem.l] Rd Rc / ] "N—| / * Re ¢2)

[0098] wherein Rc, Rd and Re are independently selected from H, alkyl, aryl and al-kylaryl or Rc and Rd, together with the carbon atoms to which they are bonded, may form a ring.

[0099] Component C2 is likely to be obtained by reaction between: - a (meth)acrylate component C2a having a (meth)acrylate group functionality greater than or equal to 2, preferably an acrylate component C2a having an acrylate group functionality greater than or equal to 2; and - an amino component C2b having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1;

[0100] the molar ratio of the (meth)acrylate groups of compound C2a to the NH bonds of compound C2b being greater than 1.

[0101] According to one embodiment, the molar ratio of the (meth)acrylate groups of compound C2a to the NH bonds of compound C2b is greater than 1.01, greater than 1.02, greater than 1.05 or even greater than 1.10.

[0102] Component C2a comprises a compound having at least 2 (meth)acrylate groups, preferably at least 2 acrylate groups. Component C2a may in particular comprise several compounds each having at least 2 (meth)acrylate groups, preferably at least 2 acrylate groups. For example, component C2a may comprise 2, 3 or 4 compounds having at least 2 (meth)acrylate groups, preferably at least 2 acrylate groups. Each compound comprises at least two (meth)acrylate functions, for example 2, 3 or 4 (meth)acrylate functions, preferably 2, 3 or 4 acrylate functions. Component C2a may consist of a mixture of compounds having at least 2 (meth)acrylate groups, for example a mixture of compounds having 2 (meth)acrylate groups and compounds having 3 (meth)acrylate groups.

[0103] Preferably, component C2a comprises a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups. Examples of monomers having 2 (meth)acrylate groups are as described above for component B1.

[0104] Component C2b comprises a compound having at least 2 NH bonds and at least 1 latent catalyst group (preferably chosen from an imidazole function or a tertiary amine function having a pKa > 9). Component C2b may in particular comprise several compounds each having at least 2 NH bonds (for example 2, 3 or 4 NH bonds) and at least 1 latent catalyst group (for example 1, 2 or 3 latent catalyst group(s)).

[0105] Component C2b may in particular comprise a compound having: - at least 1 primary amine function or at least 2 secondary amine functions; and - at least 1 function chosen from imidazole or tertiary amine having a pKa >9.

[0106] Preferably, component C2b comprises a compound having at least 1 primary amine function and at least 1 function chosen from imidazole or tertiary amine having a pKa > 9.

[0107] More preferably, component C2b comprises a compound having at least 1 primary amine function and at least 1 tertiary amine function having a pKa > 9.

[0108] Component C2b may in particular comprise a compound chosen from N,N-dimethylethylenediamine, N,N-diethylethylenediamine, dimethylaminopro-pylamine (DMAPA), 3-(diethylamino)-1-propylamine (DEAPA), 4-(dimethylamino)-1-butylamine, 4-(diethylamino)-1-butylamine, 5-(dimethylamino)-1-pentylamine, N,N-dimethyldipropylenetriamine (DMAPAPA), N-(2-aminoethyl)-N-methylcyclohexanamine, 2-morpholinoethylamine, 3-morpholinopropylamine, 2-piperidinoethylamine, 3-piperidinopropylamine, 5-piperidinopentylamine, 2-(4-methyl-1-piperidinyl)ethanamine, 2-pyrrolidinoethylamine, 3-pyrrolidinopropylamine, 2-(2-aminoethyl)-l-methylpyrrolidine, 2-(4-methyl-piperazin-l-yl)-ethylamine, l-(3-aminopropyl)imidazole, l-(3-aminopropyl)-2-methyl-lH-imidazole, l-(4-aminobutyl)imidazole, and mixtures thereof.

[0109]

[0110] [YES]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] Preferably, component C2b comprises a compound selected from dimethylaminopropylamine (DMAPA), 3-(diethylamino)-1-propylamine (DEAPA), N,N-dimethyldipropylenetriamine (DMAPAPA), and mixtures thereof. Component C2b may comprise several of these compounds, for example 2, 3 or 4 C2b compounds. According to one embodiment, the process for preparing the amino-(meth)acrylate component C2 consists of reacting: - a (meth)acrylate component C2a of formula (4): [Chem. 2] in which Ro is H or methyl, preferably H; Ri is an alkylene, a cycloalkylene, an arylene, an alkenylene, optionally substituted by at least one heteroatom; with - an amino component C2b of formula (5): [Chem. 3] H^NE.—Y P) in which R2 is an alkylene or heteroalkylene and Y is an imidazole function or a tertiary amine function having a pka > 9, preferably a pKa > 10. The term "alkylene" means a divalent saturated acyclic hydrocarbon group of formula -CnH2n in which n is 1 to 100. An alkyl may be straight or branched. Examples of alkylene groups include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, hexylene, 2-methylbutylene, 2,2-dimethylpropylene, n-hexylene, 2-methylpentylene, 2,2-dimethylbutylene, n-heptylene, 2-ethylhexylene and the like. The term "cycloalkylene" means a divalent saturated hydrocarbon group having 1 to 3 rings, having 3 to 20 carbons to form a ring, preferably 3 to 10 carbons. Examples of cycloalkylene groups include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclodecylene, cyclododecylene and isobornylene. The term "arylene" means an optionally substituted divalent aromatic group. Arylene groups may comprise any number of carbon atoms in the ring, such as C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 or C16, as well as C6-8, C6-12 or C6-20. Arylene may contain a single ring (e.g. phenylene) or multiple rings, at least one ring being aromatic. Arylene groups may be monocyclic, fused to form bicyclic (e.g. benzocyclohexyl) or tricyclic groups, or linked by a bond to form a biaryl group. Examples include phenylene, benzylene, naphthylene, biphenylene, phenanthrenylene and naphthacenylene. Arylene groups may also include saturated linear and branched aliphatic hydrocarbyl thereby forming an araliphatic group. The araliphatic groups used herein generally comprise at least one aromatic moiety (e.g., one, two or three aromatic rings, optionally substituted) and at least one non-aromatic moiety (e.g., a C1-20 (hetero)alkylene group or a C1-20 (hetero)alkenylene group).

[0120] The term "alkenylene" refers to a monovalent acyclic hydrocarbon group comprising at least one carbon-carbon double bond. An alkenyl may be straight or branched. Examples of alkenyls include vinyl, propenyl, butenyl, and 2-methylbutenyl.

[0121] The groups R 1 and R 2 are optionally substituted with one or more heteroatoms independently selected from O, N or S. The heteroatom portion may replace a hydrogen of the alkyl group to form, for example, an amino group. Alternatively, the heteroatom portion may be the connecting atom or be inserted between two carbon atoms.

[0122] Compound C2 obtained according to the process described above may in particular comprise a mixture of compounds corresponding to the following formula (3):

[0123] [Chem.4]

[0124] according to which

[0125] Ro, Ri, R2 and Y are as defined above; and

[0126] n varies between 0 and 20.

[0127] The average value of n (nmoy) of the mixture of compounds of formula (3) can in particular be calculated according to the following equation:

[0128] [Math.4] - Na nmoy - Nd.Na

[0129] in which

[0130] Na is the number of moles of amino component of formula (5) used to make the amino-(meth)acrylate

[0131] Nd is the number of moles of (meth)acrylate component of formula (4) used to make the amino-(meth)acrylate. Neutralizing component D

[0132] The crosslinkable composition according to the present invention optionally comprises a crosslinking component D (component D hereinafter). Component D is distinct from components A, B and C.

[0133] Component D according to the invention comprises at least one neutralizing compound. Component D according to the invention may in particular comprise several neutralizing compounds, for example 2, 3 or 4 neutralizing compounds.

[0134] For the purposes of the invention, a “neutralizing compound” is a compound capable of neutralizing the amine functions present in the composition. The neutralizing component D advantageously makes it possible to limit premature polymerization of the composition, which improves its storage stability and its pot life without harming the drying time of the coating obtained.

[0135] According to one embodiment, component D comprises at least one compound chosen from water, an acidic compound or a derivative thereof, and mixtures thereof.

[0136] For the purposes of the invention, an “acid compound” is a compound having at least 1 group chosen from carboxylic acid (-COOH), phosphonic acid or phosphonate (-P(=O)(OR)2), sulfonic acid or sulfonate (-S(=O)2OR), phosphoric acid or phosphate (-OP(=O)(OR)2), sulfuric acid or sulfate (-OS(=O)(OR)2), carbonate or hydrogen carbonate (-OC(=O)-OR), in which each R is independently a counterion, a hydrogen atom, or an optionally substituted hydrocarbyl.

[0137] For the purposes of the invention, a “derivative of an acidic compound” is a compound capable of generating an acidic compound in situ, in particular by hydrolysis. Examples of suitable derivatives of an acidic compound are anhydrides, more particularly cyclic anhydrides.

[0138] Preferably, component D comprises at least one acidic compound having a boiling point, measured at 101.325 kPa, greater than 200°C.

[0139] According to one embodiment, component D comprises at least one compound chosen from water, a phosphorus-based compound, a non-fatty acid, a saturated fatty acid, an unsaturated fatty acid, a resin acid, a polyacid, a cyclic anhydride and mixtures thereof.

[0140] For the purposes of the invention, a "phosphorus-based compound" is a compound having at least one phosphorus atom. Examples of suitable phosphorus-based compounds are phosphoric acid, hypophosphorous acid, pyrophosphoric acid, phosphorous acid, mono- and diesters of phosphoric acid, mono- and diesters of phosphonic acid.

[0141] For the purposes of the invention, a "non-fatty acid" is a saturated or unsaturated, aliphatic or aromatic monocarboxylic acid having from 2 to 9 carbon atoms. Examples of non-fatty acids are acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, 2-ethylhexanoic acid, octanoic acid, pentenoic acid, pentadienoic acid, hexenoic acid, hexadienoic acid, heptenoic acid, heptadienoic acid, octenoic acid, octadienoic acid, nonenoic acid, nonadienoic acid, benzoic acid, hexahydrobenzoic acid, and mixtures thereof.

[0142] For the purposes of the invention, a “saturated fatty acid” is a saturated monocarboxylic acid having from 10 to 22 carbon atoms. Examples of saturated fatty acids are capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, icosanoic acid, 14-hydroxyicosanoic acid and mixtures thereof. The saturated fatty acid may in particular be derived from palm oil, coconut oil, hydrogenated castor oil, animal fat and mixtures thereof.

[0143] For the purposes of the invention, an “unsaturated fatty acid” is a monocarboxylic acid having from 10 to 22 carbon atoms and at least one carbon-carbon double bond. Examples of unsaturated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, gadoleic acid, ricinoleic acid (12-hydroxy-9-octadecenoic acid), elaidic acid, trans-vaccenic acid, erucic acid, nervonic acid, brassidic acid, lesquerolic acid (14-hydroxy-11-icosenoic acid), 9,11-octadecadienoic acid, 10,12-octadecadienoic acid, 8,10,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, 9,11,15-octadecatrienoic acid, 9,13,15-octadecatrienoic acid, 6,9,11-octadecatrienoic acid, 10,12,14-octadecatrienoic acid, 9,11,13,15-octadecatetraenoic acid, 10,12-nonadecadienoic acid, 5,7,9,14,17-icosapentaenoic acid, 5,8,10,12,14-icosapentaenoic acid.Preferably, the conjugated fatty acid is 9,11-octadecadienoic acid, 7,10,13-hexadecatrienoic acid, 9,12,15-octadecatrienoic acid, 6,9,12,15-octadecatrienoic acid, 11,14,17-icosatrienoic acid, 8,11,14,17-icosatetraenoic acid, 5,8,11,14,17-icosapentaenoic acid, 6,9,12,15,18-heneicosapentaenoic acid, . 7,10,13,16,19-docosapentaenoic acid, 4,7,10,13,16,19-docosahexaenoic acid, 9,12,15,18,21-tetracosapentaenoic acid, 6,9,12,15,18,21-tetracosahexaenoic acid, 9,12-octadecadienoic acid, 6,9,12-octadecatrienoic acid, 11,14-icosadienoic acid, 8,11,14-icosatrienoic acid, 5,8,11,14-icosatetraenoic acid, 13,16-docosadienoic acid, 7,10,13,16-docosatetraenoic acid, 4,7,10,13,16-docosapentaenoic acid, 9,12,15,18-tetracosatetraenoic acid, 6,9,12,15,18-tetracosapentaenoic acid

[0144] For the purposes of the present invention, a “resin acid”, also called “resinous acid” or “rosin acid”, denotes a polycyclic compound, in particular a terpenoid, bearing a carboxylic acid group which is derived from resinous trees, in particular conifers. The term “resin acid derivative” means a resin acid which has been modified, for example by one or more of the following reactions: esterification, hydrogenation of a carbon-carbon double bond, epoxidation of a carbon-carbon double bond, hydroxylation of a carbon-carbon double bond, dehydration, maleinization, dimerization, trimerization or oligomerization. The term resin acid includes in particular acids corresponding to one of the following formulae (A) and (B), or one of its derivatives:

[0146] wherein the dotted bonds may be independently selected from single carbon-carbon bonds and double carbon-carbon bonds.

[0147] Examples of resin acids are abietic acid, pimaric acid, levopimaric acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, palustric acid, neoabietic acid, isopimaric acid, sandaracopimaric acid, their derivatives and their mixtures.

[0148] For the purposes of the invention, a "polyacid" is a compound having at least 2 carboxylic acid groups. Examples of suitable polyacids are malonic acid, succinic acid, 2-methylsuccinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, propane-1,2,3-tricarboxylic acid, itaconic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, cyclohexane dicarboxylic acid, tetrahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, trimellitic acid, 2,5-furan dicarboxylic acid, a fatty acid dimer or trimer and mixtures thereof.

[0149] For the purposes of the invention, a cyclic anhydride is a compound having an intracyclic -C(=O)-OC(=O)- bond. Examples of suitable cyclic anhydrides are glutaric anhydride, succinic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric anhydride, tetrahydrophthalic anhydride, phthalic anhydride and mixtures thereof.

[0150] For the purposes of the invention, a “fatty acid dimer”, respectively a “fatty acid trimer”, is a compound obtained by dimerization, respectively by trimerization, of unsaturated fatty acids, in particular of unsaturated fatty acids having from 10 to 22 carbon atoms. The unsaturated fatty acids may be as described above. Examples of fatty acid dimers are Radiacid® 0970, Radiacid® 0971, Radiacid® 0972, Radiacid® 0975, Radiacid® 0976 and Radiacid® 0977 (marketed by the company Oleon), Pripol® 1006, Pripol® 1009, Pripol® 1012 and Pripol® 1013 (marketed by the company Cargill), Empol® 100S, Empol® 1061 and Empol® 1062 (marketed by the company BASF), Unidyme® 18, Unidyme® 22 and Unidyme® 35 (marketed by the company Kraton).

[0151] According to one embodiment, the composition of the present invention comprises component D, component D being present in an amount such that the molar ratio between the neutralizing functions of D and the epoxy functions of Cl is less than 1, preferably less than 0.5, more preferably less than 0.2, even more preferably less than 0.1. Special embodiments

[0152] According to one embodiment, the molar ratio of the Michael acceptor groups of component B to the Michael donor groups of component A is between 1:1 and 3:1, for example between 1.1:1 and 2.9:1 or between 1.2:1 and 2.8:1.

[0153] According to one embodiment, the mixture of components A and B has a viscosity of less than 1500 mPa.s at 23°C according to the method described below. The mixture of components A and B may, for example, have a viscosity of less than 1300 mPa.s at 23°C, less than 1100 mPa.s at 23°C, less than 1000 mPa.s at 23°C, or less than 900 mPa.s at 23°C.

[0154] According to one embodiment, the composition comprises: a. from 20 to 80%, in particular from 30 to 60%, by weight of component A; b. from 5 to 80%, in particular from 20 to 70%, by weight of component B; and c. from 1 to 20%, in particular from 2 to 15%, by weight of component C; d. from 0 to 10000 ppm, in particular from 10 to 5000 ppm, of component D.

[0155] the quantities by weight being expressed relative to the total weight of the composition.

[0156] According to one embodiment, the composition comprises:

[0157] a) as component A: a polyester having at least one malonate group and having a residual solvent content of less than 2% by weight;

[0158] b) as component B:

[0159] - a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups, and

[0160] - a monomer having 3 or 4 (meth)acrylate groups, preferably 3 or 4 groups acrylate;

[0161] c) as component C:

[0162] - a glycidyl ether type Cl compound or a novolac epoxy resin, and

[0163] - a mixture of compounds of formula (3) as defined previously;

[0164] d) optionally as component D:

[0165] - a non-fatty acid, a saturated fatty acid, an unsaturated fatty acid, a resin acid, a polyacid, a cyclic anhydride or a mixture thereof.

[0166] According to one embodiment, the composition is crosslinkable by bringing components A, B, C and optionally D into contact and has a hardness index greater than 200, as measured 24 hours after contacting. The Persoz hardness can in particular be measured according to the method described below. Composition in several parts

[0167] The crosslinkable composition according to the invention is preferably in several parts, for example in 2 or 3 separate parts. The parts are intended to be brought into contact shortly before the application of the crosslinkable composition by an end user. Thus, the crosslinkable composition according to the invention may be in several parts distributed in separate compartments, in particular in the form of a kit, so that the constituents do not react before their use.

[0168] Bringing the epoxy components C1 and amino-(meth)acrylate C2 into contact results in the formation of a strong base which catalyzes the reaction between components A and B. It is therefore preferable to produce the crosslinkable composition by mixing its constituents shortly before use. Preferably, components C1 and C2 are intended to be brought into contact shortly before application of the crosslinkable composition by an end user. Thus, the crosslinkable composition is preferably in several parts, components C1 and C2 of the catalyst component C being in separate parts.

[0169] Thus, according to one embodiment, the composition of the present invention is in 2 parts PI and P2 distributed in two separate compartments, in particular in the form of a kit, so that the constituents of the catalytic system do not react before use.

[0170] According to one embodiment, the composition according to the invention is in 2 parts PI and P2:

[0171] - the first part PI comprising the components A, C2 and optionally the component D; and

[0172] - the second part P2 comprising the components B and Cl.

[0173] According to another embodiment, the composition according to the invention is in 2 parts PI and P2:

[0174] - the first part PI comprising the components A, B and Cl; and

[0175] - the second part P2 comprising the component C2 and optionally the component D.

[0176] According to another embodiment, the composition according to the invention is in 2 parts PI and P2:

[0177] - the first part PI comprising the components A, B, C2 and optionally the component D; and

[0178] - the second part P2 comprising the component Cl.

[0179] According to another embodiment, the composition according to the invention is in 2 parts PI and P2:

[0180] - the first part PI comprising the components A, C2 and optionally the component D; and

[0181] - the second part P2 comprising the component Cl;

[0182] - component B being distributed between part PI and part P2. Process for the preparation of a crosslinked product

[0183] A second object of the present invention also relates to a process for preparing a crosslinked product, characterized in that the process comprises: a. the preparation of a component C2 by reaction between a component C2a and a component C2b with a molar ratio of the (meth)acrylate groups of the compound C2a to the NH bonds of the compound C2b greater than 1; b. the preparation of a composition by bringing components A, B, Cl, C2 and optionally D into contact; c. applying the composition to at least a portion of a surface of a substrate; and d. crosslinking the composition, preferably at a temperature ranging from 0 to 60°C,

[0184] wherein components A, B, Cl, C2, C2a, C2b and D are as defined above.

[0185] According to one embodiment, step b) consists of bringing component C2 into contact with component Cl to form a strong base; then, in a second step, bringing the strong base into contact with component A, component B and possibly component D. According to this embodiment, step b) is broken down into two sub-steps:

[0186] bl) contacting component C2 with a component Cl to form a strong base;

[0187] b2) bringing the strong base into contact with a component A, a component B, and possibly a D component.

[0188] According to another embodiment of the crosslinking process according to the invention, step b) consists of simultaneously bringing into contact the components C1, C2, A, B, and optionally the component D. According to this embodiment, the components C1, C2, A, B and optionally D, are brought into contact in the same step, with formation of the strong base in situ.

[0189] According to the process for preparing a crosslinked product of the present invention, the drying time required after step c) is considerably reduced compared to the crosslinkable compositions described in the prior art. According to one embodiment, the process for preparing a crosslinked product is characterized in that the drying time as measured according to ASTM D1640M-14(2022) is less than 10 h, preferably less than 9 h, and more preferably less than 8 h. Catalyst system

[0190] A third object of the present invention relates to a catalyst system, in particular a catalyst system for carrying out real Michael addition (RMA) crosslinking.

[0191] The catalyst system according to the invention comprises: - an epoxy component Cl; and - an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1.

[0192] Components C1 and C2 are as described previously for the crosslinkable composition according to the invention, as is the process for preparing C2.

[0193] Said catalytic system is capable of generating a strong base in order to catalyze (or initiate) the Michael reaction between components A and B. More particularly, bringing the epoxy components C1 and amino-(meth)acrylate C2 into contact causes the formation of a strong base which, through contact with the Michael donor components A and acceptor components B, leads to an increase in viscosity. It is therefore preferable to produce the crosslinkable composition by mixing its constituents shortly before use. Thus, components C1 and C2 are preferably intended to be brought into contact shortly before application of the crosslinkable composition by an end user.

[0194] According to a preferred embodiment, the catalyst system of the present invention is in 2 parts PI and P2 distributed in two separate compartments, in particular in the form of a kit, so that the constituents of the catalytic system do not react before their use. Use of the catalyst system

[0195] The present invention also relates to the use of the catalyst system as described above to carry out real Michael addition (RMA) crosslinking in the presence of Michael donor and acceptor components.

[0196] The present invention also relates to the use of the catalyst system as described above for catalyzing the reaction between a Michael donor component and a Michael acceptor component. Uses of crosslinkable composition

[0197] The present invention further relates to the use of the crosslinkable composition as described above for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite. EXAMPLES

[0198] The invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and not intended to limit the scope of the invention. Materials

[0199] The materials used in the examples are described below:

[0200] NPG: neopentyl glycol from Sigma-Aldrich

[0201] BEPD: 2-butyl-2-ethyl-1,3-propanediol from Sigma-Aldrich

[0202] DMM: dimethyl malonate from Sigma-Aldrich

[0203] DEM: Diethyl malonate from Sigma-Aldrich

[0204] Fascat 4100: n-butylstannonic acid from BRENNTAG

[0205] TMP: trimethylolpropane from Sigma-Aldrich

[0206] 1.3 PG: 1,3-propanediol from Sigma-Aldrich

[0207] DMAPA: dimethylaminopropylamine from Sigma-Aldrich

[0208] SR238 or HDDA: 1,6-hexanediol diacrylate from Sartomer

[0209] SR355 or DiTMPTA: Sartomer di(trimethylolpropane) tetraacrylate

[0210] BDDGE: 1,4-butanediol diglycidyl ether 95% from Sigma-Aldrich

[0211] DEN 431: epoxy novolac from Dow-Chemical

[0212] EMHQ: Hydroquinone methyl ether from Sigma-Aldrich

[0213] Succinimide from Sigma-Aldrich

[0214] TB AH: tetrabutylammonium hydroxide 40% in water from Sigma-Aldrich

[0215] DEC: Diethyl carbonate from Sigma-Aldrich Preparation of Al polyester:

[0216] The raw materials composing the polyester and their proportions are identical to the polyester Al of patent application WO 2011 / 124665 A1. However, the procedure followed does not involve any solvent and the nature of the transesterification catalyst is modified as follows.

[0217] 274.04 g of NPG (2.6350 mol), 421.83 g of BEPD (2.6364 mol), 590.39 g of DMM (4.4727 mol) and 0.25 g of Fascat 4100 were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. Nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 150°C. The methanol formed during the transesterification reaction is distilled.

[0218] The synthesis is stopped when the contents of the reactor become lower than its final theoretical mass (FTM), i.e. 1000 g.

[0219] A proton NMR analysis of the product obtained shows the total disappearance of the malonate functions. Preparation of polyester 1:

[0220] 311.18 g of NPG (2.9921 mol), 170.65 g of 1,3-propanediol (2.2454 mol), 132.45 g of TMP (0.9884 mol), 907.57 g of DEM (5.6723 mol) and 0.25 g of Fascat 4100 were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. Nitrogen bubbling 50 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 160°C. The ethanol formed during the transesterification reaction is distilled.

[0221] The synthesis is stopped when the contents of the reactor become lower than its final theoretical mass (FTM) i.e. 1000 g. The final mass measured in the reactor was 999.1 g.

[0222] A proton NMR analysis of the product obtained shows the total disappearance of the malonate functions. Preparation of polyesters 2 and 3:

[0223] Proceeding as for polyester 1 with the quantities described in table 1 below, polyesters 2 and 3 were obtained with the final masses measured respectively of 998.5 g and 999.2 g.

[0224] A proton NMR analysis of the product obtained shows the total disappearance of the malonate functions for these 2 products. Preparation of comparative catalyst Cx:

[0225] The comparative catalyst Cx is prepared according to the procedure described in the patent application WO 2013 / 050622 Al from 59.4 g of TB AH (40% in water), 13.5 g of DEC and 14.5 g of isopropanol.

[0226] Preparation of the amino-acrylate compound C2 according to the invention:

[0227] 75.74 g of SR238 and 0.050 g of EMHQ were introduced into a reactor equipped a reflux column, a thermometer, an air bubbling rod, a dropping funnel and a stirrer with inclined blades. Air bubbling of 10 ml / minute was imposed throughout the synthesis. The temperature was raised to 50°C. 24.26 g of DMAPA were added over a period of 1 hour while maintaining the temperature at 50°C. After the introduction of DMAPA, the temperature was raised and maintained at 80°C for 1 h 30 min and then the reactor was cooled to room temperature.

[0228] A carbon 13 NMR analysis shows the total consumption of the primary and secondary amine functions.

[0229] Preparation of comparative formulations and according to the invention Formulations 1 to 4 (comparative):

[0230] The formulations are prepared according to the quantities described in Table 2 below.

[0231] The polyester is mixed with the acrylic monomers in a first bottle. The viscosity of the varnish obtained is then measured at 23°C according to the method: “measurement of the viscosity of a varnish with a viscosity lower than 5000 mPa.s” described below.

[0232] The comparative catalyst Cx and succinimide are introduced into a test tube. After hermetically sealing the tube, the constituents are mixed until the succinimide is completely dissolved.

[0233] The contents of the test tube are then added to the 1st bottle and then mixed.

[0234] The appearance of the formulation is recorded visually.

[0235] After applying the mixture obtained with a filmograph, the Persoz hardness is measured after 24 hours.

[0236] Formulations 1 and 3 were also applied at high thickness (1 cm). After 24 hours, the hardness and appearance of the formulation were recorded (results in Table 4). Formulations 5 to 9 (according to the invention):

[0237] The formulations were prepared according to the quantities described in Table 3 below.

[0238] The polyester was mixed in a first bottle with the amino-acrylate compound C2 according to the invention.

[0239] In a second bottle, the acrylic monomers were mixed with the epoxy component Cl according to the invention.

[0240] The contents of the 2 bottles are then mixed.

[0241] The appearance of the formulations obtained was recorded visually.

[0242] After applying the mixture obtained with a filmograph, the Persoz hardness is measured after 24 hours.

[0243] Formulation 7 was also applied at high thickness (1 cm). After 24 hours, the hardness and appearance of the crosslinked formulation were recorded (results in Table 4). Analytical methods Solvent content:

[0244] Solvent content may be calculated based on the amount by weight of solvent added in a formulation relative to the total weight of the formulation.

[0245] Solvent content can also be measured according to ISO 11890-2:2020.

[0246] Measurement of the viscosity of a varnish before a viscosity lower than 5000 mPa.s:

[0247] The viscosity of a varnish (mixture of components A and B) before application is measured at 23°C on a CAP 1000 Brookfield viscometer (high shear rate) according to ISO 2884-1:1999, with a cone adapted to the measured viscosity.

[0248] Measurement of the viscosity of a monomer having a viscosity less than 200 mPa.s:

[0249] The viscosity of a monomer (in particular component Bl) is measured at 23°C according to the ISO 3219:1993 standard with a Brookfield LVT DVII+ viscometer and an S18 spindle.

[0250] Calculation of the final theoretical mass (FTM) of the contents of a reactor during the synthesis of a malonate functionalized polyester:

[0251] The following calculation is used when the polyester is obtained from a dialkyl malonate, one or more polyols and a catalyst.

[0252] [Math.5] MTF = MI - 2 *MA*Nmalo

[0253] with

[0254] MTF: final theoretical mass

[0255] MI: initial mass of the reactor contents before heating.

[0256] MA: molar mass of the distilled alcohol

[0257] Nmalo: number of moles of malonate functions introduced into the reactor.

[0258] Calculation of the theoretical malonate function rate (fmalo in mgKOH / g) after the synthesis of a polyester:

[0259] Imalo is calculated according to the following equation:

[0260] [Math.6] Imalo =

[0261] Calculation of the average functionality in malonate functions (Fmalo) after synthesis of a polyester:

[0262] The following calculation is used when the polyester is obtained from a malonate of dialkyl, one or more polyols and a catalyst.

[0263] [Math.7] Fmalo = —

[0264] n represents the number of different polyols introduced during the synthesis and

[0265] n; represents the number of moles of each of the polyols introduced.

[0266] Determination of the molar ratio unsaturation / malonate (DL / malonate) in a formulation:

[0267] The level of α,[3-unsaturated groups] is first determined by proton NMR in each of the Michael acceptor compounds of the formulation in the presence of an internal standard (dimethyl orthophthalate). The level of α,[3-unsaturated groups] and the calculated malonate level are used to determine the unsaturation / malonate molar ratio (DL / malonate) in the varnish (mixture comprising components A + B) or the formulation (mixture comprising components A + B + C + possibly D). The DL / malonate ratio therefore takes into account the impurities present in the acrylic monomers.

[0268] Determination of the ratio (methacrylate / active hydrogen (DL / Active hydrogens) in an amino-(meth)acrylate:

[0269] The rate of (meth)acrylate functions is first determined by proton NMR in the acrylic monomer used in the presence of an internal standard (dimethyl orthophthalate). The rate of acrylic functions of the monomers is used to determine the DL / Hydrogen molar ratio. The DL / active hydrogen ratio therefore takes into account the impurities present in the acrylic monomers. Measurement of hardness in fine application:

[0270] Persoz hardness is measured according to the NF EN ISO 1522 standard of March 2007 after application with a filmograph of a composition with a thickness of 150 pm wet (50 pm dry) on a QD46 steel plate (in an air-conditioned room at 23°C, and 50% relative humidity).

[0271] Determination of hardness in thick application:

[0272] In an air-conditioned room at 23°C, and 50% relative humidity, the formulation is cast in an aluminum cup to a thickness between 0.8 cm and 1.2 cm. After 24 hours, hardness is obtained by pressing the crosslinked formulation with the index finger. “Soft” means a formulation undergoing significant deformation with little pressure. “Very hard” means a formulation undergoing no deformation despite significant pressure. Drying time measurement:

[0273] Drying time is measured according to ASTM D 1640. Application and testing at regular intervals (every 10 min after the start of curing) are carried out in an air-conditioned room at 23°C and 50% relative humidity. The drying time is reached when the index finger can be rubbed without any restraint on the applied formulation. Results

[0274] The results are detailed in the tables below.

[0275] The composition of the polyesters is described in Table 1 below.

[0276] [Tables 1] Polyester Al Polyester 1 Polyester 2 Polyester 3 NPG 274.04 311.18 359.96 214.79 BEPD 421.83 / / 220.30 DMM 590.39 / / / DEM / 907.57 901.06 836.78 1,3-PG / 170.65 169.43 209.27 TMP / 132.45 87.65 / Fascat 4100 0.25 0.25 0.25 0.25 Quantity of product obtained 1000 1000 1000 1000 Average malonate functionality 5.60 10.25 7.90 5.41 Malonate index (mgKOH / g) 251 318 316,293

[0277] The composition and properties of the comparative formulations are described in Table 2 below.

[0278] [Tables2] Formulation 1 2 3 4 Polyester Al 9.06 / / / Polyester 1 / 9.06 / / Polyester 2 / / 9.06 / Polyester 3 / / / 9.06 SR355 5.61 6.50 7.42 7.83 SR238 3.10 4.54 3.60 2.46 Catalyst Cx 1.20 1.20 1.20 1.20 Succinimide 0.24 0.24 0.24 0.24 Varnish viscosity (mPa.s) 800 800 800 800 DL / malonate ratio 1.75 1.75 1.75 1.75 Hardness 24h (150 pm) 274 276 288 271 Formulation appearance Opaque Opaque Opaque Opaque

[0279] Table 2 shows that the prior art catalyst component (catalyst Cx) is poorly suited to solvent-free formulations: the tested formulations exhibit satisfactory hardnesses in thin application after 24 hours, but they are opaque. Their appearance is not satisfactory. The prior art catalyst component is therefore not suitable for solvent-free applications.

[0280] The composition and properties of the formulations according to the invention are described in Table 3 below.

[0281] [Tables3] Formulation 5 6 7 8 9 Polyester Al 9.06 / / / / Polyester 1 / 9.06 / / / Polyester 2 / / 9.06 / 9.06 Polyester 3 / / / 9.06 / SR355 5.61 6.50 7.42 7.83 7.42 SR238 3.10 4.54 3.60 2.46 3.60 BDDGE 1.00 1.00 1.00 1.00 / DEN431 / / / / 1.00 Amino-acrylate compound C2 0.94 0.94 0.94 0.94 0.94 Varnish viscosity (mPa.s) 800 800 800 800 800 DL / malonate ratio 1.75 1.75 1.75 1.75 1.75 Hardness 24h (150 pm) 142 177 191 172 244 Formulation appearance Clear Clear Clear Clear Clear Drying time 5h40 4hl5 4hl5 4h40 4hl5

[0282] Table 3 shows that the catalyst component of the present invention comprising an epoxy component C1 (BDDGE or DEN431) and the amino-acrylate compound C2, is more suitable for solvent-free formulations: the formulations tested are clear before and after crosslinking and have satisfactory hardnesses, regardless of the polyester used.

[0283] Furthermore, the drying time is advantageously reduced when the formulations comprise polyesters having malonate indices (MI) > 260 mg KOH / g.

[0284] The hardness and drying time of the thick film formulations are described in Table 4 below.

[0285] [Tables4] Formulation 1 3 7 Hardness 24h (1cm) soft soft very hard Drying time > 12h > 12h 2h Appearance crosslinked formulation Cloudy Cloudy Transparent

[0286] Table 4 shows that formulation 7 according to the invention is suitable for thick solvent-free applications: it has a significantly reduced drying time compared to the formulations of the prior art, while having a higher hardness and a transparent appearance after crosslinking.

Claims

Claims

1. A crosslinkable composition comprising: a) a Michael donor component A; b) a Michael acceptor component B; c) a catalyst component C comprising: - an epoxy component C1; and - an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1; and d) optionally a neutralizing component D.

2. Composition according to claim 1, characterized in that the composition comprises less than 2% by weight of non-reactive organic solvent, relative to the total weight of the composition.

3. A composition according to any preceding claim, characterized in that component C1 comprises a compound selected from a glycidyl ether, a glycidyl ester, a cycloaliphatic epoxy and combinations thereof.

4. A composition according to any one of the preceding claims, characterized in that component C1 comprises a compound selected from versatic acid glycidyl ester, cardanol glycidyl ether, bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, isosorbide diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, novolac epoxy resin and mixtures thereof.

5. Composition according to any one of the preceding claims, characterized in that the latent catalyst group of component C2 is chosen from an imidazole function or a tertiary amine function having a pka > 9, preferably a pKa > 10.

6. Composition according to any one of the preceding claims, characterized in that the component C2 is capable of being obtained by reaction between: - a (meth)acrylate component C2a having a (meth)acrylate group functionality greater than or equal to 2, preferably an acrylate component C2a having an acrylate group functionality greater than or equal to 2; and - an amino component C2b having an NH bond functionality greater than or equal to 2 and a group functionality

7.

8.

9. latent catalyst greater than or equal to 1, the molar ratio of the (meth)acrylate groups of compound C2a to the NH bonds of compound C2b being greater than 1. Composition according to claim 6, characterized in that component C2b may in particular comprise at least one compound having: - at least 1 primary amine function or at least 2 secondary amine functions; and - at least 1 function chosen from imidazole or tertiary amine having a pKa > 9. Composition according to claim 6 or 7, characterized in that component C2b comprises at least one compound chosen from dimethylaminopropylamine (DMAPA), 3-(diethylamino)-1-propylamine (DEAPA), N,N-dimethyldipropylenetriamine (DMAPAPA), and mixtures thereof. Composition according to any one of the preceding claims, characterized in that compound C2 comprises a mixture of compounds corresponding to the following formula (3): [Chem. 6]

10. according to which Ro is H or methyl, preferably H; Ri is an alkylene, a cycloalkylene, an arylene, an alkenylene, optionally substituted by at least one heteroatom; R2 is alkylene or heteroalkylene; and Y is an imidazole function or a tertiary amine function having a pka > 9, preferably a pKa > 10; n varies between 0 and 20. Composition according to any one of the preceding claims, characterized in that the molar ratio of the Michael acceptor groups of component B to Michael donor groups of component A is between 1:1 and 3:

1.

11. A composition according to any one of the preceding claims, characterized in that component A comprises a compound with a malonate group Al.

12. Composition according to any one of the preceding claims, characterized in that component A comprises a compound Al chosen from a dialkyl malonate, a polymer having at least one malonate group, and mixtures thereof.

13. Composition according to claim 11 or 12, characterized in that the component Al has a malonate index (MI) greater than 260 mg KOH / g.

14. Composition according to any one of claims 11 to 13, characterized in that the component Al has an average malonate functionality (fM) greater than 4.

15. Composition according to any one of the preceding claims, characterized in that component B comprises: - a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2; and / or - a Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3.

16. Composition according to claim 15, characterized in that component B comprises component B1 and component B2.

17. Composition according to claim 15 or 16, characterized in that the mass ratio between component B1 and component B2 is between 1:0.1 and 1:100, preferably from 1:0.2 to 1:20, more preferably from 1:1 to 1:

10.

18. Composition according to any one of the preceding claims, characterized in that component B1 comprises a compound selected from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, a maleate, an itaconate, a fumarate and mixtures thereof; preferably, a compound selected from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, and mixtures thereof; more preferably, a monomer having 2 (meth)acrylate groups.

19. A composition according to any preceding claim, ca- characterized in that component B2 comprises a compound selected from a monomer having at least 3 (meth)acrylate groups, an oligomer having at least 3 (meth)acrylate groups, and mixtures thereof; preferably, a monomer having at least 3 (meth)acrylate groups.

20. Composition according to any one of the preceding claims, characterized in that the composition comprises component D, component D being present in an amount such that the molar ratio between the neutralizing functions of D and the epoxy functions of Cl is less than 1, preferably less than 0.5, more preferably less than 0.2, even more preferably less than 0.

1.

21. Composition according to any one of the preceding claims, characterized in that component D comprises at least one compound chosen from water, an acidic compound, and mixtures thereof.

22. Composition according to any one of the preceding claims, characterized in that the composition is in 2 parts PI and P2: - the first part PI comprising components A, C2 and optionally component D; and - the second part P2 comprising component B and Cl.

23. A composition according to any one of the preceding claims, characterized in that the composition comprises: a. from 20 to 80%, in particular from 30 to 60%, by weight of component A; b. from 5 to 80%, in particular from 20 to 70%, by weight of component B; c. from 1 to 20%, in particular from 1 to 15%, by weight of component C; and d. from 0 to 10000 ppm, in particular from 10 to 5000 ppm, of component D; the amounts by weight being expressed relative to the total weight of the composition.

24. Composition according to any one of the preceding claims, characterized in that the composition comprises: a) as component A: a polyester having at least one malonate group and having a residual solvent content of less than 2% by weight; b) as component B: - a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups; and - a monomer having 3 or 4 (meth)acrylate groups, preferably 3 or 4 acrylate groups; c) as component C: - a glycidyl ether type Cl compound or a novolac epoxy resin, and - a mixture of compounds of formula (3) as defined in claim 9; d) optionally as component D: - a non-fatty acid, a saturated fatty acid, an unsaturated fatty acid, a resin acid, a polyacid, a cyclic anhydride or a mixture thereof.

25. A process for preparing a crosslinked product comprising the following steps: a. the preparation of a component C2 by reaction between a component C2a and a component C2b with a molar ratio of the (meth)acrylate groups of the compound C2a to the NH bonds of the compound C2b greater than 1; b. the preparation of a composition by bringing components A, B, Cl, C2 and optionally D into contact; c. applying the composition to at least a portion of a surface of a substrate; and d. crosslinking the composition, preferably at a temperature ranging from 0 to 60°C,

26.

27. wherein components A, B, Cl, C2, C2a, C2b and D are as defined in claims 1 to 24. Catalytic system comprising: - an epoxy component Cl; and - an amino-(meth)acrylate component C2 having a (meth)acrylate group functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 1. Use of the catalytic system according to claim 26 for catalyze a real Michael addition (RMA) crosslink.

28. Use of the crosslinkable composition according to any one of claims 1 to 24, for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical sealant, an adhesive, a polymeric concrete or a composite.