Composition that is crosslinkable via michael addition

Abstract

The present invention relates to a composition that is crosslinkable via real Michael addition (RMA), and more particularly to a solvent-free crosslinkable composition, suitable for use in preparing coatings, paints, varnishes, inks, moulded objects, sealing membranes, chemical sealing agents, adhesives, polymer concretes or composites. The present invention in particular relates to a catalytic system that can be used for solvent-free RMA crosslinking, as well as to a method for preparing a crosslinked product by applying the composition to, and crosslinking the composition on, at least one substrate.

Description

[0001] DESCRIPTION

[0002] TITLE OF THE INVENTION: MICHAEL ADDITION CROSSLINKABLE COMPOSITION

[0003] FIELD OF THE INVENTION

[0004] 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.

[0005] TECHNICAL BACKGROUND

[0006] Durable, highly crosslinked coatings can be achieved using true Michael addition (RMA) chemistry. RMA-curable 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.

[0007] EP 0326723 A1 (ROHM ET 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 to improve the pot life and gloss of the coatings, and which are also used to lower the viscosity of the formulations before use.

[0008] 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, thereby generating a strong base 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 include an organic solvent whose role is to adjust the viscosity of the formulations before use so that they can be easily applied to the substrates by the formulator.

[0009] 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 systems have reduced pot lives and extended curing speeds, which do not meet market expectations.

[0010] 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.

[0011] 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).

[0012] Yet another object of the present invention is to provide crosslinkable compositions which exhibit a rapid drying time.

[0013] SUMMARY OF THE INVENTION

[0014] A first subject of the present invention relates to a crosslinkable composition, in particular a composition crosslinkable by adding a catalyst component C.

[0015] 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:

[0016] - an epoxy component Cl; and

[0017] - an amino-acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3; d) optionally a neutralizing component D.

[0018] A second subject of the present invention also relates to a process for preparing an amino-acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3, said process comprising the reaction between: a (meth)acrylate component C2a having a (meth)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, the molar ratio of the (meth)acrylate groups of the compound C2a to the NH bonds of the compound C2b being less than 1.

[0019] A third subject of the present invention relates to a process for preparing a crosslinked product, characterized in that the process comprises the following steps: a) preparing 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 less than 1; b) preparing a composition by bringing components A, B and C, 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, wherein components A, B, C1, C2, C2a and C2b, and optionally D, are as defined in the present description.

[0020] A fourth object of the present invention relates to a catalytic system comprising: an epoxy component C1; and an amino-acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3.

[0021] A fifth 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).

[0022] A sixth 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.

[0023] DETAILED DESCRIPTION

[0024] In the context of the present invention:

[0025] - the expression “between ... and ...” (for example, a range of values) must be understood as including the limits (for example, the limit values ​​of this range of values);

[0026] - the expression “includes a / an” must be understood as meaning “includes at least one”;

[0027] - any description in connection with one embodiment is applicable and interchangeable with all other embodiments of the invention; and - when an element or component is included in and / or chosen and / or selected from a list of elements or components, it is to be understood that this 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 this list.

[0028] Crosslinkable composition

[0029] A first subject of the present invention relates to a crosslinkable composition, in particular a composition crosslinkable by adding a catalyst component C.

[0030] 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:

[0031] - an epoxy component Cl; and

[0032] - an amino-acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3; d) optionally a neutralizing component D.

[0033] When brought into contact, components Cl and C2 are capable of generating a strong base to catalyze (or initiate) the Michael reaction between components A and B.

[0034] The crosslinkable composition according to the invention may in particular be a solvent-free composition.

[0035] For the purposes 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 may in particular be determined according to the method described below.

[0036] For the purposes 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.

[0037] For the purposes of the present invention, the term “organic solvent” means a solvent having carbon atoms.

[0038] For the purposes 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.

[0039] Michael A Donor Component

[0040] The crosslinkable composition according to the present invention comprises a Michael A donor component (component A hereinafter).

[0041] 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.

[0042] 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.

[0043] Each compound A contains at least one Michael donor group. A Michael donor group is a group with a labile proton alpha to a carbonyl function. Each compound A may contain multiple 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.

[0044] Preferably, component A comprises at least one compound with a malonate group and is referred to herein as component AL. Component A may comprise several Al compounds, for example 2, 3 or 4 distinct Al compounds.

[0045] According to one embodiment, the component Al comprises a polymer having at least one malonate group, said polymer being selected from a polyester, a polyurethane, a poly(meth)acrylate, an epoxy polymer, a polyamide, a polyesteramide, a polyvinyl polymer, and mixtures thereof.

[0046] 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.

[0047] 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.

[0048] Preferably, component Al comprises a polyester having at least one malonate group.

[0049] 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):

[0050] [Math 1]

[0051] 56100

[0052] Imalo = -

[0053] MT in which

[0054] Nmalo: number of moles of malonate functions introduced into the reactor

[0055] MTF: final theoretical mass, calculated according to the following equation (Math 2):

[0056] [Math 2]

[0057] MTF = MI — 2 * MA * Nmalo in which

[0058] MI: initial mass of the reactor contents before heating

[0059] MA: molar mass of the distilled alcohol

[0060] According to one embodiment, the Al component has an average malonate functionality (fM) greater than 4. The malonate functionality can in particular be calculated according to the following equation (Math 3):

[0061] [Math 3] in which n represents the number of different polyols introduced during the synthesis and represents the number of moles of each of the polyols introduced.

[0062] 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.

[0063] When component A comprises a polymer, this 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.

[0064] Michael B acceptor component

[0065] The crosslinkable composition according to the present invention comprises a Michael B acceptor component (component B hereinafter).

[0066] Component B may in particular comprise a Michael acceptor component B1 having an α,β-unsaturated group functionality ranging from 1 to 2, and / or a Michael acceptor component B2 having an α,β-unsaturated group functionality greater than or equal to 3.

[0067] For the purposes of the present invention, an α,β-unsaturated group is a group comprising a carbon-carbon double bond in the α,β position of a carbonyl function, in particular in the α,β 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 R a and Rb are independently H, alkyl or aryl.

[0068] According to one embodiment, component B comprises only component B1 having an α,β-unsaturated group functionality ranging from 1 to 2 or only Michael acceptor component B2 having an α,β-unsaturated group functionality greater than or equal to 3.

[0069] According to another embodiment, component B comprises component B1 having an α,β-unsaturated group functionality ranging from 1 to 2 and component B2 having an α,β-unsaturated group functionality greater than or equal to 3.

[0070] 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.

[0071] Component B1 of the present invention may comprise one or more distinct Michael donor compounds, each having an α,β-unsaturated group functionality ranging from 1 to 2.

[0072] 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.

[0073] 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.

[0074] According to one embodiment, component B 1 comprises a compound selected 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 B 1 comprises a monomer having 2 acrylate groups.

[0075] 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, 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)m ethyl (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.,

[0076] According to one embodiment, component B1 comprises a monomer having 2 (meth)acrylate groups selected 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, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 3-methyl-1,5-pentanediol 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; as well as alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the aforementioned compounds are particularly preferred.,

[0077] According to one embodiment, component B1 comprises a maleate selected from dimethyl maleate, diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-n-butyl maleate, diisobutyl maleate, di-tert-butyl maleate, and mixtures thereof.

[0078] 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.

[0079] According to one embodiment, component B1 comprises a fumarate selected from dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-tert-butyl fumarate, and mixtures thereof.

[0080] Preferably, component B1 comprises at least one monomer having 2 acrylate groups selected 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. Component B2 of the present invention may comprise one or more distinct Michael donor compounds, each having an α,β-unsaturated group functionality greater than or equal to 3.

[0081] According to one embodiment, 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. 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.

[0082] 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.

[0083] According to one embodiment, component B2 comprises at least one monomer having at least 3 (meth)acrylate groups selected 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 (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the compounds cited above are particularly preferred.

[0084] 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.

[0085] Preferably, component B2 comprises at least one monomer having 3 or 4 acrylate groups selected from glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate and mixtures thereof.

[0086] 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. According to one embodiment, the average functionality in the α,β-unsaturated group of the component B varies between 1.5 and 6, preferably between 2 and 4.

[0087] Catalyst component C

[0088] The present invention implements a catalyst component particularly suitable for solvent-free crosslinkable compositions. More specifically, the crosslinkable composition according to the present invention comprises a catalyst component C comprising: an epoxy component C1; and an amino-acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3.

[0089] Component C is a catalytic system capable of generating a strong base 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 the application of the crosslinkable composition by an end user.

[0090] 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-acrylate component C2, makes it possible both to produce solvent-free formulations and to produce resins having satisfactory hardnesses after crosslinking. Furthermore, their drying times are considerably reduced compared to comparative formulations.

[0091] 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.

[0092] The Cl component 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 to an aliphatic ring such as cyclohexyl) and combinations thereof. The Cl component may comprise several of these compounds, for example 2, 3 or 4 distinct Cl compounds.

[0093] The component Cl may in particular comprise at least one 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 an aliphatic or aromatic C4-C26 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 monobasic acid (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 E10P marketed by Hexion), methyl 9,10-epoxystearate, ethyl 9,10-epoxystearate, butyl 9,10-epoxystearate, 2-ethylhexyl 9,10-epoxystearate, 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, ethylene glycol di(3,4-epoxycyclohexylmethyl)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-propanediol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol, 3,3-butylethyl-1,5-pentanediol diglycidyl 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), glycerol triglycidyl ether,trimethylolmethane triglycidyl ether, 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, 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-acid,iso- or terephthalic acid, diglycidyl esters of tetrahydrophthalic acid, diglycidyl esters of hexahydrophthalic acid, epoxidized vegetable oil (in particular epoxidized soybean oil, epoxidized linseed oil), epoxidized polybutadiene, triglycidyl isocyanurate, as well as alkoxylated (in particular ethoxylated and / or propoxylated) derivatives thereof, and mixtures thereof.,

[0094] Preferably, component C1 comprises at least one 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.

[0095] In addition to the epoxy component C1, the catalyst component C also comprises an amino-(meth)acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3. Preferably, the amino-(meth)acrylate component C2 has a (meth)acrylate group functionality less than 1, or even zero (meth)acrylate group functionality.

[0096] 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).

[0097] The amino-(meth)acrylate component C2 (or component C2 hereinafter) may in particular comprise an amino-(meth)acrylate having at least 2 NH bonds and at least 3 latent catalyst groups, preferably an amino-acrylate having at least 2 NH bonds and at least 3 latent catalyst groups. The component C2 may also comprise a mixture of amino-(meth)acrylates as defined above. In this case, the NH bond functionality of the component C2 corresponds to the average NH bond functionality of the mixture. The average NH bond functionality may in particular correspond to the sum of the NH bond functionalities of each constituent of the mixture weighted by the molar fraction of each constituent of the mixture. Preferably, the NH bonds of the amino-(meth)acrylate C2 are included in a secondary amine function.Thus, component C2 preferably comprises an amino-(meth)acrylate having at least 2 secondary amine functions and at least 3 latent catalyst groups.

[0098] 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.

[0099] 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.

[0100] The tertiary amine function can notably respond to the formula -NR a Rb (1) in which R a and Rb, identical or different, represent a C1-C4 alkyl or a cycloalkyl, or R a and Rb form a C2-C6 heterocycle.

[0101] The imidazole function can notably correspond to the following formula (2): [Chem 1] in which R c , Rd and K are independently selected from H, alkyl, aryl and alkylaryl or R c and Rd, together with the carbon atoms to which they are bonded, can form a ring.

[0102] Component C2 can be obtained by reaction between:

[0103] - 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

[0104] - 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, the molar ratio of the (meth)acrylate groups of compound C2a to the NH bonds of compound C2b being less than 1.

[0105] According to one embodiment, the molar ratio of the (meth)acrylate groups of compound C2a to the NH bonds of compound C2b is less than 0.99, less than 0.98, less than 0.95 or even less than 0.90.

[0106] 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.

[0107] 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.

[0108] Component C2b comprises at least one 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)).

[0109] Component C2b may in particular comprise at least one compound having:

[0110] - at least 1 primary amine function or at least 2 secondary amine functions; and

[0111] - at least 1 function chosen from imidazole or tertiary amine having a pKa > 9.

[0112] Preferably, component C2b comprises at least one compound having at least 1 primary amine function and at least 1 function chosen from imidazole or tertiary amine having a pKa > 9.

[0113] More preferably, component C2b comprises at least one compound having at least 1 primary amine function and at least 1 tertiary amine function having a pKa > 9.

[0114] Component C2b may in particular comprise at least one compound chosen from N,N-dimethylethylenediamine, N,N-diethylethylenediamine, dimethylaminopropylamine (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.Preferably, component C2b comprises at least one compound selected from dimethylaminopropylamine (DMAPA), 3-(diethylamino)-1-propylamine (DEAPA), N,N-dimethyldipropylenetriamine (DMAPAPA), and mixtures thereof.

[0115] According to one embodiment, the method for preparing the amino-(meth)acrylate component C2 consists of reacting: a (meth)acrylate component C2a of formula (4): [Chem 2] in which

[0116] Ro is H or methyl, preferably H;

[0117] Ri is alkylene, cycloalkylene, arylene, alkenylene, optionally substituted by at least one heteroatom; with an amino component C2b of formula (5):

[0118] [Chem 3] 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.

[0119] The term "alkylene" means a divalent saturated acyclic hydrocarbon group of the formula -CnPEn 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.

[0120] 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 isobomylene.

[0121] The term "arylene" means an optionally substituted divalent aromatic group. Arylene groups may contain 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, with 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 a saturated linear and branched aliphatic hydrocarbyl thus 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).

[0122] The term "alkenylene" refers to a monovalent acyclic hydrocarbon group containing at least one carbon-carbon double bond. An alkenyl can be straight or branched. Examples of alkenyls include vinyl, propenyl, butenyl, and 2-methylbutenyl.

[0123] The R 1 and R 2 groups 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.

[0124] According to this embodiment, the compound C2 obtained according to the process described above may in particular comprise a mixture of compounds corresponding to the following formula (3):

[0125] [Chem 4] according to which:

[0126] Ro, Ri, R2 and Y are as defined above; and n varies between 0 and 20.

[0127] The average value of n (n moy ) of the mixture of compounds of formula (3) can in particular be calculated according to the following equation: [Math 4]

[0128] N D n™y Na - Nd in which

[0129] NA is the number of moles of amino component of formula (5) used to make the amino-(meth)acrylate, ND is the number of moles of (meth)acrylate component of formula (4) used to make the amino-(meth)acrylate.

[0130] Neutralizing component D

[0131] 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.

[0132] 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.

[0133] 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 affecting the drying time of the coating obtained.

[0134] According to one embodiment, component D comprises at least one compound selected from water, an acidic compound or a derivative thereof, and mixtures thereof.

[0135] For the purposes of the invention, an “acidic compound” is a compound having at least 1 group selected 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.

[0136] 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.

[0137] Preferably, component D comprises at least one acidic compound having a boiling point, measured at 101.325 kPa, greater than 200°C.

[0138] According to one embodiment, component D comprises at least one compound selected 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. 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.

[0139] 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.

[0140] 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.

[0141] 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-1 1-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, acid 6,9,12,15,18-tetracosapentaenoic acid.

[0142] 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: [Chem 5] wherein the dotted bonds may be independently selected from single carbon-carbon bonds and double carbon-carbon bonds.

[0143] 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 mixtures thereof.

[0144] 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 acid dicarboxylic acid, a dimer or a trimer of fatty acid and mixtures thereof. 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.

[0145] 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).

[0146] 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.

[0147] Special embodiments

[0148] According to one embodiment of the crosslinkable composition according to the invention, the molar ratio of Michael B acceptor groups to Michael A donor groups 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.

[0149] 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.

[0150] 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 40%, in particular from 2 to 25%, by weight of component C; 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.

[0151] According to one embodiment, 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:

[0152] - a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups, and

[0153] - a monomer having 3 or 4 (meth)acrylate groups, preferably 3 or 4 acrylate groups; c) as component C:

[0154] - a glycidyl ether type Cl compound or a novolac epoxy resin, and

[0155] - a mixture of compounds of formula (3) as defined above; d) optionally as component D:

[0156] - a non-fatty acid, a saturated fatty acid, an unsaturated fatty acid, a resin acid, a polyacid, a cyclic anhydride or a mixture thereof.

[0157] 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 contact. The Persoz hardness can in particular be measured according to the method described below.

[0158] Composition in several parts

[0159] 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.

[0160] 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, with components C1 and C2 of the catalyst component C being in separate parts.

[0161] 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 their use.

[0162] According to one embodiment, the composition according to the invention is in 2 parts PI and P2:

[0163] - the first part PI comprising components A, C2 and optionally component D; and

[0164] - the second part P2 comprising components B and CL

[0165] According to another embodiment, the composition according to the invention is in 2 parts PI and P2: - the first part PI comprising the components A, B and Cl; and

[0166] - the second part P2 comprising component C2 and optionally component D.

[0167] According to another embodiment, the composition according to the invention is in 2 parts PI and P2:

[0168] - the first part PI comprising components A, B, C2 and optionally component D; and

[0169] - the second part P2 comprising the component Cl.

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

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

[0172] - the second part P2 comprising the component Cl;

[0173] - component B being distributed between part PI and part P2.

[0174] Process for the preparation of an amino-(meth)acrylate C2

[0175] The present invention also relates to a process for preparing an amino-(meth)acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3, said process comprising the reaction between:

[0176] - 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

[0177] - 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, the molar ratio of the (meth)acrylate groups of compound C2a to the NH bonds of compound C2b being less than 1.

[0178] The particular embodiments described above for components C2, C2a and C2b also apply to the method according to the invention.

[0179] Process for the preparation of a crosslinked product

[0180] The present invention also relates to a process for preparing a crosslinked product, characterized in that the process comprises: a) preparing 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 less than 1; b) preparing 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; wherein components A, B, Cl, C2, C2a, C2b and D are as defined above.

[0181] 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: b1) bringing component C2 into contact with a component Cl to form a strong base; b2) bringing the strong base into contact with a component A, a component B and possibly a component D.

[0182] According to another embodiment of the crosslinking method according to the invention, step b) consists of simultaneously bringing into contact the components Cl, C2, A, B, and optionally the component D. According to this embodiment, the components Cl, C2, A and B, and optionally D, are brought into contact in the same step, with formation of the strong base in situ.

[0183] According to the process for preparing a crosslinked product of the present invention, the drying time required after step c) is 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 D 1640M-14(2022) is less than 7 h, preferably less than 6.5 h.

[0184] Catalyst system

[0185] The present invention also relates to a catalyst system, in particular a catalyst system for carrying out real Michael addition (RMA) crosslinking.

[0186] The catalyst system according to the invention comprises: an epoxy component C1; and an amino-(meth)acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3.

[0187] Components C1 and C2 are as described previously for the crosslinkable composition according to the invention, as is the process for preparing C2.

[0188] 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.

[0189] Thus, according to one 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.

[0190] Use of the catalyst system

[0191] 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.

[0192] The present invention also relates to the use of the catalyst system as described above to catalyze the reaction between a Michael donor component and a Michael acceptor component.

[0193] Uses of crosslinkable composition

[0194] 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 sealant, an adhesive, a polymeric concrete or a composite.

[0195] EXAMPLES

[0196] 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.

[0197] Materials

[0198] The materials used in the examples are described below:

[0199] NPG: neopentyl glycol from Sigma-Aldrich

[0200] BEPD: 2-butyl-2-ethyl-1,3-propanediol from Sigma-Aldrich

[0201] Fascat 4100: n-butylstannonic acid from BRENNTAG

[0202] TMP: Trimethylolpropane from Sigma-Aldrich

[0203] 1.3 PG: 1.3-propanediol from Sigma-Aldrich

[0204] DEM: Diethyl malonate from Sigma-Aldrich

[0205] DMAPA: dimethylaminopropylamine from Sigma-Aldrich

[0206] SR238 or HD DA: 1,6-hexanediol diacrylate from Sartomer

[0207] SR355 or DiTMPTA: Di(trimethylolpropane) tetraacrylate from Sartomer SR833S or TCDDMDA: Tricyclodecyldimethanol diacrylate from Sartomer BDDGE: 1,4-Butanediol diglycidyl ether 95% from Sigma-Aldrich DEN 431: Epoxy novolac from Dow-Chemical

[0208] EMHQ: Hydroquinone methyl ether from Sigma-Aldrich

[0209] Fatty acid dimer: Pripol 1017 from Cargill

[0210] Abietic acid: 75% technique from Sigma-Aldrich

[0211] Acetic acid: Sigma-Aldrich

[0212] Preparation of polyester A:

[0213] 214.79 g of NPG (2.0653 mol), 209.27 g of 1,3-propanediol (2.7536 mol), 220.30 g of BEPD (1.3769 mol), 836.78 g of DEM (5.2299 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.

[0214] The synthesis is stopped when the contents of the reactor become lower than its final theoretical mass (FTM), i.e. 1000 g.

[0215] The final mass measured in the reactor was 999.2 g.

[0216] A proton NMR analysis of the product obtained shows the total disappearance of the malonate functions.

[0217] Preparation of polyester B:

[0218] 359.96 g of NPG (3.4612 mol), 169.43 g of 1,3-propanediol (2.2293 mol), 87.65 g of TMP (0.6541 mol), 901.06 g of DEM (5.6316 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 a stirrer with inclined blades. A nitrogen bubbling of 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.

[0219] The synthesis is stopped when the contents of the reactor become lower than its MTF, i.e. 1000 g.

[0220] The final mass measured in the reactor was 998.5 g.

[0221] A proton NMR analysis of the product obtained shows the total disappearance of the malonate functions.

[0222] Preparation of amino-acrylate 1 (comparative):

[0223] 75.74 g of SR238 and 0.050 g of EMHQ were introduced into a reactor equipped with 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 minutes and then the reactor was cooled to room temperature.

[0224] Carbon-13 NMR analysis shows the total consumption of primary and secondary amine functions.

[0225] Preparation of amino-acrylate 2 (according to the invention):

[0226] 40.75 g of DMAPA was introduced into a reactor equipped with 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 40 ° C. 75.74 g of SR238 was added over a period of 1 hour and 30 minutes while maintaining the temperature at 40 ° C. After the introduction of SR238, the temperature was raised and maintained at 80 ° C for 2 hours and then the reactor was cooled to room temperature.

[0227] Proton NMR analysis shows the total consumption of acrylic functions.

[0228] Preparation of amino-acrylate 3 (according to the invention):

[0229] 40.75 g of DMAPA was introduced into a reactor equipped with 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 40 ° C. 75.74 g of SR833S was added over a period of 1 hour and 30 minutes while maintaining the temperature at 40 ° C. After the introduction of SR833S, the temperature was raised and maintained at 80 ° C for 2 hours and then the reactor was cooled to room temperature.

[0230] Proton NMR analysis shows the total consumption of acrylic functions.

[0231] Polyester A / amino-acrylate blends described in Table 2:

[0232] 45.29 g of polyester A was mixed with 4.71 g of amino-acrylate 1 in a sealed bottle. The viscosity according to the method "measurement of the viscosity of a mixture with a viscosity greater than 5000 mPa.s" was measured immediately after mixing, at 15 days, at 2 months and at 6 months of aging.

[0233] Similarly, a mixture was prepared from polyester A and aminoacrylate 2.

[0234] Preparation of comparative formulations and those according to the invention

[0235] Formulations 1 to 5 of Table 3:

[0236] The formulations were prepared according to the quantities described in Table 3. The polyester was mixed in a 1 er bottle with aminoacrylate. In a 2 eme In the bottle, the acrylic monomers were mixed with the epoxies.

[0237] The contents of the 2 bottles were then mixed and the viscosity was measured using the method "measuring the viscosity of a varnish with a viscosity lower than 5000 mPa.s". After applying the mixture obtained with a filmograph, the drying time and the Persoz hardness (24 hours) were measured.

[0238] Formulations 6 to 8 of Table 4:

[0239] The formulations were prepared according to the quantities described in Table 4. Polyester B was mixed in a 1 er bottle with aminoacrylate.

[0240] In a 2 eme In the bottle, the acrylic monomers were mixed with the epoxies.

[0241] The contents of the 2 bottles were then mixed and the viscosity was measured using the “measurement of the viscosity of a mixture with a viscosity lower than 5000 mPa.s” method. After applying the mixture obtained with a filmograph, the drying time, pot life and Persoz hardness (24 hours and 5 days) were measured.

[0242] Analytical methods

[0243] Solvent content:

[0244] Solvent content can 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 varnish before a viscosity greater than 5000 mPa.s:

[0249] The viscosity of a varnish (mixture of components A and B) before application is measured at 23°C according to ISO 3219: 1993 using a Brookfield LVT DVII+ viscometer and an S34 spindle.

[0250] Measurement of the viscosity of a monomer before a viscosity lower than 200 mPa.s:

[0251] The viscosity of a monomer (in particular component Bl) is measured at 23°C according to ISO 3219:1993 using a Brookfield LVT DVII+ viscometer and an S18 spindle. Calculation of the final theoretical mass (FTM) of the contents of a reactor during the synthesis of a malonate-functionalized polyester:

[0252] The following calculation is used when the polyester is obtained from a dialkyl malonate, one or more polyols and a catalyst.

[0253] [Math 5]

[0254] MT F = MI — 2 * MA * Nmalo with

[0255] MTF: final theoretical mass

[0256] MI: initial mass of the reactor contents before heating.

[0257] MA: molar mass of the distilled alcohol

[0258] Nmalo: number of moles of malonate functions introduced into the reactor.

[0259] Calculation of the theoretical malonate function rate (Imalo in mgKOH / g) after the synthesis of a polyester: Imalo is calculated according to the following equation:

[0260] [Math 6]

[0261] Calculation of the average functionality in malonate functions (Fmalo) after the synthesis of a polyester: The following calculation is used when the polyester is obtained from a dialkyl malonate, one or more polyols and a catalyst.

[0262] [Math 7] n represents the number of different polyols introduced during the synthesis and represents the number of moles of each of the polyols introduced.

[0263] Determination of the unsaturation / malonate (DL / malonate) molar ratio in a formulation:

[0264] The level of α,β-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,β-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. Determination of the (meth)acrylate / active hydrogen ratio (DL / Active hydrogens) in an amino-acrylate:

[0265] The (meth)acrylate functional group ratio is first determined by proton NMR in the acrylic monomer used in the presence of an internal standard (dimethyl orthophthalate). The acrylic functional group ratio 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.

[0266] Hardness measurement:

[0267] 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).

[0268] Drying time measurement:

[0269] 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 a climate-controlled room at 23°C and 50% relative humidity. Drying time is reached when the index finger can be rubbed without any retention on the applied formulation.

[0270] Pot-life measurement:

[0271] Pot life is the time required to measure a doubling of the initial viscosity of a formulation composition. Viscosity is measured regularly over time using the "measurement of the viscosity of a composition with a viscosity lower than 5000 mPa.s" method. All measurements are used to plot a curve. Pot life is calculated after exponential regression.

[0272] Results :

[0273] The results are detailed in the tables below.

[0274] The composition of aminoacrylates is described in Table 1 below.

[0275] [Table 1]

[0276] The evolution of the viscosity of a varnish is detailed in table 2 below.

[0277] [Table 2]

[0278] Table 2 shows the evolution of the viscosity of a comparative polyester / amino-acrylate mixture (with amino-acrylate 1) or according to the invention (with amino-acrylate 2) at 15 days, 2 months and 6 months of aging. It is noted that the mixture according to the invention does not evolve significantly during storage and therefore has better stability.

[0279] The composition and properties of formulations 1 to 5 are described in Table 3 below. [Table 3]

[0280] * The viscosity of the varnish in Table 3 is measured at 23°C according to the method “measuring the viscosity of a varnish with a viscosity lower than 5000 mPa.s”. The varnish is obtained by mixing components A and B (in the absence of component C).

[0281] 5 The composition and properties of formulations 6 to 8 are described in Table 4 below. [Table 4]

[0282] Tables 3 and 4 show that formulation 2 according to the invention produces a resin with a significantly higher hardness than comparative formulation 1. Furthermore, the drying times for all the formulations according to the invention are considerably reduced.

[0283] It is also demonstrated that the neutralizing component D advantageously improves the pot life of the formulation without affecting the drying time of the coating obtained.

Claims

CLAIMS

1. A crosslinkable composition comprising: a) a Michael A donor component; b) a Michael B acceptor component; c) a catalyst component C comprising: - an epoxy component Cl; - an amino-(meth)acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3; 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. Composition according to any one of the preceding claims, characterized in that component C2 comprises an amino-(meth)acrylate having at least 2 secondary amine functions and at least 3 latent catalyst groups.

4. Composition according to any one of the preceding claims, characterized in that 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 latent catalyst group functionality 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 less than 1.

5. Composition according to claim 4, characterized in that component C2a comprises at least one monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups.

6. Composition according to claim 4 or 5, characterized in that component C2b comprises 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.

7. Composition according to any one of claims 4 to 6, 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.

8. 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] 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 hetero atom; R2 is alkylene or heteroalkylene; Y is an imidazole function or a tertiary amine function having a pka > 9, preferably a pKa > 10; and n varies between 0 and 20.

9. A composition according to any one of the preceding claims, characterized in that component C1 comprises at least one compound selected from a glycidyl ether, a glycidyl ester, a cycloaliphatic epoxy and combinations thereof.

10. A composition according to any one of the preceding claims, characterized in that component C1 comprises at least one 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.

11. A composition according to any one of the preceding claims, characterized in that component A comprises a malonate component A1.

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

13. Composition according to claim 11 or 12, characterized in that the component Al has an average malonate functionality (fM) greater than 4.

14. Composition according to any one of the preceding claims, characterized in that the molar ratio between the Michael acceptor functions of B and the Michael donor functions of A is between 1:1 and 3:

1.

15. A composition according to any preceding claim, characterized in that component B comprises: a Michael acceptor component B1 having an α,β-unsaturated group functionality ranging from 1 to 2; and / or a Michael acceptor component B2 having an α,β-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 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 claims 15 to 17, characterized in that component B1 has a viscosity of less than 100 mPa.s, as measured according to ISO 3219:1993 with a Brookfield LVT DVII+ viscometer and an S18 spindle.

19. Composition according to any one of claims 15 to 18, characterized in that component B1 comprises at least one compound chosen 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 chosen 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.

20. Composition according to any one of claims 15 to 19, characterized in that component B2 comprises at least one 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 3 (meth)acrylate groups.

21. 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.

22. 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.

23. 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 components B and Cl.

24. 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; and c) from 1 to 40%, in particular from 2 to 25%, by weight of component C; d) from 0 to 1000 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.

25. 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 8; 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.

26. A process for preparing an amino acrylate component C2 having an NH bond functionality of greater than or equal to 2 and a latent catalyst group functionality of greater than or equal to 3, said process comprising reacting: a (meth)acrylate component C2a having a (meth)acrylate group functionality of greater than or equal to 2, preferably an acrylate component C2a having an acrylate group functionality of greater than or equal to 2; and an amino component C2b having an NH bond functionality of greater than or equal to 2 and a latent catalyst group functionality of greater than or equal to 1, wherein components C2, C2a and C2b are as defined in claims 1 to 25 and the molar ratio of (meth)acrylate groups of compound C2a to NH bonds of compound C2b is less than 1.

27. ​​A process for preparing a crosslinked product comprising the following steps: a) preparing 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 of less than 1; b) preparing a composition by bringing components A, B and 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. wherein components A, B, Cl, C2, C2a and C2b and D are as defined in claims 1 to 25.

28. Method according to claim 27, characterized in that 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 and component B, optionally component D.

29. Method according to claim 27, characterized in that step b) consists of simultaneously bringing into contact the components C1, C2, A, B, and optionally the component D.

30. A catalyst system comprising: an epoxy component C1; and an amino-acrylate component C2 having an NH bond functionality greater than or equal to 2 and a latent catalyst group functionality greater than or equal to 3.

31. Use of the catalyst system according to claim 30 for catalyzing a real Michael addition crosslinking (RM A).

32. Use of the crosslinkable composition according to any one of claims 1 to 25, 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.

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