Curable composition suitable for forming a composite material

Abstract

A curable composition which is obtained from: a) at least one epoxy multifunctional (meth)acrylate compound (A); b) at least one monofunctional (meth)acrylate monomer (B); c) at least one multifunctional (meth)acrylate polymeric compound (C) which is the reaction product of at least one hydroxy functional polyether (PE) which has a weight average molecular weight (Mw) in the range from 1000 to 5000 g / mol; with i. either, at least one polyisocyanate (P) and at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group; or ii. at least one compound (EA) containing at least one carboxylic acid group and at least one ethylenically unsaturated group; and d) optionally, at least one multifunctional (meth)acrylate monomer (D); wherein the curable composition comprises no greater than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

Description

CURABLE COMPOSITION SUITABLE FOR FORMINGA COMPOSITE MATERIALTechnical Field

[0001] The present invention relates to a curable composition which is particularly suitable for forming a composite material and to cured polymeric materials.Background

[0002] Fiber-reinforced composite (FRC) materials have gained significant attention in various industries due to their superior mechanical properties and versatility. These materials consist of a polymer matrix reinforced with high-strength fibers, which can be made from materials such as glass, carbon, aramid, or natural fibers. The combination of these components results in a composite material that exhibits enhanced strength, stiffness, and durability compared to traditional materials. In particular, glass fiber-reinforced polymeric composites (GFRP or GRP) are designed to be as strong as steel, stiffer than aluminum, and have a specific gravity of one fourth that of steel, thanks to its fiber composition and orientation.

[0003] Current technologies for forming the polymeric matrix of composite materials include the use of epoxy resins with epoxy-amine adducts as described e.g. in US Pat. No. 9,388,294 B2 (Sakane), or the use of unsaturated polyesters (UP) in styrene as disclosed in WO 2015 / 121652 Al (Pegram). The epoxy-amine based composite materials usually suffer from sub-optimal pot life due to the reliance on two-component systems (2K) and from energyintense curing mechanism. As for the composite materials based on unsaturated polyesters (UP) in styrene, these generally suffer from inadequate sustainability characteristics due to the use of hazardous and regulated compounds.

[0004] A partial solution is described e.g. in US 2022 / 0213245A1 (Snow et al.). Without contesting the technical advantages associated with the solutions known in the art, there is still a need for a curable composition suitable for forming composite materials having excellent sustainability features, and which results into a cured polymeric material provided excellent mechanical properties, in particular toughness.Summary

[0005] According to one aspect, the present disclosure relates to a curable composition which is obtained from: a) at least one epoxy multifunctional (meth)acrylate compound (A); b) at least one monofunctional (meth)acrylate monomer (B); c) at least one multifunctional (meth)acrylate polymeric compound (C) which is the reaction product of at least one hydroxy functional polyether (PE) which has a weight average molecular weight (Mw) in the range from 1000 to 5000 g / mol; with i. either, at least one polyisocyanate (P) and at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group; or ii. at least one compound (EA) containing at least one carboxylic acid group and at least one ethylenically unsaturated group; and d) optionally, at least one multifunctional (meth)acrylate monomer (D); wherein the curable composition comprises no greater than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0006] According to another aspect, the present disclosure is directed to a cured polymeric material produced by curing a curable composition as described above.

[0007] In still another aspect of the present disclosure, it is provided a method of preparing a curable composition as described above, wherein the method comprises the steps of: a) admixing the at least one epoxy multifunctional (meth)acrylate compound (A), the at least one monofunctional (meth)acrylate monomer (B), the at least one multifunctional (meth)acrylate polymeric compound (C), and optionally, the at least one multifunctional (meth)acrylate monomer (D); and b) optionally, incorporating by dissolution or mixing at least one radical initiator.

[0008] According to yet another aspect, the present disclosure relates to the use of a curable composition as described above for the manufacturing of a composite material comprising reinforcement fibers.Detailed description

[0009] According to a first aspect, the present disclosure relates to a curable composition which is obtained from: a) at least one epoxy multifunctional (meth)acrylate compound (A); b) at least one monofunctional (meth)acrylate monomer (B); c) at least one multifunctional (meth)acrylate polymeric compound (C) which is the reaction product of at least one hydroxy functional polyether (PE) which has a weight average molecular weight (Mw) in the range from 1000 to 5000 g / mol; with iii. either, at least one polyisocyanate (P) and at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group; or iv. at least one compound (EA) containing at least one carboxylic acid group and at least one ethylenically unsaturated group; and d) optionally, at least one multifunctional (meth)acrylate monomer (D); wherein the curable composition comprises no greater than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0010] In the context of the present disclosure, it has been surprisingly found that a curable composition as described above is provided with excellent formulation stability, advantageous formulation flexibility, as well as outstanding viscosity and solubility characteristics.

[0011] It has no less surprisingly been found that a curable composition as described above is particularly suitable for forming a cured polymeric material provided with excellent characteristics and performance attributes as regard to mechanical properties (in particular toughness, tensile strength, elongation at break and Young’s modulus) and impact resistance.

[0012] Those are particularly surprising and counterintuitive findings considering that combining in particular high tensile strength and high elongation at break is somewhat technically self-contradicting or at least technically challenging to achieve in combination. Similarly, materials characterized by high toughness and high Young’s modulus are also particularly challenging to design. Polymers provided with high tensile strength and high flexibility are usually characterized as having high toughness.

[0013] In the context of the present disclosure, the Applicant successfully managed to formulate a curable composition provided with excellent characteristics of the uncured composition while combining all the above-detailed excellent characteristics and performance attributes of the crosslinked (or cured) material.

[0014] Without wishing to be bound by theory, it is believed that these excellent characteristics and attributes are due in particular to the use of a specific combination of: a) at least one epoxy multifunctional (meth)acrylate compound (A), b) at least one monofunctional (meth)acrylate monomer (B), and c) at least one multifunctional (meth)acrylate polymeric compound (C) as specifically defined hereinbefore; and wherein the curable composition comprises no greater than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0015] More specifically, it is believed that compound (B) and compound (C) - in the abovespecified range - are mainly responsible for the forming of a polymerization induced (nano- or micro-) phase separation within the polymeric material after suitable polymerization conditions. This is believed to result into an interpenetrating polymer network which is assumed to provide increased toughness to the polymeric system. As for compound (A), it is believed to be mainly responsible for providing high Young’s modulus characteristics to the overall polymer matrix, although compound (A) is also believed to advantageously contribute to the polymerization induced phase separation.

[0016] In the context of the present disclosure, the Applicant was challenged to formulate a curable composition provided with excellent solubility characteristics in the uncured (wet) state and yet leading to controlled phase separation mechanism (mainly caused by controlled insolubility features) upon polymerization. This delicate balance between the solubility properties of the unpolymerized material and the ability to form an interpenetrating polymer network through controlled polymerization induced phase separation is specifically enabled by the curable composition of the present disclosure.

[0017] This technical approach to provide increased toughness to the polymeric system, i.e. through a controlled phase separation mainly induced by components (B) and (C), is seen as particularly counterintuitive and disruptive considering that the person skilled in the art of polymeric material would not have relied on such a sophisticated physicochemical state which is the controlled phase separation mechanism, but would have rather fine-tuned the intrinsic (physical) properties of the starting components of the curable composition, such as e.g. theglass transition temperature, the molecular weight, the branching, the chain length or the functional groups present in the initial constituents of the curable composition. Moreover, the skilled person would have assumed that the forming of an interpenetrating polymer network would bring unacceptable stiffness to the resulting polymeric system, which would then detrimentally affect its flexibility characteristics and therefore its toughness performance.

[0018] As such, the curable composition according to the present disclosure is outstandingly suitable for forming a composite material comprising reinforcement fibers or a three- dimensional printed article. Aided by its excellent viscosity characteristics, the curable composition as described herein enables outstanding impregnation of various reinforcement fibers, in particular glass fibers, which results into improved mechanical properties of the composite material.

[0019] The curable composition of the present disclosure comprises, as a first component, at least one epoxy multifunctional (meth)acrylate compound (A). The expression “multifunctional (meth)acrylate compound” used throughout the present disclosure, is meant to designate a compound comprising at least two (meth)acrylate functional groups. By analogy, the expression “difunctional (meth)acrylate compound” used throughout the present disclosure, is meant to designate a compound comprising exactly two (meth)acrylate functional groups. Similarly, the expression “monofunctional (meth)acrylate compound” used throughout the present disclosure, is meant to designate a compound comprising exactly one (meth)acrylate functional group. In the present disclosure, the term “(meth)acrylate compound” is to be understood as to encompass both acrylate and methacrylate compounds as well as mixtures thereof.

[0020] In the context of the present disclosure, it has been surprisingly found that compound (A) as defined hereinbefore mainly contributes in providing high Young’s modulus characteristics to the overall polymer matrix. It is also believed to advantageously affect the polymerization induced phase separation occurring upon polymerization, and various mechanical properties, in particular the impact resistance performance of the cured polymeric material.

[0021] According to an advantageous aspect of the disclosure, the curable composition comprises at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, or even at least 45 wt.% of the at least one epoxy multifunctional (meth)acrylate compound (A), based on the total weight of the curable composition.

[0022] According to another advantageous aspect, the curable composition comprises no greater than 60 wt.%, no greater than 55 wt.%, no greater than 50 wt.%, or even no greater than 45 wt.% of the at least one epoxy multifunctional (meth)acrylate compound (A), based on the total weight of the curable composition.

[0023] According to still another advantageous aspect, the curable composition of the disclosure comprises from 30 to 60 wt.%, from 35 to 60 wt.%, from 35 to 55 wt.%, from 35 to 50 wt.%, from 40 to 50 wt.%, or even from 40 to 45 wt.% of the at least one epoxy multifunctional (meth)acrylate compound (A), based on the total weight of the curable composition.

[0024] Epoxy multifunctional (meth)acrylate compounds (A) for use herein are not particularly limited. Suitable epoxy multifunctional (meth)acrylate compounds (A) for use herein will be easily identified by those skilled in the art in the light of the present disclosure.

[0025] In a typical aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use herein is selected from the group of difunctional (meth)acrylate compounds, trifunctional (meth)acrylate compounds, tetrafunctional (meth)acrylate compounds, and any mixtures thereof. Advantageously, the at least one epoxy multifunctional (meth)acrylate compound (A) is selected from the group of difunctional (meth)acrylate compounds.

[0026] In another typical aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use herein is selected from the group of monomeric, oligomeric and polymeric compounds.

[0027] In an advantageous aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) is selected from the group of oligomeric compounds, polymeric compounds, and any mixtures thereof. In the context of the present disclosure, it has been indeed surprisingly discovered that using at least one epoxy multifunctional (meth)acrylate compound (A) selected from the group of oligomeric compounds and polymeric compounds advantageously affects the polymerization induced phase separation occurring upon polymerization, due to the relatively longer chain of their chemical structure.

[0028] In a particularly advantageous aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use in the present disclosure has a glass transition temperature of the homopolymer greater than 90°C, greater than 100°C, greater than 110°C, greater than 120°C, or even greater than 130°C. In the context of the present disclosure, it has been indeed surprisingly discovered that using epoxy multifunctional (meth)acrylate compounds (A)provided with the above-described glass transition temperature characteristics advantageously contribute in providing excellent Young’s modulus characteristics to the overall polymer matrix.

[0029] In one advantageous aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use herein is selected from the group of hydroxyl functional (meth)acrylate compounds obtained from the reaction of at least one diepoxy functional compound (E) with a (meth)acrylic compound (F).

[0030] In an advantageous aspect, the at least one diepoxy functional compound (E) for use herein comprises at least one aliphatic or aromatic cycle, preferably an aromatic cycle.

[0031] In a more advantageous aspect, the at least one di epoxy functional compound (E) for use herein is (or comprises) bisphenol A diglycidyl ether.

[0032] In another advantageous aspect, the (meth)acrylic compound (F) for use herein is (or comprises) acrylic acid, methacrylic acid, or any mixtures thereof.

[0033] In a particularly advantageous aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use in the present disclosure is (or comprises) bisphenol a diglycidyl ether di(meth)acrylate.

[0034] In a preferred aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use in the present disclosure is (or comprises) bisphenol a diglycidyl ether dimethacrylate.

[0035] In still another advantageous aspect, the epoxy multifunctional (meth)acrylate compound (A) for use herein comprises a combination of epoxy multifunctional methacrylate compounds and epoxy multifunctional acrylate compounds.

[0036] According to one beneficial aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use herein is provided with a chain extension. Chain extension can be performed according to procedures and techniques well known to those skilled in the art. Suitable chain extensions for use herein may be identified by the skilled person in the light of the present disclosure.

[0037] In the context of the present disclosure, it has been indeed surprisingly discovered that using at least one epoxy multifunctional (meth)acrylate compound (A) provided with a chain extension advantageously affects the polymerization induced phase separation occurring uponpolymerization, and also improves various mechanical properties, in particular the impact resistance performance of the cured polymeric material.

[0038] According to one advantageous aspect, the at least one epoxy multifunctional (meth)acrylate compound (A) for use herein is extended with a chain extender, in particular by reaction with a diisocyanate or with a carboxylic anhydride.

[0039] Advantageously, the diisocyanate for use in the preparation of the chain extended epoxy multifunctional (meth)acrylate compound (A) is selected from the group consisting of hexane diisocyanate (HDI), toluene diisocyanate (TDI), and any mixtures thereof.

[0040] Advantageously still, the carboxylic anhydride for use in the preparation of the chain extended epoxy multifunctional (meth)acrylate compound (A) is selected from the group consisting of succinic anhydride, phthalic anhydride, and any mixtures thereof.

[0041] The curable composition of the present disclosure comprises, as a second component, at least one monofunctional (meth)acrylate monomer (B). The monofunctional (meth)acrylate monomer (B), together with the at least one multifunctional (meth)acrylate polymeric compound (C), is believed to be a main contributor to the forming of a polymerization induced phase separation within the polymeric material after suitable polymerization conditions.

[0042] According to an advantageous aspect of the disclosure, the curable composition comprises at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, or even at least 50 wt.% of the at least one monofunctional (meth)acrylate monomer (B), based on the total weight of the curable composition.

[0043] According to another advantageous aspect, the curable composition comprises no greater than 60 wt.%, no greater than 55 wt.%, or even no greater than 50 wt.% of the at least one monofunctional (meth)acrylate monomer (B), based on the total weight of the curable composition.

[0044] According to still another advantageous aspect, the curable composition of the disclosure comprises from 20 to 60 wt.%, from 25 to 60 wt.%, from 30 to 60 wt.%, from 35 to 60 wt.%, from 40 to 60 wt.%, from 45 to 60 wt.%, from 45 to 55 wt.%, or even from 50 to 55 wt.% of the at least one monofunctional (meth)acrylate monomer (B), based on the total weight of the curable composition.

[0045] Monofunctional (meth)acrylate monomers (B) for use herein are not particularly limited as long as they comprise exactly one (meth)acrylate functional group. Suitablemonofunctional (meth)acrylate monomers (B) for use herein will be easily identified by those skilled in the art in the light of the present disclosure.

[0046] In one exemplary aspect, the at least one monofunctional (meth)acrylate monomer (B) for use herein has a glass transition temperature of the homopolymer greater than 40°C, greater than 50°C, greater than 60°C, or even greater than 70°C. In the context of the present disclosure, it has been indeed surprisingly discovered that using monofunctional (meth)acrylate monomers (B) provided with the above-described glass transition temperature characteristics advantageously affects the polymerization induced phase separation occurring upon polymerization.

[0047] In an advantageous aspect, the at least one monofunctional (meth)acrylate monomer (B) for use herein is selected from the group consisting of methacrylic acid, methyl methacrylate (MMA), ethylmethacrylate, n-butylmethacrylate (BuMA), tert-butyl methacrylate (tBuMA), cyclohexyl methacrylate (CHMA), glycidyl methacrylate, isobomyl methacrylate (IBOMA), hydroxyethylmethacrylate (HEMA), hydroxypropylmethacrylate (HPMA), acrylic acid, methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BuA), tert-butyl acrylate (tBuA), 2-ethyl hexyl acrylate (2EHA), isooctyl acrylate (IOA), isobomyl acrylate (IBOA), isobomyl methacrylate (IBoMA), hydroxy ethylacrylate (HEA), hydroxypropylacrylate (HP A), tert-butyl cyclohexyl acrylate (TBCHA), cyclic trimethylol formal acrylate (CTFA), vinylacetate (Vo Ac), benzyl methacrylate (BMA), and any mixtures thereof.

[0048] In another advantageous aspect of the present disclosure, the at least one monofunctional (meth)acrylate monomer (B) is selected from the group consisting of monofunctional methacrylate monomers.

[0049] In a particularly advantageous aspect, the at least one monofunctional (meth)acrylate monomer (B) for use herein is selected from the group consisting of hydroxyl functional monofunctional (meth)acrylate monomers. In the context of the present disclosure, it has been indeed surprisingly discovered that using hydroxyl functional monofunctional (meth)acrylate monomers advantageously affects the polymerization induced phase separation occurring upon polymerization, due to the hydrophilic character induced by the hydroxyl group into the curable composition.

[0050] In a preferred aspect, the at least one monofunctional (meth)acrylate monomer (B) for use in the present disclosure is selected from the group consisting of hydroxy ethylmethacrylate(HEMA), hydroxypropylmethacrylate (HPMA), hydroxyethylacrylate (HEA), hydroxypropylacrylate (HP A), and any mixtures thereof.

[0051] In a particularly preferred aspect, the at least one monofunctional (meth)acrylate monomer (B) for use herein is (or comprises) hydroxypropylmethacrylate (HPMA).

[0052] The curable composition of the present disclosure comprises, as a third component, at least one multifunctional (meth)acrylate polymeric compound (C) as described hereinbefore.

[0053] According to the present disclosure, the curable composition comprises no greater than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0054] In the context of the present disclosure, it has been surprisingly found that confining the amount of the multifunctional (meth)acrylate polymeric compound (C) for it to be no greater than 20 wt.%, based on the total weight of the curable composition, directly impacts various beneficial aspects, in particular the solubility characteristics of the curable composition, the ability to suitably form an interpenetrating polymer network through controlled polymerization induced phase separation, and ultimately the overall mechanical properties (in particular the flexibility, the elongation at break and the toughness) of the cured polymeric material.

[0055] In one advantageous aspect, the curable composition of the present disclosure comprises less than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0056] In another advantageous aspect of the disclosure, the curable composition comprises no greater than 15 wt.%, no greater than 10 wt.%, or even no greater than 5 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0057] In still another advantageous aspect, the curable composition comprises at least 2 wt.%, at least 3 wt.%, at least 4 wt.%, or even at least 5 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0058] In yet another advantageous aspect, the curable composition comprises from 2 to 20 wt.%, from 2 to 18 wt.%, from 2 to 15 wt.%, from 2 to 12 wt.%, from 3 to 12 wt.%, from 3 to 10 wt.%, from 3 to 8 wt.%, or even from 3 to 6 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

[0059] According to the present disclosure, the at least one hydroxy functional polyether (PE) for use in the at least one multifunctional (meth)acrylate polymeric compound (C), has a weight average molecular weight (Mw) in the range from 1000 to 5000 g / mol. In the context of the present disclosure, it has been surprisingly found that using specifically at least one hydroxy functional polyether (PE) backbone for producing the at least one multifunctional (meth)acrylate polymeric compound (C), and confining its weight average molecular weight (Mw) for it to be specifically in the range from 1000 to 5000 g / mol, directly impacts various beneficial aspects, in particular the solubility characteristics of the curable composition and the ability to suitably form an interpenetrating polymer network through controlled polymerization induced phase separation.

[0060] According to a typical aspect, the at least one hydroxy functional polyether (PE) for use in the at least one multifunctional (meth)acrylate polymeric compound (C), has a weight average molecular weight (Mw) in the range from greater than 1000 to 5000 g / mol.

[0061] According to an advantageous aspect, the at least one hydroxy functional polyether (PE) for use in the at least one multifunctional (meth)acrylate polymeric compound (C), has a weight average molecular weight (Mw) in the range from 1500 to 5000 g / mol, from 1500 to 4500 g / mol, from 2000 to 4500 g / mol, from 2500 to 4500 g / mol, from 3000 to 4500 g / mol, from 3500 to 4500 g / mol, or even from 4000 to 4500 g / mol.

[0062] In a typical aspect, the at least one multifunctional (meth)acrylate polymeric compound (C) for use herein is selected from the group consisting of difunctional (meth)acrylate polymeric compounds, trifunctional (meth)acrylate polymeric compounds, tetrafunctional (meth)acrylate polymeric compounds, and any mixtures thereof.

[0063] In an advantageous aspect of the disclosure, the at least one multifunctional (meth)acrylate polymeric compound (C) is selected from the group consisting of difunctional acrylate polymeric compounds.

[0064] According to one particularly advantageous aspect of the disclosure, the at least one multifunctional (meth)acrylate polymeric compound (C) for use herein is the reaction product of the at least one hydroxy functional polyether (PE) with at least one polyisocyanate (P) and at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group. According to this particular reaction scheme, the resulting multifunctional (meth)acrylate polymeric compound (C) may be qualified as a (poly)urethane comprising ethylenically unsaturated groups.

[0065] In the context of the present disclosure, the expression “ethylenically unsaturated functional group” or “ethylenically unsaturated group” is meant to designate a carbon-carbon double bond which can undergo radical polymerization. Examples of such groups include (meth)acryloyl, (meth)acrylamide, vinyl, vinylether, allyl, styrenyl, methylstyrenyl, maleyl or fumaryl functional groups. The ethylenically unsaturated groups for use herein are generally chosen from (meth)acryloyl groups and / or allyl groups, preferably they are (meth)acryloyl groups, more preferably acryloyl groups. In the present disclosure, the term “(meth)acryloyl” is to be understood as to encompass both acryloyl and methacryloyl groups or derivatives as well as mixtures thereof.

[0066] According to a typical aspect, the at least one polyisocyanate (P) for use in the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates, and any combinations or mixtures thereof.

[0067] According to another typical aspect, the at least one polyisocyanate (P) for use in the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group of di-isocyanates.

[0068] According to a preferred aspect, the at least one polyisocyanate (P) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group consisting of hexamethylene diisocyanate (HDI), l,l’-methylene bis[4-isocyanatocyclohexane] (H12MDI), isophorone diisocyanate (IPDI), 1,4-diisocyanatobenzene (BDI), toluene diisocyanate (TDI), l,r-methylenebis[4-isocyanatobenzene] (MDI), xylylene diisocyanate (XDI), 1,5-naphtalene diisocyanate (NDI), toluidine diisocyanate (TODI), tetramethylxylylene diisocyanate (TMXDI), p-phenylene diisocyanate (PPDI), and any mixtures thereof.

[0069] According to a more preferred aspect, the at least one polyisocyanate (P) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group consisting of isophorone diisocyanate (IPDI) and toluene diisocyanate (TDI).

[0070] In one advantageous aspect, the at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group of hydroxy functional (meth)acrylates, in particular mono-hydroxy functional (meth)acrylates.

[0071] In a more advantageous aspect, the at least one compound (EH) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the groupconsisting of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HP A), hydroxypropyl methacrylate (HPMA), hydroxyethyl methacrylate (HEMA), hydroxybutyl acrylate (HBA), hydroxybutyl methacrylate (HBMA), hydroxyethyl caprolactone acrylate (HECLA), and any mixtures thereof.

[0072] In a preferred aspect, the at least one compound (EH) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group consisting of hydroxy ethyl acrylate (HEA), hydroxy ethyl methacrylate (HEMA) and any mixtures thereof.

[0073] In a more preferred aspect, the at least one compound (EH) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is (or comprises) hydroxyethyl acrylate (HEA).

[0074] According to an alternatively advantageous aspect of the disclosure, the at least one multifunctional (meth)acrylate polymeric compound (C) for use herein is the reaction product of the at least one hydroxy functional polyether (PE) with at least one compound (EA) containing at least one carboxylic acid group and at least one ethylenically unsaturated group. According to this particular reaction scheme, the resulting multifunctional (meth)acrylate polymeric compound (C) may be qualified as a (poly)ester comprising ethylenically unsaturated groups.

[0075] According to an advantageous aspect, the at least one compound (EA) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), contains at least one carboxylic acid group and at least one (meth)acrylate group.

[0076] According to a preferred aspect, the at least one compound (EA) for producing the at least one multifunctional (meth)acrylate polymeric compound (C), is selected from the group consisting of (meth)acrylic acid, 2-carboxyethyl acrylate, reaction products of hydroxyfunctional (meth)acrylates with carboxylic anhydrides or dicarboxylic acid compounds, and any mixtures thereof.

[0077] According to a more preferred aspect, the at least one compound (EA) for use herein is (or comprises) (meth)acrylic acid, in particular acrylic acid.

[0078] The curable composition of the present disclosure may comprise, as a further optional component, at least one multifunctional (meth)acrylate monomer (D). The multifunctional (meth)acrylate monomer (D) has been found to advantageously facilitate the chemical synthesis of the curable composition by enabling appropriate viscosity adjustment during the synthesis.It is also believed to advantageously affect the compatibility of the starting components of the curable composition as well as the overall solubility characteristics of the curable composition.

[0079] According to an advantageous aspect of the disclosure, the curable composition comprises no greater than 40 wt.%, no greater than 35 wt.%, no greater than 30 wt.%, no greater than 25 wt.%, no greater than 20 wt.%, or even no greater than 15 wt.% of the at least one multifunctional (meth)acrylate monomer (D), based on the total weight of the curable composition.

[0080] According to another advantageous aspect, the curable composition comprises from 0 to 40 wt.%, from 5 to 40 wt.%, from 5 to 35 wt.%, or even from 10 to 35 wt.% of the at least one multifunctional (meth)acrylate monomer (D), based on the total weight of the curable composition.

[0081] According to still another advantageous aspect of the disclosure, the combined amount of the at least one monofunctional (meth)acrylate monomer (B) and the optional at least one multifunctional (meth)acrylate monomer (D) is no greater than 65 wt.%, no greater than 60 wt.%, or even no greater than 55 wt.%, based on the total weight of the curable composition.

[0082] According to yet another advantageous aspect of the disclosure, the combined amount of the at least one monofunctional (meth)acrylate monomer (B) and the optional at least one multifunctional (meth)acrylate monomer (D) is in the range from 30 to 65 wt.%, from 35 to 65 wt.%, from 40 to 60 wt.%, from 35 to 60 wt.%, from 40 to 60 wt.%, from 45 to 60 wt.%, from 50 to 60 wt.%, or even from 50 to 55 wt.%, based on the total weight of the curable composition.

[0083] Multifunctional (meth)acrylate monomers (D) for use herein are not particularly limited. Suitable multifunctional (meth)acrylate monomers (D) for use herein will be easily identified by those skilled in the art in the light of the present disclosure.

[0084] In one advantageous aspect, the at least one multifunctional (meth)acrylate monomer (D) for use herein, has a glass transition temperature of the homopolymer greater than 70°C, greater than 75°C, greater than 80°C, greater than 85°C, greater than 90°C, or even greater than 100°C.

[0085] In a typical aspect, the at least one multifunctional (meth)acrylate monomer (D) for use herein, comprises at least two (meth)acrylate groups, in particular two or three (meth)acrylate groups.

[0086] In a more advantageous, the at least one multifunctional (meth)acrylate monomer (D) is selected from the group consisting of glycerol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene di(meth)acrylate, butane diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and any mixtures thereof.

[0087] In a particularly advantageous aspect, the at least one multifunctional (meth)acrylate monomer (D) is selected from the group consisting of dipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and any mixtures thereof.

[0088] In a preferred aspect, the at least one multifunctional (meth)acrylate monomer (D) for use in the present disclosure, is selected from the group consisting of dipropylene glycol diacrylate (DPGDA), trimethylolpropane trimethacrylate (TMPTMA), and any mixtures thereof.

[0089] In one exemplary aspect, the curable composition of the present disclosure is obtained from: a) from 30 to 60 wt.%, from 35 to 60 wt.%, from 35 to 55 wt.%, from 35 to 50 wt.%, from 40 to 50 wt.%, or even from 40 to 45 wt.% of the at least one epoxy multifunctional (meth)acrylate compound (A); b) from 20 to 60 wt.%, from 25 to 60 wt.%, from 30 to 60 wt.%, from 35 to 60 wt.%, from 40 to 60 wt.%, from 45 to 60 wt.%, from 45 to 55 wt.%, or even from 50 to 55 wt.% of the at least one monofunctional (meth)acrylate monomer(B); c) from 2 to 20 wt.%, from 2 to 18 wt.%, from 2 to 15 wt.%, from 2 to 12 wt.%, from 3 to 12 wt.%, from 3 to 10 wt.%, from 3 to 8 wt.%, or even from 3 to 6 wt.% of the at least one multifunctional (meth)acrylate polymeric compound(C); and d) optionally, from 0 to 40 wt.%, from 5 to 40 wt.%, from 5 to 35 wt.%, or even from 10 to 35 wt.% of the at least one multifunctional (meth)acrylate monomer(D); wherein the wt.% are based on the total weight of the curable composition.

[0090] In a typical of the present disclosure, the at least one epoxy multifunctional (meth)acrylate compound (A), the at least one monofunctional (meth)acrylate monomer (B), the at least one multifunctional (meth)acrylate polymeric compound (C), and the optional atleast one multifunctional (meth)acrylate monomer (D) are all different from each other. Typically still, the combined wt.% of the at least one epoxy multifunctional (meth)acrylate compound (A), the at least one monofunctional (meth)acrylate monomer (B), the at least one multifunctional (meth)acrylate polymeric compound (C), and the optional at least one multifunctional (meth)acrylate monomer (D), amount to about 100 wt.%, based on the total weight of the curable composition.

[0091] In another typical aspect, the curable composition of the present disclosure further comprises at least one radical initiator, in particular selected from group consisting of radical initiators, in particular photo-initiators and thermal initiators (such as e.g. peroxides or hydroperoxides).

[0092] In one advantageous aspect of the disclosure, the curable composition further comprises reinforcement fibers, in particular glass fibers, carbon fibers and aramid fibers. Preferably, the curable composition further comprises glass fibers.

[0093] According to the advantageous aspect wherein the curable composition further comprises reinforcement fibers, the curable composition may further comprise additional adhesion-promoting monomers, such as in particular acrylic acid monomers, which have been found to advantageously improve the adhesion between the reinforcement fibers and the polymer matrix forming the composite material.

[0094] As is customary in the technical field, the curable composition of the present disclosure may further comprise various additional ingredients depending on the targeted applications and properties for such composition. In a typical aspect, the curable composition further comprises at least one additive selected from the group consisting of radical initiators, reinforcement fibers, impact modifiers, adhesion promotors, wetting agents, further mono- or multi-functional monomers, fillers, anti-oxidants, UV stabilizers, UV absorbers, plasticizing agents, rheology modifiers, defoaming agents, fire retardant agents, matting agents, waxes, pigments, dyes, colorants, and any combinations or mixtures thereof.

[0095] In one advantageous aspect of the disclosure, the curable composition has a viscosity no greater than 1000 mPas, no greater than 900 mPa.s, no greater than 800 mPa.s, no greater than 700 mP s, no greater than 600 mPa.s, no greater than 500 mPa.s, no greater than 400 mPa.s, or even no greater than 300 mPa.s, when measured at the application temperature according to the test method described in the experimental section.

[0096] In another advantageous aspect of the disclosure, the curable composition has a viscosity no greater than 1000 mPa.s, no greater than 900 mPa.s, no greater than 800 mPa.s, no greater than 700 mPa.s, no greater than 600 mPa.s, no greater than 500 mPa.s, no greater than 400 mPa.s, or even no greater than 300 mPa.s, when measured at 25°C according to the test method described in the experimental section.

[0097] According to another aspect, the present disclosure is directed to a cured polymeric material produced by curing a curable composition as described hereinbefore. The curing of the curable composition may be performed according to any curing techniques and procedures commonly known in the art.

[0098] In a typical aspect, the curing (or crosslinking) of the curable composition may be performed using radical initiators well known to those skilled in the art. Exemplary radical initiators include, but are not limited to, photoinitiators, peroxides, hydroperoxides, and any combinations or mixtures thereof.

[0099] In another typical aspect, the curing (or crosslinking) of the curable composition may be performed by actinic radiations, in particular UV radiations, e-beam irradiation, or by thermal curing.

[0100] According to one advantageous aspect, the cured polymeric material of the disclosure has a Young’s Modulus greater than 2500 MPa, greater than 2700 MPa, greater than 3000 MPa, greater than 3200 MPa, or even greater than 3500 MPa, when measured at 23°C according to the test method described in the experimental section.

[0101] According to another advantageous aspect, the cured polymeric material of the disclosure has a tensile strength greater than 40 MPa, greater than 45 MPa, greater than 50 MPa, greater than 55 MPa, greater than 60 MPa, greater than 65 MPa, or even greater than 70 MPa, when measured at 23 °C according to the test method described in the experimental section.

[0102] According to still another advantageous aspect, the cured polymeric material has an elongation at break greater than 3.5%, greater than 4%, greater than 4.5%, greater than 5%, greater than 5.5%, greater than 6%, greater than 6.5%, greater than 7%, or even greater than 7.5%, when measured at 23°C according to the test method described in the experimental section.

[0103] According to yet another advantageous aspect, the cured polymeric material has a toughness (W) to Fmaxgreater than 3 J / cm3, greater than 4 J / cm3, greater than 5 J / cm3, greater than 6 J / cm3, greater than 7 J / cm3, greater than 8 J / cm3, greater than 9 J / cm3, or even greaterthan 10 J / cm3, when measured at 23°C according to the test method described in the experimental section.

[0104] According to yet another advantageous aspect, the cured polymeric material has a toughness (W) to break greater than 1 J / cm3, greater than 1.5 J / cm3, greater than 2 J / cm3, greater than 2.5 J / cm3, greater than 3 J / cm3, greater than 3.5 J / cm3, greater than 4 J / cm3, greater than 4.5 J / cm3, or even greater than 5 J / cm3, when measured at 23°C according to the test method described in the experimental section.

[0105] According to yet another advantageous aspect, the cured polymeric material has an impact resistance greater than 4 kJ / m2, greater than 5 kJ / m2, greater than 6 kJ / m2, greater than 8 kJ / m2, greater than 10 kJ / m2, greater than 12 kJ / m2, greater than 14 kJ / m2, greater than 16 kJ / m2, greater than 18 kJ / m2, or even greater than 20 kJ / m2, when measured according to the test method described in the experimental section.

[0106] According to yet another advantageous aspect, the cured polymeric material has a glass transition temperature (Tg) greater than 80°C, greater than 85°C, greater than 90°C, greater than 95°C, greater than 100°C, greater than 105°C, or even greater than 110°C, when measured according to the test method described in the experimental section.

[0107] In a particularly advantageous aspect of the disclosure, the cured polymeric material as described hereinbefore is a composite material further comprising reinforcement fibers, in particular glass fibers.

[0108] In another particularly advantageous aspect of the disclosure, the cured polymeric material as described hereinbefore is a three-dimensional printed article.

[0109] In still another aspect of the present disclosure, it is provided a method of preparing a curable composition as described above, wherein the method comprises the steps of: a) admixing the at least one epoxy multifunctional (meth)acrylate compound (A), the at least one monofunctional (meth)acrylate monomer (B), the at least one multifunctional (meth)acrylate polymeric compound (C), and optionally, the at least one multifunctional (meth)acrylate monomer (D); and b) optionally, incorporating by dissolution or mixing at least one radical initiator.

[0110] The curable composition may be prepared in various ways according to techniques well known to those skilled in the art. In a typical procedure, the curable composition is prepared by simply blending the various components under agitation and at elevated temperature (for example 60°C).

[0111] In yet another aspect, the present disclosure relates to a method of preparing a composite material, which comprises the steps of: a) providing a curable composition as described above; b) incorporating reinforcement fibers into the curable composition thereby forming a curable composite material; and c) curing the curable composite material.

[0112] In yet another aspect, the present disclosure is directed to a method of making a three- dimensional article, comprising the steps of: a) providing a curable composition as described above; b) incorporating reinforcement fibers into the curable composition thereby forming a curable composite material; c) curing the curable composite material thereby forming a cured cross-section; and d) repeating steps (a), (b) and (c) thereby resulting in a (cured) three-dimensional article.

[0113] According to yet another aspect, the present disclosure relates to the use of a curable composition as described above for the manufacturing of a composite material comprising reinforcement fibers.

[0114] According to yet another aspect, the present disclosure relates to the use of a curable composition as described above for the manufacturing of a three-dimensional printed article.EXAMPLES

[0115] The present disclosure is further illustrated by the following examples. These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims.

[0116] Throughout the present disclosure and example section, the following test and measurement methods are used to characterize the exemplary curable compositions and the cured polymeric material obtained therefrom.Test Methods:A) Viscosity

[0117] The viscosity of the various curable compositions is measured at the chosen temperature (either 25°C or at the application temperature such as e.g. 60°C) with a cone and plate type rheometer MCR092 (Paar-Physica) according to test method DIN EN ISO 3219. A fixed shear rate in the range from 20 to 25 s-1 is used.B) Molecular weight

[0118] The number-average molecular weight (Mn), the weight-average molecular weight (Mw) and polydispersity (D) are determined by conventional gel permeation chromatography (GPC) with Polystyrene standards EasyCal from Polymer Laboratories (Molecular Weight range: 200 - 400.000 g / mol). The sample are dissolved (1.0% wt. / wt.) in tetrahydrofuran (THF) containing 0.5% toluene as Flow rate marker. The analysis are performed by liquid chromatography (Agilent 1260) equipped with 3 PLGel Mixed-D LS polystyrene divinylbenzene GPC columns (300 X 7.5mm X 5pm). The samples are filtrated over 0.45 pm regenerated cellulose Whatman filter (SpartanTM 30 / 0.45 RC) prior to injection into the GPC system. The components of the sample are separated by the GPC columns based on their molecular size in solution and detected by a Refractive Index detector. The data are gathered and processed by Agilent GPC / SEC software.C) Glass transition temperature (Tg)

[0119] The glass transition temperature (Tg) is determined using dynamic mechanical thermal analysis (DMTA, instrument DMA800 from TA Instruments) in three-point bendingmode according to test method ASTM El 640. The span between the supporting points is 20 mm and small beam-shaped samples of suitable dimensions (30 mm x 5 mm x 1.6 mm) are supplied for analysis. The frequency of the oscillatory deformation is 1 Hz and the amplitude is 50 pm. The heating rate is 3 °C min-1. The glass transition temperature (Tg) is reported as the temperature at the maximum of the loss factor (Tg = T(tan6max)).D) Tensile properties

[0120] The uniaxial stress-strain (tensile) properties such as Young’s modulus, tensile strength, elongation at break and toughness to break are measured at 23°C according to test method ISO 527-2, using a Zwick Z050 elongation testing machine fitted with a 50 kN load cell and with a cross-head speed of 1 mm / min. Dumbbell-shaped samples with a thickness of 4 mm are used for the testing. These specimens are cured using first a LED lamp 395 nm lamp of 16W / cm2, applying 20 J / cm2in total (irradiation on both sides) followed by 120W / cm Hg lamp at both sides applying 4 J / cm2in total.E) Impact resistance

[0121] The Charpy impact strength measurement is performed on unnotched specimens according to test method ISO 179. This represents the impact energy absorbed in breaking an unnotched specimen, referred to the original cross-sectional area of the specimen, and expressed in kilojoules per square meter (kJ / m2). The test is performed edgewise, meaning direction of blow parallel to the width of the sample, with impact on the narrow longitudinal surface of the specimen. The testing is done with Pendulum Impact Tester (Tinus Olsen Model - IT 503), which automatically calculates and displays the impact energy absorbed by a specimen. The specimen size is 4x10x100 mm (thickness x width x length) and these are cured using first a LED lamp 395 nm lamp of 16W / cm2, applying 20 J / cm2in total (irradiation on both sides) followed by 120W / cm Hg lamp at both sides applying 4 J / cm2in total.Raw materials:

[0122] In the examples, the following raw materials and starting products are used:Ebecryl®6100 is an epoxy dimethacrylate oligomer, commercially available from Allnex Belgium. Referred to hereinafter referred as E-6100.LID 2382 is a chain-extended version of Ebecryl®6100, obtained from Allnex Belgium.Referred to hereinafter referred as LID-2382.LID 2500 is a chain-extended version of Ebecryl®3700 which is diacrylate ester of a bisphenol A epoxy resin, obtained from Allnex Belgium. Referred to hereinafter referred as LID-2500.LID 2541 is a chain-extended version of Ebecryl®6100, obtained from Allnex Belgium. Referred to hereinafter referred as LID-2541.HPMA is 2-hydroxypropyl methacrylate, a monofunctional acrylate monomer commercially available from GEO Specialty Chemicals under the trade designation Bisomer® HPMA.Ebecryl®250 is a high molecular weight aliphatic urethane diacrylate polymeric compound, commercially available from Allnex Germany GmbH. Referred to hereinafter referred as E- 250.SSV 387 is a high molecular weight aliphatic urethane diacrylate polymeric compound, obtained from Allnex Belgium. Referred to hereinafter referred as SSV-387.Ebecryl®210 is a high molecular weight aromatic urethane diacrylate polymeric compound, commercially available from Allnex Germany GmbH. Referred to hereinafter referred as E- 210.Ebecryl®230 is a high molecular weight aliphatic urethane diacrylate polymeric compound, commercially available from Allnex Germany GmbH. Referred to hereinafter referred as E- 230.MV 856 is a high molecular weight ester diacrylate polymeric compound, obtained from Allnex Belgium. Referred to hereinafter referred as MV-856.MV 850 is a high molecular weight ester diacrylate polymeric compound, obtained from Allnex Belgium. Referred to hereinafter referred as MV-850.TPGDA is tripropylene glycol diacrylate, a difunctional acrylate monomer commercially available from Allnex Germany GmbH.Examples:Example 1: General preparation of the exemplary curable compositions (Ex.l to Ex.13) and comparative examples (Ex, Cl to Ex,C2),

[0123] Compounds (A), (B), (C) and optionally compound (D) are simply blended at 60°C in a double- wall glass reactor equipped with a mechanical stirrer at 100 rpm. The reaction mixture is stirred for 1 hour until an homogeneous mixture is obtained, and thereafter cooled down. Thecomparative curable compositions (Ex. Cl to Ex.C2) are prepared in a manner similar as described above at the exception that no compound (C) is used in the comparative composition of Ex.Cl, and no compound (B) is used in the comparative composition of Ex.C2. Example 2: Formulation of exemplary curable compositions (Ex.l to Ex, 13) and comparative examples (Ex.Cl to Ex,C2),

[0124] The exemplary curable compositions (Ex.l to Ex.13) and comparative examples (Ex.Cl to Ex.C2) are prepared according to the procedure described hereinbefore. The corresponding formulations are presented in Table 1 below.Table 1: Formulation of exemplary curable compositions (Ex.l to Ex.13) and comparative examples (Ex.Cl to Ex.C2).Table 1 (continued) :Example 3: Characteristics and performance of exemplary curable compositions (Ex.l to Ex, 13) and comparative examples (Ex.Cl to Ex,C2).

[0125] The characteristics and performance of exemplary curable compositions (Ex.l to Ex.13) and comparative examples (Ex.Cl to Ex.C2) have been determined according to the test methods described hereinbefore. The results are presented in Table 2 below.Table 2: Characteristics and performance of exemplary curable compositions (Ex.l to Ex.13) and comparative examples (Ex.Cl to Ex.C2).Table 2 (continued) :

[0126] As can be seen from the results shown in Table 2, the curable compositions according to the present disclosure (Ex.1 to Ex.13) are provided with excellent balance of properties and performance attributes as regard to mechanical properties (in particular toughness to break, elongation at break, tensile strength, and Young’s modulus) and impact resistance. In contrast, comparative curable compositions not according to the present disclosure (Ex. Cl to Ex.C2) are less advantageous. In particular, the comparative curable compositions are typically deficient in terms of toughness to break and elongation at break performance.

Claims

CLAIMS1. A curable composition which is obtained from: a) at least one epoxy multifunctional (meth)acrylate compound (A); b) at least one monofunctional (meth)acrylate monomer (B); c) at least one multifunctional (meth)acrylate polymeric compound (C) which is the reaction product of at least one hydroxy functional polyether (PE) which has a weight average molecular weight (Mw) in the range from 1000 to 5000 g / mol; with i. either, at least one polyisocyanate (P) and at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group; or ii. at least one compound (EA) containing at least one carboxylic acid group and at least one ethylenically unsaturated group; and d) optionally, at least one multifunctional (meth)acrylate monomer (D); wherein the curable composition comprises no greater than 20 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

2. A curable composition according to claim 1, which comprises no greater than 15 wt.%, no greater than 10 wt.%, or even no greater than 5 wt.% of the at least one multifunctional (meth)acrylate polymeric compound (C), based on the total weight of the curable composition.

3. A curable composition according to any one of claim 1 or 2, which comprises at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, or even at least 45 wt.% of the at least one epoxy multifunctional (meth)acrylate compound (A), based on the total weight of the curable composition.

4. A curable composition according to any one of the preceding claims, wherein the at least one epoxy multifunctional (meth)acrylate compound (A) is (or comprises) bisphenol a diglycidyl ether di(meth)acrylate.

5. A curable composition according to any one of the preceding claims, which comprises at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, or even at least 50 wt.% of the at least one monofunctional (meth)acrylate monomer (B), based on the total weight of the curable composition.

6. A curable composition according to any one of the preceding claims, wherein the at least one monofunctional (meth)acrylate monomer (B) is selected from the group consisting of hydroxyethylmethacrylate (HEMA), hydroxypropylmethacrylate (HPMA), hydroxyethylacrylate (HEA), hydroxypropylacrylate (HPA), and any mixtures thereof.

7. A curable composition according to any one of the preceding claims, wherein the at least one hydroxy functional polyether (PE) has a weight average molecular weight (Mw) in the range from 1500 to 5000 g / mol, from 1500 to 4500 g / mol, from 2000 to 4500 g / mol, from 2500 to 4500 g / mol, from 3000 to 4500 g / mol, from 3500 to 4500 g / mol, or even from 4000 to 4500 g / mol.

8. A curable composition according to any one of the preceding claims, wherein the at least one multifunctional (meth)acrylate polymeric compound (C) is the reaction product of the at least one hydroxy functional polyether (PE) with at least one polyisocyanate (P) and at least one compound (EH) containing at least one hydroxyl group and at least one ethylenically unsaturated group.

9. A curable composition according to any one of claims 1 to 7, wherein the at least one multifunctional (meth)acrylate polymeric compound (C) is the reaction product of the at least one hydroxy functional polyether (PE) with at least one compound (EA) containing at least one carboxylic acid group and at least one ethylenically unsaturated group.

10. A curable composition according to any one of the preceding claims, which comprises no greater than 40 wt.%, no greater than 35 wt.%, no greater than 30 wt.%, no greater than 25 wt.%, no greater than 20 wt.%, or even no greater than 15 wt.% of the at least one multifunctional (meth)acrylate monomer (D), based on the total weight of the curable composition.

11. A cured polymeric material produced by curing the curable composition according to any one of the preceding claims.

12. A cured polymeric material according to claim 11, which has an elongation at break greater than 3.5%, greater than 4%, greater than 4.5%, greater than 5%, greater than 5.5%, greater than 6%, greater than 6.5%, greater than 7%, or even greater than 7.5%, when measured at 23°C according to the test method described in the experimental section.

13. A cured polymeric material according to any one of claim 11 or 12, which has a toughness (W) to break greater than 1 J / cm3, greater than 1.5 J / cm3, greater than 2 J / cm3, greater than 2.5 J / cm3, greater than 3 J / cm3, greater than 3.5 J / cm3, greater than 4 J / cm3, greater than 4.5 J / cm3, or even greater than 5 J / cm3, when measured at 23°C according to the test method described in the experimental section.

14. A method of preparing a curable composition according to any one of claims 1 to 10, wherein the method comprises the steps of: a) admixing the at least one epoxy multifunctional (meth)acrylate compound (A), the at least one monofunctional (meth)acrylate monomer (B) and the at least one multifunctional (meth)acrylate polymeric compound (C), and optionally, the at least one multifunctional (meth)acrylate monomer (D); and b) optionally, incorporating by dissolution or mixing at least one radical initiator.

15. Use of a curable composition according to any one of claims 1 to 10 for the manufacturing of a composite material comprising reinforcement fibers.

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