Curable composition comprising polyesters

Abstract

This invention relates to curable and compositions comprising polyester compounds. The invention also relates to their use for coatings, inks and adhesives, as well as in solvent-resistant encapsulant formulations, such as coatings for batteries.

Description

TITLE: CURABLE COMPOSITION COMPRISING POLYESTERSFIELD OF THE INVENTION

[0001] This invention relates to curable compositions comprising polyester compounds. The invention also relates to their use for coatings, inks and adhesives, as well as in solvent-resistant encapsulant formulations, such as coatings for batteries.BACKGROUND

[0002] The use of polyester compounds containing curable functional groups, such as acrylates, methacrylates, or epoxy groups, is well-established in the coatings, inks, and adhesives industries. These reactive groups allow the polyester compounds to undergo polymerization or crosslinking upon exposure to UV light, heat, or chemical curing agents, forming durable, resistant films or strong bonds.

[0003] These polymer compounds are typically obtained from the esterification of diols with diacids. Among others, US 4,206,025 describes the use of dicarboxylic acid selected from the group consisting of acids in which each carboxyl group is in the alpha position with respect to groups chosen from -CH2-, > CH- and quaternary-carbon groups; acids in which one carboxyl group is in the alpha position with respect to a > CH- group, the other carboxyl group being in the alpha position with respect to a quaternary -carbon group, as well as the anhydrides of said acids. Specific examples of such acids are malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic and the like acids and their anhydrides (both carboxy groups in the alpha position with respect to a -CH2- group); maleic, fumaric, cyclohexane-l,4-dicarboxylic, 1,2-dihydrophthalic, Δ4 -tetrahydrophthalic and the like acids and their anhydrides (both carboxy groups in the alpha position with respect to a > CH- group); 1,6-dihydrophthalic and the like acids and their anhydrides (one carboxy group in the alpha position with respect to a > CH- group, the other in the alpha position with respect to a quaternary -carbon group); o-phthalic, isophthalic, terephthalic, 3,6-dihydrophthalic-l,2; 4,5-dihydrophthalic-1,2; tetrachloro(or bromo)phthalic and the like acids and their anhydrides (both carboxy groups in the alpha position with respect to a quaternary-carbon group).

[0004] Most diacid products used in polyester manufacturing are not pure and often contain monoacids and polyacids due to the complexity of their production or purification processes. These by-products can interfere with the esterification process, affecting the polymerization and crosslinking efficiency of the resulting polyesters. The industry has made significant efforts to improve the purity of diacids to enhance the performance and consistency of polyesters, offering various grades of diacids with different purity levels.

[0005] In fact, some of the polyester compounds disclosed in prior art are derived from mixtures of dicarboxylic and polycarboxylic acids.

[0006] Notably, US 3,952,032 describes the use of an organic carboxylic acid radical with a hydrophobic character, typically derived from a higher fatty acid containing 14 to 90 carbon atoms, preferably 18 to 54. The acid may be saturated or unsaturated, straight or branched, and contain 1 to 6 carboxyl groups, with functional derivatives such as acid halides, anhydrides, esters, and salts also being suitable. Several examples of dicarboxylic and polycarboxylic acids which can be used are provided, including EMPOL commercial products and in particular, EMPOL®1010 (a commercial dibasic C36 dimer, containing 3% trimer and no monobasic acid), EMPOL®1022 (a dimer acid containing 19-22% trimer and 5% monobasic acid) and EMPOL® 1038 (same as EMPOL® 1022 but less colored).

[0007] US 7,875,688 B2 describes the preparation of polyesters by the conversion of corresponding acids under acid catalysis, wherein such acids may be selected from a broad list. One of the examples describe the use of EMPOL® 1008, a mixture containing 92% dimer acids and 3% trimer acids, and about 5% fatty acid monomers.

[0008] It would be desirable to improve upon the attributes of the polyesters of the prior art for use in battery coatings formulations, particularly due to their poor adhesion and flexibility. At elevated temperatures and at high relative humidities, strong adhesion and flexibility of battery coatings are crucial for ensuring environmental protection, preventing corrosion, maintaining electrical insulation and ensuring long-term durability.

[0009] One of the objects of the present invention is to provide a curable composition which is well-suited for adhesives, inks or coatings, in particular coatings for batteries that operate under harsh conditions. Another of the objects of the present invention is to provide a composition which may be efficiently cured and offers improved performance in formulations, particularly in terms of resistance to solvent and curing speed, while maintaining mechanical properties, such as impact resistance.BRIEF SUMMARY

[0010] In a first aspect, the present invention provides a curable composition comprising (A) an oligomer which is the reaction product of:(i) at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol, polyol, diepoxide or polyepoxide;(ii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl diacid;(iii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl triacid; and (iv) at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide;(B) at least one (methjacrylate monomer;(C) at least one (methjacrylate phosphate ester; and(D) optionally, at least one free radical initiator.

[0011] In particular, the curable composition may be characterized in that the weight ratio of component (ii) to component (iii) in the oligomer (A) is less than 30: 1, preferably between 30: 1 and 4.1:1, more preferably between 25:1 and 4.2:1, most preferably between 20:1 and 4.3:1.

[0012] In particular, the curable composition may be characterized in that the oligomer (A) is obtained with a reaction mixture comprising less than about 3 wt.%, preferably less than about 2.5 wt.%, most preferably less than about 2 wt.% of a residue of a monoacid other than the residue of (meth)acrylic acid.

[0013] In a second aspect, the present invention also provides the use of the curable composition of the present invention as a dielectric coating composition for batteries, preferably as a coating for at least one surface of a battery substrate, such as an exterior surface of a battery.

[0014] In a third aspect, the present invention provides a method of making a cured composition, comprising curing the curable composition of the present invention. Such method may comprise exposing the curable composition to radiation such UV, near-UV, visible, infrared, near-infrared and / or electron beam radiation or heat.

[0015] In a fourth aspect, the present invention provides the cured composition obtained by curing the curable composition of the present invention.

[0016] In a fifth aspect, the present invention provides a battery comprising such cured composition, preferably wherein the cured composition is a coating for at least one surface of a battery substrate, such as an exterior surface of a battery.

[0017] In a sixth aspect, the present invention provides a method of increasing flexibility and / or impact resistance and / or hardness and / or corrosion resistance and / or scrub resistance and / or water resistance and / or adhesion and / or electric insulation and / or matting and / or flame retardancy and / or weathering resistance of at least one surface of a battery substrate, the method comprising a) applying to the least one surface of the substrate the curable composition of the present invention, and b) curing the composition.DETAILED DESCRIPTION

[0018] In the present application:- the term “comprise(s) a / an” should be understood as meaning “comprise(s) one or more”;- the expression “comprised between... and...” should be understood as including the limits; - unless mentioned otherwise, the wt.% (or % by weight) in a compound or composition is expressed based on the total weight of the compound or composition, respectively;- any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present invention;- the term, “independently” or “independently selected” with respect to choices of groups in a structure, means that if multiple groups are present in the structure, they do not need to be identical; instead, each group can be selected from the listed options independently of the others; for example, the recitation, “R2is independently a residue of at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol or diepoxide” means that one R2in a structure may be an aliphatic diol and another may be an aryl diepoxide.- where an element or component is said to be included in and / or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components; any element or component recited in a list of elements or components may be omitted from such list; and- any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents.Definitions

[0019] The term “(meth)acrylate group” as used herein refers to an acrylate group or a methacrylate group. An acrylate group corresponds to an acryloyl group of formula -C(=O)-CH=CH2. A methacrylate group corresponds to a methacryloyl group of formula -C(=O)-C(CH3)=CH2.

[0020] The term “curable” or “curable polyester” as used herein refers to a compound or a polyester compound comprising at least one ethylenic unsaturation, i.e., at least one polymerizable carbon-carbon double bond, in particular at least one carbon-carbon double bond capable of participating in a free radical polymerization wherein at least one of the carbon atoms of the double bond becomes covalently bonded to another atom, in particular a carbon atom, in a second molecule. The ethylenic unsaturation may for example be present as part of an α,β-unsaturated carbonyl moiety, e.g., an α,β-unsaturated ester moiety such as an acrylate functional group ( — O-C(O)-CH=CH2) or a methacrylate functional group ( — O-C(O)-C(CH3)=CH2); an α,β-unsaturated amide moiety such as an acrylamide functional group ( — NH-C(O)-CH=CH2) or a methacrylamide functional group ( — NH-C(O)-C(CH3)=CH2); a vinyl group ( — CH=CH2); a vinyl ether group ( — O-CH=CH2); an allyl group ( — CH2-CH=CH2); or an allyl ether group ( — O-CH2-CH=CH2). Among others, the ethylenic unsaturation may for example be a residue of any of the following acids: acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or mixtures thereof. The ethylenic unsaturation may also be a residue of any of the following monoepoxides: glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid glycidyl ether, methacrylic acid glycidyl ether or mixtures thereof.

[0021] The term “(meth)acrylated” or “(meth)acrylated polyester” as used herein refers to a compound or a polyester compound comprising at least one (meth)acrylate group as defined herein. A (meth)acrylated polyester therefore qualifies as a curable polyester as defined herein.

[0022] The term “unsaturated” as used herein means comprising one or more double or triple carbon-carbon bonds, in particular one or more double carbon-carbon bonds. The term “ethylenically unsaturated” as used herein means comprising two double bonds separated by a carbon-carbon single bond.

[0023] The term “residue” as used herein refers to the group of atoms remaining in a product after the removal of the functional groups that react to form linkages with another compound. For example, the residue of a diol with the structure HO-R4-OH is understood to be R4.

[0024] The term “saturated” as used herein means not comprising any double or triple carboncarbon bonds.

[0025] The term “aliphatic” as used herein refers to non-aryl and encompasses non-aromatic rings (e.g., a cycloaliphatic ring). It may be linear or branched, saturated or unsaturated, cyclic or acyclic. An aliphatic ligand may be substituted by one or more groups, for example selected from alkyl, hydroxyl, halogen (Br, Cl, I), isocyanate, carbonyl (=0), amine, carboxylic acid, -C(=O)-OR’, -C(=O)-O-C(=O)-R’, each R’ being independently a C1-C6 alkyl. It may comprise one or more bonds selected from ether, ester, amide, urethane, urea, carbonate, organosiloxane, and mixtures thereof.

[0026] The term “C1-C6” as used herein refers to the number of carbon atoms comprised in a specific group or linker. For example, a C1-C6 alkyl is an alkyl comprising from 1 to 6 carbon atoms.

[0027] The term “aryl” as used herein means comprising an optionally substituted polyunsaturated aromatic group. The aryl may contain a single ring (i.e. phenyl) or more than one ring wherein at least one ring is aromatic. When the aryl comprises more than one ring, the rings may be fused or linked via a direct bond (for example biphenyl). The aromatic ring may optionally comprise one to two additional fused rings (i.e. cycloalkyl, heterocycloalkyl or heteroaryl). Examples include phenyl, naphtyl, biphenyl, phenanthrenyl and naphthacenyl.

[0028] The term “heteroaryl” as used herein means comprising an optionally substituted polyunsaturated aromatic group wherein one or more of the ring atoms is a heteroatom such as O, N and S.

[0029] The term “aralkyl” as used herein refers to an aryl substituted by an alkyl group. An example of an aralkyl group is tolyl.

[0030] The term “alkaryl” as used herein refers to an alkyl substituted by an aryl group. An example of an alkaryl group is benzyl (-CH₂-Phenyl).

[0031] The term “heteroaralkyl” as used herein refers to an aralkyl group in which the aryl contains at least one heteroatom, such as O, N or S.

[0032] The term “alkheteroaryl” as used herein refers to an heteroaryl group substituted by an alkyl.

[0033] Molecular weights herein are number averaged (Mn), weight averaged (Mw), or z-averaged molecular weights measured using gel permeation chromatography (GPC) with polystyrene standards, unless stated otherwise.Curable composition

[0034] The present invention relates to a curable composition comprising at least three components, optionally a fourth component. More precisely, the curable composition of the present invention comprises:(A) an oligomer which is the reaction product of:(i) at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol, polyol, diepoxide or polyepoxide;(ii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl diacid;(iii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl triacid; and (iv) at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide; or(B) at least one (meth)acrylate monomer;(C) at least one (meth)acrylate phosphate ester; and(D) optionally, at least one free radical initiator.

[0035] The present invention provides a curable composition which is well-suited for adhesives, inks or coatings, in particular coatings for batteries that operate under harsh conditions. In particular the compositions of the present invention have been shown to present strong adhesion, hardness, and flexibility, in comparison to hyperbranched polyester acrylate oligomer or tetrafunctional oligomer.

[0036] Additionally, the composition may be efficiently cured and offers improved performance in formulations, particularly in terms of resistance to solvent and curing speed, while maintaining mechanical properties, such as impact resistance.

[0037] The oligomer described herein is produced with low energy requirements (e.g., lower than polyurethanes) and utilizes components that pose fewer safety hazards.Oligomer (A)

[0038] One of the components of the composition of the present invention is an oligomer (A). Such oligomer comprises different segments: segments comprising ester bonds and segments comprising ethylenic unsaturations. Differently said, the oligomer comprises several ester functions in its backbone and is functionalized with groups comprising at least one ethylenic unsaturation.Based on these functionalities, the compound of the present invention may be qualified as a polyester oligomer or compound. Such oligomer may also be called interchangeably “compound”, “polyester oligomer”, “polyester compound” or “curable oligomer”.

[0039] The oligomer (A) is the reaction product of four distinct components, as detailed herein.

[0040] The oligomer (A) is the reaction product of:(i) at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol, polyol, diepoxide or polyepoxide;(ii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl diacid;(iii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl triacid; and(iv) at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide.

[0041] According to a first embodiment, components (i)-(iv) may be mixed together with no specific order of addition.

[0042] The resulting oligomer (A) may thus be the reaction product of a one-stage process.

[0043] In this first embodiment, a condensation reaction of components (i)-(iv) may be catalyzed by a strong protic acid, such as methane sulfonic acid, p-toluene sulfonic acid, or sulfuric acid. The reaction may carry out with byproduct water continuously removed (e.g., by means of reflux and condensation into a sidearm).

[0044] In a second embodiment, a polyester may first be prepared by reacting components (i)- (iii), then such polyester may be reacted with component (iv) to provide the oligomer (A).

[0045] The resulting oligomer (A) may thus be the reaction product of a two-stage process.

[0046] In this second embodiment, the reaction of components (i)-(iii) may be catalyzed by a strong nucleophile such as benzyltriethylammonium chloride, tetraphenyl phosphonium bromide, or triphenylphosphine or by a Lewis acid, such as chromium (III) acetate, to form a polyester. The polyester is then reacted with component (iv) in the same reaction vessel by addition of component (iv) to the reaction mixture. The choice of monoacid and / or monoepoxide is determined by analysis of the end groups of the polyester and each equivalent of acid end-group is reacted with a stoichiometric amount of ethylenically unsaturated monoepoxide and each equivalent of hydroxyl or epoxide end group is reacted with a stoichiometric amount of ethylenically unsaturated monoacid. If analysis shows that less than 10 meq / g of a functional group is present, its presence may optionally be neglected when calculating the addition of component (iv).

[0047] The reaction generally involves heating components (i)-(iv) / (i)-(iii) at temperatures ranging between 100 and 200°C, under pressure or vacuum to remove water and other by-products. Catalysts may be used during the reaction.

[0048] One component used to obtain oligomer (A) is component (i), i.e., at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol, polyol, diepoxide or poly epoxide.

[0049] The diol, polyol, diepoxide and polyepoxide used to prepare the polyester compound are not intended to be limited to specific structures only. The term “polyol” as used herein refers to any compound comprising at least two (two or more) hydroxyl groups, in its broadest meaning. The term “diol” as used herein refers to any compound comprising two hydroxyl groups, in its broadest meaning. The term “polyepoxide” as used herein refers to any compound comprising at least two (two or more) epoxy groups ( ° ), in its broadest meaning. The term “diepoxide” as used herein refers to any compound comprising two epoxy groups ( ° ), in its broadest meaning.

[0050] Component (i) comprises at least one diol, polyol, diepoxide or polyepoxide. Component (i) may comprise a mixture of compounds selected from a diol, a polyol, a diepoxide, and a poly epoxide.

[0051] In particular, component (i) may comprise or consist of at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol or diepoxide.

[0052] In particular, component (i) may comprise or consist of an acyclic diol or polyol, an aryl diol or polyol, an aryl polyepoxide or diepoxide, or a component comprising at least two glycidyl ether functions, for example, two, three or four glycidyl ether functions, or a mixture thereof.

[0053] In particular, component (i) may comprise or consist of a diprimary diol and / or component (ii) may comprise or consist of a diacid having its COOH groups in alpha position of methylene (-CH2) groups. The primary diol may for example be 1,4-butanediol, ethylene glycol, 1,6-hexanediol, 1,8-octandiol or a mixture thereof.

[0054] In particular, component (i) may comprise or consist of a diol comprising or substituted with at least one ester group, at least one alkoxy late group or both. In some embodiments, component (i) comprises or consists of a diol comprising or substituted with one ester group.

[0055] In particular, component (i) may comprise or consist of an acyclic polyol, preferably an acyclic diol. In particular, component (i) may comprise or consist of a linear or branched aliphatic polyol or diol, preferably a linear or branched aliphatic diol. For example, component (i) may comprise or consist of a diol selected among alkyl diols (or alkyl glycols), alkoxy lated alkyl diols, polyether diols, neopentyl glycols, alkylated neopentyl glycols, and alkoxylated neopentyl glycols. More particularly, the acyclic diol may be selected from the group consisting of propanediols (e.g., 1,2-propoanediol or 1,3-propanediol), butanediols (e.g., 1,4-butanediol), pentanediols (e.g., 1,5-pentanediol), hexanediols (e.g., 1,6-hexanediol), octanediols, decanediols, dodecanediols, 2-methyl-1,3 -propanediol, 2-methyl-2,4-pentanediol, and neopentyl glycol and mixtures thereof. The acyclic diol may be selected from the group consisting of ethoxylated alkyl diols, propoxylated alkyl diols, ethoxylated neopentyl glycol, propoxylated neopentyl glycol, and mixtures thereof. The acyclic diol may an alkylated neopentyl glycol, for example neopentyl monohydroxy pivalate (HPN glycol), also called neopentyl glycol mono(hydroxy pivalate). The acyclic diol may a poly ether diol, for example be selected from the group consisting of polyethylene oxide), polypropylene oxide), poly(butylene oxide) and mixtures thereof.

[0056] In particular, component (i) may comprise or consist of an aryl polyol or an aryl diol, preferably an aryl diol. More particularly, the aryl diol may be selected from the group consisting of hydroquinone (HQE), alkoxylated HQE (for example, ethoxylated HQE and propoxylated HQE), bisphenol-A (BP A), alkoxylated BPA (for example ethoxylated bisphenol A and propoxylated bisphenol A), propoxylated BPA, and bis-ethylene glycol terephthalate.

[0057] In particular, component (i) may comprise or consist of a first substituted or unsubstituted aliphatic, aryl, or heteroaryl diol and a second diol selected from the group consisting of tricyclodecanedimethanol, cyclohexane dimethanol, hydrogenated bisphenol A and hydrogenated bisphenol F, wherein the second diol is present in an amount of not more than 45 mol.% of the total diol content.

[0058] In particular, component (i) may comprise or consist of an aryl polyepoxide or an aryl diepoxide, preferably an aryl diepoxide. The aryl diepoxide may be selected from the group consisting of bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), bisphenol S diglycidyl ether (BPSGE), and mixtures thereof.

[0059] In particular, component (i) may comprise or consist of a diepoxide or polyepoxide or a component comprising at least two glycidyl ether functions. More particularly, the diepoxide may be selected from the group consisting of alkyl diol diglycidyl ether (e.g., 1,4-butanediol diglycidyl ether), aryl diol diglycidyl ether (e.g., hydrogenated bisphenol A diglycidyl ether), and polyether diol diglycidyl ether (e.g., dipropylene glycol diglycidyl ether). Additionally, the diepoxide may be the neopentyl glycol diglycidyl ether. The diepoxide, optionally polyepoxide, may be selected from 1,2,3,4-diepoxybutane; 1,2,4,5-diepoxypentane; 1,2,5,6-diepoxyhexane; 1,2,7,8-diepoxyoctane; 1,2, 9, 10-diepoxy decane; bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolak resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethy 1-3 ',4'-epoxy cyclohexanecarboxy late, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-l,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,3,4-epoxy-6-methylcyclohexy 1-3', 4'-epoxy-6'-m ethylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis(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, 1,7-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2 -methyl- 1,3 -propanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2, 2-diethyl- 1,3 -propane diol diglycidyl ether, 3 -methyl- 1,5 -pentanediol diglycidyl ether, 3,3-dimethyl-l,5-pentanediol diglycidyl ether, 2, 4-diethy 1-1, 5 -pentanediol diglycidyl ether, 3,3-butylethyl-l,5-pentane diol diglycidyl ether, di-, tri- or tetra(ethylene glycol) diglycidyl ether, di-, tri- or tetra(l,2-propylene glycol) diglycidyl ether, di-, tri- or tetra(l,3-propylene glycol) diglycidyl ether, di-, tri- or tetra(l,4-butylene glycol) diglycidyl ether, a polyethylene glycol) diglycidyl ether, a polypropylene glycol) diglycidyl ether, a poly(trimethylene glycol) diglycidyl ether, a poly(tetramethylene glycol) diglycidyl ether, a polyethylene glycol-co-propylene glycol) diglycidyl ether, glycerol triglycidyl ether, a polyglycerol polyglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl cyclohexanedicarboxylate, cyclohexane diglycidyl ether, cyclohexane- 1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, pyrocatechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl isophthalate, polyglycidyl ethers of a polyether polyol obtained by the addition of one or more alkylene oxides to an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, and glycerol, diglycidyl esters of aliphatic long-chain (C6-C22) dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of phenol, cresol, butyl phenol, or polyether alcohols obtained by the addition of alkylene oxide to these compounds, glycidyl esters of higher fatty acids, an epoxidized vegetable oil (such as epoxidized soybean oil and epoxidized linseed oil), epoxybutylstearic acid, epoxyoctylstearic acid, epoxidized poly butadiene, triglycidyl isocyanurate and the like.

[0060] In a preferred embodiment, component (i) comprises or consists of at least one compound selected from a diol, a polyol having at least 3 OH groups and mixtures thereof. In particular, component (i) may comprise or consist of at least one compound selected from a diol, a polyol having 3 to 6 OH groups and mixtures thereof. More particularly, component (i) may comprise or consist of at least one compound selected from a diol, a polyol having 3 or 4 OH groups, and mixtures thereof.

[0061] In a preferred embodiment, component (i) comprises or consists of at least one diol or a mixture of at least one diol and at least one polyol having at least 3, in particular 3 to 6, more particularly 3 or 4, OH groups.

[0062] When component (1) comprises at least one diol, it may correspond to the following formula (32) and when component (i) comprises at least one polyol having at least 3 OH groups, it may correspond to the following formula (33):each A is independently an aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl divalent moiety,each P is independently an aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl (x+2) valent moiety;wherein:- each R4, R’4, R7, R’7, Rs, R’s, Rio, R’10, R11, R’11, R12, R’12, R13, R’13, R14 and R’14 is independently H or alkyl;- each R5, R’S, Re, R’e, Rs, R’s, Ris and R’15 is independently H or methyl;- each W is independently -O- or -S-;- each Cy is independently an optionally substituted ring or polycyclic ring system, in particular an optionally substituted cyclopentylene, cyclohexylene, phenylene, naphthylene, bicyclooctylene or tricyclodecylene;- each Lois independently a bond or a linker such as Aik, -C(=O)-, -C(=O)-O-Alk-O- C(=O)-, -SO-, -SO2-, -C(=CCl2)- and -Alk-Ph-Alk-;- Aik is an optionally substituted alkylene;- Ph is an optionally substituted phenylene;- each e, j, m, n, o and r is independently an integer from 2 to 20;- each s is independently an integer from 0 to 20;- each s’ is independently an integer from 1 to 20;- each f, h and u is independently an integer from 2 to 4;- t is an integer equal to 0 or 1;- each g, 1, p and q is independently an integer from 1 to 20;- each v is independently an integer from 0 to 10, in particular from 1 to 6; - each i is independently an integer from 0 to 20 with the proviso that at least one i is not 0;- k is an integer from 3 to 12.

[0064] In formulae (33), P may be a (x+2)valent moiety comprising from 1 to 50 carbon atoms and optionally one or more heteroatoms independently selected from O, N and S. In particular, P may be selected from:- a trivalent moiety according to any one of formulae (15) to (20):wherein:- each R15 and R16 is independently a linear or branched alkylene;- each Ru and R’n is independently H or methyl;- each Ris and R’is is independently H, alkyl or alkoxy, preferably each RI8and R’is is alkyl;- each R19 is independently a linear or branched alkylene;- Rf is H or methyl;- w is an integer equal to 0 or 1;- each a’ is independently an integer from 0 to 2 with the proviso that not more than one a’ is equal to 0, preferably each a’ is equal to 1 or one a’ is equal to 0 and the two other a’ are equal to 1;- each a’ ’ is independently an integer from 0 to 2 with the proviso that not more than one a” is equal to 0, preferably each a” is equal to 1 or one a” is equal to 0 and the two other a” are equal to 1;- each b’ is independently an integer from 2 to 4, in particular 2;- each c’ is independently an integer from 0 to 10, in particular from 1 to 6;a tetravalent moiety according to any one of formulae (21) to (24):wherein:- each R20, R’20, R22 and R’22 is independently H or methyl;- each R21 and R25 is independently a linear or branched alkylene;- each R23 and R24 is independently H, alkyl or alkoxy, preferably alkyl;- each d’ is independently an integer from 0 to 2 with the proviso that not more than one d’ is equal to 0, preferably each d’ is equal to 1;- each d’ ’ is independently an integer from 0 to 2 with the proviso that not more than one d” is equal to 0, preferably each d” is equal to 1;- each e’ and g’ is independently an integer from 2 to 4, in particular 2;- each f ’ and h’ is independently an integer from 0 to 10, in particular from 1 to 6; - a tetra-, penta- or hexavalent moiety according to formula (25):wherein:- each R26and R’2e is independently H or methyl;- each i’ is independently an integer from 2 to 4, in particular 2;- each j ’ is independently an integer from 0 to 10, in particular from 1 to 6;- k’ is an integer from 1 to 3;- a tri-, tetra-, penta- or hexavalent moiety according to formula (26):wherein- each Rg is independently selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, -C(=O)O-Alkyl and a halogen atom;- k” is an integer from 1 to 4;- a hexavalent moiety according to any one of formulae (27) to (29):wherein- each R27, R’27, R29 and R’29 is independently H or methyl;- each R28 is independently a linear or branched alkylene;- each 1’ and n’ is independently an integer from 2 to 4, in particular 2;- each m’ and o’ is independently an integer from 0 to 10, in particular from 1 to 6.

[0065] In a preferred embodiment, component (i) comprises or consists of at least one diol selected from:- a cyclic diol, in particular a cyclic diol selected from hydroquinone (HQE), hydroquinone bis(2-hydroxyethyl) ether (HQEE), bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), as well as the alkoxy lated (e.g. ethoxylated and / or propoxylated) derivatives thereof;- a diol comprising an ester bond, in particular neopentyl glycol mono(hydroxypivalate) having the following structure:and mixtures thereof.

[0066] In another preferred embodiment, component (i) comprises or consists of a mixture of at least one diol and at least one polyol having at least 3 OH groups, in particular 3 to 6 OH groups,more particularly 3 or 4 OH groups. The molar ratio of the at least one diol to the at least one polyol having at least 3 OH groups may be from 1 to 50, preferably from 2 to 25, more preferably from 5 to 20. In particular, the at least one diol may be selected from ethylene glycol, propanediols (e.g., 1,2-propanediol or 1,3 -propanediol), butanediols (e.g., 1,2-, 1,3- or 1,4-butanediol), pentanediols (e.g., 1.5-pentanediol), hexanediols (e.g., 1,6-hexanediol), octanediols, decanediols, dodecanediols, 2-methyl-l,3-propanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 2, 2-diethyl- 1,3 -propanediol, 3-methyl-l,5-pentanediol, 3,3-dimethyl-l,5-pentanediol, 2,4-diethyl-l,5-pentanediol, 3,3-butylethyl- 1.5-pentane diol, neopentyl glycol mono(hydroxy pivalate), di-, tri- or tetra(ethylene glycol), di-, trior tetra(l,2-propylene glycol), di-, tri- or tetra(l,3-propylene glycol), di-, tri- or tetra(l,4-butylene glycol), a polyethylene glycol), a polypropylene glycol), a poly(trimethylene glycol), a poly(tetramethylene glycol), a poly(ethylene glycol-co-propylene glycol, hydroquinone (HQE), hydroquinone bis(2-hydroxyethyl) ether (HQEE), bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), as well as the alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and mixtures thereof. In particular, the at least one polyol having at least 3 OH groups may be selected from trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerol, di-, tri- or tetraglycerol, a polyglycerol, an alditol (i.e. erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol or iditol), tris(2-hydroxyethyl)isocyanurate, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, as well as the alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and mixtures thereof.

[0067] One component used to obtain oligomer (A) is component (ii), i.e. at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl diacid. Another component used to obtain oligomer (A) is component (iii), i.e. at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl triacid. Preferably, both of said diacid and triacid have at least 10, preferably at least 15, more preferably at least 21, more preferably at least 24 carbon atoms, and most preferably at least 30 carbon atoms. In some specific examples, the diacid has 36 carbon atoms and the triacid has 54 carbon atoms. Such diacid and triacid may be commercialized as a mixture. Reference can notably be made to PRIPOL commercial products from Cargill, such as PRIPOL™ 1009 (a diacid product containing about 1 wt.% of triacid and no monoacids) and PRIPOL™ 1006 (a diacid product containing about 3 wt.% of triacid and about 1 wt.% mono acids), from Cargill, as well as to UNIDYME™ 18 from KRATON (a long chain (C36) acid mixture containing about 17 wt.% trimer acids and about 1.5 wt.% monomer acids).

[0068] In particular, components (ii) and / or (iii) may respectively comprise or consist of a substituted or unsubstituted phenyl or naphthyl diacid and / or triacid; preferably, both components(ii) and (iii) comprise or consist of a substituted or unsubstituted phenyl or naphthyl diacid and triacid.

[0069] In particular, components (ii) and / or (iii) may respectively comprise or consist of a substituted or unsubstituted norbomenyl diacid and / or triacid; preferably, both components (ii) and (iii) comprise or consist of a substituted or unsubstituted norbornenyl diacid and triacid.

[0070] In particular, components (ii) and / or (iii) may respectively comprise or consist of a substituted or unsubstituted non-hydrogenated diacid and / or triacid; preferably, both components (ii) and (iii) comprise or consist of a substituted or unsubstituted non-hydrogenated diacid and triacid.

[0071] In a preferred embodiment, component (ii) may comprise or consist of at least one fatty acid dimer and component (iii) may comprise or consist of at least one fatty acid trimer.

[0072] Fatty acid dimers and trimers may be obtained by oligomerization (in particular by dimerization or trimerization) of a fatty acid. According to the present invention, a fatty acid is an acid having a fatty chain, i.e., a hydrocarbyl (non-cyclic) chain comprising from 10 to 30, in particular 12 to 26, more specifically 14 to 20, consecutive carbon atoms. A fatty acid can be saturated or unsaturated. A saturated fatty acid is a fatty acid that does not include a C=C double bond. An unsaturated fatty acid includes at least one C=C double bond. A monounsaturated fatty acid contains a single C=C double bond. A polyunsaturated fatty acid contains more than one C=C double bond. A polyunsaturated fatty acid can be conjugated or unconjugated. The hydrocarbyl chain of a fatty acid can be substituted, in particular by one or more hydroxyl, epoxide or carbonyl functions. The term "fatty acid" includes fatty acid precursors, i.e. compounds that can generate a fatty acid in situ, in particular by hydrolysis, such as fatty acid esters, including C1-C4 alkyl esters of fatty acids.

[0073] The oligomerization of fatty acids can be carried out in particular from unsaturated fatty acids and / or from fatty acids functionalized by a hydroxyl or epoxide function. Thus, two molecules of unsaturated fatty acids can react by Diels-Alder reaction to form one or more rings. Alternatively, two molecules of unsaturated fatty acids can react by radicular addition to form a covalent bond between the fatty chains. Alternatively, the hydroxyl function of a hydroxylated fatty acid can react with the acid function of a fatty acid to form an ester bond between the two molecules. Alternatively, the acid function of a fatty acid can react with the epoxide function of an epoxidized fatty acid to form an ester function between the two molecules.

[0074] The fatty acid dimer can be a fatty acid dimer having 32 to 40, preferably 34 to 38, more preferably 36 carbon atoms. Such a compound can be obtained by dimerization of fatty acids having 16 to 20, preferably 17 to 19, more preferably 18 carbon atoms. The fatty acid dimer can be an unsaturated fatty acid dimer, also known as a non-hydrogenated fatty acid dimer.

[0075] The fatty acid trimer can be a fatty acid trimer having 48 to 60, preferably 51 to 57, more preferably 54 carbon atoms. Such a compound can be obtained by trimerization of fatty acids having 16 to 20, preferably 17 to 19, more preferably 18 carbon atoms. The fatty acid trimer can be an unsaturated fatty acid trimer, also known as a non-hydrogenated fatty acid trimer.

[0076] In a preferred embodiment, the weight ratio of component (ii) to component (iii) is less than 30:1. Preferably, the weight ratio of component (ii) to component (iii) is between 30:1 and 4.1:1; more preferably, the weight ratio of component (ii) to component (iii) is between 25:1 and 4.2:1; most preferably, the weight ratio of component (ii) to component (iii) is between 20: 1 and 4.3:1.

[0077] One component used to obtain oligomer (A) is component (iv), i.e. at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide. Synthetic equivalent of monoacids, such as acyl halides and anhydrides are encompassed by the term monoacid.

[0078] In particular, component (iv) may comprise or consist of at least one ethylenically unsaturated monoacid selected from acrylic acid, methacrylic acid, an acryloyl halide (such as acryloyl chloride), a methacryloyl halide (such as methacryloyl chloride), acrylic anhydride, methacrylic anhydride or mixtures thereof; preferably acrylic acid, methacrylic acid, or mixtures thereof.

[0079] In particular, component (iv) may comprise or consist of at least one ethylenically unsaturated monoepoxide selected from glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid glycidyl ether, methacrylic acid glycidyl ether or mixtures thereof.

[0080] In particular, component (iv) may comprise or consist of at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide selected from (meth)acrylic acid, glycidyl (meth)acrylate, and the reaction products of hydroxy(alkyl) (meth)acrylates with phthalic or succinic anhydride or acid. Hydroxyalkyl (meth)acrylates include 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate. The adducts with succinic and phthalic acid with 2-hydroxyethyl (meth)acrylate are commercially available as CN146 (HEA monophthalate), CN147 (HEA monosuccinate), and CN149 (HEMA monophthalate) from Sartomer.

[0081] In a preferred embodiment, the reaction mixture used to obtain oligomer (A) comprises less than 3% of monoacid other than (meth)acrylic acid based on the total weight of the reactive species (i.e. the total weight of acids, alcohols and epoxides used to prepare oligomer (A)). Preferably, the reaction mixture contains less than 2.5 wt.%, more preferably less than 2 wt.%, most preferably less than 1.8%, less than 1.5%, less than 1.2%, less than 1 wt.%, less than 0.9% or even less than 0.5 wt.%, of monoacid other than (meth)acrylic acid based on the total weight of the reactive species.

[0082] In a preferred embodiment, the reaction mixture used to obtain oligomer (A) comprises less than 3 wt.%, preferably less than 2.5 wt.%, most preferably less than 1.8%, less than 1.5%, less than 1.2%, less than 1 wt.%, less than 0.9% or even less than 0.5 wt.%, of a monoacid having at least 10, preferably at least 12, more preferably at least 14, more preferably at least 16, and most preferably at least 18, carbon atoms, based on the total weight of the reactive species (i.e. the total weight of acids, alcohols and epoxides used to prepare oligomer (A)). Said monoacid may be saturated or unsaturated, preferably unsaturated.

[0083] The oligomer (A) may be such that it has a number average molecular weight (Mn) of at least about 750 g / mol, preferably between about 1,000 and about 15,000 g / mol, between about 1,250 and about 10,000 g / mol, or between about 1,500 and about 7,000 g / mol.

[0084] The oligomer (A) may be such that it has a weight average molecular weight (Mw) of at least about 1,000 g / mol, preferably between about 2,000 and about 30,000 g / mol, between about 3,000 and about 20,000 g / mol, or between about 3,500 and about 15,000 g / mol.

[0085] The oligomer (A) may be such that it has a polydispersity index (D) of less than about 3, preferably less than about 2.5 or more preferably less than about 2.

[0086] Number averaged (Mn), weight averaged (Mw), or Z-averaged (Mz) molecular weights may be measured using gel permeation chromatography (GPC) with polystyrene standards. Polydispersity index (D) may be calculated as Mw / Mn.

[0087] The curable composition of the invention may comprise from about 5 wt.% to about 99.9 wt.% of oligomer (A), for example from about 10 wt.% to about 99.5 wt.%, from about 20 wt.% to about 99 wt.%, from about 30 wt.% to about 98 wt.%, from about 50 wt.% to about 97 wt.%, or from about 60 wt.% to about 95 wt.%, of oligomer (A) based on the total weight of the curable composition.

[0088] The curable composition of the present invention may comprise several distinct oligomers (A), for example two or more. For example, the curable composition of the present invention comprises a mixture of oligomers (A) having distinct segments, for example prepared starting from distinct components. In such as case, the total amount of oligomer (A) based on the total weight of the curable composition may be as described in the preceding paragraph.(Meth)acrylate monomer (B)

[0089] One of the components of the composition of the present invention is component (B), i.e. at least one (meth)acrylate monomer. Component (B) may comprise one or more (meth)acrylate monomers.

[0090] (Meth)acrylate monomers can also be referred to as (meth)acry late -functionalized monomers, and refer to monomers comprising a (meth)acrylate group.

[0091] A (meth)acrylate monomer may have a molecular weight of less than about 600 g / mol, in particular from about 100 to about 550 g / mol, more particularly from about 200 to about 500 g / mol.

[0092] A (meth)acrylate monomer may have 1 to 6 (meth)acrylate groups, in particular 1 to 3 (meth)acrylate groups.

[0093] Component (B) may comprise a mixture of (meth)acrylate-functionalized monomers having different functionalities. For example, component (B) may comprise a mixture of a (meth)acry late -functionalized monomer containing a single acrylate or methacrylate group per molecule (referred to herein as “mono(meth)acrylate-functionalized monomer”) and a (meth)acry late -functionalized monomer containing 2 or more, preferably 2 or 3, acrylate and / or methacrylate groups per molecule (referred to herein as “poly(meth)acrylate-functionalized monomer”).

[0094] In particular, component (B) may comprise at least one mono(meth)acrylate-functionalized monomer for example an aliphatic monofunctional (meth)acrylate monomer. In particular, component (B) may comprise a cyclic (meth)acrylate and / or a caprolactone (meth)acrylate, for instance isobornyl (meth)acrylate and / or 3, 3, 5 -trimethyl cyclohexyl acrylate.

[0095] In particular, component (B) may comprise at least one poly(meth)acrylate-functionalized monomer, for example an aliphatic difunctional (meth)acrylate monomer. In particular, component (B) may comprise 1,12-dodecanediol dimethacrylate and / or tricyclodecane dimethanol diacrylate.

[0096] Examples of suitable mono(meth)acrylate-functionalized monomers include, but are not limited to, mono-(meth)acrylate esters of aliphatic alcohols (wherein the aliphatic alcohol may be straight chain, branched or alicyclic and may be a mono-alcohol, a di-alcohol or a polyalcohol, provided only one hydroxyl group is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of aromatic alcohols (such as phenols, including alkylated phenols); mono-(meth)acrylate esters of alkylaryl alcohols (such as benzyl alcohol); mono-(meth)acrylate esters of oligomeric and polymeric glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol); mono-(meth)acrylate esters of monoalkyl ethers of glycols and oligoglycols; mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aliphatic alcohols (wherein the aliphatic alcohol may be straight chain, branched or alicyclic and may be a mono-alcohol, a di-alcohol or a polyalcohol, provided only one hydroxyl group of the alkoxylated aliphatic alcohol is esterified with (meth)acrylic acid); mono-(meth)acrylate esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); (poly)caprolactone mono(meth)acrylates; and the like.

[0097] A (poly)caprolactone mono(meth)acrylate may be obtained by ring-opening polymerization of e-caprolactone initiated with a hydroxyalkyl (meth)acrylate. A preferred (meth)caprolactone (meth)acrylate is (poly)caprolactone 2 -hydroxy ethyl (meth)acrylate according to the following formula:wherein R5 is H or methyl and t ranges from 1 to 20, preferably from 2 to 10.

[0098] The following compounds are specific examples of mono(meth)acrylate-functionalized monomers suitable for use in component (B): methyl (meth)acrylate; ethyl (meth) aery late; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth) aery late; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxy polyethylene glycol (meth)acrylates; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylates; a (poly)caprolactone mono(meth)acrylate; as well as the alkoxylated (i.e. ethoxylated and or propoxylated) derivatives thereof and combinations thereof.

[0099] Examples of suitable poly(meth)acrylate-functionalized monomers include acrylate and methacrylate esters of polyols. Examples of suitable polyols are ethylene glycol, propanediols (e.g., 1,2-propanediol or 1,3 -propanediol), butanediols (e.g., 1,2-, 1,3- or 1,4-butanediol), pentanediols (e.g., 1,5-pentanediol), hexanediols (e.g., 1,6-hexanediol), octanediols, decanediols, dodecanediols, 2 -methyl- 1,3 -propanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 2,2-diethyl-l,3-propanediol, 3 -methyl- 1,5 -pentanediol, 3,3-dimethyl-l,5-pentanediol, 2,4-diethyl-l,5-pentanediol, 3,3-butylethyl-l,5-pentane diol, neopentyl glycol mono(hydroxypivalate), di-, tri- or tetra(ethylene glycol), di-, tri- or tetra(l,2-propylene glycol), di-, tri- or tetra(l,3-propylene glycol), di-, tri- or tetra(l,4-butylene glycol), a polyethylene glycol), a polypropylene glycol), a poly (trimethylene glycol), a poly(tetramethylene glycol), a polyethylene glycol-co-propylene glycol, hydroquinone (HQE), hydroquinone bis(2 -hydroxyethyl) ether (HQEE), bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbomane dimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, dipentaerythritol), tripentaerythritol),glycerol, di-, tri- or tetraglycerol, a polyglycerol, an alditol (i.e. erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol or iditol), tris(2-hydroxyethyl)isocyanurate, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, as well as the alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride or the like), provided they contain at least two (meth)acrylate functional groups per molecule.

[0100] Exemplary poly(meth)acry late -functionalized monomers may include bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3 -butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-nonanediol di(meth)acrylate; 1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; poly butadiene di(meth)acrylate; cyclohexane-l,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; metallic di(meth)acrylates; modified metallic di(meth)acrylates; glyceryl di(meth)acrylate; glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri (meth)acry late; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris(2-hydroxyethyl) isocyanurate tri (meth)acry late; as well as the alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof.

[0101] The poly(meth)acrylate-functionalized monomer may also be selected from glycerol tri(meth)acrylate; diglycerol tetra(meth)acrylate, triglycerol penta(meth)acrylate, tetraglycerol hexa(meth)acrylate, trimethylolethane tri(meth) acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tris (2-hydroxyethyl) isocyanurate tri(meth)acrylate, as well as the alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof, and combinations thereof.

[0102] In a preferred embodiment, component (B) comprises or consists of at least one (meth)acrylate monomer selected from isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, isosorbide di(meth)acrylate, bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, a (poly)caprolactone (meth)acrylate, and mixtures thereof.

[0103] The curable composition of the invention may comprise from about 5 wt.% to about 90 wt.% of component (B), for example from about 10 wt.% to about 80 wt.%, from about 15 wt.% to about 70 wt.%, from about 20 wt.% to about 60 wt.%, from about 25 wt.% to about 55 wt.%, or from about 26 wt.% to about 54 wt.%, of component (B) based on the total weight of the curable composition.(Meth) acrylate phosphate ester (C)

[0104] One of the components of the composition of the present invention is component (C), i.e. at least one (meth)acrylate phosphate ester. Component (C) may comprise one or more (meth)acrylate phosphate esters.

[0105] In particular, component (C) may comprise a (meth)acrylated phosphate diester and, optionally, a (meth)acrylated phosphate monoester.

[0106] In particular, component (C) may comprise a (meth)acrylated phosphate diester of structure I:wherein:each Ra, Rband Rcis independently H or a C1-C6 alkyl, preferably H or methyl;Rdis H or a cation;each n is independently from 4 to 7, preferably from 5 to 6;each m is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

[0107] In particular, component (C) may comprise a (meth)acrylated phosphate monoester of structure II:wherein:Ra, Rband Rcare independently H or a C1-C6 alkyl, preferably H or methyl;Rdand Reare independently H or a cation;n is from 4 to 7, preferably from 5 to 6;m is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

[0108] In particular, component (C) may comprise a (meth)acrylated phosphate diester of structure III:each R1is independently H or methyl; andeach p is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

[0109] In particular, component (C) may comprise a (meth)acrylated phosphate monoester of structure IV:wherein:R1is H or methyl;p is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

[0110] In particular, component (C) may comprise a (meth)acrylated phosphate diester ofwherein:each R3, R4and R5is independently H or a C1-C6 alkyl, preferably H or methyl;R6is H or a cation;each t is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

[0111] In particular, component (C) may comprise a (meth)acrylated phosphate monoester of structure VI:wherein:R3, R4and R5are each independently H or methyl;R6and R7are each independently H or a cation;t is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

[0112] In particular, the molar ratio of the monoester to diester is at least about 1.5:1, at least about 1.6:1, at least about 1.7:1, at least about 1.8:1, at least about 1.9:1, or at least about 2.0:1.

[0113] In particular, the molar ratio of the monoester to diester is at least about 2.2:1, at least about 2.5:1, at least about 3.0: 1, or at least about 3.2:1.

[0114] In particular, the molar ratio of the monoester to diester is comprised between about 1.5:1 and about 4.0:1, between about 1.6:1 to about 3.8:1 or between about 1.8 to about 3.5:1.

[0115] The curable composition of the invention may comprise from about 1 wt.% to about 30 wt.% of component (C), for example from about 1.5 wt.% to about 25 wt.%, from about 2 wt.% to about 20 wt.%, from about 3 wt.% to about 15 wt.%, from about 4 wt.% to about 10 wt.%, or from about 5 wt.% to about 8 wt.%, of component (C) based on the total weight of the curable composition.Free radical initiator (D)

[0116] One of the optional components of the curable composition of the present invention is component (D), i.e. at least one free radical initiator. Component (D) may comprise one or more free radical initiators.

[0117] Free radical initiators encompass both photoinitiators and thermal initiators.

[0118] Photoinitiators are compounds that that can generate free radicals upon exposure to light of an appropriate wavelength and / or intensity. Photoinitiators can adopt two different modes of action, and are classified by mode of action as Norrish Type I and Norrish Type II photoinitiators. As used herein, the term “activity” with reference to Norrish Type I and Norrish Type II activity is intended to relate to Norrish photoinitiation and analogous reactions. For instance, a photoinitiator having Norrish Type I activity within the scope of this invention would be a photoinitiatorcharacterized by a cleavage reaction into two radical fragments of the original photoinitiator on exposure to light. For an initiator having Norrish Type II activity, exposure to light causes the abstraction of an atom, such as hydrogen, to generate the radical.

[0119] Thermal initiators are compounds that can generate free radicals upon exposure to heat and / or in the presence of a reducing agent.

[0120] The curable composition may comprise a free radical initiator which is a photoinitiator, in particular a photoinitiator having Norrish type I activity and / or Norrish type II activity, more particularly a free radical initiator having Norrish type I activity.

[0121] In some embodiments, the curable composition of the present invention also comprises one or more cationic initiators.

[0122] Cationic initiators are often salts, for instance iodonium and sulfonium salts. When these salts are activated (i.e., by irradiation with actinic radiation such as light), they undergo homolytic bond cleavage forming radicals that react with a proton donor to give a Bronsted or Lewis acid. The generated acid then initiates the polymerization.

[0123] Classes of suitable free radical photoinitiators suitable for use in the curable compositions as described herein include, but are not limited to, benzoins, benzoin ethers, acetophenones, a-hydroxy acetophenones, benzyl ketals, anthraquinones, phosphine oxides, acylphosphine oxides, a-hydroxyketones, phenylglyoxylates, a-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives, triazines, benzoyl formates, aromatic oximes, metallocenes, acylsilyl or acylgermanyl compounds, camphorquinones, polymeric derivatives thereof, and mixtures thereof.

[0124] Examples of suitable free radical photoinitiators include, but are not limited to, 2-methylanthraquinone, 2 -ethylanthraquinone, 2 -chloroanthraquinone, 2-benzyanthraquinone, 2-tert-butylanthraquinone, l,2-benzo-9,10-anthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, Michler's ketone, 2,2-dialkoxybenzophenones, 1-hydroxyphenyl ketones, benzophenone, 4,4'-bis-(diethylamino) benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2-isopropylthioxanthone, thioxanthone, diethyl thioxanthone, 1,5 -acetonaphthylene, benzil ketone, a-hydroxy keto, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, benzyl dimethyl ketal, 2,2-dimethoxy-l,2-diphenylethanone, 1-hydroxycylclohexyl phenyl ketone, 2-methyl-l-[4-(methylthio) phenyl]-2-morpholinopropanone-l, 2-hydroxy-2-methyl-l-phenyl-propanone, oligomeric a-hydroxy ketones, benzoyl phosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, (benzene) tricarbonylchromium, benzil, benzoin isobutyl ether, benzophenone / 1-hydroxy cyclohexyl phenyl ketone (50 / 50 blend), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4-benzoylbiphenyl, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, camphor quinone, 2-chlorothioxanthen-9-one, dibenzosuberenone, 4,4'-dihydroxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4-(dimethylamino)benzophenone, 4,4'-dimethylbenzil, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide / 2-hydroxy-2-methylpropiophenone, 50 / 50 blend, 4'-ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphophine oxide, phenyl bis(2,4,6-trimethyl benzoyl)phosphine oxide, ferrocene, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3 -hydroxy benzophenone, 4-hydroxybenzophenone, 1 -hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-methylbenzophenone, 3 -methylbenzophenone, methybenzoylformate, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, phenanthrenequinone, 4'-phenoxyacetophenone, (cumene)cyclopentadienyl iron(ii) hexafluorophosphate, 9,10-diethoxy and 9,10-dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and combinations thereof.

[0125] Preferred free radical photoinitiators include a benzophenone (such as those available from Sartomer under the trademarks Speedcure™ BP, Speedcure™ 7005, and Speedcure™ 7006), a thioxanthone (such as available from Sartomer under the trademarks Speedcure™ 7010 and Speedcure™ ITX), an a-hydroxy acetophenone, an acylphosphine oxide (such as available from Sartomer under the trademarks Speedcure™ BPO, Speedcure™ TPO and Speedcure™ TPO-L) and combinations thereof.

[0126] According to the present invention, the curable composition of the present invention may comprise:about 15 to about 50 wt.%, or about 20 to about 40 wt.%, of oligomer (A);about 30 to about 60 wt. %, or about 35 to about 50 wt.%, of component (B);about 2 to about 20 wt.%, or about 4 to about 15 wt.%, of component (C); and / or0 to about 3 wt.%, or about 0.1 to about 2 wt.%, of component (D);based on the total weight of the curable composition.Other optional components

[0127] The curable composition of the invention may further comprise one or more of the following:an inhibitor; and / oran additive selected from the group consisting of antioxidants, ultraviolet absorbers, photostabilizers, foam inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents), slip additives, fillers, thixotropic agents, matting agents, waxes, any additive conventionally utilized in coating, sealant, adhesive, ink or molding compositions, and mixtures thereof.

[0128] The curable composition of the invention may comprise at least one inhibitor. According to these embodiments, the composition may comprise from about 10 ppm to about 5 wt.% of one or more inhibitors, for example from about 20 ppm to about 4 wt.%, from about 50 ppm to about 3 wt.%, from about 100 ppm to about 1 wt.%, or from about 120 ppm to about 0.1 wt.%, based on the total weight of the curable composition.

[0129] Inhibitors may be introduced in the curable composition in order to provide adequate storage stability and shelf life. As described above, an inhibitor may typically retard or prevent reaction or curing of polymerizable functional groups present in a composition, notably in the absence of radiation.

[0130] As described above, any of the inhibitors known in the art related to ethylenically unsaturated compounds may be utilized in the composition of the invention.

[0131] The curable compositions of the present invention may optionally contain one or more additives selected from the group consisting of antioxidants, ultraviolet absorbers, photostabilizers, foam inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents), slip additives, fdlers, elastomers, thixotropic agents, matting agents, waxes, any additive conventionally utilized in coating, sealant, adhesive, ink or molding compositions, and mixtures thereof.

[0132] In some embodiments, the curable compositions of the invention comprise one or more fillers. Examples of fdlers include talc, titanium dioxide, silica, glass particles, quartz, graphite powder, carbon black, aluminum oxide powder, and the likes, and mixtures thereof.

[0133] In some embodiments, the curable compositions of the invention comprise one or more elastomers. Examples of elastomers include RTV rubber and silicone rubber.Solvent-free composition

[0134] In some embodiments, the curable compositions of the invention are solvent-free. In such embodiments, they notably contain no organic solvent.

[0135] In some embodiments, the curable composition of the invention is solvent-free. Solvent-free curable compositions may be advantageous as they typically require less energy for production compared to solvent-borne compositions.

[0136] The term “solvent-free” or “solvent-free composition” as used herein refers to a composition comprising less than 2 wt.%, less than 1 wt.%, 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.

[0137] The term “solvent” as used herein refers to 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. The term “organic solvent” as used herein refers to a solvent having carbon atoms. The term “non-reactive organic solvent” as used herein refers to an organic solvent which remains unchanged during the curingprocess, i.e. it is non-reactive with respect to the components of the curable composition. 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.Two-part composition

[0138] In some embodiments, the curable composition of the present invention is defined to comprise a resin component (I) and a filler / additive component (II). The components (A)-(D) described above are included in the resin component (I), while the fillers and additives constitute component (II).

[0139] According to these embodiments, the curable composition of the present invention may comprise or consist of:about 1 to about 99 wt.% of a resin component (I), which comprises oligomer (A), at least one (meth)acrylate monomer (B), at least one (meth)acrylate phosphate ester (C); and optionally, a free radical initiator (D); andabout 1 to about 99 wt.% of a filler / additive component (II);based on the total weight of the curable composition.

[0140] In particular, the curable composition of the present invention may comprise from about 10 to about 95 wt.% of a resin component (I), from about 30 to about 90 or from about 50 to about 85 wt.% of a resin component (I), based on the total weight of the curable composition.

[0141] In particular, the curable composition of the present invention may comprise from about 10 to about 95 wt.% of a filler / additive component (II), from about 10 to about 70 or from about 15 to about 50 wt.% of a filler / additive component (II), based on the total weight of the curable composition.

[0142] In particular, the curable composition of the present invention may comprise about 80 wt.% of a resin component (I) and about 20 wt.% of a filler / additive component (II).

[0143] In particular, the curable composition of the present invention may comprise or consist of:about 15 to about 50 wt.% of the oligomer (A), or about 20 to about 40 wt.%;about 30 to about 60 wt. % of (meth)acrylate monomers (B), or about 35 to about 50 wt.%; about 2 to about 20 wt.% of (meth)acrylate phosphate esters (C), or about 4 to about 15 wt.%; 0 to about 3 wt.% of free radical initiator (D) or about 0.1 to about 2 wt.%; and0 to about 30 wt.% of fillers / additives, or about 5 to about 25 wt.%;based on the total weight of the curable composition.

[0144] Examples of fillers include talc, titanium dioxide, silica, glass particles, quartz, graphite powder, carbon black, aluminum oxide powder, and the likes, and mixtures thereof.End-use applications

[0145] The curable composition of the present invention may be used in various formulations, for example formulations for adhesives, inks, or coatings. In particular, the composition of the present invention is particularly well-suited for battery coatings.

[0146] The curable composition of the present invention may also be used as a constituent of a solvent-resistant encapsulant formulation, such as a coating for batteries.

[0147] The present invention is also directed to a method of making a formulation for an adhesive, an ink or a coating, in particular a coating for battery, comprising adding the curable composition of the present invention as one of the components of such formulation.

[0148] The curable compositions of the invention as described herein may be used as a coating for batteries (e.g., a battery for an electric machine or vehicle) on their exterior surface(s). Coatings on battery cells and modules are essential for various reasons, including providing protection, insulation, and enhancing the overall performance and durability of the battery system. At elevated temperatures and at high relative humidities, strong adhesion and flexibility of battery coatings are critical for several reasons, including, but not limited to: (1) Environmental Protection, where battery cells and modules are often exposed to harsh environmental conditions, such as high humidity and temperature fluctuations and therefore require a protective barrier, shielding the battery from moisture and contaminants, where strong adhesion ensures that the coating remains in place and effectively guards against environmental threats; (2) Corrosion Prevention, which is needed to combat high humidity and elevated temperatures which can accelerate corrosion and chemical reactions on the surface of battery cells and modules, where strong adhesion of the compositions create a barrier that inhibits moisture and contaminants from coming into contact with the battery's metallic (such as aluminum) components, reducing the risk of corrosion; (3) Maintaining Electrical Insulation, where the compositions provide electrical insulation in battery systems, where strong adhesion ensures that the insulation remains intact, preventing electrical leakage or short circuits that could result from the intrusion of moisture or contaminants; (4) Long-Term Durability, where the operational life of the battery is extended by the presence of the compositions. In addition, flexible coatings (which are characteristic of the compositions of the invention) are better equipped to endure the mechanical stresses and temperature variations experienced by batteries throughout their life spans.

[0149] The curable compositions may be used for coating an exterior surface of a battery. For example, the curable compositions may be used for coating a battery electrode or the battery separator of a lithium-ion battery. The curable compositions combine desirableperformance properties that include ease of application, improved storage stability, flow, adhesion, electric insulation, matting, flame retardancy and weathering resistance (which includes one or more of high and low temperature compatibility, salt fog resistance and humidity resistance). The curable compositions notably provide high dielectric strength and high resistivity, which are desirable for application on the outside (exterior) surface of a battery, which surface in an embodiment is metal, such as aluminum.

[0150] The polyester -based oligomers utilized herein offer a multitude of advantages for coatings applied to battery cells and modules across diverse applications. Renowned for their durability and toughness, these coatings excel in withstanding mechanical stresses, impacts, and abrasion, thereby significantly extending the lifespan of battery components. Their strong adhesion properties ensure effective bonding to various substrates, including metals and polymers commonly employed in battery construction, creating a stable and protective barrier on the surface. The flexibility inherent in polyester-based coatings proves invaluable in applications where coated materials may undergo expansion and contraction, preventing issues like cracking or delamination and maintaining the protective properties of the coating. Moreover, the cost-effectiveness of polyester as a material makes it an appealing choice for large-scale manufacturing processes, striking a balance between performance and affordability and contributing to the cost-efficient production of coated battery components. Additionally, polyester coatings can be tailored to meet specific environmental regulations and standards, with formulations low in volatile organic compounds (VOCs) offering environmentally friendly coating solutions.Method of making a cured composition

[0151] The present invention also relates to a method of making a cured composition, which comprises curing the curable composition of the present invention.

[0152] The cured compositions obtained herein exhibit mechanical properties particularly well-suited for battery coatings. These properties enable the coatings to withstand the harsh operating conditions of batteries, such as exposure to electrolytes, elevated temperatures, and repeated chargedischarge cycles, while maintaining adhesion, flexibility, and chemical resistance.

[0153] Curing may be accelerated or facilitated by supplying energy to the composition, such as by exposing the composition to a radiation source, such as visible or UV light, infrared radiation, and / or electron beam radiation and / or by heating the composition. The cured composition is the reaction product obtained from curing the curable composition described herein.

[0154] In some embodiments, the method of making a cured composition comprises exposing the curable composition to ultraviolet light (UV) radiation, electron beam (EB) radiation and / or heat.

[0155] The curable compositions of the present invention are particularly well suited to being cured using LED (Light Emitting Diode) curing, e.g., UV LED curing, using radiation from a UV LED device.

[0156] In particular, the curable compositions of the invention are well -suited for use in applications requiring a fast curing.

[0157] The curable composition of the invention may be applied to a substrate surface, then cured by exposure to a source of curing (for example a dose of radiation).ASPECTS OF THE INVENTION

[0158] The present invention may be according to any one of the following aspects.Aspect 1. A curable composition comprising(A) an oligomer which is the reaction product of:(i) at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol, polyol, diepoxide or poly epoxide;(ii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl diacid;(iii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl triacid; and(iv) at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide;(B) at least one (meth)acrylate monomer;(C) at least one (meth)acrylate phosphate ester; and(D) optionally, at least one free radical initiator.Aspect 2. The curable composition of aspect 1, wherein the weight ratio of component (ii) to component (iii) is less than 30:1, preferably between 30:1 and 4.1:1, more preferably between 25:1 and 4.2:1, most preferably between 20:1 and 4.3:1.Aspect 3. The curable composition of aspects 1 or 2, wherein the reaction mixture used to obtain oligomer (A) comprises less than 3% preferably less than 2.5 wt.%, more preferably less than 2 wt.%, most preferably less than 1.8%, less than 1.5%, less than 1.2%, less than 1 wt.%, less than 0.9% or even less than 0.5 wt.%, of monoacid other than (meth)acrylic acid based on the total weight of the reactive species.Aspect 4. The curable composition of any one of aspects 1-3, wherein component (i) comprises or consists of a diprimary diol and component (ii) comprises or consists of a diacid having its COOH groups in alpha position of methylene (-CH2) groups.Aspect 5. The curable composition of any one of aspects 1-4, wherein component (i) comprises or consists of a diol comprising or substituted with at least one ester group, at least one alkoxylate group or both.Aspect 6. The curable composition of any one of aspects 1-4, wherein component (i) comprises or consists of an acyclic diol, preferably a linear or branched aliphatic diol.Aspect 7. The curable composition of aspect 6, wherein the acyclic diol is selected from the group consisting of propanediols (preferably 1,2-propoanediol or 1,3 -propanediol), butanediols (preferably 1,4-butanediol), pentanediols (preferably 1,5-pentanediol), hexanediols (preferably 1,6-hexanediol), octanediols, decanediols, dodecanediols, 2-methyl-l,3-propanediol, 2-methyl-2,4-pentanediol, and neopentyl glycol; and mixtures thereof.Aspect 8. The curable composition of any one of aspects 1-4, wherein component (i) comprises or consists of an alkylated neopentyl glycol, preferably neopentyl monohydroxy pivalate (HPN glycol).Aspect 9. The curable composition of any one of aspects 1-4, wherein component (i) comprises or consists of an aryl polyol or an aryl diol, preferably an aryl diol; more preferably selected from the group consisting of hydroquinone (HQE), alkoxylated HQE (preferably ethoxylated HQE and propoxylated HQE), bisphenol-A (BP A), alkoxylated BPA (preferably ethoxylated bisphenol A and propoxy lated bisphenol A), propoxylated BPA, and bis-ethylene glycol terephthalate; and mixtures thereof.Aspect 10. The curable composition of any one of aspects 1-4, wherein component (i) comprises or consists of a first substituted or unsubstituted aliphatic, aryl, or heteroaryl diol and a second diol selected from the group consisting of tricyclodecanedimethanol, cyclohexane dimethanol, hydrogenated bisphenol A and hydrogenated bisphenol F, wherein the second diol is present in an amount of not more than about 45 mol.% of the total diol content.Aspect 11. The curable composition of any one of aspects 1-3, wherein component (i) comprises or consists of an aryl polyepoxide or an aryl diepoxide, preferably an aryl diepoxide; more preferably an aryl diepoxide selected from the group consisting of bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), and bisphenol S diglycidyl ether (BPSGE); and mixtures thereof.Aspect 12. The curable composition of any one of aspects 1-3, wherein component (i) comprises or consists of a diepoxide or poly epoxide or a component comprising at least two glycidyl ether functions; preferably a diepoxide selected from the group consisting of alkyl diol diglycidyl ether (preferably 1,4-butanediol diglycidyl ether), aryl diol diglycidyl ether (preferably hydrogenated bisphenol A diglycidyl ether), and polyether diol diglycidyl ether (preferably dipropylene glycol diglycidyl ether) or preferably a neopentyl glycol diglycidyl ether; and mixtures thereof.Aspect 13. The curable composition of any one of aspects 1-3, wherein component (i) comprises or consists of at least one compound selected from a diol, a polyol having at least three OH groups and mixtures thereof; in particular, component (i) comprises or consists of at least one compound selected from a diol, a polyol having 3 to 6 OH groups and mixtures thereof; more particularly, component (i) comprises or consists of at least one compound selected from a diol, a polyol having 3 or 4 OH groups, and mixtures thereof.Aspect 14. The curable composition of any one of aspects 1-3 and 13, wherein component (i) comprises or consists of at least one diol or a mixture of at least one diol and at least one polyol having at least 3, in particular 3 to 6, more particularly 3 or 4, OH groups.Aspect 15. The curable composition of aspect 13 or 14, wherein the at least one diol corresponds to the following formula (32) and the at least one polyol having at least 3 OH groups correspond to the following formula (33):A is independently an aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl divalent moiety,P is independently an aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl (x+2) valent moiety;x is independently at least 1, in particular from 1 to 4, more particularly 1 or 2.Aspect 16. The curable composition of aspect 15, wherein A is a divalent moiety according to any one of formulae (3) to (14)-(CR4R’4)e- (3)-CH2-O-CH2- (4)- [(CR8R’8)k-C(=O)O] I-(CR9R’ 9)m- (7)-(CR9R’9)m-[OC(=O)-(CR8R’8)k]i- (8)-[(CRioR’io)n-0-C(=0)-(CRiiR’ii)o-C(=0)-0]P-(CRioR’io)n- (9)-(CRi2R’i2)q-C(=O)-O-(CRi3R’i3)r-O-C(=O)-(CRi2R’i2)q- (10)-(CRi4R’i4)s-Cy-[L0-Cy]t-(CRi4R’i4)s- (11)-(CRi4R’i4)s-O-Cy-O-(CRi4R’i4)s- (12)-(CRi4R’i4)s-O-C(=O)-Cy-C(=O)-O-(CRi4R’i4)s- (13),,,,,,- each W is independently -O- or -S-;- each Cy is independently an optionally substituted ring or polycyclic ring system, in particular an optionally substituted cyclopentylene, cyclohexylene, phenylene, naphthylene, bicyclooctylene or tricyclodecylene;- each Lois independently a bond or a linker such as Aik, -C(=O)-, -C(=O)-O-Alk-O- C(=O)-, -SO-, -SO2-, -C(=CCl2)- and -Alk-Ph-Alk-;- Aik is an optionally substituted alkylene;- Ph is an optionally substituted phenylene;- each e, j, m, n, o and r is independently an integer from 2 to 20;- each s is independently an integer from 0 to 20;- each s’ is independently an integer from 1 to 20;- each f, h and u is independently an integer from 2 to 4;- t is an integer equal to 0 or 1;- each g, 1, p and q is independently an integer from 1 to 20;- each v is independently an integer from 0 to 10, in particular from 1 to 6;- each i is independently an integer from 0 to 20 with the proviso that at least one i is not 0;- k is an integer from 3 to 12.Aspect 17. The curable composition of aspect 15 or 16, wherein P is selected from: - a trivalent moiety according to any one of formulae (15) to (20):wherein:- each R15 and R16 is independently a linear or branched alkylene;- each Ru and R’n is independently H or methyl;- each Ris and R’is is independently H, alkyl or alkoxy, preferably each Ris and R’is is alkyl;- each R19 is independently a linear or branched alkylene;- Rf is H or methyl;- w is an integer equal to 0 or 1;- each a’ is independently an integer from 0 to 2 with the proviso that not more than one a’ is equal to 0, preferably each a’ is equal to 1 or one a’ is equal to 0 and the two other a’ are equal to 1;- each a’ ’ is independently an integer from 0 to 2 with the proviso that not more than one a” is equal to 0, preferably each a” is equal to 1 or one a” is equal to 0 and the two other a” are equal to 1;- each b’ is independently an integer from 2 to 4, in particular 2;- each c’ is independently an integer from 0 to 10, in particular from 1 to 6;a tetravalent moiety according to any one of formulae (21) to (24):(23)wherein:- each R2o, R’20, R22 and R’22 is independently H or methyl;- each R21 and R25 is independently a linear or branched alkylene;- each R23 and R24 is independently H, alkyl or alkoxy, preferably alkyl;- each d’ is independently an integer from 0 to 2 with the proviso that not more than one d’ is equal to 0, preferably each d’ is equal to 1;- each d’ ’ is independently an integer from 0 to 2 with the proviso that not more than one d” is equal to 0, preferably each d” is equal to 1;- each e’ and g’ is independently an integer from 2 to 4, in particular 2;- each f ’ and h’ is independently an integer from 0 to 10, in particular from 1 to 6; - a tetra-, penta- or hexavalent moiety according to formula (25):wherein:- each R26 and R’26 is independently H or methyl;- each i’ is independently an integer from 2 to 4, in particular 2;- each j ’ is independently an integer from 0 to 10, in particular from 1 to 6;- k’ is an integer from 1 to 3;- a tri-, tetra-, penta- or hexavalent moiety according to formula (26):wherein- each Rg is independently selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkoxy, -C(=O)O-Alkyl and a halogen atom;- k” is an integer from 1 to 4;- a hexavalent moiety according to any one of formulae (27) to (29):() wherein- each R27, R’27, R29 and R’29 is independently H or methyl;- each R28is independently a linear or branched alkylene;- each 1’ and n’ is independently an integer from 2 to 4, in particular 2;- each m’ and o’ is independently an integer from 0 to 10, in particular from 1 to 6. Aspect 18. The curable composition of any one of aspects 1-3 and 13-17, wherein component (i) comprises or consists of at least one diol selected from:- a cyclic diol, in particular a cyclic diol selected from hydroquinone (HQE), hydroquinone bis(2-hydroxyethyl) ether (HQEE), bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbornanedimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), as well as the alkoxy lated (e.g. ethoxylated and / or propoxylated) derivatives thereof;- a diol comprising an ester bond, in particular neopentyl glycol mono(hydroxypivalate) having the following structure:and mixtures thereof.Aspect 19. The curable composition of any one of aspects 1-3 and 13-18, wherein component (i) comprises or consists of a mixture of at least one diol and at least one polyol having at least 3 OH groups, in particular 3 to 6 OH groups, more particularly 3 or 4 OH groups.Aspect 20. The curable composition of aspect 19, wherein the molar ratio of the at least one diol to the at least one polyol having at least 3 OH groups is from 1 to 50, preferably from 2 to 25, more preferably from 5 to 20.Aspect 21. The curable composition of aspect 19 or 20, wherein the at least one diol is selected from ethylene glycol, propanediols (e.g., 1,2-propanediol or 1,3 -propanediol), butanediols (e.g., 1,2-, 1,3- or 1,4-butanediol), pentanediols (e.g., 1,5 -pentanediol), hexanediols (e.g., 1,6-hexanediol), octanediols, decanediols, dodecanediols, 2 -methyl- 1,3 -propanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 2, 2-diethy 1-1, 3 -propanediol, 3 -methyl- 1,5 -pentanediol, 3,3-dimethyl-1,5 -pentanediol, 2,4-diethyl-l,5-pentanediol, 3,3-butylethyl-l,5-pentane diol, neopentyl glycol mono(hydroxypivalate), di-, tri- or tetra(ethylene glycol), di-, tri- ortetra(l,2-propylene glycol), di-, tri- or tetra( 1,3 -propylene glycol), di-, tri- or tetra(l,4-butylene glycol), a polyethylene glycol), a polypropylene glycol), a poly (trimethylene glycol), a poly (tetramethylene glycol), a polyethylene glycol-co-propylene glycol, hydroquinone (HQE), hydroquinone bis(2 -hydroxyethyl) ether (HQEE), bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbomane dimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol (i.e. isosorbide, isomannide, isoidide), as well as the alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and mixtures thereof.Aspect 22. The curable composition of any one of aspects 19-21, wherein the at least one polyol having at least three OH groups is selected from trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, dipentaerythritol), tripentaerythritol), glycerol, di-, tri- or tetraglycerol, a polyglycerol, an alditol (i.e. erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, fucitol or iditol), tris(2-hydroxyethyl)isocyanurate, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, as well as the alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and mixtures thereof.Aspect 23. The curable composition of any one of aspects 1-22, wherein component (ii) and / or (iii) respectively comprise or consist of a substituted or unsubstituted phenyl or naphthyl diacid and / or triacid, preferably both components (ii) and (iii) comprise or consist of a substituted or unsubstituted phenyl or naphthyl diacid and triacid; preferably wherein both of the diacid and triacid have at least 10, preferably at least 15, more preferably at least 21, more preferably at least 24 carbon atoms, and most preferably at least 30 carbon atoms.Aspect 24. The curable composition of any one of aspects 1-22, wherein component (ii) and / or (iii) respectively comprise or consist of a substituted or unsubstituted norbomenyl diacid and / or triacid, preferably both components (ii) and (iii) comprise or consist of a substituted or unsubstituted norbornenyl diacid and triacid, preferably wherein both of the diacid and triacid have at least 10, preferably at least 15, more preferably at least 21, more preferably at least 24 carbon atoms, and most preferably at least 30 carbon atoms.Aspect 25. The curable composition of any one of aspects 1-22, wherein component (ii) and / or (iii) respectively comprise or consist of a substituted or unsubstituted non-hydrogenated diacid and / or triacid, preferably both components (ii) and (iii) comprise or consist of a substituted or unsubstituted non-hydrogenated diacid and triacid; preferably wherein both of the diacid and triacid have at least 10, preferably at least 15, more preferably at least 21, more preferably at least 24 carbon atoms, and most preferably at least 30 carbon atoms.Aspect 26. The curable composition of any one of aspects 1-22, wherein component (ii) comprises or consists of at least one fatty acid dimer and component (iii) comprises or consists of at least one fatty acid trimer.Aspect 27. The curable composition of aspect 26, wherein the at least one fatty acid dimer is a fatty acid dimer having 32 to 40, preferably 34 to 38, more preferably 36 carbon atoms.Aspect 28. The curable composition of aspect 26 or 27, wherein the at least one fatty acid trimer is a fatty acid trimer having 48 to 60, preferably 51 to 57, more preferably 54 carbon atoms.Aspect 29. The curable composition of any one of aspects 1-28, wherein component (iv) comprises or consists of an ethylenically unsaturated monoacid selected from acrylic acid, methacrylic acid, an acryloyl halide (such as acryloyl chloride), a methacryloyl halide (such as methacryloyl chloride), acrylic anhydride, methacrylic anhydride or mixtures thereof; preferably acrylic acid, methacrylic acid, or mixtures thereof.Aspect 30. The curable composition of any one of aspects 1-29, wherein component (iv) comprises or consists of an ethylenically unsaturated monoepoxide selected from glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid glycidyl ether, methacrylic acid glycidyl ether or mixtures thereof.Aspect 31. The curable composition of any one of aspects 1-30, wherein the oligomer (A) has a number average molecular weight (Mn) of at least about 750 g / mol, preferably between about 1,000 and about 15,000 g / mol, between about 1,250 and about 10,000 g / mol, or between about 1,500 and about 7,000 g / mol.Aspect 32. The curable composition of any one of aspects 1-31, wherein the oligomer (A) has a weight average molecular weight (Mw) of at least about 1,000 g / mol, preferably between about 2,000 and about 30,000 g / mol, between about 3,000 and about 20,000 g / mol, or between about 3,500 and about 15,000 g / mol.Aspect 33. The curable composition of any one of aspects 1-32, wherein the oligomer (A) has a polydispersity index (D) of less than about 3, preferably less than about 2.5 or less than about 2.Aspect 34. The curable composition of any one of aspects 1-33, wherein the curable composition comprises from about 5 wt.% to about 99.9 wt.% of oligomer (A), for example from about 10 wt.% to about 99.5 wt.%, from about 20 wt.% to about 99 wt.%, from about 30 wt.% to about 98 wt.%, from about 50 wt.% to about 97 wt.%, or from about 60 wt.% to about 95 wt.%, of oligomer (A) based on the total weight of the curable composition.Aspect 35. The curable composition of any one of aspects 1-34, wherein the component (B) comprises an aliphatic monofunctional or difunctional (meth)acrylate.Aspect 36. The curable composition of aspect 35, wherein the aliphatic monofunctional or difunctional (meth)acrylate is monofunctional and comprises a cyclic (meth)acrylate, preferably isobornyl acrylate or isobornyl methacrylate.Aspect 37. The curable composition of aspect 35, wherein the aliphatic monofunctional or difunctional (meth)acrylate is selected from the group consisting of caprolactone (meth)acrylates 1,12-dodecanediol dimethacrylate, isobornyl acrylate, isobornyl methacrylate, 3,3,5-trimethyl cyclohexyl acrylate, and tricyclodecane dimethanol diacrylate and mixtures thereof.Aspect 38. The curable composition of any one of aspects 1-34, wherein component (B) comprises or consists of at least one (meth)acrylate monomer selected from isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, isosorbide di(meth)acrylate, bisphenol A di(meth)acrylate,hydrogenated bisphenol A di(meth)acrylate, a (poly)caprolactone (meth)acrylate and mixtures thereof.Aspect 39. The curable composition of any one of aspects 1-38, wherein the curable composition comprises from about 5 wt.% to about 90 wt.% of component (B), for example from about 10 wt.% to about 80 wt.%, from about 15 wt.% to about 70 wt.%, from about 20 wt.% to about 60 wt.%, from about 25 wt.% to about 55 wt.%, or from about 26 wt.% to about 54 wt.%, of component (B) based on the total weight of the curable composition.Aspect 40. The curable composition of any of aspects 1-39, wherein component (C) comprises a (meth)acrylated phosphate diester and, optionally, a (meth)acrylated phosphate monoester.Aspect 41. The curable composition of any one of aspects 1 to 40, wherein component (C) comprises a (meth)acrylated phosphate diester of structure I:each Ra, Rband Rcis independently H or a C1-C6 alkyl, preferably H or methyl;Rdis H or a cation;each n is independently from 4 to 7, preferably from 5 to 6;each m is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.Aspect 42. The curable composition of any one of aspect 1 to 41, wherein component (C) comprises a (meth)acrylated phosphate monoester of structure II:wherein:Ra, Rband Rcare independently H or a C1-C6 alkyl, preferably H or methyl;Rdand Reare independently H or a cation;n is from 4 to 7, preferably from 5 to 6;m is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.Aspect 43. The curable composition of any one of aspects 1 to 42, wherein component (C) comprises a (meth)acrylated phosphate diester of structure III:wherein:each R1is independently H or methyl; andeach p is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.Aspect 44. The curable composition of any one of aspects 1 to 43, wherein component (C) comprises a (meth)acrylated phosphate monoester of structure IV:wherein:R1is H or methyl;p is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12. Aspect 45. The curable composition of any one of aspects 1 to 44, wherein component (C) comprises a (meth)acrylated phosphate diester of structure V:wherein:each R3, R4and R5is independently H or a C1-C6 alkyl, preferably H or methyl;R6is H or a cation;each t is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.Aspect 46. The curable composition of any one of aspects 1 to 45, wherein component (C) comprises a (meth)acrylated phosphate monoester of structure VI:wherein:R3, R4and R5are each independently H or methyl;R6and R7are each independently H or a cation;t is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.Aspect 47. The curable composition of any one of aspects 40 to 46, wherein the molar ratio of the monoester to diester is at least about 1.5:1, at least about 1.6:1, at least about 1.7:1, at least about 1.8:1, at least about 1.9: 1, or at least about 2.0:1.Aspect 48. The curable composition of any one of aspects 40 to 46, wherein the molar ratio of the monoester to diester is at least about 2.2:1, at least about 2.5:1, at least about 3.0:1, or at least about 3.2:1.Aspect 49. The curable composition of any one of aspects 40 to 46, wherein the molar ratio of the monoester to diester is comprised between about 1.5:1 and about 4.0:1, between about 1.6:1 to about 3.8:1 or between about 1.8:1 to about 3.5:1.Aspect 50. The curable composition of any one of aspects 1-49, wherein the curable composition comprises from about 1 wt.% to about 30 wt.% of component (C), for example from about 1.5 wt.% to about 25 wt.%, from about 2 wt.% to about 20 wt.%, from about 3 wt.% to about 15 wt.%, from about 4 wt.% to about 10 wt.%, or from about 5 wt.% to about 8 wt.%, of component (C) based on the total weight of the curable composition.Aspect 51. The curable composition of any one of aspects 1-50, wherein the composition comprises component (D) and component (D) comprises at least one of a photoinitiator and a thermal initiator.Aspect 52. The curable composition of aspect 51, wherein component (D) comprises a photoinitiator and the photoinitiator is selected from the group consisting of a Norrish Type I phosphine oxide, a Norrish Type I hydroxyacetophenone and mixtures thereof.Aspect 53. The curable composition of aspects 51 or 52, wherein component (D) comprises a thermal initiator and the thermal initiator is selected from the group consisting of benzoyl peroxide (Luperox), azo-bis isobuteronotirile (AIBN), organic peroxides, the azides class of thermal initiators and mixtures thereof.Aspect 54. Use of the curable composition of any one of aspects 1-53 as a dielectric coating composition for batteries, preferably as a coating for at least one surface of a battery substrate, such as an exterior surface of a battery.Aspect 55. Method of making a cured composition, comprising curing the curable composition of any one of aspects 1-53.Aspect 56. The method of aspect 55, comprising exposing the curable composition to radiation such UV, near-UV, visible, infrared, near-infrared and / or electron beam radiation or heat.Aspect 57. A cured composition obtained by curing the curable composition of any one of aspects 1-53.Aspect 58. A battery comprising the cured composition of aspect 57, preferably wherein the cured composition is a coating for at least one surface of a battery substrate, such as an exterior surface of a battery.Aspect 59. A method of increasing flexibility and / or impact resistance and / or hardness and / or corrosion resistance and / or scrub resistance and / or water resistance and / or adhesion and / or electric insulation and / or matting and / or flame retardancy and / or weathering resistance of at least one surface of a battery substrate, the method comprising a) applying to the least one surface of the substrate the curable composition of any one of aspects 1-53, and b) curing the composition.

[0159] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, one of skill in the art will appreciate that certain changes and modifications may be practiced within the scope of the appended claims. In addition, each reference provided herein is incorporated by reference in its entirety to the same extent as if each reference was individually incorporated by reference. Where a conflict exists between the instant application and a reference provided herein, the instant application shall dominate.EXAMPLES

[0160] The following examples illustrate the invention without limiting it.

[0161] Raw materialsTable 1

[0162] Synthesis of the oligomers of the invention

[0163] Oligomer A

[0164] 90 g toluene, 33.22 g AA, 4.41 gMA, 296.24 g UNIDYME™ 18, 0.6 gBHT, 0.6 gMeHQ, 12.5 g 70% aqueous MsOH, 0.6 g 50% aqueous HP A, and 150.84 g TCD-DM were combined in a 500 mL round bottom flask equipped with a mechanical stirrer, gas sparge line, thermocouple, and reflux condenser. The reaction mixture was sparged with dry air while heating to reflux (beginning after ~25 minutes at 104°C and reaching a maximum temperature of 123°C reached after ~2 hours). The reaction was held at reflux until the inflection point in a potentiometric acid titration associated with carboxylic acids fell to < ~2.0 mg KOH / g (approximately 3 hr.). The reaction mixture was thencooled to ambient temperature and 34.4 g MAGNESOL®, 51.2 g toluene, and 1.5 g water were added and held at 100°C until no inflection point associated with MsOH was observed in potentiometric acid titration. After the equivalence point associated with MsOH was no longer present in the acid titration, the solution was filtered through a plug of diatomaceous earth with mass equal to 2 wt.% of the reaction mixture followed by 2.5, 8, and 25 pm filter papers under 118.6 kPa to 135.4 kPa (2.5-5 psig) external pressure. After filtration, solvent was removed under reduced pressure with air sparge (50 mmHg, 45-90°C) to give the final product as a viscous yellow oil.

[0165] Oligomer B:

[0166] The procedure used in the synthesis of Oligomer A was repeated, replacing UNIDYME™ 18 with an equimolar amount of Pripol™ 1009, based on titrated acid values.

[0167] Oligomer C:

[0168] The procedure used in the synthesis of Oligomer A was repeated, replacing UNIDYME™ 18 with an equimolar amount of Pripol™ 1006, based on titrated acid values.

[0169] Oligomer D:

[0170] The procedure for oligomer B was repeated replacing TCD-DM with an equimolar amount ofHQEE.

[0171] Oligomer E:

[0172] The procedure for oligomer B was repeated replacing TCD-DM with an equimolar amount of Dianol® 320 HP.

[0173] Oligomer F:

[0174] The procedure for oligomer B was repeated replacing TCD-DM with an equimolar amount ofHPN.

[0175] Preparation of the formulation

[0176] Fillers / additives including TiO2, AEROSIL® R805, talc and an oligomer were introduced into a Flacktek® polypropylene high-speed mixer cup, and the mixture was blended for 2 minutes at 2,000 rpm. Subsequently, the blended mixture was milled using 3-roll mills until a uniform dispersion of all additives in the oligomer was achieved. Following the milling process, the mixture underwent quality assessment for dispersion using a Hegman grind gauge (0-25 pm). No discernible particles were observed on the gauge, indicating superior dispersion quality. Finally, monomers and photoinitiators were incorporated into the milled mixture, and the mixture was further blending for 2 minutes at 2,000 rpm using a high-speed mixer.

[0177] Two curable compositions a) and b) are exemplified herein, both consisting of 80 wt.% resin and 20 wt.% of fillers / additives.

[0178] Example 1 - Composition a)

[0179] Composition 1,1 (invention): the resin component consisted of 44 wt.% of SR833S, 27.33 wt.% of oligomer A, 6.67 wt.% of SR9051, 1 wt.% of SpeedCure BPO and 1 wt.% of SpeedCure73; the fdler / additive component consisted of 17 wt.% of talc, 2 wt.% of TiCL and 1 wt.% of AEROSIL® R805.

[0180] Composition 1,2 (comparative): the resin component consisted of 44 wt.% of SR833S, 27.33 wt.% of oligomer CN294, 6.67 wt.% of SR9051, 1 wt.% of SpeedCure BPO and 1 wt.% of SpeedCure73; the fdler / additive component consisted of 17 wt.% of talc, 2 wt.% of TiO2 and 1 wt.% of AEROSIL® R805.

[0181] Composition 1,3 (comparative): the resin component consisted of 44 wt.% of SR833S, 27.33 wt.% of oligomer CN991, 6.67 wt.% of SR9051, 1 wt.% of SpeedCure BPO and 1 wt.% of SpeedCure73; the fdler / additive component consisted of 17 wt.% of talc, 2 wt.% of TiO2 and 1 wt.% of AEROSIL® R805.

[0182] Example 2 - Composition b)

[0183] In the compositions exemplified in this example, 2,1 to 2,6 (inventive) and 2,7 to 2,8 (comparative), the resin component consisted of 48 wt.% of an oligomer as detailed in Tables 5-7 below, 12 wt.% of SR306F, 10 wt.% of SR833S, 5 wt.% of SR506, 3 wt.% of SR9054, 1 wt.% of SpeedCure BPO and 1 wt.% of Speedcure73, and the fdler / additive component consisted of 17 wt.% of talc, 2 wt.% of TiO2 and 1 wt.% of Aerosil R805.

[0184] Curing method

[0185] Aluminum substrates were first wiped with toluene, followed by an acetone wipe. Coatings were then applied with a thickness of 60 pm on the aluminum substrate using a drawdown bar.

[0186] For formulations a), the coatings were cured using a LED light (395 nm) and fusion lamp (H bulb). For formulations b, the coatings were cured using Fusion (H bulb) 500 mJ / cm2- 17 fpm.

[0187] Environmental and Chemical Resistance Testing

[0188] Coated specimens underwent aging in both an environmental chamber at 85°C / 85%RH and through electrolyte soaking at 25°C for a duration of up to 4 weeks. The coated specimens that had been immersed in electrolyte solvents were dried with cleanroom wipes and alcohol before testing.

[0189] The electrolyte consisted of DEC, DMC, and EC in a 1: 1: 1 ratio.

[0190] For the electrolyte and salt screening test (E+S), LiClO₄ salt was added to the above electrolyte in the following proportion: 13 wt.% LiClO4+ 29 wt.% EC + 29 wt.% DEC + 29 wt.% DMC.

[0191] The surfaces of the coated films were covered with an electrolyte-salt mixture and then subjected to an 85°C oven for 2 hours. Subsequently, they were rinsed with DI water and left at 60°C for 24 hours before measuring their properties.

[0192] Viscosity

[0193] Viscosity was measured in millipascal-seconds (mPa.s) at room temperature using a Brookfield RST CPS rheometer, with a torque setting of 50 M[%] and 60 (seconds) measurement points,

[0194] Volume resistivity (VR)

[0195] Volume resistivity was measured to determine the electrical insulating properties of the coating, more precisely how the coating material resists the flow of electrical current through its entire volume. The thickness of the cured samples was first measured using a Heidenhain Metro length gauge unit with an accuracy of ±0.2 μm and a measuring range of 0 to 12 mm. Film thickness measurements were taken at five different points within a 1.0 cm2area of the coated samples on the aluminum substrate, and their average was used to calculate volume resistivity. Volume resistivity was then measured in ohm-meters (Ω·m) using a Keithley 6517B electrometer with an 8009 resistivity test fixture at room temperature, following the ASTM D-257 standard. An alternating polarity of 500 V was applied to the cured film for 60 seconds before measurement.

[0196] Breakdown strength (BDS)

[0197] The breakdown strength of cured films was measured to assess their ability to withstand electrical stress and evaluate the coating's effectiveness as an electrical insulator in high-voltage applications. Breakdown strength of cured films was measured in volts per micrometers (V / μm) using the ASTM D-149 standard, ramping at 500 V / s. A 6.35 mm stainless steel ball on a brass substrate in 25°C silicone oil was utilized to minimize the electric field non-uniformity and the chances of a film defect being present at the test location. The cured film thickness was measured and recorded in each breakdown location prior to breakdown. Twenty measurements were taken for each film and the dataset was fitted using a 2-parameter Weibull distribution with a 95% confidence interval.

[0198] Adhesion (Adh.)

[0199] The adhesion of the coated resins to the aluminum plate was evaluated according to ASTM Standard D3359 using crosshatch test. In this test, a blade was used to cut small squares to the surface of the coatings, cutting passes make six cuts in the coating, second passes at 90° makes a square lattice pattern. A transparent tape was applied over the patterned surface and was pulled off quickly to release the amount of coating lifted off by the test tape. The crosshatch was rated on a 0 to 5 scale (with 5 being the highest adhesion strength) provided in the ASTM standard.

[0200] Pencil hardness (PH)

[0201] Graphite pencils with varied hardness were moved across a coating surface to test the hardness of the coating via ASTM D3363-05. The softest pencil creating a scratch on the surface of the coating determined its hardness in relation to graphite pencils.

[0202] H stands for “hard”, such as H, 2H, 3H. 4H and 5H (the higher the number, the harder the pencil). HB is medium hardness, balanced. F stands for “fine”, with medium hardness.

[0203] Flexibility (Flex.)

[0204] Flexibility of the coatings was assessed using a conical mandrel test instrument in accordance with ASTM D522. The bend tester consisted of a bending lever with a roller that pivots on a steel conical mandrel, allowing bends at 90° and 180° with diameters ranging from 4 mm to 34 mm. The lever was used to bend the coated substrate over the conical cone, and each sample was then inspected for cracks or crazing. A smaller diameter number indicates better flexibility; for example, a 4 mm diameter reflects superior flexibility compared to a 34 mm diameter, as it demonstrates the coating can withstand tighter bending without cracking.

[0205] Impact Resistance

[0206] Impact resistance was assessed using a TQC SP1880 Impact Tester according to ASTM D2794. Aluminum panels, with the coating side down, were positioned under the beveled die. A one- kilogram weight was dropped from a predetermined height (10 to 50 cm with a 10 cm interval) onto the beveled die, and the coatings were then inspected for visible crazing and cracking. A successful test exhibited no significant visible defects after impact.

[0207] Results

[0208] Table 2 below presents the results obtained with inventive composition 1.1. Table 3 and 4 below presents the results obtained with comparative compositions 1.2 and 1.3.Table 2Table 3Table 4

[0209] Comparative compositions 1.2 and 1.3 failed to meet the flexibility criteria and exhibited 5 issues with adhesion (Adh.) and hardness (PH) after undergoing electrolyte testing.

[0210] In contrast, the inventive composition 1.1 demonstrated strong adhesion, hardness, and flexibility.

[0211] Tables 4-6 below present the results obtained with compositions 2.1-2.8.Table 5Table 6Table 7

[0212] All inventive compositions 2.1 to 2.6 showed better performance compared to comparative composition 2.7.

[0213] With cracking occurring at larger bend diameters, all the compositions of the present invention 2.1 to 2.6 generally show better flexibility compared to the comparative compositions 2.7 and 2.8. In particular, the results in Tables 5 and 6 indicate that the compositions of the present invention 2.1 to 2.6 can endure a wider range of bending diameters, both at 90° and 180°, before and after the electrolyte and salt (E+S) screening test, compared to the comparative compositions 2.7 and 2.8 which exhibited cracking within a narrower range. The inventive compositions demonstrate enhanced flexibility in comparison to the comparative composition.

[0214] The results in Table 7 also indicate better impact resistance for the compositions of the present invention 2.1 to 2.6, with cracking occurring at a higher drop height compared to the comparative compositions 2.7 and 2.8, which exhibited cracking at 10 cm.

[0215] The detailed results indicate that compositions 2.5 and 2.6 are the most flexible and durable, consistently showing no cracking from 4 to 34 mm in both 90° and 180° mandrel bend tests (Tables 5 and 6), as well as in the impact resistance test (Table 7).

[0216] This superior performance suggests that the compositions 2.5 and 2.6 provide a higher degree of elasticity and resilience, making them particularly well suited for battery coating application where flexibility is critical.

Claims

CLAIMS1. A curable composition comprising(A) an oligomer which is the reaction product of:(i) at least one substituted or unsubstituted aliphatic, aryl, aralkyl, alkaryl, heteroaralkyl, alkheteroaryl, or heteroaryl diol, polyol, diepoxide or polyepoxide;(ii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl diacid;(iii) at least one substituted or unsubstituted aliphatic, aryl, or heteroaryl triacid; and (iv) at least one ethylenically unsaturated monoacid and / or at least one ethylenically unsaturated monoepoxide;(B) at least one (meth)acrylate monomer;(C) at least one (meth)acrylate phosphate ester; and(D) optionally, at least one free radical initiator.

2. The curable composition of claim 1, wherein the weight ratio of component (ii) to component (iii) in oligomer (A) is less than 30:1, preferably between 30:1 and 4.1:1, more preferably between 25:1 and 4.2:1, most preferably between 20:1 and 4.3:1.

3. The curable composition of claims 1 or 2, wherein the reaction mixture used to obtain oligomer (A) comprises less than 3% preferably less than 2.5 wt.%, more preferably less than 2 wt.%, most preferably less than 1.8%, less than 1.5%, less than 1.2%, less than 1 wt.%, less than 0.9% or even less than 0.5 wt.%, of monoacid other than (meth)acrylic acid based on the total weight of the reactive species.

4. The curable composition of any one of claims 1-3, wherein component (i) comprises or consists of at least one diol selected from:- a cyclic diol, in particular a cyclic diol selected from hydroquinone, hydroquinone bis(2-hydroxyethyl) ether, bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol, as well as the alkoxy lated derivatives thereof;- a diol comprising an ester bond, in particular neopentyl glycol mono(hydroxypivalate) having the following structure:and mixtures thereof.

5. The curable composition of any one of claims 1-3, wherein component (i) comprises or consists of a mixture of at least one diol and at least one polyol having at least 3 OH groups, in particular 3 to 6 OH groups, more particularly 3 or 4 OH groups.

6. The curable composition of claim 5, wherein the molar ratio of the at least one diol to the at least one polyol having at least 3 OH groups is from 1 to 50, preferably from 2 to 25, more preferably from 5 to 20.

7. The curable composition of claim 5 or 6, wherein the at least one diol is selected from ethylene glycol, propanediols, pentanediols, hexanediols, octanediols, decanediols, dodecanediols, 2-methyl-l,3-propanediol, 2-methyl-2,4-pentanediol, neopentyl glycol, 2, 2-diethy 1-1, 3 -propanediol, 3-methyl-l,5-pentanediol, 3,3-dimethyl-l,5-pentanediol, 2,4-diethyl-l,5-pentanediol, 3,3-butylethyl-l,5-pentane diol, neopentyl glycol mono(hydroxypivalate), di-, tri- or tetra(ethylene glycol), di-, tri- or tetra(l,2-propylene glycol), di-, tri- or tetra(l,3-propylene glycol), di-, tri- or tetra(l,4-butylene glycol), a polyethylene glycol), a polypropylene glycol), a poly (trimethylene glycol), a poly(tetramethylene glycol), a polyethylene glycol-co-propylene glycol, hydroquinone, hydroquinone bis(2 -hydroxyethyl) ether, bisphenol-A, B, F or S, bis-ethylene glycol terephthalate, pyrocatechol, resorcinol, cardol, cyclohexanediol, cyclohexane dimethanol, norbornene dimethanol, norbornane dimethanol, tricyclodecanediol, tricyclodecanedimethanol, dicyclopentadiene diol, hydrogenated bisphenol-A, B, F or S, a dianhydrohexitol, as well as the alkoxylated, derivatives thereof and mixtures thereof.

8. The curable composition of any one of claims 5-7, wherein the at least one polyol having at least three OH groups is selected from trimethylolmethane, trimethylolethane, trimethylolpropane, di(trimethylolpropane), triethylolpropane, pentaerythritol, di(pentaerythritol), tri(pentaerythritol), glycerol, di-, tri- or tetraglycerol, a polyglycerol, an alditol, tris(2-hydroxyethyl)isocyanurate, phloroglucinol, pyrogallol, tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, as well as the alkoxylated derivatives thereof and mixtures thereof.

9. The curable composition of any one of claims 1-8, wherein component (ii) comprises or consists of at least one fatty acid dimer and component (iii) comprises or consists of at least one fatty acid trimer.

10. The curable composition of any one of claims 1-9, wherein component (iv) comprises or consists of an ethylenically unsaturated monoacid selected from acrylic acid, methacrylic acid, an acryloyl halide, a methacryloyl halide, acrylic anhydride, methacrylic anhydride r mixtures thereof; preferably acrylic acid, methacrylic acid, or mixtures thereof.

11. The curable composition of any one of claims 1-10, wherein component (B) comprises an aliphatic monofunctional or difunctional (meth)acrylate.

12. The curable composition of any one of claims 1-11, wherein component (B) comprises or consists of at least one (meth)acrylate monomer selected from isobornyl (meth)acrylate, 3,3,5- trimethylcyclohexyl (meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, isosorbide di(meth)acrylate, bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, a (poly)caprolactone (meth)acrylate and mixtures thereof.

13. The curable composition of any one of claims 1-12, wherein component (C) comprises a (meth)acrylated phosphate diester and, optionally, a (meth)acrylated phosphate monoester.

14. The curable composition of any one of claims 1-13, wherein component (C) comprises a (meth)acrylated phosphate diester of structure I:wherein:each Ra, Rband Rcis independently H or a C1-C6 alkyl, preferably H or methyl;Rdis H or a cation;each n is independently from 4 to 7, preferably from 5 to 6;each m is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

15. The curable composition of any one of claims 1-14, wherein component (C) comprises a (meth)acrylated phosphate monoester of structure II:wherein:Ra, Rband Rcare independently H or a C1-C6 alkyl, preferably H or methyl;Rdand Reare independently H or a cation;n is from 4 to 7, preferably from 5 to 6;m is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

16. The curable composition of any one of claims 1-15, wherein component (C) comprises a (meth)acrylated phosphate diester of structure III:wherein:each R1is independently H or methyl; andeach p is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

17. The curable composition of any one of claims 1-16, wherein component (C) comprises a (meth)acrylated phosphate monoester of structure IV:wherein:R1is H or methyl;p is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

18. The curable composition of any one of claims 1-17, wherein component (C) comprises a (meth)acrylated phosphate diester of structure V:wherein:each R3, R4and R5is independently H or a C1-C6 alkyl, preferably H or methyl;R6is H or a cation;each t is independently from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

19. The curable composition of any one of claims 1-18, wherein component (C) comprises a (meth)acrylated phosphate monoester of structure VI:wherein:R3, R4and R5are each independently H or methyl;R6and R7are each independently H or a cation;t is from 1 to 25, preferably from 2 to 18, and more preferably from 3 to 12.

20. The curable composition of any one of claims 13-19, wherein:- the molar ratio of the monoester to diester is at least about 1.5:1, at least about 1.6:1, at least about 1.7:1, at least about 1.8:1, at least about 1.9:1, or at least about 2.0:1;- the molar ratio of the monoester to diester is at least about 2.2:1, at least about 2.5:1, at least about 3.0:1, or at least about 3.2:1; or- the molar ratio of the monoester to diester is comprised between about 1.5:1 and about 4.0:1, between about 1.6:1 to about 3.8:1 or between about 1.8 to about 3.5:1.

21. Use of the curable composition of any one of claims 1-20 as a dielectric coating composition for batteries, preferably as a coating for at least one surface of a battery substrate, such as an exterior surface of a battery.

22. A cured composition obtained by curing the curable composition of any one of claims 1-20.

23. A battery comprising the cured composition of claim 22, preferably wherein the cured composition is a coating for at least one surface of a battery substrate, such as an exterior surface of a battery.

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