Acidic oligomers used in deinking process

Abstract

Curable compositions which include: an optionally (meth)acrylate-functionalized acidic acrylic oligomer formed by reacting acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the copolymer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator are useful for forming primers, inks, and coatings on substrates that can undergo a triggered removal process using a water-based remover.

Description

[0001] ACIDIC OLIGOMERS USED IN DEINKING PROCESS

[0002] Field of the Invention

[0003] The present invention relates to curable compositions based on optionally (meth)acrylate- functionalized acidic acrylic oligomers, methods of using the compositions based on the optionally (meth)acrylate-functionalized acidic acrylic oligomers, and compositions and articles containing the compositions based on the optionally (meth)acrylate- functionalized acidic acrylic oligomers in cured form, especially for use in inks and coatings, to allow for easy removal of the cured inks and coatings once subjected to recycling, soaking, or delaminating conditions.

[0004] Background of the Invention

[0005] In view of the impacts of climate change and the increasing rate of consumption of our planet’s natural resources, there has been a growing desire in the chemical industry to ensure sustainable consumption and production patterns. In the market segment of curable inks and coatings, this desire manifests itself in developing technologies that would permit easy and substantially complete delamination of the inks and coatings from their substrates. Such technologies would allow for separate recycling or reuse of the substrates. Efforts have been made to permit such separation and recycling, including by Siegwerk, which has recently introduced sacrificial deinking primers for labels and sleeves.

[0006] Much literature on the removal of a paint coating or a pressure sensitive adhesive / laminating adhesive label discloses the use of either a low vapor pressure or caustictype solvent, both of which are non-biodegradable, harmful to the environment, and potentially harmful to the person using the solvent. See, e.g., US2010008952A, W02010115564A1.

[0007] There remains a need for inks and coatings with excellent properties, but that exhibit a faster and more efficient removal process using a water-based remover that gives off little to no VOCs. Summary of the Invention

[0008] In view of the prior art, it would be desirable to develop a system that permits easy and substantially complete delamination of a curable coating or ink from a substrate, without the need for a sacrificial primer layer. Furthermore, it would be advantageous to build a trigger in to the backbone of a UV curable coating (including a sacrificial primer layer or coating) or ink that can undergo removal in the presence of a non-hazardous, low VOC aqueous-based remover, but not in the presence of water alone. In many applications, it would be undesirable for a coating or ink to delaminate from its substrate in the presence of water alone. Consequently, it would be desirable to provide a coating or ink that can be removed on demand via an aqueous-based remover that can interact with the trigger in the backbone of the cured coating and prompt the coating’s removal from the substrate.

[0009] The invention relates to the use of acidic acrylic oligomers optionally functionalized with (meth)acrylates to prepare cured films that, upon exposure to basic warm water, swell and delaminate the cured film from the substrate. Primers, inks, and coatings formulated with acidic acrylic oligomers allow for easily removal of the printed cured films once placed in a recycling process to obtain a clean plastic substrate such as PET.

[0010] The presence of the optionally (meth)acrylate-functionalized acidic acrylic oligomers of the invention in coatings (including primer coatings) and inks render such coatings and inks susceptible to removal from substrates to which they are attached when subjected to recycling or soaking conditions described herein. UV curable coating and ink formulations that incorporate an optionally (meth)acrylate-functionalized acidic acrylic oligomer contain a functional group that can undergo additional crosslinking with the matrix and an acid group that helps trigger the removal process when used with a corresponding water-based remover.

[0011] An aspect of the invention is a method for recycling a substrate coated with a cured primer, coating, or ink composition, wherein the cured composition is obtained by curing a curable primer, ink, or coating composition comprising: an optionally (meth)acrylate- functionalized acidic acrylic oligomer formed by reacting acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the oligomer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator, the method comprising the steps of: contacting the substrate coated with the cured primer, coating, or ink composition with a recycling solution having a pH sufficient to delaminate the cured primer, coating, or ink composition from the substrate; and retrieving from the recycling solution the substrate substantially free from the cured primer, coating, or ink composition.

[0012] Another aspect of the invention is a curable primer, ink, or coating composition comprising: a (meth)acrylate-functionalized acidic acrylic oligomer formed by reacting acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated comonomer, the oligomer comprising at least one pendant and / or terminal acid group and at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

[0013] Another aspect of the invention is a cured composition obtained by curing the curable primer, ink, or coating composition according to the invention.

[0014] Another aspect of the invention is a substrate coated with a cured composition obtained by curing the curable primer, ink, or coating composition according to the invention.

[0015] Another aspect of the invention is a method for making an article comprising: applying the curable primer, ink, or coating composition of the invention to a substrate; and curing the composition; wherein the substrate comprises paper, fabric, metal, glass, plastic (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, and composites thereof.

[0016] Another aspect of the invention is an optionally (meth)acrylate-functionalized acidic acrylic oligomer formed by reacting acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the oligomer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof, wherein the oligomer has an acid content of at least 5x1 O'4mol acid / g oligomer, such as at least 5.25 xlO'4, such as at least 5.5xl0'4, preferably between 6 xlO'4and 9.5xl0'4, more preferably between 6.5xl0'4and 9.25xl0'4, more preferably between 7xl0'4and 9xl0'4and most preferably between 7.5x1 O'4and 8.5x1 O'4mol acid / g oligomer.

[0017] Brief Description of the Drawings

[0018] The following figures represent exemplary embodiments of the invention and are not intended to otherwise limit the description of the invention as described herein.

[0019] Figure 1 shows a printed PET substrate coated with an ink according to the invention before and after exposure to deinking solution; and

[0020] Figure 2. shows an example of methacrylate-functionalized acidic acrylic oligomer in a clear coat composition on PET substrates before and after exposure to a standard deinking composition showing the delamination of the cured film.

[0021] Figure 3 shows an IR absorbance spectrum of an acrylate-functionalized acrylic copolymer of the invention.

[0022] Figure 4 shows an IR absorbance spectrum of an acrylate-functionalized acrylic copolymer of the invention. Detailed Description of the Invention

[0023] Definitions

[0024] As used herein “acid content” is calculated as the total acid content of a compound (in moles) before any neutralization of the acid groups has taken place (i.e., assuming 100% of the acid groups are in their free acid (non-salt) form) per gram of the compound. When determining the acid content of a optionally (meth)acrylate-functionalized acidic acrylic oligomer that has at least some of its acid groups neutralized, it is presumed for purposes of this calculation that 100% of the acid groups exist in their free acid, regardless of whether the base(s) is / are provided: (1) during the preparation of the oligomer, (2) after the oligomer has been prepared but before formulation with other constituents, (3) after the oligomer has been formulated with other constituents one of which includes a base, and / or (4) in a recycling or soaking solution after the oligomer has been prepared, formulated, and cured. So, an optionally (meth)acrylate-functionalized acidic acrylic oligomer of the invention having a certain acid content encompasses such an oligomer that has none of the acid groups neutralized or at least some, including a majority and up to 100%, of its acid groups neutralized.

[0025] As used herein, “acid group” refers to any functionality present in the curable optionally (meth)acrylate-functionalized acidic acrylic oligomers of the invention that contains an acidic hydrogen atom and primarily refers to carboxylic acid groups, but also includes functional groups such as sulfonic acids, phosphoric acids, phosphonic acids and phosphinic acids as well as (cyclic) anhydrides.

[0026] As used herein, “aliphatic compound” or “aliphatic group” or “aliphatic linker” refers to a compound, group, or linker that is non-aromatic and acyclic, linear or branched, saturated or unsaturated, which may comprise one or more ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds and mixtures thereof, and which may be substituted by one or more groups independently selected from, for example, alkyl, hydroxyl, halogen (F, Cl, Br, I), isocyanate, carbonyl, amine, carboxylic acid, -C(=O)-OR’ and -C(=O)-O-C(=O)-R’, with each R’ being independently a Ci-Ce alkyl.

[0027] As used herein, “cycloaliphatic compound” or “cycloaliphatic group” or “cycloaliphatic linker” refers to a compound, group or linker that is non-aromatic and cyclic, which may comprise one or more aliphatic bonds, and which may be substituted by one or more aliphatic groups.

[0028] As used herein, “C1-C5 group or compound” refers to a group or a compound having from 1 to 5 carbon atoms.

[0029] As used herein, “photosensitive composition” refers to a composition that reacts upon exposure to light, in particular UV, near-UV, visible, infrared or near-infrared light.

[0030] As used herein, “substantially the same wavelength” refers to a wavelength that is the same as another wavelength or is higher or lower than the other wavelength by no more than 10 nm, or 8 nm or 5 nm or 4 nm or 3 nm or 2 nm or 1 nm.

[0031] As used herein, “photoinitiator” refers to a compound that, upon irradiation with light (i.e. UV, near-UV, visible, infrared or near-infrared light) forms an initiating species (i.e. radicals and / or ions) that initiate the polymerization of a polymerizable monomer. A photoinitiator may be chemically changed after the polymerization as it has reacted with other chemical species.

[0032] As used herein, the term “light” refers to electromagnetic radiation in any appropriate region of the electromagnetic spectrum and is not limited to visible light. Accordingly, the term “light” encompasses UV, near-UV, visible, infrared or near-infrared electromagnetic radiation. As used herein, the term “irradiation” refers to light directed toward a surface, composition, molecule, etc., so that it contacts the surface, composition, molecule, etc.

[0033] As used herein, a “recycling solution” or a “soaking solution” refers to a solution that when contacted with a cured composition (such a film, coating, ink or primer, ink, or coating) containing an optionally (meth)acrylate-functionalized acidic acrylic oligomer of the invention results in the release or delamination of the cured composition from a substrate to which the composition is attached. While the release or delamination of the optionally (meth)acrylate- functionalized acidic acrylic oligomer-containing composition from the substrate to which it is attached is typically complete and total, a partial release or partial delamination of the composition may also represent an acceptable or satisfactory outcome, depending on the particular technical area involved. In the case where delamination is only partial, manual means may be employed for removal of the portion of the coating / composition that remains attached to the substrate surface. The term “polymer” as used herein is meant to include organic molecules with a number average molecular weight higher than 1,000 Da, or higher than 1,500 Da, or higher than 2,000 Da, or higher than 2,500 Da, or higher than or 5,000 Da, or higher than 50,000 Da as measured by gel permeation chromatography using tetrahydrofuran as solvent and polystyrene of known molecular weight as calibration standards.

[0034] The term “(meth)acrylate” is understood to encompass either or both acrylate moieties and methacrylate functional groups.

[0035] Curable

[0036] The present invention employs a curable composition that comprises, consists essentially of, or consists of: an optionally (meth)acrylate-functionalized acidic acrylic oligomer formed by reacting acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the copolymer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

[0037] The optionally (meth)acrylate-functionalized acidic acrylic oligomer may be introduced in a composition, such as a primer, ink, or coating composition. Accordingly, the present invention also relates to a composition (in particular a primer, ink, or coating composition) comprising the optionally (meth)acrylate-functionalized acidic acrylic oligomer as defined above. As used herein, the term “curable composition” refers to the curable primer, ink, or coating composition used in the method of the present invention.

[0038] The composition may be a film or coating composition comprising optionally (meth)acrylate- functionalized acidic acrylic oligomer of the invention and a photoinitiator. Such compositions may particularly be used for forming a film on or coating at least part of the surface of a substrate, including as a primer coating formed on a substrate over which additional coating layers may be formed. The composition may be an ink composition comprising the optionally (meth)acrylate- functionalized acidic acrylic oligomer of the invention and optionally a photoinitiator. Such compositions may particularly be used to print an image or a text on at least part of a surface of a substrate.

[0039] Such compositions may be clear (such as a primer) or pigmented and are formulated to be usable as one-part systems, that is, formulations capable of being applied to a substrate surface and then cured by exposure to actinic radiation (e.g., UV or visible light). One or more additional components may additionally be present, in particular pigments and / or colorants and possibly (meth)acrylic polymers as described in more detail henceforth. The curable composition may be a liquid having a relatively high viscosity at room temperature that permits the curable composition to be applied to the surface of a substrate and then readily shaped to a desired configuration on the substrate surface, followed by exposure to ultraviolet (UV) light or other actinic radiation to photopolymerize the shaped curable composition to form a hard, durable, impact-resistant substrate coating. The curable composition alternatively may be a liquid having a relatively low viscosity at room temperature that permits the curable composition to be readily applied as a thin layer to the surface of a substrate (i.e., a substrate plate), followed by exposure to ultraviolet (UV) light or other actinic radiation to photopolymerize the thin layer of curable composition.

[0040] The amount of optionally (meth)acrylate-functionalized acidic acrylic oligomer included in the curable composition may be varied as may be desired depending upon the type of optionally (meth)acrylate-functionalized acidic acrylic oligomer used, the attributes targeted in the cured substrate coating, and the types of polymerizing organic substances used, among possibly other factors.

[0041] According to various aspects of the invention, the curable composition may comprise at least 1%, at least 5%, or at least 10% by weight of the optionally (meth)acry late- functionalized acidic acrylic oligomer, based on the total weight of the curable composition. In other aspects, the curable composition may comprise not more than 50%, not more than 45%, or not more than 40% by weight of the optionally (meth)acrylate- functionalized acidic acrylic oligomer, based on the total weight of the curable composition. The curable composition thus, for example, may be comprised of from 1 to 50%, 5 to 45%, or 10 to 40% by weight of the at least one optionally (meth)acrylate- functionalized acidic acrylic oligomer based on the total weight of the curable composition.

[0042] The composition of the invention may comprise 5 to 95%, in particular 10 to 95%, more particularly 15 to 90%, even more particularly 20 to 85%, more particularly still 25 to 80% by weight of the optionally (meth)acrylate-functionalized acidic acrylic oligomer of the invention based on the total weight of the composition. In particular, the composition may comprise 5 to 50% or 10 to 50% or 15 to 50% or 20 to 50% or 25 to 50% or 30 to 50%, by weight of the optionally (meth)acrylate- functionalized acidic acrylic oligomer of the invention based on the total weight of the composition. Alternatively, the composition may comprise 50 to 95% or 55 to 95% or 60 to 95% or 65 to 95% or 70 to 95%, by weight of the optionally (meth)acrylate- functionalized acidic acrylic oligomer of the invention based on the total weight of the composition.

[0043] In accordance with certain embodiments, the curable composition may comprise 1 to 200, 5 to 100, or 15 to 70 parts by weight optionally (meth)acrylate-functionalized acidic acrylic oligomer per 100 parts by weight of the total weight of polymerizing organic substances (e.g., the total weight of polymerizing monomer + polymerizing oligomer).

[0044] The curable composition of the invention comprises an optionally (meth)acrylate- functionalized acidic oligomer.

[0045] As used herein an acidic oligomer is an oligomer comprising at least one acid group. An acid group may be a carboxylic acid group, a salt thereof and / or an anhydride thereof (in particular a cyclic anhydride). An acid group may be pendant and / or terminal.

[0046] An acidic oligomer may be formed by reacting at least one acid monomer and at least one ethylenically unsaturated co-monomer.

[0047] As used herein, an acid monomer is an ethylenically unsaturated monomer bearing an acid group. The acid group may be as defined above.

[0048] The acid monomer is preferably selected from (meth)acrylic acid, maleic anhydride, itaconic anhydride and mixtures thereof. The acidic oligomer may be an acidic acrylic oligomer. As used herein, as acidic acrylic oligomer is an oligomer comprising at least one monomeric unit derived from the polymerization of a (meth)acrylate monomer. As used herein, a (meth)acrylate monomer is a monomer bearing a (meth)acrylate group.

[0049] The acidic oligomer may be an optionally (meth)acrylate- functionalized acidic oligomer. As used herein, an optionally (meth)acrylate-functionalized acidic oligomer is an acidic oligomer optionally comprising at least one pendant and / or terminal (meth)acrylate group. The acidic oligomer may be a (meth)acrylate-functionalized acidic oligomer. As used herein, a (meth)acrylate-functionalized acidic oligomer is an acidic oligomer comprising at least one pendant and / or terminal (meth)acrylate group.

[0050] The acidic oligomer may be an optionally (meth)acrylate- functionalized acidic acrylic copolymer. As used herein, an optionally (meth)acrylate- functionalized acidic acrylic oligomer is an acidic acrylic oligomer optionally comprising at least one pendant and / or terminal (meth)acrylate group. The acidic oligomer may be a (meth)acrylate-functionalized acidic acrylic oligomer. As used herein, a (meth)acrylate-functionalized acidic acrylic oligomer is an acidic acrylic oligomer comprising at least one pendant and / or terminal (meth)acrylate group.

[0051] According to some embodiments, the optionally (meth)acrylate-functionalized acidic oligomer may be conveniently prepared by one or both of two basic approaches. A first approach involves copolymerizing (meth)acrylic acid with one or more ethylenically unsaturated co-monomers (preferably a (meth)acrylate monomer) to form an acidic oligomer (preferably an acidic acrylic oligomer). The acidic oligomer may then be optionally reacted with an ethylenically unsaturated epoxy-functional compound (preferably an epoxy-functional (meth)acrylate), wherein at least one acid group of the acidic oligomer is esterified to form the (meth)acrylate- functionalized acidic oligomer (preferably the (meth)acrylate- functionalized acidic acrylic oligomer) .

[0052] Another approach, which may be used alone or together with the first approach, involves copolymerizing an anhydride (i.e. maleic anhydride and / or itaconic anhydride) with one or more ethylenically unsaturated co-monomers (preferably a (meth)acrylate monomer) to form an acidic oligomer (preferably an acidic acrylic oligomer). Said oligomer may also be referred to as an anhydride oligomer as it comprises anhydride groups. Said acidic oligomer may then be reacted with an ethylenically-unsaturated hydroxy-functional compound (preferably an hydroxy-functional (meth)acrylate), wherein the ring of at least one anhydride group is opened to form the (meth)acrylate-functionalized acidic oligomer (preferably the (meth)acrylate- functionalized acidic acrylic oligomer).

[0053] A combination of both of both approaches involves copolymerizing (meth)acrylic acid with at least one anhydride (i.e. maleic anhydride and / or itaconic anhydride) and at least one ethylenically unsaturated comonomer (preferably a (meth)acrylate monomer) to form an acidic oligomer (preferably an acidic acrylic oligomer). At least at least one acid group of said acidic oligomer may then be reacted with an ethylenically unsaturated epoxy-functional compound (preferably an epoxy-functional (meth)acrylate) and / or wherein the ring of at least one anhydride group of the acidic oligomer may then be reacted with an ethylenically-unsaturated hydroxy-functional compound (preferably an hydroxy-functional (meth)acrylate) to form the (meth)acrylate- functionalized acidic oligomer (preferably an (meth)acrylate-functionalized acidic acrylic oligomer).

[0054] As used herein, the term “ethylenically unsaturated” means a compound that comprises a polymerizable carbon-carbon double bond. A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. A polymerizable carbon-carbon double bond is generally comprised in a group selected from acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, preferably selected from acrylate, methacrylate, allyl and vinyl, more preferably selected from acrylate and methacrylate. The carbon-carbon double bonds of a phenyl ring are not considered as polymerizable carbon-carbon double bonds.

[0055] The ethylenically unsaturated polymerizable co-monomer may be selected in order to enhance the flexibility, strength and / or modulus, among other attributes, of a cured polymer prepared using curable composition.

[0056] According to some preferred embodiments, the ethylenically unsaturated co-monomer may comprise at least one (meth)acrylate monomer. In particular, the ethylenically unsaturated co-monomer comprises a (meth)acrylate monomer. According to some embodiments, the ethylenically unsaturated co-monomer may comprise a mixture of (meth)acrylate monomers.

[0057] As used herein, the term “(meth)acrylate monomer” means a monomer comprising a (meth)acrylate group, in particular an acrylate group. The term “(meth)acrylate group” encompasses acrylate groups (-O-CO-CH=CH2) and methacrylate groups (-O-CO- C(CH3)=CH2).

[0058] The (meth)acrylate monomer may have a molecular weight of less than 600 g / mol, in particular from 100 to 550 g / mol, more particularly 200 to 500 g / mol.

[0059] The (meth)acrylate monomer may have 1 to 6 (meth)acrylate groups, in particular 1 to 3 (meth)acrylate groups.

[0060] The (meth)acrylate monomer may comprise a mixture of (meth)acrylate monomers having different functionalities. For example, the (meth)acrylate monomer may comprise a mixture of a (meth)acrylate monomer containing a single acrylate or methacrylate group per molecule (referred to herein as “mono(meth)acrylate compounds”) and a (meth)acrylate monomer containing 2 or more, preferably 2 or 3, acrylate and / or methacrylate groups per molecule.

[0061] In one embodiment, the (meth)acrylate monomer comprises a mono(meth)acrylate monomer.

[0062] Examples of suitable mono(meth)acrylate monomers include, but are not limited to, mono- (meth)acry late 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)acry late esters of monoalkyl ethers of glycols and oligoglycols; mono- (meth)acrylate esters of alkoxy lated (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)acry late esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); caprolactone mono(meth)acrylates; and the like.

[0063] The following compounds are specific examples of mono(meth)acrylate monomers suitable for use in the preparation of the acidic oligomer: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; t-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-methoxy ethyl (meth)acrylate; 2- ethoxy ethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; 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; and combinations thereof.

[0064] In a preferred embodiment, the at least one ethylenically unsaturated co-monomer comprises a combination of methyl (meth)acrylate and n-butyl (meth)acrylate, more preferably methyl methacrylate and n-butyl acrylate.

[0065] In one embodiment, the (meth)acrylate monomer may comprise a (meth)acrylate monomer containing two or more (meth)acrylate groups per molecule.

[0066] Examples of suitable (meth)acrylate monomers containing two or more (meth)acrylate groups per molecule include acrylate and methacrylate esters of polyols. 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.

[0067] Exemplary (meth)acrylate monomers containing two or more (meth)acryloyloxy groups per molecule 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; polybutadiene di(meth)acrylate; cyclohexane- 1,4-dimethanol di(meth)acrylate; tri cyclodecane 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)acrylate; 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- hydroxy ethyl) isocyanurate tri (meth)acry late; as well as the alkoxylated (e.g., ethoxylated and / or propoxy lated) derivatives thereof; and combinations thereof.

[0068] In a preferred embodiment, the acidic oligomer comprises a copolymer of (meth)acrylic acid, methyl methacrylate, and butyl acrylate, preferably in a ratio by weight of (meth)acrylic acid : methyl methacrylate : butyl acrylate of 10-30:10-50:30-80.

[0069] In another preferred embodiment, the anhydride oligomer comprises a copolymer of maleic and / or itaconic anhydride, (meth)acrylic acid, methyl methacrylate, and butyl acrylate, preferably in a ratio of maleic and / or itaconic anhydride : (meth)acrylic acid : methyl methacrylate : butyl acrylate of 1-10:1-5:30-60:30-60.

[0070] In another preferred embodiment, the anhydride oligomer comprises a copolymer of itaconic anhydride, ethyl hexyl acrylate, and butyl acrylate, preferably in a ratio of itaconic anhydride : ethyl hexyl acrylate : butyl acrylate of 1-10:30-60:30-60.

[0071] According to some embodiments, the acidic oligomer is a (meth)acrylate- functionalized acidic oligomer, more preferably a (meth)acrylate- functionalized acidic acrylic oligomer. Said oligomer may be conveniently prepared by reacting an acidic oligomer (preferably an acidic acrylic oligomer) comprising at least one acid group with one or more ethylenically unsaturated epoxy compounds (preferably an epoxy-functionalized (meth)acrylate). Preferably, at least one acid group of an acidic oligomer (preferably an acidic acrylic oligomer) is esterified with an ethylenically unsaturated epoxy compound (preferably an epoxy-functionalized (meth)acrylate) to form the a (meth)acrylate-functionalized acidic oligomer (preferably a (meth)acrylate-functionalized acidic acrylic oligomer) . Preferably, the ethylenically unsaturated epoxy compound comprises a reaction product of acrylic or methacrylic acid or mixtures thereof with epichlorohydrin, preferably the ethylenically unsaturated epoxy compound is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and any combination thereof, most preferably glycidyl methacrylate.

[0072] According to some embodiments, the (meth)acrylate- functionalized acidic oligomer (poreferably the (meth)acrylate-functionalized acidic acrylic oligomer) may be conveniently prepared by reacting an acidic oligomer (preferably an acrylic anhydride oligomer) comprising at least one anhydride group with one or more ethylenically unsaturated hydroxyl-functional compounds (preferably one or more hydroxyl-functionalized (meth)acrylates). Preferably, at least one anhydride group of the anhydride oligomer (preferably the anhydride acrylic oligomer) is esterified with an unsaturated hydroxyl-functional compound (preferably a hydroxyl-functionalized (meth)acrylate) to form the (meth)acrylate-functionalized acidic oligomer (preferably the (meth)acry late- functionalized acidic acrylic oligomer.

[0073] Preferably, the ethylenically unsaturated hydroxyl-functional compound is a hydroxyl- functionalized (meth)acrylate, i.e. a compound bearing at least one hydroxyl group and at least one (meth)acrylate group, preferably a compound selected from the group consisting of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, glycerol diacrylate, glycerol dimethacrylate, caprolactone acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, an acrylate of phenyl glycidyl ether, a methacrylate of phenyl glycidyl ether, a (poly)caprolactone acrylate, a (poly)caprolactone methacrylate, and any combination thereof.

[0074] In a preferred embodiment, the hydroxy-functional compound is 2-hydroxyethyl acrylate (HEA) or 2-hydroxyethyl methacrylate (HEMA). Other suitable ethylenically unsaturated hydroxy-functional compounds include hydroxyl propyl acrylate, OH-terminated (poly)caprolactone including a terminal (meth) acrylate group, or other hydroxyl functionalized (meth)acrylates and combinations thereof, such as a reaction product of caprolactone with hydroxyethyl acrylate or a caprolactone-extended hydroxy-functional alcohol.

[0075] Other examples of ethylenically unsaturated hydroxy-functional compounds are palmitoleyl alcohol (cis-9-hexadecen-l-ol), erucyl alcohol (cis-13-docosen-l-ol),

[0076] According to some embodiments, the acidic oligomer (preferably the acidic acrylic oligomer) may be conveniently prepared by reacting an acidic oligomer (preferably an acidic acrylic oligomer) comprising at least one anhydride group with one or more saturated hydroxyl-functional compounds. Preferably, at least one anhydride group of an acidic oligomer (preferably an acidic acrylic oligomer) is esterified with a saturated hydroxyl- functional compound to form an acidic oligomer (preferably an acidic acrylic oligomer).

[0077] According to particular embodiments, the saturated hydroxy-functional compound may be derived from hydroxyl terminated polyalkoxylates such as a polyethylene glycol (such as polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1450, polyethylene glycol 3350, polyethylene glycol 8000), a monoalkyl ether of a polyethylene glycol (such as polyethylene glycol 350 methyl ether, polyethylene glycol 550 methyl ether), a polytetrahydrofuran, and mixtures thereof.

[0078] According to some embodiments, the saturated hydroxy-functional compound may be derived from a faty alcohol. Non-limiting examples of such branched or straight chained fatty alcohols include tert- butyl alcohol, tert-amyl alcohol, 3 -methy 1-3 -pentanol, 1 -heptanol (enanthic alcohol), 1 -octanol (capryl alcohol), pelargonic alcohol (1 -nonanol), 1 -decanol (decyl alcohol, capric alcohol), undecyl alcohol (1 -undecanol, undecanol, hendecanol), lauryl alcohol (dodecanol, 1 -dodecanol), tridecyl alcohol (1 -tridecanol, tridecanol, isotridecanol), myristyl alcohol (1 -tetradecanol), pentadecyl alcohol (1 -pentadecanol, pentadecanol), cetyl alcohol (1 -hexadecanol), heptadecyl alcohol (1-n- heptadecanol, heptadecanol), stearyl alcohol (1 -octadecanol), oleyl alcohol (1 -octadecenol), nonadecyl alcohol (1 -nonadecanol), arachidyl alcohol (1-eicosanol), heneicosyl alcohol (1-heneicosanol), behenyl alcohol (1 -docosanol), lignoceryl alcohol (1-tetracosanol), cetyl alcohol (1-hexacosanol), 1 -heptacosanol, 1- octacosanol, 1 -nonacosanolmyricyl alcohol, 1 -triacontanol, 1-dotriacontanol, or geddyl alcohol (1-tetratriacontanol). Mixtures of any two or more of these are contemplated. In some embodiments, the hydroxy-functional compound may be derived from a long chain carboxylic acid comprising a terminal hydroxyl group. Non-limiting examples of such reactants are C2- C22 carboxylic acid aliphatic alcohols, such as 12 hydroxyl lauric acid. According to particular embodiments, the saturated hydroxy-functional compound may be derived from alkoxylated faty alcohols such as 12 molar ethoxylated tri decyl alcohol.

[0079] Other non-limiting examples of saturated hydroxy-functional compounds include faty alcohol alkoxylates. The alkoxylate moiety may comprise, consist of, or consist essentially of ethylene oxide (EO), propylene oxide (PO) or butylene oxide (BO) units or mixtures thereof. The alkoxylate moiety may also be present in the form of ethylene oxide / propylene oxide block copolymer. Faty alcohol oxyalkylates may also comprise polyglycerolated faty alcohols. The ethoxylated fatty alcohols, may be primary alcohols having from 8 to 22 carbon atoms, for example coconut, palm fat, palm kernel, tallow fat, lauryl, stearyl or oleyl alcohol. These may comprise from 1 to 80 EO (ethylene oxide) units per mole of alcohol, and the alcohol radical may be linear or may be methyl-branched in the 2-position, or may contain linear and methyl-branched radicals in a mixture, as is typically the case in oxo alcohol radicals. The ethoxylated alcohols may include, for example, Cn alcohols having 3, 5, 7, 8 and 11 EO units, (C12-C15) alcohols having 3, 6, 7, 8, 10 and 13 EO units, (C14-C15) alcohols having 4, 7 and 8 EO units, (Ci6-Cis) alcohols having 8, 11, 15, 20, 25, 50 and 80 EO units and mixtures thereof. The degrees of ethoxylation specified constitute statistical averages which may be an integer or a fraction for a specific product.

[0080] Preferred structures and embodiments

[0081] In a preferred embodiment, the acidic oligomer is an acidic acrylic oligomer according to the following formula (A): wherein x, y, and z represent the molar fractions of the different monomeric units, x is a number from 0.00 to 0.99, preferably from 0.10 to 0.80, more preferably from 0.20 to 0.60, y is a number from 0.00 to 0.99, preferably from 0.05 to 0.60, more preferably from 0.10 to 0.50, z is a number from 0.01 to 0.99, preferably from 0.05 to 0.50, more preferably from 0.10 to 0.40, x and y are not 0.00 at the same time, x + y + z = 1.00, each R is independently H or methyl, and

[0082] Ri and R2 are independently selected from methyl, ethyl, n-propyl, n-butyl, t-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, tridecyl, tetradecyl, hexadecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, tetrahydrofurfuryl, alkoxylated tetrahydrofurfuryl, 2-(2-ethoxyethoxy)ethyl, cyclohexyl, 2- phenoxy ethyl, alkoxylated phenol; alkoxylated nonylphenol; (5-ethyl-l,3-dioxan-5-yl)methyl, isobornyl, tricyclodecanemethyl, tert-butylcyclohexyl, trimethylcyclohexyl, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, ethoxylated lauryl, methoxy polyethylene glycol, an alkyl substituted with an oxazolidinone, and combinations thereof.

[0083] Preferably, Ri and R2 are independently selected from methyl, ethyl, n-propyl, n-butyl, t-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl. In another preferred embodiment, the acidic oligomer is a (meth)acrylate- functionalized acidic acrylic oligomer according to the following formula (B): wherein x, y, h and (z-h) represent the molar fractions of the different monomeric units, x, y and z are as defined above for the copolymer of formula (A), h is a number greater than 0.00 and less than z, each R is independently H or methyl, and

[0084] Ri and R2 are as defined above for the copolymer of formula (A).

[0085] Said oligomer of formula (B) may be obtained by reacting part of the acid groups of the oligomer of formula (A) with glycidyl (meth)acrylate.

[0086] In another preferred embodiment, the acidic oligomer is a (meth)acrylate- functionalized acidic acrylic oligomer according to the following formula (C):

[0087] wherein x, y, h and (z-h) represent the molar fractions of the different monomeric units, x, y and z are as defined above for the copolymer of formula (A), h is a number greater than 0.00 and less than z, each R is independently H or methyl,

[0088] L is an organic linker, and

[0089] Ri and R2 are as defined above for the copolymer of formula (A).

[0090] Preferably, L is an organic linker selected from an alkylene, a (poly)oxyalkylene or an alkylene bearing one more units of formula -[O-C(=O)-(CH2)s]-,

[0091] Said oligomer of formula (C) may be obtained by reacting part of the acid groups of the oligomer of formula (A) with a hydroxyl-functional (meth)acrylate.

[0092] In another preferred embodiment, the acidic oligomer is an acidic acrylic oligomer according to the following formula (D): wherein x’, y’, and z’ represent the molar fractions of the different monomeric units, x’ is a number from 0.00 to 0.99, preferably from 0.10 to 0.80, more preferably from 0.20 to 0.60, y’ is a number from 0.00 to 0.99, preferably from 0.05 to 0.60, more preferably from 0.10 to 0.50, z’ is a number from 0.01 to 0.99, preferably from 0.02 to 0.50, more preferably from 0.05 to 0.40, x’ and y’ are not 0.00 at the same time, x’ + y’ + z’ = 1, each R is independently H or methyl, and

[0093] R3 and R4 are independently selected from methyl, ethyl, n-propyl, n-butyl, t-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, tridecyl, tetradecyl, hexadecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, tetrahydrofurfuryl, alkoxylated tetrahydrofurfuryl, 2-(2-ethoxyethoxy)ethyl, cyclohexyl, 2- phenoxy ethyl, alkoxylated phenol; alkoxylated nonylphenol; (5-ethyl-l,3-dioxan-5-yl)methyl, isobornyl, tricyclodecanemethyl, tert-butylcyclohexyl, trimethylcyclohexyl, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, ethoxylated lauryl, methoxy polyethylene glycol, an alkyl substituted with an oxazolidinone, and combinations thereof.

[0094] Preferably, R3 and R4 are independently selected from methyl, ethyl, n-propyl, n-butyl, t-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl.

[0095] In another preferred embodiment, the acidic oligomer is a (meth)acrylate- functionalized acidic acrylic oligomer according to the following formula (E):

[0096] wherein x’, y’, h’ and (z’-h’) represent the molar fractions of the different monomeric units, x’, y’ and z’ are as defined above for the copolymer of formula (D), h’ is a number greater than 0.00 and less than z’, each R is independently H or methyl,

[0097] L is an organic linker, and

[0098] R3 and R4 are as defined above for the copolymer of formula (D).

[0099] Preferably, L is an organic linker selected from an alkylene, a (poly)oxyalkylene or an alkylene bearing one more units of formula -[O-C(=O)-(CH2)s]-, Said oligomer of formula (E) may be obtained by reacting at least part of the anhydride groups of the oligomer of formula (D) with a hydroxyl-functional (meth)acrylate.

[0100] In another preferred embodiment, the acidic oligomer is an acidic acrylic oligomer according to the following formula (F): wherein x”, y’ ’, and z’ ’ represent the molar fractions of the different monomeric units, x” is a number from 0.00 to 0.99, preferably from 0.10 to 0.80, more preferably from 0.20 to 0.60, y” is a number from 0.00 to 0.99, preferably from 0.05 to 0.60, more preferably from 0.10 to 0.50, z” is a number from 0.01 to 0.99, preferably from 0.02 to 0.50, more preferably from 0.05 to 0.40, x” and y” are not 0.00 at the same time, x” + y” + z” = 1, each R is independently H or methyl, and

[0101] Rs and Re are independently selected from methyl, ethyl, n-propyl, n-butyl, t-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, tridecyl, tetradecyl, hexadecyl, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, tetrahydrofurfuryl, alkoxylated tetrahydrofurfuryl, 2-(2-ethoxyethoxy)ethyl, cyclohexyl, 2- phenoxy ethyl, alkoxylated phenol; alkoxylated nonylphenol; (5-ethyl-l,3-dioxan-5-yl)methyl, isobornyl, tricyclodecanemethyl, tert-butylcyclohexyl, trimethylcyclohexyl, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, ethoxylated lauryl, methoxy polyethylene glycol, an alkyl substituted with an oxazolidinone, and combinations thereof.

[0102] Preferably, R5 and Re are independently selected from methyl, ethyl, n-propyl, n-butyl, t-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl.

[0103] In another preferred embodiment, the acidic oligomer is a (meth)acrylate- functionalized acidic acrylic oligomer according to the following formula (G):

[0104] wherein x”, y”, h” and (z”-h”) represent the molar fractions of the different monomeric units, x”, y” and z” are as defined above for the copolymer of formula (F), h” is a number greater than 0.00 and less than z”, each R is independently H or methyl, L is an organic linker, and

[0105] Rs and Re are as defined above for the copolymer of formula (F).

[0106] Preferably, L is an organic linker selected from an alkylene, a (poly)oxyalkylene or an alkylene bearing one more units of formula -[O-C(=O)-(CH2)s]-,

[0107] Said oligomer of formula (G) may be obtained by reacting at least part of the anhydride groups of the oligomer of formula (F) with a hydroxyl-functional (meth)acrylate.

[0108] Acid Value, Acid Content, T?, and Molecular weight

[0109] The optionally (meth)acrylate-functionalized acidic oligomer may have an acid value of at least 10 mg KOH / g copolymer, preferably at least 11 mg KOH / g copolymer, more preferably at least 12 mg KOH / g copolymer, more preferably at least 13 mg KOH / g copolymer, and most preferably at least 13.5 mg KOH / g copolymer. The term ‘acid value’ is determined herein in accordance with ASTM D 974. In other embodiments, the acid value of the acidic oligomer may be at least 25 mg KOH / g copolymer, preferably at least 50 mg KOH / g copolymer, more preferably at least 75 mg KOH / g copolymer, more preferably at least 100 mg KOH / g copolymer, and most preferably at least 125 mg KOH / g copolymer. The particular acid value of the oligomer will depend on the desired delamination time based on certain conditions (temperature and pH) of the recycling solution and the specifics of the other constituents in the formulation, including the extent of their acid content, and the degree of cross-linking of the formulation.

[0110] The optionally (meth)acrylate-functionalized acidic oligomer may have an acid content of at least 1.8 x 10'4mol acid / g copolymer, preferably at least 2.0 x 10'4mol acid / g copolymer, more preferably at least 2.2 x 10'4mol acid / g copolymer, more preferably at least 2.4 x 10'4mol acid / g copolymer, more preferably at least 2.5 x 10'4mol acid / g copolymer, more preferably at least between 2.4 x 10'4and 9.5 x 10'4mol acid / g copolymer, such as between 2.5 x 10'4and 9.25 x 10'4mol acid / g copolymer, such as between 3.0 x 10'4and 9 x 10'4mol acid / g copolymer, such as between 3.5 x 10'4and 8.5 x 10'4mol acid / g copolymer.

[0111] The optionally (meth)acrylate-functionalized acidic oligomer may have a glass transition temperature Tgof from -20°C to 80°C, preferably from -10°C to 70°C, more preferably from 0°C to 60°C, more preferably from 10°C to 50°C, most preferably from 20°C to 40°C. The glass transition temperature values provided herein are determined in accordance with ASTM El 356-08.

[0112] The optionally (meth)acrylate-functionalized acidic oligomer may have a content of acid groups present in a free acid form of at least 5% (based on total weight of acids in both the free acid form and esterified acids), such as at least 10%, such as at least 15%, such as at least 20%, such as at least 25%, such as at least 30%, such as at least 35%, such as at least 40%, such as at least 45%, such as at least 50%, such as at least 55%, such as at least 60%, such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%.

[0113] The optionally (meth)acrylate-functionalized acidic oligomer may have a content of acid groups present in an ester form of at least 5% (based on total weight of acids in both the free acid form and esterified acids), such as at least 10%, such as at least 15%, such as at least 20%, such as at least 25%, such as at least 30%, such as at least 35%, such as at least 40%, such as at least 45%, such as at least 50%, such as at least 55%, such as at least 60%, such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%. The optionally (meth)acrylate-functionalized acidic oligomer may have a number average molecular weight of from 500 to 50,000 Daltons, preferably from 800 to 15,000 Daltons, more preferably 1,000 to 10,000 Daltons.

[0114] In view of their acid content, the optionally (meth)acrylate-functionalized acidic oligomers of the invention may be completely or substantially water soluble, in particular at 25°C. In particular, at least 80%, preferably at least 85%, more preferably at least 90%, even more preferably at least 95%, more preferably still at least 99% by weight of the optionally (meth)acrylate- functionalized acidic oligomer is soluble in water at 25°C.

[0115] Polymerizing Monomer and / or Oligomer

[0116] The curable compositions utilized in the present invention are comprise of at least one polymerizing monomer and / or oligomer. The at least one polymerizing monomer and / or oligomer is distinct from the optionally (meth)acrylate-functionalized acidic oligomer. As used herein, the term “polymerizing” means capable of participating in a polymerization or curing reaction to form a polymeric structure. The polymerizing monomers and / or oligomers may be monomeric and / or oligomeric in structure and may be characterized as containing one, two, three or more polymerizing functional groups per molecule. Suitable polymerizing functional groups include in particular functional groups capable of participating in chaingrowth and ring-opening polymerization mechanisms, such as ethylenically and ethynically unsaturated functional groups (e.g., (meth)acryloyl, vinyl, olefinic and alkyne functional groups) and heterocyclic-functional groups (e.g., epoxide and oxetane functional groups). Polymerizing functional groups which polymerize via free radical and / or cationic mechanisms are particularly preferred. A polymerizing organic substance may include more than one type of polymerizing functional group. The molecular weight of suitable polymerizing monomers and / or oligomers is not particularly limited and may, for example, be from 120 to 50,000 g / mol or from 150 to 25,000 g / mol (in the case where the polymerizing organic substance is an oligomer, “molecular weight” refers to number average molecular weight as determined by gel permeation chromatography using tetrahydrofuran as solvent and polystyrene calibration standards). Combinations of different polymerizing monomers and / or oligomers are used in the curable compositions of the present invention. In particular, the curable compositions may comprise at least one polymerizing monomer and / or at least one polymerizing oligomer. According to certain embodiments, the total weight of polymerizing oligomer in the curable composition is at least as much as the total weight of polymerizing monomer. For example, the weight ratio of polymerizing oligomer : polymerizing monomer may be from 50 : 50 to 90 : 10.

[0117] According to other embodiments, the total weight of polymerizing monomer in the curable composition is at least as much as the total weight of polymerizing oligomer. For example, the weight ratio of polymerizing monomer : polymerizing oligomer may be from 50 : 50 to 90 : 10.

[0118] Preferably, the polymerizing monomers and / or oligomers are selected such that in combination as present in the curable composition the combination is a liquid at least in the temperature range between 0°C and 60°C. The polymerizing monomer may advantageously function as a reactive diluent and reduce the viscosity of the composition.

[0119] Suitable illustrative types of polymerizing monomers and / or oligomers that may be mentioned include, but are not limited to, epoxides (oxiranes), oxetanes, oxolanes, cyclic acetals, and other cyclic ethers, cyclic lactones, vinyl compounds (both aliphatic and aromatic), cyanoacrylates, (meth)acrylamides, and (meth)acrylates (which are particularly preferred). As used herein, the term “(meth)acrylate” refers to both acrylate (-O-C(=O)- CH=CH2) and methacrylate (-O-C(=O)-C(CH3)=CH2) functional groups.

[0120] A polymerizing organic substance contains at least one moiety capable of participating in a polymerization or curing reaction whereby a plurality of polymerizing organic substance molecules become covalently bonded to each other to form a polymeric structure. Suitable reactive moieties include sites of ethylenic unsaturation (i.e., carbon-carbon double bonds, C=C). Such sites of ethylenic unsaturation can be provided, for example, by (meth)acryloyl, maleyl, allyl, propenyl, and / or vinyl groups. As used herein, the term "(meth)acryloyl" is intended to both include methacryloyl and acryloyl, as found in (meth)acrylates and (meth)acrylamides.

[0121] As previously mentioned, ethylenically unsaturated functional groups suitable for use in the polymerizing monomers and / or oligomers of the curable composition include groups containing at least one carbon-carbon double bond, in particular a carbon-carbon double bond capable of participating in a reaction (e.g., a free radical reaction) wherein at least one carbon of the carbon-carbon double bond becomes covalently bonded to an atom, in particular a carbon atom, in a second molecule. Such reactions may result in a polymerization or curing whereby the organic substance(s) containing one or more ethylenically unsaturated functional groups become(s) part of a polymerized matrix or polymeric chain. The carbon-carbon double bond may, for example, be present as part of an a,P-unsaturated carbonyl moiety, e.g., an a, fl- unsaturated ester moiety such as an acrylate functional group (H2C=CH-C(=O)O-) or a methacrylate functional group (H2C=C(CH3)-C(=O)O-). A carbon-carbon double bond may also be present in the ethylenically unsaturated functional group in the form of a vinyl group - CH=CH2 or an allyl group, -CH2-CH=CH2.

[0122] In certain embodiments, the at least one polymerizing monomer and / or oligomer comprisies at least one (meth)acrylate-functionalized organic substance. A (meth)acrylate- functionalized organic substance may be described as an organic substance bearing one or more (meth)acrylate functional groups per molecule. As used herein, the term “(meth)acrylate” refers to both acrylate and methacrylate functional groups. (Meth)acrylate- functionalized organic substances suitable for use in the present invention may be generally described as ethylenically unsaturated organic substances containing at least one carboncarbon double bond alpha to an ester group (a compound containing at least one a,0- unsaturated ester moiety), in particular a carbon-carbon double bond capable of participating in a free radical reaction, in particular a reaction initiated by ultraviolet radiation or electron beam radiation. Such reactions may result in a polymerization or curing whereby the (meth)acrylate- functionalized organic substance becomes part of a polymerized matrix or polymeric chain. In various embodiments of the invention, the (meth)acrylate-functionalized organic substance may contain one, two, three, four, five or more (meth)acrylate functional groups per molecule. Combinations of multiple (meth)acrylate-functionalized organic substances containing different numbers of (meth)acrylate groups may be utilized in the curable compositions of the present invention.

[0123] The curable compositions used in the present invention thus may contain one or more (meth)acrylate functionalized organic substances capable of undergoing free radical polymerization (curing) initiated by exposure to actinic radiation (e.g., ultraviolet light) or electron beam radiation. The (meth)acrylate-functionalized organic substances may be oligomers or monomers or, preferably, a combination of oligomer(s) and monomer(s). Any of the following types of (meth)acrylate-functionalized organic substances may, for example, be employed in the curable compositions of the present invention, possibly or optionally in combination with one or more other types of polymerizing monomers and / or oligomers as co-reactants. In particular, the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acry late-functionalized monomer and / or at least one (meth)acrylate- functionalized oligomer. More particularly, the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate-functionalized monomer selected from the group consisting of (meth)acrylate esters of aliphatic mono-alcohols, (meth)acrylate esters of alkoxylated aliphatic mono-alcohols, (meth)acrylate esters of aliphatic polyols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of aromatic ring-containing alcohols, and (meth)acrylate esters of alkoxylated aromatic ringcontaining alcohols; and / or at least one (meth)acrylate-functionalized oligomer selected from the group consisting of epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates (including amine- and sulfide-modified derivatives thereof); and combinations thereof.

[0124] The at least one polymerizing monomer and / or oligomer may comprise at least one hydroxyalkyl (meth)acrylate, such as hydroxy ethyl methacrylate and / or hydroxypropyl methacrylate. For example, the curable composition may contain from 5 to 30 weight % in total of hydroxyalkyl (meth)acrylate, based on the total weight of polymerizing monomers and / or oligomers in the curable composition. However, in other embodiments, the curable composition may contain little or no hydroxyalkyl (meth)acrylate (e.g., less than 5 weight % or 0 weight %, based on the total weight of polymerizing monomers and / or oligomers), since at least some hydroxyalkyl (meth)acrylates have sensitizing properties.

[0125] The at least one polymerizing monomer and / or oligomer may comprise at least one acid functionalized monofunctional (meth)acrylate. For example, the curable composition may contain from 5 to 30 weight % in total of acid functionalized monofunctional (meth)acrylate, based on the total weight of polymerizing monomers and / or oligomers in the curable composition. Some examples of acid functionalized monofunctional (meth)acrylates include 2-carboxyethyl acrylate, 2-carboxy ethyl methacrylate, the reaction product of a dicarboxylic acid with a hydroxylated (meth)acrylate with the proviso that the resulting product has a residual free carboxylic acid group (such as, for example, hydroxy ethyl methacrylate maleate, hydroxy ethyl acrylate maleate, hydroxyethyl methacrylate succinate or hydroxy ethyl acrylate succinate), a hydroxylated (meth)acrylate functionalized with a phosphate group (such as, for example, hydroxyethyl acrylate phosphate, hydroxyethyl methacrylate phosphate, a polyethylene glycol acrylate phosphate, a polyethylene glycol methacrylate phosphate, a polypropylene glycol acrylate phosphate or a polypropylene glycol methacrylate phosphate) and combinations thereof. Preferably, the acid functionalized monofunctional (meth)acrylate is selected from hydroxy ethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxy ethyl methacrylate succinate, hydroxyethyl acrylate succinate, hydroxyethyl acrylate phosphate, and hydroxy ethyl methacrylate phosphate.

[0126] The at least one polymerizing monomer and / or oligomer may comprise at least one cycloalkyl (meth)acrylate, in particular isobornyl (meth)acrylate. For example, the curable composition may contain from 1 to 25 or 5 to 15 weight % of cycloalkyl (meth)acrylate (e.g., isobornyl methacrylate), based on the total weight of polymerizing monomers and / or oligomers in the curable composition. Cyclohexyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylates, and cyclic trimethylolpropane formal (meth)acrylates represent other types of cycloalkyl (meth)acrylate useful in the present invention.

[0127] The at least one polymerizing monomer and / or oligomer may comprise at least one ethylene glycol- or poly(ethylene glycol)-based (meth)acrylate, such as a poly(ethyleneglycol) di(meth)acrylate. Such substances may be described as (meth)acrylates of ethylene glycol and poly(ethylene glycol), wherein the polyethylene glycol may contain two or more oxyethylene units derived from ethylene oxide per molecule. In certain embodiments, the substance comprises an ethylene glycol segment or polyethylene glycol segment having a number average molecular weight of from about 100 g / mol to about 1000 g / mol. Such a segment may correspond to the structural formula -(CH2CH2O)n-, wherein n is from 2 to 25 on average. For example, the curable composition may contain from 1 to 80 or 5 to 60 weight % of poly(ethylene glycol) di(meth)acrylate, based on the total weight of polymerizing monomers and / or oligomers in the curable composition. Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, PEG-9 di(meth)acrylate (containing an average of about 9 oxyethylene units per molecule), PEG200 di(meth)acrylate (containing a polyethylene glycol segment having a number average molecular weight of about 200 g / mol) and PEG600 di(meth)acrylate (containing a polyethylene glycol segment having a number average molecular weight of about 600 g / mol) represent other types of ethylene glycol- or poly(ethylene glycol)-based (meth)acrylates useful in the present invention. The use of such ethylene glycol- or poly(ethylene glycol)-based (meth)acrylates in the curable compositions is advantageous in that such substances generally are low- to nonsensitizing, unlike certain other types of (meth)acrylate- functionalized monomers.

[0128] The at least one polymerizing monomer and / or oligomer may comprise at least one (meth)acrylate- functionalized monomer containing three or more (meth)acrylate functional groups per molecule, in particular (meth)acrylates of polyols containing three or more hydroxyl groups per molecule and alkoxylated derivatives thereof such as glycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, triethylolpropane and ethoxylated and / or propoxylated derivatives thereof in which the polyol is reacted with 1 to 10 moles of ethylene oxide and / or propylene oxide per mole of polyol. For example, the curable composition may contain from 0.1 to 20 or 0.5 to 10 weight % in total of such (meth)acrylate- functionalized monomers containing three or more (meth)acrylate functional groups per molecule (e.g., trimethylolpropane trimethacrylate).

[0129] The at least one polymerizing monomer and / or oligomer preferably comprises a least one (meth)acrylate-functionalized oligomer. Suitable (meth)acrylate-functionalized oligomers include, for example, polyester (meth)acrylates, epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates (sometimes also referred to as polyurethane (meth)acrylates or urethane (meth)acrylate oligomers) and combinations thereof, as well as amine-modified and sulfide-modified variations thereof. Certain of these (meth)acrylate- functionalized oligomers may function as flexibilizers in the cured articles obtained by curing of the curable composition, i.e., their inclusion helps to increase the flexibility of the cured articles prepared therefrom. The at least one polymerizing monomer and / or oligomer preferably comprises a least one urethane (meth)acrylate.

[0130] Exemplary polyester (meth)acrylates include the reaction products of acrylic or methacrylic acid or mixtures thereof with hydroxyl group-terminated polyester polyols. The reaction process may be conducted such that a significant concentration of residual hydroxyl groups remains in the polyester (meth)acrylate or may be conducted such that all or essentially all of the hydroxyl groups of the polyester polyol have been (meth)acrylated. The polyester polyols can be made by polycondensation reactions of polyhydroxyl functional components (in particular, diols) and polycarboxylic acid functional compounds (in particular, dicarboxylic acids and anhydrides). To prepare the polyester (meth)acrylates, the hydroxyl groups of the polyester polyols are then partially or fully esterified by reacting with (meth)acrylic acid, (meth)acryloyl chloride, (meth)acrylic anhydride or the like. Polyester (meth)acrylates may also be synthesized by reacting a hydroxyl-containing (meth)acrylate such as a hydroxyalkyl (meth)acrylate (e.g., hydroxyethyl acrylate) with a polycarboxylic acid. The polyhydroxyl functional and polycarboxylic acid functional components can each have linear, branched, cycloaliphatic or aromatic structures and can be used individually or as mixtures.

[0131] Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic or methacrylic acid or mixtures thereof with glycidyl ethers or esters.

[0132] Exemplary polyether (meth)acrylate oligomers include, but are not limited to, the condensation reaction products of acrylic or methacrylic acid or mixtures thereof with polyetherols which are polyether polyols. Suitable poly etherols can be linear or branched substances containing ether bonds and terminal hydroxyl groups. Poly etherols can be prepared by ring opening polymerization of epoxides and other oxygen- containing heterocyclic compounds (e.g., ethylene oxide, 1,2-propylene oxide, butene oxide, tetrahydrofuran and combinations thereof) with a starter molecule. Suitable starter molecules include water, hydroxyl functional materials, polyester polyols and amines. Polyetherols may also be obtained by the condensation of diols such as glycols.

[0133] Urethane (meth)acrylates (sometimes also referred to as “polyurethane (meth)acrylates” or “urethane (meth)acrylate oligomers”) capable of being used in the curable compositions of the present invention include urethanes (meth)acrylates based on aliphatic and / or aromatic polyols, in particular selected from polyester polyols, polyether polyols polycarbonate polyols and mixtures thereof, and aliphatic and / or aromatic diisocyanates.

[0134] In various embodiments, the urethane (meth)acrylates may be prepared by reacting at least one aliphatic and / or aromatic polyisocyanate (e.g., diisocyanate, triisocyanate) with at least one aliphatic and / or aromatic polyol (such as a polyester polyol, a poly ether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polydimethysiloxane polyol, a polybutadiene polyol, or combinations thereof) to form isocyanate-functionalized oligomers which are then reacted with at least one hydroxyl-functionalized (meth)acrylate (such as hydroxy ethyl (meth)acrylate or hydroxypropyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, the urethane (meth)acrylate may contain two, three, four or more (meth)acrylate functional groups per molecule. Other orders of addition may also be practiced to prepare the urethane (meth)acrylate, as is known in the art. For example, at least one hydroxyl-functionalized (meth)acrylate may be first reacted with at least one polyisocyanate to obtain an isocyanate-functionalized (meth)acrylate, which may then be reacted with at least one polyol. Alternatively, all the components may be combined and reacted at the same time.

[0135] Any of the above-mentioned types of oligomers may be modified with amines or sulfides (e.g., thiols), following procedures known in the art. Such amine- and sulfide- modified oligomers may be prepared, for example, by reacting a relatively small portion (e.g., 2-15%) of the (meth)acrylate functional groups present in the base oligomer with an amine (e.g., a secondary amine) or a sulfide (e.g., a thiol), wherein the modifying compound adds to the carbon-carbon double bond of the (meth)acrylate in a Michael addition reaction.

[0136] Illustrative examples of suitable monomeric (meth)acrylate-functionalized organic substances include (meth)acrylated mono- and polyols (polyalcohols) and (meth)acrylated alkoxylated mono-alcohols and polyols. The mono-alcohols and polyols may be aliphatic (including one or more cycloaliphatic rings) or may contain one or more aromatic rings (as in the case of phenol or bisphenol A). “Alkoxylated” means that the base mono-alcohol or polyol has been reacted with one or more epoxides such as ethylene oxide and / or propylene oxide so as to introduce one or more ether moieties (e.g., -CH2CH2-O-) onto one or more hydroxyl groups of the mono-alcohol or polyol, prior to esterification to introduce one or more (meth)acrylate functional groups. For example, the amount of epoxide reacted with the monoalcohol or polyol may be from about 1 to about 30 moles of epoxide per mole of mono-alcohol or polyol. Examples of suitable mono-alcohols include, but are not limited to, straight chain, branched and cyclic C1-C54 mono-alcohols (which may be primary, secondary or tertiary alcohols). For instance, the mono-alcohol may be a C1-C7 aliphatic mono-alcohol. In another embodiment, the mono-alcohol may be a C8-C24 aliphatic mono-alcohol (e.g., lauryl alcohol, stearyl alcohol). Examples of suitable polyols include organic compounds containing two, three, four or more hydroxyl groups per molecule such as glycols (diols), e.g., ethylene glycol, 1,2- or 1,3 -propylene glycol, or 1,2-, 1,3- or 1,4-butylene glycol, neopentyl glycol, trimethylolpropane, triethylolpropane, pentaerythritol, glycerol and the like.

[0137] Representative, but not limiting, examples of suitable monomeric (meth)acrylate- functionalized compounds include: 1,3 -butylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, longer chain aliphatic di(meth)acrylates (such as those generally corresponding to the formula H2C=CRC(=O)-O-(CH2)m-O- C(=O)CR’=CH2, wherein R and R’ are independently H or methyl and m is an integer of 8 to 24), alkoxy lated (e.g., ethoxylated, propoxylated) hexanediol di(meth)acrylates, alkoxy lated (e.g., ethoxylated, propoxylated) neopentyl glycol di(meth)acrylates, dodecyl di(meth) acrylates, cyclohexane dimethanol di(meth)acrylates, diethylene glycol di(meth)acrylates, dipropylene glycol di(meth)acrylates, alkoxy lated (e.g., ethoxylated, propoxylated) bisphenol A di(meth)acrylates, ethylene glycol di(meth)acrylates, neopentyl glycol di(meth)acrylates, tricyclodecane dimethanol diacrylates, triethylene glycol di(meth)acrylates, tetraethylene glycol di(meth)acrylates, tripropylene glycol di(meth)acrylates, ditrimethylolpropane tetra(meth)acrylates, dipentaerythritol penta(meth)acrylates, alkoxylated (e.g., ethoxylated, propoxylated) pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylates, pentaerythritol tetra(meth)acrylate, alkoxylated (e.g., ethoxylated, propoxylated) trimethylolpropane tri(meth)acrylates, alkoxylated (e.g., ethoxylated, propoxylated) glyceryl tri(meth)acrylates, trimethylolpropane tri(meth)acrylates, pentaerythritol tri(meth)acrylates, tris (2-hydroxy ethyl) isocyanurate tri(meth)acrylates, 2(2-ethoxyethoxy) ethyl (meth)acrylates, 2-phenoxyethyl (meth)acrylates, 3,3,5-trimethylcyclohexyl (meth)acrylates, alkoxylated lauryl (meth)acrylates, alkoxylated phenol (meth)acrylates, alkoxylated tetrahydrofurfuryl (meth)acrylates, caprolactone (meth)acrylates, cyclic trimethylolpropane formal (meth)acrylates, dicyclopentadienyl (meth)acrylates, diethylene glycol methyl ether (meth)acrylates, alkoxylated (e.g., ethoxylated, propoxylated) nonyl phenol (meth)acrylates, isobornyl (meth)acrylates, isodecyl (meth)acrylates, isooctyl (meth)acrylates, lauryl (meth)acrylates, methoxy polyethylene glycol (meth)acrylates, octyldecyl (meth)acrylates (also known as stearyl (meth)acrylates), tetrahydrofurfuryl (meth) acrylates, tridecyl (meth)acrylates, triethylene glycol ethyl ether (meth)acrylates, t-butyl cyclohexyl (meth)acrylates, dicyclopentadiene di(meth)acrylates, phenoxyethanol (meth)acrylates, octyl (meth)acrylates, decyl (meth)acrylates, dodecyl (meth)acrylates, tetradecyl (meth)acrylates, cetyl (meth)acrylates, hexadecyl (meth)acrylates, behenyl (meth)acrylates, diethylene glycol ethyl ether (meth)acrylates, diethylene glycol butyl ether (meth)acrylates, triethylene glycol methyl ether (meth)acrylates, dodecanediol di (meth)acrylates, dipentaerythritol penta / hexa(meth)acrylates, pentaerythritol tetra(meth)acrylates, alkoxylated (e.g., ethoxylated, propoxylated) pentaerythritol tetra(meth)acrylates, di-trimethylolpropane tetra(meth)acrylates, alkoxylated (e.g., ethoxylated, propoxylated) glyceryl tri(meth)acrylates, and tris (2- hydroxyethyl) isocyanurate tri(meth)acrylates, and combinations thereof.

[0138] Other types of polymerizing monomers and / or oligomers containing ethylenically unsaturated functional groups suitable for use in the curable compositions of the present invention include cyanoacrylates, vinyl esters, 1,1 -diester- 1 -alkenes, 1 , 1 -diketo- 1 -alkenes, 1- ester-1 -keto- 1 -alkenes and itaconates, including methylene malonates and / or methylene betadiketones.

[0139] The amount of (meth)acrylate-functionalized oligomer may be varied based on the viscosity of the oligomer or the tensile properties desired in the curable composition when cured. For example, the curable composition may contain from 1 to 80 or 5 to 60 weight % of (meth)acrylate- functionalized oligomer, based on the total weight of polymerizing monomers and / or oligomers in the curable composition. A suitable (meth)acry late-functionalized oligomer could be diHEMA trimethylhexyl dicarbamate (UDMA).

[0140] According to particularly preferred embodiments of the invention, the polymerizing organic substance(s) which make up components a) and b) of the curable composition is or are selected to be compatible with the optionally (meth)acrylate-functionalized acidic oligomer(s) also present in the curable composition. As used herein, the term “compatible” means that a curable composition does not gel or increase in viscosity to an unacceptable degree when the components of the curable composition are combined (that is, the curable composition remains workable, i.e., capable of being applied and shaped in accordance with its intended end use application).

[0141] Initiator

[0142] The curable compositions described herein include at least one initiator and are curable with radiant energy (actinic radiation). An initiator may be considered any type of substance that, upon exposure to radiation (e.g., actinic radiation), forms species that initiate the reaction and curing of polymerizing monomers and / or oligomers present in the curable composition, such as monomeric polymerizing monomers and / or oligomers as well as oligomeric polymerizing monomers and / or oligomers. Suitable initiators include both free radical photoinitiators as well as cationic photoinitiators and combinations thereof. The photoinitiator should be selected so that it is susceptible to activation by photons of the wavelength associated with the actinic radiation intended to be used to cure the curable composition.

[0143] Free radical polymerization initiators are substances that form free radicals when irradiated. The use of free radical photoinitiators is especially preferred. Non-limiting types of free radical photoinitiators suitable for use in the curable compositions of the present invention include, for example, benzoin, benzoin ethers, acetophenones, benzyl, benzyl ketals, anthraquinones, phosphine oxides, a-hydroxyketones, phenylglyoxylates, a-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives and triazine compounds.

[0144] Suitable photoinitiators include those capable of generating free radicals when exposed to the requisite radiation, such as UV light. In an exemplary embodiment, the photoinitiators include acyl phosphine oxides (e.g., Irgacure® 819, Lucirin® TPO and Lucirin® TPO-L); benzil ketals (e.g., Irgacure 651); alpha-hydroxy phenyl ketones e.g., Irgacure 184 or Darocur 1173) or mixtures thereof.

[0145] When the curable composition contains polymerizing monomers and / or oligomers containing polymerizable (reactive) ethylenically unsaturated functional groups such as (meth)acrylate functional groups, the use of free radical photoinitiators is especially preferred. Non-limiting types of free radical photoinitiators suitable for use in the curable compositions of the present invention include, for example, benzoins, benzoin ethers, acetophenones, benzyl, benzyl ketals, anthraquinones, phosphine oxides, a-hydroxyketones, phenylglyoxylates, a-aminoketones, benzophenones, thioxanthones, xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives and triazine compounds. Examples of particular suitable free radical photoinitiators include, but are not limited to, 2- methylanthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 2-benzyanthraquinone, 2- t-butylanthraquinone, l,2-benzo-9,10-anthraquinone, benzyl, benzoins, benzoin ethers, 1 benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alphamethylbenzoin, alpha-phenylbenzoin, Mi chi er’ s ketone, acetophenones such as 2,2- dialkoxybenzophenones and 1 -hydroxyphenyl ketones, benzophenone, 4,4’-bis-(diethylamino) benzophenone, acetophenone, 2,2-diethyloxyacetophenone, diethyloxyacetophenone, 2- isopropylthioxanthone, thioxanthone, diethyl thioxanthone, 1,5 -acetonaphthylene, ethyl-p- dimethylaminobenzoate, 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-1, 2-hydroxy-2-methyl-l-phenyl-propanone, oligomeric a-hydroxy ketone, benzoyl phosphine oxides, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl- 4-dimethylamino benzoate, ethyl(2,4,6-trimethylbenzoyl)phenyl phosphinate, anisoin, anthraquinone, anthraquinone-2-sulfonic acid, sodium salt monohydrate, (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, camphorquinone, 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, d'ethoxyacetophenone, 2,4,6-trimethylbenzoyldiphenylphophine oxide, phenyl bis(2,4,6- trimethyl benzoyl)phosphine oxide, ferrocene, 3 '-hydroxyacetophenone, 4'- hydroxyacetophenone, 3-hydroxybenzophenone, 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-di ethoxy and 9,10- dibutoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, thioxanthen-9-one and combinations thereof.

[0146] Suitable cationic photoinitiators include any type of photoinitiator that, upon exposure to radiation such as actinic radiation, forms cations (e.g., Brbnsted or Lewis acids) that initiate the reaction of the monomeric and (if present) oligomeric polymerizing monomers and / or oligomers in the curable composition. For example, a cationic photoinitiator may be comprised of a cationic portion and an anionic portion. The cationic portion of the photoinitiator molecule can be responsible for the absorption of UV radiation while the anionic portion of the molecule becomes a strong acid after UV absorption. Suitable cationic photoinitiators include, for example, onium salts with anions of weak nucleophilicity, such as halonium salts, iodonium salts (e.g., diaryliodonium salts such as bis(4-t- butylphenyl) iodonium perfluoro- 1 -butane sulfonate) or sulfonium salts (e.g., triarylsulfonium salts such as triarylsulfonium hexafluoroantimonate salts); sulfoxonium salts; and diazonium salts. Metallocene salts are another type of suitable cationic photoinitiator.

[0147] The amount of photoinitiator may be varied as may be appropriate depending upon the photoinitiator(s) selected, the amounts and types of polymerizing monomers and / or oligomers (monomeric and oligomeric) present in the curable composition, the radiation source and the radiation conditions used, among other factors. Typically, however, the amount of photoinitiator may be from 0.05% to 10%, preferably 0.05 to 5%, more preferably 0.1% to 2%, and most preferably 1% to 2% by weight, based on the total weight of the curable composition.

[0148] (Meth)acrylic Polymers

[0149] The curable composition of the present invention may optionally contain one or more (meth)acrylic polymers. However, such a (meth)acrylic polymer is not required and curable compositions which are free of any (meth)acrylic polymer are also contemplated by the present invention. As used herein, the term "(meth)acrylic polymer" means a polymer which comprises one or more (meth)acrylic monomers (in polymerized form) wherein the (meth)acrylic monomer(s) make up 50 wt.% or more of the (meth)acrylic polymer. The term “(meth)acrylic monomer,” as used herein, means any type of polymerizable monomer containing one or more acrylic and / or methacrylic functional groups.

[0150] The presence of (meth)acrylic polymer in the curable composition can help to facilitate the dispersion and stabilization of the optionally (meth)acrylate-functionalized acidic oligomer, both in the curable composition and a cured article prepared therefrom. Thus, including the (meth)acrylic polymer may lead to a homogeneous dispersion of the optionally (meth)acrylate- functionalized acidic oligomer in the curable composition, which facilitates the formation of a homogeneous cured article prepared by curing the curable composition. An ideal homogeneous dispersion of the optionally (meth)acrylate-functionalized acidic oligomer in a matrix has no agglomerates after the optionally (meth)acrylate-functionalized acidic oligomer is combined with the monomer(s) and oligomer(s) (which may be generically referred to as “polymerizing organic substances”). Thus, a liquid curable composition comprising a (meth)acrylic polymer, an optionally (meth)acrylate-functionalized acidic oligomer and a polymerizing organic substance may possess or exhibit a better dispersion of the optionally (meth)acrylate-functionalized acidic oligomer than an analogous composition not comprising the (meth)acrylic polymer. Further, a liquid curable composition comprising a (meth)acrylic polymer, an optionally (meth)acrylate- functionalized acidic oligomer and a polymerizing organic substance may be less viscous than an analogous composition not comprising the (meth)acrylic polymer.

[0151] The molecular weight of the (meth)acrylic polymer is not particularly limited and may be varied as may be needed or desired in order to impart certain characteristics or properties to the curable composition and / or cured articles prepared therefrom. The (meth)acrylic polymer may, for example, have a weight average molecular weight of from 2000 g / mol to 1,000,000 g / mol.

[0152] In a first embodiment, the (meth)acrylic polymer may have a weight average molecular weight (Mw) of at least 100,000 g / mol, more than 100,000 g / mol, more than 105,000 g / mol, more than 110,000 g / mol, more than 120,000 g / mol, more than 130,000 g / mol, or more than 140,000 g / mol.

[0153] The (meth)acrylic polymer may have a weight average molecular weight (Mw) below 1,000,000 g / mol, below 900,000 g / mol, below 800,000 g / mol, below 700,000g / mol, below 600,000 g / mol, below 550,000 g / mol, below 500,000 g / mol, or below 450,000 g / mol.

[0154] For example, the weight average molecular weight (Mw) of the (meth)acrylic polymer (PI), according to the first preferred embodiment, is preferably between 100,000 g / mol and 1,000,000 g / mol, preferably between 105,000 g / mol and 900,000 g / mol, more preferably between 110,000 g / mol and 800,000 g / mol, advantageously between 120,000 g / mol and 700,000 g / mol, more advantageously between 130,000 g / mol and 600,000 g / mol, and most advantageously between 140,000 g / mol and 500,000 g / mol.

[0155] In a second embodiment, the (meth)acrylic polymer has a weight average molecular weight Mwof less than 100,000 g / mol, less than 90,000 g / mol, more less than 80,000 g / mol, less than 70,000 g / mol, less than 60,000 g / mol, less than 50,000 g / mol, or less than 40,000 g / mol.

[0156] In the second embodiment, the (meth)acrylic polymer may have a weight average molecular weight (Mw) above 2000 g / mol, above 3000 g / mol, above 4000 g / mol, above 5 000 g / mol, above 6000 g / mol, above 6500 g / mol, above 7000 g / mol, above 10,000 g / mol, or above 12,000 g / mol.

[0157] The weight average molecular weight (Mw) of the (meth)acrylic polymer in the second embodiment may be between 2000 g / mol and 100,000 g / mol, between 3000 g / mol and 90,000 g / mol, between 4 000 g / mol and 80,000 g / mol, between 5000 g / mol and 70,000 g / mol, between 6000 g / mol and 50,000 g / mol, or between 10,000 g / mol and 40,000 g / mol.

[0158] According to certain embodiments of the invention, the (meth)acrylic polymer may comprise at least 50 wt.%, at least 60 wt.%, or at least 70 wt.% of one or more monomers selected from the group consisting of Ci to C12 alkyl (meth)acrylates. For example, the (meth)acrylic polymer may comprise at least 50 wt.%, at least 60 wt.%, at least 70 wt.% or at least 80% of one or more monomers chosen from Ci to C4 alkyl methacrylate monomers, Ci to Cs alkyl acrylate monomers and mixtures thereof.

[0159] In certain embodiments, the glass transition temperature (Tg) of the (meth)acrylic polymer is 20°C or higher, e.g., between 30°C and 150°C. The glass transition temperature of the (meth)acrylic polymer may, for example, be between 40°C and 150°C, between 45°C and 150°C, or between 50°C and 150°C.

[0160] According to certain embodiments, the (meth)acrylic polymer is not crosslinked. According to other embodiments, the (meth)acrylic polymer is a thermoplastic polymer. The (meth)acrylic polymer may be a homopolymer or a copolymer, wherein “copolymer” refers to a polymer containing two or more different monomers in polymerized form. The term “thermoplastic polymer” as used herein means a polymer that turns to a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and pressure. The (meth)acrylic polymer, in certain embodiments, is not grafted on any other polymer or polymers, or at least a portion of the (meth)acrylic polymer is not granted on any other polymer or polymers.

[0161] In a first embodiment, the (meth)acrylic polymer comprises (in polymerized form) from 50 wt.% to 100 wt.% methyl methacrylate, from 80 wt.% to 100 wt.% methyl methacrylate, or from 80 wt.% to 99.8 wt.% methyl methacrylate and from 0.2 wt.% to 20 wt.% of a Ci to Cs alkyl acrylate monomer. The Ci to Cs alkyl acrylate monomer may be selected from the group consisting of methyl acrylate, ethyl acrylate and butyl acrylate, according to certain non- limiting embodiments.

[0162] In a second embodiment, the (meth)acrylic polymer comprises (in polymerized form) between 0 wt.% and 50 wt.% of one or more functional monomers. For example, the (meth)acrylic polymer may comprise between 0 wt.% and 30 wt.%, between 1 wt.% and 30 wt.%, between 2 wt.% and 30 wt.%, between 3 wt.% and 30 wt.%, between 5 wt.% and 30 wt.%, or between 5 wt.% and 30 wt.% of the functional monomer(s).

[0163] The functional monomer of the second preferred embodiment may be a (meth)acrylic monomer. The functional monomer(s) may have the formula (1) or (2): wherein in both formulas (1) and (2), Ri is selected from H or CH3; and in formula (1) Y is O, Rs is H or an aliphatic or aromatic radical having at least one atom that is not C or H; and in formula (2) Y is N and R4 and R3 are independently selected from H or an aliphatic or aromatic radical.

[0164] Preferably the functional monomer(s) is or are selected from the group consisting of glycidyl (meth)acrylate; (meth)acrylic acid; (meth)acrylamides such as, for example, dimethylacrylamide; 2-methoxyethyl (meth)acrylate; 2-aminoethyl (meth)acrylates (which may optionally be quaternized; (meth)acrylate monomers comprising a phosphonate or phosphate group; alkyl imidazolidinone (meth)acrylates, and polyethylene glycol (meth) acrylates and combinations thereof. Preferably, the polyethylene glycol group of a polyethylene glycol (meth)acrylate has a number average molecular weight ranging from 400g / mol to 10,000 g / mol.

[0165] According to certain embodiments of the invention, the (meth)acrylic polymer does not contain any functional groups capable of participating in the curing / polymerization which takes place when the curable composition is cured. In such embodiments, the (meth)acrylic polymer may be regarded as non-reactive.

[0166] In accordance with certain embodiments of the invention, the (meth)acrylic polymer may be soluble at 25 °C in the organic polymerizing substances (the mixture of monomer(s) and oligomer(s) present in the curable composition. That is, the organic polymerizing substances function as a solvent for the (meth)acrylic polymer(s). Thus, the combination of (meth)acrylic polymer(s), monomer(s) and oligomer(s) may be a homogeneous (single phase) liquid at 25°C. “Soluble” means that within a certain time the (meth)acrylic polymer(s) when contacted with the polymerizing organic substances dissolve and a solution of the (meth)acrylic polymer(s) in the polymerizing organic substances is obtained. The solubility of the (meth)acrylic polymer(s) in the polymerizing organic substances can be simply tested by mixing the materials at 25°C under agitation and visually inspecting the mixture.

[0167] If present in the curable composition, the (meth)acrylic polymer may be included in any suitable amount such as up to 80%, up to 70%, up to 60%, up to 50%, up to 40%, up to 30%, up to 20%, up to 10%, or up to 5% by weight based on the total weight of the curable composition.

[0168] Other Additives / Components

[0169] The curable compositions of the present invention may optionally contain one or more additives instead of or in addition to the above-mentioned ingredients. Such additives include, but are not limited to, solvents, adhesion promoters, antioxidants / photostabilizers, light blockers / absorbers, polymerization inhibitors, foam inhibitors, flow or leveling agents, colorants, pigments, dispersants (wetting agents, surfactants), slip additives, fillers, chain transfer agents, thixotropic agents, rheology modifiers, matting agents, impact modifiers (other than the optionally (meth)acrylate-functionalized acidic oligomers and polymerizing monomers and / or oligomers already mentioned), thermoplastics such as acrylic resins that do not contain any free radical-polymerizable functional groups, waxes or other various additives, including any of the additives conventionally utilized in the substrate coating art.

[0170] To protect against premature gelling or curing of the curable composition, particularly in the presence of oxygen or other oxidant, one or more antioxidants may be included in the curable composition. Any of the antioxidants known in the art may be utilized, including for example phenol-based antioxidants, phosphorus-based antioxidants, quinone-type antioxidants and combinations thereof.

[0171] Examples of suitable phenol-based antioxidants may include hindered phenol-type antioxidants such as hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thio bis(6-tert-butyl-m-cresol), 2,2' -methylene bis(4-methyl-5-tert-butylphenol), 2,2'-methylene bis(4-ethyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert- butylphenyl)butyric acid]glycol ester, 2,2'-ethylidene bis(4,6-di-tert-butylphenol), 2,2'- ethylidene bis(4-sec-butyl-6-tert-butylphenol), 1 , 1 ,3-tris(2-methyl-4-hydroxy-5-tert- butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5- methylbenzyl)phenyl]terephthalate, l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6- trimethylbenzene, 1 ,3,5-tris[(3,5-di-tert-butyl-4- hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4- hydroxyphenyl) propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5- methylbenzyl)phenol, 3,9-bis[l,l-dimethyl-2-{(3-tert-butyl-4-hydroxy-5- methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and n-octadecyl-3-(4'-hydroxy-3',5'- di-tert-butylphenyl)butane. Butylated hydroxy toluene (BHT) is an example of a preferred antioxidant.

[0172] Examples of suitable phosphorus-based antioxidants may include phosphites, phosphonites and the like such as trisnonylphenyl phosphite, tris(2,4-di-tert- butylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5- methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri- tert-butylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol)diphosphite, hexa(tridecyl)-l ,1 ,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10- phosphaphenanthrene- 10-oxide, 2,2'-methylene bis(4-methyl-6-tert-butylphenyl)-2-ethylhexyl phosphite, and 4-[3-[(2,4,8, 10-tetra-tert-butyldibenzo[d,f] [ 1 ,3,2]dioxaphosphepin)-6- yloxy]propyl]-2-methyl-6-tert-butylphenol.

[0173] Quinone-type antioxidants, such as the mono methyl ether of hydroquinone (MEHQ), may also be used. Phenothiazine (RTZ) and vitamin E are examples of other suitable antioxidants useful in the present invention.

[0174] Typically, one or more antioxidants may be included in the curable composition in a total amount of up to 4% by weight, e.g., 0.05 to 2% by weight, based on the weight of the curable composition.

[0175] Advantageously, the curable compositions utilized in the present invention may be formulated to be solvent- free, i.e., free of any non- reactive volatile substances (substances having a boiling point at atmospheric pressure of 150°C or less). For example, the curable compositions may contain little or no non-reactive solvent, e.g., less than 10% or less than 5% or less than 1% or even 0% non-reactive solvent, based on the total weight of the curable composition. In the context of the present invention, “non-reactive” refers to a substance that does not react when exposed to actinic radiation, i.e., a non-polymerizing substance. Such solvent-less or low-solvent compositions may be formulated using various components, including for example low viscosity reactive diluents (such as monomeric polymerizing monomers and / or oligomers), which are selected so as to render the curable composition sufficiently low in viscosity, even without solvent being present, that the curable composition can be easily applied at a suitable application temperature to a substrate surface such as the surface of a substrate of a subject.

[0176] However, in other embodiments, the curable composition which is used does contain some amount of non-reactive solvent, in particular some amount of volatile non-reactive solvent (having a boiling point at atmospheric pressure of not more than 150°C). As an example, if the curable composition is to be formulated for use as a relatively low viscosity top coat, base coat, color coat or substrate polish, one or more non-reactive solvents may be included. For example, the curable composition may be comprised of at least 0.5, at least 1, at least 5, or at least 10% by weight non- reactive solvent based on the total weight of the curable composition. The curable composition could comprise not more than 50, not more than 25, or not more than 15% by weight non-reactive solvent based on the total weight of the curable composition. The amount of non-reactive solvent may be adjusted to achieve a target viscosity value, as the non-reactive solvent will generally reduce the viscosity of a curable composition. Two or more non-reactive solvents may be used in combination. Suitable non- reactive solvents include esters (such as ethyl acetate and butyl acetate), ethers, ketones, glycol ethers, alcohols, hydrocarbons and combinations thereof.

[0177] Suitable solvents are any solvents that will dissolve part or all of the components in the curable composition and include aliphatic or aromatic hydrocarbons (e.g., hexane, toluene or xylene), alcohols (e.g., ethanol or propylene glycol), esters (e.g., ethyl acetate, n-butyl acetate), ketones (e.g., acetone, methyl isobutyl ketone or methyl ethyl ketone) and ethers (e.g., propylene glycol methyl ether or dimethoxy ethane). In other embodiments, however, the curable compositions of the present invention may be formulated to be solvent-free, i.e., free of any non-reactive volatile substances (substances having a boiling point at atmospheric pressure of 150°C or less). For example, the curable compositions of the present invention may contain little or no non-reactive solvent, e.g., less than 10% or less than 5% or less than 1% or even 0% of a non-reactive solvent, based on the total weight of the curable composition. In a preferred embodiment, the curable compositions of the present invention may be substantially free of water, e.g., less than 10% or less than 5% or less than 1% or even 0% of a water, based on the total weight of the curable composition.

[0178] Any of the stabilizers known in the art related to (meth)acrylate-functionalized compounds may be utilized in the present invention. Quinones represent a particularly preferred type of stabilizer which can be employed in the context of the present invention. As used herein, the term "quinone" includes both quinones and hydroquinones as well as ethers thereof such as monoalkyl, monoaryl, monoaralkyl and bis(hydroxyalkyl) ethers of hydroquinones. Hydroquinone monomethyl ether is an example of a suitable stabilizer which can be utilized. The concentration of stabilizer in the curable composition will vary depending upon the particular stabilizer or combination of stabilizers selected for use and also on the degree of stabilization desired and the susceptibility of components in the curable compositions towards degradation in the absence of stabilizer. Typically, however, the curable composition is formulated to comprise from 50 to 5000 ppm stabilizer.

[0179] Formulation of the Curable Composition

[0180] The relative weight proportions of the optionally (meth)acrylate-functionalized acidic oligomer, the at least one polymerizing monomer and / or oligomer, and the at least one initiator are not believed to be particularly critical and may be varied as desired based on the particular components selected and the characteristics sought in the curable composition and cured articles obtained therefrom. For example, the curable composition in certain embodiments may comprise 5 to 45 wt. % of the optionally (meth)acrylate-functionalized acidic oligomer (preferably of the optionally (meth)acrylate-functionalized acidic acrylic oligomer), 5 to 60 wt. % of the at least one polymerizing monomer and / or oligomer, and 0.1 to 10 wt. % of the at least one initiator, wherein the weight of the optionally (meth)acrylate-functionalized acidic oligomer, the at least one polymerizing monomer and / or oligomer, and the at least one initiator equals 100% in total (meaning that the aforementioned wt. % ranges for each of the optionally (meth)acrylate- functionalized acidic oligomer, the at least one polymerizing monomer and / or oligomer, and the at least one initiator is based on the combined weights of those components, not the total weight of the curable composition which may contain components in addition to the optionally (meth)acrylate-functionalized acidic oligomer, the at least one polymerizing monomer and / or oligomer, and the at least one initiator).

[0181] According to preferred embodiments, the components of the curable composition are selected so that the curable composition is liquid at least in the temperature range between 0°C and 60°C. As used in this context, the term “liquid” does not preclude the possibility that some portion of the curable composition may be present in the form of small, well-dispersed particles in an otherwise liquid matrix.

[0182] In certain embodiments of the invention, the curable composition is a liquid at 25°C.

[0183] For example, the curable composition may be a flowable and / or self-levelling liquid at 25°C. In other embodiments, however, the curable composition may be a gel at 25°C. Such a gel may be non-flowable.

[0184] The viscosity of the curable composition at 25°C may be varied widely, depending upon the intended end use application as discussed in more detail below. For example, the viscosity of the curable composition at 25°C may range from 100 cps to 5,000,000 cps.

[0185] In various embodiments of the invention (for example, where the curable composition is intended for use as a UV gel polish, base coat, color coat or top coat), the curable compositions described herein are formulated to have a relatively low viscosity at ambient or room temperature. For example, the viscosity of the curable composition may be selected or adjusted, by varying the components present and their relative ratios, to provide a viscosity at 25°C which is not more than 100,000 cps, not more than 50,000 cps, not more than 25,000 cps, or not more than 10,000 cps as measured by a Brookfield DV3T Cone and Plate Rheometer with measurements conducted at 25°C on 0.5 mb samples using a CPE-52Z cone. The viscosity at 25°C could, for example, be at least 100 cps or at least 500 cps.

[0186] However, in other embodiments of the invention, the curable compositions described herein are formulated to have a relatively high viscosity at ambient or room temperature. Such high viscosity curable compositions may be of interest where it is intended to be applied to a substrate surface and then sculpted (i.e., a builder gel, sculpting gel, or substrate extension). For example, the viscosity of the curable composition may be selected or adjusted, by varying the components present and their relative ratios, to provide a viscosity at 25°C which is at least 200,000 cps, at least 300,000 cps, or at least 400,000 cps, as measured by a Brookfield DV3T Cone and Plate Rheometer with measurements conducted at 25°C on 0.5 mL samples using a CPE-52Z cone. At the same time, the viscosity should not be so high that the curable composition becomes difficult to apply and / or shape on a substrate surface. The viscosity at 25°C could, for example, be not greater than 5,000,000 cps or not greater than 4,000,000 cps.

[0187] The viscosity and other rheological properties of the curable composition may be selected such that when a portion of the curable composition is applied onto a substrate surface, it does not move easily until it is pushed into a desired shape (sculpted) by a manicurist tool, such as a brush, pusher and / or spatula. The pushing and sculpting of the curable composition into a desired shape may be done neat, or it may be done with the aid of a low viscosity liquid (such as a non-reactive solvent and / or a reactive diluent, such as a (meth)acrylate- functionalized monomer) which lowers, at least locally, the viscosity of the curable composition. According to advantageous embodiments of the invention, when the curable composition is either in neat form or is admixed with such a liquid (in limited amounts), the curable composition remains firm (but shapeable) and does not run. An operator, such as a substrate technician, may optionally control the viscosity through the application of such a suitable liquid, which may be done only in selected areas of the portion of curable composition on the substrate surface, until the curable composition is cured by exposure to actinic radiation (e.g., UV light).

[0188] Cured composition, coated substrate and its method of making

[0189] The composition of the invention may be used to obtain a cured composition.

[0190] The present invention thus also relates to a cured composition obtained by curing the composition as defined above.

[0191] The cured composition may be a cured film or coating. Alternatively, the cured composition may be a cured ink. Alternatively, the cured composition may be a cured nail gel.

[0192] The invention also relates to a substrate coated with a cured composition according to the invention. Such substrate may be referred to as an article.

[0193] The invention also relates to a method for making an article comprising: applying the composition according to the invention to a substrate; and curing the composition.

[0194] The substrate may be any suitable substrate, such as metal, glass, plastic (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, stone and composites thereof. In a preferred embodiment, the substrate is plastic.

[0195] The curing of the composition of the present invention may be carried out by any suitable method, such as free radical, thermal, electron beam, redox, Michael addition, cationic and / or anionic polymerization. One or more initiators, such as a free radical initiator (e.g., a photoinitiator, a peroxide initiator) may be present in the composition. In general, the curing step may comprise one of: (1) exposing the composition is to UV light or visible light; (2) exposing the composition to or e-an electron beam radiation; (3) initiating polymerization through the use of a redox-generated radical; or (4) initiating polymerization through the use of a thermally-generated radical. 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 light or UV energy, and / or electron beam radiation. In an exemplary embodiment, the composition may be cured with UVC, UVB, UVA energy, and / or visible light. In an exemplary embodiment, the composition is cured with a UV light source utilizing UVA / UVB or UVA only and involves essentially no UVC radiation. In an exemplary embodiment, the composition is cured with high energy radiation, ranging from 0.01 to 10 W / cm2. Possible light sources include, but are not limited to, natural outdoor light, black light, fluorescent light, or high pressure mercury light.

[0196] In an exemplary embodiment, the curing is conducted by exposing the composition to ultraviolet radiation provided by one or more UV lamps delivering an irradiance level of 0.01 to 10 W / cm2, such as 1 to 10 W / cm2, for a time between 1 second and 30 minutes, such as between 1 second and 10 minutes. In another embodiment, the curing is conducted by exposing the composition to e-beam radiation. In another embodiment, the curing is conducted by exposing the composition to heat in the presence of a peroxide initiator (thermal curing). In another embodiment, the curing occurs via redox polymerization which is a two- part process involving a peroxide initiator (e.g., as hydrogen peroxide, benzoyl peroxide or t- butyl hydroperoxide) as a first part and a reducing agent (e.g., a tertiary amine such as N,N- dimethylaniline, N-(4-methoxyphenyl)pyrrolidine and N-phenyldiethanol amine, sodium sulfite, sodium metabisulfite).

[0197] The curable (meth)acrylate-containing 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) and for use in high speed applications (such as coatings).

[0198] Prior to curing, the curable acidified anhydride oligomer containing composition may be applied to at least part of the surface of a substrate in any known conventional manner, for example, by spraying, by brush, by sponge, by knife coating, by roller coating, by casting, by drum coating, by dipping, by curtain coating, by screen printing or by other methods of image transfer, by coating transfer, and the like and combinations thereof. Indirect application using a transfer process may also be used.

[0199] In an embodiment, the curable acidified anhydride oligomer containing composition may be applied directly to a substrate, either as a primer or other coating layer, or over one or more of a primer, a basecoat system or other suitable layers in order to achieve the desired final appearance and properties. For example, the curable composition can be applied over a waterborne basecoat or a solvent-borne basecoat.

[0200] A substrate may be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, such as a metal substrate or plastic substrate, respectively. The substrates may comprise metal, glass, plastics (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, stone and combinations thereof. Depending on the particular application, a suitable dry film thickness ranges from 5 to 200 microns. For 3D printing applications or electronics applications, the film may be thicker than 200 microns.

[0201] Method for recycling a substrate / removing a cured composition

[0202] The method of the invention comprises the steps of: contacting the substrate coated with the cured primer, coating, or ink composition with a recycling solution having a pH sufficient to delaminate the cured primer, coating, or ink composition from the substrate; and retrieving from the recycling solution the substrate substantially free from the cured primer, coating, or ink composition.

[0203] The invention also relates to a method for removing a cured primer, ink, or coating from a substrate, wherein the method for removing the cured primer, ink, or coating comprises: immersing a substrate coated with a cured composition according to the invention with a soaking / recycling solution having a pH sufficient to partially or fully delaminate the cured primer, ink, or coating from the substrate. If the immersing step only partially delaminates the cured primer, ink, or coating from the substrate thereby leaving a portion of the cured primer, ink, or coating from the substrate attached to the substrate, then the method may further comprise manually removing from the substrate the portion of the cured primer, ink, or coating attached to the substrate while the substrate is still present in the soaking / recycling solution or, alternatively, after the substrate is removed from the soaking / recycling solution.

[0204] The soaking / recycling solution described herein causes release (delamination) of the cured optionally (meth)acrylate-functionalized acidic oligomers of the invention (and the compositions, films, etc. in which they are present) from the substrates to which they are attached, resulting in effective removal of the cured coating from the substrate.

[0205] In an exemplary embodiment, the soaking / recycling solution is an aqueous solution of a base (such as an inorganic base or an organic base). Other components may include, but are not limited to, surfactants and defoamers. The amount of the soaking / recycling solution used to effect release (delamination) of the cured optionally (meth)acrylate- functionalized acidic oligomers is not particularly limited and may be present in a large stoichiometric excess relative to the cured optionally (meth)acry late-functionalized acidic acrylic oligomer.

[0206] In an exemplary embodiment, the pH of the soaking / recycling solution is basic - i.e., has a pH greater than 7. In an exemplary embodiment, the pH is greater than 7 and less than 13, such as greater than 7 and less than 12, such as greater than 7 and less than 11, such as greater than 7 and less than 10, such as greater than 7 and less than 9. The pH will depend on the number of acid groups of the optionally (meth)acrylate-functionalized acidic oligomer backbone by having reacted such free acid groups with an epoxy- or hydroxyl-functional compound already. When the acidic copolymer backbone has few acid groups a recycling solution or soaking solution with a lower pH can be used and have the same effect as a recycling solution or soaking solution having a higher pH on a composition having an optionally (meth)acrylate-functionalized acidic oligomer backbone having a higher number of acid groups.

[0207] As used herein, the use of the phrase “soaking solution” typically refers to a solution that is in contact with human skin via fingers or toes containing a natural human substrate or an artificial substrate (i.e., the human substrate or the artificial substrate is the substrate). As a result, the components of the soaking solution must be compatible with exposure to human skin over a period of time sufficient for release of the coating that is present on the substrate surface. In an exemplary embodiment, the maximum pH of the soaking solution is 11 or less, such as 10 or less, such as 9 or less, such as 8 or less, such as greater than 7 and less than 9, such as greater than 7 and less than 8.

[0208] Suitable bases for inclusion in the recycling / soaking solution are not particularly limited and include inorganic bases and organic bases. Suitable inorganic bases include alkali metal and alkaline earth metal bicarbonates or carbonates (e.g., sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium bicarbonate, calcium carbonate). Inorganic bases such as alkali metal and alkaline earth metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide) are typically too caustic for inclusion in a soaking / recycling solution that will contact human skin unless present in dilute amounts (e.g., 2% by weight or less in water). Suitable organic bases include ammonia, pyridine and amines (e.g., isopropylamine, trimethylamine, diethylamine, triethylamine, tripropylamine, diethanolamine, ethanolamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, dicyclohexylamine, etc.).

[0209] Ease of delamination is dependent on the ease with which the soaking / recycling solution is able to permeate the composition containing the cured optionally (meth)acrylate- functionalized acidic oligomer, which is impacted by physical properties of the composition, including the degree of cross-linking, glass transition temperature (Tg), and its hydrophilicity. Triggered removability of these coatings is influenced by four main conditions 1) crosslink density of the composition 2) number of triggered functional groups within the composition 3) removal time and 4) removal temperature. The crosslink density is important because if the composition is too highly crosslinked, the remover will not be able to penetrate through the film and trigger removability via a swelling mechanism. In addition, there has to be a certain number of acidic functional groups present in the film that can allow for enough swelling. The removal time is important because it allows the aqueous based remover to penetrate the film and temperature of the remover during removal can help with softening of the film to increase penetration and mobility. Regardless of the ease of removability of a composition containing an optionally (meth)acrylate- functionalized acidic oligomer of the present invention, the inclusion of the optionally (meth)acrylate-functionalized acidic oligomer of the invention in such a composition has been found to make such removability easier. Without attempting to assess the percentage of acid groups that are in free acid form versus the percentage of acid groups that are in an esterified form, the following test conditions may be used, in one aspect of the invention, as a standard for achieving complete delamination of a primer, ink, or coating composition containing the cured optionally (meth)acrylate- functionalized acidic oligomer from the substrate to which the primer, ink, or coating composition is attached: Upon exposure of the coated substrate to a 2% sodium hydroxide (NaOH) solution at 25°C to 85°C for 1 minute to 60 minutes, preferably within 10 minutes, complete delamination of the coating from the substrate occurs. Utilizing the optionally (meth)acrylate-functionalized acidic oligomer of the present invention can achieve this in certain formulations (e.g., ones that do not increase the cross link density and utilize a sufficient amount of the optionally (meth)acrylate- functionalized acidic oligomer of the invention) and in other formulations, utilizing the optionally (meth)acrylate- functionalized acidic oligomer of the invention increases the extent of delamination under such conditions compared to a similar formulation that does not contain a optionally (meth)acrylate- functionalized acidic oligomer of the present invention.

[0210] Aspects of the Invention

[0211] Certain, non-limiting aspects of the invention may be summarized as follows:

[0212] Aspect 1 : A method for recycling a substrate coated with a cured primer, coating, or ink composition, wherein the cured composition is obtained by curing a curable primer, ink, or coating composition comprising: an optionally (meth)acrylate-functionalized acidic oligomer formed by reacting (meth)acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the oligomer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator, the method comprising the steps of: contacting the substrate coated with the cured primer, coating, or ink composition with a recycling solution having a pH sufficient to delaminate the cured primer, coating, or ink composition from the substrate; and retrieving from the recycling solution the substrate substantially free from the cured primer, coating, or ink composition.

[0213] Aspect 2: The method according to Aspect 1, wherein the optionally (meth)acrylate- functionalized acidic oligomer is an optionally (meth)acrylate-functionalized acidic acrylic oligomer.

[0214] Aspect 3: The method according to Aspect 1 or 2, wherein the substrate comprises a plastic, preferably polyethylene terephthalate.

[0215] Aspect 4. The method of any of Aspects 1 to 3, wherein the pH of the recycling solution is greater than or equal to 7.

[0216] Aspect 5: The method of any of Aspects 1 to 4, wherein the pH of the recycling solution is greater than 7 and less than 13.

[0217] Aspect 6: The method of any of Aspects 1 to 5, wherein the pH of the recycling solution is greater than 7 and less than 12.

[0218] Aspect 7: The method of any of Aspects 1 to 6, wherein the pH of the recycling solution is greater than 7 and less than 11.

[0219] Aspect 8: The method of any of Aspects 1 to 7, wherein the pH of the recycling solution is greater than 7 and less than 10

[0220] Aspect 9: The method of any of Aspects 1 to 8, wherein the pH of the recycling solution is greater than 7 and less than 9.

[0221] Aspect 10: The method of any of Aspects 1 to 9, wherein delamination occurs within 1 minute to 60 minutes, preferably within 10 minutes of exposure to the recycling solution.

[0222] Aspect 11 : The method of any of Aspects 1 to 10, wherein when the pH of the recycling solution corresponds to a 2% NaOH solution and delamination occurs within 1 minute to 60 minutes, preferably within 10 minutes of exposure at a solution temperature of 25°C to 85°C.

[0223] Aspect 12: The method of any of Aspects 1 to 11, wherein the recycling solution comprises an inorganic base comprising at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or combination thereof.

[0224] Aspect 13: The method of any of Aspects 1 to 12, wherein the recycling solution comprises is an organic base that is an amine.

[0225] Aspect 14: The method of any of Aspects 1 to 13, wherein the acidic oligomer is a (meth)acrylate- functionalized acidic oligomer obtained by reacting at least one acid group of an acidic oligomer with an ethylenically unsaturated epoxy compound.

[0226] Aspect 15: The method of Aspect 14, wherein the ethylenically unsaturated epoxy compound is a reaction product of acrylic or methacrylic acid or mixtures thereof with epichlorohydrin.

[0227] Aspect 16: The method of Aspect 14 or 15, wherein the ethylenically unsaturated epoxy compound is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and any combination thereof.

[0228] Aspect 17. The method of any of Aspects 1 to 16, wherein the acidic oligomer is a (meth)acrylate- functionalized acidic oligomer obtained by reacting at least one acid group of an acidic oligomer is reacted with an ethylenically-unsaturated hydroxy-functional compound.

[0229] Aspect 18: The method of Aspect 17, wherein the ethylenically-unsaturated hydroxyfunctional compound is a compound selected from the group consisting of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, glycerol diacrylate, glycerol dimethacrylate, caprolactone acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, an acrylate of phenyl glycidyl ether, a methacrylate of phenyl glycidyl ether, a (poly)caprolactone acrylate, a (poly) caprolactone methacrylate, and any combination thereof, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or a combination thereof.

[0230] Aspect 19: A curable primer, ink, or coating composition comprising: a (meth)acrylate-functionalized acidic oligomer formed by reacting (meth)acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the copolymer comprising at least one pendant and / or terminal acid group and at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

[0231] Aspect 20: The curable primer, ink, or coating composition of Aspect 20, wherein the (meth)acrylate- functionalized acidic oligomer is a (meth)acrylate-functionalized acidic acrylic oligomer.

[0232] Aspect 21: The curable primer, ink, or coating composition of Aspect 19 or 20 wherein the at least one ethylenically unsaturated co-monomer comprises at least one polymerizable C-C double bond.

[0233] Aspect 22: The curable composition of any of Aspects 19 to 21, wherein the at least one ethylenically unsaturated co-monomer is selected from the group consisting of acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof.

[0234] Aspect 23: The curable composition of any of Aspects 19 to 22, wherein the at least one ethylenically unsaturated co-monomer is selected from the groups consisting of acrylate, methacrylate, allyl, vinyl, and combinations thereof.

[0235] Aspect 24: The curable composition of any of Aspects 19 to 23, wherein the at least one ethylenically unsaturated co-monomer is selected from the group consisting of 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); and caprolactone mono(meth)acrylates

[0236] Aspect 25: The curable composition of any of Aspects 19 to 24, wherein the at least one ethylenically unsaturated co-monomer is selected from the group consisting of methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; t-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-hydroxy ethyl (meth)acrylate; 2- and 3-hydroxypropyl (meth)acrylate; 2-methoxy ethyl (meth)acrylate; 2-ethoxy ethyl (meth)acrylate; 2- and 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2- ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; 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; and combinations thereof.

[0237] Aspect 26: The curable composition of any of Aspects 19 to 25, wherein the at least one ethylenically unsaturated co-monomer is methyl methacrylate, butyl acrylate, or a combination thereof. Aspect 27: The curable composition of any of Aspects 19 to 26, wherein the (meth)acrylate- functionalized acidic oligomer has an acid value of at least 10 mg KOH / g copolymer.

[0238] Aspect 28: The curable composition of any of Aspects 19 to 27, wherein the (meth)acrylate- functionalized acidic oligomer has an acid value of at least 11 mg KOH / g copolymer

[0239] Aspect 29: The curable composition of any of Aspects 19 to 28, wherein the (meth)acrylate- functionalized acidic oligomer has an acid value of at least 12 mg KOH / g copolymer

[0240] Aspect 30: The curable composition of any of Aspects 19 to 29, wherein the (meth)acrylate- functionalized acidic oligomer has an acid value of at least 13 mg KOH / g copolymer

[0241] Aspect 31: The curable composition of any of Aspects 19 to 30, wherein the (meth)acrylate- functionalized acidic oligomer has an acid value of at least 13.5 mg KOH / g copolymer.

[0242] Aspect 32: The curable composition of any of Aspects 19 to 31, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of at least 1.8 x 10-4 mol acid / g copolymer

[0243] Aspect 33: The curable composition of any of Aspects 19 to 32, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of at least 2.0 x 10-4 mol acid / g copolymer

[0244] Aspect 34: The curable composition of any of Aspects 19 to 33, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of at least 2.2 x 10-4 mol acid / g copolymer

[0245] Aspect 35: The curable composition of any of Aspects 19 to 34, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of at least 2.4 x 10-4 mol acid / g copolymer Aspect 36: The curable composition of any of Aspects 19 to 35, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of at least 2.5 x 10-4 mol acid / g copolymer

[0246] Aspect 37: The curable composition of any of Aspects 19 to 36, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of at least between 2.4 x 10- 4 and 9.5 x 10-4 mol acid / g copolymer

[0247] Aspect 38: The curable composition of any of Aspects 19 to 37, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of between 2.5 x 10-4 and 9.25 x 10-4 mol acid / g copolymer

[0248] Aspect 39: The curable composition of any of Aspects 19 to 38, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of between 3.0 x 10-4 and 9 x 10-4 mol acid / g copolymer

[0249] Aspect 40: The curable composition of any of Aspects 19 to 39, wherein the (meth)acrylate- functionalized acidic oligomer has an acid content of between 3.5 x 10-4 and 8.5 x 10-4 mol acid / g copolymer.

[0250] Aspect 41 : The curable composition of any of Aspects 19 to 40, wherein the (meth)acrylate- functionalized acidic oligomer has a glass transition temperature Tgof from - 20°C to 80°C.

[0251] Aspect 42: The curable composition of any of Aspects 19 to 41, wherein the (meth)acrylate- functionalized acidic oligomer has a glass transition temperature Tgof from - 10°C to 70°C.

[0252] Aspect 43: The curable composition of any of Aspects 19 to 42, wherein the (meth)acrylate- functionalized acidic oligomer has a glass transition temperature Tgof from 0°C to 60°C,

[0253] Aspect 44: The curable composition of any of Aspects 19 to 43, wherein the (meth)acrylate- functionalized acidic oligomer has a glass transition temperature Tgof from 10° C to 50°C. Aspect 45: The curable composition of any of Aspects 19 to 44, wherein the optionally (meth)acrylate-functionalized acidic acrylic oligomer has a glass transition temperature Tgof from 20°C to 40°C.

[0254] Aspect 46: The curable composition of any of Aspects 19 to 45, wherein the (meth)acrylate- functionalized acidic oligomer is obtained by reacting at least one acid group of an acidic oligomer with an ethylenically unsaturated epoxy compound.

[0255] Aspect 47: The curable composition of Aspect 46, wherein the ethylenically unsaturated epoxy compound is a reaction product of acrylic or methacrylic acid or mixtures thereof with epichlorohydrin.

[0256] Aspect 48: The curable composition of Aspect 46 or 47, wherein the ethylenically unsaturated epoxy compound is a compound selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and any combination thereof.

[0257] Aspect 49. The curable composition of any of Aspects 46 to 48, wherein the ethylenically unsaturated epoxy compound is glycidyl methacrylate.

[0258] Aspect 50: The curable composition of any of Aspects 19 to 49, wherein the (meth)acrylate- functionalized acidic oligomer is obtained by reacting at least one acid group of an acidic oligomer with an ethylenically-unsaturated hydroxy-functional compound.

[0259] Aspect 51 : The curable composition of Aspect 50, wherein the ethylenically- unsaturated hydroxy-functional compound is a compound selected from the group consisting of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, glycerol diacrylate, glycerol dimethacrylate, caprolactone acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, an acrylate of phenyl glycidyl ether, a methacrylate of phenyl glycidyl ether, a (poly)caprolactone acrylate, a (poly)caprolactone methacrylate, and any combination thereof. Aspect 52: The curable composition of Aspects 50 or 51, wherein the ethylenically- unsaturated hydroxy-functional compound is 2-hydroxy ethyl acrylate, 2-hydroxyethyl methacrylate, or a combinations thereof.

[0260] Aspect 53: The curable composition of any of Aspects 19 to 52, wherein the at least one polymerizing monomer and / or oligomer comprises an ethylenically unsaturated compound.

[0261] Aspect 54: The curable composition of any of Aspects 19 to 53, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate- functionalized monomer.

[0262] Aspect 55: The curable composition of any of Aspects 19 to 54, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate- functionalized monomer selected from the group consisting of (meth)acrylate esters of aliphatic mono-alcohols, (meth)acrylate esters of alkoxylated aliphatic mono-alcohols, (meth)acrylate esters of aliphatic polyols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of aromatic ring-containing alcohols, or (meth)acrylate esters of alkoxylated aromatic ring-containing alcohols.

[0263] Aspect 56: The curable composition of any of Aspects 19 to 55, wherein the at least one polymerizing monomer and / or oligomer comprises at least one monomer selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, isobornyl (meth)acrylate, polyethylene glycol dimethacrylates and trimethylolpropane trimethacrylate.

[0264] Aspect 57. The curable composition of any of Aspects 19 to 56, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate monomer containing two or more (meth)acryloyloxy groups per molecule, preferably selected from bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate; polytetramethylene glycol di(meth)acrylate; 1 ,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4- butanediol di(meth)acrylate; 1,5- pentanediol di(meth)acrylate; 1 ,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1 , 10-nonanediol di(meth)acrylate; 1,12- dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-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; trimethylol ethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) 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)acrylate; as well as the alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof.

[0265] Aspect 58: The curable composition of any of Aspects 19 to 57, wherein the at least one polymerizing monomer and / or oligomer comprises at least one a (meth)acrylate- functionalized oligomer.

[0266] Aspect 59: The curable composition of any of Aspects 19 to 58, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate- functionalized oligomer selected from epoxy (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates (including amine- and sulfide-modified derivatives thereof), and combinations thereof.

[0267] Aspect 60: The curable composition of Aspect 58 or 59, wherein the (meth)acrylate- functionalized oligomer is a urethane (meth)acrylates.

[0268] Aspect 61 : The curable composition of Aspect 60, wherein the urethane (meth)acrylate is selected from a urethane (meth)acrylate based on at least one aliphatic and / or aromatic polyol, in particular selected from a polyester polyol, a poly ether polyol a polycarbonate polyol and mixtures thereof, and at least one aliphatic and / or aromatic diisocyanate. Aspect 62: The curable composition of any of Aspects 19 to 61, wherein the at least one initiator is present in a total amount of from 0.05% to 10% by weight, based on the total weight of the curable composition.

[0269] Aspect 63: The curable composition of any of Aspects 19 to 62, wherein the at least one initiator is present in a total amount of from 0.05 to 5% by weight, based on the total weight of the curable composition.

[0270] Aspect 64: The curable composition of any of Aspects 19 to 63, wherein the at least one initiator is present in a total amount of from 0.1% to 2% by weight, based on the total weight of the curable composition.

[0271] Aspect 65: The curable composition of any of Aspects 19 to 64, wherein the at least one initiator is present in a total amount of from 1% to 2% by weight, based on the total weight of the curable composition.

[0272] Aspect 66: The curable composition of any of Aspects 19 to 65, having a viscosity of from 100 to 5,000,000 cps at 25°C.

[0273] Aspect 67: The curable composition of any of Aspects 19 to 66, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 5%.

[0274] Aspect 68: The curable composition of any of Aspects 19 to 67, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 10%

[0275] Aspect 69: The curable composition of any of Aspects 19 to 68, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 15%

[0276] Aspect 70: The curable composition of any of Aspects 19 to 69, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 20%

[0277] Aspect 71 : The curable composition of any of Aspects 19 to 70, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 25% Aspect 72: The curable composition of any of Aspects 19 to 71, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 30%

[0278] Aspect 73: The curable composition of any of Aspects 19 to 72, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 35%

[0279] Aspect 74: The curable composition of any of Aspects 19 to 73, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 40%

[0280] Aspect 75: The curable composition of any of Aspects 19 to 74, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 45%

[0281] Aspect 76: The curable composition of any of Aspects 19 to 75, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 50%

[0282] Aspect 77: The curable composition of any of Aspects 19 to 76, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 55%

[0283] Aspect 78: The curable composition of any of Aspects 19 to 77, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 60%

[0284] Aspect 79: The curable composition of any of Aspects 19 to 78, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 65%

[0285] Aspect 80: The curable composition of any of Aspects 19 to 79, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 70% Aspect 81: The curable composition of any of Aspects 19 to 81, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 75%

[0286] Aspect 82: The curable composition of any of Aspects 19 to 81, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 80%

[0287] Aspect 83: The curable composition of any of Aspects 19 to 82, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 85%

[0288] Aspect 84: The curable composition of any of Aspects 19 to 83, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid group present in a free acid form of at least 90%

[0289] Aspect 85: The curable composition of any of Aspects 19 to 84, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in a free acid form of at least 95%.

[0290] Aspect 86: The curable composition of any of Aspects 19 to 85, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of at least 5%

[0291] Aspect 87: The curable composition of any of Aspects 19 to 86, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of at least 10%

[0292] Aspect 88: The curable composition of any of Aspects 19 to 87, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of at least 15%

[0293] Aspect 89: The curable composition of any of Aspects 19 to 88, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 20% Aspect 90: The curable composition of any of Aspects 19 to 89, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 25%

[0294] Aspect 91 : The curable composition of any of Aspects 19 to 90, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 30%

[0295] Aspect 92: The curable composition of any of Aspects 19 to 91, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 35%

[0296] Aspect 93: The curable composition of any of Aspects 19 to 92, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 40%

[0297] Aspect 94: The curable composition of any of Aspects 19 to 93, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 45%

[0298] Aspect 95: The curable composition of any of Aspects 19 to 94, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 50%

[0299] Aspect 96: The curable composition of any of Aspects 19 to 95, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 55%

[0300] Aspect 97: The curable composition of any of Aspects 19 to 96, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 60%

[0301] Aspect 98: The curable composition of any of Aspects 19 to 97, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 65% Aspect 99: The curable composition of any of Aspects 19 to 98, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 70%

[0302] Aspect 100: The curable composition of any of Aspects 19 to 99, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 75%

[0303] Aspect 101 : The curable composition of any of Aspects 19 to 100, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 80%

[0304] Aspect 102: The curable composition of any of Aspects 19 to 101, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of least 85%

[0305] Aspect 103: The curable composition of any of Aspects 19 to 102, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of such as at least 90%

[0306] Aspect 104: The curable composition of any of Aspects 19 to 103, wherein the (meth)acrylate- functionalized acidic oligomer has a content of acid groups present in an ester form of, such as at least 95%.

[0307] Aspect 105: The curable composition of any of Aspects 19 to 104, wherein the pendant and / or terminal C-C double bond comprises at least one of a (meth)acrylate group, allylic group, vinylic group, or a combination thereof.

[0308] Aspect 106: The curable composition of any of Aspects 19 to 105, wherein the (meth)acrylate- functionalized acidic oligomer has a number average molecular weight of from 500 to 50,000.

[0309] Aspect 107: The curable composition of any of Aspects 19 to 106, wherein the (meth)acrylate- functionalized acidic oligomer has a number average molecular weight of from 800 to 15,000. Aspect 108: The curable composition of any of Aspects 19 to 107, wherein the (meth)acrylate- functionalized acidic oligomer has a number average molecular weight of from 1,000 to 10,000.

[0310] Aspect 109: A coating on a substrate, comprising a photocured product of the curable composition according to any of aspects 19 to 108.

[0311] Aspect 110: A method of forming a coating on a substrate, comprising the steps of: a) placing a curable composition onto a surface of a substrate; and b) exposing the curable composition to ultraviolet or visible light; wherein the curable composition is according to any one of Aspects 19 to 109.

[0312] Aspect 111 : A method according to Aspect 110, wherein the curable composition is placed onto the surface of the substrate and formed into a continuous layer before being photocured.

[0313] Aspect 112: A substrate coated with a cured composition according to the invention.

[0314] Aspect 113: A method for coating a substrate comprising: applying the composition according to the invention to a substrate; and curing the composition.

[0315] Examples

[0316] Example 1

[0317] Experiment 1 consisted of putting 30% PR015008 acidic acrylic (not (meth)acrylate- functionalized) oligomer in a flexographic formulation as shown below:

[0318] Millbase formulation:

[0319] 10% Solsperse 74000 (polymeric dispersant from Lubrizol)

[0320] 35% SR9020 (Propoxylated 3 Glyceryl Triacrylate (Arkema))

[0321] 55% Carbon Black

[0322] Finished ink formulation:

[0323] 35% Millbase formulation 30% (50%PRO 15008 / 50%SR9003B)

[0324] 20% SR9020

[0325] 6% SR9003B (Propoxylated (2) Neopentyl-glycol Diacrylate (Arkema))

[0326] 3% EDB (Ethyl 4-(dimethylamino)benzoate amine synergist for the UV cure (Arkema))

[0327] 3% Irgacure 369 (2-Benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-l (Ciba))

[0328] 2% DBK (dibenzyl ketone photoinitiator)

[0329] 1% ITX (isopropylthioxanthone photo initiator)

[0330] The finished ink has a viscosity -1300 cP at room temperature measured on a Brookfield rheometer. The ink was printed on a PET substrate by a hand proofer with a 7.2 BCM anilox. The samples were cured at different H-bulb 300 W / in2 at 80 ft / min 2 passes.

[0331] The deinking conditions were a 2% NaOH water solution kept at 80-85C and the printed film being exposed in these conditions for 10 minutes. As shown in Figure 1 the printed samples show the results of before and after exposure to the deinking conditions within the 10 min time.

[0332] Example 2

[0333] Clear coat formulation prepared with methacrylate functionalized acidic acrylic oligomer (PRO 14796) with the composition butyl acrylate / methyl methacrylate / acidic acid and 5% glycidyl ether methacrylate was used in the formulation below:

[0334] 3.8% PL460 photoinitiator

[0335] 38.5% (85%SR9020 / l 5%PRO 14796)

[0336] 57.7% Methacrylate functionalized acidic acrylic oligomer

[0337] The deinking conditions were the same as Example 1 and the results of Example 2 are shown in Figure 2. The acid content is lower when functionalized with the methacrylate groups and more material is needed to formulate when considering acid content.

[0338] Example 3 Synthesis of 46% BA / 34% MMA / 20% AA Copolymer:

[0339] (BA = butyl acrylate, MMA = methyl methacrylate, AA = acrylic acid)

[0340] 111.02 g BA (22.21 wt%), 82.06 g MMA (16.41 wt%), 48.27 g AA (9.65 wt%) were combined in a 500 mL round bottom flask. 8.634 g Vazo88 (1.15 wt%) was dissolved in 57.56 g toluene (7.67 wt%) and transferred to a 60 mL syringe. In a 1 liter four-neck round bottom flask equipped with a nitrogen sparge, condenser, stirrer and thermocouple 192.44 g toluene (38.49 wt%) was brought to reflux. Over two and a half hours the monomer and Vazo88 solutions were metered into the toluene. After ten minutes, the solution became cloudy. Once the monomers and Vazo88 were added, the reaction was held for thirty minutes at reflux before 4.32 g Vazo88 (0.58 wt%) in 28.78 g toluene (3.84 wt%) was added over half an hour. The reaction was held at reflux for 5 hours and characterized by GPC and acid titration.

[0341] Mn= 8,503

[0342] Acid Value (“AV”) = 155.89 mg KOH / g

[0343] Synthesis of 46% BA / 34% MMA / 15% AA / 5%AA-GMAAcrylate-functionalized Copolymer:

[0344] (GMA = glycidyl methacrylate)

[0345] To the above reaction, 0.125 g HQ (250 ppm) was added and the nitrogen sparge was switched to a dry air sparge. The temperature of the reaction was reduced to 80°C and 4.93 g GMA (0.035 mol) was added. The reaction proceeded for 5 hours. The polymer was characterized by IR (Fig. 3) and acid titration.

[0346] AV = 132.05 mg KOH / g

[0347] Within this specification, embodiments have been described in a way which enables a clear and concise specification to be written, but it is intended and will be appreciated that embodiments may be variously combined or separated without departing from the invention. For example, it will be appreciated that all preferred features described herein are applicable to all aspects of the invention described herein. In some embodiments, the invention herein can be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the compositions and methods described herein. Additionally, in some embodiments, the invention can be construed as excluding any element or process step not specified herein. Although the invention is illustrated and described herein with reference to specific embodiments, the invention is not intended to be limited to the details shown. Rather, various modifications may be made in the details within the scope and range of equivalents of the claims and without departing from the invention.

Claims

Claims1. A method for recycling a substrate coated with a cured primer, coating, or ink composition, wherein the cured composition is obtained by curing a curable primer, ink, or coating composition comprising: an optionally (meth)acrylate-functionalized acidic oligomer formed by reacting (meth)acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the oligomer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator, the method comprising the steps of: contacting the substrate coated with the cured primer, coating, or ink composition with a recycling solution having a pH sufficient to delaminate the cured primer, coating, or ink composition from the substrate; and retrieving from the recycling solution the substrate substantially free from the cured primer, coating, or ink composition.

2. The method of claim 1 , wherein the substrate comprises a plastic.

3. The method of claim 1 or 2, wherein the substrate comprises polyethylene terephthalate.

4. The method of any of claims 1 to 3, wherein the pH of the recycling solution is greater than or equal to 7, such as greater than 7 and less than 13, such as greater than 7 and less than 12, such as greater than 7 and less than 11, such as greater than 7 and less than 10, such as greater than 7 and less than 9.

5. The method of any of claims 1 to 4, wherein when the pH of the recycling solution corresponds to a 2% NaOH solution and delamination occurs within 1 minute to 60 minutes, preferably within 10 minutes of exposure at a solution temperature of 25°C to 85°C.

6. A curable primer, ink, or coating composition comprising: a (meth)acrylate-functionalized acidic oligomer formed by reacting (meth)acrylic acid and / or maleic and / or itaconic anhydride and at least one ethylenically unsaturated co-monomer, the oligomer comprising at least one pendant and / or terminal acid group and at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

7. The curable composition of claim 6, wherein the at least one ethylenically unsaturated co-monomer comprises at least one polymerizable C-C double bond, preferably a monomer selected from the group consisting of acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, more preferably selected from acrylate, methacrylate, allyl and vinyl, more preferably selected from acrylate and methacrylate, more preferably selected from a (meth)acrylate, preferably selected from 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)acry late esters of alkoxylated (e.g., ethoxylated and / or propoxylated) aromatic alcohols (such as alkoxylated phenols); and caprolactone mono(meth)acrylates; more preferably selected from methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; t-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-hy dr oxy ethyl (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; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2- phenoxyethyl (meth)acrylate; 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; hydroxyl ethyl-butyl curable optionally (meth)acry late-functionalized acidic acrylic oligomers; 3-(2- hydroxyalkyl)oxazolidinone (meth)acrylates; and combinations thereof, and most preferably methyl methacrylate and butyl acrylate.

8. The curable composition of claim 6 or 7, wherein the (meth)acrylate-functionalized acidic oligomer has an acid value of at least 10 mg KOH / g copolymer, preferably at least 11 mg KOH / g copolymer, more preferably at least 12 mg KOH / g copolymer, more preferably at least 13 mg KOH / g copolymer, and most preferably at least 13.5 mg KOH / g copolymer.

9. The curable composition of any of claims 6 to 8, wherein the (meth)acrylate- functionalized acrylic oligomer has an acid content of at least 1.8 x 10-4 mol acid / g copolymer, preferably at least 2.0 x 10-4 mol acid / g copolymer, more preferably at least 2.2 x 10-4 mol acid / g copolymer, more preferably at least 2.4 x 10-4 mol acid / g copolymer, more preferably at least 2.5 x 10-4 mol acid / g copolymer, more preferably at least between 2.4 x 10- 4 and 9.5 x 10-4 mol acid / g copolymer, such as between 2.5 x 10-4 and 9.25 x 10-4 mol acid / g copolymer, such as between 3.0 x 10-4 and 9 x 10-4 mol acid / g copolymer, such as between 3.5 x 10-4 and 8.5 x 10-4 mol acid / g oligomer.

10. The curable composition of any of claims 6 to 9, wherein the (meth)acry late- functionalized acidic acrylic oligomer has a glass transition temperature Tgof from -20 C to80 C, preferably from -10 C to 70 C, more preferably from 0 C to 60 C, more preferably from 10 C to 50 C, most preferably from 20 C to 40 C.

11. The curable composition of any of claims 6 to 10, wherein the (meth)acry late- functionalized acidic oligomer is obtained by reacting at least one acid group of an acidic oligomer with an ethylenically unsaturated epoxy compound, preferably a reaction product of acrylic or methacrylic acid or mixtures thereof with epichlorohydrin, preferably a compound selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and any combination thereof, most preferably glycidyl methacrylate.

12. The curable composition of any of claims 6 to 11, wherein the (meth)acry late- functionalized acidic oligomer is obtained by reacting at least one acid group of an acidic oligomer with an ethylenically unsaturated hydroxy-functional compound, preferably a compound selected from the group consisting of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, glycerol diacrylate, glycerol dimethacrylate, caprolactone acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, an acrylate of phenyl glycidyl ether, a methacrylate of phenyl glycidyl ether, a (poly)caprolactone acrylate, a (poly)caprolactone methacrylate, and any combination thereof, more preferably 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and combinations thereof.

13. The curable composition of any of claims 6 to 12, wherein the at least one polymerizing monomer and / or oligomer comprises an ethylenically unsaturated compound, preferably at least one (meth)acrylate-functionalized monomer, more preferably (meth)acrylate esters of aliphatic mono-alcohols, (meth)acrylate esters of alkoxylated aliphatic mono-alcohols, (meth)acrylate esters of aliphatic polyols, (meth)acrylate esters of alkoxylated aliphatic polyols, (meth)acrylate esters of aromatic ring-containing alcohols, (meth)acrylate esters of alkoxylated aromatic ring-containing alcohols, most preferably at least one monomer selected from the group consisting of hydroxy ethyl methacrylate, hydroxypropyl methacrylate,isobornyl (meth)acrylate, polyethylene glycol dimethacrylates and trimethylolpropane trimethacrylate.

14. The curable composition of any of claims 6 to 13, wherein the at least one polymerizing monomer and / or oligomer comprisesa (meth)acrylate-functionalized oligomer, preferably selected from epoxy (meth)acrylates, polyether (meth)acrylates, urethane(meth)acrylates, polyester (meth)acrylates (including amine- and sulfide-modified derivatives thereof), and combinations thereof, more preferably urethane (meth)acrylates, most preferably urethanes based on aliphatic and / or aromatic polyester polyols, poly ether polyols and polycarbonate polyols and aliphatic and / or aromatic polyester diisocyanates and poly ether diisocyanates capped with (meth)acrylate end-groups.

15. The curable composition of any of claims 6 to 14, wherein the at least one initiator is present in a total amount of from 0.05% to 10%, preferably 0.05 to 5%, more preferably 0.1% to 2%, and most preferably 1% to 2% by weight, based on the total weight of the curable composition.

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