Enhanced removability of nail coatings using acidic copolymers for triggered removal with aqueous based remover

Abstract

Curable compositions which include: an acidic copolymer 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 / 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 durable, impact resistant coatings on nails that can undergo a triggered removal process using a water-based remover.

Description

[0001] ENHANCED REMOVABILITY OF NAIL COATINGS USING ACIDIC COPOLYMERS

[0002] FOR TRIGGERED REMOVAL WITH AQUEOUS BASED REMOVER

[0003] Field of the Invention

[0004] The present invention relates to curable nail coating compositions containing acidic copolymers, nail coatings obtained from the curable compositions based on the acidic copolymers, methods of forming nail coatings from the curable compositions based on the acidic copolymers, articles containing the curable compositions based on the acidic copolymers which include a container with such a curable composition contained therein, kits containing a packaged curable composition for preparing nail coatings therefrom, and methods of removing the cured nail coatings under aqueous soaking conditions.

[0005] Background of the Invention

[0006] 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 nail coatings, this desire manifests itself in developing technologies that would lower energy consumption and permit easy and substantially complete delamination of the nail coatings from the consumer’s nails without the use of solvents that contain volatile organic compounds (VOCs.) Traditional nail gel removers are made up of methyl ethyl ketone (MEK) or acetone and can be harmful to consumers’ skin and nails. In addition, nail technicians who remove enamels are subjected to harsh smells and health detriments associated with exposure to these VOC solvents.

[0007] Curable nail coatings are applied to a consumer’s bare nails to enhance their appearance and protect them from stresses of everyday life. Nail coatings are typically comprised of (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, non-reactive polymers, photoinitiator(s) (included for ultraviolet (UV)-curable nail coatings), and other additives, such as pigments and fillers, to give a 100% solids UV-curable nail formulation. Curable nail coatings other than UV-curable nail coatings are common and include peroxide cure coatings (including two-part acrylic nail coatings). Curable nail coatings (also referred to as enamel) may be applied in four coats - a base coat, two color coats, and a top coat. The base coat serves as an adhesive layer, while the color coat serves as a cosmetic layer. Finally, the top coat provides durability and scratch resistance and helps to prevent removal when a consumer comes in contact with certain chemical or physical stimuli. Once the nail coating is applied and cured under ultraviolet or LED light, the coating forms a durable, cross-linked network that can last up to two weeks. Nevertheless, typical UV-curable nail coatings can be difficult to remove and, in some cases, take up to 20 minutes with a solvent-based remover.

[0008] Typical solvent-based removers can be acetone or non-acetone (methyl ethyl ketone) based. The remover is applied to a cotton pad, which is placed on the surface of each individual finger-nail and wrapped with aluminum foil. The solvent is allowed to penetrate the film to soften the film and allow it to be removed with a cuticle pusher via mechanical disruption. To speed up the removability time, a nail technician may first abrade the surface of the nail polish with a coarse buffer to break the cross-linked film for faster solvent penetration. This process can harm the nail plate and leave the consumer’s cuticles and nail surface feeling unpleasant and / or damaged.

[0009] 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 US2010008952A, WO2010115564A1. Neither of these processes is conducive for use in nail applications.

[0010] US7635504 pertains to radiation-curable white inkjet ink and, more particularly, to a radiation-curable white inkjet ink comprising a specified titanium dioxide with at least two dispersants. Ink sets containing the white inks are also described.

[0011] US906814882 discloses a blend of acrylic polymers comprising at least one crosslinked acrylic copolymer and at least one linear acrylic copolymer.

[0012] US3576673 discusses a method for stripping paint by employing a hot water bath and a liquid concentrate generally including sodium hydroxide, an accelerator, and a co-solvent.

[0013] US 5830836 discloses compositions and methods for removal of polymeric coatings from nonporous surfaces using acid / peroxide and alkaline solutions. US2014 / 0073710 Al describes compositions for nail coatings, and particularly, to methods of making a polymerizable protective and scratch resistant topcoat layer that can be easily removed.

[0014] US2012 / 0199151 Al relates to radiation curable mammalian nail coating compositions, kits containing these compositions, and methods of their use.

[0015] EP3009122A1 discloses a nail composition including an inert acrylic copolymer removable with an aqueous solution having a pH of from 8 to 11.

[0016] There remains a need for a nail coating that gives excellent adhesion, scratch resistance, abrasion resistance, and high shine, but exhibits a faster and more efficient removal process using a water-based remover that gives off little to no VOCs.

[0017] Summary of the Invention

[0018] In view of the prior art, it would be desirable to develop a system that permits easy and substantially complete delamination of a curable nail coating in the presence of a non- hazardous, low VOC aqueous-based remover, but not in the presence of water alone. Typical nail enamels should have high water resistance so that the polish is not removed during hand washing, swimming, in the shower, or washing dishes. Consequently, it would be advantageous to build a trigger into the backbone of a polymer contained within the UV curable nail enamel that can undergo removal in the presence of a non-hazardous, low VOC aqueous based remover, but not in the presence of water.

[0019] The presence of the acidic copolymers of the invention in nail gels renders such nail gels susceptible to removal from substrates to which they are attached when subjected to recycling conditions (or soaking conditions) described herein. UV curable nail formulations that incorporate an acidic copolymer 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.

[0020] It is common for a technician to use a tool to scrape the coating off of the nail. By permitting at least partial delamination of the coating, the invention permits for easier removal of the coating by providing a starting point to apply the tool. No chipping of the coating by the tool is needed to initiate the removal in accordance with aspects of this invention.

[0021] An aspect of the invention is a curable nail coating composition comprising: an acidic copolymer 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 / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

[0022] The curable compositions of the invention may be formulated to have the following further attributes or properties:

[0023] 1). The new acidic copolymer family can be prepared as is with monomer or in solvent to reduce viscosity.

[0024] 2). The acidic copolymer can be added to any UV curable formulation to trigger removability via the acid group on the backbone. This can extend to other industrial coatings applications, graphic arts, or adhesives.

[0025] 3). The backbone of the acidic copolymer can be varied based on addition of different comonomers in order to increase the hydrophobicity / hydrophilicity of the copolymer or to increase or decrease the glass transition temperature.

[0026] 4). High resistance to removal in water alone, aqueous base needed for removal.

[0027] 5). Low odor.

[0028] 6). Little or no VOCs (traditional nail gel removers are made up of MEK or acetone and can be harmful to the consumers skin and nails).

[0029] 100% solids UV / LED curable coating formulations consume less energy and / or time compared to solvent-based acrylic copolymer coatings, because they don’t require the use of driers or ventilation to remove solvent. The energy required to remove solvent is much higher compared to the energy needed to cure a 100% solids UV / LED curable coating formulation. The 100% solids UV / LED curable coating formulations contain no VOCs compared to traditional curable nail compositions that contain solvent and require no VOCs to remove the cured nail coatings.

[0030] Another aspect is a curable composition according to the invention, wherein at least one acid group of the acidic copolymer is reacted (esterified) with an unsaturated epoxy compound.

[0031] Another aspect is a curable composition according to the invention, wherein at least one acid group of the acidic copolymer is reacted with an ethylenically-unsaturated hydroxyfunctional compound.

[0032] Another aspect is a curable composition according to the invention, wherein the polymerizing monomer comprises an ethylenically unsaturated compound.

[0033] Another aspect is a curable composition according to the invention, wherein the polymerizing oligomer is a (meth)acrylate-functionalized oligomer

[0034] Another aspect of the invention is a coating on a nail, comprising a photocured product of the curable composition according to the invention, comprising an acidic copolymer.

[0035] Another aspect of the invention is a method of forming a coating on a nail, comprising the steps of: a) placing a curable composition according to the invention onto a surface of a nail; and b) exposing the curable composition to ultraviolet or visible light.

[0036] Another aspect of the invention is a packaged article comprising a container and a curable composition according to the invention disposed within the container, wherein the packaged article has a dispensing component capable of dispensing the curable composition from the container.

[0037] Another aspect of the invention is a kit, comprising a packaged article comprising a container and a curable composition according to the invention disposed within the container, at least one application device, and instructions for dispensing, applying and curing the curable composition to provide a nail coating. Another aspect of the invention is a method for removing a cured nail gel from a nail, wherein the method for removing the cured nail gel comprises: immersing a nail coated with a cured composition obtained by curing the curable composition according to the invention with a soaking solution having a pH sufficient to partially or fully delaminate the cured nail gel from the nail; wherein, if the immersing step only partially delaminates the cured nail gel from the nail thereby leaving a portion of the cured nail gel from the nail attached to the nail, then the method further comprises manually removing from the nail the portion of the cured nail gel attached to the nail while the nail is still present in the soaking solution or, alternatively, after the nail is removed from the soaking solution.

[0038] Another aspect of the invention is a nail coated with a cured composition obtained by curing the curable composition according to the invention.

[0039] Another aspect of the invention is a method for coating a nail comprising: applying the composition according to the invention to a nail; and curing the composition.

[0040] Brief Description of the Drawings

[0041] The following figures represent exemplary embodiments of the invention and are not intended to otherwise limit the description of the invention as described herein.

[0042] Figure 1 shows a graph of performance properties of nail coatings containing acidic acrylic copolymers.

[0043] Figure 2 shows photographs of glass panels coated with control and coatings according to the invention after 20 minutes of soaking in water solution (pH = 5).

[0044] Figure 3 shows a photographs of glass panels coated with control and coatings according to the invention after 20 minutes of soaking in a base solution (pH = 9).

[0045] Figure 4 shows a graph of performance properties of nail coatings containing acidic copolymers.

[0046] Figure 5 shows a photograph of glass panels coated with control and coatings according to the invention after 20 minutes of soaking in both water solution (pH = 5) and base solution (pH=9). Figure 6 shows a graph of performance properties of nail coatings containing acidic copolymers.

[0047] Figure 7 shows a photograph of glass panels coated with control and coatings according to the invention after 20 minutes of soaking in both water solution (pH = 5) and base solution (pH=9).

[0048] Figure 8 shows a schematic representation of the triggered removability process of the inventive compositions containing acidic copolymers.

[0049] Figure 9 shows an IR absorbance spectrum of an acidic copolymer of the invention.

[0050] Figure 10 shows an IR absorbance spectrum of an acidic copolymer of the invention.

[0051] Detailed Description of the Invention

[0052] Definitions

[0053] 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 an acidic copolymer 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 copolymer, (2) after the copolymer has been prepared but before formulation with other constituents, (3) after the copolymer has been formulated with other constituents one of which includes a base, and / or (4) in a recycling or soaking solution after the copolymer has been prepared, formulated, and cured. So, an acidic copolymer of the invention having a certain acid content encompasses such a copolymer that has none of the acid groups neutralized or at least some, including a majority and up to 100%, of its acid groups neutralized.

[0054] As used herein, “acid group” refers to any functionality present in the curable acrylate- functionalized acidic acrylic copolymers 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. 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.

[0055] 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.

[0056] As used herein, “C1-C5 group or compound” refers to a group or a compound having from 1 to 5 carbon atoms.

[0057] As used herein, “nail” refers to a human fingernail or toenail and includes artificial extensions present on a fingernail or toenail.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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 nail gel) containing an acidic copolymer 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 curable acidic copolymer-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, such as in the salon industry for nail treatments. In the case where delamination is only partial, manual means (such as a cuticle pusher tool or finger pressure or other known suitable means) may be employed for removal of the portion of the coating / composition that remains attached to the nail surface.

[0063] 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.

[0064] The term “(meth)acrylate” is understood to encompass either or both acrylate and methacrylate moieties or functional groups.

[0065] As used herein throughout the specification and the claims, “acidified” is equivalent to “at least partially acidified” and means that an anhydride functional group has been reacted with a reagent, such as an alcohol, to form at least one ester group and at least one acid group.

[0066] Curable Composition

[0067] The present invention employs a curable composition that comprises, consists essentially of, or consists of: an acidic copolymer 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 / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

[0068] The curable acidic copolymer may be introduced in a composition, such as a nail gel composition. Accordingly, the present invention also relates to a composition (in particular a nail gel composition) comprising the acidic copolymer as defined above.

[0069] Such compositions may be clear or pigmented and are formulated to be usable as one- part systems, that is, formulations capable of being applied to a nail 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 is used to form a cosmetic coating for nails and 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 nail (i.e., a nail plate) and then readily shaped (sculpted) by a nail technician or other operator to a desired configuration on the nail 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 nail coating.

[0070] 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 nail (i.e., a nail plate), followed by exposure to ultraviolet (UV) light or other actinic radiation to photopolymerize the thin layer of curable composition to form a hard, durable, impact-resistant nail coating. In particular, the presence of acidic copolymers help to significantly improve the impact properties of the cured coating (i.e., resistance to chipping, breaking, scuffing) while maintaining good optical transparency and high gloss over time.

[0071] The amount of acidic copolymer included in the curable composition may be varied as may be desired depending upon the type of acidic copolymer used, the attributes targeted in the cured nail coating, and the types of polymerizing organic substances used, among possibly other factors.

[0072] 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 acidic copolymer, 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 acidic copolymer, 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 acidic copolymer based on the total weight of the curable composition.

[0073] 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 acidic copolymer 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 acidic copolymer 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 acidic copolymer of the invention based on the total weight of the composition.

[0074] In accordance with certain embodiments, the curable composition may comprise 1 to 200, 5 to 100, or 15 to 70 parts by weight of the acidic copolymer per 100 parts by weight of the total weight of polymerizing organic substances (e.g., the total weight of polymerizing monomer + polymerizing oligomer).

[0075] Acidic Copolymer

[0076] The curable nail coating composition of the invention comprises an acidic copolymer. As used herein an acidic copolymer is a copolymer 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.

[0077] The acidic copolymer used in the curable nail coating composition of the invention is formed by reacting at least one acid monomer and at least one ethylenically unsaturated comonomer. As used herein, an acid monomer is an ethylenically unsaturated monomer bearing an acid group. The acid group may be as defined above.

[0078] The acid monomer is preferably selected from (meth)acrylic acid, maleic anhydride, itaconic anhydride and mixtures thereof.

[0079] The acidic copolymer may be an acidic acrylic copolymer. As used herein, as acidic acrylic copolymer is a copolymer 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.

[0080] The acidic copolymer may be an ethylenically unsaturated acidic copolymer. As used herein, an ethylenically unsaturated acidic copolymer is an acidic copolymer comprising at least one radiation curable pendant and / or terminal C-C double bond.

[0081] The acidic copolymer may be an acrylate-functionalized acidic copolymer. As used herein, an acrylate-functionalized acidic copolymer is an acidic copolymer comprising at least one pendant and / or terminal (meth)acrylate group.

[0082] The acidic copolymer may be an ethylenically unsaturated acidic acrylic copolymer. As used herein, an ethylenically unsaturated acidic acrylic copolymer is an acidic acrylic copolymer comprising at least one radiation curable pendant and / or terminal C-C double bond.

[0083] The acidic copolymer may be an acrylate-functionalized acidic acrylic copolymer. As used herein, an acrylate-functionalized acidic acrylic copolymer is an acidic acrylic copolymer comprising at least one pendant and / or terminal (meth)acrylate group.

[0084] According to some embodiments, acidic copolymer 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 copolymer (preferably an acidic acrylic copolymer) . Said acidic copolymer may then be reacted with an ethylenically unsaturated epoxy-functional compound (preferably an epoxy-functional (meth)acrylate), wherein at least one acid group of the acidic copolymer is esterified to form an ethylenically unsaturated acidic copolymer (preferably an acrylate-functionalized acidic acrylic copolymer). 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 copolymer (preferably an acidic acrylic copolymer). Said copolymer may also be referred to as an anhydride copolymer as it comprises anhydride groups. Said acidic copolymer 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 an ethylenically unsaturated acidic copolymer (preferably an acrylate-fun ctionalized acidic acrylic copolymer).

[0085] 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 copolymer (preferably an acidic acrylic copolymer). At least one acid group of said acidic copolymer may then be reacted with an ethylenically unsaturated epoxy-functional compound (preferably an epoxy-functional (meth)acrylate) and / or the ring of at least one anhydride group of the acidic copolymer may then be reacted with an ethylenically-unsaturated hydroxyfunctional compound (preferably an hydroxy-functional (meth)acrylate) to form an ethylenically unsaturated acidic copolymer (preferably an acrylate-functionalized acidic acrylic copolymer).

[0086] 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.

[0087] 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. 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.

[0088] 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).

[0089] 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.

[0090] The (meth)acrylate monomer may have 1 to 6 (meth)acrylate groups, in particular 1 to 3 (meth)acrylate groups.

[0091] 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.

[0092] In one embodiment, the (meth)acrylate monomer comprises a mono(meth)acrylate monomer.

[0093] 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.

[0094] The following compounds are specific examples of mono(meth)acrylate monomers suitable for use in the preparation of the acidic copolymer: 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.

[0095] 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.

[0096] In one embodiment, the (meth)acrylate monomer may comprise a minor amount of a (meth)acrylate monomer containing two or more (meth)acrylate groups per molecule.

[0097] 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.

[0098] 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.

[0099] In a preferred embodiment, the acidic copolymer 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.

[0100] In another preferred embodiment, the anhydride copolymer 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.

[0101] In another preferred embodiment, the anhydride copolymer 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.

[0102] According to some embodiments, the acidic copolymer may be an ethylenically unsaturated acidic copolymer, preferably an acrylate-functionalized acidic copolymer, more preferably an acrylate-functionalized acidic acrylic copolymer. Said copolymer may be conveniently prepared by reacting an acidic copolymer (preferably an acidic acrylic copolymer) comprising at least one acid group with one or more ethylenically unsaturated epoxy-functionalized compounds (preferably an epoxy-functionalized (meth)acrylate). Preferably, at least one acid group of an acidic copolymer (preferably an acidic acrylic copolymer) is esterified with an ethylenically unsaturated epoxy-functionalized compound (preferably an epoxy-functionalized (meth)acrylate) to form an ethylenically unsaturated acidic copolymer (preferably an acrylate-functionalized acidic copolymer, more preferably an acrylate-functionalized acidic acrylic copolymer). Preferably, the ethylenically unsaturated epoxy-functionalized 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.

[0103] According to some embodiments, the ethylenically unsaturated acidic copolymer (preferably the acrylate-functionalized acidic copolymer, more preferably the acrylate- functionalized acidic acrylic copolymer) may be conveniently prepared by reacting an acidic copolymer (preferably an acidic acrylic copolymer) 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 an acidic copolymer (preferably an acidic acrylic copolymer) is esterified with an unsaturated hydroxyl-functional compound (preferably a hydroxyl-functionalized (meth)acrylate) to form an ethylenically unsaturated acidic copolymer (preferably an acrylate-functionalized acidic copolymer, more preferably an acrylate-functionalized acidic acrylic copolymer). Preferably, the ethylenically unsaturated hydroxyl-functional compound is a hydroxylfunctionalized (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.

[0104] In a preferred embodiment, the ethylenically unsaturated 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 hydroxy ethyl acrylate or a caprolactone-extended hydroxyfunctional alcohol.

[0105] Other examples of ethylenically unsaturated hydroxy-functional compounds are palmitoleyl alcohol (cis-9-hexadecen-l-ol), erucyl alcohol (cis-13-docosen-l-ol),

[0106] According to some embodiments, the acidic copolymer (preferably the acidic acrylic copolymer) may be conveniently prepared by reacting an acidic copolymer (preferably an acidic acrylic copolymer) comprising at least one anhydride group with one or more saturated hydroxyl-functional compounds. Preferably, at least one anhydride group of an acidic copolymer (preferably an acidic acrylic copolymer) is esterified with a saturated hydroxyl- functional compound to form an acidic copolymer (preferably an acidic acrylic copolymer).

[0107] 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. According to some embodiments, the saturated hydroxy-functional compound may be derived from a fatty 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-heptacosanoll- octacosanol, 1-nonacosanol, myricyl alcohol, 1 -triacontanol, 1 -dotriacontanol, or geddyl alcohol (1-tetratriacontanol). Mixtures of any two or more of these are contemplated. In some embodiments, the saturated 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 fatty alcohols such as 12 molar ethoxylated tridecyl alcohol.

[0108] Other non-limiting examples of saturated hydroxy-functional compounds include fatty 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. Fatty alcohol oxyalkylates may also comprise polyglycerolated fatty 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.

[0109] Preferred structures and embodiments

[0110] In a preferred embodiment, the acidic copolymer is an acidic acrylic copolymer 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

[0111] 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.

[0112] 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.

[0113] In another preferred embodiment, the acidic copolymer is an acrylate-functionalized acidic acrylic copolymer 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

[0114] Ri and R2 are as defined above for the copolymer of formula (A). Said copolymer of formula (B) may be obtained by reacting part of the acid groups of the copolymer of formula (A) with glycidyl (meth)acrylate.

[0115] In another preferred embodiment, the acidic copolymer is an acrylate-functionalized acidic acrylic copolymer according to the following formula (C): 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,

[0116] L is an organic linker, and

[0117] Ri and R2 are as defined above for the copolymer of formula (A).

[0118] 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]-,

[0119] Said copolymer of formula (C) may be obtained by reacting part of the acid groups of the copolymer of formula (A) with a hydroxyl-functional (meth)acrylate.

[0120] In another preferred embodiment, the acidic copolymer is an acidic acrylic copolymer 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

[0121] 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.

[0122] Preferably, R? 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.

[0123] In another preferred embodiment, the acidic copolymer is an acrylate-functionalized acidic acrylic copolymer according to the following formula (E):

[0124] 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,

[0125] L is an organic linker, and

[0126] R? and R4 are as defined above for the copolymer of formula (D).

[0127] 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 copolymer of formula (E) may be obtained by reacting at least part of the anhydride groups of the copolymer of formula (D) with a hydroxyl-functional (meth)acrylate.

[0128] In another preferred embodiment, the acidic copolymer is an acidic acrylic copolymer 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

[0129] 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.

[0130] 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.

[0131] In another preferred embodiment, the acidic copolymer is an acrylate-functionalized acidic acrylic copolymer according to the following formula (G):

[0132] 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

[0133] Rs and Re are as defined above for the copolymer of formula (F).

[0134] 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]-,

[0135] Said copolymer of formula (G) may be obtained by reacting at least part of the anhydride groups of the copolymer of formula (F) with a hydroxyl-functional (meth)acrylate.

[0136] Acid Value, Acid Content, Ts, and Molecular weight

[0137] The acidic copolymer 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 copolymer 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 copolymer will depend on the desired delamination time based on certain conditions (temperature and pH) of the recycling / soakingsolution 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. acidic copolymer 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.

[0138] The acidic copolymer may have a glass transition temperature Tgof from -60°C to 80°C, preferably from -40°C to 70°C, more preferably from -20°C to 60°C, more preferably from 0°C to 50°C, most preferably from 20°C to 40°C.

[0139] The acidic copolymer may have a content of acid groups present in a free acid form of at least 5%, 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%.

[0140] The acidic copolymer may have a content of acid groups present in an ester form of at least 5%, 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%.

[0141] The acidic copolymer may have a number average molecular weight of from 500 to 100,000, preferably from 5,000 to 60,000, more preferably 10,000 to 40,000.

[0142] In view of their acid content, the acidic copolymer 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 acidic copolymer is soluble in water at 25°C.

[0143] Polymerizing Monomer and / or Oligomer

[0144] The curable compositions utilized in the present invention comprise at least one polymerizing monomer and / or oligomer. The at least one polymerizing monomer and / or oligomer is distinct from the acidic copolymer. 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 chain-growth and ringopening polymerization mechanisms, such as ethylenically and ethylenically 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 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.

[0145] 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.

[0146] 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.

[0147] 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 monomers may advantageously function as a reactive diluent and reduce the viscosity of the composition.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] In certain embodiments, the at least one polymerizing monomer and / or oligomer comprises 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.

[0152] 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).

[0153] 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.

[0154] 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.

[0155] 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

[0156] 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.

[0157] 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. 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).

[0158] 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.

[0159] 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.

[0160] Examples of suitable epoxy (meth)acrylates include the reaction products of acrylic or methacrylic acid or mixtures thereof with glycidyl ethers or esters.

[0161] 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.

[0162] 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.

[0163] In various embodiments, the urethane (meth)acrylates may be prepared by reacting at least one aliphatic and / or aromatic poly isocyanate (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.

[0164] 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.

[0165] 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.

[0166] 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, 1 alkoxylated (e.g., ethoxylated, propoxylated) glyceryl tri(meth)acrylates, and tris (2- hydroxyethyl) isocyanurate tri(meth)acrylates, and combinations thereof.

[0167] 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.

[0168] 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).

[0169] 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 acidic copolymer(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).

[0170] Initiator

[0171] 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 oliogomeric 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. Preferably, the photoinitiator or combination of photoinitiators should be active at the wavelength(s) of the ultraviolet light emitted by lamps commonly or conventionally found in nail salons.

[0172] 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, 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.

[0173] 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.

[0174] 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, 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.

[0175] 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.

[0176] 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.

[0177] (Meth)acrylic Polymers

[0178] 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.

[0179] The presence of (meth)acrylic polymer in the curable composition can help to facilitate the dispersion and stabilization of the acidic copolymer, 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 acidic copolymer 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 acidic copolymer in a matrix has no agglomerates after the acidic copolymer 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 acidic copolymer and a polymerizing organic substance may possess or exhibit a better dispersion of the acidic copolymer than an analogous composition not comprising the (meth)acrylic polymer. Further, a liquid curable composition comprising a (meth)acrylic polymer, an acidic copolymer and a polymerizing organic substance may be less viscous than an analogous composition not comprising the (meth)acrylic polymer.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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).

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] Other

[0198] 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, 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 acidic copolymers and polymerizing monomers and / or oligomers already mentioned), waxes or other various additives, including any of the additives conventionally utilized in the nail coating art.

[0199] 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. 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, l,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.

[0200] 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. 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.

[0201] 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.

[0202] 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 nail of a subject.

[0203] 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 nail 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.

[0204] Suitable solvents are any solvents that will dissolve part or all of the components of 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.

[0205] 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.

[0206] 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.

[0207] Formulation of the Curable

[0208] The relative weight proportions of the acidic copolymer, 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 acidic copolymer (preferably the acrylate- functionalized acidic acrylic copolymer), 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 acidic copolymer, 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 acidic copolymer, 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 acidic copolymer, the at least one polymerizing monomer and / or oligomer, and the at least one initiator).

[0209] 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.

[0210] In certain embodiments of the invention, the curable composition is a liquid at 25°C. 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.

[0211] 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.

[0212] 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 mL samples using a CPE-52Z cone. The viscosity at 25°C could, for example, be at least 100 cps or at least 500 cps.

[0213] 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 nail surface and then sculpted (i.e., a builder gel, sculpting gel, or nail 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 nail 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.

[0214] 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 nail 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 shapable) and does not run. An operator, such as a nail 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 nail surface, until the curable composition is cured by exposure to actinic radiation (e.g., UV light).

[0215] Use of the Curable Nail The curable compositions utilized in the present invention are photocured (i.e., cured by exposure to actinic radiation such as light, in particular visible or UV light). However, such photocuring is not conducted until after the curable composition is applied to a nail surface and, in certain embodiments, shaped into a desired configuration. For example, a method of forming a cosmetic nail coating comprises the steps of placing the above-described curable composition onto a nail of a subject, optionally shaping the curable composition, and exposing the curable composition to UV light.

[0216] The placement of a portion (such as a bead) of the curable composition may be directly performed by the operator (which may be a technician or the individual whose nails are being coated) directly by squeezing it from a tube container or pushing it from a syringe with a plunger on to the nail or an application tool. Alternatively, the application of the curable composition may be completed with the help of an application tool such as an acrylic or gel brush, pusher and / or a spatula or other such tool conventionally used for applying nail coating products.

[0217] After the placement of the bead of the photopolymerizable composition onto the nail, the operator may work the curable composition to move it into a desired location and form it into a desired shape with or without the use of a nail form. A nail mold could also be used, wherein a portion of the curable composition (preferably in the form of a high viscosity liquid or gel) is applied to a surface of the nail mold, the applied portion of curable composition is shaped within the nail mold, the nail mold containing the shaped portion of curable composition is applied to a nail of a subject (the surface having the shaped portion of the curable composition being brought into contact with the surface of the nail), the curable composition being cured by exposure to actinic radiation to provide a cured nail coating, and the nail mold then separated from the cured nail coating.

[0218] Although in one embodiment only a single portion of a curable composition is applied to an individual nail prior to a photocuring step, it is also possible in other embodiments of the invention for a plurality of curable composition portions to be applied. For example, a portion of a first curable composition may be applied and shaped followed by a portion of a second curable composition (which may be pigmented or colored differently from the first curable composition or which may differ compositionally in other ways) with the second curable composition portion being shaped prior to both portions being photocured to provide the cured nail coating.

[0219] After the curable composition is applied to a nail surface and optionally shaped or formed, the nail having the curable composition disposed thereon is exposed to actinic radiation, such as UV light, under conditions effective to cure the curable composition. A suitable source of UV light may be a UV lamp, such as the UV lamps commonly used in nail salons. Such a UV lamp may operate at any wavelength required to cure the curable composition, such as between 320 nm and 420 nm. The exposure time should be as long enough to achieve curing of the curable composition. This may be 5 seconds to 6 minutes, for example.

[0220] The term "UV lamp" is meant to be interpreted broadly. It refers to any source of electromagnetic radiation that exhibits light in the 320 nm to 420 nm range at sufficient enough strength to cure the curable composition used in the present invention. The term "UV lamp" includes traditional UV lamps that contain fluorescent lamps, such as compact fluorescent light bulbs, that give off UV light in the above-described ranges. The term "UV lamp" also refers to newer sources of light or UV radiation, such as light- emitting diode lamps (commonly referred to as "LED lamps") that emit electromagnetic radiation which includes UV light in the 320 nm to 420 nm range at sufficient enough strength to cure the curable composition. The term "UV lamp" also refers to any other type of source of light that comprises UV light in the 320 nm to 420 nm range at sufficient enough strength to cure the curable composition.

[0221] Following a curing step, the cured nail coating may be subjected to one or more further procedures such as trimming, sanding, buffing, polishing, decorating or the like. It is also possible to form multiple layers of photocured coatings on a nail surface, wherein a first layer of the curable composition is applied to a nail surface, optionally shaped and cured and at least one further layer of the curable composition thereafter applied on top of the first cured layer, optionally shaped and then also cured.

[0222] The above-described curable compositions may be packaged in a suitable container and stored and / or transported prior to use in forming the curable composition into a cured nail coating. The packaged article may thus comprise a container and a curable composition disposed within the container, wherein the packaged article has a dispensing component capable of dispensing the curable composition from the container. Suitable types of containers include tubes, bottles (including jars or pots), and syringes (equipped with plungers). The container may be rigid or flexible; for example, the container may be a flexible tube or bottle which allows a user to squeeze the container to facilitate dispensing of the curable composition through an aperture in the container. The container may be fitted with a releasable closure such as a screw or press-on cap or flap that permits the contents of the container to be sealed for protection or against accidental discharge when not in use. Such a releasable closure may include an application tool such as a brush. It will generally be preferred for the container to be opaque, to enhance the storage stability of the curable composition contained therein. The dispensing component could, for example, be a brush, foam applicator, wick, nozzle, roller, needle or aperture (orifice) or the like. As an example, the dispensing component could be an aperture that is configured to deliver a desired portion, such as a bead, of the curable composition, either directly onto a nail surface or onto an applicator (application device) such as a brush, pusher or spatula which is then used to transfer the portion of curable composition onto the nail surface.

[0223] Also contemplated by the present invention are kits comprised of a packaged article comprising a container and a curable composition disposed within the container, at least one application device, and instructions for dispensing, applying and curing the curable composition to provide a nail coating. The packaged article may have a dispensing component as previously described. The instructions may be provided in the form of an instruction sheet and / or printed on a package which contains the components of the kit.

[0224] Method of Removing

[0225] The invention also relates to a method for removing a cured nail gel from a nail, wherein the method for removing the cured nail gel comprises: immersing a nail coated with a cured composition according to the invention with a soaking solution having a pH sufficient to partially or fully delaminate the cured nail gel from the nail; wherein, if the immersing step only partially delaminates the cured nail gel from the nail thereby leaving a portion of the cured nail gel from the nail attached to the nail, then the method further comprises manually removing from the nail the portion of the cured nail gel attached to the nail while the nail is still present in the soaking solution or, alternatively, after the nail is removed from the soaking solution.

[0226] The soaking solution described herein causes release (delamination) of the cured acidic copolymers 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.

[0227] In an exemplary embodiment, the soaking 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 solution used to effect release (delamination) of the cured acidic copolymers is not particularly limited and may be present in a large stoichiometric excess relative to the cured acidic copolymer.

[0228] In an exemplary embodiment, the pH of the soaking 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 acidic copolymer backbone. 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 acidic acrylic copolymer backbone having a higher number of acid groups.

[0229] 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 nail or an artificial nail (i.e., the human nail or the artificial nail 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 nail 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.

[0230] Suitable bases for inclusion in the 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 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.).

[0231] Ease of delamination is dependent on the ease with which the soaking solution is able to permeate the composition containing the cured acidic copolymer, 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 acidic copolymer of the present invention, the inclusion of the acidic copolymer of the invention in such a composition has been found to make such removability easier.

[0232] 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 nail gel composition containing the cured acidic copolymer from the substrate to which the nail gel composition is attached: Upon exposure of the coated substrate to a 5% sodium bicarbonate (NaHCCh) solution at 25°C to 40°C, complete delamination of the coating from the substrate occurs. Utilizing the acidic copolymer 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 acidic copolymer of the invention) and in other formulations, utilizing the acidic copolymer of the invention increases the extent of delamination under such conditions compared to a similar formulation that does not contain the acidic copolymer of the present invention.

[0233] Aspects of the Invention

[0234] Certain, non-limiting aspects of the invention may be summarized as follows:

[0235] Aspect 1 : A curable nail coating composition comprising: an acidic copolymer 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 / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

[0236] Aspect 2: The curable composition of Aspect 1, wherein the acidic copolymer is an acidic acrylic copolymer.

[0237] Aspect 3: The curable composition of Aspect 1 or 2, wherein the acidic copolymer is an ethylenically unsaturated acidic acrylic copolymer comprising at least one radiation curable pendant and / or terminal C-C double bond.

[0238] Aspect 4: The curable composition of any of Aspects 1 to 3, wherein the acidic copolymer is an acrylate-functionalized acidic acrylic copolymer comprising at least one pendant and / or terminal (meth)acrylate group.

[0239] Aspect 5: The curable composition of any of Aspects 1 to 4, wherein the at least one ethylenically unsaturated co-monomer comprises at least one polymerizable C-C double bond.

[0240] Aspect 6: The curable composition of any of Aspects 1 to 5, 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.

[0241] Aspect 7: The curable composition of any of Aspects 1 to 6, wherein the at least one ethylenically unsaturated co-monomer is selected from the groups consisting of acrylate, methacrylate, allyl, vinyl, and combinations thereof.

[0242] Aspect 8: The curable composition of any of Aspects 1 to 7, 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

[0243] Aspect 9: The curable composition of any of Aspects 1 to 8, 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. Aspect 10: The curable composition of any of Aspects 1 to 9, wherein the at least one ethylenically unsaturated co-monomer is methyl methacrylate, butyl acrylate, or a combination thereof.

[0244] Aspect 11 : The curable composition of any of Aspects 1 to 10, wherein the acidic copolymer 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.

[0245] Aspect 12: The curable composition of any of Aspects 1 to 11, wherein the acidic copolymer has an acid content of at least 1.8 x 10-4 mol 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

[0246] Aspect 13: The curable composition of any of Aspects 1 to 12, wherein the acidic copolymer has a glass transition temperature Tgof from -60°C to 80°C, preferably from -40°C to 70°C, more preferably from -20°C to 60°C, more preferably from 0°C to 50°C, most preferably from 20°C to 40°C.

[0247] Aspect 14: The curable composition of any of Aspects 1 to 13, wherein at least one acid group of the acidic copolymer is reacted with an ethylenically unsaturated epoxy compound.

[0248] Aspect 15: The curable composition of Aspect 14, wherein the ethylenically unsaturated epoxy compound is a reaction product of acrylic or methacrylic acid or mixtures thereof with epichlorohydrin.

[0249] Aspect 16: The curable composition 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, preferably glycidyl methacrylate. Aspect 17: The curable composition of any of Aspects 1 to 16, wherein at least one acid group of the acidic copolymer is reacted with an ethylenically-unsaturated hydroxyfunctional compound.

[0250] Aspect 18: The curable composition of Aspect 17, 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, preferably 2-hydroxyethyl acrylate, 2- hydroxy ethyl methacrylate, or a combination thereof.

[0251] Aspect 19: The curable composition of any of Aspects 1 to 18, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate-functionalized monomer.

[0252] Aspect 20: The curable composition of any of Aspects 1 to 19, 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 monoalcohols, (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.

[0253] Aspect 21 : The curable composition of any of Aspects 1 to 20, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate-functionalized monomer selected from the group consisting of hydroxy ethyl methacrylate, hydroxypropyl methacrylate, isobornyl (meth)acrylate, polyethylene glycol dimethacrylates and trimethylolpropane trimethacrylate. Aspect 22: The curable composition of any of Aspects 1 to 21, wherein the at least one polymerizing monomer and / or oligomer comprises at least one acid functionalized monofunctional (meth)acrylate.

[0254] Aspect 23. The curable composition of Aspect 22, wherein the at least one acid functionalized monofunctional (meth)acrylate is selected from 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, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxy ethyl methacrylate succinate or hydroxy ethyl acrylate succinate), a hydroxylated (meth)acrylate functionalized with a phosphate group (such as, for example, hydroxy ethyl acrylate phosphate, hydroxy ethyl 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 selected from hydroxy ethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxy ethyl methacrylate succinate, hydroxy ethyl acrylate succinate, hydroxyethyl acrylate phosphate, and hydroxyethyl methacrylate phosphate and combinations thereof.

[0255] Aspect 24. The curable composition of Aspect 22 or 23, wherein the curable composition comprises 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.

[0256] Aspect 25: The curable composition of any of Aspects 1 to 24, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acry late-functionalized oligomer.

[0257] Aspect 26: The curable composition of any of Aspects 1 to 25, 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.

[0258] Aspect 27: The curable composition of Aspects 25 or 26, wherein the at least one (meth)acrylate- functionalized oligomer is a urethane (meth)acrylate. Aspect 28: The curable composition of Aspect 27, 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.

[0259] Aspect 29. The curable composition of any of Aspects 1 to 28, wherein the curable composition comprises from 1 to 80 weight % or from 5 to 60 weight % of (meth)acrylate- functionalized oligomer, based on the total weight of polymerizing monomers and / or oligomers in the curable composition

[0260] Aspect 30: The curable composition of any of Aspects 1 to 29, wherein the at least one initiator is present in a total amount of from 0.05% to 10% by weight, 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.

[0261] Aspect 31: The curable composition of any of Aspects 1 to 30, having a viscosity of from 100 to 5,000,000 cps at 25°C.

[0262] Aspect 32: The curable composition of any of Aspects 1 to 31, wherein the acidic copolymer has a content of acid groups present in a free acid form of at least 5%, preferably at least 10%, more preferably at least 15%, more preferably at least 20%, more preferably at least 25%, more preferably at least 30%, more preferably at least 35%, more preferably at least

[0263] 40%, more preferably at least 45%, more preferably at least 50%, more preferably at least

[0264] 55%, more preferably at least 60%, more preferably at least 65%, more preferably at least

[0265] 70%, more preferably at least 75%, more preferably at least 80%, more preferably at least

[0266] 85%, more preferably at least 90%, more preferably at least 95%.

[0267] Aspect 33: The curable composition of any of Aspects 1 to 32, wherein the acidic copolymer has a content of acid groups present in an ester form of at least 5%, preferably at least 10%, more preferably at least 15%, more preferably at least 20%, more preferably at least

[0268] 25%, more preferably at least 30%, more preferably at least 35%, more preferably at least

[0269] 40%, more preferably at least 45%, more preferably at least 50%, more preferably at least

[0270] 55%, more preferably at least 60%, more preferably at least 65%, more preferably at least 70%, more preferably at least 75%, more preferably at least 80%, more preferably at least 85%, more preferably at least 90%, more preferably at least 95%.

[0271] Aspect 34: The curable composition of any of Aspects 3 to 33, 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.

[0272] Aspect 35: The curable composition of any of Aspects 1 to 34, wherein the acidic copolymer has a number average molecular weight of from 500 to 50,000, preferably from 800 to 15,000, more preferably froml,000 to 10,000.

[0273] Aspect 36: A coating on a nail, comprising a photocured product of the curable composition according to any of Aspects 1 to 35.

[0274] Aspect 37: A method of forming a coating on a nail, comprising the steps of: a) placing a curable composition according to any of Aspects 1 to 35 onto a surface of a nail; and b) exposing the curable composition to ultraviolet or visible light.

[0275] Aspect 38: A method according to Aspect 37, wherein the curable composition is placed onto the surface of the nail and formed into a continuous layer before being photocured.

[0276] Aspect 39: A packaged article comprising a container and a curable composition disposed within the container, wherein the packaged article has a dispensing component capable of dispensing the curable composition from the container and the curable composition is as defined in any of Aspects 1 to 35.

[0277] Aspect 40: The packaged article of Aspect 39, wherein the container is a tube, bottle or syringe.

[0278] Aspect 41 : The packaged article of Aspect 39 or 40, wherein the dispensing component is a brush, foam applicator, wick, nozzle, roller, needle or aperture.

[0279] Aspect 42: A kit, comprising a packaged article comprising a container and a curable composition disposed within the container, at least one application device, and instructions for dispensing, applying and curing the curable composition to provide a nail coating, wherein the curable composition is as defined in any of Aspects 1 to 35. Aspect 43: The kit of Aspect 42, wherein the at least one application device includes at least one of a brush, pusher or spatula.

[0280] Aspect 44: A method for removing a cured nail gel from a nail, wherein the method for removing the cured nail gel comprises: immersing a nail coated with a cured composition obtained by curing the curable composition according to any of Aspects 1 to 35 with a soaking solution having a pH sufficient to partially or fully delaminate the cured nail gel from the nail; wherein, if the immersing step only partially delaminates the cured nail gel from the nail thereby leaving a portion of the cured nail gel from the nail attached to the nail, then the method further comprises manually removing from the nail the portion of the cured nail gel attached to the nail while the nail is still present in the soaking solution or, alternatively, after the nail is removed from the soaking solution.

[0281] Aspect 45: The method of Aspect 44, wherein the pH of the soaking solution is >7.

[0282] Aspect 46: The method of Aspect 44 or 45, wherein the pH of the soaking solution is greater than 7.

[0283] Aspect 47: The method of any of Aspects 44 to 46, wherein the pH of the soaking solution is greater than 7 and less than 11, preferably greater than 7 and less than 10, more preferably greater than 7 and less than 9, more preferably greater than 7 and less than 8.

[0284] Aspect 48: The method of any of Aspects 44 to 47, wherein the soaking solution comprises a base selected from an inorganic base or an organic base.

[0285] Aspect 49: The method of Aspect 48, wherein the base is an inorganic base selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0286] Aspect 50: A nail coated with a cured composition obtained by curing the curable composition according to any of Aspects 1 to 35.

[0287] Aspect 51 : A method for coating a nail comprising: applying the composition according to any of Aspects 1 to 35 to a nail; and curing the composition. Examples

[0288] Synthesis Data

[0289] Acidic Acrylic Copolymer I: 49 mol% BA / 21 mol% MMA / 29 mol% AA

[0290] (BA = butyl acrylate, MMA = methyl methacrylate, AA = acrylic acid)

[0291] This acid functionalized acrylic copolymer was synthesized in toluene to give high MW (>10000 g / mol) polymer that had a workable viscosity with which to utilize in further studies.

[0292] A mixture of 57.99 g BA, 19.33 g MMA, and 19.33 g AA was prepared in a 250 mL round bottom flask and sparged with nitrogen for 10 minutes. 2.23 g Vazo88 was dissolved in 14 g toluene and transferred to a 20 mL syringe. In a 500 mL four-neck round bottom flask equipped with a nitrogen sparge, condenser, stirrer and thermocouple 74.56 g toluene was brought to reflux. Over two and a half hours the monomer and Vazo88 solutions above were metered into the reactor through Kel-F tubing using a peristaltic pump and a syringe pump, respectively. After ten minutes, the solution became cloudy. Once the monomers and Vazo88 were added, the reaction was held for thirty minutes at reflux before 1.1 g Vazo88 in 7.44 g toluene was added over half an hour. The reaction was held at reflux for 5 hours and characterized by GPC and acid titration.

[0293] Mn= 6,467

[0294] Mw = 18,999

[0295] PDI = 2.93

[0296] Acid Value (“AV”) = 155.89 mg KOH / g

[0297] Acidic Acrylic Copolymer II: 46 mol% BA / 34 mol% MMA / 23 mol% AA / 5 mol%AA- GMA

[0298] (BA = butyl acrylate, MMA = methyl methacrylate, AA = acrylic acid, AA-GMA = AA reacted with glycidyl methacrylate)

[0299] This acidic copolymer was synthesized in two-steps:

[0300] Step 1 : Preparation of acidic copolymer 46 mol% BA / 34 mol% MMA / 28 mol% AA

[0301] 111.02 g BA , 82.06 g MMA , 48.27 g AA 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.

[0302] Mn= 8,503

[0303] AV = 155.89 mg KOH / g

[0304] Step 2 : Functionalization of the acidic copolymer with glycidyl methacrylate

[0305] To the reaction obtained in Step 1, 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. 9) and acid titration.

[0306] AV = 132.05 mg KOH / g

[0307] Formulation

[0308] UV-curable nail gel compositions were made by adding the components detailed in Figures 1, 4 and 6 (amounts are in wt% based on the total weight of the composition) to a Flacktek polypropylene cup and mixing until homogenous at 2000 rpm for 2 minutes using a Flacktek® DAC 400.2 VAC high speed mixer. Compositions according to the invention and Comparative compositions comprise a urethane methacrylate oligomer (CN 1968), a monofunctional monomer (SRI 70 or CN147MA), a photoinitiator (TPO-L) along with the acid functionalized acrylic copolymer I or II in toluene. Control formulations contained CN1968, SRI 70 or CN147MA and TPO-L without any acid functionalized acrylic copolymer.

[0309] Testing Procedures

[0310] Nail Gel Compositions

[0311] To prepare UV nail gel coatings compositions, a sample was pipetted onto a clean glass panel (4-inch X 4-inch). A ByK 3 Mil draw down bar was used to draw down the sample onto the glass. The coating was placed in an oven (60C) to remove residual toluene from the coating. The coating was cured in a Gelish 18G LED nail lamp for 60 seconds. Once cured, initial color, haze and yellowness of the films were measured using a Hunter Lab ColorQuest XE spectrometer with glass as reference. Other performance properties such as surface tack, Konig hardness, and adhesion were also measured. Konig hardness of the coatings formulations were measured using ASTM D4366. Surface tack was determined qualitatively by assigning a number from the arbitrary scale between 0-5 (0 for no tack / 5 for very tacky). Cross hatch adhesion was measured using ASTM D3359.

[0312] Removability Testing

[0313] A sample of UV curable nail gel composition was pipetted onto a clean glass panel (4 inch X 4 inch). A ByK 3 Mil draw down bar was used to draw down the sample onto the glass. The coating was placed in an oven (60C) to remove residual toluene from the coating. The coating was placed in a Gelish 18G LED nail lamp for 60 seconds to cure. Once cured, the glass panel was allowed to equilibrate at room temperature overnight. The glass panel with coating was immersed in either water or 5% sodium bicarbonate solution for an allotted period of time (5 min, 10 min, 15 min, 20 min) at 40°C. The coated panels were removed and swellability / removability was measured visually.

[0314] Results and Discussion

[0315] Acid functionalized acrylic copolymers have been gaining traction in the adhesives industry due to their preferable properties over traditionally used polymers like epoxies and urethanes. Not only are acid functionalized acrylic copolymers easier to process than their competitors, due to their low molecular weight and dispersibility in different solvents or acrylate monomer, but they also have better adhesion to a majority of materials, including metals. There is very limited literature on the use of acrylic copolymers in 100% solids UV curable nail gel coatings. Nail coatings can benefit from the addition of an acrylic copolymer because the acrylic copolymer acts as a secondary film former that can improve the removability of the coating if utilized in conjunction with a remover that can trigger delamination.

[0316] Moreover, acrylic copolymers have their own intrinsic properties that make them good candidates for use as film formers in UV curable nail enamel because their glass transition temperature can be varied based on application and acrylic copolymers have better adhesion compared to other materials, which will allow the consumer to have good wear properties.

[0317] The backbone of an acid functionalized acrylic copolymer consists of a high glass transition temperature (Tg) monomer, such as acrylic acid (AA), copolymerized with a low Tg monomer, such as butyl acrylate (BA), in various ratios. Additional high Tg or low Tg monomers can be co-polymerized in to the backbone. The ratio of high Tg monomer to low Tg monomer is important since it influences the overall Tg of the resultant acrylic copolymer; more AA results in a higher Tg while more BA results in a lower Tg. The acid functionalized acrylic copolymers can be synthesized in either solvent (50% solids) or acrylate monomer (40- 60% solids) to give an acid functionalized acrylic copolymer in solvent or a 100% solids acid functionalized acrylic copolymer in acrylate monomer.

[0318] An acrylic copolymer was synthesized that contains acid functionality (see Scheme 1) along the backbone that can undergo triggered removability with a weak base solution. This acid functionalized acrylic copolymer was synthesized in toluene to give high MW (>10000 g / mol) polymer that had a workable viscosity with which to utilize in our further studies.

[0319] R = H, CH3

[0320] Scheme 1 : Acid functionalized acrylic copolymer I

[0321] As detailed in Figure 1 (amounts are in wt% based on the total weight of the composition), UV curable nail formulations were made containing a 14% by wt., 25% by wt. and 33% by wt. loading of the acidic acrylic copolymer I along with the urethane methacrylate oligomer (CN1968), a hydroxyl-functionalized methacrylate monomer (SRI 70) and a photoinitiator (TPO-L) (Comparative 1-3). These formulations were compared to a control that did not contain the acid functionalized acrylic copolymer I (Control 1). Furthermore, to determine whether an acid-functionalized methacrylate monomer, CN147MA, would help contribute to the removability of the nail gel coating, CN147MA was added along with the urethane methacrylate oligomer (CN1968), and a photoinitiator (TPO-L) (Control 2, Inventive 1-3).

[0322] The formulations were mixed, drawn down on glass, and cured for 60s using a Gelish 18G LED nail lamp. The performance properties were tested and are shown in Figure 1.

[0323] The performance properties of the nail gel compositions containing the acid functionalized acrylic copolymer I were very similar to the performance of the control formulations. The initial color (APHA, 10 mm), haze, and yellowness (b*) of the films after photocuring for both the inventive and control samples were very low. Konig hardness was similar for all samples before and after IPA wipe. The only differences shown were in the adhesion of the samples containing the acid functionalized acrylic copolymer I. Adhesion of the formulations increased from 32% (Control 2) to 100% and 96% for the formulations containing 25% by wt. and 33% by wt. of the acid functionalized acrylic copolymer I. The comparative examples showed very low adhesion on glass, presumably due to the high loading of SRI 70 in the formulations.

[0324] In order to determine whether the inventive compositions offered a triggered removal process, the control samples and comparative samples were compared to the inventive compositions for removability in water solution (pH = 5) and sodium bicarbonate solution (pH = 9). Figure 2 shows a picture of each of the glass panels with the nail coating applied after 20 minutes of soaking in water solution (pH = 5) and base solution (pH = 9) at 40°C (Figure 2). For Control 1, Comparative 1, Comparative 2 and Comparative 3, the coating remains intact and adhered to the glass panel after 20 minutes of soaking in water solution and base solution. While formulations containing acidic groups can be very hydrophilic, the nail compositions wouldn't remove from the glass panels when submerged in water for up to 20 minutes at 40°C.

[0325] Removability of the nail compositions for Control 2, Inventive 1 , Inventive 2 and Inventive 3 was tested in water solution (pH = 5) and sodium bicarbonate base solution (pH = 9) for 20 minutes at 40°C. Figure 3 shows a picture of each of the glass panels with the nail coating applied after 20 minutes of soaking in water solution and base solution. The coatings remain intact and adhered to the glass panel after 20 minutes of soaking in water solution. However, for the coatings that were soaking in base solution, both the Control 2 composition, which does not contain the acid functionalized acrylic copolymer I, and inventive compositions 1, 2, and 3 (all of which contain the acid functionalized acrylic copolymer), were able to remove after 15 minutes. The solution was able to penetrate the films causing them to wrinkle and bubble up off the substrate due to swelling that is occurring from the interaction between the acid functionalized acrylic copolymer I, CN147MA and the base solution.

[0326] The pictures in Figure 3 show that the acidic acrylic copolymer I could help with the removability of the coating when soaking in base solutions. Control 2 also showed removability of the coating. This is due to the high amount of CN147MA in the formulation. When formulations contain >25% CN147MA alone, the films can be removed in base solution, however, the rheological properties and performance properties of these formulations suffer. The addition of higher amounts of acidic monomer can cause the formulation to have low viscosity, which could lead to difficulty in manicurist application. The addition of the acidic acrylic copolymer gives the formulation a secondary film former which helps with overall wear performance and abrasion resistance.

[0327] Further testing was conducted to determine whether a methacrylate- functionalized acidic acrylic copolymer II could be used in place of the acidic acrylic copolymer I for removal of nail coatings. The pendant acrylate group increased crosslinking density of the system, while still maintaining easy removability. An acrylic copolymer that contains around 5 mol% acrylate functionality and 23 mol% acid functionality (see Scheme 2) along the backbone was synthesized, which can undergo additional crosslinking and triggered removability with a weak base solution. This methacrylate-functionalized acidic acrylic copolymer was synthesized in toluene to give high MW (>10000 g / mol) polymer that had a workable viscosity with which to utilize in our further studies.

[0328] R = H, CH3

[0329] Scheme 2: Methacrylate-functionalized Acidic Acrylic Copolymer II As detailed in Figure 4 (amounts are in wt% based on the total weight of the composition), UV curable nail formulations were made as explained for the previous study. All inventive formulations contained either a 14% by wt., 25% by wt. and 33% by wt. loading of the methacrylate- functionalized acidic acrylic copolymer II along with the urethane methacrylate oligomer (CN1968}, an acid functionalized acrylate monomer (CN147) and a photoinitiator (TPO-L) (Inventive 5-7). These formulations were compared to control formulations that did not contain the methacrylate-functionalized acid acrylic copolymer II (Controls 2-4). The formulations were mixed, drawn down on glass, and cured for 60s using a Gelish 18GLED nail lamp. The performance properties were tested and are shown in Figure 4.

[0330] The performance properties of the nail gel compositions containing the methacrylate- functionalized acidic acrylic copolymer II were very similar to the performance of the previous inventive formulations containing acidic acrylic copolymer I. The initial color (APHA, 10 mm}, haze, and yellowness (b*) of the films after photocuring for both the inventive and control samples were very low. Konig hardness and adhesion was similar for all samples before and after IPA wipe.

[0331] In order to determine whether the inventive compositions offered a triggered removal process, the control samples and comparative samples were compared to the inventive compositions for removability in water solution (pH = 5) and sodium bicarbonate solution (pH = 9) at 40°C. Figure 5 shows a picture of each of the glass panels with the nail coating applied after 20 minutes of soaking in water solution (pH = 5) and base solution (pH = 9) at 40°C. For all nail compositions, the coating remains intact and adhered to the glass panel after 20 minutes of soaking in water solution. This is important because formulations containing the methacrylate-functionalized acidic acrylic copolymer II and CN147 can be very hydrophilic.

[0332] For Inventive 5-7, the coatings were able to remove after 15 minutes in base solution (pH = 9), while the control formulations remained adhered to glass after 20 minutes.

[0333] Next, it was determined how much acid functionalized monomer, CN147, was needed in order to remove the nail compositions. As seen above, all Inventive formulations contained between 22- 30% CN147, which helped with removability. The amount of CN147 was lowered to see if the inventive compositions could still remove in base solution. Figure 6 shows the amounts used to make the nail gel compositions (amounts are in wt% based on the total weight of the composition). The performance properties of the nail gel compositions containing the methacrylate- functionalized acidic acrylic copolymer II were very similar to the performance of the previous inventive formulations. The initial color (APHA, 10 mm), haze, and yellowness (b*) of the films after photocuring for both the inventive and control samples were very low. Konig hardness was similar for all samples before and after IPA wipe. Adhesion was much higher (100%) for samples containing the methacrylate- functionalized acidic acrylic copolymer II along with lower loadings of CN147.

[0334] The new inventive compositions (Inventive 8-13) with the methacrylate-functionalized acidic acrylic copolymer II with lower loadings of CN147 were tested for removability in water solution (pH = 5) and sodium bicarbonate solution (pH = 9) at 40°C. Figure 7 shows a picture of each of the glass panels with the nail coating applied after 20 minutes of soaking in water solution (pH = 5) and base solution (pH = 9) at 40°C. For all nail compositions, the coating remains intact and adhered to the glass panel after 20 minutes of soaking in water solution. However, for Inventive 11-13, that coatings were able to remove after 20 minutes in base solution (pH = 9), while the control formulations remained adhered to glass after 20 minutes. These results show that by lowering the amount of CN147, a removable coating after 20 minutes can still be achieved, compared to previous systems that take 15 minutes to remove but have a higher loading of CN147. The optimum range of CN147 would be between 18-22 wt% for these systems.

[0335] The higher loading of CN147 can lead to less crosslinking density, which can cause the control samples to remove prematurely especially if loadings of CN147 are in excess of 25%. The addition of the methacrylate-functionalized acidic acrylic copolymer II gives a higher crosslink density to the formulation, resulting in easily removable coatings without sacrificing the removability of the control formulations.

[0336] 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 functional groups present in the film that can allow for enough swelling. It was seen that 14% by wt., 25% by wt. and 33% by wt. of the acidic copolymer did not allow for triggered removability after 20 minutes soaking in base solution. However, once we add the CN147MA, which has additional acid functionality, it allowed for better solvent penetration through the film and had much better swellability after 20 minutes soaking in base solution. Without being bound by theory, we hypothesize that the crosslinked matrix has a low enough crosslinking density that the sodium bicarbonate solution is able to penetrate the film. Due to the acidic nature of the acrylic copolymer, the acid groups will deprotonate and the salt is formed (Na+O ). This causes the matrix to swell, which triggers the delamination process (Figure 8). The removal time is important because it allows the aqueous based remover to penetrate the film and the temperature of the solution during the removal process can help with softening of the film to increase penetration and mobility.

[0337] 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.

[0338] 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.

[0339] 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 curable nail coating composition comprising: an acidic copolymer 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 / or a salt and / or an anhydride thereof; at least one polymerizing monomer and / or oligomer; and at least one initiator.

2. The curable composition of claim 1 , wherein the acidic copolymer is an acidic acrylic copolymer.

3. The curable composition of claim 1 or 2, wherein the acidic copolymer is an ethylenically unsaturated acidic acrylic copolymer comprising at least one radiation curable pendant and / or terminal C-C double bond.

4. The curable composition of any of claims 1 to 3, wherein the acidic copolymer is an acrylate-functionalized acidic acrylic copolymer comprising at least one pendant and / or terminal (meth)acrylate group.

5. The curable composition of any of claims 1 to 4, 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.

6. The curable composition of any of claims 1 to 5, wherein the at least one ethylenically unsaturated co-monomer is methyl methacrylate, butyl acrylate, or a combination thereof.

7. The curable composition of any of claims 1 to 6, wherein the acidic copolymer 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.

8. The curable composition of any of claims 1 to 7, wherein the acidic copolymer has an acid content of at least 1.8 x 10-4 mol acid / g copolymer, preferably at least 2.0 x 1 O'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 copolymer9. The curable composition of any of claims 1 to 8, wherein the acidic copolymer has a glass transition temperature Tgof from -60°C to 80°C, preferably from -40°C to 70°C, more preferably from -20°C to 60°C, more preferably from 0°C to 50°C, most preferably from 20°C to 40°C.

10. The curable composition of any of claims 1 to 9, wherein at least one acid group of the acidic copolymer is reacted with an ethylenically unsaturated epoxy compound.

11. The curable composition of claim 10, wherein the ethylenically unsaturated epoxy compound is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, and any combination thereof, preferably glycidyl methacrylate.

12. The curable composition of any of claims 1 to 11, wherein at least one acid group of the acidic copolymer is reacted with an ethylenically-unsaturated hydroxy-functional compound.

13. The curable composition of claim 12, 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, preferably 2-hydroxyethyl acrylate, 2- hydroxy ethyl methacrylate, or a combination thereof.

14. The curable composition of any of claims 1 to 13, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acrylate-functionalized monomer.

15. The curable composition of any of claims 1 to 14, wherein the at least one polymerizing monomer and / or oligomer comprises at least one acid functionalized monofunctional (meth)acrylate.

16. The curable composition of claim 15, wherein the at least one acid functionalized monofunctional (meth)acrylate is selected from 2-carboxy ethyl acrylate, 2-carboxyethyl 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, hydroxyethyl acrylate maleate, hydroxyethyl methacrylate succinate or hydroxyethyl acrylate succinate), a hydroxylated (meth)acrylate functionalized with a phosphate group (such as, for example, hydroxy ethyl acrylate phosphate, hydroxy ethyl 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 selectedfrom hydroxyethyl methacrylate maleate, hydroxy ethyl acrylate maleate, hydroxyethyl methacrylate succinate, hydroxyethyl acrylate succinate, hydroxyethyl acrylate phosphate, and hydroxy ethyl methacrylate phosphate and combinations thereof.

17. The curable composition of claim 15 or 16, wherein the curable composition comprises 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.

18. The curable composition of any of claims 1 to 17, wherein the at least one polymerizing monomer and / or oligomer comprises at least one (meth)acry late-functionalized oligomer.

19. The curable composition of any of claims 1 to 18, 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.

20. The curable composition of claim 18 or 19, wherein the at least one (meth)acrylate- functionalized oligomer is a urethane (meth)acrylate.

21. The curable composition of any of claims 1 to 20, wherein the curable composition comprises from 1 to 80 weight % or from 5 to 60 weight % of (meth)acrylate- functionalized oligomer, based on the total weight of polymerizing monomers and / or oligomers in the curable composition22. The curable composition of any of claims 1 to 21, wherein the acidic copolymer has a number average molecular weight of from 500 to 50,000, preferably from 800 to 15,000, more preferably froml,000 to 10,000.

23. A coating on a nail, comprising a photocured product of the curable composition according to any of claims 1 to 22.

24. A method of forming a coating on a nail, comprising the steps of: a) placing a curable composition according to any of claims 1 to 22 onto a surface of a nail; andb) exposing the curable composition to ultraviolet or visible light.

25. A method according to claim 24, wherein the curable composition is placed onto the surface of the nail and formed into a continuous layer before being photocured.

26. A packaged article comprising a container and a curable composition disposed within the container, wherein the packaged article has a dispensing component capable of dispensing the curable composition from the container and the curable composition is as defined in any of claims 1 to 22.

27. A kit, comprising a packaged article comprising a container and a curable composition disposed within the container, at least one application device, and instructions for dispensing, applying and curing the curable composition to provide a nail coating, wherein the curable composition is as defined in any of claims 1 to 22.

28. A method for removing a cured nail gel from a nail, wherein the method for removing the cured nail gel comprises: immersing a nail coated with a cured composition obtained by curing the curable composition according to any of claims 1 to 22 with a soaking solution having a pH sufficient to partially or fully delaminate the cured nail gel from the nail; wherein, if the immersing step only partially delaminates the cured nail gel from the nail thereby leaving a portion of the cured nail gel from the nail attached to the nail, then the method further comprises manually removing from the nail the portion of the cured nail gel attached to the nail while the nail is still present in the soaking solution or, alternatively, after the nail is removed from the soaking solution.

29. The method of claim 28, wherein the pH of the soaking solution is greater than 7 and less than 11, preferably greater than 7 and less than 10, more preferably greater than 7 and less than 9, more preferably greater than 7 and less than 8.

30. The method of claim 28 or 29, wherein the soaking solution comprises a base selected from an inorganic base or an organic base., preferably an inorganic base selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

31. A nail coated with a cured composition obtained by curing the curable composition according to any of claims 1 to 22.

32. A method for coating a nail comprising: applying the composition according to any of claims 1 to 22 to a nail; and curing the composition.

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