Curable compositions comprising an acidified anhydride oligomer useful in deinking processes

Abstract

A acidified anhydride oligomer is formed by reacting an anhydride monomer, a monomer comprising at least one polymerizable group, and a hydroxyl-functional compound, wherein the acidified anhydride oligomer has an acid value of at least 10 mg KOH / g oligomer, with some of the acid groups optionally neutralized. A cured ink or coating made from the oligomer, along with at least one of a (meth)acrylate monomer or a (meth)acrylate oligomer and, optionally, at least one additive, can be easily removed from the substrate by treatment with aqueous base, thus allowing for recycling the substrate cleaned of any ink or coating. Nail gel compositions including the oligomer can also be more easily removed from nails.

Description

[0001] CURABLE COMPOSITIONS COMPRISING AN ACIDIFIED ANHYDRIDE OLIGOMER USEFUL IN DEINKING PROCESSES

[0002] Field of the Invention

[0003] The invention relates to acidified anhydride oligomers, curable compositions based on the acidified anhydride oligomers, methods of using the acidified anhydride oligomers, and compositions and articles containing the acidified anhydride oligomers in cured form, especially for use in inks and coatings, to allow for easy removal of the cured inks and coatings once subjected to recycling, soaking, or delaminating conditions.

[0004] Background of the Invention

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

[0006] Another area of coatings that could benefit from improved ease of separation from its underlying substrate is the curable nail enamel segment. 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 cure coatings).

[0007] 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. In order 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 to allow for faster solvent penetration. This process can harm the nail plate and may leave the consumer’s cuticles and nail surface feeling unpleasant and / or damaged.

[0008] Most literature that describes the removal of a paint coating or a pressure sensitive adhesive / laminating adhesive label uses either low vapor pressure or caustic-type solvent, both of which are non-biodegradable, harmful to the environment, and potentially harmful to the person using the solvent. See US2010008952A, W02010115564A1. Neither of these removal processes are conducive for use in nail applications.

[0009] Summary of the Invention

[0010] In view of the prior art, it would be desirable to develop a system which permits easy and substantially complete delamination of a curable coating or ink from a substrate, without the need for a sacrificial primer layer. Furthermore, it would be advantageous to build a trigger into the backbone of a UV curable coating (including a sacrificial primer layer), ink, or a 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 alone. In many applications, it would be undesirable for a coating or ink to delaminate from its substrate in the presence of water alone. Also, 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 desirable to provide a polish that can be removed on demand via an aqueous-based remover that can interact with the trigger in the backbone of the nail enamel and prompt the enamel’s removal from the substrate.

[0011] The presence of the acidified anhydride oligomers (also referred to as acidic or acidfunctional anhydride oligomers) of the invention in inks, coatings (including primer coatings) and nail gels render such inks, coatings and nail gels susceptible to removal from substrates to which they are attached when subjected to recycling conditions (or soaking conditions) described herein.

[0012] An aspect of the invention is an acidified anhydride oligomer formed by reacting at least the following:

[0013] (A) an anhydride; and

[0014] (B) a monomer having at least one polymerizable group, to form an anhydride oligomer; and reacting the anhydride oligomer with:

[0015] (C) a hydroxy-functional compound, to form the acidified anhydride oligomer, wherein the acidified anhydride oligomer has an acid value of at least about 10 mg

[0016] KOH / g oligomer.

[0017] Another aspect of the invention is a curable composition comprising the acidified anhydride oligomer of the invention a dispersing agent; and optionally, at least one pigment.

[0018] Another aspect of the invention is a cured composition obtained by curing the curable composition according to the invention.

[0019] Another aspect of the invention is a substrate coated with a cured composition according to the invention.

[0020] Another aspect of the invention is a nail coated with a cured composition according to the invention.

[0021] Another aspect of the invention is a method for making an article comprising: applying the composition according to the invention to a substrate; and curing the composition, wherein the substrate is metal, glass, plastic, composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, stone and composites thereof.

[0022] Another aspect of the invention is a method for recycling a substrate coated with a cured composition according to the invention, wherein the method for recycling comprises: contacting the substrate coated with the cured composition with a recycling solution having a pH sufficient to delaminate the cured composition from the substrate; and retrieving from the recycling solution the substrate free from the cured composition. 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.

[0023] 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 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.

[0024] 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 for the technician a starting point for applying the tool. No chipping of the coating by the tool to initiate the removal is needed in accordance with this method of the invention.

[0025] Brief Description of the Drawings

[0026] The following figures represent exemplary embodiments of the invention and are not intended to otherwise limit the description of the invention as described herein.

[0027] Figure 1 shows photographs of PET films coated with a flexographic formulation according to the invention before and after 10 minutes of soaking in 2% NaOH solution at SO- 85 C.

[0028] Figure 2 shows photographs of PET films coated with a flexographic formulation according to the invention before and after 10 minutes of soaking in 2% NaOH solution at SO- 85 C.

[0029] Figure 3 shows photographs of PET films coated with an inkjet formulation according to the invention before and after [insert conditions for Example 3],

[0030] Detailed Description of the Invention Definitions

[0031] As used herein “acid content” is calculated as the total acid content of a compound (in moles) before any neutralization of the acid groups has taken place (i.e., assuming 100% of the acid groups are in their free acid (non-salt) form) per gram of the compound. When determining the acid content of a acidified anhydride oligomer that has at least some of its acid groups neutralized, it is presumed for purposes of this calculation that 100% of the acid groups exist in their free acid, regardless of whether the base(s) is / are provided: (1) during the preparation of the oligomer, (2) after the oligomer has been prepared but before formulation with other constituents, (3) after the oligomer has been formulated with other constituents one of which includes a base, and / or (4) in a recycling or soaking solution after the oligomer has been prepared, formulated, and cured. So, an acidified anhydride oligomer of the invention having a certain acid content encompasses such an oligomer that has none of the acid groups neutralized or at least some, including a majority and up to 100%, of its acid groups neutralized.

[0032] As used herein, “acid group” refers to any functionality present in the acidified anhydride oligomers of the invention that contains an acidic hydrogen atom and primarily refers to carboxylic acid groups, but also includes functional groups such as sulfonic acids, phosphoric acids, phosphonic acids and phosphinic acids as well as (cyclic) anhydrides.

[0033] 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.

[0034] 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. As used herein, “C1-C5 group or compound” refers to a group or a compound having from 1 to 5 carbon atoms.

[0035] As used here, the term “organic moiety” is used to signify a moiety based on carbon atoms, hydrogen atoms and optionally one or more heteroatoms independently selected from oxygen, nitrogen and sulfur.

[0036] As used herein, “nail” refers to a human fingernail or toenail and includes artificial extensions present on a fingernail or toenail.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 acidified anhydride oligomer of the invention results in the release or delamination of the cured composition from a substrate to which the composition is attached. While the release or delamination of the acidified anhydride oligomer-containing composition from the substrate to which it is attached is typically complete and total, a partial release or partial delamination of the composition may also represent an acceptable or satisfactory outcome, depending on the particular technical area involved, 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.

[0042] 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.

[0043] As used herein, number average molecular weight refers to number average molecular weight as determined by gel permeation chromatography using tetrahydrofuran as solvent and polystyrene calibration standards.

[0044] The term “(meth)acrylate” is understood to encompass either or both acrylate moieties and methacrylate functional groups.

[0045] 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.

[0046] Acidified Anhydride copolymer

[0047] The curable composition comprises an acidified anhydride oligomer. As used herein, the term “acidified anhydride oligomer” may be defined as a oligomer comprising anhydride groups that have been at least partly opened by reacting with a hydroxylated compound.

[0048] The acidified anhydride oligomer may be an acidified anhydride (co)polymer. Throughout the present application, the terms “oligomer” and “(co)polymer” may be used indifferently.

[0049] The acidified anhydride oligomer comprises at least one pendant and / or terminal acid group and / or a salt and / or an anhydride thereof. The acidified anhydride oligomer may further optionally comprise at least one radiation curable pendant and / or terminal C-C double bond. Preferably, the acidified anhydride oligomer comprises at least one radiation curable pendant and / or terminal C-C double bond. When the acidified anhydride oligomer comprises at least one radiation curable pendant and / or terminal C-C double bond, the acidified anhydride oligomer may be referred to as a curable acidified anhydride oligomer.

[0050] According to some embodiments, the acidified anhydride oligomer may be conveniently prepared by reacting one or more hydroxyl-functional reactants with an anhydride oligomer, i.e. an oligomer or (co)polymer comprising anhydride functionalized units along its backbone. The anhydride oligomer may be a copolymer of maleic anhydride and at least one co-monomer. The at least one co-monomer may be selected from the group consisting of styrene, ethylene, vinyl methyl ether, octadecene and mixtures thereof, preferably styrene.

[0051] The hydroxyl-functional reactant may be a compound bearing at least one hydroxyl group and optionally at least one (meth)acrylate group.

[0052] Preferably, the hydroxyl-functional reactant may be a compound bearing at least one hydroxyl group and at least one (meth)acrylate group. More preferably, the hydroxyl- functional reactant may be 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, 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. Even more preferably, the hydroxyl-functional reactant may be selected from the group consisting of hydroxyalkyl (meth)acrylates and alkoxy lated hydroxyalkyl (meth)acrylates.

[0053] The hydroxy-functional reactant may be a compound bearing at least one hydroxyl group and no (meth)acrylate group. In particular, the hydroxy-functional reactant may be selected from the group consisting of a C8-C26 aliphatic alcohol, an ethoxylate of a C8-C26 aliphatic alcohol or an alkyl ether of a polyalkylene glycol, and mixtures thereof, preferably an ethoxylate of a C8-C26 aliphatic alcohol. The hydroxy-functional reactant may be a mixture of a compound bearing at least one hydroxyl group and at least one (meth)acrylate group and a compound bearing at least one hydroxyl group and no (meth)acrylate group.

[0054] According to some embodiments, the anhydride oligomer may comprise a styrenemaleic anhydride (SMA) copolymer. Said SMA copolymer may be functionalized with (meth)acrylate functionality.

[0055] According to another embodiment, the anhydride oligomer may comprise a poly(ethylene-maleic anhydride) copolymer. Said poly(ethylene-maleic anhydride) copolymer may be functionalized with (meth)acrylate functionality.

[0056] According to another embodiment, the anhydride oligomer may comprise a copolymer of maleic anhydride and vinyl methyl ether. Said copolymer of maleic anhydride and vinyl methyl ether may be functionalized with (meth)acrylate functionality.

[0057] According to yet another embodiment, the anhydride oligomer may comprise a copolymer of maleic anhydride and octadecene. Said copolymer of maleic anhydride and octadecene may be functionalized with (meth)acrylate functionality.

[0058] The (meth)acrylate functionality may be obtained by reacting a hydroxylfunctionalized (meth)acrylate with the anhydride functionality of the anhydride oligomer to produce a (meth)acrylate functionalized polymer, in which the (meth)acrylate functionality is pendant to the polymer backbone, and linked thereto with an ester linkage.

[0059] According to certain embodiments, at least 25-50 molar percent of backbone units in the copolymer, prior to the reaction with one or more hydroxyl functionalized reactants comprise anhydride functionality. For example, from 30%-45%, 35%-50%, 30%-50%, 25%- 40%, 45%-50% by moles of the copolymer, preferably the SMA copolymer, may comprise, prior to a reaction with a hydroxyl functional reactant, maleic anhydride units (i.e. units derived from the polymerization of maleic anhydride). The number average molecular weight of the base backbone (i.e. the copolymer), preferably the base SMA backbone (i.e; the SMA copolymer), prior to being functionalized, may be from 1000 - 50,000 Daltons. The base copolymer, preferably the SMA base polymer, may be a random copolymer or a block copolymer. A random copolymer is preferred. According to some embodiments the molar ratio of styrene or ethylene or vinyl methyl ether or C3-C22 alkenes or other comonomer to maleic anhydride monomers in the base SMA copolymer (or other copolymer) is from 1 : 1 to 4:1, and is preferably about 1 :1. According to certain embodiments, a maleic anhydridestyrene copolymer base resin containing in the backbone an approximate mole ratio of 1.3 moles styrene to 1 mole maleic anhydride having a number average molecular weight (Mn)of about 2000 Daltons may be functionalized with a (meth)acrylate. The base copolymer thus may have 8 moles of anhydride per chain. According to certain embodiments, one mole of this styrene maleic anhydride resin maybe reacted with 2 to 4 moles of a hydroxyl function (meth)acrylate such as 2-hydroxy ethyl acrylate and optionally 1 to 3 moles of hydroxyl functional hydrophilic and / or hydrophobic pendant groups.

[0060] Thus, an acidified anhydride oligomer is provided. The acidified anhydride oligomer may comprise a (co)polymer comprising, consisting of, or consisting essentially of repeating units of structure [A] and repeating units of structure [B] , and repeating units of structure [C], The acidified anhydride oligomer may comprise a (co)polymer comprising, consisting of, or consisting essentially of at least one unit of structure [A], at least one unit of structure [B] and at least one unit of structure [C],

[0061] Structure FA] is: wherein Ri and R3 are the same or different and are H or alkyl. The alkyl groups Ri or R3 are not particularly limited and may comprise, consist of, or consist essentially of, for example, straight chain or branched, saturated or unsaturated hydrocarbons. Non-limiting examples include Ci - Ce hydrocarbons for example.

[0062] R2 and R4 are different and are either an organic moiety bearing at least one (meth)acrylate functional group or H. For example, if not H, R2 or R4 may be derived from 2- hydroxy ethyl acrylate. For example, besides 2-hydroxy ethyl acrylate, R2 or R4 may be derived from hydroxyl propyl acrylate, OH-terminated polycaprolactone including a terminal (meth) acrylate group or other hydroxyl functionalized (meth)acrylates and combinations thereof.

[0063] According to particular embodiments, one of R2 or R4 may be:

[0064] In some embodiments of the invention, R5 may be a divalent alkylene or an oligooxyalkylene or a poly( ester) moiety. According to particular embodiments, Rs may be a poly(ester) moiety comprising caprolactone residues. According to embodiments, Re may be H or CH3. According to certain embodiments Re is H. According to other embodiments, Rs may be an ethylene or oligooxyethylene.

[0065] Structure FBI is: wherein R7 and R9 are the same or different and are H or alkyl, and Rs and Rio are different from each other. Rs and Rio do not comprise (meth)acrylate functionality, and are independently selected from H or the following:

[0066] • (RnO)nRi2, wherein Rn is a divalent alkylene moiety, R12 is a C1-C26 alkyl, and n is an integer of 1 or more. For example R12 may be a Cl alkyl, such that Rs or Rio is a polyalkylene oxide. Such moieties may be derived from hydroxyl terminated polyalkoxy lates such as polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1450, polyethylene glycol 3350, polyethylene glycol 8000, polyethylene glycol 350 methyl ether, polyethylene glycol 550 methyl ether, polytetrahydrofuran, and mixtures thereof. It is understood that the number in the preceding recitation refers to the average molecular weight of each respective moiety. According to some embodiments, Rs or Rio may comprise, consist of, or consist essentially of polyethylene oxide, or polypropylene oxide or poly (ethylene oxide / propylene oxide) blocks or may comprise ethylene oxide / propylene oxide / hydrocarbon blocks.

[0067] • R19, wherein R19 is a C8-C26 branched or straight chained alkyl. For example , in some embodiments, Rs or Rio 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 -methyl-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), palmitoleyl alcohol (cis-9-hexadecen-l-ol), 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), erucyl alcohol (cis-13-docosen-l- ol), lignoceryl alcohol (1-tetracosanol), cetyl alcohol (1-hexacosanol), 1- heptacosanol, montanyl alcohol, cluytyl alcohol, 1-octacosanol, 1- nonacosanolmyricyl alcohol, 1 -triacontanol, 1 -dotriacontanol, or geddyl alcohol (1- tetratriacontanol). Mixtures of any two or more of these are contemplated.

[0068] • R20 (C=O)OH wherein R20 is a C8-C26 alkyl. For example, Rs or Rio 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.

[0069] According to particular embodiments of the (meth)acrylate-functionalized polymer, Ri, R3, R7, and R9 are each H. According to other embodiments, Rs or Rw may be derived from alkoxylated faty alcohols such as 12 molar ethoxylated tri decyl alcohol, such that Rio or Rs = (RnO)nRi2, and Rn is CH2CH2, R12 is a C13 straight chain saturated alkyl, and n =12.

[0070] Non-limiting examples of Rio or Rs 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 faty 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, Cl l 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, (C16- C18) 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.

[0071] According to particular embodiments of the (meth)acrylate functionalized polymer, Rn may be a divalent ethylene or propylene moiety. In some embodiments, of the (meth)acrylate functionalized polymer, R12 is a C8-C26 straight chain saturated alkyl. In some embodiments of the (meth)acrylate functionalized polymer, n may be an integer of from 3 to 30. For example, n may be 3, 4, 5 ,6 ,7 , 8 ,9 , 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30. According to some embodiments of the (meth)acrylate-functionalized polymer, R19 may be a branched saturated alkyl moiety.

[0072] Structure FC1 is: wherein R43, R14, R15, and Ri6 are the same or different and are independently selected from the group consisting of H and organic moieties. Suitable organic moieties include but are not limited to phenyl groups, methyl groups. According to particular embodiments of the (meth)acrylate- functionalized polymer, R13 may be phenyl, alpha methyl phenyl, methyl or methoxy, or ethoxy, or any C2-C20 alkyl, and R14, R15 and Ri6 may each be H. According to particular embodiments, R13, R14, R15, and Ri6 may all be H. For example, the (meth)acrylate functionalized polymer disclosed herein may be derived from methyl vinyl ether co-maleic anhydride polymer, such as Gantrez™ copolymers available from Ashland Chemical. According to certain embodiments the (meth)acrylate functional copolymer provided herein is comprise of a base polymer chain that may be derived from a copolymer of maleic anhydride and styrene or methyl vinyl ether or a C2-C22 alkene. For example, other co-monomers suitable for copolymerization with maleic anhydride, or other anhydride functionalized co-monomer may be selected from ethylene, propylene, butene, pentene, hexene, heptene, octane, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, icosene, henicosene, docosene, styrene, alpha-methyl styrene, methyl vinyl ether, isomers thereof, and mixtures thereof.

[0073] The anhydride oligomer provided is subject to the proviso that structure [C] is different from structure [A] and structure [B], and further, that one or more repeating units of structure [C] are located between at least one of i) two units of structure [A], ii) two units of structure [B] or iii) one unit of structure [A] and one unit of structure [B],

[0074] The acidified anhydride oligomer may be obtained by reacting the anhydride oligomer, preferably a styrene-maleic anhydride co-oligomer, with a compound bearing at least one hydroxyl group and optionally 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, 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. In a preferred embodiment, the hydroxy-functional compound is 2-hydroxyethyl acrylate (HEA) or 2-hydroxyethyl methacrylate (HEMA). Other suitable hydroxy-functional compounds include hydroxyl propyl acrylate, OH-terminated polycaprolactone including a terminal (meth)acrylate group, or other hydroxyl functionalized (meth)acrylates and combinations thereof.

[0075] According to particular embodiments, the hydroxy-functional compound may be derived from hydroxyl terminated polyalkoxylates such as polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1450, polyethylene glycol 3350, polyethylene glycol 8000, polyethylene glycol 350 methyl ether, polyethylene glycol 550 methyl ether, polytetrahydrofuran, and mixtures thereof. According to some embodiments, the 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-methyl-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 -tri decanol, tri decanol, isotridecanol), myristyl alcohol (1 -tetradecanol), pentadecyl alcohol (1 -pentadecanol, pentadecanol), cetyl alcohol (1- hexadecanol), palmitoleyl alcohol (cis-9-hexadecen-l-ol), 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), erucyl alcohol (cis-13-docosen-l-ol), lignoceryl alcohol (1-tetracosanol), cetyl alcohol (1-hexacosanol), 1-heptacosanol, montanyl alcohol, cluytyl alcohol, 1-octacosanol, 1-nonacosanolmyricyl alcohol, 1 -triacontanol, 1- dotriacontanol, or geddyl alcohol (1-tetratriacontanol). Mixtures of any two or more of these are contemplated. In some embodiments, the hydroxy-functional compound may be derived from a long chain carboxylic acid comprising a terminal hydroxyl group. Non-limiting examples of such reactants are C2-C22 carboxylic acid aliphatic alcohols, such as 12 hydroxyl lauric acid. According to particular embodiments, the hydroxy-functional compound may be derived from alkoxylated fatty alcohols such as 12 molar ethoxylated tridecyl alcohol.

[0076] Other non-limiting examples of 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, Cl 1 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, (C16-C18) 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.

[0077] Acid content, solubility and molecular weight

[0078] The acid value of the acidified anhydride oligomers of the invention is at least 10 mg KOH / g oligomer, preferably at least 11 mg KOH / g oligomer, more preferably at least 12 mg KOH / g oligomer, more preferably at least 13 mg KOH / g oligomer, and most preferably at least 13.5 mg KOH / g oligomer. The term ‘acid value’ is determined herein in accordance with ASTM D 974. In other embodiments, the acid value of the acidified anhydride oligomers may be at least 25 mg KOH / g oligomer, preferably at least 50 mg KOH / g oligomer, more preferably at least 75 mg KOH / g oligomer, more preferably at least 100 mg KOH / g oligomer, and most preferably at least 125 mg KOH / g oligomer. Although references are made above to the oligomer in the denominator, if the oligomer is provided as a preblended constituent along with a monomer diluent, the denominator is actually the weight of the preblended constituent (i.e., the weight of the oligomer plus the monomer). The particular acid value of the oligomer will depend on the desired delamination time based on certain conditions (temperature and pH) of the recycling solution and the specifics of the other constituents in the formulation, including the extent of their acid content, and the degree of cross-linking of the formulation.

[0079] The acid content of the acidified anhydride oligomers of the invention is at least 1.8 x 10'4mol acid / g oligomer, preferably at least 2.0 x 10'4mol acid / g oligomer, more preferably at least 2.2 x 10'4mol acid / g oligomer, more preferably at least 2.4 x 10'4mol acid / g oligomer, more preferably at least 2.5 x 10'4mol acid / g oligomer, more preferably at least between 2.4 x 10'4and 9.5 x 10'4mol acid / g oligomer, such as between 2.5 x 10'4and 9.25 x 10'4mol acid / g oligomer, such as between 3.0 x 10'4and 9 x 10'4mol acid / g oligomer, such as between 3.5 x 10'4and 8.5 x 10'4mol acid / g oligomer. In an embodiment, the upper limit of the acid content is not so high that the cured acidified anhydride oligomer undesirably easily delaminates in the presence of water. For example, the acid content may be below 10x1 O'4mol acid / g oligomer. As used herein unless otherwise noted, the acid content refers to the number of moles of acid per gram of acidic (or acid-functional) acidified anhydride oligomers.

[0080] In the acidified anhydride oligomers of the invention, the percent of acid groups present in a free acid form (i.e., fully protonated) can range from 0% (i.e., all of the acid groups are in a neutralized (salt) form) to 100%. In various embodiments, preferably 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% of the acid groups neutralized (i.e., in a salt form). As mentioned above, this extent of neutralization will depend on a number of factors, including the expected recycling or soaking conditions.

[0081] In view of their acid content, the acidified anhydride oligomers of the invention are 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 acidified anhydride oligomer is soluble in water at 25°C. The solubility may be determined at 25°C and 0.101 MPa according to the method described in W02005116635A1.

[0082] The acidified anhydride oligomer may have a number average molecular weight of from 1000 to 75,000 Daltons. For example, the number average molecular weight may be from 1000 to 50,000 Daltons. In a preferred embodiment, the acidified anhydride oligomers of the invention have a number average molecular weight of 500 to 20,000 g / mol, preferably 800 to 10,000 g / mol, more preferably 1,000 to 5,000 g / mol. Alternatively, the acidified anhydride oligomers of the invention may have a number average molecular weight from 500 to 50,000 Daltons, preferably from 800 to 15,000 Daltons, more preferably 1,000 to 10,000 Daltons.

[0083] Preferred structures and embodiments

[0084] In at least one embodiment, the acidified anhydride oligomer comprises an esterified styrene-maleic anhydride (SMA) oligomer having a structure according to Formula I: wherein n, Ri, R2, x, y, and z are as described below.

[0085] The number of repeat units n may be from 2 to about 20, preferably about 8 to about 12. Ri and R2 may be independently hydrogen, an acrylate moiety or a methacrylate moiety. In a preferred embodiment at least one of Ri or R2 is H and at least one of Ri or R2 is an acrylate moiety or a methacrylate moiety. The esterified SMA copolymer may have different molar ratios of styrene (S) / maleic anhydride (MA) co-monomer compositions, such as a molar ratio (x : (y + z)) in the range from about 1 :1 to 3: 1 and more preferably from about 1.4: 1 to 1.6:1. The molecular variables x, y, and z, relate to the molar ratios of S:MA such that x is from 1 to 4, a molar ratio of (x: (y + z)) is in the range from about 1: 1 to 3 : 1 , and the monoesterification molar ratio of (z / (y + z)) ranges from about 1 :4 to 1: 1, more preferably 1 :2 to 1:1.

[0086] Compositions

[0087] The acidified anhydride oligomer may be introduced in a composition, such as an ink composition, a film composition or a coating composition (including a primer coating composition) or a nail gel composition. Accordingly, the present invention also relates to a composition (in particular an ink composition, a film composition, a coating composition or a nail gel composition) comprising the acidified anhydride oligomer as defined above. The composition of the invention may comprise 5 to 100%, 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 acidified anhydride oligomer of the invention based on the total weight of the composition. In particular, the composition may comprise 5 to 50% or 10 to 50% or 15 to 50% or 20 to 50% or 25 to 50% or 30 to 50%, by weight of the acidified anhydride oligomer of the invention based on the total weight of the composition. Alternatively, the composition may comprise 50 to 100% or 55 to 100% or 60 to 100% or 65 to 100% or 70 to 100%, by weight of the acidified anhydride oligomer of the invention based on the total weight of the composition.

[0088] The composition of the invention preferably further comprises at least one ethylenically unsaturated compound other than the acidified anhydride oligomer of the invention.

[0089] As used herein, the term “ethylenically unsaturated compound” 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.

[0090] The composition of the invention may comprise 0 to 95%, in particular 5 to 90%, more particularly 10 to 80%, even more particularly 15 to 75%, more particularly still 20 to 70% by weight of ethylenically unsaturated compound 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 ethylenically unsaturated compound based on the total weight of the composition. Alternatively, the composition may comprise 50 to 99.5% or 55 to 99.5% or 60 to 99.5% or 65 to 99.5% or 70 to 99.5%, by weight of ethylenically unsaturated compound based on the total weight of the composition. These percentages do not include the amount of acidified anhydride oligomer in the composition as it is distinct from the ethylenically unsaturated compound(s).

[0091] According to some preferred embodiments, the ethylenically unsaturated compound may comprise at least one of a (meth)acrylate monomer or a (meth)acrylate oligomer. In particular, the ethylenically unsaturated compound comprises a (meth)acrylate monomer.

[0092] 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 oligomer” means an oligomer 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).

[0093] According to some embodiments, the ethylenically unsaturated compound comprises a (meth)acrylate monomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate monomers.

[0094] 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.

[0095] The (meth)acrylate monomer may have 1 to 6 (meth)acrylate groups, in particular 1 to 3 (meth)acrylate groups.

[0096] 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.

[0097] In one embodiment, the (meth)acrylate monomer comprises a mono(meth)acrylate monomer. The mono(meth)acrylate monomer may advantageously function as a reactive diluent and reduce the viscosity of the composition.

[0098] 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.

[0099] The following compounds are specific examples of mono(meth)acrylate monomers suitable for use in the composition: methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2- ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2- hydroxy ethyl (meth)acrylate; 2- and 3 -hydroxy propyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2- and 3- ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; alkoxylated phenol (meth)acrylates; alkoxylated nonylphenol (meth)acrylates; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecanemethanol (meth)acrylate; tert-butylcyclohexanol (meth)acrylate; trimethylcyclohexanol (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monoethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; ethoxylated lauryl (meth)acrylate; methoxy polyethylene glycol (meth)acrylates; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylates; and combinations thereof. In one embodiment, the (meth)acrylate monomer may comprise a (meth)acrylate monomer containing two or more (meth)acrylate groups per molecule.

[0100] 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.

[0101] 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; (alkoxy lated) neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane- 1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; metallic di(meth)acrylates; modified metallic di(meth)acrylates; (alkoxylated) glyceryl di(meth)acrylate; (alkoxylated) glyceryl tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylol ethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) diacrylate; di(trimethylolpropane) triacrylate; di(trimethylolpropane) tetraacrylate, sorbitol penta(meth)acrylate; di(pentaerythritol) tetraacrylate; di(pentaerythritol) pentaacrylate; di(pentaerythritol) hexa(meth)acrylate; tris (2-hydroxyethyl) isocyanurate tri(meth)acrylate; as well as the alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and combinations thereof. The composition of the invention may comprise 0 to 95%, in particular 5 to 90%, more particularly 10 to 80%, even more particularly 15 to 75%, more particularly still 20 to 70% by weight of (meth)acrylate monomer 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 (meth)acrylate monomer based on the total weight of the composition. Alternatively, the composition may comprise 50 to 99.5% or 55 to 99.5% or 60 to 99.5% or 65 to 99.5% or 70 to 99.5%, by weight of (meth)acrylate monomer based on the total weight of the composition.

[0102] In one embodiment, the ethylenically unsaturated compound comprises a (meth)acrylate oligomer. The ethylenically unsaturated compound may comprise a mixture of (meth)acrylate oligomers.

[0103] The (meth)acrylate oligomer may be selected in order to enhance the flexibility, strength and / or modulus, among other attributes, of a cured polymer prepared using the composition.

[0104] The (meth)acrylate oligomer may have 1 to 18 (meth)acrylate groups, in particular 2 to 6 (meth)acrylate groups, more particularly 2 to 6 acrylate groups.

[0105] The (meth)acrylate oligomer may have a number average molecular weight equal or more than 600 g / mol, in particular 800 to 15,000 g / mol, more particularly 1,000 to 5,000 g / mol.

[0106] In particular, the (meth)acrylate oligomers may be selected from the group consisting of acidified anhydride oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polydiene (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, polyester (meth)acrylate oligomers and mixtures thereof.

[0107] The composition of the invention may comprise 0 to 95%, in particular 5 to 90%, more particularly 10 to 80%, even more particularly 15 to 75%, more particularly still 20 to 70% by weight of (meth)acrylate oligomer 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 (meth)acrylate oligomer based on the total weight of the composition. Alternatively, the composition may comprise 50 to 99.5% or 55 to 99.5% or 60 to 99.5% or 65 to 99.5% or 70 to 99.5%, by weight of (meth)acrylate oligomer based on the total weight of the composition.

[0108] The composition further comprises a dispersing agent. The dispersing agent is distinct from an acidified anhydride copolymer.

[0109] The dispersing agent may be used to disperse an insoluble material such as a pigment or filler in the curable composition.

[0110] The dispersing agent may comprise a polymeric dispersing agent, a surfactant and mixtures thereof.

[0111] In a preferred embodiment, the dispersing agent comprises a polymeric dispersing agent selected from polyesters, polyurethanes, polyalkylene imines, (meth)acrylic (co)polymers, ethylene oxide-propylene oxide copolymers (EO-PO copolymers) or combinations thereof, in particular polyesters, polyurethanes, polyalkylene imines or combinations thereof.

[0112] One type of preferred dispersing agents are block copolymers of ethylene oxide (EO) and propylene oxide (PO).

[0113] Another type of preferred dispersing agents are (meth)acrylic copolymers based on two, three, four, five or even more monomers, wherein at least one of the monomers is a (meth)acrylic monomer. The properties of polymeric dispersing agents depend on both the nature of the monomers and their distribution in the polymer. Copolymeric dispersing agents preferably have the following polymer compositions: random copolymer (e.g. ABBAABAB); alternating copolymer (e.g. AB AB AB AB); gradient copolymer (e.g. AAABAABBABBB) ; block copolymers (e.g. AAAAABBBBBB); graft copolymers (polymeric backbone with polymeric side chains attached to the backbone); and mixed forms of these copolymers.

[0114] The polymeric dispersing agent may comprise a functional group selected from a basic functional group (such as an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group), an alkylol ammonium salt, an acid group and mixtures thereof.

[0115] The polymeric dispersing agent may have a number average molecular weight Mn between 500 and 30,000 g / mol, more preferably between 1,500 and 10,000 g / mol.

[0116] Commercial examples of polymeric dispersing agents include:

[0117] DISPERBYK® dispersants available from BYK CHEMIE GMBH;

[0118] SOLSPERSE® dispersants available from LUBRIZOL;

[0119] TEGO® DISPERSE dispersants from EVONIK;

[0120] DISPEX®, EFKA® and JONCRYL® dispersants from BASF;

[0121] DISPONER® dispersants from ELEMENHS.

[0122] In another preferred embodiment, the dispersing agent comprises a surfactant selected from non-ionic, anionic, cationic or amphoteric surfactants or combinations thereof.

[0123] Examples of preferred surfactants include, but are not limited to an alkyl sulfate, an alkyl ether sulfate, an alkyl sulfonate, an alkyl benzenesulfonate, an optionally substituted diphenyl oxide disulfonate, an optionally ethoxylated sulfosuccinate mono- or diester, a phosphonate mono- or diester, a phosphate mono- or diester, an ethoxylated fatty alcohol, an optionally ethoxylated fatty acid, salts thereof, and mixtures thereof. A list of suitable surfactants is available in the book “Surfactants and Polymers in Aqueous solutions” (Holmberg et al., 2002, John Wiley & Sons). The surfactant may be a polymerizable surfactant, preferably a mixture of a polymerizable anionic surfactant and a polymerizable non-ionic surfactant.

[0124] The curable composition may comprise from 0.1 to 20 wt% of dispersing agent, by weight of the curable composition.

[0125] The composition may further optionally comprise at least one pigment. The term “pigment” may be as defined in DIN 55943:2001-10, namely a colorant that is practically insoluble in the composition at 25 °C and 1 atm, hence having a solubility of less than 10 mg / L therein at 25°C and 0.101 MPa.

[0126] The at least one pigment may be an organic and / or inorganic pigment. The at least one pigment may be selected from a black pigment , a cyan pigment, a magenta pigment, a yellow pigment, a red pigment, an orange pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment a white pigment, and mixtures thereof. Pigments may be chosen from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH , 2004. ISBN 3527305769.

[0127] Examples of pigments include (the term “C.I.” is used as an abbreviation for Colour Index):

[0128] Carbon black;

[0129] - C.I. Pigment White 1, 3, 4, 5, 6, 7, 10, 11, 12, 14, 17, 18, 19, 21, 24, 25, 27, 28 and 32;

[0130] - C.I. Pigment Yellow 1, 3, 10, 12, 13, 14, 17, 55, 65, 73, 74, 75, 83, 93, 97, 109, 111, 120, 128, 138, 139, 150, 151, 154, 155, 180, 185 and 213;

[0131] - C.I. Pigment Red 17, 22, 23, 41, 48:1 , 48:2, 49: 1, 49:2, 52: 1, 57: 1, 81 : 1, 81 :3, 88, 112, 122, 144, 146, 149, 169, 170, 175, 176, 184, 185, 188, 202, 206, 207, 210, 216, 221, 248, 251, 254, 255, 264, 270 and 272;

[0132] - C.I. Pigment Violet 1, 2, 19, 23, 32, 37 and 3;

[0133] C.I. Pigment Blue 15: 1, 15:2, 15:3, 15:4, 15:6, 16, 56, 61 and (bridged) aluminium phthalocyanine pigments;

[0134] - C.I. Pigment Orange 5, 13, 16, 34, 40, 43, 59, 66, 67, 69, 71 and 73;

[0135] C.I. Pigment Green 7 and 36;

[0136] C.I. Pigment Brown 6 and 7; and mixtures thereof.

[0137] The curable composition may comprise from 10 to 75 wt% of pigment, by weight of the curable composition.

[0138] The composition may comprise one or more of additives that include, but are not limited to, antioxidants, ultraviolet absorbers, photostabilizers, foam inhibitors, solvents, flow or leveling agents, colorants, adhesion promoters, slip additives, fillers, thixotropic agents, matting agents, thermoplastics such as acrylic resins that do not contain any free radical- polymerizable functional groups, waxes or other various additives, including any of the additives conventionally utilized in the coating, sealant, adhesive, molding or ink arts.

[0139] In certain embodiments of the invention (including curable compositions intended to be cured by actinic radiation, including UV radiation), the acidified anhydride oligomer containing compositions described herein include at least one photoinitiator. A photoinitiator 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 organic substances present in the curable composition.

[0140] 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.

[0141] 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.

[0142] The amount of photoinitiator may be varied as may be appropriate depending upon the photoinitiator(s) selected, the amounts and types of polymerizable species 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 15%, preferably 0.05% to 10% by weight, preferably 0.1% to 5% by weight, preferably 0.1% to 2% by weight, based on the total weight of the curable composition.

[0143] Suitable solvents are any solvents that will dissolve all other components in the acidified anhydride oligomer containing 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 dimethoxyethane). 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 acidified anhydride oligomer containing 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 acidified anhydride oligomer containing 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. Accordingly, the acidified anhydride oligomer containing compositions of the invention may not be in the form of an aqueous curable anhydride oligomer dispersion.

[0144] 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.

[0145] 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.

[0146] The composition may be a film or coating composition comprising the acidified anhydride oligomer of the invention and optionally a photoinitiator. Such compositions may particularly be used for forming a film on or coating at least part of the surface of a substrate, including as a primer coating formed on a substrate over which additional coating layers may be formed.

[0147] The composition may be an ink composition comprising the acidified anhydride oligomer of the invention and optionally a photoinitiator. Such compositions may particularly be used to print an image or a text on at least part of a surface of a substrate.

[0148] The composition may be a nail gel composition comprising the acidified anhydride oligomer of the invention and optionally a photoinitiator. Such compositions may particularly be used to coat at least part of a surface of a nail. Nail gel compositions of the present invention intended for curing by actinic radiation, including UV radiation, include a photoinitiator. Nail gel compositions of the present invention intended for curing in some other manner, such as peroxide cure (including two-part curing), need not and typically do not contain a photoinitiator.

[0149] Such compositions may further comprise at least one of a (meth)acrylate monomer or a (meth)acrylate oligomer; and optionally, at least one additive.

[0150] Cured composition, coated substrate and its method of making

[0151] The composition of the invention may be used to obtain a cured composition.

[0152] The present invention thus also relates to a cured composition obtained by curing the composition as defined above.

[0153] The cured composition may be a cured film or coating. Alternatively, the cured composition may be a cured ink. Alternatively, the cured composition may be a cured nail gel.

[0154] The invention also relates to a substrate coated with a cured composition according to the invention. Such substrate may be referred to as an article.

[0155] The invention also relates to a method for making an article comprising: applying the composition according to the invention to a substrate; and curing the composition.

[0156] The substrate may be any suitable substrate, such as metal, glass, plastic (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, stone and composites thereof. In a preferred embodiment, the substrate is plastic.

[0157] The curing of the composition of the present invention may be carried out by any suitable method, such as free radical, thermal, electron beam, redox, Michael addition, cationic and / or anionic polymerization. One or more initiators, such as a free radical initiator (e.g., a photoinitiator, a peroxide initiator) may be present in the composition. In general, the curing step may comprise one of: (1) exposing the composition is to UV light or visible light; (2) exposing the composition to or e-an electron beam radiation; (3) initiating polymerization through the use of a redox-generated radical; or (4) initiating polymerization through the use of a thermally-generated radical. Curing may be accelerated or facilitated by supplying energy to the composition, such as by exposing the composition to a radiation source, such as visible light or UV energy, and / or electron beam radiation. In an exemplary embodiment, the composition may be cured with UVC, UVB, UVA energy, and / or visible light. In an exemplary embodiment, the composition is cured with a UV light source utilizing UVA / UVB or UVA only and involves essentially no UVC radiation. In an exemplary embodiment, the composition is cured with high energy radiation, ranging from 0.01 to 10 W / cm2. Possible light sources include, but are not limited to, natural outdoor light, black light, fluorescent light, or high pressure mercury light.

[0158] In an exemplary embodiment, the curing is conducted by exposing the composition to ultraviolet radiation provided by one or more UV lamps delivering an irradiance level of 0.01 to 10 W / cm2, such as 1 to 10 W / cm2, for a time between 1 second and 30 minutes, such as between 1 second and 10 minutes. In another embodiment, the curing is conducted by exposing the composition to e-beam radiation. In another embodiment, the curing is conducted by exposing the composition to heat in the presence of a peroxide initiator (thermal curing). In another embodiment, the curing occurs via redox polymerization which is a two- part process involving a peroxide initiator (e.g., as hydrogen peroxide, benzoyl peroxide or t- butyl hydroperoxide) as a first part and a reducing agent (e.g., a tertiary amine such as N,N- dimethylaniline, N-(4-methoxyphenyl)pyrrolidine and N-phenyldiethanol amine, sodium sulfite, sodium metabisulfite).

[0159] The curable (meth)acrylate-containing compositions of the present invention are particularly well suited to being cured using LED (Light Emitting Diode) curing (e.g., UV LED curing, using radiation from a UV LED device) and for use in high speed applications (such as coatings).

[0160] Prior to curing, the acidified anhydride oligomer containing composition may be applied to at least part of the surface of a substrate in any known conventional manner, for example, by spraying, by brush, by sponge, by knife coating, by roller coating, by casting, by drum coating, by dipping, by curtain coating, by screen printing or by other methods of image transfer, by coating transfer, and the like and combinations thereof. Indirect application using a transfer process may also be used. In an embodiment, the acidified anhydride oligomer containing composition may be applied directly to a substrate, either as a primer or other coating layer, or over one or more of a primer, a basecoat system or other suitable layers in order to achieve the desired final appearance and properties. For example, the curable composition can be applied over a waterborne basecoat or a solvent-borne basecoat.

[0161] A substrate may be any commercially relevant substrate, such as a high surface energy substrate or a low surface energy substrate, such as a metal substrate or plastic substrate, respectively. The substrates may comprise metal, glass, plastics (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, stone and combinations thereof. Depending on the particular application, a suitable dry film thickness ranges from 5 to 200 microns. For 3D printing applications or electronics applications, the film may be thicker than 200 microns.

[0162] The invention also relates to a nail coated with a cured composition according to the invention.

[0163] The invention also relates to a method for coating a nail comprising: applying the composition according to the invention to a nail; and curing the composition.

[0164] The curing may be carried out as described above. The nail may be a human nail or an artificial nail which is adhered to or intended to be adhered to a human nail.

[0165] Method for recycling a substrate / removing a cured composition

[0166] The invention also relates to a method for recycling a substrate coated with a cured composition according to the invention, wherein the method for recycling comprises: contacting the substrate coated with the cured composition with a recycling solution having a pH sufficient to delaminate the cured composition from the substrate; and retrieving from the recycling solution the substrate free from the cured composition.

[0167] 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.

[0168] The recycling / soaking solution described herein causes release (delamination) of the cured acidified anhydride oligomers of the invention (and the compositions, films, etc. in which they are present) from the substrates to which they are attached, resulting in effective recycling of the substrate.

[0169] In an exemplary embodiment, the recycling / 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 recycling / soaking solution used to effect release (delamination) of the cured acidified anhydride oligomers is not particularly limited and may be present in a large stoichiometric excess relative to the cured acidic anhydride oligomer.

[0170] In an exemplary embodiment, the pH of the recycling solution or 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 extent of neutralization of the free acid groups of the anhydride oligomer backbone by having reacted such free acid groups with a base already. With increasing prior neutralization, 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 anhydride oligomer (meth)acrylate backbone having a lower extent of neutralization.

[0171] 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.

[0172] Suitable bases for inclusion in the recycling / soaking solution are not particularly limited and include inorganic bases and organic bases. Suitable inorganic bases include alkali metal and alkaline earth metal bicarbonates or carbonates (e.g., sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, calcium bicarbonate, calcium carbonate). Inorganic bases such as alkali metal and alkaline earth metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide) are typically too caustic for inclusion in a soaking 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.).

[0173] Ease of delamination is dependent on the ease with which the recycling solution is able to permeate the coating or ink or film composition containing the cured acidified anhydride oligomer, which is impacted by physical properties of the composition, including the degree of cross-linking, glass transition temperature (Tg), and its hydrophilicity. Triggered removability of these coatings is influenced by four main conditions 1) crosslink density of the composition 2) number of triggered functional groups within the composition 3) removal time and 4) removal temperature. The crosslink density is important because if the composition is too highly crosslinked, the remover will not be able to penetrate through the film and trigger removability via a swelling mechanism. In addition, there has to be a certain number of acidic functional groups present in the film that can allow for enough swelling. The removal time is important because it allows the aqueous based remover to penetrate the film and temperature of the remover during removal can help with softening of the film to increase penetration and mobility. Regardless of the ease of removability of a composition containing an anhydride oligomer of the present invention, the inclusion of the anhydride oligomer of the invention in such a composition has been found to make such removability easier.

[0174] Without attempting to assess the percentage of acid groups that are in free acid form versus the percentage of acid groups that are in a neutralized form, the following test conditions may be used, in one aspect of the invention, as a standard for achieving complete delamination of a coating or film or ink or other composition containing the cured acidified anhydride oligomer from the substrate to which the coating or film or ink or other composition is attached: Upon exposure of the coated substrate to a 2% sodium hydroxide (NaOH) solution at 25°C to 85 °C for 10 minutes, complete delamination of the coating from the substrate occurs. Utilizing the anhydride oligomer of the present invention can achieve this in certain formulations (e.g., ones that do not increase the cross-link density and utilize a sufficient amount of the anhydride oligomer of the invention) and in other formulations, utilizing the anhydride oligomer of the invention increases the extent of delamination under such conditions compared to a similar formulation that does not contain an anhydride oligomer of the present invention.

[0175] Aspects of the Invention

[0176] Aspect 1 : A curable composition comprising: an acidified anhydride oligomer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; a dispersing agent; and optionally, at least one pigment, wherein the acidified anhydride oligomer has an acid value of at least 10 mg KOH / g oligomer, preferably at least 11 mg KOH / g oligomer, more preferably at least 12 mg KOH / g oligomer, more preferably at least 13 mg KOH / g oligomer, and most preferably at least 13.5 mg KOH / g oligomer.

[0177] Aspect 2. The curable composition of Aspect 1 , wherein the acidified anhydride oligomer is a curable acidified anhydride oligomer comprising at least one radiation curable pendant and / or terminal C-C double bond.

[0178] Aspect 3. The curable composition of Aspect 1 or 2, wherein the acidified anhydride oligomer has an acid content of at least 1.8 x 10'4mol acid / g oligomer, preferably at least 2.0 x 10'4mol acid / g oligomer, more preferably at least 2.2 x 10'4mol acid / g oligomer, more preferably at least 2.4 x 10'4mol acid / g oligomer, more preferably at least 2.5 x 10'4mol acid / g oligomer, more preferably at least between 2.4 x 10'4and 9.5 x 10'4mol acid / g oligomer, such as between 2.5 x 10'4and 9.25 x 10'4mol acid / g oligomer, such as between 3.0 x 10'4and 9 x 10'4mol acid / g oligomer, such as between 3.5 x 10‘4and 8.5 x 10‘4mol acid / g oligomer.

[0179] Aspect 4. The curable composition of any of Aspects 1 to 3, wherein the acidified anhydride oligomer comprises a copolymer comprising at least one unit of structure [A] : wherein Ri and R3 are the same or different and are H or alkyl, R2 and R4 are different and are either an organic moiety bearing at least one (meth)acrylate functional group or H; and at least one unit of structure [B]: wherein R7 and R9 are the same or different and are H or alkyl, Rs and Rio are different and are independently selected from:

[0180] (RnO)nRi2, wherein Rn is a divalent alkylene moiety, R12 is a C8-C26 alkyl, and n is an integer of 1 or more;

[0181] R19 wherein R19 is a C2-C30 branched or straight chained alkyl;

[0182] R20 (C=O)OH wherein R20 is a C8-C26 branched or straight chained alkyl; or

[0183] H; and at least one unit of structure [C]: wherein R43, R14, R15, and Ri6 are the same or different and are independently selected from the group consisting of H and organic moieties, and wherein structure [C] is different from structure [A] and structure [B], and wherein one or more repeating units of structure [C] are located between at least one of i) two units of structure [A], ii) two units of structure [B], or iii) one unit of structure [A] and one unit of structure [B],

[0184] Aspect 5. The curable composition of any of Aspects 1 to 4, wherein the acidified anhydride oligomer has a percent of acid groups present in a free acid form of 0% (i.e., all of the acid groups are in a neutralized (salt) form) to 100% (i.e., fully protonated).

[0185] Aspect 6. The curable composition of any of Aspects 1 to 5, wherein the percent of acid groups present in a free acid form is 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%.

[0186] Aspect 7. The curable composition of any of Aspects 1 to 6, wherein the acidified anhydride oligomer has a percent of acid groups present in a neutralized (salt) 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%. 1

[0187] Aspect 8. The curable composition of any of Aspects 1 to 7, wherein 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 acidified anhydride oligomer is soluble in water at 25°C.

[0188] Aspect 9. The curable composition of any of Aspects 1 to 8, 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.

[0189] Aspect 10. The curable composition of any of Aspects 1 to 9, wherein the at least one pendant and / or terminal acid or anhydride group comprises at least one carboxylic acid group.

[0190] Aspect 11. The curable composition of any of Aspects 1 to 10, wherein the acidified anhydride oligomer comprises a reaction product of an anhydride oligomer, preferably a styrene-maleic anhydride copolymer, and a hydroxyl-functional reactant bearing at least one hydroxyl group and optionally at least one (meth)acrylate group, preferably a hydroxyl-functional reactant 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, 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.

[0191] Aspect 12. The curable composition of any of Aspects 1 to 11, wherein the acidified anhydride oligomer comprises an esterified styrene-maleic anhydride oligomer of Formula I: wherein Ri and R2 may be independently hydrogen or an acrylate or methacrylate moiety or wherein at least one of Ri or R2 is H and at least one of Ri or R2 is an acrylate or methacrylate moiety, n is 2 to about 20, preferably about 8 to about 12, x is 1 to 4, a molar ratio of (x:(y+z)) ranges from about 1: 1 to 3: 1, and a molar ratio of (z / (y+z)) ranges from about 1 :4 to 1: 1, more preferably 1:2 to 1:1.

[0192] Aspect 13. The curable composition of any of Aspects 1 to 12, wherein the number average molecular weight of the acidified anhydride oligomer is from 500 to 50,000 Daltons, preferably from 800 to 15,000 Daltons, more preferably 1,000 to 10,000 Daltons.

[0193] Aspect 14. The curable composition of any of Aspects 1 to 13, wherein the curable composition comprises 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 acidified anhydride oligomer based on the total weight of the composition.

[0194] Aspect 15. The curable composition of any of Aspects 1 to 14, further comprising at least one ethylenically unsaturated compound comprising at least one radiation curable pendant and / or terminal C-C double bond, preferably selected from the group consisting of acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, more preferably selected from acrylate, methacrylate, allyl and vinyl, more preferably selected from acrylate and methacrylate.

[0195] Aspect 16. The curable composition of Aspect 15, wherein the at least one ethylenically unsaturated compound comprises a mono(meth)acrylate monomer preferably selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- and 3 -hydroxypropyl (meth)acrylate, 2-methoxy ethyl (meth)acrylate, 2- ethoxyethyl (meth)acrylate, 2- and 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, alkoxylated phenol (meth)acrylates, alkoxylated nonylphenol (meth)acrylates, cyclic trimethylolpropane formal (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanemethanol (meth)acrylate, tert-butylcyclohexanol (meth)acrylate, trimethylcyclohexanol (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, ethoxylated lauryl (meth)acrylate, methoxy polyethylene glycol (meth)acrylates, , 3-(2- hydroxyalkyl)oxazolidinone (meth)acrylates, and combinations thereof .

[0196] Aspect 17. The curable composition of Aspect 15 or 16, wherein the at least one ethylenically unsaturated compound comprises a (meth)acrylate monomer containing two or more (meth)acrylate groups per molecule, preferably selected from full or partial acrylate and methacrylate esters of polyols containing at least two (meth)acrylate functional groups per molecule, more preferably selected from bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,2- butanediol di(meth)acrylate, 2,3-butanediol di(meth)acrylate, 1,3 -butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5 -pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- nonanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, polybutadiene di(meth)acrylate, cyclohexane- 1,4-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, metallic di(meth)acrylates, modified metallic di(meth)acrylates, glyceryl di(meth)acrylate, glyceryl tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolpropane tri(meth)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.

[0197] Aspect 18. The curable composition of any of Aspects 15-17, wherein the composition comprises 5 to 90%, in particular 10 to 80%, more particularly 15 to 75%, more particularly still 20 to 70%, by weight of ethylenically unsaturated compound based on the total weight of the composition.

[0198] Aspect 19. The curable composition of any of Aspects 1 to 18, wherein the dispersing agent comprises a polymeric dispersing agent, a surfactant and mixtures thereof.

[0199] Aspect 20. The curable composition of any of Aspects 1 to 19, wherein the dispersing agent comprises a polymeric dispersing agent selected from polyesters, polyurethanes, polyalkylene imines, (meth)acrylic (co)polymers, ethylene oxide-propylene oxide copolymers (EO-PO copolymers), or combinations thereof.

[0200] Aspect 21. The curable composition of any of Aspects 1 to 20, wherein the dispersing agent comprises a polymeric dispersing agent comprising a functional group selected from a basic functional group (such as an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group), an alkylol ammonium salt, an acid group and mixtures thereof.

[0201] Aspect 22. The curable composition of any of Aspects 1 to 21, wherein the dispersing agent comprises a polymeric dispersing agent having a number average molecular weight Mn between 500 and 30,000 g / mol, more preferably between 1,500 and 10,000 g / mol.

[0202] Aspect 23. The curable composition of any of Aspects 1 to 22, comprising from 0.1 to 20 wt% of dispersing agent, by weight of the curable composition.

[0203] Aspect 24. The curable composition of any of Aspects 1 to 23, comprising from 10 to 75wt% of pigment, by weight of the curable composition.

[0204] Aspect 25. A curable composition of any of Aspects 1 to 24, wherein the composition further comprises at least one photoinitiator.

[0205] Aspect 26. The curable composition of any of Aspects 1 to 25, wherein the composition is a film or a coating, including a primer coating, composition. Aspect 27. The curable composition of any of Aspects 1 to 25, wherein the composition is an ink composition.

[0206] Aspect 28. The curable composition of any of Aspects 1 to 25, wherein the composition is a nail gel composition.

[0207] Aspect 29. A cured composition obtained by curing the curable composition according to any one of Aspects 1 to 28.

[0208] Aspect 30. The cured composition according to Aspect 29, wherein the cured composition is a cured film or coating, including a primer coating.

[0209] Aspect 31. The cured composition according to Aspect 29, wherein the cured composition is a cured ink.

[0210] Aspect 32. The cured composition according to Aspect 29, wherein the cured composition is a cured nail gel.

[0211] Aspect 33. A substrate coated with a cured composition according to any of Aspects 29 to 32.

[0212] Aspect 34. A nail coated with a cured composition according to Aspect 32.

[0213] Aspect 35. A method for making an article comprising: applying the curable composition of any of Aspects 1 to 28 to a substrate; and curing the composition; wherein the substrate comprises paper, fabric, metal, glass, plastic (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, and composites thereof.

[0214] Aspect 36. The method of Aspect 35, wherein the substrate comprises plastic.

[0215] Aspect 37. A method for recycling a substrate coated with the cured ink composition of Aspect 31, wherein the method for recycling comprises: contacting the article to which the cured ink composition is attached with a recycling solution having a pH sufficient to delaminate the cured ink composition from the substrate; and retrieving from the recycling solution the substrate substantially free from the cured ink composition. Aspect 38. The method of Aspect 37, wherein the substrate comprises plastic.

[0216] Aspect 39. The method of Aspect 37 or 38, wherein the pH of the recycling solution is greater than or equal to 7, such as greater than 7 and less than 13, such as greater than 7 and less than 12, such as greater than 7 and less than 11, such as greater than 7 and less than 10, such as greater than 7 and less than 9.

[0217] Aspect 40. The method of any of Aspects 37 to 39, wherein delamination occurs within 10 minutes of exposure to the recycling solution.

[0218] Aspect 41. The method of any of Aspects 37 to 40, wherein when the pH of the recycling solution corresponds to a 2% NaOH solution and delamination occurs within 10 minutes of exposure at 85°C.

[0219] Aspect 42. The method of any of Aspects 37 to 41, wherein the recycling solution comprises an inorganic base, preferably an inorganic base comprising at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or combination thereof.

[0220] Aspect 43. The method of any of Aspects 37 to 42, wherein the recycling solution comprises an organic base, preferably an organic base that is an amine.

[0221] Aspect 44. A method for coating a nail comprising: applying the curable composition of Aspect 28 to a nail; and curing the composition.

[0222] Aspect 45. 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 Aspect 32 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.

[0223] Aspect 46. The method of Aspect 45, wherein the pH of the soaking solution is 5= 7. Aspect 47. The method of Aspect 45 or 46, wherein the pH of the soaking solution is 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, such as greater than 7 and less than 8.

[0224] Aspect 48. The method of any of Aspects 45 to 47, wherein the soaking solution comprises a base selected from an inorganic base or an organic base.

[0225] Aspect 49. The method of Aspects 48, wherein the base is an inorganic base selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0226] Examples

[0227] Example 1

[0228] A flexographic formulation containing 30% by weight of SB520M35 Sarbox oligomer, which has an acid value of at least 130 mg KOH / g, was prepared as follows:

[0229] Mill base formulation (wt% based on the weight of the Mill base formulation):

[0230] 10% Solsperse 74000 (polymeric dispersant from Lubrizol)

[0231] 35% SR9020 (Propoxylated 3 Glyceryl Triacrylate (Arkema))

[0232] 55% Carbon Black

[0233] Finished ink formulation (wt% based on the weight of the Finished ink formulation):

[0234] 35% Mill base formulation

[0235] 30% SB520M35 (acrylate functional oligomer comprising carboxylic acid and / or anhydride groups (Arkema))

[0236] 20% SR9020

[0237] 6% SR9003B (Propoxylated (2) Neopentyl-glycol Diacrylate (Arkema))

[0238] 3% EDB (Ethyl 4-(dimethylamino)benzoate amine synergist for the UV cure

[0239] (Arkema))

[0240] 3% Irgacure 369 (2-Benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-l

[0241] (Ciba))

[0242] 2% DBK (dibenzyl ketone photoinitiator)

[0243] 1% ITX (isopropylthioxanthone photo initiator) The finished ink has a viscosity 552 cP at room temperature measured on a Brookfield rheometer. The ink was printed on a PET substrate by a hand proofer with a 7.2 BCM anilox. The samples were cured at different H-bulb 300 W / in2at 80 ft / min for 3 and 4 passes to determine the best cure conditions. There was no difference in the final deinking results from the number of passes that the films were cured. The deinking conditions were a 2% NaOH water solution kept at 80-85C and the printed film being exposed in these conditions for 10 minutes. As shown in Figure 1 the printed samples show the results of before and after exposure to the deinking conditions within the 10 min time.

[0244] Example 2

[0245] A flexographic ink formulation containing 15% by weight Sarbox SB520M35 in the formulation is prepared as follows:

[0246] Mill base Formulation (wt% based on the weight of the Mill base Formulation):

[0247] 10% Solsperse 74000

[0248] 35% SR9020

[0249] 55% Carbon Black

[0250] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0251] 35% Mill base

[0252] 15% SB520M35

[0253] 35% SR9020

[0254] 6% SR9003B (Propoxylated (2) Neopentyl-glycol Diacrylate (Arkema))

[0255] 3% EDB

[0256] 3% Irgacure 369

[0257] 2% DBK

[0258] 1% ITX

[0259] The curing conditions and the deinking conditions are the same as the example 1. As shown in Figure 2 the printed samples show the results of before and after exposure to the deinking conditions within the 10 min time.

[0260] Example 3 An Inkjet formulation containing Sarbox SB500 styrene-maleic anhydride oligomer in SR420 monomer, the blend of oligomer in monomer having an acid value of at least 100 mg KOH / g of the mixture of the oligomer and monomer, was prepared as follows:

[0261] Carbon Black Dispersion (wt% based on the weight of the Carbon Black Dispersion):

[0262] 46.4% Mogul E (carbon black)

[0263] 51.3% SR420 (3,3,5-Trimethylcyclohexyl acrylate)

[0264] 2.3% Solsperse 86000 (polymeric dispersant; Lubrizol)

[0265] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0266] 15% Carbon Black Dispersion

[0267] 40% SB500 (30%SR420)

[0268] 10% TPO 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide

[0269] 35% SR285 (tetrahydrofurfuryl acrylate (Arkema))

[0270] The curing conditions and the deinking conditions are the same as the example 1. As shown in Figure 3 the printed samples show the results of before and after exposure to the deinking conditions within the 10 min time.

[0271] An Inkjet formulation containing 15% by weight of SB520M35 Sarbox oligomer, which has an acid value of at least 130 mg KOH / g, was prepared as follows:

[0272] Carbon Black Dispersion (wt% based on the weight of the Carbon Black Dispersion):

[0273] 46.4% Mogul E (carbon black)

[0274] 51.3% SR420 (3,3,5-Trimethylcyclohexyl acrylate)

[0275] 2.3% Solsperse 86000 (polymeric dispersant; Lubrizol)

[0276] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0277] 15% Carbon Black Dispersion

[0278] 15% SB520M35

[0279] 10% TPO 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide

[0280] 60% SR285 (tetrahydrofurfuryl acrylate (Arkema)) The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0281] An Inkjet formulation containing 20% by weight of SB520M35 Sarbox oligomer, which has an acid value of at least 130 mg KOH / g, was prepared as follows:

[0282] Carbon Black Dispersion (wt% based on the weight of the Carbon Black Dispersion):

[0283] 46.4% Mogul E (carbon black)

[0284] 51.3% SR420 (3,3,5-Trimethylcyclohexyl acrylate)

[0285] 2.3% Solsperse 86000 (polymeric dispersant; Lubrizol)

[0286] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0287] 15% Carbon Black Dispersion

[0288] 20% SB520M35

[0289] 10% TPO 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide

[0290] 55% SR285 (tetrahydrofurfuryl acrylate (Arkema))

[0291] The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0292] An Inkjet formulation containing 25% by weight of SB520M35 Sarbox oligomer, which has an acid value of at least 130 mg KOH / g, was prepared as follows:

[0293] Carbon Black Dispersion (wt% based on the weight of the Carbon Black Dispersion):

[0294] 46.4% Mogul E (carbon black)

[0295] 51.3% SR420 (3,3,5-Trimethylcyclohexyl acrylate)

[0296] 2.3% Solsperse 86000 (polymeric dispersant; Lubrizol)

[0297] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0298] 15% Carbon Black Dispersion

[0299] 25% SB520M35

[0300] 10% TPO 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide

[0301] 50% SR285 (tetrahydrofurfuryl acrylate (Arkema)) The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0302] An Inkjet formulation containing 30% by weight of SB520M35 Sarbox oligomer, which has an acid value of at least 130 mg KOH / g, was prepared as follows:

[0303] Carbon Black Dispersion (wt% based on the weight of the Carbon Black Dispersion):

[0304] 46.4% Mogul E (carbon black)

[0305] 51.3% SR420 (3,3,5-Trimethylcyclohexyl acrylate)

[0306] 2.3% Solsperse 86000 (polymeric dispersant; Lubrizol)

[0307] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0308] 15% Carbon Black Dispersion

[0309] 30% SB520M35

[0310] 10% TPO 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide

[0311] 45% SR285 (tetrahydrofurfuryl acrylate (Arkema))

[0312] The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0313] A flexographic ink formulation containing Sarbox SB500 styrene-maleic anhydride oligomer in SR420 monomer, the blend of oligomer in monomer having an acid value of at least 100 mg KOH / g of the mixture of the oligomer and monomer, was prepared as follows:

[0314] Mill base Formulation (wt% based on the weight of the Mill base Formulation):

[0315] 10% Solsperse 74000

[0316] 35% SR9020

[0317] 55% Carbon Black

[0318] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0319] 35% Mill base

[0320] 30% SB500 (containing 30 wt% SR420) 20% SR9020

[0321] 6% SR9003B (Propoxylated (2) Neopentyl-glycol Diacrylate (Arkema))

[0322] 3% EDB

[0323] 3% Irgacure 369

[0324] 2% DBK

[0325] 1% ITX

[0326] The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0327] An Inkjet formulation containing Sarbox SB500 styrene-maleic anhydride oligomer in SR420 monomer, the blend of oligomer in monomer having an acid value of at least 100 mg KOH / g of the mixture of the oligomer and monomer, was prepared as follows:

[0328] Carbon Black Dispersion (wt% based on the weight of the Carbon Black Dispersion):

[0329] 46.4% Mogul E (carbon black)

[0330] 51.3% SR420 (3,3,5-Trimethylcyclohexyl acrylate)

[0331] 2.3% Solsperse 86000 (polymeric dispersant; Lubrizol)

[0332] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0333] 15% Carbon Black Dispersion

[0334] 30% SB500 (containing 30 wt% SR420)

[0335] 10% TPO 2,4,6-Trimethylbenzoyldiphenyl phosphine oxide

[0336] 45% SR285 (tetrahydrofurfuryl acrylate (Arkema))

[0337] The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0338] A flexographic ink formulation containing Sarbox SB500 styrene-maleic anhydride oligomer in SR420 monomer, the blend of oligomer in monomer having an acid value of at least 100 mg KOH / g of the mixture of the oligomer and monomer, was prepared as follows:

[0339] Mill base Formulation (wt% based on the weight of the Mill base Formulation): 10% Solsperse 74000

[0340] 35% SR9020

[0341] 55% Carbon Black

[0342] Ink Formulation (wt% based on the weight of the Ink Formulation):

[0343] 35% Mill base

[0344] 15% SB500 (containing 30 wt% SR420)

[0345] 35% SR9020

[0346] 6% SR9003B (Propoxylated (2) Neopentyl-glycol Diacrylate (Arkema))

[0347] 3% EDB

[0348] 3% Irgacure 369

[0349] 2% DBK

[0350] 1% ITX

[0351] The curing conditions and the deinking conditions were the same as example 1. The coating was as least partially delaminated from the substrate.

[0352] 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.

[0353] 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.

[0354] 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 composition comprising: an acidified anhydride oligomer comprising at least one pendant and / or terminal acid group and optionally at least one radiation curable pendant and / or terminal C-C double bond and / or a salt and / or an anhydride thereof; a dispersing agent; and optionally, at least one pigment, wherein the acidified anhydride oligomer has an acid value of at least 10 mg KOH / g oligomer, preferably at least 11 mg KOH / g oligomer, more preferably at least 12 mg KOH / g oligomer, more preferably at least 13 mg KOH / g oligomer, and most preferably at least 13.5 mg KOH / g oligomer.

2. The curable composition of claim 1, wherein the acidified anhydride oligomer has an acid content of at least 1.8 x 10'4mol acid / g oligomer, preferably at least 2.0 x 10'4mol acid / g oligomer, more preferably at least 2.2 x 10'4mol acid / g oligomer, more preferably at least 2.4 x 10'4mol acid / g oligomer, more preferably at least 2.5 x 10'4mol acid / g oligomer, more preferably at least between 2.4 x 10'4and 9.5 x 10'4mol acid / g oligomer, such as between 2.5 x 10'4and 9.25 x 10'4mol acid / g oligomer, such as between 3.0 x 10'4and 9 x 10'4mol acid / g oligomer, such as between 3.5 x 10'4and 8.5 x 10'4mol acid / g oligomer.

3. The curable composition of claim 1 or claim 2, wherein the acidified anhydride oligomer comprises a copolymer comprising at least one unit of structure [A]:wherein Ri and R3 are the same or different and are H or alkyl, R2 and R4 are different and are either an organic moiety bearing at least one (meth)acrylate functional group or H; and at least one unit of structure [B]:wherein R7 and R9 are the same or different and are H or alkyl,Rs and Rio are different and are independently selected from:(RnO)nRi2, wherein Rn is a divalent alkylene moiety, R12 is a C8-C26 alkyl, and n is an integer of 1 or more;R19, wherein R19 is a C2-C30 branched or straight chained alkyl;R20, wherein R20 is a C8-C26 branched or straight chained alkyl; orH; and at least one unit of structure [C]:wherein R13, R14, R15, and Rie are the same or different and are independently selected from the group consisting of H and organic moieties, and wherein structure [C] is different from structure [A] and structure [B], and wherein one or more repeating units of structure [C] are located between at least one of i) two units of structure [A], ii) two units of structure [B], or iii) one unit of structure [A] and one unit of structure [B] .

4. The curable composition of any of claims 1 to 3, wherein the acidified anhydride oligomer has a percent of acid groups present in a free acid form of 0% to 100%.

5. The curable composition of any of claims 1 to 4, wherein the percent of acid groups present in a free acid form is 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%.

6. The curable composition of any of claims 1 to 5, wherein the acidified anhydride oligomer has a percent of acid groups present in a neutralized (salt) 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%.

7. The curable composition of any of claims 1 to 6, wherein 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 acidified anhydride oligomer is soluble in water at 25°C.

8. The curable composition of any of claims 1 to 7, 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.

9. The curable composition of any of claims 1 to 8, wherein the at least one pendant and / or terminal acid or anhydride group comprises at least one carboxylic acid group.

10. The curable composition of any of claims 1 to 9, wherein the acidified anhydride oligomer comprises a reaction product of an anhydride oligomer, preferably a styrene-maleic anhydride copolymer, and a hydroxyl-functional reactant bearing at least one hydroxyl group and optionally at least one (meth)acrylate group, preferably a hydroxyl-functional reactant 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, 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.

11. The curable composition of any of claims 1 to 10, wherein the acidified anhydride oligomer comprises an esterified styrene maleic anhydride oligomer of Formula I:wherein Ri and R2 may be independently hydrogen, an acrylate or methacrylate moiety, or , wherein at least one of Ri or R2 is H and at least one of Ri or R2 is an acrylate or methacrylate moiety, n is 2 to about 20, preferably about 8 to about 12, x is 1 to 4, a molar ratio of (x:(y+z)) ranges from about 1: 1 to 3: 1, and a molar ratio of (z / (y+z)) ranges from about 1 :4 to 1: 1, more preferably 1:2 to 1:1.

12. The curable composition of any of claims 1 to 11, wherein the number average molecular weight of the curable acidified anhydride oligomer is from 500 to 50,000 Daltons, preferably from 800 to 15,000 Daltons, more preferably 1,000 to 10,000 Daltons.

13. The curable composition of any of claims 1 to 12, wherein the curable composition comprises 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 acidified anhydride oligomer based on the total weight of the composition.

14. The curable composition of any of claims 1 to 13, further comprising at least one ethylenically unsaturated compound comprising at least one radiation curable pendant and / or terminal C-C double bond, preferably selected from the group consisting of acrylate (including cyanoacrylate), methacrylate, acrylamide, methacrylamide, styrene, maleate, fumarate, itaconate, allyl, propenyl, vinyl and combinations thereof, more preferably selected fromacrylate, methacrylate, allyl and vinyl, more preferably selected from acrylate and methacrylate.

15. The curable composition of claim 14, wherein the at least one ethylenically unsaturated compound comprises a mono(meth)acrylate monomer preferably selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- and 3 -hydroxypropyl (meth)acrylate, 2-methoxy ethyl (meth)acrylate, 2- ethoxyethyl (meth)acrylate, 2- and 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, alkoxylated phenol (meth)acrylates, alkoxylated nonylphenol (meth)acrylates, cyclic trimethylolpropane formal (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanemethanol (meth)acrylate, tert-butylcyclohexanol (meth)acrylate, trimethylcyclohexanol (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, ethoxylated lauryl (meth)acrylate, methoxy polyethylene glycol (meth)acrylates, 3-(2- hydroxyalkyl)oxazolidinone (meth)acrylates, and combinations thereof .

16. The curable composition of claim 14 or 15, wherein the at least one ethylenically unsaturated compound comprises a (meth)acrylate monomer containing two or more (meth)acrylate groups per molecule, preferably selected from full or partial acrylate and methacrylate esters of polyols containing at least two (meth)acrylate functional groups per molecule, more preferably selected from bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,2- butanediol di(meth)acrylate, 2,3-butanediol di(meth)acrylate, 1,3 -butanediol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 1,5 -pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- nonanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, polybutadiene di(meth)acrylate, cyclohexane- 1,4-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, metallic di(meth)acrylates, modified metallic di(meth)acrylates, glyceryl di(meth)acrylate, glyceryl tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolpropane tri(meth)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.

17. The curable composition of any of claims 14 to 16, wherein the composition comprises 5 to 90%, in particular 10 to 80%, more particularly 15 to 75%, more particularly still 20 to 70%, by weight of ethylenically unsaturated compound based on the total weight of the composition.

18. The curable composition of any of claims 1 to 17, wherein the dispersing agent comprises a polymeric dispersing agent, a surfactant and mixtures thereof.

19. The curable composition of any of claims 1 to 18, wherein the dispersing agent comprises a polymeric dispersing agent selected from polyesters, polyurethanes, polyalkylene imines, (meth)acrylic (co)polymers, ethylene oxide-propylene oxide copolymers (EO-PO copolymers), or combinations thereof.

20. The curable composition of any of claims 1 to 19, wherein the dispersing agent comprises a polymeric dispersing agent comprising a functional group selected from a basic functional group (such as an amino group, an imino group, an amide group, an imide group, and a nitrogencontaining heterocyclic group), an alkylol ammonium salt, an acid group and mixtures thereof.

21. The curable composition of any of claims 1 to 20, wherein the dispersing agent comprises a polymeric dispersing agent having a number average molecular weight Mn between 500 and 30,000 g / mol, more preferably between 1,500 and 10,000 g / mol.

22. The curable composition of any of claims 1 to 21, comprising from 0.1 to 20 wt% of dispersing agent, by weight of the curable composition.

23. The curable composition of any of claims 1 to 22, comprising from 10 to 75 wt% of pigment, by weight of the curable composition.

24. The curable composition of any of claims 1 to 23, wherein the composition further comprises at least one photoinitiator.

25. The curable composition of any of claims 1 to 24, wherein the composition is an ink composition or a nail gel composition.

26. A cured composition obtained by curing the curable composition according to any one of claims 1 to 25.

27. The cured composition according to claim 26, wherein the cured composition is a cured ink or a cured nail gel.

28. A substrate coated with a cured composition according to claim 26 or 27.

29. A nail coated with a cured composition according to claim 26 or 27.

30. A method for making an article comprising: applying the curable composition of any of claims 1 to 25 to a substrate; and curing the composition; wherein the substrate comprises paper, fabric, metal, glass, plastic (e.g., thermoplastics such as polyolefins, polycarbonate, acrylonitrile butadiene styrene (ABS), and blends thereof), composites, wood, carbon, fiberglass, nonwovens, ceramics, concrete, and composites thereof.

31. A method for recycling a substrate coated with a cured ink composition according to claim 27, wherein the method for recycling comprises: contacting the article to which the cured ink composition is attached with a recycling solution having a pH sufficient to delaminate the cured ink composition from the substrate; andretrieving from the recycling solution the substrate substantially free from the cured ink composition.

32. The method of claim 31, wherein the pH of the recycling solution is greater than or equal to 7, such as greater than 7 and less than 13, such as greater than 7 and less than 12, such as greater than 7 and less than 11, such as greater than 7 and less than 10, such as greater than 7 and less than 9.

33. A method for coating a nail comprising: applying the curable composition of any one of claims 1 to 25 to a nail; and curing the composition.

34. 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 claim 27 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.

35. The method of claim 34, wherein the pH of the soaking solution is 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, such as greater than 7 and less than 8.

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