NAIL COATINGS INCLUDING FATTY ACID ESTERS

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority of U.S. Provisional Application No. 61/894,741, filed on October 23, 2013.

TECHNICAL FIELD

Embodiments of the present disclosure relate to nail coatings.

BACKGROUND

The nail plate (i.e., the natural nail) is primarily composed of keratin, a water-insoluble, fibrous protein that is a major structural component of skin, hair, wool, silk, feathers, scales, nails and hooves. While keratins can obviously differ greatly in their amino acid makeup, hard keratins may all be generally characterized as cross-linked polypeptides. Alpha-keratins such as nails and hooves may be further characterized by their relatively higher percentages of the amino acid cysteine. Typically, the alpha-helix coils of the polypeptides are cross-linked with disulphide bonds between adjacent cysteines. The resulting plate-like cells are cemented to each other with a sticky substance and held together by rivet-like structures called desmosomes. Many cell layers adhere to each other to form the nail plate, a structure that resembles a brick and mortar wall.

Conventional coatings for natural nails may be generally classified into three categories: nail polishes (also laiown as lacquers, varnish or enamels), artificial nails (also known as gels or acrylics) and hybrids. Nail enamels typically comprise various solid components which are dissolved and/or suspended in non-reactive solvents, Upon application and drying, the solids deposit on the nail surface as a clear, translucent or colored film. Typically, nail polishes are easily scratched and are easily removable with solvent, usually within one minute and if not removed as described, will chip or peel from the natural nail in one to five days.

Nail enamels coat the surface of the nail plate to provide a decorative finish with a characteristic glossy finish. Nail enamels conventionally comprise a film forming component, which is frequently nitrocellulose, cellulose acetate butyrate, or a combination of one or both of those cellulosics with a polyester or other polymeric compound. Most nail polishes are made of nitrocellulose dissolved in a solvent (e.g. butyl acetate or ethyl acetate) and either left clear or colored with various pigments. Typical components may include: film forming agents, resins and plasticizers, solvents, and coloring agents.

Artificial nails polymerize on the surface of a natural nail to form a hard, tough surface. Artificial nails conventionally include one or more (meth)acrylate monomers and a

photoinitiator or hardener which may be mixed immediately before use. Optionally, the artificial nail composition may include a solvent or may utilize a liquid (meth)acrylate as a solvent.

Artificial nails of this sort typically bond tightly and possibly irreversibly to the nail plate and must be removed by physical means such as filing.

Hybrid systems include both film-forming components and polymerizable components. In exemplary hybrid systems, the polymerizable components, for example (meth)acrylates, form a 3-dimentional (3-D) thermoset lattice and the film forming component, for example nitrocellulose or cellulose acetate butyrate is dispersed within the 3-D network. The 3-D thermoset lattice provides enhanced durability, toughness, and scratch-resistance over conventional nail enamels while the interdispered film-forming component provides a soluble network to allow for improved removability characteristics over artificial nails.

The toughness and scratch resistance of artificial nails and hybrid systems are generally based on the use of polymerizable materials, notably polymerizable (meth)acrylates.

Polymerizable materials are useful for nail coatings in that they can be applied to the nail in a liquid form (e.g., as liquid monomers or a solution of monomers in a solvent) and subsequently polymerized to form the solid nail coating. Many polymerizable materials used in current nail coatings are derived from non-natural sources, e.g., from petroleum products. There remains a need for polymerizable materials derived from renewable/natural sources.

Application of nail coatings to the surface of the nail plate typically requires the surface of the nail plate to be treated. The surface treatment typically involves the use of a primer and/or roughening of the nail plate such as with the use of a file. This treatment process may cause damage to the nail plate, which is particularly problematic for individuals having thin nails. Primers are adhesion promoters that improve adhesion by increasing interfacial compatibility between surfaces, e.g., the nail plate and an applied coating. For example, a coating of nail polish may resist chipping and peeling if a good primer is used. Primers are more compatible with the nail plate than the nail polish. Primers act as the "go-between" or "anchor", to improve adhesion.

Primers are also frequently used with artificial nail enhancements since acrylic nail products normally have poor adhesion to nail plates. In general, nail plate primers can be thought of as double-sided sticky tape, joining the nail plate to the nail enhancement. The nail plate surface is made up of chemical groups possessing specific structures. Primer components must interact with the nail plate and the (meth)acrylic monomers in the enhancement. With these types of primers, physical abrasion of the nail plate is required to achieve proper levels of adhesion to the keratin substrate. Moreover, these primers can be destructive, and if used improperly they can cause damage to the nail plate and surrounding tissue. These primers can also cause discoloration of the nail enhancement.

SUMMARY

In one aspect, a curable nail coating composition includes an epoxy resin composed of an ester fraction of an epoxidized esterified plant oil or derivative thereof, synthetically derived epoxy resin or derivative thereof, or a combination thereof The ester fraction includes one or more natural or synthetic epoxidized fatty acid esters, or derivatives thereof, wherein each of the one or more fatty acid ester(s) is not a mono-, di- or triglyceride; and wherein the composition provides sufficient adhesion when applied to a keratinaceous surface and cured.

The curable nail coating composition can further include at least one polyhedral oligomeric silsesquioxane. The fatty acid ester(s), or derivative(s) thereof, can be an alkyl ester, such as a methyl ester. The resin can include an ester fraction of one or more additional epoxidized esterified plant oils, naturally or synthetically derived, ΘΪ derivatives thereof, or a combination thereof.

The polyhedral oligomeric silsesquioxane (POSS) can be selected from the group consisting of: TrisFluoro(13)Cyclopentyl-POSS (FL0590); Mercaptopropyllsobutyl-POSS (TH1550); Mercaptopropyllsooctyl-POSS (TH1555); Poly(methacrylpropylisooctylPOSS-co- methymethacrylate) 60% wt (PM 1275.4-60); Poly(MefhacrylpropylisooctylPOSS-co- methylmethacrylate) 80% wt (PM1275.4-80); Octalsobutyl-POSS (MS0825); OctaPhenyl-POSS (MS0840); Isooctyl-POSS Cage Mixture, 95% (MS0805); EpoxyCyclohexylCyclohexyl-POSS (EP0399); EpoxyCyclohexyllsobutyl-POSS (EP0402); Glycidyl POSS Cage Mixture (EP0409); GlycidylCyclohexyl-POSS (EP0415); Glycidyllsobutyl-POSS (EP0418);

TrisGlycidylCyclohexyl-POSS (EP0421); and OctaEpoxyCyclohexyldimethylsilyl-POSS (EP0430); OctaAminophenyl-POSS (AM0280); OctaAminophenyl-POSS (AM0285);

Trimethoxy-[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane, hydrolyzed (EP0408); Hydrolyzed [3-(Trimethoxysilyl)propyl]aniline (AM0281);

[(dimethyl(norborncnylcthyl)silyloxy)dihydroxy]-POSS® (NB1038); vinyl silsesquioxane resin - liquid (PM1285MV); Acrylo POSS® Cage Mixture (MA0736); and OctaTMA-POSS

(MS0860).

The nail coating can further include an epoxy co-resin including a natural or synthetic fatty-acid based component, wherein the fatty-acid based component is a fatty acid mono-, di-, or triglyceride, or a derivative thereof. The co-resin can be composed of an epoxidized plant oil or derivative thereof, synthetically derived epoxy resin or derivative thereof, or combinations thereof. The co-resin can have a higher viscosity than the resin.

The ester fraction of the resin can be an ester fraction of an epoxidized esterified oil derived from the same type of plant as is the plant oil of the co-resin. The co-resin can include a blend of epoxidized esterified plant oils, or derivatives thereof.

The nail coating composition can further include a photoinitiator.

In another aspect, a method of making a curable nail coating composition includes providing an epoxy resin composed of an ester fraction of an epoxidized esterified plant oil or derivative thereof, synthetically derived epoxy resin or derivative thereof, or combinations thereof wherein the ester fraction includes one or more natural or synthetic epoxidized fatty acid esters, or derivatives thereof, wherein each of the one or more fatty acid ester(s) is not a mono-, di- or triglyceride; wherein the composition provides sufficient adhesion when applied to a keratinaceous surface and cured. The method of making a curable nail coating composition can further include combining the epoxy resin with at least one polyhedral oligomeric silsesquioxane. The polyhedral oligomeric silsesquioxane can be selected from the group consisting of:

TrisFluoro(13)Cyclopentyl-POSS (FL0590); Mercaptopropyllsobutyl-POSS (TH1550);

Mercaptopropyllsooctyl-POSS (TH1555); Poly(methacrylpropylisooctylPOSS-co- methymethacrylate) 60% wt (PM1275.4-60); Poly(MethacrylpropylisooctylPOSS-co- methylmethacrylate) 80% wt (PM 1275.4-80); Octalsobutyl-POSS (MS0825); OctaPhenyl-POSS (MS0840); Isooctyl-POSS Cage Mixture, 95% (MS0805); EpoxyCyclohexylCyclohexyl-POSS (EP0399); EpoxyCyclohexyllsobutyl-POSS (EP0402); Glycidyl POSS Cage Mixture (EP0409); GlycidylCyclohexyl-POSS (EP0415); Glycidyllsobutyl-POSS (EP0418);

TrisGlycidylCyclohexyl-POSS (EP0421); and OctaEpoxyCyclohexyldimethylsilyl-POSS (EP0430); OctaAminophenyl-POSS (AM0280); OctaAminophenyl-POSS (AM0285);

Trimethoxy-[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane, hydrolyzed (EP0408); Hydrolyzed [3-(Trimethoxysilyl)propyl]aniline (AM0281);

[(dimethyl(norbornenylethyl)silyloxy)dihydroxy]-POSS® (NB1038); vinyl silsesquioxane resin - liquid (PM1285MV); Acrylo POSS® Cage Mixture (MA0736); and OctaTMA-POSS

(MS0860).

The method can further include combining the epoxy resin and the at least one polyhedral oligomeric silsesquioxane with an epoxy co-resin including a fatty-acid based component, wherein the fatty-acid based component is a fatty acid mono-, di-, or triglyceride, or a derivative thereof.

The epoxy co-resin can be composed of one or more epoxidized plant oils, derivatives of epoxidized plant oils, synthetically derived epoxy resins, derivatives of synthetically derived epoxy resins or combinations thereof.

In another aspect, a method of making a curable nail coating composition having a predetermined viscosity includes providing an epoxy resin having a first viscosity, wherein the epoxy resin is composed of an ester fraction of an epoxidized esterified plant oil or derivatives thereof, a synthetically derived epoxy resins or derivative thereof, or combinations thereof. The ester fraction includes one or more epoxidized fatty acid esters, or derivatives thereof, wherein each of the one or more fatty acid ester(s) is not a mono-, di- or triglyceride; providing an epoxy co-resin resin including having a second viscosity which is higher than the first viscosity, wherein the epoxy co-resin includes a natural or synthetic fatty-acid based component, wherein the fatty-acid based component is a fatty acid mono-, di-, or triglyceride, or a derivative thereof; mixing the resin and the co-resin in the proportions required to produce a curable formulation having a predetermined viscosity having a value between the first viscosity and second viscosity; and wherein the composition provides sufficient adhesion when applied to a keratinaceous surface and cured.

The method of making a curable nail coating composition having a predetermined viscosity can further include providing a polyhedral oligomeric silsesquioxane, and mixing the polyhedral oligomeric silsesquioxane with the resin and the co-resin in the proportions required to produce a curable formulation having a predetermined viscosity having a value between the first viscosity and second viscosity.

In another aspect, a method of coating a nail includes providing a curable nail coating composition according to the present embodiments, and applying the curable nail coating composition to a nail.

Other features, objects and embodiments will be apparent from the description and the claims.

DETAILED DESCRIPTION

Embodiments of the invention are discussed in detail below. In describing embodiments, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. While specific exemplary embodiments are discussed, it should be understood that this is done for illustration purposes only. A person skilled in the relevant art will recognize that other components and configurations can be used without departing from the spirit and scope of the invention. All references cited herein are incorporated by reference as if each had been individually incorporated.

The terms "nail" and "nail surface" mean the natural, keratinaceous nail surface, or a natural nail to which an artificial nail or nail tip is adhered. In other words, the polymerizable compositions of the invention may be applied directly to the keratinaceous surface of the natural nail, or to a nail surface having affixed thereto an artificial nail or nail tip enhancement. The term "adhesion" refers to the strength of the interaction of a coating with its underlying substrate. Adhesion is one aspect of the robustness of a coating to wear and tear, and helps to resist chipping and peeling. Greater adhesion promotes a long-wearing coating. In particular, adhesion can refer to the strength of the interaction of a coating to an underlying keratinaceous substrate, such as a nail plate.

The term "sufficient adhesion" refers to a degree of adhesion of a coating that provides wearability under normal conditions of wear and tear for a length of time that is currently acceptable to the consumer. An acceptable length of time can be for 1 day or longer, 2 days or longer, 3 days or longer, 4 days or longer, 5 days or longer, 6 days or longer,7 days or longer, 8 days or longer,9 days or longer, 10 days or longer, 11 days or longer, 12 days or longer, 13 days or longer, or 14 days or longer. Thus, a curable nail coating composition that provides adhesion to a keratinaceous surface such as a nail plate can, when cured, adhere to the surface for 1 day or longer, 2 days or longer, 3 days or longer, 4 days or longer, 5 days or longer, 6 days or longer,7 days or longer,8 days or longer,9 days or longer,10 days or longer,l 1 days or longer,12 days or longer, 13 days or longer, or 14 days or longer.

The adhesion of a coating to its underlying substrate can be assessed using the cross hatch adhesion test (ASTM D3359). Briefly, a Crosshatch pattern is made though the film to the substrate. Detached flakes of coating are removed by brushing with a soft brush. Pressure- sensitive tape is applied over the Crosshatch cut. Tape is smoothed into place by using a pencil eraser over the area of the incisions. Tape is removed by pulling it off rapidly back over itself as close to an angle of 180°. Adhesion is assessed on a 0 to 5 scale. Sufficient adhesion can represent a score on the cross hatch adhesion test of 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.8 or greater, 0.9 or greater, 1.0 or greater, 1.2 or greater, 1.4 or greater, 1.6 or greater,1.8 or greater, 2.0 or greater, 2.5 or greater, 3.0 or greater, 3.5 or greater, 4.0 or greater, 4.5 or greater, or up to 5.

The term "fatty acid-based component" refers to a component of a composition that include a fatty acid moiety, R-CO2-, where R is an optionally substituted, saturated, monounsaturated, or polyunsaturated, branched or unbranched, C ₆ -C ₂ 4 carbon chain. Fatty acid- based components include fatty acids and fatty acid mono, di- and/or triglycerides. The term "fatty acid ester" refers to an ester of a fatty acid. In some embodiments, the fatty acid ester has the formula R-C0 ₂ -R', where R is defined above and R' is an optionally substituted, branched or unbranched Ci-C ₆ alkyl group.

The term "epoxidized fatty acid-based component" refers to an epoxidized fatty acid- based component, wherein epoxide groups are present in place of a proportion of, or all of, the carbon-carbon double bonds of the corresponding unsaturated fatty acid-based component.

The term "epoxidized fatty acid ester", refers to the ester of an unsaturated fatty acid- based component with an epoxide group in place of a proportion or all of the carbon-carbon double bonds of the unsaturated fatty acid upon which it is based.

The terms "curable composition," "curable formulation," or "curable material," refer to a composition, formulation or material which can be caused to react such that chemical constituents present in the composition, formulation or material become chemically bonded and larger (i.e., higher molecular weight) chemical entities are formed. A curing reaction can be a polymerization reaction and can optionally occur simultaneously with cross-linking (described below). Curable compositions can be, for example, photocurable, cationically curable, or thermally curable.

The terms "photocurable," or "radiation curable," composition, formulation or material, refers to a curable composition, formulation or material which is curable by a chain reaction initiated by incident light, or other radiation. The curing reaction of a photocurable, or radiation curable, composition, formulation or material may take place when light, or other radiation, is incident thereon, and may cease in the absence of such light, or other radiation (or when one or more reagents have been consumed.

The term "cationically curable" composition, formulation or material, refers to a curable composition, formulation or material which is curable by a chain reaction which is propagated, and typically also initiated, by the addition of cationic species to electron-rich function groups, to form a higher molecular weight cationic species.

The term "thermally curable" composition, formulation or material, refers to a curable composition, formulation or material which is curable by a chain reaction initiated by an elevation in temperature. The curing reaction of a thermally curable composition, formulation or material may take place above a temperature threshold and may cease (or the reaction rate be substantially decreased) below a temperature threshold (or when one or more reagents have been consumed).

A curing reaction can include a cross-linking reaction, whereby chemical bonds are established between constituents of the composition, formulation or material so as to form an extended, cross-linked, and in some embodiments, disordered, network (e.g., wherein cross-links are formed between different polymer chains). Cross-links can be formed directly between chemical constituents present in the curable composition, formulation or material, or optionally via a cross-linker. The term "cross-linker" refers to a chemical species able to react with other constituents of the composition, formulation or material at more than one position, but the cross- linker, when taken alone, cannot be cured to form a cross-linked material.

The terms "resin," or "resinous material," refer to a material which, when taken alone or when mixed with one or more other resins, is curable, and which may be curable to form a cross-linked material, A resin can be a liquid or a solid at room temperature, containing a chemical compound or compounds which react during curing to make up a substantial proportion, by mass, of the cross-linked material.

The term "a substantial part of the curable composition, formulation, or material," or "the curable composition, formulation, or material is substantially composed of refers to 50wt% or more, 60wt% or more, or 65wt% or more of the curable composition, formulation, or material. The term "a substantial part of the resin," or "the resin is substantially composed of," refers to 80wt% or more, 90wt% or more, or 95wt% or more, of the resin. For example, a resin can include 80wt%, or 90wt%, or 95wt% or more of a fatty acid ester, or derivative thereof, and smaller amounts of one or more impurities (as might be present in embodiments where the resin is obtained from natural materials such as one or more plant oils), or one or more additives (as may be required, in some embodiments, to adjust the rheology of the resin) which may or may not participate in a curing reaction. Similarly, a co-resin can include 80wt%, or 90wt%, or 95wt% or more of a fatty acid based component.

The term "plant oil," refers to fatty acids and fatty acid mixtures as generally derived from plants, whether the fatty acid mixture is natural or synthetic. Examples of plant oils include borage oil, calendula oil, camelina oil, castor oil, coconut oil, cotton seed oil, crambe oil, echium oil, hemp oil, jatropha oil, jojoba oil, lequerella oil, nutmeg oil, peanut oil, olive oil, soybean oil, corn oil, linseed oil, lunaria oil, meadowfoam oil, canola oil, cocoa butter, palm oil, high erucic rape rape seed oil, safflower oil, sesame oil, sunflower oil, almond oil, beech nut oil, cashew oil, hazelnut oil, macadamia oil, mongongo nut oil, pecan oil, pin nut oil, pistachio oil, grapefruit seed oil, tall oil, tung oil, vernonia oil, walnut oil, lemon oil, orange oil, and other plant oil. The fatty acid composition of various plant oils are well known in the art. Synthetic plant oils can include a mixture of fatty acids or a single fatty acid (as well as two, three or more fatty acids) as found in plant oils. The fatty acid composition of a synthetic plant oil may mimic the composition in a natural oil or have a composition differing from typical plant oils.

The term "epoxidized plant oil," refers to a plant oil where a proportion or all of the carbon-carbon double bonds of one or more unsaturated fatty acid components have been replaced by epoxide group(s).

The terms "reactive," or "active," components of the curable composition, refer to components which participate in the curing reaction, for example with the first and/or second resins. Unlike a resin, a reactive, or active, component of a curable composition is not, when taken alone or mixed with other non-resinous components, curable to form a cross-linked material.

The term "passive" components of the curable composition, refers to components which do not participate in the curing reaction and which therefore remain permanently within the resulting cross-linked material, or which evaporate over time.

Nail Coatings

The present disclosure describes nail coatings. As compared to conventional nail enamels, the nail coating of the present embodiments has an advantage in that it enables the nail coating, which may also contain color, to adhere to the natural nail for long wear periods without adhesion loss or other signs of breakdown of the coating. The improved wear is achieved without the need of surface prepping the nail, such as with the use of primers or by slightly roughing the surface with a file or other means. For example, the nail coating of the present embodiments may be applied directly to the nail. Another advantage of nail coatings of the present invention is the ability to use polymerizable materials based on or derived from natural materials such as fatty acids. Fatty acids can be obtained from, for example, plants, plant oils or synthetically prepared. For example, a fatty acid can be derived from a natural material, such as a plant oil, and

subsequently modified (e.g., esterified and/or epoxidized) in a synthetic process. Furthermore, a combination of natural and synthetically derived plant oils may be used in the nail coatings.

In some embodiments, it may be recommended to simply clean the surface of the nail to remove excess dirt and/or excess of natural oils. Cleaning of the nail surface may be achieved with the light use of solvent such as isopropyl alcohol or acetone.

According to one aspect, the invention is a single layer nail coating that may contain color and exhibits sufficient adhesion to the nail surface. According to an aspect, the disclosure provides a primer for pre-treating a nail surface before application of a nail coating that may, for example, improve adhesion of the nail coating to the nail surface, compared to an untreated nail. According to an aspect, the disclosure provides a nail coating that is a basecoat interposed between the nail surface and an additional layer that may enhance appearance, e.g. by providing a gloss finish or containing color or may provide a protective surface. According to an aspect, the disclosure provides a color layer that is applied to an exposed surface of a basecoat.

According to an aspect, the disclosure provides a protective topcoat that is applied to an exposed surface of a color layer or basecoat.

Nail coatings of the invention demonstrate sufficient adhesion, e.g., sufficient to achieve wearability under normal conditions of wear and tear for 1 day or longer, 2 days or longer, 3 days or longer, 4 days or longer, 5 days or longer, 6 days or longer, 7 days or longer, 8 days or longer, 9 days or longer, 10 days or longer, 11 days or longer, 12 days or longer, 13 days or longer, or 14 days or longer. In some embodiments, the nail coatings achieve enhanced adhesion by the incorporation of a polyhedral oligomeric silsesquioxane, as defined further below, into the composition that is applied to the nail. Nail coatings of the invention provide enhanced adhesion to the nail surface, including natural nails and artificial nails, and, when used in multilayer systems, interlaminar adhesion between the various layers. As such, the nail coatings have longer wear characteristics, i.e., remain intact on the nail surface for longer periods of time. In most cases, the nail coatings described herein remain readily removable by use of suitable solvents. A number of nail coating systems can demonstrate enhanced adhesion by the

incorporation of a polyhedral oligomeric silsesquioxane. Among these are polymerizable nail coating systems, including polymerizable systems which include a resin including one or more fatty acid esters or derivatives thereof; film-forming nail coating systems; water based nail coating systems; and liquid-and-powder nail coating systems. Each of these nail coating systems, and the components that may be used in nail coating formulations according to each system, is described in greater detail below.

In some embodiments, a nail coating composition includes a resin including one or more fatty acid esters or derivatives thereof, and a polyhedral oligomeric silsesquioxane. Other embodiments include methods of making the nail coating composition; of making a nail coating composition having a predetermined viscosity; and of coating a nail with the nail coating composition. Below, nail coating compositions are first described with reference to resin components. Next, polyhedral oligomeric silsesquioxanes, which are included in the nail coating compositions are described. Resin-based compositions suitable for use with polyhedral oligomeric silsesquioxanes in making nail coating compositions are described, for example, WO 201 1/030143, which is incorporated by reference in its entirety.

In some embodiments, a nail coating composition includes a resin including one or more fatty acid esters or derivatives thereof, wherein each said fatty acid ester is not a mono-, di- or triglyceride, and at least one polyhedral oligomeric silsesquioxane. The one or more fatty acid esters or derivatives thereof, can represent all, or a substantial part, of the resin. Alternatively, in some embodiments, the resin can consist essentially of (or consist of) the one or more fatty acid esters or derivatives thereof.

Epoxy Resin

Fatty acid ester derivatives include epoxidized fatty acid esters, and include epoxidized fatty acid esters, hydroxylated fatty acid esters, and further derivatized fatty acid esters.

Exemplary epoxy resins are composed of an ester fraction of an epoxidized esterified plant oil or derivative thereof, synthetically derived epoxy resin or derivative thereof, or a combination thereof. The ester fraction can include one or more natural or synthetic epoxidized fatty acid esters, or derivatives thereof, wherein each of the one or more fatty acid ester(s) is not a mono-, di- or triglyceride; and wherein the composition provides sufficient adhesion when applied to a keratinaceous surface and cured. In exemplary embodiments, an epoxy resin is substantially composed of an ester fraction of an epoxidized esterified plant oil or derivative thereof, synthetically derived epoxy resin or derivative thereof, or a combination thereof.

In embodiments including a plurality of fatty acid esters or derivatives thereof, each said fatty acid ester or derivative thereof, can be based on the same fatty acid, or based on one or more different fatty acids. One or more of the fatty acid esters can be a fatty acid ester derivative. One or more derivatized fatty acid esters, can be an epoxidized fatty acid ester.

The resin can be an epoxy resin. Thus, in some embodiments, the composition includes an epoxy resin including one or more epoxidized fatty acid esters, or derivatives thereof, wherein each said epoxidized fatty acid ester is not a mono-, di- or triglyceride.

In some embodiments, the resin includes at least one unsaturated fatty acid ester, or derivative thereof. An unsaturated fatty acid can be described as a C:D fatty acid, where C is the fatty acid carbon chain length, and D is the number of carbon-carbon double bonds in the fatty acid. In some embodiments, C is at least 6 and can be from 6 to 24; from 12 to 24; from 12 to 22; or from 18 to 22; and D is from 1 to 4.

In some embodiments, the fatty acid ester or derivative thereof, includes a C _n hydrocarbon group on the ester oxygen, wherein n is from 1 to 4. The fatty acid ester or derivative thereof can be an alkyl ester, such as, for example, a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, or t-butyl ester. In some embodiments, the fatty acid ester or derivative thereof is a methyl ester.

Fatty acid esters, or derivatives thereof, including a small hydrocarbon group on the ester oxygen, such as alkyl esters, and in particular methyl esters, can have a lower viscosity than other comparable fatty acid esters (or derivatives thereof). Therefore a curable composition having a given viscosity can be prepared having a minimum quantity of reactive, or passive, diluents by using a fatty acid esters or derivative thereof including a small hydrocarbon group on the ester oxygen (e.g., an alkyl ester, such as a methyl ester). In some embodiments, the diluent can be omitted entirely, and thus the compositions may, in some embodiments, include no reactive diluents and/or no passive diluents. In their raw state, many plant oils, such as linseed oil, are known to include a mixture of fatty-acid based components. The fatty acid-based components exist predominantly as fatty acid triglycerides, with smaller proportions of di- and monoglycerides, and free fatty acids. The oils contain both mixed triglycerides and diglycerides (based upon more than one fatty acid) and triglycerides and diglycerides based upon a single fatty acid. The composition of plant oils may be expressed in terms of the equivalent molar percentages of the free fatty acids, that is to say the molar percentages of the fatty acid units RCO2, where R is the saturated or unsaturated fatty acid carbon backbone, present in the oil in any form.

Fatty acid esters can be prepared by esterifying or transesterifying one or more fatty acid-based components, to thereby provide the one or more fatty acid esters, or derivatives thereof, of the resin. The terms "esterifying" and transesterifying" refer to chemical

transformations of a fatty acid based component into a fatty acid ester, and can include forming an ester from a fatty acid, and/or converting a fatty acid ester into a different fatty acid ester (e.g., a glycerol ester to an alkyl ester). The method may include esterifying one, or more, or a blend of plant oils, or derivatives thereof, to thereby provide the one or more ester fractions of the resin. The step of esterifying typically involves a further step of separating an ester fraction from a glycerol fraction (which may include glycerol and/or water). Separating may, for example, include the steps of allowing an ester fraction and a glycerol fraction to separate, and drawing off the ester fraction.

Preparing the resin can include derivatizing (for example epoxidizing) one or more plant oils, or a blend of plant oils, or the ester fraction of a blend of plant oils, or the ester fractions of one or more plant oils, or one or more fatty acid-based components, or one or more synthetically derived plant oils, or a combination thereof. The procedure for epoxidizing unsaturated plant oils is known to those skilled in the art. One such method is described in the Journal of Polymer Science, Part A: Polymer Chemistry, 2002, 451 - 458, which is incorporated by reference in its entirety. Derivatizing (for example, epoxidizing) may involve one or more further steps.

In some embodiments, the ester fraction of an esterified plant oil represents all, or a substantial part, of the resin, where the ester fraction does not include a mono-, di- or triglyceride. Alternatively, in some embodiments, the resin consists essentially of (or consists of) the ester fraction of an esterified plant oil. The ester fraction of an esterified plant oil can be an epoxidized esterified plant oil. A substantial portion of a plant oil can include a fatty acid-based component, such as a fatty acid mono-, di-, or triglyceride. A plant oil can include a mixture of fatty acid-based components. For example, a plant oil can include a fatty acid triglyceride and smaller amounts of the mono- and/or diglycerides of the same fatty acid, and/or the free fatty acid. A plant oil typically includes a mixture of fatty acid-based components, based on more than one fatty acid, and typically includes one or more mixed fatty acid-based components, such as mixed fatty acid di- and triglycerides.

Each said fatty-acid based component of a plant oil is chemically similar and behaves similarly in a number of common chemical reactions. Thus, an esterified plant oil can include a fatty acid ester of each fatty acid-based component present in the plant oil. Similarly a plant oil derivative can include a derivative of each fatty acid-based component present in the plant oil.

The ester fraction of an esterified plant oil, or derivative thereof, includes esters of one or more fatty-acid based components present in the plant oil, or derivative thereof, and is separable from other components of the esterified plant oil, or derivative thereof, including the reaction products of esterification, for example water and glycerol.

The resin can include small amounts of components of the plant oil, which have not reacted during esterification, such as mono-, di- and triglycerides of the fatty acid based components of the plant oil (or derivative thereof).

In some embodiments, each said fatty acid ester, or derivative thereof, is the ester of an epoxidized fatty acid ester, or derivative thereof. In some embodiments, each said ester fraction of an esterified plant oil, or derivative thereof, is the ester fraction of an epoxidized plant oil. Accordingly, the resin may be an epoxy resin.

In some embodiments, the ester fraction of an esterified plant oil, or derivative thereof (which can be an esterified epoxidized plant oil), is an ester fraction of a purified plant oil.

The esterified plant oil derivative can be an epoxidized esterified plant oil, or the plant oil may be epoxidized and further derivatized.

In some instances, plant oils in their raw state contain a number of impurities which may be undesirable, for example due to their solubility. Plant oils may be purified by filtration and/or solvent extraction (wherein oil is typically washed with a common solvent such as an ether or hexane, in which the or each said fatty acid-based component has a high solubility) in order to decrease impurity levels and increase the proportion of fatty acid-based components of the oil.

In some embodiments, the resin can include the ester fractions of two or more esterified plant oils (which may be epoxidized esterified plant oils), or derivatives thereof. Thus, the resin can include an esterified plant oil blend. The plant oils may be derived from the same type of plant, or from different types of plants.

A curable composition with a resin including the ester fractions of a plurality, or blend, of ester fractions of esterified plant oils, or derivatives thereof; or a plurality, or blend, of fatty acid esters, or derivatives thereof (in particular where the plurality of fatty acid esters are based upon a plurality of fatty acids) can be less prone to crystallisation than curable formulations with a resin including the ester fraction of a single plant oil, or derivative thereof, or of formulations with a resin including a single fatty acid ester, or derivative thereof.

The fatty acid ester, or derivative thereof, can be based on a fatty acid selected from the group consisting of: caproic acid, caprylic acid, pelargonic acid, azelaic acid, capric acid, lauric acid, brassylic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, dihydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, vernolic acid, dimorphecolic acid, densipolic acid, alpha linolenic acid, gamma linolenic acid, calendic acid, eleostearic acid, stearidonic acid, arachidic acid, gondoic acid, eicosenoic acid, gadolenic acid, lesquerolic acid, gadoleic acid, auricolic acid, behenic acid, erucic acid, docosadienoic acid, tetracosanoic acid, and nervonic acid.

The esterified plant oil, or derivative thereof, can be selected from the group consisting of: borage oil, calendula oil, camelina oil, castor oil, coconut oil, cotton seed oil, crambe oil, echium oil, hemp oil, jatropha oil, jojoba oil, lequerella oil, linseed oil, lunaria oil, meadowfoam oil, high erucic rape seed oil, rape seed oil, safflower oil, sunflower oil, soya oil, tall oil, tung oil, vernonia oil, and walnut oil. Synthetic plant oils can have a composition that mimics one of the above oils or can be composed of fatty acids contained in the plant oils in different proportions. The esterified plant oil, or derivative thereof, can be obtained from a plant crop which is not a food crop. Preferably the plant is suitable to be cultivated on marginal land (such as contaminated land, or land having saline soil).

In some embodiments, the composition further includes a co-resin. The co-resin can have a different viscosity than the resin. For example, a co-resin can have a higher viscosity than the resin, such that the viscosity of a composition can be adjusted by adjusting the relative proportions of the resin and the co-resin in the composition. A composition including a resin and a co-resin is curable to form a cross-linked material, having chemical cross linking between constituents of the resin, between constituents of the co-resin, and between constituents of the resin and co-resin.

Synthetically derived epoxy resin can include any suitable curable resin material. In some embodiments, the co-resin is a synthetic co-resin, or includes a synthetic co-resin material, such as a linear or cyclic epoxide or di-epoxide. The co-resin can include a synthetic

cycloaliphatic di-epoxide such as Cyracure resins 61 10. 6107 and 6105 (the major constituent of which is 3,4-epoxy cyclohexyl methyl-3,4 epoxy cyclohexane carboxylate), or can include a compound with one or more heterocyclic functional groups, such as a lactone or an oxetane, or a compound include one or more vinyl ether functional groups. Synthetically derived epoxy resins also epoxy resins of synthetic plant oils.

The co-resin can be any suitable curable resin material. In some embodiments, the co- resin is a synthetic co-resin, or includes a synthetic co-resin material, such as a synthetic di- epoxide or other synthetically derived epoxy resin. The co-resin can include a synthetic cycloaliphatic di-epoxide such as Cyracure resins 61 10. 6107 and 6105 (the major constituent of which is 3,4-epoxy cyclohexyl methyl-3,4 epoxy cyclohexane carboxylate), or can include a compound with one or more heterocyclic functional groups, such as a lactone or an oxetane, or a compound include one or more vinyl ether functional groups.

In some embodiments, the co-resin includes at least one fatty acid-based component, where the fatty acid-based component is a fatty acid mono-, di- or triglyceride, or derivative thereof. The at least one fatty acid-based component can represent all, or a substantial portion of, the co-resin. Alternatively, in some embodiments, the co-resin can consist essentially of (or consist of) the at least one fatty acid-based component or derivative thereof. In embodiments where more than one fatty acid-based component is present, they may be based on the same fatty acid, or based on different fatty acids.

In some embodiments, the fatty acid-based component is chemically similar to the fatty acid ester, or derivative thereof, of the resin. Therefore, the fatty acid-based component reacts similarly to the fatty acid ester or derivative thereof, in a number of chemical reactions, including a curing reaction. Thus, the relative proportions of the resin and co-resin in a composition can be adjusted without significantly affecting the rate and extent of a curing reaction of the composition. Therefore, because properties of the cured, cross-linked material (such as surface adhesion, hardness and flexibility) depend on the rate and extent of the curing reaction, use of a co-resin allows the viscosity of the composition to be adjusted with less effect on the properties of the cured, cross-linked material, than from the use of alternative co-resins, or diluents.

In some embodiments, the fatty acid-based component can be a mixed fatty acid-based component, or derivative thereof. A mixed fatty acid-based component is based on more than one fatty acid, as in the case of, for example, a mixed fatty acid di- or triglyceride. In other embodiments, the fatty acid-based component can be a fatty acid-based component of a single fatty acid, or derivative thereof.

In some embodiments, the fatty acid-based component includes at least one unsaturated fatty acid or derivative thereof. An unsaturated fatty acid can be described as a C:D fatty acid, where C is the fatty acid carbon chain length, and D is the number of carbon-carbon double bonds in the fatty acid. In some embodiments, C is at least 6 and can be from 6 to 24; from 12 to 24; from 12 to 22; or from 18 to 22; and D is from 1 to 4.

In some embodiments, the co-resin includes a plant oil, or derivative thereof, which includes at least one fatty acid-based component. The plant oil or derivative thereof can represent all, or a substantial part of the co-resin. Alternatively, in some embodiments, the co- resin can consist essentially of (or consist of) the plant oil or derivative thereof. The co-resin may be an epoxy resin and may, for example, include or consist of an epoxidized plant oil, or derivative thereof. A substantial portion of a plant oil can include a fatty acid-based component, such as a fatty acid triglyceride. A plant oil can include a mixture of fatty acid-based components. For example, a plant oil can include a fatty acid triglyceride and smaller amounts of the mono- and/or diglycerides of the same fatty acid, and/or the free fatty acid. A plant oil typically includes a mixture of fatty acid-based components, based on more than one fatty acid, and typically includes one or more mixed fatty acid-based components.

In some embodiments, each said fatty-acid based component of a plant oil is chemically similar, and behaves similarly in a number of chemical reactions. Thus, a plant oil derivative can include a derivative of the at least one fatty acid-based component present in the plant oil.

In some embodiments, one or more of the fatty acid-based component(s) of the co-resin is based on the same fatty acid(s) as one or more of the fatty acid esters of the resin.

In some embodiments, the ester fraction of an esterified plant oil, or derivative thereof, of the resin, is an ester fraction of an esterified oil of the same plant as the plant oil, or derivative thereof, of the co-resin. In some embodiments, the ester fraction of an esterified plant oil, or derivative thereof, of the resin, is an ester fraction of an esterified oil of a different plant as the plant oil, or derivative thereof, of the co-resin.

Plant oils are natural products and the precise composition and physical properties, such as viscosity, of a given plant oil variety may vary depending on its source. The provision of a plant oil based or fatty acid based co-resin (typically having a higher viscosity than the resin) allows the viscosity of the composition to be adjusted by adjusting the relative proportions of the resin and co-resin, while having a minimal effect on the properties (other than the viscosity), of the composition and of the resulting cross-linked material, is advantageous since a composition with a predetermined viscosity to be prepared, regardless of the precise viscosity of the plant oils from which it has been derived and, despite variations in the properties of the raw materials, a product with consistent properties may be produced.

In some embodiments, the co-resin can include a blend of plant oils, or derivatives thereof. In some embodiments, the plant oil is an epoxidized plant oil, or derivative thereof.

A curable composition with a co-resin including a plurality, or blend, of fatty acid based components, or derivatives thereof (in particular where the plurality of fatty acid based components are based upon a plurality of fatty acids), or include a plurality or blend of plant oils, or derivatives thereof, can be less prone to crystallisation than curable formulations with a co-resin including a single fatty-acid based component, or derivative thereof, or a single plant oil, or derivative thereof (as the case may be). The solubility of certain components (for example initiators) can be greater in such blended compositions. hi some embodiments, the resin includes esterified plant oils or derivatives thereof derived from the same type of plant as one or more plant oils of the co-resin; or in other embodiments, the resin includes esterified plant oils or derivatives thereof derived from a different type of plant than one or more plant oils of the co-resin.

In some embodiments, the esterified plant oil blend, or derivative thereof, of the resin, and the plant oil blend, or derivative thereof, of the co-resin are blends of oils of the same plants, which may be blended in similar, or the same, proportions. Thus, a greater degree of chemical similarity between the resin and the co-resin may be provided, such that variations in the relative proportions of the resin and co-resin will have a minimal effect on the properties of the formulation, other than viscosity, or of the cured, cross-linked material obtained therefrom.

The fatty acid-based component can be based on a fatty acid selected from the group consisting of: caproic acid, caprylic acid, pelargonic acid, azelaic acid, capric acid, lauric acid, brassylic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, dihydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, vernolic acid, dimorphecolic acid, densipolic acid, alpha linolenic acid, gamma linolenic acid, calendic acid, eleostearic acid, stearidonic acid, arachidic acid, gondoic acid, eicosenoic acid, gadolenic acid, lesquerolic acid, gadoleic acid, auricolic acid, behenic acid, erucic acid, docosadienoic acid, tetracosanoic acid, and nervonic acid.

The plant oil, or derivative thereof, can be selected from the group consisting of: borage oil, calendula oil, camelina oil, castor oil, coconut oil, cotton seed oil, crambe oil, echium oil, hemp oil, jatropha oil, jojoba oil, lequerella oil, linseed oil, lunaria oil, meadowfoam oil, high erucic rape seed oil, rape seed oil, safflower oil, sunflower oil, soya oil, tall oil, tung oil, vernonia oil, and walnut oil. The plant oil, or derivative thereof, can be obtained from a plant crop which is not a food crop. In embodiments, the plant is suitable to be cultivated on marginal land (such as contaminated land, or land having saline soil).

In some embodiments, a curable composition includes a first resin and a second resin, where the first resin has a first viscosity and the second resin has a second viscosity that is less than the first viscosity; the first resin includes a first fatty acid-based component, where the fatty acid-based component is a fatty acid, fatty acid mono-, di-, or triglyceride, or derivative thereof; and the second resin includes a fatty acid ester of a second fatty acid-based component, wherein the fatty acid ester is not a mono-, di- or triglyceride.

In some embodiments, the first fatty acid-based component is based on the same fatty acid as the second fatty acid based component; in other embodiments, the first fatty acid-based component is based on a different fatty acid as the second fatty acid based component. In some embodiments, the first and second fatty acid-based components are the same fatty acid-based component.

In some embodiments, the second viscosity is less than half; less than a third; less than a quarter; or less than one sixth of the first viscosity. In some embodiments, the second viscosity has a magnitude of less than 10% of the first viscosity, or less than 5%, or less than 1 %. The viscosity of the resin may be less than half; less than a third; less than a quarter; or less than one sixth of the viscosity of the co-resin. In some embodiments, the viscosity of the resin has a magnitude of less than 10% of the first viscosity, or less than 5% or less than 1 % of the viscosity of the co-resin.

In some embodiments, a method is provided of preparing a curable composition having a predetermined viscosity, which includes providing a resin having a first viscosity, where the ester includes the ester fraction of an esterified plant oil, and the ester fraction does not include a mono-, di- or triglyceride; providing a co-resin resin having a second viscosity which is higher than the first viscosity, where the co-resin includes plant oil, or derivative thereof; and mixing the first resin and the second resin in the proportions required to produce a curable composition having a predetermined viscosity having a value between the first viscosity and second viscosity. In some embodiments, a method is provided for adjusting the viscosity of a curable composition including a resin and/or a co-resin, the method including adding a portion (or a further portion) of the co-resin, or a portion (or further portion) of the resin, to adjust the viscosity of the curable composition.

The fatty acid-based component(s), and/or plant oil(s), or derivative thereof, and each said fatty acid ester(s), or derivative thereof, and/or the ester fraction(s) of each said plant oil, or derivative thereof, are mutually miscible. Accordingly, it will be understood that preparing the resin and/or co-resin can involve a mixing. Furthermore it will be understood that, in embodiments that involve providing a plurality of fatty acid-based components, or plant oils, or derivatives thereof, or fatty acid esters, or derivatives thereof, or the ester fraction of a plurality of plant oils, or derivatives thereof, each said material may be mixed with any combination of other materials of the formulation, at any stage. The plant oils may be natural or synthetically derived. As a consequence of the similar chemical behavior, and mutual miscibility, of the materials in the resin and/or co-resin and/or curable composition, it will be understood that the step or steps of mixing, esterifying and derivatizing (where applicable) may be conducted in any sequence.

Polyhedral Oligomeric Silsesquioxanes or "POSS"

Embodiments of the present invention incorporate Polyhedral Oligomeric (or Oligo) Silsesquioxane (POSS) into nail coatings. These compounds are distinguished from other silicone resins by their rigid three-dimensional cage-like structures. In some embodiments, the POSS used in the present embodiments has a three dimensional cage structure formed of a plurality of Si subunits, i.e. Si-0 subunits, at least one of the subunits having one or more R groups. In some embodiments, the term "POSS" may refer to POSS molecules having 8 Si atoms or less (e.g., 6, 7 or 8), while EPOSS (extended Polyhedral Oligomeric (or Oligo) Silsesquioxane) may be used to refer to structures those cage structures having greater than 8 Si atoms. All silicone resins forming the cage structure may be used in the present embodiments. Accordingly, unless indicated otherwise, the term "POSS" refers to POSS or EPOSS molecules regardless of the number of Si atoms. Other nail coatings including POSS are described in, for example, U.S. Patent

Application no. 61/814,691 , filed April 22, 2013, which is incorporated by reference in its entirety.

POSS are inorganic materials with a silica core and reactive functional groups on the surface and represented by the general formula of RSiO . Generally POSS are nano-sized, but may be larger depending upon the number of Si and O atoms in the structure, as well as substituents that might be present as described elsewhere herein. Cubic silsesquioxanes, such as octa(dimethylsiloxy) silsesquioxane (RsSisO^), consist of a rigid, crystalline silica-like core that is well-defined spatially (0.5-0.7 nm) which can be linked covalently to 8 R groups. A description of possible cages is discussed in U.S. Pat. No. 5,942,638, which is incorporated by reference in its entirety. Each of the cages can be further modified by attaching reactive moieties to the cage atoms. Depending upon the substituents, the core can account for approximately 5% of the total volume and the highly enhanced surface effects. The structure of the organic phase between the rigid, hard particles can be varied systematically; the potential exists to carefully tune mechanical, optical properties to establish structure-property relationships. For example, by varying the functionality of the R group it is possible to create multi-functionalized

macromonomers, for example octa-functional macromonomers that will self-polymerize or copolymerize with other functionalized cubes to provide nanocomposites whose length scales and interfacial interactions are well-defined. Also by varying the functionality of the R group it is possible to enhance physical and chemical interactions between a nail surface and the coating.

In some embodiments, POSS refers to only those compounds existing in a rigid, "cage"- type configuration, examples of which are shown in Formulas I-V, below. In some

embodiments, POSS refers to only certain structures, such as, by way of non-limiting examples, those illustrated in Formulas I, III and IVA, which are referred to herein as being "complete cages" wherein all of the sides of the three-dimensional structure are completed sides and all of the Si atoms are completely saturated.

In some embodiments, the nail coatings of the present disclosure do not include other

POSS that can exist, for example, in the ladder configuration of Formula VI and such as the polymethylsilsesquioxane known as Resin MK, has previously been disclosed in connection with cosmetic formulations in U.S. Pat. App. Pub. No. 2002/0114773, which is incorporated by reference in its entirety. As disclosed therein, the belief is that the compounds exist in both a "cage" (i.e., Formula I, wherein Ri-R.8 are CH3--) and "ladder" configuration (Formula VI). It is also believed that the majority of the silicone polymers are present in the "ladder" configuration (Formula VI). To the extent that this composition contains the "ladder" configuration, it is not POSS as that term is used with respect to the present invention.

The POSS used in the nail coatings of the present embodiments may form the three- dimensional cage structure. In some embodiments, the POSS has at least 6 Si molecules. In some embodiments, the POSS contains 8 Si atoms. POSS may also include greater than 8 Si atoms or in mixtures containing, for example, 6-12 Si atoms or 8-12 Si atoms, for example as a mixture of compounds containing 8, 10 and 12 Si atoms. The number of Si atoms can also range from 6 to 1 O0, alternatively 6 to 30, also alternatively 6 to 20 and finally alternatively 6 to 16, either as a single POSS structure (i.e. having the same configuration of Si and O atoms even if other substituents vary) or as a mixture of compounds with varying numbers of Si atoms with the same or varying R groups. In some embodiments, at least 4 of the Si atoms are bound, through an oxygen atom, to at least 3 other Si atoms (referred to herein as being "completely saturated"). All of the Si atoms are bound to at least one other Si atom through an oxygen bridge.

As shown in the exemplary and non-limiting structures of Formulas I through V and VII through X, POSS forms a rigid three-dimensional cage structure having at least two completed sides. This rigid cage structure is distinguished from ladders and other structures which are not held in place in three directions (see Formula VI for an exemplary ladder structure). Each of the Si atoms is bound to at least 1 R group with no more than 3, no more than 2 or no more than 1 Si atom being bound to more than 2 R groups. For example, the POSS molecule illustrated by Formula III has 6 saturated Si atoms and 5 complete sides (2 sides bounded by 3 Si atoms connected through oxygen bridges and 3 sides bounded by 4 Si atoms connected through oxygen bridges). Formula IIB has 4 such saturated Si atoms and 2 completed sides, both bounded by 4 Si atoms connected through oxygen bridges. Formula IIC has 6 saturated Si atoms and 3 completed sides all bounded by 4 Si atoms connected through oxygen bridges.

POSS molecules in accordance with some embodiments have the complete cage structure of Formula I:

Formula I

It is also possible that one or even two of the oxygen bridges between successive Si atoms are broken or missing, in which case the "POSS" is referred to as having an "incomplete' cage structure. By way of non-limiting examples, consider the rigid three-dimensional cage structures illustrated in Formulas IIA-E:

Formula IIA Formula IIB

Formula IIC Formula IID

A

Formula HE

Formula III is a complete cage, but produced from 6 Si atoms.

Formula III

In Formula IVA, the number of Si atoms in the cage is 10, in Formula IVB, the number of Si atoms is 10 and in Formula IVC, the number of Si atoms in the cage is 12. In Formula IVD and IVE, the number of Si atoms in the cage or core is 16.

Formula IVA

 Formula IVD

Formula IVE

An example of an "incomplete" cage structure, wherein one or more of the oxygen bridges between successive Si atoms is broken or missing, is illustrated in Formula V:

la V

Formula VI, a ladder configuration (not a POSS according to the present

embodiments/disclosure), can be a monomer linked end to end to other similar structures. It is not rigid within the meaning of this document as it can fold or flex around each R— Si~0~Si— R axis of the molecule. No such movement is possible in the rigid 3-D cage structures (whether complete or incomplete) of the POSS of the present embodiments. Thus, the molecules of this formula are not POSS.

R R R R

I I

Ό- - Si— o- ^■ Si— o - ^■ Si I- o— si I— o- o I o I 0 I o I

Ό- ^■ si I— o- ^■ si I— o - o— Si I— o-

R I R I R I

Formula VI

Note also that when referencing POSS molecules as being in accordance with Formula II, having the structure of Formula II, or being other than a completed cage, the sides which are illustrated as "open," "missing" or "broken" are illustrative only. When reference is made to Formula II, it is understood that any one or two sides, or any one or two oxygen bridges, may be broken or missing. The structure of the POSS molecule can be roughly thought of as a box (prism in the case of Formula III) or cage in shape with silicon (Si) atoms at each corner. Each Si atom is connected to at least one other Si atom through bonds to an oxygen atom (also referred to as an "oxygen bridge"). Preferably, at least 4 of the Si atoms in the POSS structure are "completely saturated." As used herein, a Si atom is "completely saturated" if bound, through oxygen atoms, to three other Si atoms within the cage as shown in Formulas I, III and IVA, most preferably, all of the Si atoms are "completely saturated". While illustrated in Formula I as Si atoms, the groups at each corner may be the same or different and may be one or more atoms or groups including, without limitation, silicon, silane, siloxane, silicone or organometallic groups. The POSS used in the invention can have a rigid 3-dimensional cage structure as illustrated, for example, in Formulas I-V and VII-X and the cage has at least two completed sides A. Each Si is bound to at least 1 R group. In some embodiments no more than 1 Si atom is bound to more than 2 R groups. In some embodiments no more than 2 Si atoms are bound to more than 2 R groups. In some embodiments no more than 3 Si atoms are bound to more than 2 R groups.

In some embodiments, POSS materials can be represented by the formula [RSi01.5]∞ where∞ represents molar degree of polymerization and R represents an organic substituent (H, siloxy, cyclic or linear aliphatic or aromatic groups that may additionally contain reactive functionalities such as alcohols, esters, amines, ketones, olefins, ethers or halides or which may contain fluorinated groups). The POSS used in the invention may be either homoleptic or heteroleptic. Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group. In embodiments, the internal cage like framework is primarily composed of inorganic silicon-oxygen bonds while the exterior of the nanostructure is covered by reactive and/or nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic monomers and polymers.

POSS compositions can be represented by the formulas:

[(RSiOi,5)n]∑# for homoleptic compositions;

[(RSiOi.5)n(R'SiOi.5)m]∑# for heteroleptic compositions (where R≠ R'),

[(RSiOi.5)n(XSiOi.5)m]∑# for functionalized heteroleptic compositions having a closed cage structure (where R groups can be equivalent or inequivalent). A functionalized heteroleptic POSS composition having an open cage structure may be represented by the formula

[(RSiO,. ₅ ) _n (RXSiOi.o)m]∑#. By way of example, homoleptic POSS of Formulas III, I, IVA and IVC are designated as [(RSiOi.s)6]∑6, [(RSi0 ₁ . ₅ )6]∑6, [(RSiO, . ₅ )8]∑8, [(RSiOi.s)io]∑io and [(RSiOi.s)i ₂ ]∑i2, respectively. Similarly, functionalized heteroleptic open cage POSS can have the following structures and designations:

[(RSiO _L5 ) ₆ (R(HO)SiO) ₂ ]∑ ₈ Formula VII

[(RSiO _L5 ) ₆ (R(HO)SiO) ₂ ]∑ ₈ Formula VIII

[(RSiO _L5 )4(R(HO)SiO) ₃ ]∑ ₇ Formula IX.

In all of the above structures and formulas, R is the same or different and can be any of the moieties as defined elsewhere herein and X includes but is not limited to OH, CI, Br, I, alkoxide (OR), acetate (CH3COOR), acid (COOH), ester (COOR), peroxide (OOR), amine (NR2), isocyanate (NCO), epoxy, olefin and R. The symbols m and n refer to the stoichiometry of the composition. The symbol∑ indicates that the composition forms a nanostructure and the symbol # refers to the number of Si atoms contained within the nanostructure. The value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m ranges typically from 1 to 12. It should be noted that∑# is not to be confused as a multiplier for determining

stoichiometry, as it merely describes the overall nanostructural characteristics of the system (aka cage size).

Examples of attributes that enable nanostructured chemicals to function as 1-10 nm reinforcing and adhesion promoting agents include: (1) their unique size with respect to polymer chain dimensions, and (2) their ability to be made compatible with polymer systems to overcome repulsive forces that promote incompatibility and expulsion of the nanoreinforcing agent by the polymer chains. That is, nanostructured chemicals can be tailored to exhibit preferential affinity/compatibility with a wide range of nail coating compositions through variation of the R groups on each nanostructure. Therefore, the factors to effect a selective nanoreinforcement include specific nanosizes of nanostructured chemicals, distributions of nanosizes, and compatibilities and disparities between the nanostrucutured chemical and the nail coating system.

The POSS used in the present invention is typically "derivatized" with one or more R groups that include a functional group. Other R groups may not include functional groups, but can be varied to modify the POSS by, for example, enhancing compatibility with solvents or other components of the nail coating, varying the size of the POSS to alter physical

characteristics of the final coating, or enhancing solubility of the POSS in the nail coating. As non-limiting examples, one or more R groups could be an alkyl group, alkene, alkyne, hydroxyl, thiol, ester, acid, ether. In some embodiments, the "R groups" include, without limitation, one or more of the following: hydrogen, methyl, ethyl, propyl, isobutyl, isooctyl, phenyl, cyclohexyl, cyclopentyl, -OSi(CH ₃ )2-CH2-CH2-(CF ₂ )5CF3, -(CH ₂ ) ₃ SH, N ⁺ (CH ₃ ) ₃ , 0 ^" N ⁺ (CH ₃ ) ₃ , -OH, -(CH ₂ ) _n N ⁺ H ₃ X ^" wherein n is 0-30 and X is a counter ion,

In some embodiments, R can also be a silane or siloxane structure, including a ladder structure. Formula X is a non-limiting example of a siloxane substituted POSS:

Formula X

As previously illustrated (see Formulas IVD and IV E, the substituent can be an additional caged structure. In these instances, the structure can be considered conceptually as either a single POSS stmcture, as identified above, or as a POSS structure substituted by another POSS structure.

For example, the one remaining bond of each silicon of Formula I, III and IVA can bind to a variety of substituents or groups specified, as "R" groups (Ri-Rs), ((R1-R5) in Formula III). As used herein, when multiple R groups are present on the same POSS molecule, each R group may be the same or different whether all are designated as simply R or differentiated as Rj, R ₂ , R3, . . . Rn. In some embodiments illustrated in Formulas II, IVB and V a POSS molecule in which one or two of the oxygen bridges between adjacent silicon molecules have been eliminated, a greater number of R groups are possible. When a POSS having 8 Si atoms is employed, it is preferred that no more than two of these inter-silicon connections (oxygen bridges) be eliminated. However, it is possible to eliminate as many as three such bridges (Formula HE). More preferably, only a single oxygen bridge would be eliminated (Formula IIA). As stated above, the Si molecules not completely bound may have one or more additional positions available for binding additional substituents. In the case of a single missing side, the POSS molecule may include additional R groups R9 and Rio, which may be the same or different as the Ri-Rs. When 2 or 3 bridges are missing, the POSS molecule may include additional R groups R9, Rio, R11 and R12 (as appropriate), which all may be the same or different and may be the same as the groups identified for Ri-Rs. POSS compounds with various R groups are known in the literature. They are described in a number of patents including, without limitation, U.S. Pat. Nos. 5047492, 5389726,

5484867, 5589562, 5750741, 5858544, 5939576, 5942638, 6100417, 6127557, 6207364, 6252030, 6270561, 6277451 , 6362279 and 6486254, each of which is incorporated by reference in its entirety. These patents describe in detail various methods of producing the basic POSS cage structure and various derivatives thereof, including POSS based polymers. To the extent that these patents identify and describe various POSS molecules having the structures of Formulas I-V and VII-X, derivatives and polymers thereof, they are incorporated by reference. The discussions of techniques for manufacturing and derivatizing this class of compounds described in each of these patents is also hereby incorporated by reference.

In general, R groups (for example, Ri, R ₂ , R ₃ , R4, R5, 6, R7, Rs, R9, Rio, R11 and R] ₂ as shown in the figures and any other R groups appropriate) can be the same or different and may be reactive or nonreactive groups. They may be, in replacing a methyl or H, for example, hydroxy (--OH), alkane derivatives (missing a hydrogen) also known as alkyl groups (other than methyl), alkenyl groups also referred to as derivatives of alkenes (having one or more double bonds), usually missing an H where they are bound to Si in POSS or to some other molecule, alkynyl groups also referred to as derivatives of alkynes (having one or more triple bonds) usually missing an H where they are bound to Si in POSS or to some other molecule, aryl groups (either the 6-carbon ring of benzene or the condensed 6-carbon rings of other aromatic derivatives such as naphthalene) also referred to as derivatives of arenes, usually missing an H where they are bound to Si in POSS or to some other molecule, heteroaryl groups (either a 6- membered or 5- membered aromatic ring containing one or more atoms other than carbon in the ring, e.g. N, S or O, or structures containing condensed hetero aromatic rings) acyl groups (organic acids without the OH group, e.g., CH ₃ CO~ or C6H5CO--), alkoxy groups (alkyl radicals attached to the remainder of a molecule by oxygen), such as methoxy, ester groups, acid groups, acrylate groups, alkyl acrylate groups, hydroxy groups, halogens, amino groups, alkylamino groups, aminoalkyl groups, groups containing one or more tertiary or quaternary nitrogens, silicone containing groups, sulfur containing groups, epoxides, azo groups, diazo groups, halogens, cyclic compounds which can undergo ring opening polymerization or ring opening metathesis polymerization. R groups may also be monomers or polymers where POSS will be used as a pendant substituent of the polymer. Acrylates and cationic polymers providing conditioning properties are provided in some embodiments. Where appropriate, any of these R groups may themselves be substituted or

unsubstituted, saturated or unsaturated, linear or branched. Possible substitutions include C1-C30 alkyl groups, C1-C30 alkenyl groups, C1 -C30 alkynyl groups, C ₆ -Ci 8 aryl groups, acyl groups, alkoxy or other groups, carboxy groups, ester groups, acrylate groups, alkyl acrylate groups, trihydroxy groups, amino groups, alkylamino groups including mono and dialkylamino groups, mono and dihydroxy alkylamino groups, cyano groups, aminoalkyl groups, groups containing one or more tertiary or quaternary nitrogens, silicone containing groups, sulfur and/or phosphorous containing groups, SO2X, SO3X, where X is H, methyl or ethyl, epoxides and epoxide containing groups, azo groups, diazo groups, halogens, cyclic compounds which can undergo ring opening polymerization or ring opening metathesis polymerization. Indeed, any group which can be attached to a corner of a POSS molecule can be used.

When these R groups are carbon containing fatty acids or fatty alcohols, aromatic or cyclic groups, they generally may contain between 6 and 50 carbon atoms and may be saturated or unsaturated, substituted as discussed above or unsubstituted and branched or linear, as appropriate for a given group.

More specifically, possible R groups include, without limitation, hydroxy groups including mono or poly hydroxy groups, phenols, alkoxy, hydroxy alkyls, silanes, amino and in particular, quats, halosilanes, epoxides, alkyl carbonyls, alkanes, haloalkyls, halogens, acrylates, methacrylates, thiols, nitriles, norbornenyls, branched alkyl groups, polymers, silanes, silanols, styryls and thiols. In a single POSS molecule of Formula I, Ri could be H, R ₂ -OH, R3 --NH2, R4 ~CH ₂ CH ₂ N ⁺ CH3(OCH ₂ CH3)CH2CH2CH3, R ₅ ~CH ₂ CH ₂ CHOCH ₂ (epoxide), Re ~OC(CH ₃ )3, R7 ~OOC(CH2)i6CH3 and R ₈ could be CI. This is a hypothetical example, merely to illustrate that each of the R groups can be derivatized separately and to emphasize the wide variety of possible substitutions.

In some embodiments, these POSS molecules are not completely substituted with the same R groups (e.g., not all R1-R6, Ri-R ₈ , R1-R10 or Ri-Ri ₂ (and any other R groups, as appropriate, given the number of Si atoms and available bonds in a given POSS molecule) are methyl, isobutyl or phenyl). This is particularly preferred for POSS molecules that have the structure of Formula I. Moreover, when a POSS molecule having 8 Si subunits, as depicted in

Formula I, is employed, at least one of the R groups is a group other than a methyl, particularly where the silicon resin is a T resin and, even more particularly, Resin MK. Also contemplated under the term POSS is the family of commercially available compounds available from Hybrid Plastics, 55 W.L. Runnels Industrial Drive

Hattiesburg, MS 39401 and Mayaterials, Inc. P.O. Box 87, South Lyon, Mich. 48178-0087.

In some embodiments, the POSS used in the coatings (nail coating or nail topcoat) of the present embodiments has the formula of (C6Hn02) _n (SiOi.5)n, where n is 6 (see Formula III), 8(see Formula I), 10 (see Formula IV A), or 12 (see Formula IVC) and C6H1 1 O2 represents a glycidyl epoxide having the structure:

In some embodiments, the POSS used in the coatings of the present embodiments has the formula of (C6Hi i0 ₂ ) _n (SiOi.5)n, where n is 8, 10, or 12. In some embodiments, the POSS used in the coatings of the present embodiments has formula of (C6Hi i02) _n (SiOi .5)n, where n is 8 or 10. In some embodiments, the POSS used in the coatings of the present embodiments has the formula of (C6Hn0 ₂ )n(SiOi.s)n, where n is 8. In some embodiments, the POSS used in the coatings of the present embodiments is a mixture of POSS structures having the formula (C6Hi i02)n(SiOi.5)n, where n is 6, 8, 10, and 12. In some embodiments, the POSS used in the coatings of the present embodiments is a mixture of POSS structures having the formula (C6Hi i02)n(SiOi.5)n, where n is 8, 10 and 12. In some embodiments, the POSS used in the coatings of the present embodiments is a mixture of POSS structures having the formula of (C ₆ Hn02)n(SiOi. ₅ )n, where n is 8 and 10.

In some embodiments, the POSS molecules are functionalized with at least one group or a plurality of groups. Examples of functional groups on the polymer and POSS materials include, but are not limited to, functional silicones~for example, hydroxy, urethane, acrylate, vinyl, Si~H, amides, functional acrylates, functional polyamides, PVK, PVA, PS, PEG, PPG, polysaccharides or modified starch, functional block copolymers, functional polyesters and polyethers, fluorinated polymers and wax to bring about the cross-linking reaction between the polymer chains and POSS materials to provide desired properties. Other nail coatings including POSS, and other POSS materials suitable for use in nail coatings are described in, for example, U.S. Patent Application no. 61/814,691, filed April 22, 2013, which is incorporated by reference in its entirety.

The POSS of the present invention may be prepared by hydrolytic condensation reactions of trifunctional organosilicone monomers, e.g. RSi(OMe). Methods of preparing POSS are described in U.S. Pat. Nos. 8133478 and 6372843, which are incorporated herein by reference in their entireties.

In some embodiments, the POSS used in the coatings of the present embodiments is EP0409, which is a blend of caged and non-caged structures as described in, for example, U.S. Pat. Nos. 6716919 and 6927270, each of which is incorporated herein by reference in its entirety. In some embodiments, the POSS used in the coatings of the present embodiments is MA0736, EP0408, NB1038, AL0104, AL0125, AL0130, AL0136, CA0295, CA0296, CA0298, EP0402, EP0417, EP0418, EP0419, EP0421, EP0423, EP0430, EP0435, FL0578, FL0583, HA0605, HA0615, HA0635, HA0640, IM0670, IM0673, MA0701, MA0702, MA0703, MA0706, MA0716, MA0717, MA0718, MA0719, MA0734, MA0735, MA0736, MS0802, MS0805, MS0813, MS0814, MS0815, MS0825, MS0830, MS0840, MS0860, MS0865, NI0914, NB 1000, NB1010, NB1017, NB1021, NB1022, NB1038, NB1070, OL1118, OL1123, OL1159, OL1160, OL1163, OL1170, PG1190, SH1310, SH1311, SO1400, SO1440, S01444, SO1450, SOH55, S01457, S01458, SO1460, SA1532, SA1533,TH1550, TH1555, AM0285, AM0273, PM1285MV, ΛΜ0280, AM0281 , AM0282, AM0290, AM0291, AM0292, AM0293, AM0275, AM0265, PG1190, AM0270, or a mixture thereof.

POSS Functionalized Monomers

POSS Functionalized Monomers possess a hybrid inorganic-organic three-dimensional structure which contains one or more reactive organic functional groups. Although referred to herein as "monomers", it is to be understood that the term reactive organic functional groups include groups that can polymerizable groups or groups that can otherwise interact with additional nail coating components or other POSS molecules to enhance physical properties of the nail coating such as adhesion and toughness. POSS Functionalized Monomers may contain non-reactive organic groups with one functionalized reactive group, multiple non-reactive organic groups and multiple functionalized reactive groups, or only functionalized reactive groups. For example, a POSS having eight R groups may contain seven non-reactive organic groups with one functionalized reactive group, six non-reactive organic groups and two functionalized reactive groups, five non-reactive organic groups and three functionalized reactive groups, etc. up to a POSS containing eight functionalized reactive groups. The unique functional groups can include, but are not limited to, amines, esters, epoxides, methacrylates, olefins, silanes, styryls, and thiols. By varying the functional group(s) and non-reactive organic group(s), a multitude of POSS Functionalized Monomers can be prepared. While the monofunctional POSS Monomers can be incorporated by copolymerization or grafting, multifunctional POSS Monomers, i.e. POSS containing more than one functionalized reactive group, can be utilized as effective cross-linkers. POSS Functionalized Monomers react similarly in polymerization, grafting and cross-linking reactions to standard organic monomers. While they react like simple organic monomers, when incorporated into a polymeric material, POSS Functionalized Monomers impart significant improvements in the thermal, mechanical, and gas separation properties of traditional plastics.

POSS Polymers and Resins

POSS Polymers and Resins possess a hybrid inorganic-organic composition and can be either thermoplastic or thermoset materials. As a class of materials, POSS Polymers and Resins are composed of either (1) polymers in which a POSS Functionalized Monomer has been co- polymerized or grafted onto a polymer chain, or (2) silsesquioxane resins possessing some cage structure (see, e.g. Formula X). POSS Polymers and Resins can be used as stand-alone replacements for traditional materials or they may be compounded or solution blended into traditional polymeric materials to enhance the properties of the base resin. The types of POSS Polymers and Resins that are currently available include, but are not limited to, silicones, styrenics, acrylics, and norbornenes.

POSS molecules are available from Hybrid Plastics and include, without limitation, those based on Formulas I-IV. Other POSS products may be purchased from ALDRICH. Still others are described in U.S. Pat. Nos. 8133478, 5047492, 5858544 and 2465188, each of which is hereby incorporated by reference in its entirety.

Particularly preferred POSS molecules useful for producing coating compositions in accordance with the present embodiments include: TrisFluoro(13)Cyclopentyl-POSS (FL0590); Mercaptopropyllsobutyl-POSS (TH1550); Mercaptopropyllsooctyl-POSS (TH1555);

Poly(methacrylpropylisooctylPOSS-co-methymethacrylate) 60% wt (PM 1275.4-60);

Poly(MethacrylpropylisooctylPOSS-co-methylmethacrylate) 80% wt (PM1275.4-80);

Octalsobutyl-POSS (MS0825); OctaPhenyl-POSS (MS0840); Isooctyl-POSS Cage Mixture, 95% (MS08O5); EpoxyCyclohexylCyclohexyl-POSS (EP0399); EpoxyCyclohexyllsobutyl- POSS (EP0402); Glycidyl POSS Cage Mixture (EP0409); GlycidylCyclohexyl-POSS (EP0415); Glycidyllsobutyl-POSS (EP0418); TrisGlycidylCyclohexyl-POSS (EP0421); and

OctaEpoxyCyclohexyldimethylsilyl-POSS (EP0430); OctaAminophenyl-POSS (AM0280); OctaAminophenyl-POSS (AM0285); Trimethoxy-[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane, hydrolyzed (EP0408); Hydrolyzed [3-(Trimethoxysilyl)propyl]aniline (AM0281);

[(dimethyl(norbornenylethyl)silyloxy)dihydroxy]-POSS® (NB1038); vinyl silsesquioxane resin - liquid (PM1285MV); Acrylo POSS® Cage Mixture (MA0736); and OctaTMA-POSS

(MS0860.

According to the present invention, nail coatings can be obtained by either adding an appropriate POSS component to an existing nail coating system or by formulating an entirely new system. The nail coating system may be, for example, a curable composition including a resin including one or more fatty acid esters or derivatives thereof; a single layer system, such as an enamel containing only a film forming component; a single layer photocurable system that includes polymerizable monomers such as a gel or acrylic; a solvent based system that includes both a film-forming component and a polymerizable component; or a water based nail coating. The POSS may be added in an amount of from about 0.01wt% to about 20 wt% of the total composition before it is applied. For example, the POSS may be present in an amount of from about 0.05 wt% to about 10 wt%; from about 0.05 wt% to about 8 wt%; from about 0.05 wt% to about 5 wt%; from about 1 wt% to about 10 wt%; from about 1 wt% to about 8 wt%; from about 1 wt% to about 5 wt%; from about 2 wt% to about 10 wt%; from about 2 wt% to about 8 wt%; or from about 2 wt% to about 5 wt%. The POSS may be added in an amount of no greater than 20 wt%, no greater than 15 wt%, no greater than 10 wt%, no greater than 8 wt%, no greater than 5 wt%, no greater than 2 wt%, no greater than 1 wt%, or less.

POSS can be added to formulations described in WO 2011/030143, which is

incorporated by reference in its entirety. Other nail coatings to which POSS can be added include those disclosed in, for example, US Patent Nos. 8124058, 6818207, 8399537, 8263677, 8367742, 5985951 , 5785958, 5576509, 5965147, 5639447, 6051242, 5130125, 5512273, 5662891, 5720804, 4871534, 5785958 and 7678321 ; in US Patent Application Publication Nos. 2010/0012263, 2005/0065297 and 2007/0286827; in PCT Application Publication Nos. WO 201 1/01 1304, WO 2011/031578, WO 201 1/043880 and WO 201 1/043879; and in U.S.

Application Nos. 13/846024 filed 18 March 2013, 12/573633 filed 5 October 2009, 12/573640 filed 5 October 2009, 13/042436 filed 7 March 2011, 13/827483 filed 14 March 2013 and 61/692096 filed 22 August 2012. The disclosures of each of these patents, publications, and patent applications are hereby incorporated by reference in their entirety.

Solvents

In some embodiments, the nail coating composition further includes a solvent. In some embodiments, the solvent used is water, or an organic solvent, such as a polar organic solvent. Non-limiting organic solvents include acetone, butyl acetate, isopropyl alcohol, ethanol, ethyl acetate, methyl ethyl ketone, and mixtures thereof. In some embodiments, the solvent is acetone. In some embodiments, the solvent is butyl acetate. In some embodiments, the solvent is ethyl acetate. In some embodiments, the solvent is butyl acetate, ethyl acetate, and mixtures thereof.

In some embodiments, the solvent is acetone, butyl acetate, butylene glycol, dipropylene glycol, disiloxane, ethyl acetate, ethyl ether, heptane, hexylene glycol, ethanol (denatured) isopropyl alcohol, limonene, n-butyl alcohol, propyl acetate, propylene carbonate, or propylene glycol.

In some embodiments, the solvent is ethyl acetate, butyl acetate, ethanol (denatured), isopropyl alcohol, acetone or mixtures and combinations thereof.

In some embodiments, the solvent is a ketone which is liquid at room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone. In some embodiments, the solvent is an alcohol, such as ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol and cyclohexanol. In some embodiments, the solvent is a glycol such as ethylene glycol, propylene glycol, pentylene glycol and glycerol. In some embodiments, the solvent is a propylene glycol ether which is liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and dipropylene glycol niono-n-butyl ether. In some embodiments, the solvent is a short-chain ester (containing from 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate and isopentyl acetate. In some embodiments, the solvent is an ether which is liquid at room temperature, such as diethyl ether, dimethyl ether and dichlorodiethyl ether. In some embodiments, the solvent is an alkane which is liquid at room temperature, such as decane, heptane, dodecane and cyclohexane. In some embodiments, the solvent is an aromatic cyclic compound which is liquid at room temperature, such as toluene and xylene. In some embodiments, the solvent is an aldehyde which is liquid at room temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof.

Film-forming agents

In some embodiments, the at least one film-forming agent in the coating (nail coating or nail topcoat) is a film-forming polymer. Film-forming polymers include polyesters; resins, such as polyurethane resins, alkyd resins, and polyvinyl resins such as polyvinyl acetate, polyvinyl chloride, polyvinylbutyrate; (meth)acrylic and vinyl copolymers such as styrene/butadiene copolymers, acrylate/vinyl acetate copolymers, acrylonitrile/butadiene copolymers,

ethylene/vinyl acetate copolymers, and silicone resins other than POSS resins as defined herein. In some embodiments, the at least one film-forming agent is a cellulosic resin. According to some embodiments, the at least one film-forming agent is at least one cellulosic resin. In some embodiments, the cellulosic resin is the major film former in the enamel.

Suitable cellulosic resins include nitrocellulose or other cellulose derivative, such as a cellulose ester, cellulose acetate alkylate (e.g., cellulose acetate propionate, cellulose acetate butyrate) and ethyl cellulose. Nitrocellulose and cellulose esters useful in accordance with the present invention are identified in U.S. Pat. No. 6,333,025, the text of which is hereby incorporated by reference. In some embodiments, the cellulosic resin is a cellulose ester. In some embodiments the cellulose ester is a cellulose acetate alkylate. The cellulose acetate alkylate may be selected from the group consisting of cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof.

In some embodiments of the invention, the nail coatings may also include an additional film-forming agent, such as polymers such as polyesters; resins, such as polyurethane resins, alkyd resins, and polyvinyl resins such as polyvinyl acetate, polyvinyl chloride, polyvinylbutyrate; (meth)acrylic and vinyl copolymers such as styrene/butadiene copolymers, acrylate/vinyl acetate copolymers, acrylonitrile/butadiene copolymers, and ethyl ene/vinyl acetate copolymers.

Plasticizers

The nail coating of the present embodiments may also include an amount of plasticizer, which can be chosen by a person skilled in the art on the basis of his or her general knowledge, so as to obtain a composition which has cosmetically acceptable properties.

Plasticizers useful in the presently disclosed nail coating composition include plasticizers commonly employed in nail enamel compositions. These plasticizers encompass, but are not limited to, dibutyl phthalate, dioctyl phthalate, tricresyl phthalate, butyl phthalate, dibutoxy ethyl phthalate, diamylphthalate, tosyl amide, N-ethyl-tosyl amide, sucrose acetate isobutyrate, camphor, castor oil, citrate esters, glyceryl diesters, glyceryl triesters, tributyl phosphate, tri- phenyl phosphate, butyl glycolate, benzyl benzoate, butyl acetyl ricinoleate, butyl stearate, and dibutyl tartrate.

Additional examples of plasticizers suitable for use in the present invention, alone or as a mixture, include: glycols and derivatives thereof such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether and ethylene glycol hexyl ether; glycerol esters; propylene glycol derivatives including propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, diethylene glycol methyl ether and propylene glycol butyl ether; acid esters, including carboxylic acid esters, such as citrates, phthalates, adipates, carbonates, tartrates, phosphates and sebacates; and

oxyethylenated derivatives, including oxyethylenated oils, for example, plant oils such as castor oil; and mixtures thereof.

According to some embodiments, the plasticizer is a biodegradable plasticizer. In some embodiments, the plasticizer is an acetylated monoglyceride.

In some embodiments, the plasticizer is an alkyl citrate. In some embodiments, the alkyl citrates contemplated for use in the present embodiments are those resulting from esterification of citric acid with alcohols containing three or more carbon atoms, for example, tripropyl citrate, tributyl citrate, trihexyl citrate, etc. These esters may be derived from either primary or secondary alcohols. Esters derived from glycol and glycerol ethers containing one or more unetherified hydroxyl groups are also suitable plasticizers of similar characteristics.

In some embodiments, a plasticizer used in the present invention may be the mixture of acetyl tributyl and N-ethyl tosyl amide. The plasticizer may, for example, be present in an amount of from about 3% to about 12% by weight relative to the weight of the composition.

In some embodiments, the plasticizer is triethyl citrate (TEC). In some embodiments, the plasticizer is acetyl triethyl citrate (ATEC). In some embodiments, the plasticizer is tributyl citrate (TBC). In some embodiments, the plasticizer is acetyl tributyl citrate (ATBC). In some embodiments, the plasticizer is trioctyl citrate (TOC). In some embodiments, the plasticizer is acetyl trioctyl citrate (ATOC). In some embodiments, the plasticizer is trihexyl citrate (THC). In some embodiments, the plasticizer is acetyl trihexyl citrate (ATHC). In some embodiments, the plasticizer is butyryl trihexyl citrate (BTHC, trihexyl o-butyryl citrate). In some embodiments, the plasticizer is trimethyl citrate (TMC). In some embodiments, the plasticizer is alkyl sulphonic acid phenyl ester (ASE). In some embodiments, the plasticizer is vinyl chloride copolymer. In some embodiments, the plasticizer is 1 ,2-cyclohexane dicarboxylic acid diisononyl ester.

In some embodiments, the plasticizer is a tri-lower alkyl citrate. This includes triethyl citrate, tributyl citrate and triamyl citrate.

In some embodiments, the plasticizer is an acyl tri(lower alkyl) citrate where the alkyl group contains 2-4 carbon atoms. This includes acetyl triethyl citrate and acetyl tributyl citrate.

Color Agents

"Colorants" or "coloring agents" useful in the cosmetic compositions of the invention may include, for example, pigments, including nacreous pigments, solid particles (for example, glitter flakes) and liposoluble colorants. Pigments may be white, transparent or colored, and mineral and/or organic. Among the mineral pigments which may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and iron oxide or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments which may be mentioned are carbon black, pigments of D&C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminum.

Conventional coloring agents can be used, and examples include inorganic pigments such as titanium dioxide, iron oxides, titanated mica, iron oxide coated mica, ultramarine, chromium oxide, chromium hydroxide, manganese violet, bismuth oxychloride, guanine, and aluminum; pearlescent materials; and organic coloring agents such as ferric ammonium ferrocyanide, and D&C Red Nos. 6, 7, 34; Blue No. 1 ; Violet No. 2; and Yellow No. 5.

In some embodiments, the color agent is one or more lake pigments, A "lake pigment" is a pigment manufactured by precipitating a dye with an inert binder, or "mordant", usually a metallic salt. The metallic salt or binder used is typically inert and insoluble in the vehicle, and is typically white or very neutral. In some embodiments, the metallic salt or binder has low tinting strength so that the dye itself determines which wavelengths are absorbed and reflected by the resulting precipitate.

The colorant can also include one or more pigments. These pigments can be white or colored, and inorganic or organic. Examples of inorganic pigments include titanium dioxide, which has optionally been surface-treated, zirconium oxide and cerium oxide, as well as iron oxide and chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metallic pigments such as aluminum and bronze. Examples of organic pigments include carbon black, pigments of D&C type and lakes based on cochineal carmine, barium, strontium, calcium, aluminum, and guanine.

The nacreous pigments can be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with, for example, iron oxides, ferric blue, chromium oxide, or with an organic pigment of the above-mentioned type, as well as nacreous pigments based on bismuth oxychloride.

The inorganic pigments may be surface-treated as is customary to prevent migration or striation. Silicones and polyethylenes are most often used as the coatings for inorganic pigments and thus may be used according to the present invention. Colorant materials may also include chips or powder of mica or diamonds in the nail composition. Also useful are specialty materials giving rise to two-tone color effects such as liquid crystal silicones or multi-lamellar metallic particulates, which generally can be mixed with pigments or dyes to obtain a broader spectrum of brilliant color and increased luminous reflectance. Such materials are described in, e.g., U.S. Pat. Nos. 3438796; 4410570; 4434010; 4838648; 4930866; 5171363; 5364467; 5569535;

5607904; 5624486; 5658976; 5688494; 5766335; N. Hatberle et al., "Right and Left Circular Polarizing Colorfilters made from Crosslinkable Cholesteric LC-Silicones," Conference Record of the 1991 International Display Research Conference (IEEE), pp. 57-59; R. Maurer et al, "Polarizing Color Filters made from Cholesteric LC-Silicones," SID 90 Digest (1990), pp. 110- 1 13; H.-J. Eberle et al., "Inverse Angle Dependence of the Reflection Colours of Cholesteric Polymeric Liquid Crystals Mixed with Pigments," Liquid Crystals, 5(3), (1989), pp. 907-916; J. Pinsl et al., "Liquid Crystalline Polysiloxanes for Optical Once-Write Storage," J. Molec.

Electr., Vol. 3 (1987), pp. 9-13; and D. Makow, "Reflection and Transmission of Polymer Liquid-Crystal Coatings and their Application to Decorative Arts and Stained Glass," Color Res. Applic. Vol. 11, No. 3, (1986), pp. 205-208, all of which are incorporated herein by reference in their entirety.

The nail coating composition can be cured by any suitable means; for example, the composition can be photocurable, thermally curable, or cationically curable.

In some embodiments, the composition is photocurable, and curable to form a cross- linked material in response to radiation, for example light, such as ultraviolet (UV) light. In other embodiments, the composition can be electron beam curable or thermally curable.

In some embodiments, the composition further includes an initiator. The initiator is present to initiate the curing process by reacting in response to a stimulus and may, or may not, function catalytically. The initiator may be any type of suitable initiator. The initiator may be a radical initiator, a cationic initiator, or a hybrid initiator. The initiator may be a thermal initiator, which reacts so as to initiate curing in response to a rise in temperature, or the initiator may be a photoinitiator, which reacts so as to initiate curing in response to light, for example visible or ultraviolet light. In embodiments including a photoinitiator, the formulation may further include a photosensitizer. Photosensitizers are compounds added to the composition to modify the absorption spectrum of the photoinitiator so as to increase the efficiency with which it absorbs radiant energy. A curable formulation including a photoinitiator may be a photo-curable formulation (such as a UV-curable formulation). Both UV and visible light activated photoinitiators may be suitable for the present invention. Suitable photoinitiator systems include aromatic alpha-hydroxy ketones,

alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphine oxides, and a tertiary amine plus a diketone, mixtures thereof and the like. Illustrative examples of photoinitiators are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phenyl-propan-l- one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide (DMBAPO), bis(2,4,6- trimethylbenzoyl)-phenyl phosphineoxide (Irgacure 819), 2,4,6-trimethylbenzyldiphenyl phosphine oxide and 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ester, camphorquinone, and a combination of camphorquinone and ethyl 4-(N,N- dimethylamino)benzoate. Commercially available visible light initiator systems include Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850 (all from Ciba Specialty Chemicals) and Lucirin TPO initiator (available from BASF). Commercially available UV photoinitiators include Darocur 1 173 and Darocur 2959 (Ciba Specialty Chemicals). The initiator is used in the reaction mixture in effective amounts to initiate photopolymerization of the reaction mixture, e.g., from about 0.01 to about 5 parts per 100 molar parts of reactive monomer. Alternatively, initiation can be conducted without a photoinitiator using, for example, e-beam. Preferred initiators include bisacylphosphine oxides, such as bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide (Irgacure 819®) or a combination of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide (DMBAPO), and the preferred method of polymerization initiation is visible light.

In some embodiments, visible light activated photoinitiators are preferred. The most preferred can be bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide (Irgacure 819®).

Optionally, the formulation includes an initiator solvent. It is a known problem of some initiators, in particular cationic photoinitiators such as arylsulfonium salts, to suffer from low solubility in the resins of cationically curable formulations, and to therefore require the presence of a solvent (for example propylene carbonate, CAS No. 108-32-7).

The solubility of initiators in some embodiments (in particular, compositions including a blend of fatty acid esters, or derivatives thereof, or curable compositions including the ester fractions of a blend of esterified plant oils, or derivatives thereof) can be higher, and in some cases considerably higher, than the solubility of the initiators in known curable compositions.

Accordingly, one advantage of such blended formulations that less initiator solvent, or no initiator solvent, is required. Thus, curable compositions according to some embodiments omit an initiator solvent.

In some embodiments, the composition further includes one or more reactive modifiers. One or more reactive modifiers may be added to a composition to modify the properties of the cured cross-linked material, such as surface adhesion, hardness or flexibility. Reactive modifiers participate in the curing reaction and may terminate cross linking reactions or may function as cross linkers. However, unlike resins, reactive modifiers when taken alone, are not curable, or curable to form a cross-linked material.

Each said reactive modifier may, for example, be a polyol (such as ethylene glycol, glycerol, or sugars such as glucose, or dendritic polyester polyols) or a small molecule epoxide, such as limonene oxide, CAS No. 1 195-92-2, limonene dioxide, CAS No. 96082 (which may function as a cross linker), or a substance containing limonene oxide or limonene dioxide (for example epoxidized lemon oil) or cyclohexene oxide, CAS No. 286-20-4, or a strained heterocycle such as 3,3-dimethyloxetane, CAS No. 6921-35-3, or trimethylpropane oxetane (TMPO), CAS No. 3047-32-2, or a terpenoid such as abietic acid, CAS No. 514-10-3, or a terpenoid containing material such as pine rosin. Reactive modifiers of this type can be suitable for curable compositions including an epoxidized fatty acid-based component, or an epoxidized plant oil, or derivative thereof.

In some embodiments the composition can further include one or more passive modifiers. One or more reactive modifiers may be added to a formulation to modify the properties of the formulation or of the cured cross-linked material. A passive modifier does not participate in the curing reaction and may, for example, function as a plasticizer, or as a dispersant, or a surfactant or a rheology modifier.

Some resin materials, including some curable epoxy resins, are of relatively high viscosity, typically of the order of several hundred centipoises (cP). Reactive diluents can therefore be added to formulations including curable resins to reduce viscosity in order render them suitable for certain methods of application. The term "reactive diluent" refers to a constituent of a formulation that participates in the curing reaction. The reactive diluent can in some cases terminate cross linking reactions, or in other cases can function as a cross linker. A "passive diluent" refers to a constituent of a formulation that does not participate in the curing reaction.

The embodiments illustrated and discussed in this specification are intended only to teach those skilled in the art the best way loiown to the inventors to make and use the invention. Nothing in this specification should be considered as limiting the scope of the present invention. All examples presented are representative and non-limiting. The above-described embodiments of the invention may be modified or varied, without departing from the invention, as appreciated by those skilled in the art in light of the above teachings. It is therefore to be understood that, within the scope of the claims and their equivalents, the invention may be practiced otherwise than as specifically described.