BACKGROUND OF THE INVENTION Consumers use nail polishes to cosmetically enhance their nails or protect the nails from everyday conditions and stressors. However, the nail polishes of which the present inventors are aware are deficient in many respects, including their inability to provide long wear. Such nail polishes often exhibit deterioration, particularly in the form of chipping or peeling, in as few as one or two days. Such deterioration is exhibited primarily at the tip of the nail. The occurrence of this deterioration often forces consumers to remove their nail polish soon after original application and reapply additional nail polish to the nails. Consumers may also attempt to correct the unsightly appearance of the deteriorating nail polish by "touching-up"the areas of the nail which exhibit the deterioration, a practice which actually impairs the overall look of the nail polish. Finally, consumers may choose to do nothing about the deterioration and allow, for example, chipping and peeling to progress, resulting in nails which are not only minimally protected from the environment but are unsightly as well.

Extreme examples of nail polish compositions which exhibit inadequate wear are those which are easily and completely peeled or stripped off the nails without the use of a solvent. Other nail polish compositions are completely removable with water and, therefore, are not practical for normal use and do not provide long wear under everyday conditions.

The art is replete with nail polish compositions which are promoted as having long wear, good adhesion, and/or resistance to chipping. While some nail polish compositions provide better wear than others, a need remains for nail polishes

which provide improved wear. It would therefore be desirable to provide nail polish compositions having improved wear properties including, for example, improved adhesion to the nail.

The present inventors have surprisingly discovered compositions which provide films having improved adhesion to the nail and in-use wear reflected by defined Tip Wear Indexes and/or Total Wear Indices. The present compositions provide nail polish films exhibiting wear at a superior level to nail polishes of which the present inventors are aware.

SUMMARY OF THE INVENTION The present invention relates to compositions suitable for application to the nails, e. g., as a nail polish, which provide films exhibiting defined wear properties, namely Tip Wear Indices and/or Total Wear Indices. The films having these properties exhibit improved wear.

Compositions having these properties preferably comprise: a) from about 5% to about 20%, by weight of the composition, of film forming cellulosic polymer; b) from about 1.25% to about 8%, by weight of the composition, of film forming polyurethane polymer; c) from about 3% to about 20%, by weight of the composition, of plasticizer; and d) from about 55% to about 90%, by weight of the composition, of volatile, organic solvent.

The compositions advantageously provide films having a Tip Wear Index and/or Total Wear Index of less than about 1.00. The films preferably further have a Coverage Factor of from 0 to 1.0, more preferably from about 0.1 to about 0.9.

The invention also relates to films formed from the compositions, and methods of treating the nails comprising application of the composition to the nails.

DETAILED DESCRIPTION OF THE INVENTION The essential components of the present invention are herein described below. Also included are non-limiting descriptions of various optional and preferred components useful in the compositions of the present invention.

The present invention can comprise, consist of, or consist essentially of any of the required or optional components and/or limitations described herein.

In the description of the invention various embodiments and/or individual features are disclosed. As will be apparent for the skilled practitioner all combinations of such embodiments and features are possible and can result in preferred executions of the invention.

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages are calculated based on the total composition unless otherwise indicated.

All component or composition levels are in reference to the active level of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources.

Referred to herein are trade names for materials including, but not limited to, polymers and optional components. The inventors herein do not intend to be limited by materials under a certain trade name. Equivalent materials (e. g., those obtained from a different source under a different name or catalog (reference) number) to those referenced by trade name may be substituted and utilized in the compositions herein.

Active and other ingredients useful herein may be categorized or described herein by their cosmetic and/or therapeutic benefit or their postulated mode of action. It is to be understood that the active and other ingredients useful herein can in some instances provide more than one cosmetic and/or therapeutic benefit or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit an ingredient to the particularly stated application or applications listed.

All documents referred to herein, including all patents, patent applications, and printed publications, are hereby incorporated by reference in their entirety.

The compositions of the present invention are suitable for application to animal nails, including human nails. The compositions of the present invention are useful, for example, for providing aesthetic, cosmetic, therapeutic, and/or prophylactic benefits to the nails. As used herein, the term"nail polish"is a

comprehensive term describing a nail polish composition, product (including coloring products), or the like, which is useful for providing, for example, aesthetic, cosmetic, therapeutic, and/or prophylactic benefits to the nails.

As used herein, the term"animal nail"means a keratinaceous plate present at the upper surface of the end of a finger or toe of a primate or the analogous claw, hoof or the like of other animals.

As used herein, the term"suitable for application to animal nails"means that the compositions are suitable for use in contact with animal nails without undue toxicity, incompatibility, instability, allergic response, and the like in regard to a given animal species. Preferred compositions are those suitable for application to human nails.

In addition to natural nails, the compositions herein may also be used for application to synthetic (artificial) nails.

Film-forming polymers (a) and (b) The present compositions comprise one or more film-forming, solvent-borne, cellulosic polymers and polyurethane polymers.

The film-forming polymers herein are solvent-borne polymers. As used herein, the term"solvent-borne", with reference to a film-forming polymer, means that the polymer was prepared under substantially anhydrous conditions and is preferably added to the composition which it comprises as a substantially anhydrous solution (or other mixture, whether heterogeneous or homogeneous, preferably homogeneous). As used in reference to a composition suitable for application to the nails, a solvent-borne composition means that the composition comprises one or more organic solvents and is substantially anhydrous, preferably comprising less than 2% water, more preferably less than 1% water, most preferably less than 0.25% water. Solvent-borne polymers and compositions are preferred.

The term"film-forming polymer"means a homopolymer, copolymer, or mixture thereof which, as recognized in the polymer arts, forms an adherent continuum from a composition when applied to a substrate (in the present invention, nails). See, e. g., Polymer Colloids, Robert M. Fitch, ed., New York: Plenum Press, pp. 173-183 (1971). As used herein, the term"copolymer"includes linear, block, branched, graft, comb, and star copolymers. The film-forming polymers useful

herein are self-curing polymers. That is, they do not require chemical reaction or introduction of energy (e. g., exposure to ultraviolet rays) to form the adherent continuum.

The film-forming polymers herein can be selected from nonionic, ionic (anionic or cationic), and amphoteric (including zwitterionic) polymers.

The film-forming cellulosic polymers may be selected from polymers derived from cellulose such as are known in the art, including but not limited to cellulose esters. Preferred cellulosic polymers are nitrocellulose, nitrocellulose esters such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof. More preferred are nitrocellulose, cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof. Nitrocellulose polymers are most preferred. Exemplary nitrocellulose polymers are nitrocellulose RS types (nitrogen <BR> <BR> <BR> content of 11.5-12.2%) of Hercules, such as nitrocellulose-RS'/2 second,-RS 1/4 second,-RS 1/8 second,-RS 1/16 second or the like.

The compositions hereof preferably comprise a total of from about 5% to about 20%, more preferably from about 6% to about 20%, even more preferably from about 10% to about 17%, most preferably from about 13% to about 16%, cellulosic polymer.

The present compositions also comprise a film-forming polyurethane.

Preferred polyurethanes are selected from aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes, aromatic polycaprolactam polyurethanes, aliphatic polycaprolactam polyurethanes, urethane acryl copolymers, siloxane-urethane copolymers, and mixtures thereof. More preferred are aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes, aromatic polycaprolactam polyurethanes, aliphatic polycaprolactam polyurethanes, and mixtures thereof. Aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes and mixtures thereof are even more preferred.

Aliphatic polyether polyurethanes, aliphatic polyester polyurethanes, and mixtures thereof are most preferred.

Preferred solvent-borne polyurethanes include Sanres EX519@, Sanres EX499 (hexylene glycol/neopentyl glycol/IPDI [isophorone diisocyanate] copolymer), Sanres 12711@, Sanres 6010@, and Sanres 6012@ (all of which are available from B. F. Goodrich). The most preferred polyurethane is Sanres EX519@.

Preferred polyurethanes are those having a number average molecular weight of from about 10,000 to about 80,000, more preferably from about 15,000 to about 50,000, most preferably from about 20,000 to about 35,000.

The present compositions preferably comprise a total of at least about 1.25% film forming polyurethane, e. g., at least about 2%, 3%, 3.5% or 5% film-forming polyurethane. The present compositions preferably comprise a total of from about 1.25% to about 8%, more preferably from about 1.5% to about 5%, most preferably from about 2% to about 4%, film-forming polyurethane.

Plasticizers (c) The compositions hereof further comprise one or more plasticizers such as are known in the art. The plasticizer is generally used in an amount to plasticize the film forming polymers so that the nail polish has acceptable flexibility on the nail.

The compositions preferably comprise from about 3% to about 20%, more preferably from about 5% to about 20%, even more preferably from about 6% to about 15%, most preferably from about 6% to about 10%, plasticizer.

Preferred plasticizer systems are those which reduce brittleness and increase toughness of the nail polish films and which do not inordinately increase viscosity of the nail polish at the level used.

Preferred plasticizers are selected from the group consisting of polar plasticizers comprising epoxy linkages, linkages comprising a nitrogen atom such as amide, imide, urea and/or urethane linkages, (including polar resin plasticizers comprising the foregoing linkages), polyesters, polyester acids (e. g., di-and tri- acids), phthalates, camphor and mixtures thereof. The compositions hereof preferably comprise a plasticizer selected from the group consisting of polar plasticizers comprising amide linkages, polyesters, polyester acids, and mixtures thereof.

Nonlimiting examples of suitable plasticizers are alkyl toluene-sulfonamides, e. g., ethyl toluene-sulfonamide (e. g., Uniplex PX-45 commercially available from Unitex Chemical Corp. of Greensboro, NC); toluene-sulfonamide formaldehyde ("TSF"); polyesters, e. g., Uniplex 670P (commercially available from Unitex Chemical Corp. of Greensboro, NC); polyester acids, e. g., C3-C20, preferably C4-Cl2, more preferably Ce-Cio polyester acids (including di-and tri-acids) such as polyester sebaceates (e. g., Paraplex G-25, commercially available from C. P. Hall, Bedford Park, IL) and polyester adipates (e. g., Paraplex G-50, commercially available from C. P. Hall); those disclosed in WO 97/00664, Chen et al, assigned to Eastman Chemical Co; phthalates, e. g., diethyl phthalate, dibutyl phthalate, and dioctyl phthalate; nonionic surfactant polymers, e. g., tartrates (e. g., diethyl tartrate and dibutyl tartrate), phosphates (e. g., diethyl phosphate and dibutyl phosphate) and glycols (e. g., tetraethylene glycol di-2-ethylhexoate, commercially available from C. P. Hall as Tegmer (t); camphor; sucrose acetate isobutyrate; and castor oil.

Preferred plasticizers have a number average Molecular Weight of about 10,000 or less. Preferred compositions are essentially free of, and preferably contain no formaldehyde resins.

Plasticizer mixtures comprising at least one alkyl toluene-sulfonamide (e. g., Ci-Cio, preferably C2-C4 alkyl toluene-sulfonamides) are preferred. A blend of ethyl toluene-sulfonamide and at least one other plasticizer is most preferred. Preferred compositions comprise from about 3% to about 8% (more preferably from about 4% to about 7%, most preferably from about 4% to about 6%) alkyl toluene-sulfonamide and a total of from about 0.1 % to about 6% (more preferably from about 1 % to about 5%, most preferably from about 2% to about 3%) of one or more other plasticizers.

Preferred other plasticizers are polyesters, polyester acids, camphor, phthalates, and mixtures thereof.

Particularly preferred compositions comprise a plasticizer selected from the group consisting of polyesters, polyester acids, and mixtures thereof, more preferably selected from the group consisting of polyester acids. Polyester adipates are preferred polyester acids. Such plasticizers are preferably used in an amount of

from 0.1% to about 6%, more preferably from about 1% to about 5%, most preferably from about 2% to about 3%.

Carrier (d) The compositions of the present invention further comprise a carrier comprising a liquid diluent. Suitable diluent systems are those which solubilize (i. e., dissolve) the polymers and dry in a reasonable time on nails. The liquid diluent comprises one or more volatile, organic solvents.

Preferred volatile organic solvents have a boiling point at latm of from about 50 °C to about 140 °C, more preferably from about 56 °C to about 125 °C. Preferred organic solvents are selected from alcohols, esters, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, ethers, and mixtures thereof (more preferably C,-C, o, most preferably C2-C4). Alcohols and esters are more preferred, esters being most preferred. Preferred alcohols are monohydric. Preferred monohydric alcohols are ethanol, iso-propanol, and n-propanol. Preferred esters are butyl-, ethyl-, isopropyl- and propyl-acetate, and mixtures thereof. More preferred esters are ethyl acetate, butyl acetate, isopropyl acetate, and mixtures thereof. Other non-limiting examples of suitable organic solvents are benzyl alcohol, amyl acetate, acetone, heptane, iso- butyl acetate, toluene, methyl acetate, iso-butanol, n-amyl alcohol, n-butyl alcohol, hexane, and methyl ethyl ketone.

The present compositions preferably comprise from about 55% to about 90%, more preferably from about 62% to about 78%, most preferably from about 66% to about 74%, volatile, organic solvent.

Optional Components The compositions of the present invention may additionally comprise optional components such as are known in the art to enhance their performance as a nail polish. For example, antifoams, buffers, chelating agents, coalescents, dispersing agents, dyes, epoxies, fillers, pigments, preservatives, resins, other film forming polymers, therapeutic and/or prophylactic agents, thickeners, wax additives, wetting agents, and the like can be included in the compositions herein. Such optional components may be dispersed, solubilized, or otherwise mixed into the composition. These components may be added to the compositions hereof singularly

or in admixture provided they do not substantially reduce the wear properties of the compositions. Non-limiting examples of optional components are given below.

Pigments or Dyes One or more pigments and other suitable coloring agents, such as dyes, may be incorporated into the compositions. Suitable pigments are inorganic or organic pigments known as, for example, the FD&C and D&C colors, lakes, and iron oxides.

Such pigments are disclosed in the C. T. F. A. Cosmetic Ingredient Handbook, First Edition, 1988. Organic pigments include, for example, D and C Red, Nos. 10,11, 12, and 13, D and C Red No. 7, D and C Red Nos. 5 and 6, D and C Red Nos. 30 and 34, lacquers such as D and C Yellow No. 5 and D and C Red No. 2, and guanine. Inorganic pigments include, for example, titanium dioxide, bismuth oxychloride, brown iron oxide, and the red iron oxides.

Preferred compositions comprise from 0% to about 10%, by weight of the composition, of pigment and/or dye. More preferably, the compositions comprise from about 0.1% to about 10%, even more preferably from about 0.25% to about 5%, and most preferably from about 0.5% to about 2%, by weight of the composition, of pigment and/or dye.

Preservatives One or more preservatives such as are known in the art may be added to the present compositions to prevent, inhibit, or retard microbial growth in the composition. Preferred preservatives include benzophenone, methyl paraben, ethyl paraben, propyl paraben, benzyl alcohol, benzoic acid, benzoates, sorbates, sodium dehydroacetate, 1- (3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride (which may be obtained commercially as Quaternium-15 from Dow Chemical Co., Midland, MI). Benzophenone is preferred.

The compositions preferably comprise from 0% to about 0.1%, by weight of the composition, of preservative.

Resins One or more resins may be added to the present compositions, e. g., to promote adhesion, to strengthen the film forming polymers, and/or to increase gloss.

The resins, for example, epoxy resins such as toluene-sulfonamide-epoxy, can also plasticize the composition. Examples of suitable resins include epoxies and

polyacrylics including Polytex E75 (toluene-sulfonamide-epoxy) and NX-55 (both commercially available from Estron Chemical, Inc., Calvert City, KY), Acryloid B66 (commercially available from Rohm and Haas, Philadelphia, PA) and Avalure AC315 (commercially available from B. F. Goodrich, Cleveland, OH). Preferred compositions comprise both epoxy and polyacrylic resin. A composition preferably comprises from 0% to about 15%, more preferably from about 0.5% to about 10%, even more preferably from about 0.5% to about 6%, most preferably from about 1% to about 5%, resin by weight of the composition.

Slip Aids One or more slip aids may be added, e. g., to improve surface friction, water resistance, abrasion resistance, and mechanical properties. Slip aids which may be used include wax additives including, for example, animal, fossil, vegetable, mineral, or synthetic waxes. Suitable wax additives include beeswax, carob, candelilla, ozocerite, polyethylene waxes, paraffin waxes, polypropylene waxes, polytetrafluoroethylene (commercially available as Teflon from DuPont, Wilmington, DE), nylons, polyamides, and materials containing silicone such as dimethicone and copolymers of polyether and polysiloxane.

The present compositions preferably comprise from 0% to about 1%, more preferably from about 0.001% to about 0.50%, and most preferably from about 0.001% to about 0.05% of slip aid.

Therapeutic and/or Prophylactic Agents One or more therapeutic and/or prophylactic agents, for example, vitamins, proteins, anti-fungal agents, anti-microbial agents, and sunscreens (including UV-A, UV-B, and broad spectrum solar filters) may be added to the present compositions for the further care and protection of the nails.

Stabilizers One or more stabilizers may be added to the compositions herein, e. g., to prevent pigment from settling and to achieve desired application properties.

Preferred stabilizers include clays, e. g., organically modified bentonites and hectorites such as stearalkonium bentonite and stearalkonium hectorite (commercially available from Rheox, Inc. of Hightstown, NJ).

The present compositions preferably comprise from 0.25% to about 3%, more preferably from about 0.5% to about 2.5%, and even more preferably from about 1 % to about 2% of stabilizer, by weight of the composition.

Other Film-Forming Polymers The compositions hereof may contain one or more additional film-forming polymers such as are known in the art, e. g., polyacryls, polymethacryls, styrene- acryl copolymers, polystyrenes, polysiloxanes, polyesters, silicone-acryl copolymers, vinyl acetate polymers, and mixtures thereof. Solvent-borne or water- borne polymers may be used, however solvent-borne polymers are preferred.

The present compositions may contain up to about 10%, e. g., up to about 5% or up to about 4%, of additional film-forming polymer.

Method of Making and Using The compositions of the present invention can be made using conventional formulation and mixing techniques.

A layer of nail polish may be prepared by standard application of the composition to the nail using a standard brush-applicator as is commonly utilized in the art (or equivalent thereof) and drying, that is, removing sufficient liquid diluent (through evaporation of volatiles, most preferably at ambient pressures and temperatures), to form a substantially dry layer, i. e., a layer which feels dry, smooth, and not tacky when it is touched with a human fingertip.

One or more layers of the composition may be applied to the nail. Generally from 1-4 layers, and preferably from 1-2 layers, is applied to the nail. Typically, on each application about 25 mg of the composition is applied per nail and allowed to dry to form a layer about 35 microns thick.

The compositions may be used as a clear coat (non-colored), color coat, basecoat, topcoat, or other coating on the nail. Accordingly, other nail treatment compositions such as are known in the art, including nail polishes, may be applied to the nail in addition to the compositions hereof. However, the compositions hereof are preferably used as the sole nail polish composition, e. g., as a clear coat or color coat.

The compositions of the present invention may be presented to a user or potential user (hereinafter"users") of the composition in association with information which informs such users that use of the composition will provide one or more benefits, including, but not limited to, high gloss, good coverage, and/or wear properties such as resistance to chipping, peeling, scratching or denting, and the like. Such information may also include instructions for use to obtain such benefits, e. g., including the method steps described above. By"in association with information"it is meant that the information is either directly printed on the container for the composition itself (including direct printing on the container per se or indirectly via a label or the like affixed to the container), or presented in a different manner including, but not limited to, a brochure, print advertisement,

electronic advertisement and/or other advertisement, so as to communicate the information to a consumer of the composition. Such information may accordingly comprise words, pictures, and the like.

Properties of Compositions/Films of the Present Invention & Test Methods Wear Properties Known nail polishes tend to exhibit deterioration on the nail after a short period of use. The present inventors have surprisingly discovered compositions which provide films exhibiting long wear. Such long wear is experienced over the entire surface of the nail and is quantitatively expressed herein by the Total Wear Index for a particular nail polish. Furthermore, the present inventors have discovered compositions which exhibit long wear at the tip of the nail. Such long wear is quantitatively expressed herein by the Tip Wear Index for a particular nail polish. As used herein, the lower the Total Wear Index and/or Tip Wear Index for a particular nail polish, the less deterioration is exhibited by that nail polish, relative to a control nail polish.

It has been found that the Wear Indices are a function of the type and level of cellulosic film forming polymer, polyurethane film forming polymer, and/or non- epoxy containing plasticizer in the composition. Preferred compositions have Wear Indices predicted by the following equation: Technical Film Wear Value = (Equation 1) (Equation 2), wherein: Equation 1 = [ (0.134) (wt % cellulosic polymer) 2]- [ (0.0083) (wt % cellulosic polymer) 3] + [ (0.098) (wt% polyurethane) 2] + [ (7.33) (wt% cellulosic polymer/wt% non-epoxy plasticizer)]- [ (1.73) [ (wt % cellulosic polymer) 2/ (wt% non-epoxy plasticizer)]] + [ (0.08) [ (wt % cellulosic polymer) 3/ (wt% non-epoxy plasticizer)]]

Equation 2 = (207) (wt % cellulosic polymer)- (241) (wt% non-epoxy plasticizer) The higher the Technical Film Wear Value, the lower the Wear Indices when worn on people. Wear Indices may also be lowered, for example, by including slip promoting agents to the composition or by using an underlayment of false acrylic nails.

The compositions advantageously provide films having a Tip Wear Index and/or Total Wear Index of less than about 1.00, preferably less than about 0.90, more preferably less than about 0.80, most preferably less than about 0.70.

According to one embodiment of the present invention, the composition comprises a film-forming polyurethane polymer and a suitable carrier comprising a volatile, organic solvent, which provide a film having a Tip Wear Index and/or Total Wear Index of less than about 1.00, preferably less than about 0.90, more preferably less than about 0.80, most preferably less than about 0.70. The films preferably have a Coverage Factor of greater than 0.4, more preferably greater than about 0.5.

According to another embodiment of the present invention, the composition comprises a film-forming polymer and a suitable carrier comprising a volatile, organic solvent, is essentially free of formaldehyde resins (e. g., toluene-sulfonamide formaldehyde or"TSF"resin), and provides a film having a Tip Wear Index and/or Total Wear Index of less than about 1.00, preferably less than about 0.90, more preferably less than about 0.80, most preferably less than about 0.70. The films preferably have a Coverage Factor of greater than 0.4, more preferably greater than about 0.5.

According to another embodiment of the present invention, the composition comprises a film-forming polymer and a suitable carrier comprising a volatile, organic solvent, has a Coverage Factor of greater than 0.4, preferably greater than about 0.5, and provides a film having a Tip Wear Index and/or Total Wear Index of less than about 1.00, preferably less than about 0.90, more preferably less than about 0.80, most preferably less than about 0.70.

Total Wear Indices and Tip Wear Indices are determined using the following test method.

Human female subjects are chosen who are accustomed to applying nail polish to, and wearing nail polish on, their own nails and who do not use synthetic nails such as, for example, acrylic nails. Individuals are initially categorized according to the percentage of total deterioration (as defined herein below) they typically experience with nail polish by following this complete method using a control product (defined below) on all ten fingers. Individuals who exhibit greater than 12% total deterioration after 5 days of normal use without touch-up, as measured by this method, are designated heavy stressors; individuals who exhibit between 6% and 12% total deterioration are designated moderate stressors; and individuals who exhibit less than 6% total deterioration are designated light stressors. Following this method, a subject group of approximately twenty subjects (not less than sixteen) is selected which contains about one-third heavy and one-third moderate stressors, and no more than one-third light stressors.

Application of nail polish takes place in a room maintained at a controlled temperature between 70 °F and 75 °F, in the morning on a Friday. Subjects wash their hands, dry them, and allow at least ten minutes before application of nail polishes. No nail pre-treatments, mechanical or otherwise, are done or allowed on the nails prior to application.

An alternate finger method of application is employed as follows. The fingers are numbered sequentially, one through ten, from the left pinky finger to the right pinky finger. The odd numbered fingers are denoted"A"fingers; even numbered fingers denoted"B"fingers. Subjects are randomly assigned to wear the control on either the"A"fingers or the"B"fingers, dividing the subject group in half such that two subject groups are formed. The two subject groups are balanced so that the number of right-handed and left-handed individuals is the same in the group applying the control to the"A"fingers as the group applying the control to the "B"fingers. Each subject is given a weighed, numbered bottle of the control and a timer, and is instructed to apply a coat of nail polish to the designated fingers (either the"A"or"B"set), allow the coat to dry (forming a layer) for five minutes, and then apply a second coat of the control contiguous to the first layer, applying the polish as

the subject normally would. The average weight of the control applied for five fingers by this process should be about 225 milligrams but will vary depending on the size of each subject's nails.

Each subject is then given the nail polish to be tested (test nail polish) and is instructed to apply it in the above manner to the five fingers which were not coated with the control (the remaining fingers). For convenience of subsequent capturing of images and analysis, a brightly colored red nail polish may be used, but this method is not limited by color of the nail polish. Test nail polishes that are not colored or are insufficiently opaque to adequately distinguish them from the nail as required for subsequent image taking are tested by incorporating one or more suitable dyes or pigments in the test nail polish at a level sufficient to see the color of the film and differentiate it from the color of the nail. After applying the test nail polish to the designated fingers in the order and manner instructed, application is complete and individuals are instructed not to damage the nail polishes as they continue to set over the next two to three hours. The subjects attend to their usual activities until they return for image taking.

On the Wednesday following application of the nail polish, subjects return to have images of their nails taken. Beginning with finger number one and proceeding through finger number ten, each subject places the palm of her hand on a flat surface on which a transom, or finger rest (described below), is positioned underneath a camera to capture an image of each fingernail, without axial rotation and without pressure except due to the weight of the finger. This positioning allows optimum lighting to all areas of the nail, and a reproducible fingernail area to be presented to the camera for imaging.

Images are taken with a Zeiss SV-11 stereomicroscope and a Sony 3-C-CD camera (or equivalents thereof). A 1.0 zoom ring is used, with a 1/4x lens, the working distance above the finger set by focus (approximately 37 cm).

Magnification is approximately 15x. A Fostec 8375 (EJA) light ring (or equivalent thereof) is placed 3.5 cm above the finger rest base, and is set at 70% of maximum power. At the bottom, a dark green finger positioning transom on the tabletop is used as a rest for the finger being imaged. The wedge-shaped transom slopes up from front to back, measuring 5 mm in height off the tabletop in front and 12 mm in

height off the tabletop in back over a span of 8 cm. Two polarizing filters are used, set in crosspole position to eliminate shine from the nail surface. Optimas 4.1 software (commercially available from Media Cybernetics, L. P., of Silver Spring, Maryland), or a suitable equivalent thereof,) is used for image grabbing. All lighting, camera and software settings are maintained constant through a study.

Software contrast and brightness settings are optimized at the start of the study to maximize contrast between the nail and nail polish, and to determine if any colorants or opacifiers need to be added as described herein above.

Percent deterioration analysis is based on area measurement of nail polish remaining on the nail, in a manner similar to the method of analysis of second-phase constituents of metals as described in ASTM E1245-95,"Standard Practice for Determining the Inclusion or Second-Phase Constituent Content of Metals by Automatic Image Analysis". There are three steps involved in analysis of nails for percent deterioration. First, the total area of the nail is determined. Second, the north-south center line of the nail is determined. Third, the remaining polish area is determined in both halves of the nail; and also is categorized as to whether it adjoins a nail edge, and the percentage of tip deterioration, cuticle deterioration, and internal deterioration of an individual nail is determined.

To start, a suitable image is retrieved for viewing on the computer screen.

That is, the image must be sufficiently large and of sufficient quality to allow an operator to easily determine by eye the location of all nail edges and all edges of the nail polish. The working image presented to the operator should be magnified approximately 10-15 times actual size, and the entire image must be evenly lit, with no shadows around the nail-cuticle boundary. The image should be bright enough so that the edges of polish and the nail are easily visible to the eye, with high resolution comparable to that of 35 mm film printed on photograph quality paper, or alternatively a 640 x 480 pixel on-screen digital color image.

As an operator identifies by sight the field of the nail, a computer program such as Optimas 4.1 is used to measure area and perform calculations by the following method. Many such computer programs are available or can be tailored to perform the functions described herein, as is known by one skilled in the field of image analysis and as described in § 12.4.1 of ASTM E1245-95.

The total nail area is determined by tracing the outline of the nail with a cursor on the computer screen controlled by a mouse. The nail is traced exclusive of cuticle or other finger skin. After tracing the entire nail, the total nail area is determined by the Optimas software in arbitrary units (e. g., square mm; the units utilized should be consistent for all area measurements). This measurement is referred to herein as Am ("area of the measurement field"in ASTM E 1245-95).

Second, the image is divided in half in north-south directions (i. e., the north half-field comprises the whole tip of the nail and the south half-field comprises the whole edge of the nail adjoining the cuticle), by area. The total area of each half- field is At. Third, area of nail polish deterioration in each half is determined using a suitable image analysis detection software program that detects only the nail polish covered (colored or opacified) area (Ac) (such as, for example, Optimas 4.1).

Percent wear for each half-field (P,/2) is expressed as: P)/2= [ (At-Ac)-Amj* 100% The percentages derived from each half are added together to give a percent total deterioration for a given finger.

The ability of the image analysis software to accurately detect the nail polish area must be manually verified, such as described in § 12.2.1 of ASTM E1245-95.

This measurement is obtained for each nail, individually.

The Total Wear Index for a test nail polish is determined as follows. For each subject, the average percent total deterioration for the test nail polish (Total) (calculated by adding the percent total deterioration for each of the five fingers having test nail polish applied to them and dividing this by five) is determined. The average percent total deterioration for the test nail polish for the subject group (TWtal) is then determined. Similarly, for each subject, the average percent total deterioration for the control (TWa2) (calculated by adding the percent deterioration for each of the five fingers having the control applied to them and dividing by five) is determined. The average percent total deterioration for the control for the subject group (TW, is then determined. The Total Wear Index for the test nail polish (TWItest) is then calculated as follows:

TWI=TWtai-TW Accordingly, the lower the Total Wear Index, the better the wear properties are for that particular nail polish relative to the control.

In each half of the field, the deterioration area is calculated as 100% minus the remaining polish area, also expressed as a percentage (the Optimas 4.1 software automatically performs these calculations). The deterioration areas are categorized as to whether they adjoin an outside edge of the nail, or not. Deterioration which does not adjoin an outside edge of the whole nail, being completely enclosed by nail polish, is separately calculated and expressed as internal deterioration. Deterioration in the north half of the nail that adjoins a nail edge is expressed as percent tip deterioration, and is expressed as a percentage based on the area of the whole nail.

The Tip Wear Index for a test nail polish is determined as follows. For each subject, the average percent tip deterioration for the test nail polish (PWal) is determined (calculated by adding the percent tip deterioration for each of the five fingers having test nail polish applied to them and dividing this by five). The average percent tip deterioration for the test nail polish for the subject group (PWtal) is then determined. Similarly, for each subject, the average percent tip deterioration for the control (PWa2) is determined (calculated by adding the percent deterioration for each of the five fingers having the control applied to them and dividing by five).

The average percent tip deterioration for the control for the subject group (PWta2) is then determined. The Tip Wear Index for the test nail polish (PWItest) is then calculated as follows: PWItest=PW-PWta2 Accordingly, the lower the Tip Wear Index, the better the wear properties are for that particular nail polish, at the tip of the nail, relative to the tip deterioration exhibited by the control.

Control Formula: wt% Solid Nitrocellulose'/4"'14. 00 Epoxy (Polytex E-75) 2 9. 00 Clay/Bentonite/Hectorite solids 3 1.00 Red #7 Lake 4 0. 43 Red #6 Lake'0. 37 Ti02 Solid 6 0. 10 Red Iron Oxide Solid 7 0. 08 Black Iron Oxide Solid 0. 02 Butyl Acetate 33.00 Isopropyl Acohol 7.00 Ethyl Acetate 28.00 Camphor 1.00 Dibutyl Phthalate (Kodaflex DBP) 6. 00

1-from NC Slurry 50-C3-690; Akzo Nobel, Somerset, NJ 2-Estron Chemical, Calvert City, KY 3-50/50 Stearalkonium bentonite/stearalkonium hectorite from slurry; Kirker Enterprises Inc., Patterson, NJ 4-from slurry, AN596; Kirker Enterprises 5-from slurry, DB300; Kirker Enterprises 6-from slurry, AN2928; Kirker Enterprises 7-from slurry, AN559; Kirker Enterprises 8-from slurry, AN702; Kirker Enterprises The control composition is prepared by combining the ingredients in a suitable container and mixing on a paint shaker (such as commonly used to shake paint cans, available from Paul N. Gardner Company, Pompano Beach, FLA, USA) until homogeneous, typically for about 30 minutes. The clay and pigments are added as slurries prepared by the pigment milling manufacturer, the slurries comprising a suitable amount of one or more of the solvents in the control composition. The slurries are prepared by milling until homogeneous.

Coverage Factor The present compositions can be characterized by their Coverage Factor.

Coverage Factor is influenced by the solids content, e. g., the pigment content, of the composition, and tends to increase with solids content. Coverage Factors may range from 0 to 1.0, and are preferably from about 0.1 to about 0.9. The Coverage Factor is preferably greater than 0.4, more preferably greater than about 0.5.

Coverage Factor is determined by the following method: (a) Sample preparation The nail polish to be tested is cast on smooth, clear polyester sheets available from the Leneta Company, Mahwah, NJ, USA (Size: 0.18 mm thick X 194 mm X 260 mm; Form: P300-7C), or an equivalent. The polish is drawn down using a 3.0 mil bird-applicator-draw-down bar, across the sheet over a period of about 8-10 seconds to cover an area of about 9-10 inches long and 3 inches wide. The wet draw down should have a consistent, even color across the draw-down area, indicating a consistent film thickness exists at all points across the draw-down. The polyester sheet is then placed on a level oven rack in a convection oven at 87° F for 24 hours.

After drying, the thickness of the polyester sheet plus dried polish should be about 7.8 +/-0.3 mils (0.0078 +/-0.0003 inches).

(b) Testing & calculation The Coverage Factor is measured by placing the polyester sheet over a "black & white"Leneta card (available from Leneta Company, Mahwah, NJ, USA.

(Form: 2A-Opacity). Microflash 200D (available from Data Color International, Lawrenceville, NJ) is used to measure the Y-value of the black and white portion of the card covered with the polyester sheet. The Coverage Factor is defined by the ratio of Y-value of the black portion over the Y-value of the white portion. The Coverage Factor by this method may range from 1.0 (for a film that provides complete coverage (complete hiding power)) to essentially zero (a transparent film).

Rheological Properties The compositions hereof have rheological properties as defined by Yield Value and Plastic Viscosity. As will be understood by those skilled in the art, rheological properties are influenced by the level of solids and diluents present in the composition, including the level of any thickeners. For example, Plastic Viscosity tends to increase with increasing solid level, decreasing diluent level, and increasing thickener level. The Yield Value is preferably from about 0.3 Pascals ("Pa") to about 3.0 Pa, more preferably about 0.75 Pa to about 2.5 Pa. The Plastic Viscosity is preferably about 600 centipoise ("cP") or less, more preferably about 500 cP or less, even more preferably from about 200 cP to about 500 cP, most preferably from

about 300 cP to about 450 cP. These rheological properties are measured using a controlled stress rheometer in a shear rate ramp. A Haake Model RS 100 rheometer (or equivalent thereof) can be used, with a 60 mm parallel plate geometry set to operate with a 0.5 mm gap. Procedural details such as calibration, zero point determination, gap setting, and filling sample volume are straightforward to one skilled in the art, and are guided by the RS 100 software. A water bath cools the base plate to 20 degrees Celsius. The software is programmed in controlled rate mode to ramp shear rate from 0 to 300 inverse seconds over a 2 minute time period, and collects 100 data points in that time. The data are modeled by the Casson equation, conveniently provided by the software. A linear regression of the square root of stress versus the square root of shear rate obtains the slope and intercept according to the equation:

Where: stress (measured, Pa) 7 shear rate (measured, 1/seconds) T 0 = Yield Value (calculated by regression) llp = Plastic Viscosity (calculated by regression) Examples The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.

In the examples below, all polymer component percentages are expressed in weight percent of solid polymer (based on the total composition).

The compositions of Examples 1-19 are suitable for use as nail polish compositions. Ingredient Example 1 Example 2 Example 3 Example 4 Solid NC 1/4" 15.4 15. 4 15.4 13.3 Solid Sanres EX 499 2 2 2 2.85 Solid Epoxy E-75 1.195 1.195 1.195 1.195 0000.999Uniplex670P Uniplex PX45 6 6 6 4 Clay/bentonite/hectorite 1. 2 1. 2 1. 2 1. 2 Red #7 lake 0.555 0.007 0.182 0.555 Red #6 lake 0.485 0.099 0.087 0.485 Yellow #5 lake 0 0.038 0 0 0.88400.13TiO20.13 Red Iron Oxide 0.104 0. 215 0 0. 104 Black Iron Oxide 0.026 0.059 0.017 0.026 Mica Pearl (Flamenco 0 0 1.014 0 Velvet) Butyl acetate 32.863 32.863 32.863 33.573 Ethyl acetate 27.386 27.386 27.386 27.977 Isopropyl alcohol 10 10 10 9. 15 Benzophenone 0. 026 0. 013 0. 007 0.026 111Camphor1 Propyl Acetate 0.042 0.112 0.027 0.042 Paraplex G-501 1. 035 1.478 2. 8 Dibutyl phthalate 0.589 0.497 0.144 0.589 Ingredient Example 5 Exam le 6 Example 7 Exam le 8 Solid NC 1/4" 13.3 13.3 15.3 15.3 Solid Sanres EX 499 2. 85 2. 85 2. 5 2. 5 Solid Epoxy E-75 1.195 1.195 1.011 1.011 Uniplex 670P 0. 999 0.999 0. 9 0. 9 Uniplex PX45 4 4 5. 5 5. 5 1.21.11.1Clay/bentonite/hectorite1.2 Red #7 lake 0.007 0.006 Red #6 lake 0.099 0.084 Yellow #5 lake 0. 038 0 0 0.032 Ti02 0. 884 0 0.11 0.748 Red Iron Oxide 0. 215 0 0.088 0.182 Black Iron Oxide 0.059 0.017 0.022 0.05 Mica Pearl (Flamenco 0 1. 014 0 0 Velvet) Butyl acetate 33.573 33.573 32.473 32.473 Ethyl acetate 27.977 27.977 27.061 27.061# Isopropyl alcohol 9. 15 9. 15 10 10 Benzophenone 0. 013 0.007 0.022 0.011 Camphor 1 1 1 Propyl Acetate 0.112 0.027 0.035 0.095 Paraplex G-50 2. 834 1.529 Dibutyl phthalate 0. 497 0.144 0.498 0.42 In redient Exam le 9 Exam le 10 Exam le 11 Exam le 12 Solid NC'/4"15. 3 15.15 15.15 15.15 Solid Sanres EX 499 2. 5 2. 35 2. 35 2.35 Solid Epoxy E-75 1.011 1.103 1.103 1.103 Solid Uniplex 670P 0. 9 1 1 1 SolidUniplex PX45 5. 5 5. 2 5. 2 5. 2 Clay/bentonite/hectorite 1. 1 1. 2 1. 2 1. 2 Red #7 lake 0.154 0.512 0.006 0.168 Red #6 lake 0.074 0.448 0.091 0.08 Yellow #5 lake 0 0 0. 035 0 0.120.8160TiO20 Red Iron Oxide 0 0.096 0.198 0 Black Iron Oxide 0.014 0.024 0.054 0.016 Mica Pearl (Flamenco 0.858 0 0 0.936 Velvet) Butyl acetate 32.473 32.832 32.832 32.832 Ethyl acetate 27.061 27.36 27.36 27.36 Isopropyl alcohol 10 10 10 10 Benzophenone 0. 006 0.024 0.012 0.007 Camphor 1 1 1 1 Propyl Acetate 0.023 0.038 0.104 0.025 Paraplex G-50 1. 905 1 1.032 1.441 Dibutyl phthalate 0.122 0.543 0.458 0.133

Preparation of pigment slurries: The mixtures should only be prepared under the direction of experienced operators who have been trained in safe practices for milling or otherwise mixing volatile solvents. Use only safely installed, wired, ventilated, temperature controlled and monitored equipment.

Blend the solvent, nitrocellulose and plasticizer together at room temperature or below until homogeneous by combining in a jar or other suitable container a portion of nitrocellulose (about 1/3 of the nitrocellulose needed to prepare a batch of nail polish), a portion of the total plasticizer (about one half the plasticizer), and sufficient solvent to reduce the viscosity to less than about 1,000 cP (about 50-75%

of the available solvent) and shaking on a paint shaker until homogeneous, about 1/2 hour. An industrial paint shaker such as are commonly used to shake paint cans can be used (available from Paul N. Gardner Company, Inc. of Pompano Beach, Florida). To allow for any material losses during processing or for making a master batch, an excess of ingredients can be used to prepare the slurry.

Add all the dry pigment, excluding the mica if present, and clay to the container and shake for about !/2 hour to wet the pigment and clay. Transfer the mixture to a high shear mixer such as a MiniZeta 03 mill (manufactured by Netzsch of Germany, employing about 300 ml of 0.6-1 mm Yttrium-Doped Zirconium beads (or an equivalent). The mill is preferably powered by an air compressor or house air supplying about 100-120 psi. The milling chamber and shaft should be cooled to below 20°C prior to and during milling, e. g., using a suitable re-circulating cooling bath set to cool to between 0°C and-10°C. Mill until the average particle size is less than about 5 microns, determined using a A Horiba LA-910 particle size analyzer equipped with a fraction cell holder and cell (available from Horiba, Ltd, Irvine CA, USA). Transfer the slurry to a jar or other suitable container and store until needed for preparation of a nail polish.

Suitable pigment slurries are typically, alternatively prepared by a pigment supplier as a raw material for sale to the cosmetics industry. One such supplier is Kirker Enterprises, Inc. of Paterson, NJ. The pigment slurries contain the ground (i. e., milled) pigment in solvent with clay, nitrocellulose polymer and plasticizer, the pigment being ground to a particle size of about 1-10 microns average.

Preparation of nail polish: Combine the balance of the solvent, plasticizer, mica and other nail polish ingredients exclusive of the pigment/clay slurry in a jar or other suitable container.

Add an appropriate amount (formula proportion) of the pigment slurry to this mixture. Seal and shake the container on a paint shaker for about 30 minutes.

Package in suitable storage containers, e. g., small nail polish bottles, at or below room temperature. Ingredient Exam le 13 Example 14 j Example 15 Sotid NC 1/4w 15. 15 15.1 ? 15.15 Solid Sanres EX 499 2. 35 2. 35 2.35 Solid 1.103E-75 1.103 111Uniplex670P Uniplex PX45 5. 2 5. 2 5. 2 Clay/bentonite/hectorite 1. 2 1. 2 1. 2 Red #7 lake (Soft-tex) 0.512 0.006 0.168 Red #6 lake (Soft-tex) 0.448 0.091 0.08 Yellow #5 lake (Soft-tex) 0 0.035 0 Ti02 lake 0.12 0.816 0 Red Iron Oxide (Soft-tex) 0.096 0. 198 0 Black Iron Oxide (Soft-tex)'0. 024 0.054 0.016 Mica Pearl (Flamenco Velvet) 0 0 0.936 Butyl acetate 32.832 32.832 32.832 Ethyl acetate 27.36 27.36 27.36 Isopropyl alcohol 10 10 10 Benzophenone 0 0 0 Camphor 1 1 1.062ParaplexG-50 1.473 Dibutyl 0.4580.1330.543

'Sun Chemical, primary particle size about 20 nm to about 200 nm by microscopic particle size analysis Preparation of nail polish: The mixtures should only be prepared under the direction of experienced operators who have been trained in safe practices for milling or otherwise mixing volatile solvents. Use only safely installed, wired, ventilated, temperature controlled and monitored equipment.

Blend all materials except the pigment and clay together at room temperature or below until homogeneous by combining in a jar or other suitable container and shaking on a paint shaker until homogeneous, about'4 hour. An industrial paint shaker such as are commonly used to shake paint cans can be used (available from Paul N. Gardner Company, Inc. of Pompano Beach, Florida).

Weigh an excess of pigments, excluding mica, in proper proportion and dry mix in an Osterizer food blender or equivalent about 1 minute until homogeneously mixed. Add this blended mixture to a Model 0 jet mill manufactured by Fluid Energy Aljet of Plumsteadville, PA, USA. Use compressed nitrogen as the fluid gas and set the grinding nozzles to 100 psi, the feed nozzle to 85 psi, and the vibration-

feeding device to a feed rate of 30-40 on the Model-O dial. The feed rate is about 100 g per hour. Jet mill and collect the pigments.

Add the correct amount of jet milled pigment blend and clay to the liquid ingredient mix and shake for 1/2 hour on paint shaker. Transfer the mixture to a high shear mixer such as a MiniZeta 03 mill (manufactured by Netzsch of Germany, employing about 300 ml of 0.6-1 mm Yttrium-Doped Zirconium beads). The mill is powered by an air compressor or house air supplying about 100-120 psi. The milling chamber and shaft are cooled to below 20°C prior to and during milling, using a re-circulating cooling bath set to cool to between 0°C and-10°C. Mill until 99% of the particles are less than 1 micron diameter, determined using a Horiba LA- 910 particle size analyzer equipped with a fraction cell holder and cell (available from Horiba, Ltd, Irvine CA, USA).

Add the mica in proportion and wet mill just until dispersed, for a period less than 10 minutes. Viscosity can be adjusted, e. g., by adding more clay (such as milled in solvents at ca. 4%-8% clay solids) (to increase viscosity), or by adding more solvent (to lower viscosity), followed by paint shaking to blend. Package in suitable storage containers, e. g., small nail polish bottles, at or below room temperature.

The above compositions are independently contiguously applied to human fingernails using a standard brush-applicator. A nail polish layer is allowed to form by drying under ambient conditions for a period of five minutes. Then a second layer is applied. The nail polish is allowed to dry for at least several minutes to form a wear-resistant film. Ingredient Example 16 Example 17 Example 18 Example 19 Solid NC 1/4"15.0 13. 0 12. 0 11.0 SolidSanres EX519 2. 0 4. 0 5. 5 7. 0 1.11.63.11.6EpoxyNX-55 3.02.51.53.0AvalureAC315 Uniplex PX45 5. 5 4. 5 5. 5 4. 0 Clay/bentonite/hectorite 1. 2 1. 2 1. 2 1. 2 Red #7 solid (Soft-tex) 0.156 0.156 0.156 0.156 Red #34 solid (Soft-tex) 0.031 0.031 0.031 0.031 Ti02 solid 0. 281 0.281 0. 281 0. 281 Red Iron Oxide solid 0.460 0.460 0.460 0.460 (Soit-tex)' Black Iron Oxide solid 0.229 0.229 0.229 0.229 (Soit-tex)' ButylAcetate 29. 7 30. 3 30. 0 29.7 EthylAcetate 24. 8 25. 2 25. 0 24.8 15.015.015.015.0IsopropylAcetate 1.51.50.01.5ParaplexG-50 1Sun Chemical, primary particle size about 20 nm to about 200 nm by microscopic particle size analysis Nail polishes of Examples 16-19 are prepared in the manner described for Examples 1-12 or 13-15.