WO1999055290A1

WO1999055290A1 - Nail polish compositions

Info

Publication number: WO1999055290A1
Application number: PCT/IB1999/000634
Authority: WO
Inventors: Katherine Eleanor Flynn; Peter Christopher Ellingson; David Harry Melik; Amy Jo Menke; Francisco Antonio Pichardo; Gillian Scott Briggs; David William Walling; Edward Dewey Smith, Iii
Original assignee: The Procter & Gamble Company
Priority date: 1998-04-24
Filing date: 1999-04-12
Publication date: 1999-11-04
Also published as: AU2952399A

Abstract

The present invention relates to compositions suitable for cosmetic and/or therapeutic treatment of the nails, e.g., nail polishes. The invention particularly relates to nail polish compositions which provide improved wear. Preferred compositions contain, by weight of the composition, from about 5 % to about 20 % of a film forming cellulosic polymer; from about 1.25 % to about 8 %, of a film forming polyurethane polymer; from about 3 % to about 20 % of a plasticizer; and from about 55 % to about 90 % of a volatile, organic solvent. The invention also relates to films formed from the compositions, and methods of treating the nails comprising application of the composition to the nails.

Description

NAIL POLISH COMPOSITIONS

TECHNICAL FIELD

The present invention relates to compositions suitable for cosmetic and/or therapeutic treatment of the nails, e.g., nail polishes. The invention particularly relates to nail polish compositions which provide improved wear.

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. The present inventors have surprisingly discovered defined compositions comprising a cellulosic film former, a 2

polyurethane film former, a plasticizer and a solvent, which when applied to the nails, provide films exhibiting superior long wear.

SUMMARY OF THE INVENTION The present invention relates to compositions suitable for application to the nails, e.g., as a nail polish, preferably comprising: 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 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, 3

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. 4

95 In addition to natural nails, the compositions herein may also be used for application to synthetic (artificial) nails. Film-forming polymers (a) and (fr)

The present compositions comprise one or more film-forming, solvent- borne, cellulosic polymers and polyurethane polymers.

100 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,

105 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 no 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:

115 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.

120 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

125 esters such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof. More preferred are nitrocellulose, cellulose 5

acetate butyrate, cellulose acetate propionate, and mixtures thereof. Nitrocellulose polymers are most preferred. Exemplary nitrocellulose polymers are nitrocellulose RS types (nitrogen content of 1 1.5-12.2%) of Hercules, such as nitrocellulose - RS no Vi second, - RS ^lA 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.

135 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

140 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

145 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]

150 copolymer), Sanres 1271 1®, 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

155 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- 6

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%,

160 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

165 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 no 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-

175 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-

180 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- C₁₂, more preferably C₆- C₁₀ polyester acids (including di-and tri-

185 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 7

phthalate, and dioctyl phthalate; nonionic surfactant polymers, e.g. tartrates, (e.g.,

190 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®); camphor; sucrose acetate isobutyrate; and castor oil.

Preferred plasticizers have a number average Molecular Weight of about

195 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 C -C₄ alkyl toluene-sulfonamides) are preferred. A blend of ethyl toluene-sulfonamide and at least one other plasticizer is most preferred.

200 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,

205 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

210 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

215 (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 8

220 hydrocarbons, aliphatic hydrocarbons, ethers, and mixtures thereof (more preferably C,-C₁₀, most preferably C₂-C₄). Alcohols and esters are more preferred, esters being most preferred. Preferred alcohols are monohydric. Preferred monohydric alcohols are ethanol, wo-propanol, and «-propanol. Preferred esters are butyl-, ethyl-, isopropyl- and propyl-acetate, and mixtures thereof. More

225 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, wo-butyl acetate, toluene, methyl acetate, wo-butanol, «-amyl alcohol, «-butyl alcohol, hexane, and methyl ethyl ketone.

The present compositions preferably comprise from about 55% to about

230 90%, more preferably from about 62% to about 78%, most preferably from about 66% to about 74%, volatile, organic solvent. Properties of compositions of the present invention

The compositions hereof have rheological properties as defined by Yield Value and Plastic Viscosity. As will be understood by those skilled in the art,

235 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

240 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 RSI 00 rheometer (or equivalent thereof) can be used, with a 60 mm parallel plate

245 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 RSI 00 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

250 minute time period, and collects 100 data points in that time. The data are modeled 9

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: ^l/2

(measured, Pa)

γ = shear rate (measured, 1 /seconds) ₀ = Yield Value (calculated by regression) η_p = Plastic Viscosity (calculated by regression)

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 10

and C Red Nos. 30 and 34, lacquers such as D and C Yellow No. 5 and D and C 280 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

285 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

290 composition. Preferred preservatives include benzophenone, methyl paraben, ethyl paraben, propyl paraben, benzyl alcohol, benzoic acid, benzoates, sorbates, sodium dehydroacetate, l-(3-chloroallyl)-3,5,7-triaza-l-azoniaadamantane chloride (which may be obtained commercially as Quaternium-15® from Dow Chemical Co., Midland, MI). Benzophenone is preferred. 295 The compositions preferably comprise from 0% to about 0.1% 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

300 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) 305 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. 1 1

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, polymefhacryls, 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. 12

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

345 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

350 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.

355 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

360 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

365 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

370 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 13 different manner including, but not limited to, a brochure, print advertisement, electronic advertisement and/or other advertisement, so as to communicate the 375 information to a consumer of the composition. Such information may accordingly comprise words, pictures, and the like.

Examples

The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the 380 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). 385 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

Uniplex 670P 0 0 0 0.999

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

TiO2 0.13 0.884 0 0.13

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

Camphor 1 1 1 1

Propyl Acetate 0.042 0.1 12 0.027 0.042

Paraplex G-50 1 1.035 1.478 2.8

Dibutyl phthalate 0.589 0.497 0.144 0.589 14

Ingredient Example 5 Example 6 Example 7 Example 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

Clay/bentonite/hectorite 1.2 1.2 1.1 1.1

Red #7 lake 0.007 0.182 0.47 0.006

Red #6 lake 0.099 0.087 0.41 0.084

Yellow #5 lake 0.038 0 0 0.032

TiO2 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 1C 10

Benzophenone 0.013 0.007 0.022 0.011

Camphor 1 1 1 1

Propyl Acetate 0.112 0.027 0.035 0.095

Paraplex G-50 2.834 3.278 l.f 1.529

Dibutyl phthalate 0.497 0.144 0.49Σ 0.42

Ingredient Example 9 Example 10 Example 11 Example 12

Solid NC %" 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

Solid Uniplex 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

TiO2 0 0.12 0.816 0

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 15

Paraplex G-50 1.905 1 1.032 1.441

Dibutyl phthalate 0.122 0.543 0.458 0.133

Preparation of pigment slurries:

390 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

395 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

400 homogeneous, about Vz 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.

405 Add all the dry pigment, excluding the mica if present, and clay to the container and shake for about V2 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

410 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

415 (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. 16

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

420 (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.

425 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 Example 13 Example 14 Example 15

Solid NC ^lA" 15.15 15.15 15.15

Solid Sanres EX 499 2.35 2.35 2.35

Solid Epoxy E-75 1.103 1.103 1.103

Uniplex 670P 1 1 1

Uniplex PX45 5.2 5.2 5.2

C lay/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

TiO₂ lake 0.12 0.816 0

Red Iron Oxide (Soft-tex)¹ 0.096 0.198 0

Black Iron Oxide (Soft-tex)¹ 0.024 0.054 0.016

Mica Pearl (Flamenco 0 0 0.936 Velvet)

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

Paraplex G-50 1.062 1.147 1.473

Dibutyl phthalate 0.543 0.458 0.133

¹ Sun Chemical, primary particle size about 20 nm to about 200 nm by microscopic particle

430 size analysis

Preparation of nail polish: 17

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

435 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 V hour. An industrial paint shaker such as are commonly used to shake paint cans can be used

440 (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

445 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 ! hour on paint shaker. Transfer the mixture to a

450 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.

455 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

460 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 18 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

Solid Sanres EX519 2.0 4.0 5.5 7.0

Epoxy NX-55 1.1 1.6 3.1 1.6

Avalure AC315 3.0 2.5 1.5 3.0

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

TiO2 solid 0.281 0.281 0.281 0.281

Red Iron Oxide solid 0.460 0.460 0.460 0.460 (Soft-tex) '

Black Iron Oxide solid 0.229 0.229 0.229 0.229 (Soft-tex) ^l

Butyl Acetate 29.7 30.3 30.0 29.7

Ethyl Acetate 24.8 25.2 25.0 24.8

Isopropyl Acetate 15.0 15.0 15.0 15.0

Paraplex G-50 1.5 1.5 0.0 1.5

¹ Sun 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.

Claims

19WHAT IS CLAIMED IS:

1. A composition suitable for application to the nails, characterized in that it comprises: a) from 5% to 20%, by weight of the composition, of film-forming cellulosic. polymer; b) from 1.25% to 8%, by weight of the composition, of film-forming polyurethane polymer; c) from 3% to 20%, by weight of the composition, of plasticizer; and d) from 55% to 90%, by weight of the composition, of volatile, organic, solvent.

2. The composition of Claim 1 characterized in that the cellulosic polymer is selected from the group consisting of nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof.

3. The composition of any of the preceding claims characterized in that the cellulosic polymer is nitrocellulose.

4. The composition of any of the preceding claims characterized in that the composition comprises at least 2% of film-forming polyurethane.

5. The composition of any of the preceding claims characterized in that the polyurethane is selected from the group consisting of aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes, aromatic polycaprolactam polyurethanes, aliphatic polycaprolactam polyurethanes, and mixtures thereof.

6. The composition of any of the preceding claims characterized in that the polyurethane is selected from the group consisting of aliphatic polyether polyurethanes, aliphatic polyester polyurethanes, and mixtures thereof. 20

7. The composition of any of the preceding claims characterized in that the polyurethane has a number average molecular weight of from 10,000 to 80,000.

8. The composition of any of the preceding claims characterized in that the plasticizer is selected from the group consisting of polar plasticizers comprising epoxy, amide, imide, urea and/or urethane linkages, polyesters, polyester acids; phthalates, camphor; and mixtures thereof

9. The composition of any of the preceding claims characterized in that the plasticizer comprises a polyester acid

10 The composition of any of the preceding claims characterized in that the plasticizer comprises an alkyl toluene-sulfonamide

11. The composition of any of the preceding claims characterized in that the composition further comprises resin selected from the group consisting of epoxy resins, polyacrylic resins, and mixtures thereof

12 The composition of any of the preceeding Claims characterized in that the composition is essentially free of formaldehyde resins