Nail Compositions Containing Cyanoacrylate and Graphite

[54] [76] [21] [22] [51] [52] [58] [56] United States Patent [19] [11] Patent Number: 4,646,765 Cooper et al. [45] Date of Patent: Mar. 3, 1987 NAIL COMPOSITIONS CONTAINING 4,547,363 10/1985 .1005 ..................................... .. 424/61 CYANOACRYLATE AND GRAPHITE FOREIGN PATENT DOCUMENTS Inventors: Donald E. Cooper; David A. Cooper, 2902029 8/1979 Fed Re . p. of Germany ...... .. 132/73 13°11‘ °f 5319 5W- Westgate Dr-a 2451724 11/1930 France ................................ .. 132/73 511116 113,P0rt1and: 0reg- 97221 0226077 12/1984 Japan .... .. 132/73 App1_ Na: 825,220 0118776 6/1985 Japan ................................. .. 252/511 Filed: Feb_ 3, 1936 OTHER PUBLICATIONS Int. Cl.4 ................... .. A45D 29/00; A45D 31/00; Chem Abs‘ 3771530822 (19771 C03K 3/ 04 Primary Examiner—-Herbert J. Lilling U.S. C1. .................................... .. Aftgrney, Agenf’ gr Fjrm__K]arqui5[, Sparkman’ 424/61; 427/155; 523/105; 524/496; 524/700; campben, Leigh & Whjnston 524/ 850 Field of Search ..................... .. 524/496, 700, 350; 1571 ABSTRACT 523/ 105; 132/ 73; 424/51; 427/ 155; 252/511 A composition for adhering to human nails includes a References Cited mixture of a cyanoacrylate compound and/or graphite fibers. Such composition can take the form of either an US‘ PATENT DOCUMENTS artificial nail extender or a nail coating. The composi- 2,794,788 6/1957 Coover et a1. .................... .. 524/850 tion for forming an artificial nail includes gra hite fi- P .-FWG1 ---- --1 ----- -- bers, a cyanoacrylate, and a hardening accelerator con- , , ewe eta. ' ' ' t f ' h] NN_ W756 11/1969 Sewer at a1 -- 132/73 31112311 1-1-?‘.Z’§,1L’1‘f11§’1e‘1ZeZZ‘§§ie£?£?iZh§3§ ‘I23 10’ be 3,896,077 7/1975 Leonard et a1, .. 524/850 y ' , , , P . 4,007,748 2/1977 Mammga at al_ _ 132/73 sprayed onto a base material containing the graphite 4,104,333 8/1973 Lee, j;-_ et a1_ 260/335 fibers and cyanoacrylate in the form of a mist. Nail 4,229,431 10/1980 Lee, Jr. etal.. 424/61 compositions containing graphite fibers have signifi- 4,260.701 4/1981 Lee, Jr- -------- -. 525/ 303 cantly increased strength yet remain flexible to allow 1(9); gqzkata 5131' ~' for flexure of the nail. The cyanoacrylate compounds , , a ow .......... .. .. - . . - - 4,440,910 4/1984 Ocmmor 525/295 increase the chemical bonding of the compositions to a 4,465,092 8/1984 Vitale ..................... .. 137/385 "311- 4,495,172 1/1985 Orlowski et a1. .. 424/61 4,526,636 7/1985 Mader ............................... .. 427/203 23 Claims, N0 Drawings 4,646,765 1 NAIL COMPOSITIONS CONTAINING CY ANOACRYLATE AND GRAPHITE BACKGROUND OF THE INVENTION This invention relates generally to nail compositions. More particularly, the invention relates to nail composi- tions for coating nails and for extending nails. Nail compositions can take varying forms, for exam- ple, nail coatings in the form of nail polishes and remov- ers. Other compositions are designed for forming arti- ficial nail extensions for lengthening or mending nails. Such compositions must be easy to apply and non-yel- lowing to be acceptable to a consumer. Present state-of-the-art nail extender and repair com- positions are generally described in U.S. Pat. Nos. 3,478,756 to Sautter et al., 4,104,333 to Lee, Jr. et al, 4,229,431 to Lee, Jr. et al, and 4,260,701 to Lee, Jr. Such compositions are available in the form of kits containing acrylic polymers in one container and a separate con- tainer of activator compounds. The polymers and acti- vator when mixed form a doughy material which is troweled onto the upper surface of the existing nail and onto a template positioned at the end of the nail to form the extension. Drying time upon forming is several minutes before the forming template can be safely re- moved. Such products have the drawback of being slow to mix from two containers onto a mixing surface and having a short shelf or pot life. The mixture produced is also thick and hard to form. In addition, the texture of the hardened nail is generally quite rough requiring many minutes of filing to smooth the surface into an acceptable shape and finish. Furthermore, the resulting nail extension is commonly so hard that it is brittle and easily breaks, or so flexible that it lacks strength. Current state-of-the-art nail coatings such as nail polishes have similar drawbacks. Such nail polishes are commonly comprised of nitrocellulose and polymer resins which do not bond properly to the nail keratin. Accordingly, a user must repolish the nails often as the polish chips away. Nail polishes also do not provide much added strength to an existing nail. Hardening nail coatings are known but also lack proper adhesion and become so brittle that they crack and break upon impact with hard objects. Such products have increased strength over ordinary nail polishes, but lack flexibility and bonding power. Nail coatings having drawbacks such as these are described in U.S. Pat. Nos. 4,495,172 to Orlowski et al., 4,547,363 to J oos, 3,301,760 to Jewel, 3,342,686 to Jewel et al., and 4,407,310 to Jadow. SUMMARY OF THE INVENTION It is an object of the present invention to provide a nail composition which upon hardening forms a coating which is strong and flexible. Another object of the present invention is to provide an artificial nail extender or repair composition that can be applied to a nail by both professional applicators and average consumers. Still another object of the present invention is to provide a nail extender or repair composition which is inert to body tissue. Yet another object of the present invention is to pro- vide a nail extender or repair composition which rap- idly hardens upon application of an accelerator. Another object of the present invention is to provide a nail coating having greater adhesion to a nail. 5 10 15 20 25 30 35 45 50 55 65 2 Yet still another object of the present invention is to provide a nail coating which is non-irritating to the cuticle and inert to body tissue. Still a further object of the present invention is to provide a nail coating which is inert to detergent solu- tions. Yet another object of the present invention is to pro- vide a nail coating which is color compatible with vari- ous tints. Still a further object of the present invention is to provide a nail coating which when applied and dried has great film strength to resist abrasion and chipping. Yet another object of the present invention is to pro- vide such a nail coating which is thin, flexible, yet strong. The foregoing objects are achieved by the nail com- positions of the present invention. Such compositions include graphite fibers and/or cyanoacrylate com- pounds. These and other objects, advantages, and features of the invention will become more readily apparent from the following detailed description. DETAILED DESCRIPTION There are two aspects of the present invention. First, cyanoacrylate compounds in nail coatings have been discovered to greatly increase the adherence of a coat- ing to a nail. Second, graphite fibers have been discov- ered to be useful in nail composition to significantly increase the strength of the hardened composition ap- plied to nails. The nail compositions of the present in- vention can be in the form of artificial nail extenderand repair compositions, or nail coatings. Artificial Nail Extender and Repair Compositions The base material for the artificial nail composition of this embodiment of the invention comprises a mixture of a cyanoacrylate compound and graphite fibers which forms a base material. This base material hardens when mixed with a hardening accelerator which includes a mixture of trichloro-trifluoroethane and a methylaniline compound, such as N,N-dimethyl-P,to1uidine. The hardened product when coated on a nail and an at- tached template forms a nail extension that is strong and flexible. The graphite fibers in the base material are translu- cent graphite fibers which are whitish in color and provide an artificial nail which is translucent and thereby natural appearing. Such graphite fibers can be purchased from Hercules Incorporated, 910 Market St., Wilmington, Del. 19899, as the precursor, or raw, graphite fiber. It is the raw, precursor form of the graphite fiber which is preferred as it is this fiber that has the whitish color. Precursor graphite fibers can also be purchased from the Courtalds Company of Coven- try, England. The graphite fibers usable for the instant invention can be round and vary in diameter from 0.3 mils to 0.75 mils. Most preferred are round fibers having a diameter ranging from 0.3 mils to 0.4 mils. The fibers can be present in the base material in a concentration ranging from 1.0% to 4.0% by weight. Most preferred is a concentration ranging from 2.0% to 4.0% by weight of the base material. The fibers can be of uniform length but are preferably of varying lengths, from 1/32 inch to 6/32 inch. Most preferred are fibers varying in length from 1/32 inch to 5/32 inch. It is also preferred that the medium length, for example the 2/32 inch and 3/32 inch, fibers predom- 4,646,765 3 inate over the long, 5/32 inch, and short, 1/32 inch, fibers. This variety of length provides a smoother fin- ished matrix of maximum strength and flexure. Any of a variety of cyanoacrylate compounds or mixtures of cyanoacrylate compounds can be used. The viscosity of the cyanoacrylate compound or com- pounds used for the extender repair compositions should be from 500 centipoise to 2,500 centipoise in viscosity. Most preferred are cyanoacrylate composi- tions having a viscosity somewhere between 800 centi- poise and 2,000 centipoise. The accelerator is adapted to be applied to the base material by spraying it thereon in the form of a mist, as more fully described below. The accelerator includes a mixture of trichloro-trifluoroethane and a methylaniline such as N,N-dimethyl-P-toluidine. The trichloro-tri- fluoroethane can be present in the accelerator in a con- centration ranging from 35% to 60% by weight. Most preferred is a concentration ranging from 40% to 50% by weight. The N,N-dimethyl-P-toluidine can be pres- ent in the accelerator in a concentration ranging from 20% to 40% by weight. Most preferred is a concentra- tion ranging from 25% to 30% by weight. Preferably the accelerator is augmented with ethyl chloride which further accelerates the curing time of the matrix and enhances the dispersion of any heat generated. The ethyl chloride can be present in the accelerator in a concentration ranging from 15% to 40% by weight of .'the accelerator. Most preferred is a concentration rang- ..ing from 20% to 30% by weight of the accelerator. Liquid freon is also usable as an accelerator and cooling . agent. Acrylic polymers can also be added to the accelera- tor to enhance the smoothness of the resulting matrix. The acrylic polymers can be present in a concentration ranging from 1.0% to 5.0% by weight of the accelera- tor. Most preferred is a concentration ranging from .2.0% to 4.0% by weight of the accelerator. When acrylic polymers are used, it is desirable to add an aromatic scent to the accelerator to counteract the polymer odor. Such aromatic scents can be included in the accelerator in concentrations ranging from 0.01% to 1.0% by weight of the accelerator. It is recommended, although not necessary, that the nail and cuticle be sterilized as by swabbing the same with hydrogen peroxide or another conventional steril- izing solution prior to applying the extender and repair composition. This will reduce the possibility of any trapped bacteria starting an infection after the composi- tion has been applied. The base material can be brushed or applied by spatula to a template positioned at the end of the nail to be extended or reconstructed. A thin coat of base material should extend back to the half-moon of the nail to provide a sufficiently large surface area for adhering the extension to the nail to prevent the exten- sion from separating from the nail after hardening. After the base material is applied to the template and existing nail and formed to the desired shape, the accel- erator is sprayed onto the base material in the form of a mist. This causes the mixture to harden almost instantly into a flexible, durable artificial nail which can be filed or polished similar to a natural nail. The accelerator mist cures the cyanoacrylategraphite fiber matrix within three seconds without irritation to the surround- ing skin or cuticle. The heat generated by the polymeri- zation of the matrix is dissipated by the vaporization of the mist. Various tinting materials can be incorporated into the base material if so desired to impart a color 10 15 20 25 30 35 45 50 55 65 4 throughout the artificial nail. Nail polishes can be ap- plied to the hardened artificial nail as with natural nails. The nail extender composition is also usable to repair chipped or otherwise damaged nails without causing the nail to be extended by troweling the base material to the damaged area followed by application of the accel- erator to cause it to harden. EXAMPLE I A base material was prepared having the following composition by weight: Cyanoacrylate 96.4% (2000 + / —-400 centipoise) Graphite fiber 3.6% 100.0% The graphite fibers had a diameter of 0.31 mils and were present in lengths varying from 1/32 inch to 5/ 32 inch in the following proportions: 1/32 inch 10% 2/32 inch 40% 3/32 inch 40% 5/ 32 inch 10% 100% A liquid accelerator material was prepared having the following compositions by weight: trichloro-triflucroethane 47.4% N,N—dimethyl-P—toluidine 26.3% ethylene glycol dimethlacrylate 2.0% aromatic scent 0.6% ethyl chloride 23.7% 100.0% The nail to be extended was disinfected with a cotton ball moistened in a disinfectant solvent sold under the trademark Cuti-Clean TM . Thereafter, the nail surface was lightly sanded to remove any oily glaze from the nail to facilitate adhesion of the base material to the nail. A template made of teflon for forming the nail extension was positioned at the end of and just undemeath the nail to be extended. Teflon is used as a material for the tem- plate as it does not stick to the base material before or after hardening. The base material in the form of a cream was applied to the nail and template with a spat- ula. The base material was applied first to the back end of the nail near the half—moon and troweled forward onto the teflon template for forming the shape of the desired nail. The base material remains workable until the accelerator is applied for achieving the desired shape. The accelerator was sprayed onto the base material in the form of a mist with a suitable mist applicator in one thorough spray covering the upper surface of the base material which hardened the base material in about one second. The teflon template was then carefully re- moved from the underside of the formed extension. Thereafter the extended nail was filed to the desired fmal shape and finish. Nail Coating Compositions Cyanoacrylates have been discovered as useful in nail coating compositions to significantly improve the adhe- 4,646,765 5 sion of the coating to the nail. The cyanoacrylate com- pounds bond chemically to the fingernail keratin thus minimizing chipping. When combined with the graphite fibers used in the artificial nail composition described above, a strong, flexible nail coating results which readily adheres to the surface of a nail. As with the extender/repair composition, any of a variety of cyanoacrylate compounds or mixtures of cyanoacrylate compounds can be used. It is preferable that the viscosity of the cyanoacrylate portion be thin- ner than that of the extender/repair composition. For example, for nail coatings the viscosity range should be from 100 centipoise to 600 centipoise, with 150 centi- poise to 300 centipoise being the preferred range. Two methods may be used for applying coatings to nails. One such method is a two step process wherein a base coat is applied to a nail followed by a top coat after the base coat has dried. Another such method is a one step process which entails the application of just a single coat to the nail. The nail coating compositions of the instant invention include a base coat product and top coat product, usable in the.two step process, and a sin-‘ gle coat product usable in the one step process. The base coat, top coat, and single coat products should each include at least fifty percent nitrocellulose as a carrier material. The base coat product should be a relatively thick material, heavy in both fiber and cyanoacrylate to pro- vide strong bonding and high flexure strength. For example, it should contain from 0.01% to 0.030% graphite fibers and from 1.0% to 4.0% cyanoacrylate. The preferred range is from 0.020% to 0.030% graphite fibers and from 2.0% to 3.0% cyanoacrylate. The top coat product is a relatively thin material and light in both fiber and cyanoacrylate, since those prop- erties are provided by the base coat. It should contain from 0.003% to 0.010% graphite fibers and from 0.10% to 1.0% cyanoacrylate. The preferred ranges are from 0.003% to 0.008% graphite fibers and from 0.30% to 0.80% cyanoacrylate. The top coat should also include polymers that do not age rapidly or react to light. The single coat product is a judicious choice of the above noted materials to allow for a rapid application of one coat to achieve both goals of added bonding and 10 15 20 25 30 35 flexure strength. It should contain from 0.003% to 45 0.03% graphite fibers and from 0.5% to 4.0% cyanoac- rylate. The preferred ranges are from 0.005% to 0.015% graphite fibers and from 1.5% to 2.5% cyanoacrylates. It is possible to provide more than one coating to the nail in either of the one or two step processes, if desired, without adversely affecting the previously covered nail. Acrylic polymers may be added to the above compo- sitions at from 0.001% to 3.0% percent by weight to further increase the flexure and pliability of the coating film. Most desired is the addition of acrylic polymers at from 1.0% to 2.0% by weight. EXAMPLE II A base coat material referred to above was prepared having the following composition by weight: Base lacquer #2548-1 62.000% Acetone 35.475% Cyanoacrylate 2.500% (200+/-50 centipoise) Graphite fiber 0.025% (same as Example I) Tinting material trace 50 55 65 6 -continued 100% Base lacquer #2548-1 contains nitrocellulose and other ingredients and can be purchased from Scholls Chemi- cal Corporation, 200 West North Ave., Northlake, Ill. A top coat material referred to above was prepared having the following composition by weight: Base lacquer #2548-1 60.000% Acetone 32.495% Cellovar #160 5.000% Ethylene glycol dimethacrylate 2.000% Cyanoacrylate .500% (200+/ -50 centipoise) Graphite fiber .005% (same as Example I) Tinting material trace 100% Cellovar #160 contains nitrocellulose and other ingre- dients and can be purchased from Cellofilm Corpora- tion, P. O. Box 223, Woodridge, N.J. 07075. The base coat was applied first by brushing a gener- ous coat of the material onto a nail and allowing it to dry for 15 seconds. Next, the top coat material was applied by brushing it over the base coat and allowing it to dry for 15 seconds. The coating on the nail will reach its maximum strength at between three and four hours, although the nail is usable as soon as the top coat dries. The resulting hardened coating was smooth and adher- ent to the nail. EXAMPLE III A single coat material referred to above was prepared having the following composition by weight: Base lacquer #2548-1 55.000% Acetone 35.990% Cellovar #160 5.000% Ethylene glycol dimethacrylate 2.000% Cyanoacrylate 2.000% (200+/ -50 centipoise) Graphite fiber 0.010% (same as Example 1) Timing material trace 100% The single coat material was applied by brushing it onto a nail and allowing it to dry for 15 seconds. The single coating on the nail will reach its maximum strength at between three and four hours after applica- tion, although the nail is usable as soon as the single coat dries. The resultant ‘hardened coating was smooth and adherent to the nail. Having illustrated and described the principles of my invention with reference to several preferred embodi- ments, it should "be apparent to those persons skilled in the art that such invention may be modified in arrange- ment and detail without departing from such principles. I claim as my invention all such modifications as come within the true spirit and scope of the following claims. We claim: 1. A composition for adhering to human nails com- prising a mixture of a cyanoacrylate compound and graphite fibers. 4,646,765 7 2. The composition of claim 1 wherein the graphite fibers are translucent graphite fibers which are whitish in color. 3. The composition of claim 1 wherein the graphite fibers vary in length from approximately 1/32 inch to 5/32 inch and have a diameter ranging from 0.3 mils to 0.75 mils. 4. The composition of claim 1 wherein the graphite fibers are present in an amount from 0.003% to 0.030% by weight of the composition. 5. The composition of claim 1 wherein the graphite fibers are present in an amount from 1.0% to 4.0% by weight of the composition. 6. A composition for forming an artificial human nail comprising a mixture of: a cyanoacrylate compound, graphite fibers, and a hardening accelerator including a mixture of tri- chloro-trifluoroethane and a methylaniline com- pound. 7. The composition of claim 6 wherein the methylani- line compound comprises N,N-dimethyl-P-toluidine. 8. The composition of claim 7 wherein the accelera- tor comprises trichloro-trifluoroethane from 35% to 60% by weight and N,N-dimethyl-P-toluidine from 25% to 40% by weight. 9. The composition of claim 6 wherein the graphite fibers are translucent graphite fibers which are whitish in color and provide an artificial nail which is translu- cent. 10. The composition of claim 6 wherein the graphite fibers are present in lengths varying from 1/32 inch to 5/ 32 inch and have a diameter ranging from 0.3 mils to 0.75 mils. 11. The composition of claim 6 wherein the graphite fibers are present in an amount from 1.0% to 4.0% by weight of the composition. 12. The composition of claim 6 wherein the accelera- tor includes ethyl chloride to accelerate curing time and enhance heat dispersion. l0 15 20 25 30 35 45 50 55 60 65 8 13. The composition of claim 12 wherein the acceler- ator comprises ethyl chloride from 15% to 40% by weight of the accelerator. 14. The composition of claim 6 wherein the accelera- tor includes an acrylic polymer. 15. The composition according to claim 8 wherein the accelerator comprises an acrylic polymer from 7 1.0% to 5.0% by weight of the accelerator. 16. A method for forming an artificial human nail comprising: adhesively bonding a base material containing graph- ite fibers and cyanoacrylate to a nail; shaping the base material to simulate the appearance of a natural nail; and spraying, in the form of a mist, the base material with a hardening accelerator including a mixture of trichloro-trifluoro-ethane and a methylaniline com- pound to harden the base material. 17. The method according to claim 16 wherein the methylaniline compound comprises N,N-dimethyl-P- toluidine. 18. The method according to claim 17 wherein the accelerator includes ethyl chloride to accelerate curing time and enhance heat dispersion. 19. A composition for coating a human nail compris- ing nitrocellulose, a cyanoacrylate compound and graphite fibers. 20. The composition of claim 19 wherein the graphite fibers are translucent graphite fibers which are whitish in color to provide a translucent coat on the nail, the fibers being present in the composition in an amount from 0.003% to 0.030% by weight of the composition. 21. The composition of claim 19 comprising an acrylic polymer from 0.001% to 3.0% by weight of the composition mixture. 22. A nail composition for coating a human nail which comprises graphite fibers and a cyanoacrylate compound for increasing the adherence of the coating to the nail. 23. The nail composition according to claim 22 wherein the cyanoacrylate is present as a liquid having a viscosity varying from 100 centipoise to 600 centi- poise. * * * II! it