US3928113A - Method for coating human nails - Google Patents

Abstract

A method for coating human nails in which a basecoat composition comprising a water-soluble or water-swellable polymer dissolved in a solvent is first applied to the nails and allowed to dry. This is followed by the application of a photocurable polymer composition which is then exposed to a light source to cure the coating of photocurable polymer.

Description

Umted States Patent 1191 1111 3,928,] 13

Rosenberg Dec. 23, 1975 METHOD FOR COATING HUMAN NAILS 2,887,116 5/1959 Wooding 132/73 3,216,983 11/1965 Shelanski et a1...... 424/61 X [75] Rmnberg, west Now/an" 3,274,017 9/1966 Borrajo 117/3.6 x Com 3,483,289 12/1969 Michaelson et al 132/73 x 73 Assignee. Clairol Incorporated, New York, 3,661,744 5/1972 Kehr et a1. ll7/93.31 X

OTHER PUBLICATIONS [22] Filed: Oct. 24, 1973 Adler, Wash. Dail News, Feb. 16, 1972, Sealin Out T th D L K'd g 00 ecay urmg 1 s 21 A 1. N 1 1 PP 0 409 359 Schmeck, New York Times, Feb. 8, 1970, Halt in Related US. Application Data Tooth Decay 1 [63] Continuation-impart of Ser. No. 370,071, June 14,

1973. Primary Examiner-Harry J. Gwinnell Attorney, Agent, or Firm-Irving Holtzman; George A. [52] US. Cl. 156/344; 132/73; 204/l59.14; Mentis; David J. Mugford 428/515; 428/543; 428/913 AB TRA [51] Int. C1. A61K 7/043; BOSD 3/06 [57] S 1 [58] Field of Search 117/3, 93.31, 72, 141, A R? whch a basewat 117/161 UT, 6-, 424/61; 204/15914, 159.18; ';f:; g 'f i l s: 132 73; 156 427 swe a e p0 ymer lSSO ve 1n aso ven 1s rs app 1e 428/16 to the nails and allowed to dry. This is followed by the application of a photocurable polymer composition [56] References Cited which is then exposed to a light source to cure the UNITED STATES PATENTS coating of photocurable polymer. 2,764,168 9/1956 l-lerz 424/61 x 41 Claims Drawings METHOD FOR COATING HUMAN NAILS COPENDING CASES This applicationis a continuation-in-part of U.S. Pat. application Ser. No. 370,07l, filed June 14, 1973.

This invention relates to a method for coating human nails. More particularly, it concerns a method of this character which employs the application of a basecoat comprising a water-soluble or water-swellable polymer in a solvent system followed by the application of a photocurable nail lacquer composition and the curing of the same by means of a light source. This invention also concerns a method for the removal of this nail coating.

It has long been the practice in this art, in order to prepare human nails for better acceptance of the nail lacquers or enamels, to help in building film thickness and to increase adhesion of the enamel or nail lacquer to the human nails to first apply a basecoat to said human nails. Basecoat compositions of the prior art generally comprise a l% solution of nitrocellulose as the film former. When this is applied to nails and allowed to dry and then coated with a nail lacquer which is also allowed to dry, a nail coating is obtained which is difficult to remove. Organic solvents are ordinarily required to remove these coatings which tend to defat and thereby dry the nails in the process of removing the nail coating. This obviously is an undesirable result.

It has now been found that the aforesaid disadvantages may be readily avoided in accordance with the present invention by employing a two-part nail coating system comprising as a first part (a) basecoat composition of a water-soluble or water-swellable polymer in a solvent and as a second part (b), a photocurable nail lacquer composition adopted to be cured to a hard nail coating on its exposure to a light source described in more detail below. it has further been discovered that when the aforesaid basecoat composition is applied to human nails and allowed to dry and this is then followed with an overcoating of a photocurable nail lacquer which is cured by exposing it to an appropriate light source that both the basecoat and the nail lacquer composition are readily removable by the simple expedient of soaking the nails in water for a short period of time. This causes the basecoat to be released from the nail whereby the whole coating may be easily peeled off.

It is accordingly an object of the present invention to provide a method for applying a nail coating system to human nails which is readily removed when desired.

It is also an object of the present invention to provide a method for applying a basecoat and photocurable nail lacquer composition to human nails which greatly facilitates the subsequent removal of said nail lacquer.

It is a further object of this invention to provide a method for the removal of such basecoat photocurable nail lacquer compositions from human nails.

Other and more detailed objects of this invention will be apparent from the following description and claims.

As mentioned above, the basecoat compositions of this invention are characterized by the fact that they employ a water-soluble or water-swellable polymer system as the film former. These serve to facilitate the removal of the nail lacquer when both basecoat and photocurable nail lacquer have been applied to the nail. Soaking the nails so coated in hot water, preferably warm water, for a few minutes causes the basecoat to swell with the result that the overlaying layer of nail lacquer as well as the basecoat can be lifted up and released from the nail. The term water-swellable polymer is used in the present context to designate a polymeric material which has the capability of picking up a certain quantity of water without being dissolved therein. This water pick-up is accompanied by an increase in volume of the polymeric material. The term water-soluble polymer is used herein to mean a polymer that is soluble in waterat least to the extent of 1% by weight.

A class of water-soluble or water-swellable polymers that is particularly useful for the purpose of the present invention can be described as water-soluble or waterswellable polymers made by the polymerization of one or more vinylic compounds of the formula:

in which a a. R is hydrogen, alkyl, phenyl, halide or pyrrolidonyl i.e.

E E"; H

b. R is hydrogen, alkyl, phenyl, halide or ,COOH;

c. R is hydrogen, alkyl, carboxyalkyl, phenyl or halide;

d. X is hydrogen, -COO alkyl, COOH-O alkyl,

--CN, halide; Within this group of monomers is a preferred class of monomers having the same general formulas as formulas I above. However, in this case R R R and X have the following values:

a. R is hydrogen or pyrrolidonyl;

b. R is hydrogen, alkyl or COOl-l;-

. c. R is hydrogen; and

d. X is C00 alkyl; COOH, hydrogen or .-CN.

The term polymer is used herein in its generic sense to cover polymeric material which would be derived from the polymerization of one monomer described in formula I or a mixture of monomers of said formula. It is thus intended to cover homopolymers, copolymers, terpolymers, tetrapolymers, etc.

When R R or R in the above formula is an alkyl group or the alkyl moiety of a complex group containing an alkyl group (e.g. carboxyalkyl), the alkyl group or alkyl moiety preferably contains from 1 to 6 carbons e.g. methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl and n-hexyl. In addition any other substituent designated as alkyl the alkyl will also contain from 1 to 6 carbons e.g. methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, hexyl. When R R R or X are halide, they may be Cl, Br, F, I.

To illustrate more specifically preferred monomers that are included within formula I in accordance with the present invention, mention may be made of the following: vinyl acetate, crotonic acid, vinyl pyrrolidone, methyl vinyl ether, maleic anhydride, maleic acid, acrylic acid, acrylonitrile.

By way of further illustrating specific water-swellable or water-soluble polymers that are useful for the present purposes the following may be mentioned which may be used singularly or in combination: Amphomer 2844910; PVP/VA 535 (vinyl pyrrolidone/vinyl ace tate copolymer 50/50 mole percent); PVP/VA 335 (copolymer vinyl pyrrolidone/vinyl acetate 35/65 mole percent); Gantrez AN 119 (methyl vinyl ether/maleic anhydride copolymer, 1:1 molar relationship, low molecular weight grade Av. M.W. 250,000); Gantrez AN 139 (methyl vinyl ether/maleic anhydride copolymer, 1:1 molar relationship, medium molecular weight grade, Av. M.W. 500,000); Gantrez AN 169; Gantrez ES 425 (monobutyl ester of poly(methyl vinyl ether/- maleic acid); Gantrez ES 225 (monoethyl ester of poly(methyl vinyl ether/maleic acid); Gafquat (quaternized vinyl pyrrolidone copolymer); National Starch Resyn 26-2905; National Starch Resyn 2261; National Starch Resyn 28-2930 (terpolymer of crotonic acid and mixture of vinyl acetate and vinyl ester of C -C fatty acids (90%) mole percent) (See US. Pat. No. 2,996,471); National Starch Resyn 28-1310 (copolymer vinyl acetate (10% )lcrotonic acid (90%) mole percent). Photocurable polymers may also be used if they are water swellable. The Amphomer and the various National Starch Resyn products described in this case are manufactured by the National Starch Company. The various Gantrez" products mentioned herein are manufactured by General Aniline and Film (GAF).

The water-swellable or water-soluble polymers that are particularly useful in the present invention are further characterized by the fact that they are film forming polymers which form flexible films, as distinguished from rigid films. Since these polymers are intended to form a film which adheres to human nails and which at the same time forms a base on which a photocured polymeric top coat. may adhere, it is important to select a water-soluble or water swellable polymer that will have these adhesive properties.

Any one of the aforesaid water-soluble or water-swellable polymers or combinations thereof may be employed in formulating the basecoat compositions of the present invention.

These compositions will generally be in the form of solution of one or more of said polymers in a solvent system. A variety of solvents or combinations of so]- vents may be employed for this purpose. However, the solvent system will preferably be a relatively volatile solvent that is predominantly organic in character which may contain small amounts of an inorganic solvent e.g. water. By way of illustrating solvents that may be used advantageously in this connection, mention may be made of the following: ethanol, acetone, cosmetic solvents, ethyl acetate, toluene, isopropanol, methyl ethyl ketone. These may be used singularly or in combination.

The quantity of water-soluble or water-swellable polymer that may be contained in the present basecoat compositions may vary somewhat. Usually, it will constitute between about 5% to 30% by weight of the basecoat compositions.

In addition to the water-soluble or water-swellable film forming polymers mentioned above, the basecoat composition of this invention may contain other conventional ingredients commonly employed in compositions. These may be such things as pigments, plasticizers, surfactants, auxiliary solvents, perfumes, etc. Among the pigments that may be used, mention may be made of the D&C colors that are soluble in organic solvents. Typical of the plasticizers that can be incorporated in the present basecoat composition are dibutyl phthalate, dibutyl citrate, etc. As a suitable surfactant for these purposes is sorbitan trioleate.

Of special utility in connection with the present basecoat compositions are the photocurable nail lacquer compositions described in Applicants copending application Ser. No. 370,071, filed June 14, 1973 which is incorporated herein by way of reference. These nail lacquer compositions comprise generally a photocurable liquid system containing as essential ingredients at least one polyene, polythiol, photocuring rate accelerator, and one or more of a class of special surfactants described in more detail below. This liquid system is adopted to form cohesive film when applied to human nails and exposed to actinic light and particularly ultraviolet light (e.g. 3660A).

The aforesaid photocurable nail lacquer compositions are particularly suited for use with the present basecoat compositions because their mode of application and composition are such that they do not mix with the layer of basecoat that is previously laid down on the nails. Because of this, there is no interference with the capability of releasing the basecoat from the nails by the simple expedient of soaking the coated nails in warm water. This is to be contrasted with the situation in which an attempt would be made to use one of the prior art nail lacquers in conjunction with the present basecoats e.g. nitrocellulose in an organic solvent system. In this case, the application of the nail lacquer to the basecoat causes the softening of the basecoat and a comingling of the layers. This seriously influences the ability to get release of the basecoat from the nails by soaking them in water.

In addition to the aforesaid essential ingredients for the photocurable liquid system, other auxiliary components may be added to these compositions which do not interfere with the curing process. Thus, for example, the compositions may contain pigments, dyes, organic solvents (which serve as viscosity regulating agents), plasticizers, etc. There may also be incorporated in these nail lacquer compositions auxiliary resins which do not interfere with the principal curing reaction. Since these compositions are subject to be cured by the action of light which may be initiated by opening and closing the container in which the material is stored, it is often advisable to add a stabilizing agent or system to the composition to prolong the shelf life of the product.

The viscosity of these liquid photocurable nail lacquer compositions may vary somewhat. Generally, however, this will be in the range of from about 20 to 10,000 CPS at 25 to 28C using the Brookfield Model LV with Spindle 4 at 60 rpm. The preferred viscosity is about 4300 CPS at 27C. The viscosity of the system may be varied by means of a viscosity modifier (e.g. ethyl acetate, ethanol, isopropyl alcohol, methanol, butyl acetate, glyme, diglyme, methyl ethyl ketone, diethyl ketone, acetone, toluene, and proprietary cosmetic solvents.

The aforesaid polyene component may be represented by the formula:

llwherein m is an integer of at least 2, wherein X is a member selected from the group consisting of:

In the groups (a) to (e),fis an integer from 1 to 9; R is a radical selected from the group consisting of hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl' and substituted phenyl, benzyl and substituted benzyl, alkyl and substituted alkyl, alkoxy and substituted alkoxy, and cycloalkyl and substituted cycloalkyl. The substituentson the substituted members are selected from the group consisting of nitro, chloro, fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cy-' cloalkyl. Alkyl and alkoxy have froml to 9 carbon atoms and cycloalkyl has from 3 to 8 carbon atoms.

The members (a) to (e) are connectedv to [A] through divalent chemically compatible derivative members. The members (a) to (e) maybe connected to [A] through a divalent chemically compatible derivative member of the group consisting of Si(R) carbonate, carboxylate, sulfone, O-,

N, alkyl and substituted alkyl, cycloalkyl and substituted cycloalkyl, urethane and substituted urethane,

R and said members substituted being defined above. B is a member of the group'consisting of 'O, S, and NR.

The member [A] is polyvalent; free of reactive nonaromatic carbon to carbon unsaturation; free of highly water sensitive members; and consisting of atoms selected from the group consisting of carbon, oxygen, nitrogen, chlorine, bromine, fluorine, phosphorus, silicon and hydrogen.

The polyene component has a molecular weight in the range from about 64 to 20,000, preferably about 200 to about 10,000; and a viscosity in the range from essentially 0 to 20 million centipoises at 70C, as measured by a Brookfield Viscometer.

More particularly, the member [A] of the polyene composition may be formed primarily of alkyl radicals, phenyl and urethane derivatives, oxygenated radicals, and nitrogen substituted radicals. The member [A] may also be represented by the formula:

wherein j and k are integers greater than 1; R is a member of the group consisting of hydrogen, and alkyl having 1 m9 carbon atoms; R is a member of the group consisting of hydrogen and saturated alkyl having 1 to 9 carbon atoms; R, is a divalent derivative of the group consisting of phenyl, benzyl, alkyl, cycloalkyl, substituted phenyl, substituted benzyl, substituted alkyl and substituted cycloalkyl; with the terms alkyl, cycloalkyl and members substituted being defined above.

The polythiol component of said photocurable compositions are simple or complex organic compounds having a multiplicity of pendant or terminally positioned SH functional groups per average molecule. On the average, the polythiol must contain two or more Sl-l groups/molecule and have a viscosity range of essentially 0 to 20 million centipoises (cps) at 70C as measured by a Brookfield viscometer either alone or when in the presence of an inert solvent, aqu'eous dispersion or plasticizer. Operable polythiols employed herein usually have molecular weights in the range about 50 to about 20,000 and preferably from about 100 to about 10,000.

The polythiols used herein may be exemplified by the general formula R,,--(Sl-l wherein n is at least 2 and R, is a polyvalent organic moiety free from reactive non-aromatic carbon to carbon unsaturation. Thus,'R may contain cyclic groupings and hetero atoms such as N, P or O and primarily contains carbon-carbon, carhon-hydrogen, carbon-oxygen, or silicon-oxygen containing chain linkages free of any reactive nonaromatic carbon to carbon unsaturation.

One class of polythiols operable with polyenes to obtain essentially odorless polythioether products are esters of thiol containing acids of the formula l-lS-R- ,,COOH where R, is an organic moiety containing no reactive non-aromatic carbon to carbon unsaturation with polyhydroxy compounds of structure R ,(Ol-l), where R is an organic moiety containing no reactive non-aromatic carbon to carbon unsaturation, and n is 2 or greater. These components will react under suitable conditions to give a polythiolhaving the general struc- 'ttll'el RmiH-Rg-SH) 11 polythiol compounds preferred because of relatively low odor level include but are not limited to esters of thioglycollic acid (HSCH COOH), a-mercaptopropionic acid (HSCH(CH )COOH)and B-mercaptopropionic acid HS(CH CH COOH) with polyhy- 5 droxy compounds such as glycols, triols, tetraols, pentaols, hexaols, and the like. Specific examples of the preferred polythiols include but are not limited to ethylene glycol bis (thioglycolate), ethylene glycol bis(B- mercaptopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris (B-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (B-mercaptopropionate), all of which are commercially available and dipentaerylthritol hexakis (B-mercaptopropionate). A specific example of a preferred polymeric polythiol is polypropylene ether glycol bis([3-mercaptopropionate) which is prepared from polypropylene ether glycol (e.g. Pluracol P201, Wyandotte Chemical Corp.) and B- mercaptopropionic acid by esterification.

The preferred polythiol compounds are characterized by a low level of mercaptan-like odor initially, and after reaction, give essentially odorless polythioether end products which are commercially attractive and practically useful resins or elastomers.

Also of use as the polythiol component is a class of isocyanurate containing polythiols described in U.S. Pat. No. 3,676,440. These are defined generally by the formula:

HSR-N in which y is hydro en, methyl or eth l and z is an integer from O to 10. are part culerly, t ese isoeyenu= rate containing polythiols are illustrated by the follow tris( 2-hydroxyethyl )isocyanurate;

tris(2-mercaptoethoxyethyling compounds: tris(3-mercaptopropionate)ester of tris(2-mercaptoethyl)isocyanurate; )isocyanurate; tris(2-thiocarboxyethyl)isocyanurate; tris(2-mercaptoethyl)ester of tris(2ecarboxyethyl- )isocyanurate; tris(l 1-mercaptoundecanoate)ester of tris( 2-hyd roxyethyl )isocyanurate; tris( 3 -mercaptopropionate)ester of tris(2-hydroxypropyl)isocyanurate; and tris(Z-mercaptopropionate)ester of tris(Z-hydroxyethyl)isocyanurate.

Certain specific polyenes and polythiols are of special interest and are preferred in the practice of the present invention. These are given below together with a short statement of how they may be prepared. For convenience of identification, these materials are given a Polythiol or a Polyene number.

Polythiols Polyenes Polyene No. 1: This polyene is a tri-ene. It is made from allyl alcohol, malic acid and toluene diisocyanate. To prepare the polyene, one first reacts 2 moles of allyl alcohol with malic acid to give the diallyl malate ester. Separately, one then reacts 1 mole of allyl alcohol with 1 mole of toluene diisocyanate in such a way as to form the mono-adduct of these two compounds with the structure:

One mole of this adduct is next reacted with 1 mole of dlallyl malate ester to give the product tri-ene which has the structure:

Polyene No. 1

Polyene No. 2: This polyene is a tetraene. It is made from allyl alcohol, malic acid, and toluene diisocyanate (TDI).

Either the 2,4 or the 2,6 TDI isomer may be used or mixtures thereof. To prepare the polyene, one first prepares diallyl malate by esterification. Two moles of diallyl malate ester are then reacted with 1 mole of TDI to give the product. A small amount of dibutyltin dilaurate is used as a catalyst. Polyene No. 2 has the following structure:

Polyene No 2 Polyene No. 3: This polyene is a diene. It is made from bisphenol A and allyl chloride by standard etherification techniques. The structure is:

- CH=CH Polyene No. 4: This polyene is made from malic acid, allyl alcohol and isophorone diisocyanate. Isophorone diisocyanate has the following structure:

3 Nco H C H C CH NCO The polyene is prepared by reacting 2 moles of diallyl malate with one mole of isophorone diisocyanate in the presence of small amounts of dibutyltin dilaurate catalyst. The polyene is tetrafunctional and has the following structure:

Poly-ene No. 4

Polyene No. 5: This polyene is a diene. It is made from TDI and allyl alcohol. Two moles of allyl alcohol are reacted with one mole of TDI in the presence of small amounts of dibutyltin dilaurate catalyst. The polyene has the following structure:

Polyene No. 6: This polyene is a tri-ene. It is triallylisocyanurate. Its structure is as follows:

CH,CH=CH,

The relative quantities of polyene and polythiol that To obtain the maximum strength, solvent resistance, may be incorporated in the photocurable compositions creep resistance, heat resistance and freedom from may vary considerably. This seems best expressed by tackiness, the reaction components consisting of the relating the amount of polythiol to polyene by means of polyenes and polythiols of this invention are formua molar ratio i.e. SH groups to unsaturated groups and 5 lated in such a manner as to give solid, crosslinked, relating the combined amounts of polythiol to polyene three dimensional network polythioether polymer systo the total weight of the composition as a percent by terns on curing. In order to achieve such infinite netweight based on the total weight of th om iti work formation the individual polyenes and polythiols Accordingly, the molar ratio of the polythiol to polyene must have a functionality of at least 2 and the sum of will ordinarily be in the range of from about 0.50: l .0 to the functionalities of the polyene and polythiol compol.5:l.0 and preferably in the range of from about nents must always be greater than 4. Blends and mix- 0,67;1 0 t 1;1 Moreover, h mixture f l hi l tures of the polyenes and the polythiols containing said and polyene usually comprises between about 10 to functionality are lso Operable herein.

99% b i ht f th t l il lacquer composition, Conventional curing inhibitors or retarders may be 'A third s nti l component f h h bl used in order to stabilize the components or curable composition used herein is the photocuring rate accelcompositions so as to pr n premature onset of curerator. it is understood that the photocuring rate accelg- These c ude such things as hydroquino P- erator may be present as a separate and distinct combutyl catecbol; 2,6-di tert.-butyl-p-methylphenol; phepound such as azobenzene, as a mixture of two or more notbialine; -p y p yl min e t gas at separate components, such as benzophenone; benzan- Spheres such as helium, argon, nitrogen and carbon throne; anthrone, and dibenzosuberone; carbon tetradioxide.

chloride and phenanthrene; and the like, or in a chemi- A fourth component of the photocurable nail lacquer cally combined form within the molecular structure of composition employed herein is one or more of a cereither the polyene or the polythiol. An example of this tain class of certain specific surfactants. Among the latter condition wherein the photocuring rate accelerapreferred surfactants in this group are sorbitan sesquitor is present not as a separate component but rather in, oleate, sorbitan dioleate, sorbitan trioleate, pentaerytha form chemically combined within the polyene comritol dioleate, and pentaerythritol trioleate. ponent is the following structure which contains four The following surfactants are less effective but are reactive carbon to carbon unsaturated groupings and nevertheless operative for the present purposes: alone diaryl ketone grouping per average molecule: kenyldimethylethyl ammonium bromide; di coco 5% ll CH =CH-CH O-C O C-OCI-I CH=CH It is further understood that the polyene, the polydimethyl ammonium chloride; quaternary thiol or the photocuring rate accelerator may be imidazolinium salt (from stearic acid); glyceryl monoformed in situ in the photocurable composition without oleate; glyceryl dioleate; glyceryl trioleate and polyglydeparting from the spirit of this invention. cerol ester of oleic acid.

Specifically useful herein are chemical photocuring The quantity of surfactant component which may be rate accelerators such as benzophenone, acetopheincorporated into the present photocurable liquid comnone, acenapthene-quionone, o-methoxy benzophenone, thioxanthen-9-one, xanthen-9-one, 7-H-Benzposition may vary somewhat. Ordinarily, it will constitute between about .5% to 1.0% based on the total [de]anthracen-7-one, dibenzosuberone, l-napthweight of the composition. thaldehyde, 4,4-bis(dimethylamino) benzophenone, The basecoat compositions of the present invention fluorene-9-one, l'-acetonaphthone, 2'-acetonaphare applied in any suitable fashion. Ordinarily, it will be thone, anthraquinone, l-indanone, 2-tert.-butyl anthrabrushed on or wiped on and allowed to air dry. This will quinone, valerophenone, hexanophenone, 8-phenylso usually take about 30 seconds to a minute.

butyrophenone, p-morpholinopropiophenone, 4mor- Following the application of the basecoat, the photopholino-benzophenone, 4-morpholinodeoxybenzoin, curable lacquer can then be applied with a brush or a pdiacetylbenzene, 4-aminobenzophenone, 4'-methox porous tipped applicator. The lacquer should be apyacetophenone, benzaldehyde, a-tetralone, 9-acetylphenanthrene, Z-acetylphenanthrene, IO-thioxantheplied carefully. Only when the user is satisfied with the none, 3-acetylphenanthrene, 3-acetylindole, 1,3,5-triathe light. The nails are then exposed to an actinic light cetylbenzene, and the like including blends thereof, to source and particularly to an ultraviolet light source. greatly reduce the exposure times. These include such light sources as Type R.S. Sun- The curing rate accelerators are usually added in an lamp carbon are lamps, xenon arc lamps, mercury amount a ging from about 1% to about 10% y e g vapor lamps, tungsten halide lamps, etc. However, the of the photocurable composition based on the total most efficient process is obtained by employing a light weight of the nail lacquer composition. Preferred phosource wherein the wave length of the light is primarily tocuring rate accelerators are the aldehyde and ketone about 3660A. When employing a light source of the carbonyl compounds having at least one aromatic nulatter character, the coated nails may be exposed to this cleus attached directly to the light for a period of from 10 seconds to 15 minutes. This is adequate time to cure the nail lacquer composi E tion to a suitable hardness and finish. A typical light source is a mercury arc lamp of low or medium pressure type with a suitable phosphor for low pressure arc group benzophenonetube to yield sufficient radiation in 3660A radiation.

3 ,928 ,1 l 3 13 In order to remove the nail polish composition applied as described above, the following procedure is employed:

EXAMPLE B-6 Gantrez AN 139 (methyl vinyl ether/ maleic anhydride copolymer 1:1 molar v 1. The nails are placed in hot water; gggg 1- 5001000) :8

2. Allowed to soak for 3 to minutes; and p d 3. The polish can then be released from the nails by Same as p e B-l.

Peeling EXAMPLE 13-7 The following Examples are further illustrative of the present invention. It is to be understood, however, that z g L g'ggg gggiiflf they arenot limitative of this invention. All percentages 10 l 10 are given below in terms of percent by weight, unless f zg f p gg gg gy l I 8110 ISO ropano otherw1se specified. (anhydrous) P 90 Procedure: Basecoat Com sitions I 5 Same as Example EXAMPL by weight EXAMPLE 13-8 PvP/vA 335 (copolymer vinyl National Starch Resyn 2261 pyrmlidonelvinyl acetate (Acryhc copolymer latex copolymer 35/65 mole percent) suspended 1n water; 47% sollds; Ethanol (95%) 80 contammg .04% formaldehyde as 0 preservatwe) 10 Cosmetic Solvent (Shellsolve 1460) (50% ethanol (95%)/50% isopropanol Procedure P (anlydrous) 90 I roce ure: The resm 1s placed 1n the solvent and the m1xture 1sv s as gxampie stirred until all the resin goes into solution.

Nail Lacquer Compositions EXAMPLE B-Z Below are Examples of nail lacquer compositions Amphomer 28 4910 20 which may be used in conjunction with the basecoat gzgggghg 30 compositions of this invention.

Sanie as Example B-l. EXAMPLE EXAMPLE All the ingredients listed in the formula below were National starch Resyn 28.1310 placed in a mixing vessel and thoroughly stirred. The opolymer vinyl acetate mix was then milled to insure the production of a hogz g zggg? (90%) "39 pe'cem) 5g mogeneous product in which the solids are uniformly Procedure: distributed:

Same as Example B-l.

EXAMPLE B-4 Ingredient Percent National Starch Resyn 28-2930 0 40 2 (terpolymer crotonic acid (10%) y 1 43-20 mixture of vinyl acetate and gegzophgnone vinyl ester of C -C fatty S y i q J2 acids (90%) mole percent 10 of TnOleate Ethanol 90 Rubme Lake .95 pmcedu'e t c (Cl 38 01 73360) D Red No. s as Example 45 1 D&C Yellow No. 5 01 19140 .13 EXAMPLE Titanium Dioxide .85

Gantrez AN 119 (methyl vinyl ether/ maleic anhydride copolymer 1:1 molar relationship MW. 250,000) 20 The followmg Examples are g1ven in tabular form. Acetone g0 The formulas were compounded using the same proce- Pmcedgrel E I B l dure described in Example L-l. Similar results were ame as xamp e obtained Table 1 by weight Ingredients 'Ex. L-2 Ex. L-3 Ex. L-4 Ex. L-S Ex. L-6 Ex. L-7 Ex. L-8 Ex. L-9 Ex. L-10 Polyene N0. 2 48.178 48.298 48.30 48.44 48.25 47.75 '-''--'L Polythiol No. 1 43.598 43.715 43.61 43.79 43.68 43.20- Benzophenone 5.468 1 5.481 5.62 5.49 5.47 5.42 l-lydroquinone .127 .128 .13 .13 .13 .12----- Sorbitan trioleate 1.000 1.000 1.00 1.00 1.00 Sorbitan dioleate 1.00 Sorbitan sesquioleate 1.00 Pentaerythritol dioleate 1.00 Pentaerythritol trioleate 1.00 Rubine Lake (C1 15850) .953 .95 Black 0177499 1 .004 .06 D&C Red No. 30 (CI 73360) .043 .52 D&C Yellow No. 5 (Cl 19140) .13 Titanium dioxide 1.586 .85 D&C Red No. 6 (C1 15850) 5 .009 D&C Red No. 7 (Cl [5850:1) I .412 Cosmetic umber (CI 77491) 1.07 D&C Red No. 13 (C1 1563013) .27 1.47

The following Examples are also given in tabular relative amounts of polyene and polythiol contained in form. The compositions are prepared using the procedure given in Example L-l The percentages of polyene l and polythioi contained in the composition are given as polythiol to polyene 1.6. the molar ratio of unsaturated the combined weight of polyene and polythiol, the groups to SH groups.

the combination being expressed as the molar ratio of TABLE 11 Ex. L-11 Ex. L-12 Ex. L-13 Polyene No. No. 1 No. 1 No. 1 P01 thiol No. No. 1 No. 3 No. 4 Mo ar ratio PolythiolzPolyene 1:1 1:1 1:1 Polyene Polythiol 90.95 91.90 90.95 Benzophenone Acetophenone 5.42 o-Methoxy benzophenone 5.62 Dibenzosuberone 5.42 Hydroquinone .12 .13 12 Sorbitan trioleate 1.00 Sorbitan dioleate 1.00 Sorbitan sesquioleate 1.00 Pentaerythritol dioleate Pentaerythritol trioleate Rubine Lake (C1 15850) .95 .95 Black (CI 77499) .06 .06 D&C Red No. 30 (C173360) .52 .52 D&C Yellow No. 5 (C1 19140) .13 .13 Titanium dioxide .85 .85 Cosmetic umber (CI 77491) 1.07 D&C Red No. 13 (C1 15630z3) .28

Ex. Ex. Ex. Ex, Ex Ex.

No.2 No.2 No.3 No.3 No.3 No.3 No.4 No.1 No.2 No.3 .80:1 .8421 1 ;1 1:1 1:1

Polyene No. No 2 P01 thiol No. No 2 Mo ar ratio PolythiolzPolyene 1:1 Polyene Polythiol 90.95 5 42 Benzophenone Acetophenone o-Methoxy benzophenone Dibenzosuberone Hydroquinone Sorbitan trioleate Sorbitan dioleate Sorbitan sesquioleate gull Pentaerythritol dioleate 1.00 Pentaerythritol trioleate Rubine Lake (CI 15850) .95 Black (Ci 77499) .06 D&C Red No. (CI 73360 .52 D&C Yellow No. 5 (C1 19140) .13 Titanium dioxide .85

% Cosmetic umber (CI 77491) D&C Red No. 13 (C1 15630z3) Ex. Ex. Ex. Ex. Ex. L-20 L-21 L-22 L-23 L-24 Polyene No. No.3 No.4 No.4 No.4 No.4 Polythiol No. No.4 No.1 No.2 No.3 No.4 Molar ratio PolythiolzPolyene 1:1 1:1 .67:1.0 1:1 1:1 Polyene Polythiol 90.95 Benzophenone 5.42 Acetophenone o-Methoxy benzophenone Dibenzosuberone Hydroquinone .12 Sorbitan trioleate 1.00 Sorbitan dioleate Sorbitan sesquioleate Pentaerythritol dioleate Pentaerythritol trioleate Rubine Lake (C1 15850) .95 Black (C1 77499) .06 D&C Red No. 30 (C173360) .52 D&C Yellow No. 5 (C1 19140) .13 Titanium dioxide .85 Cosmetic umber (Cl 77491) D&C Red No. 13 (C1 1563023) Ex. Ex. Ex. Ex. Ex. L-25 L-26 L-27 L-28 L-29 Polyene No. No.5 No.5 No.5 No.5 No.6 Polythiol No. No.1 No.2 No.3 No.4 No.1 Molar ratio Polythiol:

Polyene 1:1 1:1 .80:1.0 1:1 1:1 Polyene Polythiol 90.95 Benzophenone 5.42

% Acetophenone TABLE ll-continued o-Methoxy benzophenone Dibenzosuberone Hydroquinone Sorbitan trioleate Sorbitan dioleate Sorbitan sesquioleate Pentaerythritol dioleate Pentaerythritol trioleate Rubine Lake (Cl 15850) Black (Cl 77499) D&C Red No. 30 (CI 73360) D&C Yellow No. (Cl 19140) Titanium dioxide Cosmetic umber (CI 77491) D&C Red No. 13 (Cl l5630:3)

Polyene No.

Polythiol No.

Molar ratio PolythiolzPolyene Polyene Polythiol Benzophenone Acetophenone o-Methoxy benzophenone Dibenzosuberone Hydroquinone Sorbitan trioleate Sorbitan dioleate Sorbitan sesquioleate Pentaerythritol dioleate Pentaerythritol trioleate Rubine Lake (Cl 15850) Black (Cl 77499) D&C Red No. (CI 73360) D&C Yellow No. 5 (Cl 19140) Titanium dioxide Cosmetic umber (Cl 77491) D&C Red No. 13 (Cl 156303) Method for Applying and Removing Basecoat and Nail Lacquer Composition EXAMPLE M-l The nails of a human subject were first cleaned with a solvent i.e. acetone, ethyl acetate to remove all dirt and debris. Basecoat B-5 was then applied to the nails. The product is brushed on or wiped on the nail with a cotton ball and allowed to air dry. A coat of nail lacquer L-l was then brushed onto the nails. The coated nails were then exposed to the light from a 4FT5BL lamp for a minute to 1 minute and 15 seconds. This light source is in the range of from 3500 to 3880A and is predominantly light having a wave length of about 3660A. At the end of this exposure, the nail lacquer was cured to a tough nail coating.

To remove the coating the nails were soaked in hot water for approximately four minutes. The nails were removed from the water and the lacquer was peeled off. If there is any resistance to peeling, the nails are soaked for a longer period of time.

The same procedure of Example M-l is used in connection with all of the basecoats B-l to B-4 and 8-6 to B-8 described above in combination with each of the nail lacquers L-2 to L-32 also described above. The results obtained are similar to those obtained with basecoat B-5 and nail lacquer L-l.

Although the invention has been described with reference to specific forms thereof, it will be understood that many changes and modifications may be made without departing from the spirit of this invention.

What is claimed is:

l. A method for coating human nails with compositions that are adopted to be readily removable from the nails by soaking the nails in water which comprises:

35 a. applying to said nails a liquid basecoat composition containing a water-soluble or water-swellable flexible film forming polymer; b. allowing said composition to dry on said nails whereby a film of said water-soluble or water-swellable polymer is deposited on and adheres to said nails; c. applying to said dried film of water-soluble or water-swellable polymer a second layer of liquid photocurable nail lacquer composition capable of being polymerized by an actinic light source; and d. exposing said layer of photocurable nail lacquer composition to a source of actinic light for a sufficient period of time to cure said nail lacquer composition whereby a hard polymerized layer of nail lacquer is obtained which overlies and adheres to said basecoat layer; said water-soluble or water-swellable polymer being a polymerization product of one or more 5 (i). R is hydrogen, alkyl, phenyl, halide or pyrrolidonyl (ii). R is hydrogen, alkyl, phenyl, halide r -COOH;

(iii). R is hydrogen, alkyl, carboxyalkyl, phenyl or halide;

(iv). X is hydrogen, -COO alkyl, COOH, 0 alkyl,

-CN or halide.

2. A method according to claim 1 wherein said watersoluble polymer is soluble in water at least to the extent of 1% by weight.

3. A method according to claim 2 wherein said watersoluble polymer is a copolymer of vinyl pyrrolidone and vinyl acetate.

4. A method according to claim 2 wherein said watersoluble polymer is a copolymer of methyl vinyl ether and maleic anhydride.

5. A method according to claim 2 wherein said watersoluble polymer is a terpolymer of crotonic acid, vinyl acetate and a vinyl ester of a higher fatty acid having from C -C carbons.

6. A method according to claim 1 wherein said liquid photocurable nail lacquer comprises a liquid composition containing a polyene component, a polythiol component and a photocuring rate accelerator.

7. A method according to claim 6 wherein said liquid photocurable nail lacquer composition also contains a surfactant selected from the group consisting of sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, pentaerythritol trioleate, glyceryl monooleate, gylceryl dioleate, glyceryl trioleate, polyglycerol ester of oleic acid, alkenyldimethylethyl ammonium bromide, di coco dimethyl ammonium chloride, and quaternary imidazolinium salt.

8. A method according to claim 7 wherein:

a. said polyene component is a terminally unsaturated polyene which comprises the formula: ti l-i wherein m is an integer of at least 2, wherein X is R I U wherefis an integer from 1 to 9; R is a radical selected from the group consisting of hydrogen, fluorine, chlorine, furyl, thienyl, pyridyl, phenyl and substituted phenyl, benzyl and substituted benzyl, alkyl and substituted alkyl, alkoxy and substituted alkoxy, cycloalkyl and substituted cycloalkyl; said substituents on said substituted members being selected from the group consisting of nitro, chloro, fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl; said alkyl and alkoxy having from 1 to 9 carbon atoms and said cycloalkyl having from 3 t0 8 carbon atoms; wherein A is free of reactive non-aromatic carbon to carbon unsaturation; free of highly water sensitive members, and is a polyvalent member of the group consisting of car bonate, carboxylate, carbonyl, ether, silane, silicate, phosphonate, phosphite, phosphate, alkyl and substituted alkyl, cycloalkyl and substituted cycloalkyl, aryl and substituted aryl, urethane and substituted urethane, urea and substituted urea, amine and substituted amine, amide and substituted amide, hydroxyl, heterocyclic carbon containing radical, and mixtures thereof, said substituents on said members being selected from the group consisting of nitro, chloro, fluoro, acetoxy, acetamide, phenyl, benzyl, alkyl, alkoxy and cycloalkyl; said alkyl and alkoxy having from 1 to 9 carbon atoms and said cycloalkyl having from 3 to 8 carbon atoms; said component having a molecular weight in the range from about 64 to 20,000; and a viscosity in the range from essentially 0 to 20 million centipoises at C; and

b. said polythiol component has a molecular weight in the range from about 50 to about 20,000 and is of the general formula:

Il -(8H),,

wherein R is a polyvalent organic moiety free from reactive non-aromatic carbon to carbon unsaturation and n is at least 2, the sum of m and n being greater than 4, with the ene/thiol mole ratio being selected so as to provide a cross-linked solid, self-supporting cured product.

9. A method according to claim 8 wherein said liquid photocurable nail lacquer composition additionally contains a photocuring rate accelerator selected from the group consisting of aryl aldehyde, diaryl ketone, alkyl aryl ketone, triaryl phosphine and a blend of carbon tetrahalide with polynuclear aromatic hydrocarbon.

10. A method according to claim 9 wherein said liquid photocurable nail lacquer composition contains from about 0.5% to 1.0% by weight of said surfactant, about l% to 10% by weight of said photocuring rate accelerator and from about 1% to about 98.5% by weight of a mixture of said polythiol and said polyene, the molar ratio of polythiol to polyene in said mixture being in the range of about .50:l.0 to 1.5110.

11. A method according to claim 10 wherein said polyene is CH n 2 OH r CH ll CH 12. A method according to claim 11 wherein said polythiol is pentaerythritol tetrakis (fi-mercaptopropionate).

13. A method according to claim 11 wherein said polythiol is tris(2-hydroxyethyl)isocyanurate tris (B- mercaptopropionate).

14. A method according to claim 11 wherein said polythiol is trimethylolpropane tris (B-mercaptopropionate).

15. A method according to claim 11 wherein said polythiol is dipentaerythritol hexakis (B-mercaptopropionate).

16.'A method according to claim 10 wherein said polyene is 17. A method according to claim 16 wherein said polythiol is pentaerythritol tetrakis (B-mercaptopro- 27. A method according to claim 26 wherein said polythiol is pentaerythritol tetrakis (B-mercaptopropionate). 30 pionate).

f P accordmg to clfllm 16 Said 28. A method according to claim 26 wherein said p y y y y y trls (B- polythiol is tris (2-hydroxyethyl)isocyanurate tris (13- p p p I mercaptopropionate).

P Q accordmg to claim 16 wherem Sald 29. A method according to claim 26 wherein said P9 3 1S trlmethylolpropane (fip p polythiol is trimethylolpropane tris (B-mercaptopro- Plonate pionate 20. method according to claim 16 wherein said 30. A method according to claim 26 wherein said polythiol 1s dipentaerythritol hexakis (B-mercaptopropolythiol is dipentaerythritol hexakis (B-mercaptopropionate). pionate).

21. A method according to claim 10 wherein said 31. A method according to claim 10 wherein said polyene is polyene is 3 CH ==CH-CH 0 C) (I O-CH CH=CH 22. A method according to claim 21 wherein said polythiol is pentaerythritol tetrakis (B-mercaptopro- P pionate).

23. A method according to claim 21 wherein said CH2 cH 2 0 c NH NH A 0 2 Q polythiol is tris (2-hydroxyethyl)isocyanurate tris (B- mercaptopropionate). v

24. A method according to claim 21 wherein said polythiol is trimethylolpropane tris (Ii-mercaptopropionate).

25. A method according to claim 21 wherein said polythiol is dipentaerythritol hexakis (fit-mercaptopropionate).

26. A method according to claim 10 wherein said polyene is 32. A method according to claim 31 wherein said polythiol is pentaerythritol tetrakis (Ii-mercaptopropionate).

33. A method according to claim 31 wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris (B- mercaptopropionate).

34. A method according to claim 31 wherein said polythiol is trimethylolpropane tris (B-mercaptopro-' c- CH -CH CH CH CH-CH 37. A method according to claim 36 wherein said polythiol is pentaerythritol tetrakis (B-mercaptopropionate).

38. A method according to claim 36. wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris (flmercaptopropionate).

39. A method according to claim 36 wherein said polythiol is trimethylolpropane tris (B-mercaptopropionate).

40. A method according to claim 36 wherein said polythiol is dipentaerythritol hexakis (B-mercaptopropionate).

41. A method for removing from human nails the nail covering applied by the method of claim 1 which comprises soaking said covered nails in water for a period of from 3 to 6 minutes until said water-soluble film has sufficiently swelled to lift said nail covering from said nails and then stripping said nail covering from said nails.

UNITED STATES PATENT OFFHIE QE'HFICATE 0F i EUHQN Patent No. $9 13 Dated December 23, 1975 Inventor(s) Ira Rosenberg 6 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Page 2, line 7, under ABSTRACT OF DISCLOSURE, after "polymer 0" should read A method for removing the g aforesaid coating from human nails by soaking the coated nails in water and stripping the coating is also disclosed.

twenty-third 0% March 1976 [SEAL] Attest:

a RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nj'Patents and Trademarks

Claims (41)

1. A METHOD FOR COATING HUMAN NAILS WITH COMPOSITIONS THAT ARE ADOPTED TO BE READILY REMOVABLE FROM THE NAILS BY SOAKING THE NAILS IN WATER WHICH COMPRISES: A. APPLYING TO SAID NAILS A LIQUID BASECOAT COMPOSITION CONTAINING A WATER-SOLUBLE OR WATER-SWELLABLE FLEXIBLE FILM FORMING POLYMER; B. ALLOWING SAID COMPOSITION TO DRY ON SAID NAILS WHEREBY A FILM OF SAID WATER-SOLUBLE OR WATER-SWELLABLE POLYMER IS DEPOSITED ON AND ADHERES TO SAID NAILS; C. APPLYING TO SAID DRIED FILM OF WATER-SOLUBLE OR WATER-SWELLABLE POLYMER A SECOND LAYER OF LIQUID PHOTOCURABLE NAIL LACQUER COMPOSITION CAPABLE OF BEING POLYMERIZED BY AN ACTINIC LIGHT SOURCE; AND D. EXPOSING SAID LAYER OF PHOTOCURABLE NAIL LACQUER COMPOSITION TO A SOURCE OF ACTINIC LIGHT FOR A SUFFICIENT PERIOD OF TIME TO CURE SAID NAIL LACQUER COMPOSITION WHEREBY A HARD POLYMERIZED LAYER OF NAIL LACQUER IS OBTAINED WHICH OVERLIES AND ADHERES TO SAID BASECOAT LAYER; SAID WATER-SOLUBLE OR WATER-SWELLABLE POLYMER BEING A POLYMERIZATION PRODUCT OF ONE OR MORE VINYLIC COMPOUNDS OF THE FORMULA:

2. A method according to claim 1 wherein said water-soluble polymer is soluble in water at least to the extent of 1% by weight.

3. A method according to claim 2 wherein said water-soluble polymer is a copolymer of vinyl pyrrolidone and vinyl acetate.

4. A method according to claim 2 wherein said water-soluble polymer is a copolymer of methyl vinyl ether and maleic anhydride.

5. A method according to claim 2 wherein said water-soluble polymer is a terpolymer of crotonic acid, vinyl acetate and a vinyl ester of a higher fatty acid having from C10-C18 carbons.

6. A method according to claim 1 wherein said liquid photocurable nail lacquer comprises a liquid composition containing a polyene component, a polythiol component and a photocuring rate accelerator.

7. A method according to claim 6 wherein said liquid photocurable nail lacquer composition also contains a surfactant selected from the group consisting of sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, pentaerythritol dioleate, pentaerythritol trioleate, glyceryl monooleate, gylceryl dioleate, glyceryl trioleate, polyglycerol ester of oleic acid, alkenyldimethylethyl ammonium bromide, di coco dimethyl ammonium chloride, and quaternary imidazolinium salt.

8. A method according to claim 7 wherein: a. said polyene component is a terminally unsaturated polyene which comprises the formula: ti (A-X)m wherein m is an integer of at least 2, wherein X is

9. A method according to claim 8 wherein said liquid photocurable nail lacquer composition additionally contains a photocuring rate accelerator selected from the group consisting of aryl aldehyde, diaryl ketone, alkyl aryl ketone, triaryl phosphine and a blend of carbon tetrahalide with polynuclear aromatic hydrocarbon.

10. A method according to claim 9 wherein said liquid photocurable nail lacquer composition contains from about 0.5% to 1.0% by weight of said surfactant, about 1% to 10% by weight of said photocuring rate accelerator and from about 1% to about 98.5% by weight of a mixture of said polythiol and said polyene, the molar ratio of polythiol to polyene in said mixture being in the range of about .50:1.0 to 1.5:1.0.

11. A method according to claim 10 wherein said polyene is

12. A method according to claim 11 wherein said polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).

13. A method according to claim 11 wherein said polythiol is tris(2-hydroxyethyl)isocyanurate tris ( Beta -mercaptopropionate).

14. A method according to claim 11 wherein said polythiol is trimethylolpropane tris ( Beta -mercaptopropionate).

15. A method according to claim 11 wherein said polythiol is dipentaerythritol hexakis ( Beta -mercaptopropionate).

16. A method according to claim 10 wherein said polyene is

17. A method according to claim 16 wherein said polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).

18. A method according to claim 16 wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris ( Beta -mercaptopropionate).

19. A method according to claim 16 wherein said polythiol is trimethylolpropane tris ( Beta -mercaptopropionate).

20. A method according to claim 16 wherein said polythiol is dipentaerythritol hexakis ( Beta -mercaptopropionate).

21. A method according to claim 10 wherein said polyene is

22. A method according to claim 21 wherein said polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).

23. A method according to claim 21 wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris ( Beta -mercaptopropionate).

24. A method according to claim 21 wherein said polythiol is trimethylolpropane tris ( Beta -mercaptopropionate).

25. A method according to claim 21 wherein said polythiol is dipentaerythritol hexakis ( Beta -mercaptopropionate).

26. A method according to claim 10 wherein said polyene is

27. A method according to claim 26 wherein said polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).

28. A method according to claim 26 wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris ( Beta -mercaptopropionate).

29. A method according to claim 26 wherein said polythiol is trimethylolpropane tris ( Beta -mercaptopropionate).

30. A method according to claim 26 wherein said polythiol is dipentaerythritol hexakis ( Beta -mercaptopropionate).

31. A method according to claim 10 wherein said polyene is

32. A method according to claim 31 wherein said polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).

33. A method according to claim 31 wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris ( Beta -mercaptopropionate).

34. A method according to claim 31 wherein said polythiol is trimethylolpropane tris ( Beta -mercaptopropionate).

35. A method according to claim 31 wherein said polythiol is dipentaerythritol hexakis ( Beta -mercaptopropionate).

36. A method according to claim 10 wherein said polyene is

37. A method according to claim 36 wherein said polythiol is pentaerythritol tetrakis ( Beta -mercaptopropionate).

38. A method according to claim 36 wherein said polythiol is tris (2-hydroxyethyl)isocyanurate tris ( Beta -mercaptopropionate).

39. A method according to claim 36 wherein said polythiol is trimethylolpropane tris ( Beta -mercaptopropionate).

40. A method according to claim 36 wherein said polythiol is dipentaerythritol hexakis ( Beta -mercaptopropionate).

41. A method for removing from human nails the nail covering applied by the method of claim 1 which comprises soaking said covered nails in water for a period of from 3 to 6 minutes until said water-soluble film has sufficiently swelled to lift said nail covering from said nails and then stripping said nail covering from said nails.