CA1225035A - Latex nail coating - Google Patents

Abstract

"LATEX NAIL COATING"
Hector J. Gonzalez and Janiana Z. Pilch ABSTRACT OF THE DISCLOSURE

An aqueous latex nail coating emulsion of copolymers of at least three monomers and methods of formulating such coating are disclosed. One monomer comprises at least one or .beta. mono ethylenically unsaturated mono or polycarboxylic acid monomer having from 3-10 carbon atoms. A second monomer comprises at least one ethylenically unsaturated ester. The third monomer comprises at least one additional monomer of an ethylenically unsaturated ester other than the last mentioned ester monomer, a monovinylidene, a vinyl ester or an acrylamide.
Emulsifying agents may be added to emulsify these monomers in the aqueous emulsion and at least some of these emulsifiers may be copolymerizable with the monomers. Following copoly-merization, a salt of a di- or trivalent metal is added to the emulsion for crosslinking the copolymers. Following copoly-merization, one or more alkali soluble resins, plasticizing agents, coalescing agents, antifoaming agents, viscosifying agents, leveling aids and pigments may also be added, as desired, to form the nail coating.

Description

~;2S~35 BACKGROUND END SUMMARY OF THE INVENTION

The present invention is directed to a finger-nail coating and method of formulation thereof and, more particularly, to a water-based latex fingernail coating 5 and method of formulation.
Prior fingernail coatings have generally been formulated using nitrocell~lose in organic solvents Such fingernail coatings suffer several important disadvantages.
Nitrocellulose it highly flammable requiring careful handling 10 in storage, manufacture and in the application of the coating to the consumers nail. moreover, the solvents which are employed in finch nitrocellul~se coatings are also usually flammable, frequently Coffey discoloration of the Courtney of the net 1, and require extended drying times .
Automatic have been made to formulate water-based fingernail coatings which avoid Rome or all of the aforementioned disadvantage However, these prior water-based ormulati~
have not heretofore been able to achieve many or most of the physical properties which are desired in a fingernail coating 20 or example prior waterbed coatings which have heretofore been developed have suffered from one or more of the following di~advarltages: poor adhesion to the net 1 keratln poor glow qualities, incompatibility with patentor, poor leveling properties, difficulty of application/ find poor bxu~h drag characteristic 25 additional disadvantage of prior water-~ased nail coating ~s~5~3~j;

also are high film forming temperatures, lack of resistance to water or detergents, and slow drying times.
It is known in the art of water-based emulsion polymerization, that monomeric substances comprising one or 5 more polymerizable, ethylenically unsaturated monomers Jay be emulsified in an aqueous medium which contains an emulsifying agent and a polymerization catalyst and these monomers may be polymerized or copolymerized therein. Such emulsion polymer-lion techniques are, for example, known in the paint coating 10 arts However, the emulsion polymer and copolymer coating products of that art art not subjected to the tame problems as are fingernail coatings in which the coatings must be coated upon the nail Courtney of the human ode and exposed to sub-~tantially more severe mechanical, chemical and other physical 15 stresses which water-hased paint coatings do not generally experience.
A nail coating and method of formulation incorporating the principles of the present invention overcomes many, if not all of the aforementioned disadvantages of both vent 20 and water-based coatings. A nail coating incorporating the principles of the present invention is not flammable and will not discolor the nail Courtney. A nail coating incorporating the principles of the present invention is capable of rapid drying and of employing waxer as a base, rather than exotic 25 solvents with their attendant disadvantages. A nail crating ~5~3~i;

incorporating the principles of the present invention exhibit excellent adhesion to the nail Courtney and a high gloss, it highly compatible with a wide rinse of coloring pigments, and has excellent theological properties, thereby S resulting in improved leveling, ease of application and brush drag characteristics. nail coating incorporating the principles of the present invention also exhibits excellent low film forming temperatures well blow 25C and is highly resistant to water and detergents after it has teen applied 10 to the nail and, because it is waterbed, any spills or the like may be readily cleaned with water prior to hardening of the coating.
In one principal aspect of the present invention, a latex nail coating comprises an emulsion of copolymers of 15 at least three monomers. A first monomer comprises at least one or moo ethylenically unsaturated moo or polycarboxylic acid monomer having from 3-10 carbon atoms. A second monomer comprises at least one ethylenically unsaturated ester which is copolymerized with the acid monomer. A third monomer 20 includes at least owe additional monomer selected from the group consisting essentially of an ethylenically unsaturated ester other than the last mentioned ester monomer, a moo-vinylidene, a vinyl ester and an acrylaminde, the third monomer also being copolymerized with the aforementioned monomers. A
25 Walt of a do or trivalent metal for cross linking the copolymers is also included in the emulsion.
In another principal aspect of the present invention the aforementioned emulsion is an aqueous emulsion In till another principal aspect of the present invention, the aforementioned nail coatings include at least one emulsifying agent.
In still another principal aspect of the present 5 invention, at least some of the aforementioned emulsifying agents are copolymerized with at least one of the monomers.
In still another principal aspect of the present invention, the aforementioned salt of a dip or trivalent metal is present in an amount surf fishnet to cross link about 10 60-80~ of the functional groups of the copol~mers.
In still another principal aspect of the present invention, the aforementioned nail coatings may include an alkali soluble resin.
In till another principal aspect of the present 15 invention, the emulsions of the aforementioned nail coatings also include one or more composition selected from the group consisting essentially of plasticizing agents, coalescing agents, anti foaming agents, viscosifying agents leveling aids and pigments.
In still another principal aspect of the present invention, a method of formulating a latex nail coating emulsion comprises emulsion copolymerizing in a liquid at least three monomers. A first monomer comprises at least one or B
moo ethylenically unsaturated moo or polycarboxylic acid 25 monomer having from 3-10 carbon atoms. A second monomer comprises at least one ethylenically unsaturated ester. the ~%~;~35 third monomer comprises at least one additional monomer selected from the group consisting essentially of an ethylenically unsaturated ester other than the last mentioned ester monomer, a monovinylidene, a vinyl ester and an acrylamide.
A salt of a dip or trivalent metal is added to the liquid emulsion to cross link the copolymers.
In still another principal aspect of the present invention, the aforementioned emulsion is an aqueous emulsion.
In still another principal aspect of the present invention, the aforementioned methods include the audition of at least one emulsifying agent.
In still another principal aspect of the present invention, at least some of the aforementioned emulsifying agents are copolymerized with at least one of the monomers.
In still another principal aspect of the present invention, the aforementioned salt of a dip or trivalent metal is added in an amount sufficient to cross link about 60-80 of the functional groups of the copolymers.
In still another principal aspect of the present invention, the aforementioned methods may include the addition of an alkali soluble resin.
In still another principal aspect of the present invention, the aforementioned methods may also include the addition to the emulsion of one or more compositions selected from the group consisting essentially of plasticizing agents, coalescing agents, anti foaming agent, viscosifying agents, leveling aids and pigments.

33~

hose and other objects, features and advantages of the present invention will be understood upon consideration of the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In a preferred embodiment of latex nail coating of the present invention, at least three monomers are emulsion copolymerized with each other, preferably in an aqueous emulsion, and a cross linking agent for cross linking these copolymerized copolymers is present in the emulsion.
first of the preferred monomers comprises one or more monomers of an or moo ethylenically unsaturated moo or polycarboxylic acid. This acid monomer is preferably one which has from about 3-10 carbon atoms. By way of example, such acid monomers may include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid or malefic acid.
The acid monomer is dispersed in an aqueous medium for Capella-merization with toe other monomers, preferably in an amount of about 0.5-10,0 weight percent of the emulsion.
The second of the preferred monomers comprises one or more ethylenically unsaturated esters which are capable of copolymerization with the acid monomer. Such ester monomers are preferably esters of one or more of the last mentioned acid monomer. By way of example, the ester monomer may be the esters of an acrylic acid including methyl acrylate, ethyl acrylate, propel acrylate, bottle acrylate, isobutyl ~2~3~;
acrylate, Amy acrylate, isoamyl acrylate, Huxley acrylate,

2-ethylhexyl acrylate, decal acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propel methacrylate, bottle and isobutyl methacrylate, namely methacrylate, isoamyl methacrylate and 2-ethyl bottle methacrylate.
The third of the preferred monomers which is incorporated in the emulsion copolymer of the preferred embodiment of nail coating may include one or more selected monomers, such as an additional ester monomer of the kind last described, but different than the second monomer which has been selected. The third monomer may also include a monovinylidene, a vinyl ester anchor an acrylamide.
Examples of suitable monovinylidenes include styrenes methyl styrenes vinyl Tulane, left bottle styrenes ethyl vinyl Bunsen, acrylonitrile and methacrylonitrile.
Examples of suitable vinyl esters include vinyl acetate, vinyl preappoint and vinyl bitterroot.
Examples of suitable acrylamides include acrylamide and methylol acrylamide.
The specific monomers are selected to achieve the physical properties desired in the final coating. By way of example, the monomers may be selected to achieve the necessary balance to obtain a desired hardness of the coating. As a general rule, as the monomers become larger they become softer. For example, ethyl acrylates are softer than methyl acrylates and ethyl methacrylates are softer than methyl methacrylates.

I

Thus, the first, second and third monomers may be selected so as to impart the desired quality, such as dried coating hardness, keeping these individual monomer characteristics in mind.
The monomers are preferably dispersed in the emulsion liquid for copolymerization with the assistance of emulsifying agents. As such liquid, water is preferred. The emulsifying agents may be either non-ionic agents, such as alkyd phonics polyethoxyethan~ls having alkyd groups of about Rio 8-12 carbon atoms ego. Briton X-100, Room & Hays). suitable emulsifying agents may also include anionic agents or mixtures of polar-anionio groups with non-polar, non anionic groups such as disodium ethoxylated alcohol half esters of ~ul~osuccinic acids (e.g. Aerosol A-102, American Cyanamid In certain preferred embodiments of the coatings of the present invention, the emulsifiers are preferably copol~nerizable with the monomers and, a such, result in superior water and detergent resistance properties in the dry coating. Examples of such copolymeri~able emulsifying agents 20 include anionic ~urfactants, such as the sodium Walt of vinyl sulfonate ego. Cops I, Alcoholic Chemical Co. ) .
additional emulsifying agents may eye used, either alone or in combination with the aforementioned emulsifying agents. For example, other well known anionic surfactants~ such 25 as tetrasodium N-(1,2 dicarboxyethyl~ N-octadecyl sulfosuccinate Do (e.g. Aerosol 22, American Cyanamid), sodium ductile sulfosuccinate twig. aerosol OTT American Cyanamid), ammonium and sodium laurel sulfate may also be incorporated in the emulsion.
Copolymexization is preferably achieved in the emulsion through the use of any one or more of a number of known emulsion cupolymerization catalysts. By way of example, potassium, sodium or ammonium per sulfates may be employed as copolymerization catalysts.
Under certain circumstances, it may be desirable to limit the molecular weight of the copolymers. For example, copolymers having a molecular weight of greater than about 75,000 generally result in a milky emulsion, whereas emulsions of copolymers having molecular weights of between about 25, 000 15 to 75,000 are relatively clear. If the nail coating it to be colored or pigmented; it is not generally important whether the emulsion is milky or clear because the pigment will likely mask the coating emulsion. However, if the coating it to be a clear, unpigmented coating, it is preferable to limit the 20 molecular weights of the copolymers to 75,000 or lest. This may be readily accomplished by the addition of small mounts of chain terminating agents, either at the same time that the monomers are added to the emulsion or as copolymerization it advancing. Such chain terminating agents may be organic sulfur compounds, such as mercaptans.

~2~35 An important feature of the resent invention is the incorporation of one or more cross linking agents in the emulsion to produce cross linking of the copolymerized monomers Although, in some instances, the cross linking agents may be present in the emulsion while copolymerization is proceeding, it is preferred that the cross linking agents be added to the emulsion after copolyermization has substantially advanced or has been completed. The preferred cros51inking agents of the present invention include the salts of dip and trivalent metals, such as zinc, calcium, zirconium, cobalt, nickel and the like.
Examples of such salts include metal complexes, such as zinc ammonium carbonate or acetate The cross linking agent are preferably added in an amount sufficient to cross link from 60-80% of the functional groups remaining on the already Capella-merited monomers. Although cross linking of a greater percentage of these functional groups may ye acceptable, the danger arises that undesirable golfing will occur at these high percentages.
Thereby, it is preferred to add only enough of the cross linking agent to achieve such 60-80% cross linking. Where the cross-20 linking agent is zinc ammonium carbonate, 0.1-Q.5 White I, based upon the metal, of the cross linking agent is satisfactory.
As the emulsion dries after application to the fingernail, the dip or trivalent metals will form the cxo~slinks between functional groups of the already formed copolymers I

and the metals will, thereby, become part ox the polymer coating. Such cross linking of the copolymers substantially improves the water and detergent resistance of the dried coating.
Other compositions may also be added to the emulsion following copolymerization to further enhance the final properties of the coating, either or both to improve its else of application to the fingernail or its properties after drying.
One such additional composition may include alkali 10 soluble resins. Such resins, for example the ammonium salt of Turin malefic android resins may be prepared by adding ammonium hydroxide to an aqueous slurry of the resin and stabilizing its final pi at abut 8-9~ Partial esters of malefic android resins are alto preferred. Partial ester 15 resins are generally preferred which have lower viscosities and molecular weights of, for example, SPA 1,000-4,000. One supplier of suitable partial ester resins is Argo Chemical.
the styrenes malefic android resins form protective colludes in the aqueous emulsion and improve adhesion of the coating.
Another alkali soluble resin which may be incur-prorated into the emulsion coating to promote adhesion, leveling and gloss has the general formula OH - OH - - OH - OH - SHEA OH - OH - OH - - H

I OKAY C-O CHIC COO
o OH OR n ~:;25~13S

where R it alkyds and alkaline -oxy-alkyls, R contains from 1 to 10 carbon atoms, and n it a number from 1 to 9. The molecular weight can vary from about 410 to 1800.
Still other types of alkali soluble resins which S can be incorporated into the emulsion to promote leveling and gloss are the partially hydroli~ed methyl methacrylate solution polymers with acid number 90-200 and molecular weights of about 700-2000. Such resins are commercially available from Room Hays Co. under the generic name of acrylic oligomers.
Another composition which may be incorporated into the emulsion following copolymerization is a plasticizing agent, such as tributyl phosphate, tributoxyethyl phosphate, dibutyl phthalate, diisobutyl phthalate and various mixtures thereof.
Coupling or coalescing Anita may also be incorporated in the emulsion, such as n-propanol, i~opropanol, methyl cello solve, bottle cello solve, Huxley cello solve, methyl carbitol, carbitol solvent, bottle carbitol and mixtures thereof.
Antifoamin~ and leveling agents may also be incur 20 prorated into the emulsion. Such agents are known in the emulsion coating art, and may include, for example Do Lola of Dow Corning, or SOWS 211 of Union Carbide.
-. Viscosifying agents may also be added, if desired, to thicken the coating emulsion. Veegum of Vanderbilt Chemical 25 is one of a number of acceptable vi~cosifying agents.

so Leveling rids, such as ~C-129 of Minnesota Mining and Mfr., may also be incorporated in the coating emulsion to enhance the smoothness ox the dried coating.
Finally, pigments and other suitable coloring agents may be incorporated in the nail coating emulsion of the present invention in proportions ranging from 0.05-5% by weight of the total solids, the amount of such pigments being limited by their water volubility and cost. Such pigments may include any one or more of a umber of well known pigments 10 which are dispensable in water and commonly used in water-based paints and other coatings.
In the preferred nail coatings incorporating the principles of the present invention, the couplers may comprise 50-90% by weight of the total solids, the alkali soluble resins 0-35~ by weight, with the remainder of the coating being plasticizers, coalescing agents, anti foaming agents, viscosifying agents; leveling aids or pigment which may comprise of from 1-15% by weight. The solids may be adjusted to 15-40 wt. of the coating emulsion, and preferably to 20-35 wt. with water as a delineate.
Several specific examples of nail coatings and methods of formulation of such coatings incorporating the preferred embodiments of the present invention follow.

Example Jo. 1 Into a 2 1. reaction vessel equipped with agitator, reflex condenser, dropping funnel, thermometer inert gas 2~;~)3~

line and pi probe, 55.04 wt. % ox water, 0.6 wt. of emulsifying agent comprising an anionic copolymerizable ~urfactant of the sodium salt of vinyl silent cops I, Alcoholic CheJnical), and 1.7 wt. % of ammonium laurel sulfate 5 anionic emulsifying agent were added. This aqueous system was heated to gawk and 0.2 wt. % of potassium persulfa~e was added to the aqueous system as a copolymerization catalyst or the monomers together with the following monomer charge:
monomer White methacrylic acid 0.7S
methyl methacrylate 11.6 styrenes 15.4 bottle acrylate 14.7 This monomer charge was gradually adder to the 15 reactor over a 120 minute period along with sufficient inert gas (No) bubbled in the reactor.
The mixture was reacted at 80C fur an additional 30 minutes and the pi of the emulsion was then raised to OWE
by the addition of ammonium hydroxide. At this time the 20 cro~slinking agent zirconium ammonium carbonate is alto added to the latex emulsion in the amount of 0.4 wt. % based upon the metal.
A nail coating emulsion is then formulated by adding the following to 78.0 wt. 4 of the last mentioned latex5 emulsion wt.
alkali soluble resin (partial 10.0 ester of malefic android-SPA 2625~ Argo Chemicals) it.

plasticizer agent (tributoxyethyl phosphate) 0.1 coalescing agent bottle cello~olve) 2.

leveling aid (FC-129, Minnesota Mining 6 Mar 0.1 anti foaming agent (DUB Lola, Dow Corning) 0.01 viscosifying agent (Veegum, Vanderbilt Chemical) 0.1 water 9.69 Example No 2 To the apparatus as set forth in Example 1, 55.06 wt. % of water, 0.6 wt. of emulsifying agent comprising 15 an anionic copolymerizable ~urfactant of the sodium Walt of vinyl sulfonate (Cops I, Alcoholic Chemical), and 1.68 wt.
of sodium laurel sulfate anionic emulsifying agent were added.
This aqueous stem was heated to 87-90C and 0.2 we. % of ammonium per sulfate was added to the aqueous system a a I copolymerization catalyst for the monomer together with the following monomer charge:
monomer wt. %

methacrylic acid OWE
methyl methacrylate ll.Ç
methyl Turin 15.4 Boyle acrylate 14.7 1~2~;~3~5 This monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert gas (No) bubbled in the reactor.
The mixture was reacted at 80C for an additional 30 minutes and the pi of the emulsion was then raised to 7.0 by the addition of ammonium hydroxide. At this time the cross-linking agent zinc ammonium carbonate was also added to the latex emulsion in an amount of 0.4 wt. based upon the metal.
A nail coating emulsion was then formulated by 10 adding the following to 78.4 wt. of the last mentioned latex emulsion:
wt. %

plasticizer agent ~tributoxyethyl phosphate) 1.8 coalescing agent (bottle cello solve) 5.B
leveling aid 5FC-l~9, Minnesota wining fry.) 0.3 anti foaming agent (DUB Lowe Dow Corning) 0.01 water 13.69 Example No. 3 To the apparatus as set forth in Example 1, 57.5 wt. of water and 3.4 wt. of ammonium laurel sulfate anionic 25 emulsifying agent were added. This aqueous system was heated to 80-85~C and 0.2 wt. of potassium per5ulfate was added to the aqueous system a a copolymerization catalyst for the ~2~35 monomers together with the following monomer charge:
monomer . , wit .

methacrylic acid 0.7 acrylamide 1.4 methyl methacrylate 15.3 styrenes 10.3 2-ethylhexyl acrylate 11.2 This monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert 10 gas (No) bubbled in the reactor.
The mixture was reacted at 80C for an additional 30 minutes an the pi ox the emulsion was then raised to 7.0 by the addition of ammonium hydroxide. At this time the cross-linking agent cobalt ammonium carbonate is also added to the5 latex emulsion in an amount of 0.4 wt. % based upon the metal.
A nail coating emulsion is then formulated by adding the following to 78.0 wt. % of the last mentioned latex emulsion:
wt.

alkali soluble resin (partial ester of malefic android-SPA 2625, Argo Chemicals) 705 coalescing agent (bottle cello solve) 2.0 leveling aid (FC~129, Minnesota Mining & Mfr.) 0.1 anti foaming agent (DUB Lola, Dow Corning) 0.01 ~5~5 wt.
viscosifying agent (Vèegum, Vanderbilt Chemical) I
water 12.27 Example No. 4 To the apparatus as set forth in Example 1, 59.82 wt. of water, 0.7 wt. % of emulsifying agent comprising a non-ionic octal phonics polyethoxy ethanol surfactant (Briton X-100, Room & Hays), and 2.0 wk. of sodium laurel sulfate anionic emulsifying agent were added This aqueous system was heated to 80-85C and 0.18 wt. of ammonium per sulfate was added to the aqueous system a a copolymerization catalyst for the monomers together with the hollowing monomer charge:
monomer wt. %

methacrylic acid 0.6 acrylamide 3.0 methyl methacrylate 10.3 yearn 10.3 bottle acrylate 13.1 This monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert gas (No) bubbled in top reactor.
The mixture was reacted at 80~C for an additional 30 minutes and the pi of the emulsion was then raised to 7~0 I

by the addition ox ammonium hydroxide. At this time the cross linking agent zinc ammonium carbonate was also added- .
to the latex emulsion in the amount of 0.3 wt. based upon the metal A nail coating emulsion was then formulated by adding the following to 65.0 wt. of the last mentioned latex emulsion:
wt. %
alkali soluble resin (partial I ester of malefic android-SPA 2625, Argo Chemicals) 25.0 coalescing agent (bottle cello solve) 3.0 (Dalpad A, Dow Comical anti foaming agent (DUB Lola, Dow Corning) 0.03 viscosifying agent (Veegum, Vanderbilt Chemical) .12 . water 6.18 Example Jo. 5 To the apparatus as set forth in Example 1, 59.2 wt. 4 of water, 0~12 wt. % of emulsifying agent comprising non-ioni~ octal phonics polyethoxy ethanol surf lent Briton X-100, Room Hess, and 2.0 wt. of sodium laurel sulfate 25 anionic emulsifying agent were added. This aqueous system was heated to 80-85C and 0.2 wt. 4 of ammonium per sulfate was added to the aqueous system as a copolymerization catalyst for the monomers together with the following monomer charge:
monomer wt.
acrylic acid 0.78 ~.~25~3~3 monomer wt. %
. .
styrenes 7.1 methyl methacrylate 14.9 ethyl a~rylate 11.8 acrylonitrile 3.9 This monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert gas (My) bubbled in the reactor.
The mixture was reacted at 80C for an additional 30 minutes and the pi of the emulsion was then raised to 7.
by the addition of ammonium hydroxide. At this time the cross-linking agent zinc amm~nium carbonate was alto added to the latex emulsion in an amount of 0.2 Wed % based upon the metal.
A nail coating emulsion was then formulated by adding the following tug 78 O woo of the last mentioned latex emulsion:
wt. %
alkali voluble resin (partial ester of malefic android-SPA 2625, Argo Chemicals 10.0 coalescing agent (Boyle cello solve) 2.0 leveling aid I 129, Minnesota Mining 6 MfrO)Ool anti faming agent DUB Lola, Dow Corning) 0~01 viscosifying agent (Veegum, Vanderbilt Chemical ~12 water 9.77 owe Example No. 6 To the apparatus as set worth in Example 1, 55.58 wt. % of water, 0.6 wt. of emulsifying agent comprising an anionic copolymerizable surfactant of the sodium salt of 5 vinyl ~ulfonate (Cops I, Alcoholic Chemical), and 2.6 wt.
of ammonium laurel sulfate anionic emulsifying agent were added. This aqueous system was heated to 80-55C and 0.34 wt. of ammonium per sulfate was added to the aqueous system as a copolymerization catalyst for the monomers together with 10 the following monomer charge:
monomer wt.
methacrylic acid 4.3 methyl methacrylate 21.9 bottle acrylate 14.5 15 Alto 0018 wt. % of n-dodecyl mercaptan was added together with the monomers as a chain terminating agent to limit the molecular weight of the copolymers to between 25,000-75,00D.
this monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert0 gas (No) bubbled in the reactor.
The mixture was reacted at 80~C for an additional 30 minutes and the pub of the emulsion was then raised to 7. 0 by the addition of ammonium hydroxide. At this time the cross-linking agent zinc ammonium carbonate was also added to the5 latex emulsion in the amount of 0.2 wt. based upon the metal.

I

I

A nail coating emulsion was then formulated by adding the following to 68.0 wt. % of the last mentioned latex emulsion:
wt. %

alkali soluble resin (acrylic oligomer-Acrysol 644, Room & Hays) 3.8 plasticizer agent ~tributoxy ethyl phosphate) 0.5 coalescing agent (bottle cello solve 2.0 leveling aid IFC-129, Minnesota Mining & Mfr.) 0.3 an~ifoaming agent (DUB AYE, Dow Corning) 0.01 water 25.39 , Example Jo. 7 To the apparatus as set forth in Example 1, 56.71 wt. % of water, 0.42 wt. % of emulsifying agent comprising an anionic sodium ductile sulfosuccinate (Aerosol OTT American Cyanamid), and 0.76 wt. of ammonium laurel sulfate anionic emulsifying agent were added. This aqueous system was heated to 80-85C and 0.25 wt. % of ammonium per sulfate was added to the aqueous system as a copolymerization catalyst for the monomers together with the followl~g monomer charge:
monomer wt.
methacrylic acid 4.59 -23~

~22~3~

monomer wt.
. . .

methyl methacrylate 21.0 bottle acrylate 13.1 styrenes 3.0 S Also 0~17 wt. % of t-dodecyl mercaptan was added together with the monomers as a chain terminating agent to limit the molecular weight of the copolymers to between 25,000-75 r -this monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert 10 gas (No) bubbled in the reactor.
The mixture was reacted at 80~C for an additional 30 minutes and the pi of the emulsion was then raised to 7.0 by the addition of ammonium hydroxide. At this time the cross-linking agent zinc ammonium carbonate was also added to the5 latex emulsion in the amount of 0.2 wt. based upon the metal.
A nail coating emulsion was then formulated by adding the following to 68.0 wt. % of the last mentioned latex emulsion:
w . %

alkali voluble resin (partial ester of malefic android-SPA 2625, Argo Chemicals)15.0 plasticizer agent ItributsxY
ethyl phosphate) 0.5 coalescing agent (bottle cello solve) 2.0 I

Sue wt.
leveling aid t~C-129,~
Minnesota Mining & Mfr. ) O . 3 anti foaming agent DUB Lola, Dow Corning) O . I
water 14.19 Example No. 8 To the apparatus as set forth in Example 1, 58.42 wt. ox water, 0.12 wt. % of emulsifying agent comprising a non-ionic octal phonics polyethoxy ethanol surfactant (Briton X-100, Room & Hays), and 2.0 wt. 4 of sodium laurel sulfate anionic emulsifying agent were added. This aqueous system was heated to 80-85C and 0.2 wt. % of ammonium per sulfate was added to the aqueous system as a copolymerization catalyst for the monomers together with the following monomer charge:
monomer wt. %
methacrylic acid/itaconic acid (1:1 ratio) 1.56 styrenes 7.1 ethylacrylate 14.9 methyl methacrylate 11.8 acrylonitrile 3 . 9 his monomer charge was gradually added to the reactor over a 120 minute period Lyon with sufficient inert5 gas No bubbled in the reactor The mixture was reacted at 80C for an additional 30 minutes and the pi of the emulsion was then raised to 7.0 by the addition ox amm~nium hydroxide. At this time the cross-linking agent zinc ammonium carbonate was also added to the latex emulsion in the amok t of 0.2 wt. % based upon the metal.
A nail coating emulsion was then formulated by adding the following to 68.0 wt. of the last mentioned latex emulsion:
wt.
alkali soluble resin partial ester of malefic android-SPA ark Chemicals)15.0 plasticizer agent ~tributoxy ethyl phosphate) OHS
coalescing agent (bottle cello solve) 2.0 leveling aid (FC-129, Minnesota Mining Mfr.)0.3 anti foaming agent (DUB Lola, Dow Corning 0.01 water 14.19 Example No. g To the apparatus as set forth in Example 1, 4~,9 wt. of water, 3.44 wt. of emulsifying agent comprising a non~ionic/anionic surfactant of disodium ethoxylated alcohol half ester of sulfosuccinic acid (Aerosol A-102, American Cyanamid) and 1.3 wt. of sodium laurel sulfate anionic emulsifying agent were added. This aqueous system was heated to 60-65C and 0.43 wt. of ammonium per sulfate was added to the aqueous system as a copolymeriza~ion catalyst for the ~2é~5~33~j monomers together with the following monomer charge:
monomer we. %
.
itaconic acid 0.43 ethyl acrylate 28.64 methyl methacrylate 11.12 N-methylol acrylamide 4.3 methanol 1.44 This monomer charge was gradually added to the reactor over a 120 minute period along with sufficient inert gas No bubbled in the reactor.
The mixture was reacted at 60~C for an additional 30 minutes and the pi of the emulsion was then raised to 7.0 by the addition of ammonium hydroxide. At this time the cross linking agent zinc am Nemo carbonate was also added to 15 the latex emulsion in the amount of 0.2 wt. % based upon the metal.
A nail coating emulsion was then formulated by adding the following to 68.0 wt. of the last mentioned latex emulsion:
wt. %
alkali soluble resin partial ester of malefic android-SPA awry Chemicals)1500 plasticizer agent (tributoxy ethyl phosphate) 005 coalescing agent (bottle cello solve) 2.0 leveling aid (FC-129, Minnesota wining Mfr.)0.3 I

I

wt.

anti foaming agent (DUB Lola, Dow Corning) Ø01 water 14.19 Table I - Example Results is-Solids costly, Drying Dune-in cups at Time, ability, Example Emulsion 25C Gloss min._ Adhesion A days 1 28~6 7.7270 good 3 acceptable 2 18.1 8.9100 good 3 acceptable

3 27.0 7~560 good 3 acceptable

4 28.1 7.950 good 2+ acceptable 29.0 7.B35 good I acceptable 6 29.8 8.5530 gory 3 acceptable 2 7 ~7.0 8~5125 OWE 3 acceptable 3 8 27.5 8.245 gveOy 3 acceptable 3 9 27.0 8.3100 good 5 acceptable Film forming temperature of the coatings of all of these examples was satisfactorily below 25C.
The adhesion tests were conducted utilizing Scotch Brand tape on the dried coatings. This test is a test which is conventionally used in testing adhesion in coatings in which the tape is applied to the dried coating on the nail of a tested individual and is then rapidly pulled from the nail.
The term actable" jeans that all of the coating remained on the nail and none stuck to the tape The gloss test consisted of a visual comparison of the gloss of the dried coating Oil the nail of the tested individual to a dried, conventional solvent control coating.
The control coating used for the tests was Revlon 61 (clear

5 nail polish). The term "good" mean that the coating of the example had a gloss which was as Good as the gloss of the control coating and the term "very good" means that the gloss was superior to the control coating.
The durability tests for each example were con-10 dueled with a test panel of ten women The coating of the example was applied to the nails of each of these women and they proceeded with their normal daily routines. During this time, each of the women visually observed the test coating on their nails for loss of gloss, peeling and chipping and 15 when either such event occurred, it was deemed that durability had ended. The number of days set forth in Table I for durability is the approximate average of the tests for each of the women in the test group rounded to the nearest whole number.

It will be understood that the embodiments of the present invention which have been described are merely illustrative of a few of the applications of the principles of the present invention. Numerous modifications may be made by those skilled in the art without departing from the true spirit and scope of the invention.

Claims (31)

The embodiments of the invention in which an exclusive property or privilege is claimed is defined as follows:

1. A latex nail coating comprising:
an emulsion of copolymers of at least three monomers including:
a first monomer comprising at least one .alpha. or .beta.
mono ethylenically unsaturated mono or polycarboxylic acid monomer having from 3-10 carbon atoms, said first monomer being present in an amount between about 0.5 and about 10 weight percent of said emulsion;
a second monomer comprising at least one ethylenically unsaturated ester copolymerized with said acid monomer, said ethylenically unsaturated ester being an ester of an acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and maleic acid;
a third monomer comprising at least one additional monomer selected from the group consisting essentially of an ethylenically unsaturated ester other than said second monomer, a monovinylidene, a vinyl ester and an acrylamide, said third monomer also being copolymerized with the aforementioned monomers to form at least one emulsion copolymer; and a complex salt of a di- or trivalent metal for crosslinking said copolymers, said metal complex salt being present in an amount sufficient to crosslink between about 60 and about 80 percent of the functional groups of said copolymers to form a crosslinked emulsion copolymer.

2. The nail coating of claim 1, wherein said emulsion is an aqueous solution.

3. The nail coating of claim 1, wherein said ester monomers are selected fron the group consisting essentially of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate and 2-ethyl butyl methacrylate.

4. The nail coating of claim 1, wherein said third monomer includes a monovinylidene monomer selected from the group consisting of styrene, .alpha. methyl styrene, vinyl toluene, tert butyl styrene, ethyl vinyl benzene, acrylonitrile and methacrylonitrile.

5. The nail coating of claim 1, wherein said third monomer includes a vinyl ester selected from the group consisting essentially of vinyl acetate, vinyl proprionate and vinyl butyrate.

6. The nail coating of claim 1, wherein said third monomer includes an acrylamide selected from the group consisting essentially of acrylamide and methylol acrylamide.

7. The nail coating of claim 1, including at least one emulsifying agent.

8. The nail coating according to claim 7, wherein said emulsifying agent includes anionic groups.

9. The nail coating according to claim 7, wherein at least some of said emulsifying agent is copolymerized with at least one of said monomers.

10. The nail coating according to claim 1, wherein said copolymers and the metal complex salt crosslinked emulsion copolymer comprise between about 50 and about 90 weight percent of the total solids in the coating.

11. The nail coating of claim 1, including an alkali soluble resin.

12. The nail coating of claim 11, wherein said resin is a partial ester.

13. The nail coating of claim 1, wherein said emulsion also includes one or more compositions selected from the group consisting essentially of plasticizing agents, coalescing agents, antifoaming agents, viscosifying agents, leveling aids and pigments.

14. A method of formulating a latex nail coating emulsion comprising:
A. emulsion copolymerizing in a liquid (1) a first monomer comprising at least one .alpha.
or .beta. mono ethylenically unsaturated mono or polycarboxylic acid monomer having from 3-10 carbon atoms, said first monomer being present in an amount of between about 0.5 and about 10 weight percent of said emulsion;
(2) a second monomer comprising at least one ethylenically unsaturated ester; and (3) a third monomer comprising at least one additional monomer selected from the group consisting essentially of an ethylenically unsaturated ester other than said second monomer, a monovinylidene, a vinyl ester and an acrylamide, said third monomer also being copolymerized with the aforementioned monomers to form at least one emulsion copolymer; and B. adding a complex salt of a di- or trivalent metal to the emulsion liquid to crosslink said copolymers, said metal complex salt being present in an amount sufficient to crosslink between about 60 and about 80 percent of the functional groups of said copolymer to form a crosslinked emulsion copolymer.

15. The method of claim 14, wherein said liquid is aqueous.

16. The method of claim 14, wherein said first monomer is selected from the group consisting essentially of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and maleic acid.

17. The method of claim 16, wherein said ester monomers are the esters of one of said acids.

18. The method of claim 14, wherein said ester monomers are esters of an acrylic acid.

19. The method of claim 14, wherein said ester monomers are selected from the group consisting essentially of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate and 2-ethyl butyl methacrylate.

20. The method of claim 14, wherein said third monomer includes a monovinylidene monomer selected from the group consisting essentially of styrene, methyl styrene, vinyl toluene, tert butyl styrene, ethyl vinyl benzene, acyrlonitrile and methacrylonitrile.

21. The method of claim 14, wherein said third monomer includes a vinyl ester selected from the group consisting essentially of vinyl acetate, vinyl proprionate and vinyl butyrate.

22. The method of claim 14, wherein said third monomer includes an acrylamide selected from the group consisting essentially of acrylamide and methylol acrylamide.

23. The method of claim 14, including the addition of at least one emulsifying agent to said liquid.

24. The method of claim 23, wherein said emulsifying agent includes anionic groups.

25. The method of claim 23, wherein at least some of said emulsifying agent is copolymerized with at least one of said monomers.

26. The method of claim 14, wherein said copolymers and the metal complex salt crosslinked emulsion copolymer are present in said emulsion in an amount of between about 50 and 90 weight percent of the total solids in the coating.

27. The method of claim 14, including the addition of an alkali soluble resin to said emulsion.

28. The method of claim 27, wherein said resin is added following copolymerization of said monomers.

29. The method of claim 27, wherein said resin is a partial ester.

30. The method of claim 14, including the addition following copolymerization of one or more compositions selected from the group consisting essentially of plasticizing agents, coalescing agents, antifoaming agents, viscosifying agents, leveling aids and pigments.

31. The method of claim 28, including the addition following copolymerization of one or more compositions selected from the group consisting essentially of plasticizing agents, coalescing agents, antifoaming agents, viscosifying agents, leveling aids and pigments.