WO2001003655A1

WO2001003655A1 - Coating composition for physiological substrates and physiological substrates coated therewith

Info

Publication number: WO2001003655A1
Application number: PCT/US2000/017611
Authority: WO
Inventors: Robert A. Gelman
Original assignee: Hercules Incorporated
Priority date: 1999-07-08
Filing date: 2000-06-23
Publication date: 2001-01-18
Also published as: AU6338500A

Abstract

Coating composition for substrates selected from toenails, fingernails, artificial nails and combinations thereof, the coating composition comprising: (A) at least one polyamidoamine-epihalohydrin; and (B) at least one material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on a keratinous substrate. (B) is preferably selected from copolymers of alkyl halides and alkenes; copolymers of methyl methacrylate, butyl acrylate, styrene vinylidene chloride, acrylic acid, and methacrylic acid; acrylic and vinyl acrylic-based materials; and mixtures thereof. Coating methods and substrates such as fingernail, toenails, artificial nails and combinations thereof are also provided.

Description

COATING COMPOSITION FOR PHYSIOLOGICAL SUBSTRATES AND PHYSIOLOGICAL SUBSTRATES COATED THEREWITH

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to coating compositions for coating various physiological substrates, including compositions for coating keratinous substrates such as fingernails, and toenails, and similar substrates such as artificial nails, and the like.

2. Background of the Invention and Related Art

Nail polish, applied to finger or toenails or artificial nails, performs a cosmetic function, among other functions. Nail polish is most commonly a colored liquid that dries, not unlike paint, into a hard, shiny coating. Nail polishes sold as articles of commerce are typically solutions and/or dispersions in an organic solvent, such as toluene or acetone. Depending on the formulation, solvent-based nail polish can be brittle, tend to yellow, not have sufficient adhesion to the substrate, release volatile organic compounds, and/or create allergenic problems for some users. Moreover, repeated uses of some solvents can damage nails, as described, for example, in U.S. Patent No. 5,120,259.

Conventional nail polishes generally employ nitrocellulose as the film former. Typical formulations are disclosed in "Formulating Nail Lacquer", B. Albert, Drug and Cosmetic Industry. Vol. 48, November 1998), which is hereby incorporated by reference as though set forth in full herein, for its background information on such nail formulations.

U.S. Patent No. 5,120,259 discloses a water-based nail polish consisting of at least one polyurethane and/or polyurethane copolymer in dispersed form as a binder, with a thickener and acrylated-styrene copolymer. The acrylated-styrene copolymer is employed to increase hardness of the dried coating. U.S. Patent No. 5,716,603 discloses a nail polish composition comprising an aqueous solution containing an acrylic resin cross linked with a difunctional acrylated urethane oligomer. This patent notes that nail polish formulations contain other additives, such as plasticizers and coalescents to modify the film and/or provide other desired or functional properties such as gloss, uniform color or resistance to chipping.

The use of organic solvents has resulted in shortcomings as described above. An aqueous-based composition would eliminate some of these problems. Further, an aqueous-based composition would eliminate the characteristic solvent odor. Thus, there is a need for a water-based nail polish. However, aqueous-based products can exhibit poor adhesion, poor freeze-thaw stability and, in many areas (i.e., for many applications) often require a thickener. There are other difficulties that would be expected to be associated with aqueous-based nail polish. These include the fact that the high latent heat of evaporation of water makes drying of the material difficult. Various porous substrates have been coated or otherwise treated with coating compositions to impart desired characteristics to the substrate, including the surface thereof.

Paper for certain applications has been customarily strengthened with resins to impart strength thereto when the paper is wet. Such resins are commonly referred to as "wet strength resins". A frequently employed wet-strength resin for use in papers is that of the broad class of polyamidoamine-epihalohydrin polymers for resins. Such resins are marketed under the trademark KYMENE®. Such resins, and processes for their manufacture, are disclosed in U.S. Patents No. 2,926,116 and 2,926,154, both to KEIM; U.S. Patent No. U.S. Pat. 5,614,597 to BOWER; U.S. Patents Nos. 5,644,021 and 5,668,246, both to MASLANKA; all assigned to Hercules Incorporated, all of which patents are hereby incorporated by reference as though set forth in full herein.

U.S. Patent No. 4,859,527 discloses cellulosic non-woven products of enhanced water and/or solvent resistance obtained by pre-treatment of the cellulosic fibers. In some embodiments, this patent discloses that suitable pre-treatment agents include poly(aminoamide) epichlorohydrin resins. Suitable overcoat binders are disclosed as including ethylene- vinyl chloride-acrylamide polymers. Specific examples of the pre- treatment agents include KYMENE®, including KYMENE 557^®; overcoat binders include AIRFLEX binders including AIRFLEX® ΕVC1" co-polymers (AIRFLEX® 4500). There has also been a need for flexible coatings such as pretreatments and precoats on various substrates. Such substrates on which a need for a flexible coating exists include substrates subject to bending and flexing. Such substrates also can include those which must be cut. Fingernails and toenails and artificial nails are exemplary of such substrates. SUMMARY OF THE INVENTION

The present invention provides a coating composition for various substrates, such as keratinous substrates selected from toenails and fingernails, as well as artificial nails, and combinations of such substrates.

The invention provides coating compositions for substrates selected from fingernails, toenails, artificial nails, combinations thereof and the like, which exhibit improved characteristics, as shown by low levels of flaking and/or chipping, especially under conditions of routine wear, hygiene and grooming.

The invention provides coating compositions for substrates selected from fingernails, toenails artificial nails, combinations thereof and the like, which achieve a desired finish color and scratch durability (such as scratch resistance, abrasion resistance and similar properties).

Also preferably, the invention provides coating compositions for substrates selected from fingernails, toenails, artificial nails, combinations thereof and the like, which, when finger, toenails and artificial nails and the like are coated with the composition and the composition is cured, exhibit a combination of the foregoing attributes.

The invention also provides a composition that can be easily used, that, in certain preferred embodiments, does not exhibit solvent odor and which, in certain preferred embodiments, does not include organic solvents. The invention provides compositions which when curing do not require a high degree of ventilation.

Compositions of the invention are also stable over time. The invention also provides methods of treating and/or coating substrates selected from fingernails, toenails, artificial nails, combinations thereof and the like with such compositions. The invention provides coating compositions for substrates selected from toenails, fingernails, artificial nails and combinations thereof, the coating composition comprising:

(A) at least one polyamidoamine-epihalohydrin; and

(B) at least one material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on the substrate. The invention also provides nail polishes comprising:

(A) at least one polyamidoamine-epihalohydrin; and

(B) at least one polymer comprising repeating units derived from an alkyl halide having at least one double bond and an alkene.

The invention also provides substrates comprising a member selected from a fingernail, a toenail, an artificial nail or combinations thereof, coated with such a nail polish.

The invention also provides combination comprising, a substrate selected from finger nails, toenails, artificial nails and combinations thereof, and a composition comprising at least one polyamidoamine-epihalohydrin. In such combinations the composition can furhter comprise at least one additional material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on the substrate.

The invention also provides methods of coating a substrate selected from finger nails, toenails, artificial nails and combinations thereof, comprising: coating the substrate with a coating composition comprising: at least one polyamidoamine-epihalohydrin. In such methods the coating composition can comprise:

(A) at least one polyamidoamine-epihalohydrin; and

(B) at least one material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on a keratinous substrate. In the compositions and methods above, the weight ratio of (A):(B) can be from about 0.05 to about 19, preferably from about 4 to about 12, more preferably from about 6 to about 8, more preferably from about 6.5 to about 7.0, and most preferably about 6.75.

The compositions include those wherein (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 5% to about 95%> by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 5% to about 95% by weight based on the total weight of all components of the composition. In such coating compositions component (A) preferably comprises an aqueous solution of component (A) present in an amount in a range of from about 50% to about 85% by weight based on the total weight of all components of the composition, and component (B) preferably comprises an aqueous emulsion of component (B) present in an amount in a range of from about 8% to about 50%) by weight based on the total weight of all components of the composition. In such coating compositions component (A) preferably comprises an aqueous solution of component (A) present in an amount of about 75% by weight based on the total weight of all components of the composition, and component (B) preferably comprises an aqueous emulsion of component (B) present in an amount of 11% by weight based on the total weight of all components of the composition. Component (B) comprises a flexibilizing material, or a crosslinking inhibiter, which may be selected from copolymers which may be derived from monomers including at least one of alkyl halides, alkenes, methyl methacrylate, butyl acrylate, styrene vinyhdene chloride, acrylic acid, methacrylic acid, and vinyl acrylic-based materials.

The alkyl halide can comprise a vinyl halide, preferably vinyl chloride and the alkene can comprise an olefin, preferably ethylene.

The compositions of the invention, such as nail polishes, preferably comprise a pigment, and/or a surfactant. Preferably, the surfactant comprises an octylphenoxypolyethoxyethanol nonionic surfactant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to the discovery that compositions comprising mixtures comprising: at least one component (A) comprising a polyamidoamine- epihalohydrin, and component (B) comprising a component which cooperates with or moderates the properties of component (A) and preferably selected from flexibilizing components, components which inhibit cross-linking, and mixtures thereof, provide an unexpectedly superior spectrum of properties when applied as a coating to various substrates such as keratinous substrates. Compositions of the invention are especially suitable for coating keratinous substrates including fingernails and toenails, as well as artificial nails, and combinations thereof. Without wishing to be bound by theory, it is believed that the polyamidoamine-epihalohydrin functions, at least in part, to adhere to keratinous substrate while component (B) functions, at least in part, moderate component (A) at least in part, such as by acting to hinder cross-linking of component (A). Moreover, also without wishing to be bound by theory, it is believed that the polyamidoamme epihalohydrin resin undergoes reaction with nucleophiles and will react with both the protein components of the finger and/or toenail and unsubstituted amine groups with the backbone of the resin. Thus, by cross linking with both the substrate and itself, the polyamidoamme epihalohydrin will form a flexible film that provides functional properties needed for use as a nail polish. Moreover, this system is compatible with most pigments and other additives to provide a smooth consistent film upon application and curing.

Component (A) can comprise any polyamidoamine-epihalohydrin resin. Preferred materials for component (A) include polyamidoamine-epihalohydrin resins such as those disclosed in U.S. Patents No. 2,926,116 and 2,926,154, to KEIM, incorporated by reference in their entirety herein. Preferred polyamidoamine- epihalohydrin resins can also be prepared in accordance with the teachings of U.S. Patent No. 5,614,597 to BOWER and commonly assigned to Hercules Incorporated, incorporated by reference in their entirety herein. As discussed in U.S. Patent No. 5,614,597 to BOWER, these processes typically involve reacting aqueous polyamidoamme with an excess of epihalohydrin to completely convert amine groups in the polyamidoamine to epihalohydrin adducts. During the reaction halohydrin groups are added at the secondary amine groups of the polyamidoamine as shown in the following example, using epichlorohydrin as the epihalohydrin:

R₂NH + H₂CI

where R₂N- represents a secondary amine group of the polyamidoamine.

After the epihalohydrin has been added and when heat evolution has subsided, the reaction mixture is heated to effect crosslinking and viscosity increase. During this reaction, azetidinium groups are formed. These functional groups are typically employed to impart wet strength to paper by forming a strong crosslinked network with the paper fibers.

Preferred polyamidoamine-epihalohydrin resins include polyamidoamine- epichlorohydrins such as those sold by Hercules Incorporated of Wilmington, Delaware, under various trade names. Preferred polyamidoamine-epihalohydrin resins available from Hercules include the KYMENE® resins and the HERCOBOND® resins. KYMENE 557H® resin; KYMENE 557LX® resin; KYMENE 557SLX^® resin; KYMENE 557ULX® resin; KYMENE 557ULX2® resin; KYMENE 709® resin; KYMENE 736® resin; and HERCOBOND 5100® resin. Of these, KYMENE 557H® resin and HERCOBOND 5100® are especially preferred polyamidoamines, available in the form of aqueous solutions. KYMENE 763® resin (a polyamine) can also be employed as component (A). It is expressly contemplated that equivalents to each of the foregoing resins are within the scope of the present invention.

Component (B) can comprise any component that functions to cooperate with or moderate the properties of component (A). In accordance with one definition herein, materials for component (B) comprise materials that function to flexibilize component (A) after the compositions of the invention are applied as a coating, materials that tend to inhibit crosslinking of component (A), and mixtures of such materials are considered exemplary. Materials for component (B) are not limited to these exemplary definitions, however.

Preferred materials for component (B) include copolymers of alkyl halides and alkenes, such as copolymers of vinyl or allyl halides and alkenes. Any akyl halide and any alkene, which copolymerize to form copolymers with each other, may be employed. Standard textbooks list exemplary materials. See, for example, Organic Chemistry. Morrison & Boyd, Allyn and Bacon, Inc. 1973, which is hereby incorporated by reference as though set forth in full herein for its disclosure of such materials. Preferred alkyl halides include allyl and/or vinyl halides of from 2-12 C atoms, preferably from 2-6 C atoms, more preferably from 2-4 C atoms and most preferably about 2 C atoms. Copolymers of vinyl halides (especially vinyl chloride) and alkenes, preferably of from 2-12 C atoms, preferably from 2-6 C atoms, more preferably from 2-4 C atoms and most preferably of about 2-3 C atoms, especially propylene and/or ethylene, are especially preferred.

Any copolymers of vinyl chloride and ethylene may be employed as component (B). Exemplary copolymers of vinyl chloride and ethylene are disclosed in U.S. Patent No. 4,673,702 to IACOVIELLO, and U.S. Patent No. 4,962,141 to IACOVIELLO, et al., incorporated by reference in their entireties herein. These copolymers (also referred to herein as "EVC1" copolymers) may be prepared in any way. By way of example, they may be prepared (preferably in the form of an emulsion) as described in U.S. Patent No. 4,962,141 to IACOVIELLO et al. by the following procedures.

Suitable EVC1 copolymer emulsions may be prepared by copolymerizing the monomers in the presence of suitable emulsifying agents, i.e., protective colloids and surfactants, in an aqueous medium under pressures generally not exceeding about 100 arm and in the presence of a redox system which is added incrementally. The copolymerization reaction is performed under an ethylene pressure which is sufficient to provide the copolymer with about 5 to 35 wt% ethylene content, preferably about 15 to 25 wt%. Pressures of about 50 to 100 arm are generally used to afford such an ethylene content.

The EVC1 copolymer emulsions may additionally contain from 0.1 to 30 wt% of an external crosslinking agent based upon the total weight of the copolymer. Suitable external crosslinking agents include melamine/formaldehyde resins, polyisocyanates such as water dispersible polymeric methyl diphenyl diisocyanates and water based phenolic resins.

In carrying out the polymerization, substantially all of the polyvinyl alcohol and a portion of the vinyl chloride is initially charged into the polymerization vessel which is then pressurized with ethylene. Most advantageously, at least about 5 wt% and preferably, at least about 15 wt% of the total vinyl chloride to be polymerized is initially charged into the reactor. The remainder of the vinyl chloride is added, desirably at a substantially uniform rate, after the initially charged vinyl chloride monomer content has been substantially reduced as evidenced by a decrease in the rate of polymerization. This controlled addition avoids over pressurization of the reactor. No more than about 60% of the vinyl chloride should be charged initially since a prepolymer must be generated in- situ in order to obtain the desired stable emulsions.

The quantity of ethylene entering the copolymer is influenced by the pressure, the mixing, the addition rate and amount of free radical generating source. The ethylene content of the copolymer can be increased by utilizing a higher ethylene pressure, increasing agitation during mixing or employing a higher free radical source rate.

The process of forming the EVC1 copolymer emulsions may comprise preparing an aqueous solution containing substantially all of a polyvinyl alcohol dispersing agent. This aqueous solution and the initial charge of vinyl chloride may be added to the polymerization vessel and ethylene pressure may then be applied to the desired value. The mixture is mixed thoroughly to dissolve ethylene in the vinyl chloride and into the water phase. The charge can be conveniently elevated to polymerization temperature during this mixing period. A polymerization temperature of about 55° C. and an ethylene pressure in the range of 750 psig to 1000 psig may be employed to provide a copolymer with about 20-30 wt% ethylene. Mixing can be effected by means of an agitator or other known mechanism.

The polymerization is initiated by introducing initial amounts of a free radical generating source into the reactor vessel containing the monomer premix. When employing a redox system, either the oxidant or reductant component can be added initially to the aqueous medium containing the polyvinyl alcohol and vinyl chloride with the other redox component added to initiate the reaction. Upon initiating the polymerization, any desired monomer such as the hydroxyalkyl- or carboxylic acid- containing functional co-monomers disclosed herein may be added incrementally to the reaction vessel.

The reaction may generally be continued until polymerization is no longer self- sustaining and desirably until the residual vinyl chloride content is below 0.5%>. The completed reaction product is removed from the presence of ethylene and maintained at a temperature above the Tg of the copolymer while sealed from the atmosphere. The reaction mixture can also be transferred to a degasser for removal of unreacted ethylene.

It will be readily appreciated by those of ordinary skill in the art that the foregoing is exemplary only, and that the generically and/or specifically defined reactants and conditions can be substituted by equivalent reactants and conditions. Especially preferred copolymers for component (B) include those marketed by Air Products and Chemicals, Inc., of Allentown, Pennsylvania, under the trade name AIRFLEX®; especially, AIRFLEX 4530®. It is expressly contemplated that equivalents to such vinyl chloride/ethylene copolymers are within the scope of the present invention. Thus, for example, any polymer or copolymer which moderates component (A) such as by functioning to flexibilize component (A), and/or any polymer or copolymer that inhibits crosslinking such that when the water from the composition is driven off, and the coating is cured, is flexible and can be bent without delaminating from the substrate and/or cracking, and resists chipping is within the scope of the invention. Preferably any copolymer which functions to flexibilize component (A), and/or any polymer or copolymer that inhibits crosslinking such that when the coating is applied to a substrate, such as a sheet or foil, and the water from the composition is driven off, the coating can be bent is flexible and can be bent, without delaminating from the substrate and/or cracking, and resists chipping, is within the scope of the invention. Preferably, the combination of components (A) and (B) result in compositions exhibiting good memory, in addition to the good flexibility discussed above. For example, such compositions preferably exhibit good memory such that a cured coating when deformed will return to the position or configuration in which it was before it was deformed. It is expressly contemplated that equivalents to such vinyl chloride/ethylene copolymers are within the scope of the present invention, and thus other materials may be employed as component (B).

Without intending to limit the same, other materials for component (B) include FLEXBOND 325® (vinyl acetate-acrylic copolymer latex, available from Air Products and Chemicals, Allentown, PA), LUCIDENE 243® (styrene-acrylic polymer emulsion available from Morton International, Chicago, IL), HYCAR 26256® (acrylic ester copolymer latex available from BF Goodrich, OHIO) and MORKOTE 1725® (acrylic copolymer emulsion available from Morton International, Chicago, IL).

Again without intending to limit the same, other materials for component (B) include water compatible systems such as copolymers that can contain the following monomers: methyl methacrylate, butyl acrylate, styrene vinyhdene chloride, acrylic acid, and methacrylic acid. Suitable copolymers include acrylated urethanes prepared by reacting a hydroxy acrylate or methacrylate; a diol, polyester or diamine; and a diisocyanate can be used. Preferred monomers are disclosed in U.S. Patent 5,716,603, which is hereby incorporated by reference as though set forth in full herein for its teachings in this regard. Other copolymers that appear to be useful include acrylic and vinyl acrylic-based materials.

The coating compositions of the invention are preferably employed in the form of an aqueous admixture, preferably an aqueous emulsion, and conveniently in preferred embodiments, in the form of an aqueous emulsion system resulting from the admixture of an solution of component (A) and an emulsion of component (B), and optionally water and a surfactant.

Thus, compositions of the invention may be prepared by mixing commercially available solutions of component (A) and component (B). Because such products are commercially available, it is expedient and convenient to employ components (A) and (B) "as received" from the suppliers, although this is not required. As illustrative examples, such solutions are available in concentrations of about 12.5% ((conveniently expressed as percent solids)based on weight of resin to total weight of "as received" solution) for component (A), and concentrations of about 50% (based on weight of resin to total weight of "as received"emulsion) for component (B). At concentrations of about 12.5% for a solution of component (A) and about 50% for an emulsion of component (B), solutions of component (A) are employed in the compositions in amounts of from about 5 to about 95%>, preferably from about 50%> to about 85%), more preferably about 75% (based on the total weight of all components of the composition), and emulsions of component (B) are employed in the compositions in amounts of from about 5%> to about 95%>, preferably from about 8%> to about 50%>, more preferably about 11%> (based on the total weight of all components of the composition).

Compositions of about 75%> for component (A) and 11.11% for component (B) have been found to be particularly preferred, with the remaining components of the composition being surfactant (preferably in an amount of about 0.06%>), and water. This may also be expressed such that, the compositions of the invention may have content of solids of component (A) (in terms of active ingredient, j_^g., resin) in a range of from about 1%> to about 85%, preferably about 1.5% to about 82.5%>, most preferably about 63% (based on the total weight of the two resins, i.e., based on the total weight of the resins of component (A) and (B)), and content of resin of component (B) (in terms of active ingredient, L , resin) in a range of from about 15%> to about 99%>, more preferably about 17.4%> to about 98.7%>, most preferably about 38%> (based on the total weight of the two resins, i.e., based on the total weight of the resins of component (A) and (B)).

The amounts of component (A) and component (B) employed in the compositions of the invention may also be expressed in terms of a ratio (A):(B), based on the weight of polymer of component (A) to the weight of the polymer of component (B) (that is (A)/(B), compositions of the invention include those wherein the ratio of (A):(B) is from about 0.05 to about 19, preferably from about 4 to about 12, more preferably from about 6 to about 8, more preferably from about 6.5 to about 7.0, most preferably about 6.75. In preparing compositions of the invention, solutions of component (A) and component (B), water, and, optionally, a surfactant, may be mixed in any suitable mixing vessel, preferably with agitation, such as stirring. A mixing vessel equipped with a stirrer may be employed particularly for this purpose. These components may be added to the mixing vessel in any order of addition, or concurrently. The compositions also preferably comprise a surfactant. Suitable surfactants include non-ionic, anionic and cationic surfactants. TERGITOL®, TRITON GR7M®, TRITON X 100^®, Triethylamine (TEA), AQUAQUEST 2120® (available from GEO Specialty Chemicals, Cedertown, GA) and water are exemplary. A preferred surfactant is TRITON X-100^® (an octylphenoxypolyethoxyethanol nonionic surfactant) available from Union Carbide Chemicals and Plastics Company, Incorporated, Danbury, Connecticut. Surfactants are preferably employed in amounts of up to about 10%, by weight. Preferred ranges for amounts of surfactant are in the range of about 0-5%, by weight; more preferably about 0-1 %>, most preferably, surfactants are employed in amounts of about 0.05-0.25% by weight, based on the total weight of the composition. Preferably, pigments may also be employed to provide color. Suitable pigments include those of the organic type and those of the inorganic type. Prefeπed organic pigments include D and C Red, Nos. 10, 11, 12 and 13, D and C Red No. 7, D and C Red Nos. 5 and 6, D and C Red Nos.30 and 40, D and C Yellow No. 5 and D and C Red No. 2. Inorganic pigments include titanium dioxide, bismuth oxychloride, brown iron oxide and the red iron oxides.

The pigments may preferably be employed in amounts of up to about 5% by weight, preferably from about 0.01% to about 5% by weight, more preferably in amounts of from about 0.5% to about 2 %, by weight.

Other ingredients may be added to accelerate drying. These include glycol esters, such as butyl glycol acetate, and volatile alcohols such as ethanol and 2-propanol.

Drying accellerators may be added in amounts of from of up to about 5%, by weight, more preferably from about 0.01%ι by weight to about 5%> by weight; more preferably from about 0.5%> to about 2.5%> by weight.

Other ingredients such as plasticizers and coalescing agents may also be employed. These include, for example, those disclosed in U.S. patent No. 5,716,603, which patent is hereby incorporated by reference as though set forth in full herein.

Thickeners may also be employed, in amounts in a range of from about 0.01 % to about 5% by weight, for example. Suitable thickeners include cellulose and derivatives, including carboxymethylcellulose and hydroxyethyl cellulose, natural gums such as carrageenan, pectin and xanthan gum, silicates, clays, such as laponite and synthetic polymers such as ethylene oxide, vinyl alcohol, acrylic or polyurethane-type polymers, and the like.

Additionally, other materials such as additives can also be employed.

The unexpectedly superior spectrum of properties provided by the compositions of the invention is more favorable than that which would be expected to be supplied by each component, separately, particularly in view of the fact that the resultant composition exhibits positive aspects of each the components, while certain negative aspects that would be expected by the use of each component, separately, are not exhibited.

Artificial fingernail compositions and methods are disclosed in U.S. Patents 5,738,843 to MONTGOMERY; 5,770,184 to KELLER; 4,104,333; 4,229,431; 4,260,701; 4,626,428; 4,669,491; 4,708,866; 4,718,957; 4,871,534; 2,633,139; 2,746,460; 2,764,166; 2,941,535; 2,979,061; 3,037,514; 3,157,912; 3,277,900; 3,425,426; 3,483,289; 3,487,831; 3,552,401; and, 4,106,614, all of which patents are hereby incorporated by reference as though set forth in full herein.

This application is being filed concurrently (on even date) with U.S. patent application No. [Attorney's docket No. PI 7779] which application is hereby incorporated by reference as though set forth in full herein.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent.

The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. In the following examples, all temperatures are set forth uncorrected in degrees Celsius; unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE Formulations A composition according to the invention was prepared comprising 75%

HERCOBOND 5100®, 11.1% AIRFLEX 4530®, and 13.9% water. This was compared with two commercial nail polishes: Naturistics SuperSHINE (color: Azurite Pearl), from Del Laboratories, Farmington, NY; and Revlon Creme Nail Polish (color: "Wine with Everything"), Revlon Consumer Products Corporation, NY. These formulations were also compared to HERCOBOND 5100®, by itself without other components. Application and General Observations

Each material was applied, using a brush essentially equivalent to that incorporated into a commercial bottle of nail polish, to Vitro-Nails™ substrate, a product of IMS, Inc. of Milford, CT, a product used in the industry as a test substrate for nail material. The formulation according to the invention formed a smooth, level film on the substrate. It provided a thin coating that had a more uniform appearance than the commercial nail polish and which exhibited better "leveling". It also formed a clear film exhibiting higher gloss than the commercial nail polish.

The HERCOBOND 5100® formed a poor film and dried very slowly, contracting as it dried. It did not wet the substrate surface nor adhere as well as the formulation of the invention. Spatula Test

The commercial nail polish films and the film from the formulation of the invention which were dried on the Vitro-Nails™ substrate were pushed with the blunt end of a spatula. The film from the HERCOBOND 5100® did not form a film which was suitable to being subjected to this test. Pushing the spatula into the commercial nail polish resulted in a chip being made in the coating and the substrate was exposed. In comparison, pushing the spatula into the film formed by drying the formula of the invention on the substrate resulted in the separation of the film from the substrate. Unlike the commercial materials, the formulation did not chip. Instead, it appeared to roll out, acting like an intact flexible film that had been debonded from its substrate. This demonstrated that the formulation provides a more elastic, chip resistant film.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims

WHAT IS CLAIMED IS :

1. A coating composition for substrates selected from toenails, fingernails, artificial nails and combinations thereof, the coating composition comprising:

(A) at least one polyamidoamine-epihalohydrin; and

(B) at least one material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on the substrate.

2. The coating composition of claim 1, wherein (B) comprises a flexibilizing material.

3. The coating composition of claim 1, wherein (B) comprises a crosslinking inhibiter.

4. The composition of claim 1, wherein (B) is selected from copolymers of monomers selected from copolymers derived from monomers including at least one of alkyl halides, alkenes, methyl methacrylate, butyl acrylate, styrene vinyhdene chloride, acrylic acid, methacrylic acid, and vinyl acrylic-based materials.

5. The coating composition of claim 4, wherein component (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 5%> to about 95% by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 5% to about 95%) by weight based on the total weight of all components of the composition.

6. The coating composition of claim 5, wherein component (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 50% to about 85%) by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 8% to about 50%> by weight based on the total weight of all components of the composition.

7. The coating composition of claim 6, wherein component (A) comprises an aqueous solution of component (A) present in an amount of about 75%> by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount of 11%> by weight based on the total weight of all components of the composition.

8. A nail polish comprising: (A) at least one polyamidoamine-epihalohydrin; and

9. The nail polish of claim 8, further comprising a pigment.

10. The nail polish of claim 8, wherein the alkyl halide comprises a vinyl halide.

11. The nail polish of claim 8, wherein the alkyl halide comprises a vinyl halide and the alkene comprises an olefin.

12. The nail polish of claim 11, wherein the alkyl halide comprises a vinyl halide and the alkene comprises ethylene.

13. The nail polish of claim 11, wherein the vinyl halide comprises vinyl chloride.

14. The nail polish of claim 12, wherein the alkyl halide comprises a vinyl chloride and the alkene comprises ethylene.

15. The nail polish of claim 14, further comprising a surfactant.

16. The nail polish of claim 15, wherein the surfactant comprises an octylphenoxypolyethoxyethanol nonionic surfactant.

17. The nail polish of claim 8, wherein component (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 5%> to about 95%o by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 5%> to about 95%> by weight based on the total weight of all components of the composition.

18. The nail polish of claim 17, wherein component (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 50%> to about 85% by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 8%» to about 50%> by weight based on the total weight of all components of the composition.

19. The nail polish of claim 18, wherein component (A) comprises an aqueous solution of component (A) present in an amount of about 75%₀ by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount of 11%> by weight based on the total weight of all components of the composition.

20. A substrate comprising a member selected from a fingernail, a toenail, an artificial nail or combinations thereof, coated with the nail polish of claim 9.

21. The coated substrate of claim 20, wherein the substrate comprises a finger nail.

22. The coated substrate of claim 20, wherein the substrate comprises a toenail.

23. The coated substrate of claim 20, wherein the substrate comprises an artificial nail.

24. In combination, a substrate selected from finger nails, toenails, artificial nails and combinations thereof, and a composition comprising at least one polyamidoamine- epihalohydrin.

25. The combination of claim 24, comprising at least one additional material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on the substrate.

26. The coating composition of claim 25, wherein the at least one additional material comprises a flexibilizing material.

27. The coating composition of claim 25, wherein the at least one additional material comprises a crosslinking inhibiter.

28. The composition of claim 25, wherein the at least one additional material is selected from copolymers of monomers selected from copolymers derived from monomers including at least one of alkyl halides, alkenes, methyl methacrylate, butyl acrylate, styrene vinyhdene chloride, acrylic acid, methacrylic acid, and vinyl acrylic- based materials.

29. A method of coating a substrate selected from finger nails, toenails, artificial nails and combinations thereof, comprising: coating the substrate with a coating composition comprising: at least one polyamidoamine-epihalohydrin.

30. The method of claim 29, wherein the coating composition comprises: (A) at least one polyamidoamine-epihalohydrin; and (B) at least one material selected from flexibilizing materials, crosslinking inhibiters and mixtures thereof in an amount sufficient to impart flexibility and chip resistance to a cured coating made from such a composition on a keratinous substrate.

31. The method of claim 30, wherein (B) comprises a flexibilizing material.

32. The method of claim 30, wherein (B) comprises a crosslinking inhibiter.

33. The method of claim 30, wherein (B) is selected from copolymers of derived from monomers including at least one of alkyl halides, alkenes, methyl methacrylate, butyl acrylate, styrene vinyhdene chloride, acrylic acid, methacrylic acid, and vinyl acrylic- based materials.

34. The method of claim 33, wherein (B) comprises at least one polymer comprising repeating units derived from an alkyl halide having at least one double bond and an alkene.

35. The method of claim 34, wherein the alkyl halide comprises a vinyl halide.

36. The method of claim 34, wherein the alkyl halide comprises a vinyl halide and the alkene comprises an olefin.

37. The method of claim 36, wherein the alkyl halide comprises a vinyl halide and the alkene comprises ethylene.

38. The method of claim 37, wherein the vinyl halide comprises vinyl chloride.

39. The method of claim 30, wherein component (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 5%> to about 95%> by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 5% to about 95%> by weight based on the total weight of all components of the composition.

40. The method of claim 39, wherein component (A) comprises an aqueous solution of component (A) present in an amount in a range of from about 50%> to about 85% by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount in a range of from about 8%> to about 50% by weight based on the total weight of all components of the composition.

41. The method of claim 40, wherein component (A) comprises an aqueous solution of component (A) present in an amount of about 75% by weight based on the total weight of all components of the composition, and component (B) comprises an aqueous emulsion of component (B) present in an amount of 11%> by weight based on the total weight of all components of the composition.

42. The method of claim 30, wherein the substrate comprises a finger nail.

43. The method of claim 30, wherein the substrate comprises a toenail.

44. The method of claim 30, wherein the substrate comprises an artificial nail.

45. The composition of claim 1, wherein wherein the weight ratio of (A):(B) is from about 0.05 to about 19.

46. The composition of claim 1, wherein the weight ratio of (A):(B) is from about 4 to about 12.

47. The composition of claim 1 , wherein the weight ratio of (A):(B) is from about 6 to about 8.

48. The composition of claim 1, wherein the weight ratio of (A):(B) is from about 6.5 to about 7.0

49. The composition of claim 1, wherein the weight ratio of (A):(B) is about 6.75.

50. The nail polish of claim 8, wherein wherein the weight ratio of (A):(B) is from about 0.05 to about 19.

51. The nail polish of claim 8, wherein the weight ratio of (A):(B) is from about 4 to about 12.

52. The nail polish of claim 8, wherein the weight ratio of (A):(B) is from about 6 to about 8.

53. The nail polish of claim 8, wherein the weight ratio of (A):(B) is from about 6.5 to about 7.0

54. The nail polish of claim 8, wherein the weight ratio of (A):(B) is about 6.75.

55. The method of claim 29, wherein the weight ratio of (A):(B) is from about 0.05 to about 19.

56. The method of claim 29, wherein the weight ratio of (A):(B) is from about 4 to about 12.

57. The method of claim 29, wherein the weight ratio of (A):(B) is from about 6 to about 8.

58. The method of claim 29, wherein the weight ratio of (A):(B) is from about 6.5 to about 7.0

59. The method of claim 29, wherein the weight ratio of (A):(B) is about 6.75.