CA1101336A - Ester of alkylvinylether/maleic anhydride copolymer in plasticized nail enamel - Google Patents
Ester of alkylvinylether/maleic anhydride copolymer in plasticized nail enamelInfo
- Publication number
- CA1101336A CA1101336A CA307,137A CA307137A CA1101336A CA 1101336 A CA1101336 A CA 1101336A CA 307137 A CA307137 A CA 307137A CA 1101336 A CA1101336 A CA 1101336A
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- Prior art keywords
- nail enamel
- nail
- film
- solvent
- composition
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
Abstract
NAIL ENAMEL COMPOSITIONS, METHODS AND PROCESSES ABSTRACT OF DISCLOSURE Novel nail enamel compositions comprising alkylvinyl-ether/maleic ester copolymers, hydroxy fatty acid oil, alkyl phthalate and/or abietyl alcohol plasticizers, and solvent axe provided as well as method for their preparation and process for their use.
Description
. .
The present inventlon relates to certain alkylvinyl-ether/maleic ester copolymer-based nail coating compositions, their concentrates, a method for their preparation, and processes for their use.
Nail-coating compositions (hereafter called "nail enamels'l) are applied on keratinous nails, e.g., fingernails and toenails (hooves are also included and hereafter finger-nails, toenails and hooves will collectively be referred to -as "nails"), to coat nails with a film, primarily for cosmetic purposes and in addition, the film provides prot~ction against chipping and breaking of the nails. The character of, and requirements for, nail enamels which provide such films are multifaceted and complex.
Nail enamels preferably should possess certain rheological characteristics, e.g., thixotropic behaviour, for ease of application (heavy-bodied but spreading easily and not running at the edges~, particularly since a brush is generally used to apply the composition; be non-allergenic; have an acceptable odor; not "body~up" in the bottle; be compatible with color imparting ingredients such as soluble dyes, insoluble pigments, or both; deposit a smooth film which will (a) dry quickly at ambient temperatures, (b) be flexible to withstand the flexin~ of the nails; (c) strongly adhere to the surface of the nail; (d) not shrink; (e~ be long-wearing; (f) be durable from the standpoint of abrasion resistance (due to mechanical wear) and freedom from cracking, chipping and peeling tendencies; (g? not discolor; (h) be tack-free;
;~ (i) be stable with respect to dye-tinting and pigmentation;
(j) be glossy; (k) not deleteriously affect "breathing" of the nalls; and (1) be removable with ease without adverse physiological effect to the nail or surrounding tissues.
The present inventlon relates to certain alkylvinyl-ether/maleic ester copolymer-based nail coating compositions, their concentrates, a method for their preparation, and processes for their use.
Nail-coating compositions (hereafter called "nail enamels'l) are applied on keratinous nails, e.g., fingernails and toenails (hooves are also included and hereafter finger-nails, toenails and hooves will collectively be referred to -as "nails"), to coat nails with a film, primarily for cosmetic purposes and in addition, the film provides prot~ction against chipping and breaking of the nails. The character of, and requirements for, nail enamels which provide such films are multifaceted and complex.
Nail enamels preferably should possess certain rheological characteristics, e.g., thixotropic behaviour, for ease of application (heavy-bodied but spreading easily and not running at the edges~, particularly since a brush is generally used to apply the composition; be non-allergenic; have an acceptable odor; not "body~up" in the bottle; be compatible with color imparting ingredients such as soluble dyes, insoluble pigments, or both; deposit a smooth film which will (a) dry quickly at ambient temperatures, (b) be flexible to withstand the flexin~ of the nails; (c) strongly adhere to the surface of the nail; (d) not shrink; (e~ be long-wearing; (f) be durable from the standpoint of abrasion resistance (due to mechanical wear) and freedom from cracking, chipping and peeling tendencies; (g? not discolor; (h) be tack-free;
;~ (i) be stable with respect to dye-tinting and pigmentation;
(j) be glossy; (k) not deleteriously affect "breathing" of the nalls; and (1) be removable with ease without adverse physiological effect to the nail or surrounding tissues.
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Moreover, the e.f fect of components employed in such compo-sitions is empirical. For instance, an alteration in a nail enamel formulation to overcome one problem (e.g., obtain quick-drying) may result in other problems (sacriflce of smoothness, flexibility and adhesion characteristics).
Nail enamels are composed of several basic ingredients, viz, (1) a film-former, ~2) a plasticizer, and (3) a solvent system, with or without (4) a colorant. The most common film-former is ni-trocellulose (cellulose nitrate), modified with a suitable resin, e.g., formaldehyde resin, or other additive to provide sufficient hardness, resistance to chipping, ~' and to improve adhesion and gloss. The solvent system employed as the volatile portion of the enamel generally includes (a) one or more active solvents, (b~ couplers or latent solvents and (c) diluents. Typical active solvents for nitrocellulose include, for example, ethyl acetate and n-butyl acetate; i~
typical latent solvents include, for example, alcohols such as ethanol and butanol; and typical diluents include, for example, toluene and xylene.
Nitrocellulose is a fire and explosive hazard. Many localities have ordinances which forbid manipulation of it within their jurisdictions. The use of solvents with it to formulate nail enamels increases the fire and explosive hazard.
Thus nitrocellulose can only be formulated into nail enamels under very restrictive conditions and then only in plants adapted for that puxpose. Most cosmetic plants are not ad~pted to handle nitrocellulose as such. As a result, a number of specialists exlst in the chain of manufacture. One such specialist manufactures nitrocellulose chips. These chips are generally composed of nitrocellulose~ a pigment and a plasticizer. They serve as the source of color in the final _ nall enamel. Another specialist, using these chips, manufac-tures the nail enamel bulk in many shades. Cosmetic makers purchase this nail enamel bulk and then bottle, package and distribute. Considering the inherent lack of stability of nitrocellulose nail enamel, the cosmetic makers are confronted with scheduling and inventory contro:l problems ~urther com~
plicated by the many shades oE nail enamel involved. Fre-quently, complaints arise in the field.
The incorporation of colorants in nitrocellulose-based nail enamels also presents major problems. These multifaceted problems are described, for example, ln "~laking and Coloring Nail Varnishes Made From Chips", Grizzo, Cosmetics and Toiletries, Vol. 92, pp. ~3-65, April 1977. Pigments, although they must meet many criteria, are generally used with nitrocellulose.
The complex "solution and dilution" procedure involved ~ `
in the formulation of nail enamels from nitrocellulose chips is described on page 65 of the Grizzo article. This procedure is not only cumbersome and time-consuming but it also fails `
to provide uniformity in the composition of nail enamels.
The necessity of making the chips in the first instance for later solution and dilution into nail enamels is expensive.
The nitrocellulose in nail enamels normally deteriorates (chemical breakdown) on aging and results in enamels which discolor and which exhiblt loss of the characteristic of drying to a hard film and loss of viscosity. These enamels are often characterized as having sharp, unpleasant odors ~-which are disagreeable to the user. Moreover, the removal of the film deposited by these nail enamels on the nail has required the use of acetone or ethyl acetate, both of which ~,,1, are odoriferous, volatile liquids and are generally considered to be moderately toxic by inhalation and skin absorption.
Accordingly, alternatives to these conventional nitro-cellulose-based nail enamels have been sought. However, ; -~
despite the long recognized shortcomings of these enamels, ~;
no previous alternative composition has as yet been commer-cially acceptable so as to supplant them as the primary type of nail enamel on the market. This is due to the demanding requirements, described supra, placed on the performance of 10 nail enamels. There are certain minimum criteria which can delineate "nail enamel characteristics," i.e., the nail enamel when applied to the nail should dry sufficiently in about one minute or so to permit an additional coating; form a liquid coating on the nail which solidifies without flowing;
appear as a nail enamel in about thirty seconds to one minute with glossiness flow, level and deposit a uniform smooth, non-lumpy coating which hardens within about five minutes; and provide a coating exhibiting nail enamel~
lasting quality for at least about two days.
An object of the present invention is to provide a nail enamel which obviates the use of nitrocellulose as a film-former; employs a simple solvent system; uses ingre-dients which are safe and easy to use; is stable with respect ;~
to color, viscosity and film-forming characteristics; does not exhibit an offensive odor; provides an effective coating of film on nails; is easily removed from nails; and can be ~ manufactured with facility, even in concentrates which can ; be later diluted with facility, to provide uniform but `' ~' ' ' .
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versatile compositions exhibiting na11 enamel characteristics.
Another object is the provision of such enamel which deposits a film which is clear when color-imparting ingredients are absent; can incorporate color-imparting ingredients with facility; is durable; will "breathe"; will hold its integrity (not crack or chip); is flexible and relatively soft but tack-free, tough and very adhesive; and employs a simple, physiologi-cally acceptable (problem-free) solvent system.
The nail enamel and nail enamel concentrate compositions of the present invention essentially include a particular alkylvinylether/maleic anhydride ester~based resin film-former;
and a plasticizer which can be either a hydroxy fatty acid oil, an alkyl phthalate, an abietyl alcohol or mixtures of these plasticizers; and solvent. Such compositions can optionally include modified resins, supplemental plasticizers, colorants and other conventional cosmetic product adjuvants. The basis components, except the solvent system, in the compositions herein are non-volatile materials. Such non~volatile materials are referred to herein as "solids".
The essential film-forming material of the compositions of the invention comprlses an alcohol miscible, linear half ester of an aliphatic, e.gO, alkyl, vinyl ether-maleic anhydride copolymer. The ester moiety may be alkyl of, e.g., 1 to about 10 or more, preferably lower alkyl of about 2 to 6j carbon atoms, e.g., ethyl, isopropyl, butyl, amyl and hexyl. The alkyl viny-lether may be a lower alkyl vinylether, e.g., in which the alkyl group contains 1 to about 4 carbon atoms, and preferably is methyl vinylether. Generally, the molecular weight of the copolymer is at least about 200, e.g., within the range of about 200 to 500,000 e.g., 51 to 500,000 or about 10,000 to 100,000, and preferably from about 300 to 100,000.
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Preferred copolymers for use herein are the water insoluble, normally liquid, monoesters of methyl vinyl-ether-maleic anhydride copolymers which are available from the GAF Corporation under the tradename GANTREZ ES monoester ~ ~-resins. Monoester resins of this type have been characterized as having the general structural formula:
fCH
- CEI2 CH fH- - fH - - ;~
o= f ~=o OH R n ~
. `' '' wherein R is the ester moiety of 1 to about 10 (preferably 2 to 6) carbon atoms and n is selected to provide resins having molecular weights within the range of from about 300 to 70,000. Such preferred copolymers often have an acid number (100% solids) of about 245 to 300. Generally, such ; monoester resins are available in a viscous alcoholic, e.g., ethanol or isopropanol, solutions of about 50 percent by weight solids, are water-resistant (e.g., essentially non-neutralized), and have a specific gravity within the range of about 0.95 to 0.99. Examples of such preferred monoester resins include the butyl monoester of a me~hylvinylether/maleic anhydride copolymer having a weight average. molecular weight (Mw) of about 7850 and a number average molecular weight (Mn) of about 3150; the ethyl monoester of a methylvinyl ether/maleic anhydride copolymer having an MW of about 4075 and an Mn of about 1785; and the isopropyl monoester of a methylvinylether/ ~-.
~ 7 ~ ~
3~i maleic anhydride copolymer having an ~w of about 11200 and an Mn of about 4050. (Such molecular weight determinations are made by gel permeation chromatography.) Combinations of the monoester resins can be employed as the essential film-former.
In addition to the above described essential film-forming resins, the nail enamel compositions of the present invention can optionally include modifier resins. Modifier-resins can be incorporated to modify the characteristics of the essential film-former employed, for instance, to modify hardness, resistance to chipping, adhesive charac-teristics, viscosity and the like. Such resin-modifiers include synthetic resins such as arylsulfonamide-formaldehyde resins (e.g., Santolite MS-80go or Santolite MHP, products of Monsanto); alcohol-soluble, hydrolyzed protein (e.g., Crotein ASC or Crotein AD-X, products of Croda); hydroxy-propyl cellulose (e.g., Klucel, a product of Hercules); ~ `
ethyl cellulose (e.g., Ethocel, a product of Dow Chemical);
amino-functional silicones (eOg., DC531 and DC536, products . ~ .
of Dow Corning) and polyamide resin (e.g., Versamid 940, a product of General Mills). The resin modifiers are employed in resin modifying amounts, generally from about 20 to 90, preferably 30 to 70, weight percent based upon the essential resin film-former (solids basis~.
A second essential component of the nail enamel and nail enamel concentrate compositions herein is a plasticizer selected from the group consisting of alcohol-soluble, hydroxy fatty acid oils, alkyl phthalates wherein each alkyl group contains from 1 to about 15 carbon atoms, abietyl ~lcohol and mixtures of such plasticizers.
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The alcohol-soluble fatty oil (e.g., hydroxy fatty acid oil~ which can serve as the essential plasticizer in the com-positions herein is a triglyceride of a hydroxy-substituted fatty, i.e. C12 22' acid. Such an oil is normally liquid at ambient temperatures and is a non-drying, non-volatile triglyceride.
The preferred hydroxy fatty acid oil is castor oil, the chief constituent of which is the triglyceride of ricinoleic (12-hydroxy-9-octadecanoic) acid. Castor oil, in addition to performing a plasticizing function, also acts as an emollient and imparts gloss to the film-coatings formed on the nail substrate by the nail enamel compositions of the present invention. Castor oil can also serve as a suspending medium ~or pigments which can optionally be introduced into the present compositions and in this connection can also serve as a medium for pigment grinding and dispersion. Furthermore, castor oil enhances the solubility of o-ther plasticizers such as alkyl phthalates or abietyl alcohols in the nail enamel systems of the present invention.
Alkyl phthalates can also serve as the essential -plasticizer in the nail enamels o~ the present invention.
The alkyl phthalate employed can include, e.g., alkyl aryl ;
; phthalates (e.g., butyl benzyl phthalate), dialkyl phthalates for instance, wherein each alkyl group contains from 1 to about 15 carbon atoms including the dimethyl, diethyl, dlbutyl and dioctyl phthalates. The di-lower alkyl phthalates are preferred. Dibutyl phthalate and butyl benzyl phthalate (e.~., Santicizer~160, a product of Mon-santo) are especially preferred plasticizers.
Abietyl alcohols can also serve as the essential plas-ticizer in the compositions herein. Abietyl alcohols are derivatives of abietic acid which has the empirical formula _g_ 3~
C19H29COOH. Such a material ineludes a phenanthrene ring system in its structure and is derived from rosin. Abietyl alcohols are commercially available under -the tradename Abitol from Hercules. Abitol~is a mixture of tetra-, di-and dehydro abietyl alcohols.
Mixtures of hydroxy fatty acid oils,alkyl phthalates and abietyl alcohols can also serve as the essential plasticizer in the nail enamels herein and, in fact, such mixtures con-stitute the preferred essential plasticizer component.
Mixtures of castor oil and butyl benzyl phthalate are especially preferred. The essential plasticizers employed herein must, of course, be present in plasticizing amounts.
In addition to the essential hydroxy fatty acid oil, alkyl phthalate, abietyl alcohol or mixed essential plas-ticizers, the nail enamel and nail enamel concentrate com-positions herein can optionally include a variety of supplemental plastieizers which must, of course, be compatible with the film-forming resin. Optional supplemental plasticizers include non-volatile organic liquids and low- ;
melting (melting point below 1~0C) organic solids such as polyols (e.g., polyethylene glycol and its derivatives);
polysiloxanes (alcohol-soluble, silicone oils, e.g., alkyl aryl polysiloxanes, e.g., methyl phenyl polysiloxane, also known as phenyl dimethicone); saturated and unsaturated mono- and dicarboxylic aeids, esters and fatty alcohols having at least about 10, perferably about 12 to 24, carbon atoms (e.g., stearic acid, oleic acid, lauric acid, ricinoleic acid, linoleic acid, vegetable oils such as almond, corn, cottonseed and olive oils, Citroflex A2, cetyl alcohol, myristyl alcohol and the like); and 3~ ~
lanolin and lanolin derivatives (e.g., acetylated, ethoxylated compounds). Citroflex A2 is acetyl triethyl citrate and is a product of Chas. Pfizer & co.
Silicone oils are the pre~erred supplemental plasticizer in that they improve the brushing characteristics (flow and leveling~ of the nail enamel and enhance the glossiness o~ the film deposited on the nail. Combinations of supplemental plasticizers can also be advantageously employed.
The third essential component of the nail enamel and na enamel concentrate compositions herein is a solvent. The solvent system employed is one that is physiologically acceptable and nail enamel compatible (e.g., is solvent for the resin film formers, and essential and supplemental plastici~ers while not ; deleteriously affecting the purpose and characteristics of nail enamels)~ It can advantageous]y be a simple solvent, expediently a lower alkanol, e.g., ethanol, and/or isopropanol. Combinations of solvents can also be used. Solvent can be provlded in part - by the solution in which commercial resin film-former is provided.
Other operable solvents include ethyl acetate, butyl acetate, toluene, xylene and acetone.
The nail enamel compositions of the present invention exhibit nail enamel characteristics which include a brushing viscosity, e.g., a heavy-bodied brushing viscosity which picks up a substantial amount of the nail enamel without dripping and yet flows freely when applied to provide a smooth coating on the nails. Viscosity of the nail enamel compositions of the present invention generally ranges from about 20 centipoises (cps.) to ~ 1500 centipoises (cps.) or more, advantageously from about 50 cps.
-~ to 1400 cps., and preferably from about 200 cps. to 500 cps.
Such viscosity values are established at 70-72F using a Model ~VT Brookfield Viscosimeter. (No. 2 spindle at 10 rpm) `'t~
.
The nail enamel characteristics exhibited by the com-positions herein also include a solids content, provided by the resin film-former (which includes the total of essential resin film-former present and, also when present, modifier~
resin) and the essential and supplemental plasticizer(s).
Such a solids content should be sufficient to impart nail enamel constitution but insuf~icient to prevent brush-application of the enamel on nails. These solid, i.e., non-volatile, contents will generally be in the range of about 10 to 45, preferably from about 12 to 35 or 40, weight percent based upon the total of the resin film-former(s), plasticizer(s) and solvent(s) present. The solids content is basically provided by the resin film-former(s) and the balance by plasticizer(s) which are incorporated in nail enamel-plasticizing amounts, e.gO, to enhance flexibility or durability of the film deposited by the nail enamel. The part of the solids content provided by film-former i5 generally from about 40 to 96, preferably from about 60 to 95, and that provided by the plasticizer(s) is generally from about 1 to 40, preferably from 2 to 35, weight percent based upon the solids content provided by resin film-former(s), and plasticizer(s) on a solven-t-free (dry) basis. The weight - ratio of resin film-formers (solvent-free basis) to total plasticiæer is preferably about 2:1. When a hydroxy fatty acid oil îs present in combination with another essential plasticizer, the hydroxy fatty acid oil generally constitutes from about 0.1 to 25, preferably from about 1 to 20, weight percent of the solids content of the nail enamel. The balance of the nail enamel constitutes the other optional ~;~
non-volatile materials and the solvent(s).
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' ' ' ~ ' ,36 The solvent(s) is employed in nail enamel-solvent amounts, e.g., amounts sufficient to solubilize resin film-former(s), essential and supplemental plasticizer(s), and other ingredients present while not deleteriously a~fecting the viscosi-ty of the nail enamel. These amounts generally - range from about 55 to 90, usually from about 65 to 8~
weigh-t percent, based upon resin film former(s), essential and supplemental plasticizer(s) and solvent.
~` The nail enamels of this invention may also contain conventional ad~uvants such as diluents (hydrocarbons, e.g., toluene and xylene); colorants including dyes and pigments including iron oxides, organic and nacreous pigments; fillers;
stabilizers; thickeners; leveling agents; conditioners;
perfumes; antiseptics; bacteriostats and the like. These adjuvants, when employed, are provided in minor amounts sufficient to impart the intended qualities to, but not adverse to, the desired properties of the nail enamels~
The colorant is generally employed in amounts of about 0.01 to 5, usually about 0.5 to 2, weight percent based upon the nail enamel composition. One of the advantages provided by the present invention resides in the provision of nail : ~ i enamels which can utilize either dyes or pigment colorants.
Suitable colorants include pigments such as, for example, iron oxide, xanthene red organic, titanium dioxide, and ferric ;~ ferrocyanide in a blue nacreous pigment; and alcohol-soluble - dyes such as, for example, triphenylmethane blue dye, xanthene -red dye, and ~luoran yellow dye.
In a particular advantageous aspect of the present in-~ vention, nail enamel concentrates can be formed which can be -~ 30 later diluted with facility by formulators to provide the ultimate nail enamel ~or use by consumers. The concentrates ~-.
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advantageously contain the plasticizer(s), all or partial amounts of the film-forming resinls) and partial amounts of solvent. This is particularly significant when pigment colorants are desired in the nail enamels since the pigments can be pre-dispersed in the hydroxy fatty acid oil. ~he employment of the relatively simple solvent system in the nail enamels of this invention enables the preparation of concentratesr e.g. r as low as about 8 or 10 percent, e.g., from about 10 to 45 percent concentrate, which are uniform, clear and viscous concentrate solutions. Such numerical "percent concentrate" values refer to ~he percentage of the complete nail enamel composition which the concentrate components comprise. The nail enamel concentrates generally contain partial amounts of solvent which comprise from - about 15 to 50 weight percent of the conc~ntrate, and when containing partial amounts of resin film-former, generally the film-former is present in the concentrate in amounts from about 15 to 50 weight percent, based on the concentrate.
The nail enamels of the present invention are advan-tageously prepared by a method which comprises mixing, under ambient conditions, the essential and supplemental plasticizers with resin film-former to provide a homogenous mixture, and diluting the mixture with mixture-dissolving amounts of alcohol solvent to provide a nail enamel. When colorants are incorporated into the enamel, pigment-colorants are advantageously pre-dispersed in the hydroxy fatty acid oil, (if present in sufficient amounts, otherwise in hydroxy fatty acid oil and other essential or supplemental plasti-~izer) and dyes are advantageously pre-dissolved in the alcohol solvent before, respectively, the pigment dispersion and alcohol are contacted with resin film-former. The pigments are advantageously dispersed in the hydroxy fatty acid oil, e.g., castor oil, which is stable and not volatile 3~ `
under roller mill conditions, using a roller mill, usually water-cooled, at pressures up to about 4,000 p.s.i. to obtain a substantially uniform dispersion. `
The concentrates can be prepared by combining partial amounts of one or more of the components, preferably the solvent or resin film-former which are to form the ultimate ~-nail enamel, with the essential and supplemental plastici-zers. For instance, amounts of solvent or resin and solvent can be advantageously withheld for later dilution. The pigments can be ground in 25~ and higher concentrations in the hydroxy fatty acid oil, e.g., castor oil, or other plasticizer to provide a dispersion and the resulting dispersion can be used in making concentrates containing resin film-former and plasticizer with dispersed pigment which on further dilution, for instance with solvent, or solvent and resin, results in the final nail enamel.
The process of using the nail enamels to cosmetically improve nails comprises applying nail enamel to a nail substrate in nail-coating amounts to coat the nail, and ; 20 drying applied nail enamel to form a film-coating on the ;~
nail. The enamel is conveniently applied, e.g., by brushing it, on the portion of the nail intended to be coated. The coating dries rapidly on the substrate to form an adherent, tough, glossy film which is water-resistant. When desired, the coating is easily removed by applying an alcoholic or alkaline solution to soften the coating and the softened ~; coating can be conveniently wiped off.
- The invention is further illustrated by the following - illustrative examples, which are not in limitation of the invention. All parts and percentages are by weight unless otherwise indicated.
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Example I
The following nail enamel is prepared by mixing the ~:
castor oil and resin film-Eormer and dissolving the mixture with the solvent to produce a uniform, viscous solution having a brushing viscosity (92 cps.) and a total solids content of 23 weight percent:
Component Percent *GANTREZ ~S-425 (resin film-former) 40 Castor Oil (hydroxy fatty acid oil plasticizer) 3 **Alcohol SD 40 (solvent) 57 100%
*GANTREZ ES-425 is a 50 percent ethanol solution of the monobutylester of methyl vinylether-maleic anhydride copolymer available from GAF Corporation.
**A 95 percent ethyl alcohol solution.
On application to the fingernail, a smooth glossy coat ~ was obtained. On the first application, the enamel dried l; sufficiently in about a minute to permit a second application.
On the secona application, the enamel showed very little tack in two minutes and was tack-free in three minutes. The ~; enamel lasted over two days and retained good gloss.
Example II
The following horse hoof enamel is prepared by grinding the iron oxide pigment together with the castor oil in a mortar and the mix is added to a solution composed of the resin film-former and solvent~
Component Percent GANTREZ ES-425 Resin 50 Castor Oil 3 Alcohol SD40 45 ;
Iron Oxide Pigment (black)2 100%
~:
The enamal is applied to a hoof or nail to provide a good film with excellent sheen and color coverage. The pigment which separates on standing is readily redispersed by shaking prior to use.
- Example III
The following horse hoof enamel is prepared:
Component Percent GANTR~Z ES-425 Resin 30 Castor Oil 1 Ethyl Alcohol SD40 67.95 *FD&C Blue #1 0.15 **FD&C Red ~3 0.30 ***D&C Yellow y7 0.60 100. 00%
*An alcohol-soluble tripenylmethane blue dye (Chem.
Abstracts Service Number ("CAS"): 2650-18-2)~
**An alcohol-soluble xanthene red dye (CAS: 563-63-8). `
***An alcohol-soluble fluoran yellow dye (CAS: 518-45-6).
A good black film with blue violet overtones and good gloss was obtained. It is best with two applicationsD ;~
; The colors were added to the alcohol und~r ambient conditions and dissolved by stirring. The solution may be warmed to 40C to facilitate solution. The solution was then filtered and added to a mix of the GANTREZ ES-425 and the castor oil. The mix was stirred until the solution was uniform.
Example IV
.
The procedure of Example I is essentially followed to prepare the following nail enamel:
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Component Percent , GANTREZ ES Resin 36.0 *Castor Oil 1.6 *D&C Red #19 Aluminum Lake Mix 0.4 **Klucel M 0.6 **Ethanol 30 9 Toluene 30 5 ;
100~0%
*An organic xanthene red pigment (RD No. 977054~33-3) (Kohnstamm K-7040), the colorant was ground in castor -~
oil at a 25 percent concentration.
**Solubilized in ethanol to provide a two percent solution.
:
` The castor oil-pigment mix was added to the Gantrez and ~`
mixed thoroughly. The Klucel-alcohol solution was mixed in -thoroughly and then toluene was stirred in. A good film ~ ~
was produced. The color--a pretty pink, was somewhat trans- ~ ~;
parent on one application~ The enamel had a good brushing ~iscosity (1360 cps.).
.; :
This example shows that toluene is compatible in the nail enamel and can be used to modify (cut) the viscosity of the enamel. Klucel can be used to increase the viscosity of the enamel without significantly increasing the solids content, the increase in viscosity being desired to stabilize the dispersion of pigment in the enamel.
Example V
~ The procedure of Example I is essentially followed ; to prepare the following nail enamel: -Component Percent Gantrez ES-425 ~esin 30.0 Castor Oil 1.0 ; Alcohol SD40 65.0 Diethyl Phthalate 4.0 100. 0%
3~6i This exemplifies a combination of castor oil as the hydroxy fatty acid oil plasticizer, and diethyl phthalate as a supplemental plasticizer. Such a composition has a viscosity of about 60 cps.
Example VI
The procedure of Example I is essentlally followed, except the Silicone 556 and dimethyl phthalate are adde~
in turn after the castor oil, to prepare the following nail enamel:
Component Percent Gantrez ES-425 Resin 36 Castor Oil *Silicone 556 2 - Dimethyl Phthalate 2 ~ Alcohol SD40 59 :. ~ 100~
*Silicone 556 is an alcohol-soluble, methylphenyl polysiloxane, a product of Dow Corning (It has also been designated phenyl dimethicone CTFA). It has a viscosity at 25C of 22.5 centistokes.
, ..
The enamel, when applied to a fingernail, provided ; a very glossy finish. The silicone, in addition to plasticizing, also enhances the brushing characteristics (flow and leveling) of the nail enamel. The nail enamel composition has a viscosity of about 72 cps.
Example VII
The procedure of Example VI is essentially followed to prepare the following nail enamel:
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:` :
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Component Percent Gantrez ES-425 Resin 36.0 Castor Oil 2.0 *Santolite MS-80% Resin 12.0 Alcohol SD40 46.0 Sil7cone 556 2.0 Diethyl Phthalate 2 0 100. 0% ,"
*Santolite MS~80% is an 80 percent sulfonamide-formaldehyde resin in butyl acetate solution, a product of Monsanto Industrial Chemicals.
~;
Good clear films were deposited upon application of this enamel to nails.
A white taffy-like mix resulted when the Gantrez and Santolite were combined. The final addition of the alcohol resulted in a clear bright solution.
A coat of the enamel on fingernails lasted almost five days. ~;
Examples VIII to X
These examples, A Group Examples, show concentrate preparations in the 38 to 44 weight percent range, e.g., 41 to 43 percent, which are diluted with ethanol to produce the corresponding final nail enamels set forth in B Group Examples:
A Group Componen-t Parts ~IIIA IXA XA
Gantrez ES-425 Resin 36.0 36.0 36.0 ` *Castor Oil 1.0 2.0 1.75 Silicone 556 2.0 2.0 2.0 Diethyl Phthalate 2.0 2.0 2.0 **4500 Chromalite Light Blue - 1.0 - ;
*D&C Red #19 (Kohnstamm K-7040) - - 0.25 ~ a336 *In Example XA, two parts of a 25% color mix of D&C
Red ~19 ground in castor oil was used.
**A blue nacreous pearlescent pigment using fQrric ferrocyanide, a product of Mallinckrodt, Inc.
` Concentrate VIIIA on dilution to 100 parts by the addition of Alcohol SD 40 formed a clear polish, the composition of which is set forth below in B Group~
Concentrates IXA and XA formed colored nail polishes on dilution to 100 parts using Alcohol SD40 and stirring, and the compositions of these are also set forth in B Group below.
B Group ;~ Component Parts VIIIB IXB XB
Gan-trez ES-425 Resin 36.0 36.0 36.0 ~ ,: . :.
*Castor Oil 1.0 2.0 1.75 ; Silicone 556 2.0 2.0 2.0 Diethyl Phthalate 2.0 2.0 2.0 4500 Chromalite Light Blue - 1.0 *D&C Red #19 (Kohnstamm K-7040) - - 0.25 .. .
-Alcohol SD40 59.0 57.0 58.0 ~ _ 100.0 100.0 100.0 *In XB, 2.0 parts of 25% color mix of D&C Red #19 in castor oil was used.
~xamples XI to XIII
, These examples show 20 percent concentrates, which are diluted with resin and solvent to produce the corres-ponding final nail compositions.
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Component Parts XI XII XIII ;~
Gantrez ES-425 Resin 13.0 14.0 14.0 Castor Oil Z.0 2.0 3.0 Silicone 556 2.0 2.0 2.0 Diethyl Phthalate 2.0 - -4500 Chromalite Light Blue 1~0 2.0 -D & C Red #19 (Kohnstamm K-7040) - - 1.0 Nail enamels XI through XIII are 20% concentrates. All formed uniform heavy-bodied products (just barely flowing).
By diluting to 100 parts by the addition of 22 parts Gantrez ES-425 and 58 parts Alcohol SD40, final nail polishes were formed.
The additional Gantrez in the concentrate solubilized all the components (except the colors which were held in stable suspension).
Examples XIV to XIX
These examples show nail enamels using combinations of resin film-formers.
Component Percent XIV XV XVI XVII XVIII XIX
: :
*Gantrez ES-225 Resin 18.0 36.0 Gantrez ES-425 Resin 18.0 - - - 18.0 **Gantrez ES-435 Resin - - 36.036.018.0 36.0 Castor Oil 2.0 2.0 20 0 2.0 2~0 2.0 Silicone 556 2.0 2.0 - - 2.0 2.0 Diethyl Phthalate 2.0 2.0 - - 2.0 2.0 Isopropyl Alcohol - - 62.0 Alcohol SD40 58.0 58.0 - 62.0 58.0 58.0 ~-, ;. :
-~ 30 100.0% 100.~% 100.0% 100.0% 100.0% 100.0%
.
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*Is a 50 weight percent ethanol solution of the mono- `
ethyl ester of methyl vinylether maleic anhydride co-polymer available from GAF.
**Is a 50 weight percent isopropanol solution of the monobutyl ester of methyl vinylether maleic anhydride copolymer available from GAF.
Nail enamels XIV to XIX produced brilliant clear nail polishes that deposited good glossy films; XV had least gloss;
XVI had best gloss; XIV had intermediate gloss. Nail polish produced by XVII lasted at least 4 days with good gloss; after
Moreover, the e.f fect of components employed in such compo-sitions is empirical. For instance, an alteration in a nail enamel formulation to overcome one problem (e.g., obtain quick-drying) may result in other problems (sacriflce of smoothness, flexibility and adhesion characteristics).
Nail enamels are composed of several basic ingredients, viz, (1) a film-former, ~2) a plasticizer, and (3) a solvent system, with or without (4) a colorant. The most common film-former is ni-trocellulose (cellulose nitrate), modified with a suitable resin, e.g., formaldehyde resin, or other additive to provide sufficient hardness, resistance to chipping, ~' and to improve adhesion and gloss. The solvent system employed as the volatile portion of the enamel generally includes (a) one or more active solvents, (b~ couplers or latent solvents and (c) diluents. Typical active solvents for nitrocellulose include, for example, ethyl acetate and n-butyl acetate; i~
typical latent solvents include, for example, alcohols such as ethanol and butanol; and typical diluents include, for example, toluene and xylene.
Nitrocellulose is a fire and explosive hazard. Many localities have ordinances which forbid manipulation of it within their jurisdictions. The use of solvents with it to formulate nail enamels increases the fire and explosive hazard.
Thus nitrocellulose can only be formulated into nail enamels under very restrictive conditions and then only in plants adapted for that puxpose. Most cosmetic plants are not ad~pted to handle nitrocellulose as such. As a result, a number of specialists exlst in the chain of manufacture. One such specialist manufactures nitrocellulose chips. These chips are generally composed of nitrocellulose~ a pigment and a plasticizer. They serve as the source of color in the final _ nall enamel. Another specialist, using these chips, manufac-tures the nail enamel bulk in many shades. Cosmetic makers purchase this nail enamel bulk and then bottle, package and distribute. Considering the inherent lack of stability of nitrocellulose nail enamel, the cosmetic makers are confronted with scheduling and inventory contro:l problems ~urther com~
plicated by the many shades oE nail enamel involved. Fre-quently, complaints arise in the field.
The incorporation of colorants in nitrocellulose-based nail enamels also presents major problems. These multifaceted problems are described, for example, ln "~laking and Coloring Nail Varnishes Made From Chips", Grizzo, Cosmetics and Toiletries, Vol. 92, pp. ~3-65, April 1977. Pigments, although they must meet many criteria, are generally used with nitrocellulose.
The complex "solution and dilution" procedure involved ~ `
in the formulation of nail enamels from nitrocellulose chips is described on page 65 of the Grizzo article. This procedure is not only cumbersome and time-consuming but it also fails `
to provide uniformity in the composition of nail enamels.
The necessity of making the chips in the first instance for later solution and dilution into nail enamels is expensive.
The nitrocellulose in nail enamels normally deteriorates (chemical breakdown) on aging and results in enamels which discolor and which exhiblt loss of the characteristic of drying to a hard film and loss of viscosity. These enamels are often characterized as having sharp, unpleasant odors ~-which are disagreeable to the user. Moreover, the removal of the film deposited by these nail enamels on the nail has required the use of acetone or ethyl acetate, both of which ~,,1, are odoriferous, volatile liquids and are generally considered to be moderately toxic by inhalation and skin absorption.
Accordingly, alternatives to these conventional nitro-cellulose-based nail enamels have been sought. However, ; -~
despite the long recognized shortcomings of these enamels, ~;
no previous alternative composition has as yet been commer-cially acceptable so as to supplant them as the primary type of nail enamel on the market. This is due to the demanding requirements, described supra, placed on the performance of 10 nail enamels. There are certain minimum criteria which can delineate "nail enamel characteristics," i.e., the nail enamel when applied to the nail should dry sufficiently in about one minute or so to permit an additional coating; form a liquid coating on the nail which solidifies without flowing;
appear as a nail enamel in about thirty seconds to one minute with glossiness flow, level and deposit a uniform smooth, non-lumpy coating which hardens within about five minutes; and provide a coating exhibiting nail enamel~
lasting quality for at least about two days.
An object of the present invention is to provide a nail enamel which obviates the use of nitrocellulose as a film-former; employs a simple solvent system; uses ingre-dients which are safe and easy to use; is stable with respect ;~
to color, viscosity and film-forming characteristics; does not exhibit an offensive odor; provides an effective coating of film on nails; is easily removed from nails; and can be ~ manufactured with facility, even in concentrates which can ; be later diluted with facility, to provide uniform but `' ~' ' ' .
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versatile compositions exhibiting na11 enamel characteristics.
Another object is the provision of such enamel which deposits a film which is clear when color-imparting ingredients are absent; can incorporate color-imparting ingredients with facility; is durable; will "breathe"; will hold its integrity (not crack or chip); is flexible and relatively soft but tack-free, tough and very adhesive; and employs a simple, physiologi-cally acceptable (problem-free) solvent system.
The nail enamel and nail enamel concentrate compositions of the present invention essentially include a particular alkylvinylether/maleic anhydride ester~based resin film-former;
and a plasticizer which can be either a hydroxy fatty acid oil, an alkyl phthalate, an abietyl alcohol or mixtures of these plasticizers; and solvent. Such compositions can optionally include modified resins, supplemental plasticizers, colorants and other conventional cosmetic product adjuvants. The basis components, except the solvent system, in the compositions herein are non-volatile materials. Such non~volatile materials are referred to herein as "solids".
The essential film-forming material of the compositions of the invention comprlses an alcohol miscible, linear half ester of an aliphatic, e.gO, alkyl, vinyl ether-maleic anhydride copolymer. The ester moiety may be alkyl of, e.g., 1 to about 10 or more, preferably lower alkyl of about 2 to 6j carbon atoms, e.g., ethyl, isopropyl, butyl, amyl and hexyl. The alkyl viny-lether may be a lower alkyl vinylether, e.g., in which the alkyl group contains 1 to about 4 carbon atoms, and preferably is methyl vinylether. Generally, the molecular weight of the copolymer is at least about 200, e.g., within the range of about 200 to 500,000 e.g., 51 to 500,000 or about 10,000 to 100,000, and preferably from about 300 to 100,000.
~6--~;~
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Preferred copolymers for use herein are the water insoluble, normally liquid, monoesters of methyl vinyl-ether-maleic anhydride copolymers which are available from the GAF Corporation under the tradename GANTREZ ES monoester ~ ~-resins. Monoester resins of this type have been characterized as having the general structural formula:
fCH
- CEI2 CH fH- - fH - - ;~
o= f ~=o OH R n ~
. `' '' wherein R is the ester moiety of 1 to about 10 (preferably 2 to 6) carbon atoms and n is selected to provide resins having molecular weights within the range of from about 300 to 70,000. Such preferred copolymers often have an acid number (100% solids) of about 245 to 300. Generally, such ; monoester resins are available in a viscous alcoholic, e.g., ethanol or isopropanol, solutions of about 50 percent by weight solids, are water-resistant (e.g., essentially non-neutralized), and have a specific gravity within the range of about 0.95 to 0.99. Examples of such preferred monoester resins include the butyl monoester of a me~hylvinylether/maleic anhydride copolymer having a weight average. molecular weight (Mw) of about 7850 and a number average molecular weight (Mn) of about 3150; the ethyl monoester of a methylvinyl ether/maleic anhydride copolymer having an MW of about 4075 and an Mn of about 1785; and the isopropyl monoester of a methylvinylether/ ~-.
~ 7 ~ ~
3~i maleic anhydride copolymer having an ~w of about 11200 and an Mn of about 4050. (Such molecular weight determinations are made by gel permeation chromatography.) Combinations of the monoester resins can be employed as the essential film-former.
In addition to the above described essential film-forming resins, the nail enamel compositions of the present invention can optionally include modifier resins. Modifier-resins can be incorporated to modify the characteristics of the essential film-former employed, for instance, to modify hardness, resistance to chipping, adhesive charac-teristics, viscosity and the like. Such resin-modifiers include synthetic resins such as arylsulfonamide-formaldehyde resins (e.g., Santolite MS-80go or Santolite MHP, products of Monsanto); alcohol-soluble, hydrolyzed protein (e.g., Crotein ASC or Crotein AD-X, products of Croda); hydroxy-propyl cellulose (e.g., Klucel, a product of Hercules); ~ `
ethyl cellulose (e.g., Ethocel, a product of Dow Chemical);
amino-functional silicones (eOg., DC531 and DC536, products . ~ .
of Dow Corning) and polyamide resin (e.g., Versamid 940, a product of General Mills). The resin modifiers are employed in resin modifying amounts, generally from about 20 to 90, preferably 30 to 70, weight percent based upon the essential resin film-former (solids basis~.
A second essential component of the nail enamel and nail enamel concentrate compositions herein is a plasticizer selected from the group consisting of alcohol-soluble, hydroxy fatty acid oils, alkyl phthalates wherein each alkyl group contains from 1 to about 15 carbon atoms, abietyl ~lcohol and mixtures of such plasticizers.
;.
3~ ~
The alcohol-soluble fatty oil (e.g., hydroxy fatty acid oil~ which can serve as the essential plasticizer in the com-positions herein is a triglyceride of a hydroxy-substituted fatty, i.e. C12 22' acid. Such an oil is normally liquid at ambient temperatures and is a non-drying, non-volatile triglyceride.
The preferred hydroxy fatty acid oil is castor oil, the chief constituent of which is the triglyceride of ricinoleic (12-hydroxy-9-octadecanoic) acid. Castor oil, in addition to performing a plasticizing function, also acts as an emollient and imparts gloss to the film-coatings formed on the nail substrate by the nail enamel compositions of the present invention. Castor oil can also serve as a suspending medium ~or pigments which can optionally be introduced into the present compositions and in this connection can also serve as a medium for pigment grinding and dispersion. Furthermore, castor oil enhances the solubility of o-ther plasticizers such as alkyl phthalates or abietyl alcohols in the nail enamel systems of the present invention.
Alkyl phthalates can also serve as the essential -plasticizer in the nail enamels o~ the present invention.
The alkyl phthalate employed can include, e.g., alkyl aryl ;
; phthalates (e.g., butyl benzyl phthalate), dialkyl phthalates for instance, wherein each alkyl group contains from 1 to about 15 carbon atoms including the dimethyl, diethyl, dlbutyl and dioctyl phthalates. The di-lower alkyl phthalates are preferred. Dibutyl phthalate and butyl benzyl phthalate (e.~., Santicizer~160, a product of Mon-santo) are especially preferred plasticizers.
Abietyl alcohols can also serve as the essential plas-ticizer in the compositions herein. Abietyl alcohols are derivatives of abietic acid which has the empirical formula _g_ 3~
C19H29COOH. Such a material ineludes a phenanthrene ring system in its structure and is derived from rosin. Abietyl alcohols are commercially available under -the tradename Abitol from Hercules. Abitol~is a mixture of tetra-, di-and dehydro abietyl alcohols.
Mixtures of hydroxy fatty acid oils,alkyl phthalates and abietyl alcohols can also serve as the essential plasticizer in the nail enamels herein and, in fact, such mixtures con-stitute the preferred essential plasticizer component.
Mixtures of castor oil and butyl benzyl phthalate are especially preferred. The essential plasticizers employed herein must, of course, be present in plasticizing amounts.
In addition to the essential hydroxy fatty acid oil, alkyl phthalate, abietyl alcohol or mixed essential plas-ticizers, the nail enamel and nail enamel concentrate com-positions herein can optionally include a variety of supplemental plastieizers which must, of course, be compatible with the film-forming resin. Optional supplemental plasticizers include non-volatile organic liquids and low- ;
melting (melting point below 1~0C) organic solids such as polyols (e.g., polyethylene glycol and its derivatives);
polysiloxanes (alcohol-soluble, silicone oils, e.g., alkyl aryl polysiloxanes, e.g., methyl phenyl polysiloxane, also known as phenyl dimethicone); saturated and unsaturated mono- and dicarboxylic aeids, esters and fatty alcohols having at least about 10, perferably about 12 to 24, carbon atoms (e.g., stearic acid, oleic acid, lauric acid, ricinoleic acid, linoleic acid, vegetable oils such as almond, corn, cottonseed and olive oils, Citroflex A2, cetyl alcohol, myristyl alcohol and the like); and 3~ ~
lanolin and lanolin derivatives (e.g., acetylated, ethoxylated compounds). Citroflex A2 is acetyl triethyl citrate and is a product of Chas. Pfizer & co.
Silicone oils are the pre~erred supplemental plasticizer in that they improve the brushing characteristics (flow and leveling~ of the nail enamel and enhance the glossiness o~ the film deposited on the nail. Combinations of supplemental plasticizers can also be advantageously employed.
The third essential component of the nail enamel and na enamel concentrate compositions herein is a solvent. The solvent system employed is one that is physiologically acceptable and nail enamel compatible (e.g., is solvent for the resin film formers, and essential and supplemental plastici~ers while not ; deleteriously affecting the purpose and characteristics of nail enamels)~ It can advantageous]y be a simple solvent, expediently a lower alkanol, e.g., ethanol, and/or isopropanol. Combinations of solvents can also be used. Solvent can be provlded in part - by the solution in which commercial resin film-former is provided.
Other operable solvents include ethyl acetate, butyl acetate, toluene, xylene and acetone.
The nail enamel compositions of the present invention exhibit nail enamel characteristics which include a brushing viscosity, e.g., a heavy-bodied brushing viscosity which picks up a substantial amount of the nail enamel without dripping and yet flows freely when applied to provide a smooth coating on the nails. Viscosity of the nail enamel compositions of the present invention generally ranges from about 20 centipoises (cps.) to ~ 1500 centipoises (cps.) or more, advantageously from about 50 cps.
-~ to 1400 cps., and preferably from about 200 cps. to 500 cps.
Such viscosity values are established at 70-72F using a Model ~VT Brookfield Viscosimeter. (No. 2 spindle at 10 rpm) `'t~
.
The nail enamel characteristics exhibited by the com-positions herein also include a solids content, provided by the resin film-former (which includes the total of essential resin film-former present and, also when present, modifier~
resin) and the essential and supplemental plasticizer(s).
Such a solids content should be sufficient to impart nail enamel constitution but insuf~icient to prevent brush-application of the enamel on nails. These solid, i.e., non-volatile, contents will generally be in the range of about 10 to 45, preferably from about 12 to 35 or 40, weight percent based upon the total of the resin film-former(s), plasticizer(s) and solvent(s) present. The solids content is basically provided by the resin film-former(s) and the balance by plasticizer(s) which are incorporated in nail enamel-plasticizing amounts, e.gO, to enhance flexibility or durability of the film deposited by the nail enamel. The part of the solids content provided by film-former i5 generally from about 40 to 96, preferably from about 60 to 95, and that provided by the plasticizer(s) is generally from about 1 to 40, preferably from 2 to 35, weight percent based upon the solids content provided by resin film-former(s), and plasticizer(s) on a solven-t-free (dry) basis. The weight - ratio of resin film-formers (solvent-free basis) to total plasticiæer is preferably about 2:1. When a hydroxy fatty acid oil îs present in combination with another essential plasticizer, the hydroxy fatty acid oil generally constitutes from about 0.1 to 25, preferably from about 1 to 20, weight percent of the solids content of the nail enamel. The balance of the nail enamel constitutes the other optional ~;~
non-volatile materials and the solvent(s).
` ::
-12- ~
' ' ' ~ ' ,36 The solvent(s) is employed in nail enamel-solvent amounts, e.g., amounts sufficient to solubilize resin film-former(s), essential and supplemental plasticizer(s), and other ingredients present while not deleteriously a~fecting the viscosi-ty of the nail enamel. These amounts generally - range from about 55 to 90, usually from about 65 to 8~
weigh-t percent, based upon resin film former(s), essential and supplemental plasticizer(s) and solvent.
~` The nail enamels of this invention may also contain conventional ad~uvants such as diluents (hydrocarbons, e.g., toluene and xylene); colorants including dyes and pigments including iron oxides, organic and nacreous pigments; fillers;
stabilizers; thickeners; leveling agents; conditioners;
perfumes; antiseptics; bacteriostats and the like. These adjuvants, when employed, are provided in minor amounts sufficient to impart the intended qualities to, but not adverse to, the desired properties of the nail enamels~
The colorant is generally employed in amounts of about 0.01 to 5, usually about 0.5 to 2, weight percent based upon the nail enamel composition. One of the advantages provided by the present invention resides in the provision of nail : ~ i enamels which can utilize either dyes or pigment colorants.
Suitable colorants include pigments such as, for example, iron oxide, xanthene red organic, titanium dioxide, and ferric ;~ ferrocyanide in a blue nacreous pigment; and alcohol-soluble - dyes such as, for example, triphenylmethane blue dye, xanthene -red dye, and ~luoran yellow dye.
In a particular advantageous aspect of the present in-~ vention, nail enamel concentrates can be formed which can be -~ 30 later diluted with facility by formulators to provide the ultimate nail enamel ~or use by consumers. The concentrates ~-.
3~
advantageously contain the plasticizer(s), all or partial amounts of the film-forming resinls) and partial amounts of solvent. This is particularly significant when pigment colorants are desired in the nail enamels since the pigments can be pre-dispersed in the hydroxy fatty acid oil. ~he employment of the relatively simple solvent system in the nail enamels of this invention enables the preparation of concentratesr e.g. r as low as about 8 or 10 percent, e.g., from about 10 to 45 percent concentrate, which are uniform, clear and viscous concentrate solutions. Such numerical "percent concentrate" values refer to ~he percentage of the complete nail enamel composition which the concentrate components comprise. The nail enamel concentrates generally contain partial amounts of solvent which comprise from - about 15 to 50 weight percent of the conc~ntrate, and when containing partial amounts of resin film-former, generally the film-former is present in the concentrate in amounts from about 15 to 50 weight percent, based on the concentrate.
The nail enamels of the present invention are advan-tageously prepared by a method which comprises mixing, under ambient conditions, the essential and supplemental plasticizers with resin film-former to provide a homogenous mixture, and diluting the mixture with mixture-dissolving amounts of alcohol solvent to provide a nail enamel. When colorants are incorporated into the enamel, pigment-colorants are advantageously pre-dispersed in the hydroxy fatty acid oil, (if present in sufficient amounts, otherwise in hydroxy fatty acid oil and other essential or supplemental plasti-~izer) and dyes are advantageously pre-dissolved in the alcohol solvent before, respectively, the pigment dispersion and alcohol are contacted with resin film-former. The pigments are advantageously dispersed in the hydroxy fatty acid oil, e.g., castor oil, which is stable and not volatile 3~ `
under roller mill conditions, using a roller mill, usually water-cooled, at pressures up to about 4,000 p.s.i. to obtain a substantially uniform dispersion. `
The concentrates can be prepared by combining partial amounts of one or more of the components, preferably the solvent or resin film-former which are to form the ultimate ~-nail enamel, with the essential and supplemental plastici-zers. For instance, amounts of solvent or resin and solvent can be advantageously withheld for later dilution. The pigments can be ground in 25~ and higher concentrations in the hydroxy fatty acid oil, e.g., castor oil, or other plasticizer to provide a dispersion and the resulting dispersion can be used in making concentrates containing resin film-former and plasticizer with dispersed pigment which on further dilution, for instance with solvent, or solvent and resin, results in the final nail enamel.
The process of using the nail enamels to cosmetically improve nails comprises applying nail enamel to a nail substrate in nail-coating amounts to coat the nail, and ; 20 drying applied nail enamel to form a film-coating on the ;~
nail. The enamel is conveniently applied, e.g., by brushing it, on the portion of the nail intended to be coated. The coating dries rapidly on the substrate to form an adherent, tough, glossy film which is water-resistant. When desired, the coating is easily removed by applying an alcoholic or alkaline solution to soften the coating and the softened ~; coating can be conveniently wiped off.
- The invention is further illustrated by the following - illustrative examples, which are not in limitation of the invention. All parts and percentages are by weight unless otherwise indicated.
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,:
Example I
The following nail enamel is prepared by mixing the ~:
castor oil and resin film-Eormer and dissolving the mixture with the solvent to produce a uniform, viscous solution having a brushing viscosity (92 cps.) and a total solids content of 23 weight percent:
Component Percent *GANTREZ ~S-425 (resin film-former) 40 Castor Oil (hydroxy fatty acid oil plasticizer) 3 **Alcohol SD 40 (solvent) 57 100%
*GANTREZ ES-425 is a 50 percent ethanol solution of the monobutylester of methyl vinylether-maleic anhydride copolymer available from GAF Corporation.
**A 95 percent ethyl alcohol solution.
On application to the fingernail, a smooth glossy coat ~ was obtained. On the first application, the enamel dried l; sufficiently in about a minute to permit a second application.
On the secona application, the enamel showed very little tack in two minutes and was tack-free in three minutes. The ~; enamel lasted over two days and retained good gloss.
Example II
The following horse hoof enamel is prepared by grinding the iron oxide pigment together with the castor oil in a mortar and the mix is added to a solution composed of the resin film-former and solvent~
Component Percent GANTREZ ES-425 Resin 50 Castor Oil 3 Alcohol SD40 45 ;
Iron Oxide Pigment (black)2 100%
~:
The enamal is applied to a hoof or nail to provide a good film with excellent sheen and color coverage. The pigment which separates on standing is readily redispersed by shaking prior to use.
- Example III
The following horse hoof enamel is prepared:
Component Percent GANTR~Z ES-425 Resin 30 Castor Oil 1 Ethyl Alcohol SD40 67.95 *FD&C Blue #1 0.15 **FD&C Red ~3 0.30 ***D&C Yellow y7 0.60 100. 00%
*An alcohol-soluble tripenylmethane blue dye (Chem.
Abstracts Service Number ("CAS"): 2650-18-2)~
**An alcohol-soluble xanthene red dye (CAS: 563-63-8). `
***An alcohol-soluble fluoran yellow dye (CAS: 518-45-6).
A good black film with blue violet overtones and good gloss was obtained. It is best with two applicationsD ;~
; The colors were added to the alcohol und~r ambient conditions and dissolved by stirring. The solution may be warmed to 40C to facilitate solution. The solution was then filtered and added to a mix of the GANTREZ ES-425 and the castor oil. The mix was stirred until the solution was uniform.
Example IV
.
The procedure of Example I is essentially followed to prepare the following nail enamel:
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3~ ~
Component Percent , GANTREZ ES Resin 36.0 *Castor Oil 1.6 *D&C Red #19 Aluminum Lake Mix 0.4 **Klucel M 0.6 **Ethanol 30 9 Toluene 30 5 ;
100~0%
*An organic xanthene red pigment (RD No. 977054~33-3) (Kohnstamm K-7040), the colorant was ground in castor -~
oil at a 25 percent concentration.
**Solubilized in ethanol to provide a two percent solution.
:
` The castor oil-pigment mix was added to the Gantrez and ~`
mixed thoroughly. The Klucel-alcohol solution was mixed in -thoroughly and then toluene was stirred in. A good film ~ ~
was produced. The color--a pretty pink, was somewhat trans- ~ ~;
parent on one application~ The enamel had a good brushing ~iscosity (1360 cps.).
.; :
This example shows that toluene is compatible in the nail enamel and can be used to modify (cut) the viscosity of the enamel. Klucel can be used to increase the viscosity of the enamel without significantly increasing the solids content, the increase in viscosity being desired to stabilize the dispersion of pigment in the enamel.
Example V
~ The procedure of Example I is essentially followed ; to prepare the following nail enamel: -Component Percent Gantrez ES-425 ~esin 30.0 Castor Oil 1.0 ; Alcohol SD40 65.0 Diethyl Phthalate 4.0 100. 0%
3~6i This exemplifies a combination of castor oil as the hydroxy fatty acid oil plasticizer, and diethyl phthalate as a supplemental plasticizer. Such a composition has a viscosity of about 60 cps.
Example VI
The procedure of Example I is essentlally followed, except the Silicone 556 and dimethyl phthalate are adde~
in turn after the castor oil, to prepare the following nail enamel:
Component Percent Gantrez ES-425 Resin 36 Castor Oil *Silicone 556 2 - Dimethyl Phthalate 2 ~ Alcohol SD40 59 :. ~ 100~
*Silicone 556 is an alcohol-soluble, methylphenyl polysiloxane, a product of Dow Corning (It has also been designated phenyl dimethicone CTFA). It has a viscosity at 25C of 22.5 centistokes.
, ..
The enamel, when applied to a fingernail, provided ; a very glossy finish. The silicone, in addition to plasticizing, also enhances the brushing characteristics (flow and leveling) of the nail enamel. The nail enamel composition has a viscosity of about 72 cps.
Example VII
The procedure of Example VI is essentially followed to prepare the following nail enamel:
~' ~ .
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Component Percent Gantrez ES-425 Resin 36.0 Castor Oil 2.0 *Santolite MS-80% Resin 12.0 Alcohol SD40 46.0 Sil7cone 556 2.0 Diethyl Phthalate 2 0 100. 0% ,"
*Santolite MS~80% is an 80 percent sulfonamide-formaldehyde resin in butyl acetate solution, a product of Monsanto Industrial Chemicals.
~;
Good clear films were deposited upon application of this enamel to nails.
A white taffy-like mix resulted when the Gantrez and Santolite were combined. The final addition of the alcohol resulted in a clear bright solution.
A coat of the enamel on fingernails lasted almost five days. ~;
Examples VIII to X
These examples, A Group Examples, show concentrate preparations in the 38 to 44 weight percent range, e.g., 41 to 43 percent, which are diluted with ethanol to produce the corresponding final nail enamels set forth in B Group Examples:
A Group Componen-t Parts ~IIIA IXA XA
Gantrez ES-425 Resin 36.0 36.0 36.0 ` *Castor Oil 1.0 2.0 1.75 Silicone 556 2.0 2.0 2.0 Diethyl Phthalate 2.0 2.0 2.0 **4500 Chromalite Light Blue - 1.0 - ;
*D&C Red #19 (Kohnstamm K-7040) - - 0.25 ~ a336 *In Example XA, two parts of a 25% color mix of D&C
Red ~19 ground in castor oil was used.
**A blue nacreous pearlescent pigment using fQrric ferrocyanide, a product of Mallinckrodt, Inc.
` Concentrate VIIIA on dilution to 100 parts by the addition of Alcohol SD 40 formed a clear polish, the composition of which is set forth below in B Group~
Concentrates IXA and XA formed colored nail polishes on dilution to 100 parts using Alcohol SD40 and stirring, and the compositions of these are also set forth in B Group below.
B Group ;~ Component Parts VIIIB IXB XB
Gan-trez ES-425 Resin 36.0 36.0 36.0 ~ ,: . :.
*Castor Oil 1.0 2.0 1.75 ; Silicone 556 2.0 2.0 2.0 Diethyl Phthalate 2.0 2.0 2.0 4500 Chromalite Light Blue - 1.0 *D&C Red #19 (Kohnstamm K-7040) - - 0.25 .. .
-Alcohol SD40 59.0 57.0 58.0 ~ _ 100.0 100.0 100.0 *In XB, 2.0 parts of 25% color mix of D&C Red #19 in castor oil was used.
~xamples XI to XIII
, These examples show 20 percent concentrates, which are diluted with resin and solvent to produce the corres-ponding final nail compositions.
~-'':
Component Parts XI XII XIII ;~
Gantrez ES-425 Resin 13.0 14.0 14.0 Castor Oil Z.0 2.0 3.0 Silicone 556 2.0 2.0 2.0 Diethyl Phthalate 2.0 - -4500 Chromalite Light Blue 1~0 2.0 -D & C Red #19 (Kohnstamm K-7040) - - 1.0 Nail enamels XI through XIII are 20% concentrates. All formed uniform heavy-bodied products (just barely flowing).
By diluting to 100 parts by the addition of 22 parts Gantrez ES-425 and 58 parts Alcohol SD40, final nail polishes were formed.
The additional Gantrez in the concentrate solubilized all the components (except the colors which were held in stable suspension).
Examples XIV to XIX
These examples show nail enamels using combinations of resin film-formers.
Component Percent XIV XV XVI XVII XVIII XIX
: :
*Gantrez ES-225 Resin 18.0 36.0 Gantrez ES-425 Resin 18.0 - - - 18.0 **Gantrez ES-435 Resin - - 36.036.018.0 36.0 Castor Oil 2.0 2.0 20 0 2.0 2~0 2.0 Silicone 556 2.0 2.0 - - 2.0 2.0 Diethyl Phthalate 2.0 2.0 - - 2.0 2.0 Isopropyl Alcohol - - 62.0 Alcohol SD40 58.0 58.0 - 62.0 58.0 58.0 ~-, ;. :
-~ 30 100.0% 100.~% 100.0% 100.0% 100.0% 100.0%
.
3~
*Is a 50 weight percent ethanol solution of the mono- `
ethyl ester of methyl vinylether maleic anhydride co-polymer available from GAF.
**Is a 50 weight percent isopropanol solution of the monobutyl ester of methyl vinylether maleic anhydride copolymer available from GAF.
Nail enamels XIV to XIX produced brilliant clear nail polishes that deposited good glossy films; XV had least gloss;
XVI had best gloss; XIV had intermediate gloss. Nail polish produced by XVII lasted at least 4 days with good gloss; after
4 days, fine crazin~ was observed under 10X magnification which was not visible to eye, and no chipping was observed.
The sheen of the polish produced by nail enamel XV disappeared after the second day of wear. Nail polishes produced by nail enamels XIV and XVI lasted about 4 days. Nail polishes produced by nail enamels XVIII and XIX both lasted 3 days with fine cracking seen.
Examples XX and XXI
These examples, A Group Examples, present particularly advantageous embodiments of the present invention involving the preparation of unique concentrates which are as low as about 10 percent concentrate.
A Group Component Parts XXAXXIA
Gantrez ES-435 5.05.0 Castor Oil 3O03.0 D&C Red #7 (Rohnstamm K-7044) - 1.0 Chromalite Magenta (Mallinckrodt) 45051.25 Isopropyl Alcohol 1.01.0 In connection with XXA, the isopropyl alcohol was stirred into the Gantrez ES-435 followed by the castor oil and the pigment. A heavy-bodied concentrate (carmine color) resulted.
In connection with XXIA, the procedure of XXA was followed except that a mixture of D&C Red #7 ground in the castor oil was added to the Gantrez ES-435. A smooth heavy-bodied pink-colored concentrate resulted.
Component Parts XXB XXIB
Gantrez ES-435 38.0 38.0 Castor Oil 3.0 3.0 Dibutyl Phthalate - 2.0 .
Alcohol SD40 56.75 55.0 Isopropyl Alcohol 1.0 1.0 ; D&C Red #7 (Kohnstamm K-7044) - 1.0 Chromalite Magenta 1.25 (Mallinckrodt) 4505 100.0 100.0 Nail enamel XXB was made by diluting 10.25 parts of Concentrate XXA with 5.0 parts of ethyl alcohol while stirring.
Then 33.0 parts of Gantrez ES-435 were added while stirring.
The balance of the ethyl alcohol~ 51.75 parts was added while stlrrlng.
Nail enamel XXIB was made by diluting 10.0 parts of Concentrate XXIA with 5.0 parts of ethyl alcohol while stirring.
Then 33.0 parts of Gantrez ES-435 were added while stirring followed by addition of 2.0 parts of dibutyl phthalate with stirring. The balance of the ethyl alcohol, 50.0 parts, was added while stirring.
These examples present particularly advantageous concentrates containin~ ground and dispersed pi~ment, having flexibility, and whicn can be easily processed into final nail enamels. The use of isopropanol is advantageous in that a concentrate as low a~ about 10 percent can be prepared.
Although the isopropyl ester of the resin is employed, there is no restriction on use of other resin film-formers of the present invention in making the final nail enamel since the isopropyl ester is used in the concentrate in small amounts which are compa~ible with larger amounts of other resins.
These concentrates advantageously serve the purpose of introducing pigments into the final nail enamel which have been properly ground and dispersed in the concentrate.
Examples XXII and XXIII
The following nail enamel compositions are formulated to illustrate compositions employing relatively high solids contents.
Component Concentration (Wt XXIIXXIII
Gantrez ES-435 (resin~ 40.0 50.0 Castor Oil (plasticizer) 5.0 5.0 *Santicizer 160 (plasticizer) 5.0 5.0 Silicone 556 (plasticizer) 2,0 2.0 SD-40-A Al¢~hol(solvent) ~8.0 38.0 (Anhydrous) 100.0%100.0 *Butyl benzyl phthalate available commercially from Monsanto.
Notwithstanding the relatively high solids contents, both Rxamples XXII and XXIII exhibit acceptable brushing viscosities (XXII = 240 cps~ and XXIII = 320 cps.). These nail enamel compositions employing a mixed ethanol/isopropanol solvent system also exhibited acceptahle drying time charac-teristics once applied to the nail substrates.
Compositions of subtantially similar nail enamel characteristics are realized when in 1he Example XXII and XXIII `~
compositions the Santicizer 160 plasticizer is replaced with an equivalent amount of Abitol , a mixture of abietyl alcohols commercially available from ~ercules~
Example XXIV
The following nail enamel is prepared by mixing the butyl benzyl phthalate and resin film former and dissolving the mixture with the solvent to produce a uniform, viscous solution having a brushing viscosity and a total solids content of 22 weight percent~
Component Percent *GANTREZ ES-425 (r-sin film-former) 36 Butyl Benzyl Phthalate (plasticizer) 4 Isopropanol (solvent) 60 *A 50 weight percent isopropanol solution of the monobutyl ester of methylvinylether/maleic anhydride copolymer available from GAF Corporation.
.:
The nail enamel is applied to fingernails to provide a smooth, clear, glossy coat on the nails.
A nail enamel composition of substantially similar characteristics is realized if, in the Example XXIV composition, the butyl benzyl phthalate plasticizer is replaced with an equivalent amount of Abitol~, a commercially-available 133~
.
mix-ture of tetra-, di- and dehydro-abietyl alcohol.s.
The nail enamel coating formed on the nail by the Example XXIV composition is removed by applying isopropanol to the coating and 3 minutes thereafter wiping the softened coating from the nail.
Example XXV
The following nail enamel is prepared by mixing the dimethyl phthalate and resin film-former and dissolving the mixture with the solvent to produce a uniform, viscous 10solution having a brushing viscosity and a total solids content of 22 weight percent:
_mponent Percen *GANTREZ~ ES-425 (resin film-former) 36 Dime~hyl Phthalate 4 **Alcohol SD40 (solvent) 60 *GANTREZ ES-425 is a 50 percent ethanol solution of the monobutylester of methyl vinylether-maleic anhydride copolymer available from General Aniline &
Film Corporation ("GAF").
**A 95 percent ethyl alcohol solution.
The nail enamel is applied to a fingernail to provide `
a smooth, clear, glossy coat on the nail.
Examples XXVI to XXVIII ~.
The procedure of Example XXV is essentially followed to prepare the following nail enamel.:
_omponent Percent XXVI XXVII XXVIII
GANTREZ ES-425 Resin 36 36 36 Dibutyl Phthalate 4 4 - ~.
Dioctyl Phthalate - - 4 Alcohol SD40 60 - -Isopropyl Alcohol - 60 60 100 %10~ %100 %
3 Ei Example XXIX
This example, A Part E~ample, shows a concentrate preparation in the 38 to 44 weight percent range, which is diluted with ethanol to produce the corresponding final nail enamel set forth in B Part Example:
A Part Component Parts XXIXA -Gantrez ES-425 Resin 36.0 Dimethyl P.hthalate 4.0 Nail polish concentrate XXIXA was clear. ~;
B Part _omponent Parts XXIXB
Gantrez ES-425 Resin 36.0 ~ ~
Dimethyl Phthalate 4.0 ~ :
Alcohol SD40 60.0 :
100.O
~, . , '' :' :' ,.' ' ~ :' . ~ -: . .:
' ' ` ' .;', ~'
The sheen of the polish produced by nail enamel XV disappeared after the second day of wear. Nail polishes produced by nail enamels XIV and XVI lasted about 4 days. Nail polishes produced by nail enamels XVIII and XIX both lasted 3 days with fine cracking seen.
Examples XX and XXI
These examples, A Group Examples, present particularly advantageous embodiments of the present invention involving the preparation of unique concentrates which are as low as about 10 percent concentrate.
A Group Component Parts XXAXXIA
Gantrez ES-435 5.05.0 Castor Oil 3O03.0 D&C Red #7 (Rohnstamm K-7044) - 1.0 Chromalite Magenta (Mallinckrodt) 45051.25 Isopropyl Alcohol 1.01.0 In connection with XXA, the isopropyl alcohol was stirred into the Gantrez ES-435 followed by the castor oil and the pigment. A heavy-bodied concentrate (carmine color) resulted.
In connection with XXIA, the procedure of XXA was followed except that a mixture of D&C Red #7 ground in the castor oil was added to the Gantrez ES-435. A smooth heavy-bodied pink-colored concentrate resulted.
Component Parts XXB XXIB
Gantrez ES-435 38.0 38.0 Castor Oil 3.0 3.0 Dibutyl Phthalate - 2.0 .
Alcohol SD40 56.75 55.0 Isopropyl Alcohol 1.0 1.0 ; D&C Red #7 (Kohnstamm K-7044) - 1.0 Chromalite Magenta 1.25 (Mallinckrodt) 4505 100.0 100.0 Nail enamel XXB was made by diluting 10.25 parts of Concentrate XXA with 5.0 parts of ethyl alcohol while stirring.
Then 33.0 parts of Gantrez ES-435 were added while stirring.
The balance of the ethyl alcohol~ 51.75 parts was added while stlrrlng.
Nail enamel XXIB was made by diluting 10.0 parts of Concentrate XXIA with 5.0 parts of ethyl alcohol while stirring.
Then 33.0 parts of Gantrez ES-435 were added while stirring followed by addition of 2.0 parts of dibutyl phthalate with stirring. The balance of the ethyl alcohol, 50.0 parts, was added while stirring.
These examples present particularly advantageous concentrates containin~ ground and dispersed pi~ment, having flexibility, and whicn can be easily processed into final nail enamels. The use of isopropanol is advantageous in that a concentrate as low a~ about 10 percent can be prepared.
Although the isopropyl ester of the resin is employed, there is no restriction on use of other resin film-formers of the present invention in making the final nail enamel since the isopropyl ester is used in the concentrate in small amounts which are compa~ible with larger amounts of other resins.
These concentrates advantageously serve the purpose of introducing pigments into the final nail enamel which have been properly ground and dispersed in the concentrate.
Examples XXII and XXIII
The following nail enamel compositions are formulated to illustrate compositions employing relatively high solids contents.
Component Concentration (Wt XXIIXXIII
Gantrez ES-435 (resin~ 40.0 50.0 Castor Oil (plasticizer) 5.0 5.0 *Santicizer 160 (plasticizer) 5.0 5.0 Silicone 556 (plasticizer) 2,0 2.0 SD-40-A Al¢~hol(solvent) ~8.0 38.0 (Anhydrous) 100.0%100.0 *Butyl benzyl phthalate available commercially from Monsanto.
Notwithstanding the relatively high solids contents, both Rxamples XXII and XXIII exhibit acceptable brushing viscosities (XXII = 240 cps~ and XXIII = 320 cps.). These nail enamel compositions employing a mixed ethanol/isopropanol solvent system also exhibited acceptahle drying time charac-teristics once applied to the nail substrates.
Compositions of subtantially similar nail enamel characteristics are realized when in 1he Example XXII and XXIII `~
compositions the Santicizer 160 plasticizer is replaced with an equivalent amount of Abitol , a mixture of abietyl alcohols commercially available from ~ercules~
Example XXIV
The following nail enamel is prepared by mixing the butyl benzyl phthalate and resin film former and dissolving the mixture with the solvent to produce a uniform, viscous solution having a brushing viscosity and a total solids content of 22 weight percent~
Component Percent *GANTREZ ES-425 (r-sin film-former) 36 Butyl Benzyl Phthalate (plasticizer) 4 Isopropanol (solvent) 60 *A 50 weight percent isopropanol solution of the monobutyl ester of methylvinylether/maleic anhydride copolymer available from GAF Corporation.
.:
The nail enamel is applied to fingernails to provide a smooth, clear, glossy coat on the nails.
A nail enamel composition of substantially similar characteristics is realized if, in the Example XXIV composition, the butyl benzyl phthalate plasticizer is replaced with an equivalent amount of Abitol~, a commercially-available 133~
.
mix-ture of tetra-, di- and dehydro-abietyl alcohol.s.
The nail enamel coating formed on the nail by the Example XXIV composition is removed by applying isopropanol to the coating and 3 minutes thereafter wiping the softened coating from the nail.
Example XXV
The following nail enamel is prepared by mixing the dimethyl phthalate and resin film-former and dissolving the mixture with the solvent to produce a uniform, viscous 10solution having a brushing viscosity and a total solids content of 22 weight percent:
_mponent Percen *GANTREZ~ ES-425 (resin film-former) 36 Dime~hyl Phthalate 4 **Alcohol SD40 (solvent) 60 *GANTREZ ES-425 is a 50 percent ethanol solution of the monobutylester of methyl vinylether-maleic anhydride copolymer available from General Aniline &
Film Corporation ("GAF").
**A 95 percent ethyl alcohol solution.
The nail enamel is applied to a fingernail to provide `
a smooth, clear, glossy coat on the nail.
Examples XXVI to XXVIII ~.
The procedure of Example XXV is essentially followed to prepare the following nail enamel.:
_omponent Percent XXVI XXVII XXVIII
GANTREZ ES-425 Resin 36 36 36 Dibutyl Phthalate 4 4 - ~.
Dioctyl Phthalate - - 4 Alcohol SD40 60 - -Isopropyl Alcohol - 60 60 100 %10~ %100 %
3 Ei Example XXIX
This example, A Part E~ample, shows a concentrate preparation in the 38 to 44 weight percent range, which is diluted with ethanol to produce the corresponding final nail enamel set forth in B Part Example:
A Part Component Parts XXIXA -Gantrez ES-425 Resin 36.0 Dimethyl P.hthalate 4.0 Nail polish concentrate XXIXA was clear. ~;
B Part _omponent Parts XXIXB
Gantrez ES-425 Resin 36.0 ~ ~
Dimethyl Phthalate 4.0 ~ :
Alcohol SD40 60.0 :
100.O
~, . , '' :' :' ,.' ' ~ :' . ~ -: . .:
' ' ` ' .;', ~'
Claims (18)
1. A nail enamel composition exhibiting nail enamel characteristics including a brushing viscosity and a solids content of about 10 to 45 weight percent consisting essentially of nail enamel film-forming amounts of an alcohol soluble, water-resistant, film-forming resin which is a half ester of an alkylvinylether/maleic anhydride copolymer having a molecular weight of at least about 200; nail enamel-plasticizing amounts of a plasticizer selected from the group consisting of alcohol-soluble, hydroxy fatty acid oils, alkyl phthalates wherein each alkyl group contains from 1 to about 15 carbon atoms, abietyl alcohols and mixtures of said hydroxy fatty acid oilds, alkyl phthaltes and abietyl alcohols; and nail enamel-solvent amounts of a nail enamel compatible, physiologically acceptable solvent.
2. The nail composition of claim 1 wherein a) the film-forming resin has the structural formula:
wherein R is alkyl of about 2 to 6 and n is selected to provide resins having molecular weights of from about 300 to 70,000; b) the essential plasticizer is selected from the group consisting of castor oil, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate and mixtures of castor oil and butyl benzyl phthalate; and c) the solvent is selected from ethanol, isopropanol and mixtures thereof.
wherein R is alkyl of about 2 to 6 and n is selected to provide resins having molecular weights of from about 300 to 70,000; b) the essential plasticizer is selected from the group consisting of castor oil, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate and mixtures of castor oil and butyl benzyl phthalate; and c) the solvent is selected from ethanol, isopropanol and mixtures thereof.
3. The nail enamel composition of claim 2 wherein the composition contains nail enamel plasticizing amounts of an alcohol soluble, supplemental nail enamel plasticizer and color-imparting amounts of a nail enamel colorant.
4. The composition of claim 3 wherein the colorant is an alcohol-soluble dye.
5. The composition of claim 3 wherein the colorant is an alcohol-insoluble pigment.
6. The composition of claim 2 wherein the essen-tial nail enamel plasticizer is a mixture of castor oil and butyl benzyl phthalate.
7. The composition of claim 6 wherein the film-forming resin is a monobutyl ester of a methyvinylether/maleic anhydride copolymer, the solvent is ethanol and the supplemental plasticizer is phenyl dimethicone.
8. A method for preparing the nail enamel composition of claim 1 which comprises combining the resin film-former and plasticizer to form a mix, and diluting the mix with the solvent to produce a nail enamel composition.
9. A method for preparing the nail enamel composition of claim 4 which comprises combining the resin film-former, essential plasticizer, and supplemental plasticizer to form a mix, and diluting the mix with solvent containing the dye to produce a nail enamel composition.
10. A method for preparing the nail enamel composition of claim 5 which comprises pre-dispersing the pigment in the essential or supplemental plasticizer, com-bining the resin film-former, essential plasticizer, and supplemental plasticizer to form a mix, and diluting the mix with the solvent to produce a nail enamel composition.
11. A process for using the nail enamel composition of claim 1 to cosmetically improve nails which comprises applying the enamel to a nail substrate in nail-coating amounts to coat the nail, and drying the applied nail enamel to form a film-coating on the nail.
12. A process for removing from a nail substrate a dried film-coating formed by the application to said substrate of the nail enamel composition of claim 1, said process comprising applying an alcoholic or alkaline solution to said dried film-coating in order to soften said film-coating and thereafter wiping said softened film coating off the nail substrate.
13. A nail enamel concentrate for dilution into nail enamel compositions which exhibit nail enamel characteristics including a brushing viscosity and a solids content of about 10 to 45 weight percent, the concentrate consisting essentially of nail enamel film-forming amounts of an alcohol-soluble, water resistant film-forming resin which is a half ester of an alkyl-vinylether/maleic anhydride copolymer having molecular weight of at least about 200; nail enamel plasticizing amounts of a plasticizer selected from the group consisting of alcohol-soluble, hydroxy fatty acid oils, alkyl phthalates wherein each alkyl group contains from 1 to about 15 carbon atoms, abietyl alcohols and mixtures of said hydroxy fatty acid oils, alkyl phthalates and abietyl alcohols; and a partial amount of nail enamel-solvent amounts of nail enamel compatible, physiologically acceptable solvent.
14. A nail enamel concentrate for dilution into nail enamel compositions which exhibit nail enamel characteristics including a brushing viscosity and a solids content of about 10 to 45 weight percent, the concentrate consisting essentially of a partial amount of nail enamel film-forming amounts of an alcohol-soluble, water-resistant film-forming resin which is a half ester of an alkylvinylethyl/maleic anhydride copolymer having a molecular weight of at least about 200; nail enamel plasticizing amounts of a plasticizer selected from the group consisting of alcohol soluble/ hydroxy fatty acid oils, alkyl phthalates wherein each alkyl group contains from 1 to about 15 carbon atoms, abietyl alcohols and mixtures of said hydroxy fatty acid oils, alkyl phthalates and abietyl alcohols; and a partial amount of nail enamel-solvent amounts of a nail enamel compatible, physiologically acceptable solvent.
15. The nail enamel concentrate of claim 13 wherein the partial amount of solvent in the concentrate comprises from about 15 to 50 weight percent of the concentrate.
16. The nail enamel concentrate of claim 14 wherein the partial amount of resin fim-former comprises from about 15 to 50 weight percent, and the partial amount of solvent comprises from about 15 to 50 weight percent of the concentrate.
17. The composition of claims 1, 13 or 14 wherein the film-forming resin has a molecular weight of from about 300 -to 100,000 and the solvent is a lower alkanol.
18. The composition of claims 15 or 16 wherein the film-forming resin has a molecular weight of from about 300 to 100,000 and the solvent is a lower alkanol.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US81602477A | 1977-07-15 | 1977-07-15 | |
| US81608377A | 1977-07-15 | 1977-07-15 | |
| US816,083 | 1977-07-15 | ||
| US816,024 | 1986-01-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1101336A true CA1101336A (en) | 1981-05-19 |
Family
ID=27124018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA307,137A Expired CA1101336A (en) | 1977-07-15 | 1978-07-11 | Ester of alkylvinylether/maleic anhydride copolymer in plasticized nail enamel |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5420143A (en) |
| AU (1) | AU523438B2 (en) |
| CA (1) | CA1101336A (en) |
| DE (1) | DE2830958A1 (en) |
| FR (1) | FR2397186A1 (en) |
| GB (1) | GB2002795B (en) |
| NL (1) | NL7807585A (en) |
| SE (1) | SE7807815L (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740370A (en) * | 1984-03-16 | 1988-04-26 | Faryniarz Joseph R | Process for preparing nail coating compositions |
| US4749564A (en) * | 1984-03-16 | 1988-06-07 | Chesebrough-Pond's, Inc. | Nail coating compositions having high pigment content and low viscosity |
| ZA852103B (en) * | 1984-06-29 | 1985-12-24 | Chesebrough Ponds | Nail polish compositions and means for applying same |
| US4712571A (en) * | 1984-06-29 | 1987-12-15 | Chesebrough-Pond's, Inc. | Nail polish compositions and means for applying same |
| US4643532A (en) * | 1985-06-24 | 1987-02-17 | At&T Bell Laboratories | Field-assisted bonding method and articles produced thereby |
| EP0260859A1 (en) * | 1986-09-19 | 1988-03-23 | SMITH & NEPHEW UNITED, INC. | A medicated skin preparation |
| US5066484A (en) * | 1990-04-30 | 1991-11-19 | Revlon, Inc. | Nail enamels containing glyceryl, glycol or citrate esters |
| US5145671A (en) * | 1990-04-30 | 1992-09-08 | Revlon, Inc. | Nail enamels containing glyceryl, glycol or citrate esters |
| US5225185A (en) * | 1990-04-30 | 1993-07-06 | Revlon Consumer Products Corporation | Nail enamels containing glyceryl, glycol or citrate esters |
| US5227155A (en) * | 1990-04-30 | 1993-07-13 | Revlon Consumer Products Corporation | Nail enamels containing glyceryl, glycol or citrate esters |
| US5145670A (en) * | 1990-04-30 | 1992-09-08 | Revlon, Inc. | Nail enamels containing glyceryl, glycol or citrate esters |
| HU219480B (en) * | 1991-05-23 | 2001-04-28 | Novartis Ag. | Process for producing locally applicable pharmaceutical compositions comprising allylamine derivative against fungus infection of nails |
| FR2679445B1 (en) * | 1991-07-26 | 1995-04-14 | Oreal | COLORLESS OR COLORFUL NAIL VARNISH CONTAINING AN AMINOFUNCTIONAL SILICONE AS AN ADHESIVE AGENT. |
| US5843412A (en) * | 1993-01-25 | 1998-12-01 | L'oreal | Quick-drying colored or clear nail varnish |
| FR2700692B1 (en) * | 1993-01-25 | 1995-03-03 | Oreal | Colorless or colored nail varnish, containing an amino- or thiosilicone and an organofluoric hydrocarbon compound in order to improve drying time. |
| FR2718349B1 (en) * | 1994-04-07 | 1996-05-31 | Oreal | Cosmetic compositions to be applied to the nail. |
| JP2000512265A (en) * | 1996-03-16 | 2000-09-19 | ヘキスト・アクチエンゲゼルシヤフト | Topical formulations for the treatment of nail psoriasis |
| DE602004028284D1 (en) | 2003-12-08 | 2010-09-02 | Cpex Pharmaceuticals Inc | PHARMACEUTICAL COMPOSITIONS AND METHODS FOR INSULIN TREATMENT |
| FR2878157B1 (en) * | 2004-11-23 | 2007-03-02 | Durlin France Sa | SOLVENT-BASED VARNISH COMPOSITION BASED ON SOLVENT OF VEGETABLE ORIGIN |
-
1978
- 1978-06-17 GB GB7830111A patent/GB2002795B/en not_active Expired
- 1978-07-11 CA CA307,137A patent/CA1101336A/en not_active Expired
- 1978-07-13 SE SE787807815A patent/SE7807815L/en unknown
- 1978-07-13 FR FR7821056A patent/FR2397186A1/en active Pending
- 1978-07-13 AU AU38012/78A patent/AU523438B2/en not_active Expired
- 1978-07-14 JP JP8666678A patent/JPS5420143A/en active Pending
- 1978-07-14 NL NL7807585A patent/NL7807585A/en not_active Application Discontinuation
- 1978-07-14 DE DE19782830958 patent/DE2830958A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| AU3801278A (en) | 1980-01-17 |
| GB2002795B (en) | 1982-03-17 |
| SE7807815L (en) | 1979-01-16 |
| JPS5420143A (en) | 1979-02-15 |
| GB2002795A (en) | 1979-02-28 |
| AU523438B2 (en) | 1982-07-29 |
| FR2397186A1 (en) | 1979-02-09 |
| DE2830958A1 (en) | 1979-02-01 |
| NL7807585A (en) | 1979-01-17 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19980519 |