US 3697644 A
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United States Patent Laiderman  COSMETIC COMPOSITION  Inventor: Donald David Laiderman, Deerfield,
 Assignee: The Gillette Company, Boston,
 Filed: Oct. 18, 1966  App]. No.: 587,387
 US. Cl. ..424/70, 8/l0.l, 424/71, 424/78, 424/80, 424/81, 424/361, 424/362,
 Int. Cl. ..A6lk 7/06  Field of Search ..424/47, 59, 70, 362, 363; 252/308  References Cited OTHER PUBLICATIONS Remington No. l, Remingtons Practice of Pharmacy, Martin et al., Mack Publishing Co., Easton, Pa. 9th Ed. p. I375 (i948) Remington No.
2, Remingtons Pharmaceutical 51 Oct. 10,1972
Sciences, Martin et al., Mack Publishing Co., Easton, Pa. llth Ed. p. 292- 299, 302 & 303 (1965) Pickthall, Jack, J. Soc. Cos. Chem, Vol. 2, No. 3 p. 141- 156(1951) Greenberg, Leon A. et al., Handbook of Cos. Man, Interscience Pub. p. 26 (1954) Harry, R. G., Cosmetic Materials, (Prin. & Pract. of Mod. Cos.) Chemical Publishing Co. NY, NY (1963) Primary ExaminerAlbert T. Meyers Assistant Examiner-Allen J. Robinson. Att0rneyR. W. Furlong ABSIRACT 5 Claims, No Drawings COSMETIC COMPOSITION This invention relates to stable aqueous cosmetic compositions containing substantially water-insoluble cosmetic materials and capable of depositing a smooth film of the cosmetic material on the skin or hair by means of a rinse-on application.
There exists a variety of cosmetic materials of very limited water solubility which are able to confer useful properties to skin and hair when deposited thereon in a smooth even layer. While this can be done by employing solutions of such material in a volatile organic solvent, the large volume of solvent required to permit even application of a smooth thin layer is undesirable from the standpoint of both cost and of possible effects of the solvent on the skin or hair. Although it is also possible to prepare oil-in-water emulsions of liquid cosmetic materials of limited water solubility, the presence of residual surface active emulsifying agents in the resulting film often renders it subject to removal by water, or even by normal perspiration.
One object of the present invention is to provide a cosmetic composition in the form of an aqueous dispersion of a substantially water-insoluble film-forming material which composition is capable of being applied to the skin or hair and of depositing a thin smooth film of such material on the skin or hair when rinsed, i.e. diluted, with water.
Another object of the present invention is to provide a cosmetic composition capable of depositing on the skin or hair a thin smooth layer of a substantially waterinsoluble material which layer is resistant to subsequent removal by aqueous compositions. I
A further object of the present invention is to provide a method of applying to the skin or hair a thin smooth layer of a substantially water-insoluble material, said method making use of an aqueous composition containing a minor proportion of organic solvent for said material.
Other and further objects will be apparent from the description which follows.
It has been found that thin smooth films of substantially water-insoluble materials can be laid down on the skin or hair from compositions which comprise an emulsion having water thickened with a protective colloid in the external phase and having as the disperse phase a solution of the water-insoluble cosmetic material in a cosmetically acceptable organic solvent of special characteristics.
In the present invention, conventional surfactants (i.e. surface active agents) are not employed. Instead, the substantially water-insoluble non-volatile cosmetic material is dissolved in an organic solvent in which it is soluble and this solution then dispersed in a thickened aqueous medium in which the thickener serves as a protective colloid to hold the dispersed phase in suspension for long periods of time.
When these new compositions are applied to the skin or hair as a coating and subsequently rinsed with water or allowed to dry, there is deposited on the skin or hair a smooth thin semi-continuous film of the cosmetic material. Because of the absence of any surface active agent the film cannot easily be removed with water.
The cosmetic materials which may be applied to the skin or hair in accordance with this invention include a wide variety of substantially water-insoluble nonvolatile materials which have utility in the cosmetic art.
The term substantially water-insoluble cosmetic materials is intended to include all those substantially colorless fats, oils, waxes, and polymers which have a cosmetic utility and a solubility in water at room temperature (23 C.) of less than 0.5% by weight. Examples of such materials are mineral oils derived from petroleum; fatty materials of vegetable or animal origin such as lanolin, sperm oil, coconut oil, olive oil, peanut oil and the like; saturated and unsaturated fatty acids and fatty alcohols having 10 or more carbon atoms; esters of fatty acids such as isopropyl myristate; and fatty amines such as stearylamine and amides thereof with fatty acids containing up to five carbon atoms. Included also are the animal waxes such as beeswax and spermaceti; the vegetable waxes such as carnauba, bayberry and candelilla; the mineral waxes including m'ontan, ozokerite, ceresin and paraffin and the synthetic waxes as exemplified by the medium molecular weight polyethylenes, polyethylene glycols, and polyoxyethylene esters such as sorbitan monostearate; and natural gums and resins such as shellac and benzoin. Other examples of synthetic polymeric cosmetic materials which may be formulated in accordance with the teachings of this invention include water-insoluble copolymers of vinyl pyrollidone with vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl butyrate and the like; copolymers of vinyl alkyl ethers with maleic anhydride; copolymers of ethylene and maleic anhydride and esters such as cellulose acetate or cellulose butyrate. In a preferred embodiment of the invention, esters of polysaccharides such as dextran, amylose, amylopectin, etc., with fatty acids containing 10 to 18 carbon atoms may be employed as the cosmetic material to yield skin creams capable of depositing on the hands a water barrier film highly resistant to aqueous detergent compositions.
The organic solvent employed, in addition to being cosmetically acceptable and having the ability to dissolve the water-insoluble cosmetic material, must itself be either insoluble (i.e. less than 0.1% by weight at room temperature) in water (in which case it must be volatile) or soluble only to a limited extent. For best results, the solvent should be soluble in water at room temperature to the extent of l to 10% by weight of the water; however, solvents having a solubility of up to 20% by weight in water have been found to be operable. Among the solvents which have been found to be satisfactory are benzyl alcohol; 2-ethy1-l ,3-hexanediol; bis(2-butoryethyl) ethers, butanol; isopropyl acetate; diethyl ketone, chloroform; carbon tetrachloride; and numerous others having the requisite solubility. Solvents which are soluble in water to the extent of 0.1% by weight or more are readily removed from the skin or hair by rinsing with water to leave the film of cosmetic material. Solvents which are less soluble in water must be volatile, i.e. must evaporate from the skin or hair during a relatively short period of time, e.g. a few seconds up to two minutes, at room temperature to leave a film of water-insoluble cosmetic material.
The amount of solvent used must be enough to dissolve or disperse all of the cosmetic material present; however, large excesses are preferably avoided. When the cosmetic material itself has a very limited solubility in a given solvent or when an extremely thin film is desired, solutions containing as little as 0.1% cosmetic material based on the weight of organic solvent may be used. In general, it is preferred to employ solutions containing 30 to 100% by weight of cosmetic material based on the weight of organic solvent. However, where the cosmetic material is very soluble in the organic solvent such as, for example, the case of mutually miscible liquids, up to 300% by weight of the cosmetic material may be employed based on the weight of the solvent.
The relative proportions of organic solvent and water may also vary over a wide range. It is normally preferred to limit the amount of solvent employed to that which is necessary to dissolve the water-insoluble cosmetic material. However, where desirable for esthetic or other reasons, the organic solvent may be present in larger amounts. In no event should this exceed 20% by weight of the total composition.
Any of the well known water-soluble or dispersible protective colloids may be used in the formulation of the composition of this invention. Among the materials which may be used are the natural or synthetic watersoluble or water-dispersible gums such as guar, karaya, tragacanth, the alginates, Irish moss, and the like; cellulose derivatives including methyl cellulose, hydroxy methyl cellulose, hydroxy ethyl cellulose, sodium carboxymethyl cellulose, and the like; and vinyl polymers such as polyvinyl pyrollidone, polyvinyl alcohol,
-copolymers of vinyl alkyl ethers (in which the alkyl groups have from one to five carbon atoms) with maleic anhydride, water-soluble salts of polyacrylic acid, etc. The protective colloid is present in an amount sufficient to provide a relatively stable dispersion, as is well known in the art, usually from 0.1 to 5.0 percent based on the water, depending on the identity of the particular protective colloid used.
Other conventional ingredients having esthetic, therapeutic or other utilities may be present in the cosmetic compositions in addition to the foregoing. For example, where the film-forming cosmetic material is effective as a binder to skin or hair, there may be added various medicaments such as germicides, anti-inflammatories, etc.; deodorants or anti-perspirants; sunscreen agents; perfumes; coloring dyes or pigments; optical brighteners; etc.
The following specific examples are intended to illustrate more clearly the nature of the present invention without acting as a limitation upon the scope of the patent.
EXAMPLE 1 Parts by Weight Benzyl alcohol 5.0 Ethyl alcohol l.0 Half ethyl ester ofa l:l copolymer of vinylmethyl ether and maleic anhydride 0.5 stearyldimcthyl benzyl ammonium chloride 0.9 Hydroxyethyl cellulose 1.2 Triethanol amine 0.4 Polydimethylsiloxane oil 0.l Perfume 0.5 Water 90.4
In the foregoing composition, the benzyl alcohol, which has only limited solubility in water, serves as a solvent for the cosmetic material (the copolymer, the
quaternary ammonium compound, the siloxane oil, and the perfume), and the hydroxyethyl cellulose acts as the protective colloid. The triethanol amine functions to control the pH of the composition.
All of the ingredients except the hydroxyethyl cellulose, water and perfume are dissolved using agitation with the triethanolamine being added last. A thickened water phase is separately prepared by adding the hydroxyethyl cellulose to the water and heating to S0 C. with agitation. After cooling to 30 C., the first composition is dispersed in the thickened water phase using vigorous stirring for two minutes at 30 C. The composition is then further agitated at a slow roll with no visible vortex until a uniform mixture is obtained. The perfume is then added and the composition agitated for 25 to 30 minutes more. The resulting product is a body imparting hair rinse having a medium viscosity and a pH of about 7.3.
One tablespoon of the composition is worked with the fingers through a head of damp, towel blotted, freshly shampooed hair. After combing to distribute the rinse evenly, the hair is thoroughly rinsed with warm water. Microscopic examination of fibers so treated shows that a semi-continuous polymer film has been deposited. The film provides easy combing in both the wet and dry states and leaves the dried hair with an attractive luster and added body.
EXAMPLE 2 Parts by Weight Amylopectin decanoate Polydimethylsiloxane oil 2-ethyll ,3-hexane diol Diethylene glycol dibutyl ether Carboxypolymethylene (Carbopol 934) Sodium hydroxide Perfume Water In the above composition, the 2-ethyl-l ,3-hexanediol and diethylene glycol dibutyl ether which have only limited solubility in water, serve as solvent for the cosmetic materials amylopectin decanoate, siloxane oil and perfume. The carboxypolymethylene acts as the protective colloid. The sodium hydroxide functions merely to adjust the pH to within the desired range of 6 to 8.
The composition of this example is prepared in a manner analogous to that of Example 1. The resulting product is a water barrier hand cream which is applied by rubbing into the skin followed by a warm water rinse. The resulting film a mixture of amylopectin decanoate and polydimethylsiloxane, gives excellent protection against the effects of aqueous detergent compositions such as anionic dishwashing products. This composition can also be prepared using 6% dibutyl carbitol as the sole organic solvent for the amylopectin decanoate and polymethylsiloxane oil. While the resulting product has barrier properties equal to the mixed solvent example, the emulsion is less creamy.
EXAMPLE 3 The composition of Example 1 is prepared with the addition of another water insoluble cosmetic material,
0.5% of a disperse dye (Latyl Blue RB, Du Pont). Rinse-on deposition of the composition onto a tress of white human hair yields a strong blue color in addition to the body and conditioning benefits described above. The dyed composition can be readily removed by the usual shampoo procedure. Any desired shade can be achieved by the proper choice or blending of organic dyes or inorganic pigments.
EXAMPLE 4 EXAMPLE 5 Parts by Weight Lanolin 2.0 Benzyl alcohol 4.0 Hydroxycthyl cellulose 1.2 Perfume 0.3 Water 92.5
The lanolin and perfume cosmetic materials are dissolved in the benzyl alcohol solvent and the resulting solution dispersed in the aqueous hydroxyethyl cellulose as described in Example 1. Rinse-on deposition onto damp, shampooed hair yields a thin lustrous coating of lanolin oil, evenly distributed throughout the hair.
EXAMPLE 6 Parts by Weight Montan wax (Wax W, Hostachem) 4.0 Benzyl alcohol 4.0 Carboxypolymethylene (Carbopol 934) 1.0 Sodium hydroxide 0.5 Perfume 0.5 Water 90.0
The composition is prepared by dissolving the montan wax and perfume cosmetic materials in benzyl alcohol, then dispersing the solution in water containing carboxypolymethylene protective colloid, the sodium hydroxide being used to adjust the pH to within the desired range of 6 to 8. Rinse-on deposition onto skin or hair yields a thin even wax coating resistant to soap or shampoo removal.
The composition is prepared by dissolving the dextran stearate and perfume cosmetic materials in chloroform as the solvent, then dispersing the solution into water containing guar gum protective colloid. The composition is applied by rubbing it onto the skin and allowing the chloroform and water to evaporate, leaving an evenly deposited film of polymer which is resistant to soap or shampoo removal.
Although specific embodiments of the invention have been described herein, it is not intended to limit the invention solely thereto but to include all of the variations and modifications which suggest themselves to a person skilled in the art.
What is claimed is:
1. An aqueous cosmetic composition adapted to be coated on the skin or hair and to deposit a thin film of water-insoluble cosmetic material comprising an aqueous medium containing from 0.1 to 5%, based on the weight of the water, of a water-soluble or water-dispersible protective colloid, and dispersed therein an organic solvent solution containing from 0.1 to 300%, based on the weight of the solvent, of cosmetic material which is a substantially colorless fat, oil, wax or polymer and which is less soluble in water at room temperature than 0.5% by weight, the maximum amount of said solvent being 20% by weight of the total composition, said solvent being volatile and less soluble in water than 0.1% by weight at room temperature or being soluble in water to an extent from 0.1 to 20% by weight at room temperature.
2. An aqueous composition as claimed in claim 1 in which the solvent is a volatile solvent less soluble than 0.1% by weight in water.
3. An aqueous composition as claimed in claim 1 in which the solvent is soluble in water to the extent of 1 to 10% by weight.
4. An aqueous composition as claimed in claim 3 in which the solvent is benzyl alcohol.
5. An aqueous composition as claimed in claim 3 in which the solvent is 2-ethyl-l ,3-hexanediol.