US3198708A

US3198708A - Antiperspirant-deodorant composition

Info

Publication number: US3198708A
Application number: US35893A
Authority: US
Inventors: Henkin Hyman; Messina Ralph Paul
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1960-06-14
Filing date: 1960-06-14
Publication date: 1965-08-03
Anticipated expiration: 1982-08-03
Also published as: BR6129948D0; DK105826C; DE1467806A1; GB967591A; DK104642C

Description

United States Patent ANTE 'ERSPERANT-EEUBORANT QOWDdITEQh-l Hyman Henlrin, Bayside, Queens, N.Y., and Ralph Paul Messina, Hachensaeir, N.J., assignors to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Fiied June 14, 1960, Ser. No. 35,893

7 Claims. (Cl. 167-90) The present invention relates to an antiperspirantdeodorant composition comprising an aluminum astringent compound, neomycin and a fabric-corrosion inhibitor which does not inactivate said neomycin upon aging at elevated temperatures, as hereinafter described and claimed.

Various antiperspirant compositions are known which contain an aluminum astringent ingredient for retarding or inhibiting the flow of perspiration. Examples of such materials are aluminum sulfate, chloride, sulfamate, chlorhydroxide, and the like.

In general, the aluminum compounds, particularly the salts of strong inorganic acids, such as aluminum chloride and sulfate, have the disadvantage of corrod-ing and/ or discoloring clothing fabric, e.g., the portions of the garment which come in contact with areas of the body to which the aluminum-containing preparation has been applied. The degree of deterioration of the clothing fabric is variable depending upon a number of factors, including the concentration and strength of the aluminum compound, the nature of the other ingredients in the composition and the type of fabric. In general, the corrosive action is particularly noticeable on fabrics containing cellulosic materials such as cotton, rayon and the like.

In order to avoid or decrease this corrosive action upon the fabric, it has been proposed to include in the composition a suitable buffering agent or fabric-corrosion inhibitor. Many types of such inhibitors have been suggested but the agent which is in Widespread commercial use at the present time in such antiperspirant compositions is urea. It is known by publications in the art that urea is a particularly effective agent for reducing fabric damage and has a number of other desirable properties.

In the manufacture of antiperspirant compositions, other ingredients may be added for special efiects depend ing upon the type of composition to be prepared, such as a cream or a liquid. For example, a commercial type of liquid antiperspirant comprises aluminum chlorhydroxide, urea, a surface-active material as a wetting and solubilizing agent, a gum or gum-like material to modify the viscosity, perfume and color in aqueous ethanol.

It has been suggested to add suitable deodorant or antibacterial substances to antiperspirant compositions. More particularly, it has been proposed to incorporate neomycin in an antiperspirant composition containing aluminum chlorhydroxide for the purpose of obtaining improved deodorant properties.

In the course of manufacture, packaging, shipping and aging of the product on the shelf, before and after sale to the consumer, the composition may be subjected to extreme variations in temperature conditions. it is considered that the antiperspirant composition should be effective, not only when formulated and at ambient temperature, but also after being subjected to adverse temperature conditions.

In the course of our research, it was found that samples of the liquid composition described above containing added neomycin exhibited substantially reduced levels of neomycin activity after storage at elevated temperatures. As this adverse efiect was not in accord with the known stability of neomycin per so under such storage conditions, this discovery represents a problem in the formulaice tion of such antipaspirant-deodorant compositions. The inactivation of neomycin can be considered as involving a number of possible factors, such as a degradation of the neomycin due to any of the other ingredients in the composition, the possible formation of incompatible decomposition products, a physical complex of the neomycin formed in the composition, or even the method of examination.

In accordance with the present invention, it has now been found that there may be prepared antiperspirantdeodorant compositions containing neomycin, an aluminum astringent compound and a fabric-corrosion inhibitor which are stable and effective, even after aging at elevated temperatures, without adverse effect upon the neomycin activity.

More particularly, such compositions comprise the aluminum astringent, such as aluminum chlorhydroxide, neomyoin, and an organic fabric-corrosion inhibitor which does not decompose at elevated temperatures in an aqueous medium with release of a cyanate radical normally tending to inactivate the neomycin. A preferred embodiment relates to a liquid composition containing effective amounts within the ranges of about 8 to 30% of aluminum chlorhydroxide, 0.1 to 0.5% of neomycin, and 0.1 to 5% of an amino carboxylic acid such as glycine, said composition maintaining a high level of neomycin activity after aging at elevated temperatures of the order of F. and exhibiting a high level of antibacterial, antiperspirant and deodorant activity. Various other embodiments of the present invention will be apparent in the following description.

Neomycin is an antibiotic material which is known in the art and is described more fully in the book entitled Neomycin, Its Nature and Practical Application, by S. A. Waksrnan, Editor, (1958), published for the Institute of Microbiology, Rutgers University, by the Williams & Wilkins Company, Baltimore, Maryland. The term includes the mixtures of several closely related neomycins known as Neornyoin B and Neomycin C. In addition to the free base, the term is inclusive herein of the salts of such mixtures and the individual components thereof. Various inorganic and organic salts have been described in the art. It is preferred to use the salts of the mineral acids such as the ueomyoin sulfate and hydrochloride. Other salts such as the fatty acid salts, e.g., palrnitate, are less water-soluble and may be used in appropriate liquid solvent mediums. The purity of the material is not considered critical and either the commercial, technical or the US. Pharmaceutical (USP) grades of neomycin sul ate, for example, may be used appropriatay. The amount of neomycin (calculated as neoinycin base) can vary as desired, but is an effective amount from about 0.05 to about 2%, usually 0.1 to 0.5 by weight of the composition.

The aluminum compound which is preferred in aluminum chlorhydroxide (which has also been referred to in the art as aluminum chlorhydnoxide complex and basic aluminum chloride). In general, the commercial material has an approximate atomic ratio of aluminum to chlorine of 2:1 (e.g., 2.1 to 1.9:1) and an empirical formula Al (Oi-i) Cl in aqueous solution. The term aluminum chlorhydroxide includes herein other equivalent aluminum chlorhydroxy complexes and their salts. Such materials are known in the art also, e.g., aluminum chlorhydroxide ethylate complex, odium aluminum chlorhydroxy lactate, and the like. The problem of inactivation of the neomycin by materials such as urea, as hereinafter more fully described, is most acute in compositions containing aluminum chlorhydroxide as one of the active ingredients.

Satisfactory compositions may be prepared in accord ance with the present invention containing other antiperspirant ingredients in suitable amounts in partial or full substitution of the alurnnum chlorhydroxide. Examples of known aluminum astringent ingredients from which suitable selection may be made include aluminum chloride, aluminum sulfate, aluminum sulfamate, aluminum phenolsulfonate, and the like.

The proportion of the aluminum compound in the final composition is variable, but in general, should be an effective amount selected from the range of 5 to 40% and preferably from about 8 to 30% by weight of the composition, said amounts being on an anhydrous basis. It will be understood that the aluminum compound will be proportioned so as to be dissolved in the liquid or solvent medium of the composition during manufacture.

The preparation of a stable and effective composition required extensive research in view of the inactivation of the neomycin in said liquid composition containing aluminum chlorhydrate, urea, and the other ingredients in aqueous ethanol under the conditions described. There was not significant inactivation upon aging at ambient temperatures but only upon aging at elevated temperatures. Among the specific factors requiring consideration were the concentration of materials such as urea, the effect of pH changes upon aging, the type and effect of possible decomposition products, the possibility of remedial measures therefor, etc. It was found ultimately that the development which appeared to inactivate the neomycin resulted from the presence of the urea. While ammonia and carbon dioxide are normally the final decomposition products of urea upon heating in water, an intermediate product is the cyanate radical which was confirmed as the casual factor in the inactivation.

Accordingly, the selected fabric-corrosion inhibitor should not decompose or hydrolyze in an aqueous medium with the release of cyanate. There are a number of materials known in the art to inhibit a corrosive or discoloration eifect on fabrics. Various examples thereof can be found in US. Patents No. 2,586,287 and No. 2,586,288, issued February 19, 1952, to Apperson and Richardson. These patents describe various suitable buffering materials which would not release cyanate including neutral amides, e.g., acetamide, amino carboxylic acids, e.g., glycine and alanine, salts of nonhydroxy saturated carboxylic acids and ammonia bases, e.g., ammonium acetate, etc. An effective amount of the inhibitor should be employed and it is usually a minor proportion, such. as within the range of about 0.1 to 5%, preferably 0.1 to 2%, by weight of the composition.

The use of amino carboxylic acids such a glycine represents a feature of the present invention since it has been found that the maximum combination of stability, anti-bacterial activity and fabric protection of the final composition is obtained with the use of this material which is markedly superior to the use of urea under equivalent conditions. Furthermore, the composition does not exhibit the gelation tendencies which characterize urea-containing compositions at elevated temperatures, and there is also an improvement in the light stability of the glycine-containing products. Other water-soluble aliphatic amino acids having an equal number of amino and carboxylic groups such as alphaand beta-alanine may be used also.

In compositions containing an aqueous medium, the solvent can be water or an aqueous alcoholic solution. It may contain varying amounts of a water-soluble or miscible saturated lower aliphatic alcohol such as ethanol, isopropanol, propylene glycol or the like, if desired. In a liquid product, it is preferred to employ a minor proportion of an alcohol, preferably ethanol, in an amount from about 5 to 30% by weight of the composition to aid in fast drying of the product after application and in the solubilization of certain materials such as Waterinsoluble perfume and the like. It will be understood that the water and alcohol and any other ingredients in the solvent medium should be proportioned so as to form a homogeneous or uniform solvent medium effective to disproduct.

or by use of fingers or an instrument.

solve or solubilize the aluminum material, neomycin, the glycine or the like, the gum if employed, etc.

The contrasting effect on neomycin activity in said antiperspirant compositions by urea which produces cyanate upon hydrolysis and glycine which does not release such material may be illustrated by suitable tests wherein the compositions were subjected to accelerated aging tests at elevated temperatures and then analyzed for the activity of the neomycin. Two compositions, A and B, were prepared corresponding to the formulation of Example I described hereinafter which contained 12.5% aluminum chlorhydroxide and 0.175% neomycin except that Composition A contained 2% urea and Composition B contained 1% glycine as the particular fabric-corrosion inhibitor in each case. The compositions were heated at the reiluxin temperature (about 89 C.) for various time intervals and then each was analyzed for neomycin activity. In the table below, the percent of the original neomycin activity is given for each formulation as determined after the stated time treatment at the elevated temperature:

a marked detrimental effect on the activity of the neomycin in the Composition A whereas the use of glycine in Composition B did not adversely affect the neomycin activity.

Similarly, after aging the same compositions for a period of 3 months at 120 F., the Composition A containing the urea retained only 30% of its original activity whereas the Composition B with glycine did not suifer any loss in activity.

In general, the mixture containing the aluminum compound, neomycin and inhibitor in the aqueous medium may be prepared in any suitable form. It is preferred to utilize it in the form of a liquid (including clear solutions and emulsion types). Such liquid may be adapted for various methods of application. It may be dispensed or applied by means of a roll-on applicator, by spraying from a squeeze bottle, by use of propellant gas from a valved container commonly known as an aerosol type The viscosity of the liquid will be adjusted so as to achieve the desired flow for the particular means of dispensation.

Thus, it is desirable in certain instances to incorporate a gum or gum-like material in order to have a more viscous flow. For example, liquid compositions designed for application by use of a roll-on apparatus must flow from a reservoir to a passage between the ball and the adjacent Wall or neck of the container. The viscosity of the liquid should be controlled taking into consideration the clearance of the passage so that the product flows in a smooth manner without dripping or gelling of the Any suitable gum may be employed, particularly a cellulosic compound such as a methyl ether of cellulose. In general, the amount of thickening agent used, depending upon its thickening power, is within the range of about 0.1 to 2% by weight.

It is a further feature of the present invention to ern ploy an hydroxypropyl methyl cellulose, particularly one having a methoxy content of about 25% and an hydroxypropoxy content of about 5%. A preferred material has a methoxy content of 24.625.4%, an hydroxypropoxy s eaves content of 4.85.4% and a viscosity of about 1200 to 1800 centipoises in 2% solution in water at 20 C. It has been found that, using such gum material, the liquid product is more stable physically at elevated temperatures without undue clouding or separation.

Any suitable surface-active agent may be incorporated in the product also which is compatible in said liquid. It is desirable to include a water-soluble non-ionic surface-active agent in the composition. Such material possesses dispersing or solubiiizing properties in the solvent medium, e.g., solubilization of insoluble perfumes, and contributes increased wetting characteristics. It is employed in a minor amount in the solution which is usually within the range of about A to 2% by weight of the composition.

The preferred surface-active agents contain usually a long-chain aliphatic hydrophobic organic group, e.g., having at least about 5 and usually about 8 to 30 carbon atoms, condensed with an alkylene oxide of about 2-4 carbons in an amount sufiicient to render the product water-soluble, and usually within the range of about 5 to 100 alkylene oxide groups. Suitable examples are polyethyleneoxide ethers of an alkyl phenol or a higher aliphatic alcohol. The alkyl phenol ethers usually have about 6 to carbons in the alkyl group and about 5 to moles of ethylene oxide, specific examples of which are Igepal CO-630 and 710. The polyethylene oxide condensates, preferably having about 6 to moles, with a fatty alcohol of 8 to 22 carbons such as lauryl, tridecyl, myristyl, cetyl and stearyl alcohols, may be used also. A typical product is a fatty alcohol of 12 to 14 carbons condensed with about 10 moles of ethylene oxide.

As indicated, various adjuvant materials may be incorporated in the compositions in suitable amounts. Thus, the product will ordinarily contain perfume and coloring material which should be compatible therewith. Minor amounts of materials considered as having an emollient effect, such as glycerine, allantoin, and lanolin derivatives such as a water-soluble acetylated ethoxylated lanolin derivative, may be incorporated therein.

There may be included a suitable ultra-violet absorber in the product, if desired, to inhibit fading of the color of the composition in sunlight. Any suitable ultra-violet absorber compatible and soluble in the liquid medium may be employed. In general, they are substantially invisible when applied to human tissue. It is preferred to employ ultra-violet absorbers having a 2-hydroxy benzophenone group or nucleus, and particularly 2,2,4,4-tetrahydroxy benzophenone.

Other materials which may be added include preservative, additional anti-bacterial materials, opacifying agents such as stearic acid or the like in compatible amounts to form an opaque liquid, silicone fluids, etc.

The liquid composition may be admixed with a propellant material and dispensed as an aerosol. Any suitable normally gaseous substance may be employed in known manner such as the liquefied normally gaseous low molecular weight aliphatic hydrocarbons, e.g., mixture of propane and isobutane, and halogenated hydrocarbon propellants lrnown in the art as the Genetrons and Freons which dispense the product in the form of a mist or spray. Other inert propellant materials which dispense the product as a viscous liquid from a valved container rather than as a spray may be employed also, such as nitrogen or the like.

In the manufacture of a cream, suitable fatty material and an emulsifying agent will be combined with the aluminum chlorohydroxide neomycin and fabric-corrosion inhibitor in water to form an aqueous phase and an oily or fatty phase which are combined in the form of a cream. Suitable fatty and emulsifying materials may be selected from those disclosed in said US. Patents Nos. 2,586,287 and 2,586,288.

The following examples are further illustrative of the nature of the present invention and it is to be under- 6 stood that the invention is not limited thereto. All amounts are by weight unless otherwise indicated.

Examples I-V Ingredients I II III IV V Aluminum clilorhydroxide 12. 5 22 22 24 24 Aluminum chloride hexahydrate 1.0 1. 5 Neomycin 0. 175 0. 175 0. 175 0. 175 0. 115 Glycine 0.25 0.5 1. 5 0.5 1.5 Ethyl alcohoL. 17. 5 17. 5 17. 5 l7. 5 l7. 5 Surface-active age 1. 0 1. 0 1. 0 1. 0 1. 0 Gum 0. 7 0. 65 0. 65 0. 65 0. 65 Allantoinun 0. l 0. 1 0. 1 0. 1 0. 1 Glycerine 3.0 3. 0 3. 0 3.0 3.0 Water Bal. Bal. Bal. Bal. Bel.

with minor amounts of perfume, color, water-soluble lanolin derivative and ultra-violet absorber.

The compositions are prepared by blending the ethyl alcohol (SD. perfume and surface-active agent (Igepal CO-630), warming the mixture, and slowly adding the gum (hydroxypropyl methylcellulose) with stirring for a sufiicient time to permit swelling of the gum and form a homogeneous solution. The major part of the water is then added and the remaining ingredients are added slowly in any desired order to the warmed solution with stirring. The 0.175% neomycin is calculated on the amount of base present and is a technical grade active) of neomycin sulfate which is added in the form of a powder with stirring. The amount of aluminum chlorhydroxide is on a solids basis and it is added in the form of an approximate 50% aqueous solution to form a clear homogeneous liquid. The products of Example I, II and IV have a pH of about 4.2 and the products of Examples III and V containing a minor proportion of aluminum chloride have a pH of about 3.5. These liquid products are particularly suitable for use in a roll-on applicator.

These compositions have been found to be highly effective in the reduction of perspiration and axillary odor, and for anti-bacterial activity. The use of these products results in considerable reduction in axillary odor with the effects being noticeable for several days after use. The testing of representative portions of the bacteria flora found in the axillary region shows that the bacterial count was low for several days after use also.

All of the products are stable upon aging at ambient temperatures and under cold temperature conditions, e.g., 40 F., and under elevated temperatures, e.g., F. Examination of samples after such aging disclosed that there was no decrease in the activity of the neomycin also. The products proved to be essentially non-corrosive t0 fabrics with those having the lesser amounts of aluminum material showing optimum effects in fabric corrosion tests. 7

Example VI A typical formulation for a cream is:

Ingredients Percent Aluminum chlorhydroxide l8 Glyceryl monostearate 11 N (lauroyl colamino formyl methyl) pyridinium chloride 1 Glycine 2.5 Neomycin in form of sulfate salt 0.175

with the balance being primarily water, and small amounts of perfume, emollient materials, preservative, etc.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted for various ingredients without departing from the principles and true spirit of the invention.

7 Having thus described the invention, What is claimed is: 1. A liquid antiperspirant-deodorant composition stable at a temperature of from about 120 F. to about 136 F.

.comprising an aluminum astringent compound, 0.1 to

0.5% by weight of neomycin sulfate, 0.1 to 2% by weight of glycine, 0.1 to 5% by weight of a water-soluble noning 5 to 40% by Weight of an aluminum astringent compound, 0.05 to 2% by weight of neomycin in the form of its water-soluble inorganic salt, and 0.1 to 5% by weight of a fabric corrosion inhibitor selected from the class consisting of glycine and alanine and which does not decompose upon aging in an aqueous medium at elevated temperature with the release of cyanate material normally tending to inactivate neomycin, and from about 0.1 to about 2% by weight of hydroxypropyl methyl cellulose, said ingredients being dissolved in an aqueous medium.

3. An antiperspirant-deodorant composition comprising 8 to 30% by weight of aluminum chlorhydroxide, 0.1 to 0.5% by weight of neomycin, and 0.1 to 5% by weight of a fabric corrosion inhibitor selected from the class consisting of glycine and alanine and which does not decompose upon aging in an aqueous medium at elevated temperature with the release of cyanate material normally tending to inactivate neomycin, and from about 0.1 to about 2% by weight of hydroxypropyl methyl cellulose, said ingredients being dissolved in an aqueous medium.

4. A liquid antiperspirant-deodorant composition which is particularly suitable for use in a roll-on applicator,

comprising 8 to 30% by weight of aluminum chlorhydroxide, 0.1 to 0.5 by weight of neomycin in the form of its sulfate salt, 0.1 to 2% by Weight of glycine, 0.1 to 5% -by weight of a water-soluble non-ionic surfaceactive agent and 0.1 to 2% by weight of hydroxypropyl methyl cellulose in an aqueous alcoholic medium containing 5 to 30% by weight of ethanol, said cellulose having a methoxy content of 24.6-25.4%, a hydroxypropoxy content of 4.85.4% and a viscosity of about 1200 to about 1800 centipoises in 2% solution in water at 20 C.

5. An antiperspirant-deodorant composition in the form of a liquid comprising 8 to 30% by weight of aluminum chlorhydroxide, 0.05 to 2% by weight of neomycin, 0.1 to 5% by weight of glycine and from about 0.1 to 2% by weight of hydroXypropyl methyl cellulose in an aqueous solvent medium.

6. A liquid antiperspirant-deodorant composition comprising 8 to 30% by weight of aluminum chlorhydroxide, 0.1 to 0.5% by weight of neomycin base in the form of neomycin sulfate, about 0.1 to 5% by weight of glycine and from about 0.1 to 2% by weight of hydroxypropyl methyl cellulose in an aqueous alcoholic solvent medium containing 5 to 30% by weight of a water-soluble lower aliphatic saturated alcohol.

7. A liquid antiperspirant-deodorant composition which is particularly suitable for use in a roll-on applicator comprising 8 to 30% by weight of aluminum chlorhydroxide, 0.1 to 0.5% by weight of neomycin in the form of its sulfate salt, 0.1 to 2% by Weight of glycine, 0.1 to 5% by weight of a water-soluble non-ionic surface-active agent and 0.1 to 2% by weight of hydroxypropyl methyl cellulose in an aqueous alcoholic medium containing 5 to 30% by weight of ethanol.

References Cited by the Examiner UNITED STATES PATENTS 2,814,585 11/57 Daley 1679O 2,854,382 9/58 Grad l6790 2,955,983 10/60 Messina 16790 3,018,223 1/62 Siegal 167-90 OTHER REFERENCES Chlorhydrol, Reheis Co., Berkeley Heights, N.J., 1951, pp. 6-8 and 13.

Dale: J.A.Ph.A., Prac. Pharm. Ed, 18:7, July 1957, pp. 421-425.

Klarmann: Drug and Cos. Ind., 81:2, August 1957, pp.

JULIAN S. LEVITT, Primary Examiner.

MORRIS O. WOLK, FRANK CACCIAPAGLIA, JR.,

LEWIS GOTTS, Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,198,708 August 3, 1965 Hyman Henkin et al.

aid Letters Patent should read as corrected below.

Column 2, line 55, for "in" read is column 3, line 19, for "not" read ho Signed and sealed this 17th day of May 1966.

(SEAL) Attest:

ERNEST w. SWIDER meetin Officer EDWARD J. BRENNER Commissioner of Patents

Claims

1. A LIQUID ANTIPERSPIRANT-DEODORANT COMPOSITION STABLE AT A TEMPERATURE OF FROM ABOUT 120*F. TO ABOUT 136*F. COMPRISING AN ALUMINUM ASTRINGENT COMPOUND, 0.1 TO 2% BY WEIGHT OF GLYCINE, 0.1 TO 5% BY WEIGHT OF A WATER-SOLUBLE NONIONIC SURFACE-ACTIVE AGENT AND 0.1 TO 2% BY WEIGHT OF HYDROXYPROPYL METHYL CELLULOSE IN AN AQUEOUS ALCOHOLIC MEDIUM CONTAINING 5 TO 30% BY WEIGHT OF ETHANOL, SAID CELLULOSE HAVING A METHOXY CONTENT OF 24.6-25.4%, A HYDROXYPROPOXY CONTENT OF 4.8-5.4% AND A VISCOSITY OF ABOUT 1200 TO ABOUT 1800 CENTIPOISES IN 2% SOLUTION IN WATER AT 20%C.