US3355388A - Cleansing compositions adapted to inhibit the formation of body odor - Google Patents

Description

United States Patent Office 3,355,388 Patented Nov. 28, 1967 3,355,388 CLEANSING (:(BMPOSHTIONS ADAPTED T 1N- HIBIT THE FORMATION OF BODY ODOR Kenneth S. Karsten, Westport, Conn, assignor to R. T.

Vanderbiit ('10., inc, New York, N.Y., a corporation of New York No Drawing. Filed Apr. 7, 1967, er. No. 629,115

5 Claims. (Cl. 252-107) ABSTRACT (BF THE DISCLOSURE This invention relates to a cleansing composition for inhibiting the formation of body odors. It comprises as the detergent base one or more water soluble toilet soaps, anionic detergents or nonionic detergents, and, as odorinhibiting constituents, an effective amount, about 1% to 4%, of a skin-substantive antioxidant, optionally used together with about 0.1% to about 3% of a skin-substantive bacteriostat. Such antioxidants include styrenated phenols, tri-alkylated phenyl phosphites, 2,2'-ditertiary butyl-4,4'- isopropylidene diphenol (para intermediate-alkyl phenyl) phosphites, and 2,2-methylenebis [6-(1-methylcyclohexyl)-para-cresol]. Such bacteriostats include bithionol, metal salts of bithionol, hexachlorophene, the zinc salt of 1-hydroxy-Z-pyridinethione, tribromosalicylanilide, and trichlorocarbanilide.

This application is a continuation-in-part of currently copending application Serial No. 462,728 filed June 9, 1965, now abandoned, which in turn was copending with and is a continuation-in-part of application Serial No. 321,799, filed November 6, 1963, now abandoned.

The elimination of human body odor has long been an objective in the field of proprietary medicine. The prevailing theories on the causes of human body odor are based on the underlying assumption that body odor is caused by the secretion of perspiration. Thus, if perspiration is minimized, the formation of odors is inhibited. Accordingly, there are currently available deodorants which, in effect, are antiperspirants. These products usually embody aluminum compounds and are generally applied to the axillary regions of the body. The aluminum compounds act as astringents and thereby reduce perspiration in the regions where applied.

A more sophisticated approach to the problem has taken the form of embodying bacteriostats in water soluble soaps and detergent compositions intended for use in cleansing the body. Skin-substantive bacteriostats are chosen so that the bacteriostat remains on the surface of the body for a period of time subsequent to the use of soap or detergent. This type of product has been developed because of the theory that body odor is not due simply to the presence of the perspiration, but rather that body odor is caused by bacteria on the skin which break down the perspiration and natural body oils into odoriferous products. Thus, the presence of a bacteriostat on the skin is expected to reduce the multiplication and growth of bacteria and thereby inhibit the undesirable action of the bacteria on the perspiration. That this theory is at least partially correct is proven by the success in reducing body odors by the use of a soap or detergent composition embodying a skin-substantive bacteriostat. However, that such theory does not entirely explain the phenomenon of body odor formation is indicated by the fact that even a drastic (99%) reduction in skin bacterial population as a result of using a bacteriostat-containing soap still does not eliminate the subsequent formation of odor. Therefore, improved and alternative cleansing compositions are still desirable.

Accordingly, it is an object of this invention to provide an improved composition for inhibiting body odor.

It is a further object of this invention to provide a cleansing composition for inhibiting body odor which embodies an antioxidant.

Another object of the present invention is to provide a cleansing composition for inhibiting body odor which embodies a combination of an antioxidant and a bacteriostat.

Briefly stated, one embodiment of the present invention is a composition comprising a water soluble soap and/or an anionic or nonionic detergent, and a skin-substantive antioxidant in an amount of at least about 1% by weight and sufiicient to inhibit the formation of body odor following the cleansing of the body with such composition.

Another embodiment of the present invention is a composition comp-rising a water soluble soap and/or an anionic or nonionic detergent, and a combination of an active proportion of a skin-substantive antioxidant and an active proportion of a skin-substantive bacteriostat, wherein the antioxidant and bacteriostat retain their activities and skin-substantivities in the composition.

It has been discovered that the presence of a skinsubstantive antioxidant in such composition provides body odor inhibition when the composition is used to cleanse the human body. As indicated above, heretofore the prevailing theory of body odor prevention was that odor could be prevented by eliminating or minimizing the presence of bacteria on the surface of the skin. It was believed that these bacteria were responsible for convetting body perspiration and body oils into odoriferous products.

The unexpected property of skin-substantive antioxidants in reducing body odor does not appear to be the result of anti-bacterial action. Instead, it is theorized that the antioxidant functions to prevent oxidation of the perspiration and body oils into odoriferous products. Thus, it would appear that an entirely new approach is provided for eliminating body odor.

The unique property of the skin-substantive antioxidants contemplated by this invention suggests their use in combinations with skin-substantive bacteriostats which, when used alone, do not provide adequate deodorant action. Thus, a two-pronged eifect is obtained by the use of such combinations-the bacteriostat serves to inhibit multiplication of bacteria and thereby aids in preventing odor formation by minimizing or eliminating the odor causing element, and the skin-substantive antioxidant serves to prevent body odor by preventing oxidative breakdown of perspiration and natural body oils into odoriferous materials.

The eifectiveness of such compositions comprising an antioxidant alone or in' combination with a bacteriostat to inhibit the formation of body odors following the cleansing of the body with such compositions has been demonstrated in clinical tests. Such clinical tests were conducted using bars of Ivory brand (Reg. T.M., Procter & Gamble Co.) soap, which is a neutral white, high grade toilet soap comprising a mixture of 80% sodium soap and 20% potassium soap derived from a blend of tallow and 30% coconut oil-glyceride blend (made in ac cordanoe with US. Patent No. 2,295,594). The soap bars used in such tests had incorporated therein additives of the character and amounts set forth below:

Table I Soap Formulation Antioxidant Bacteriostat Code None None. Styrenated phenols 2%. Do. Styrenated phenols 4% Do. None Sodium bithionolate 2%. E Styrenated phenols 4% D0.

The mixture of styrenated phenols referred to in Table I is further characterized hereinafter in connection with the structural formula for such phenols.

The test soaps were evaluated in pairs, each subject person using one test soap on one axillary area and a second test soap on the other axillary area. This method of testing eliminates differences in exposure to contamination, diet, illness or exercise which might be encountered when soaps are tested on two different individuals. The scores of the nine or more persons in each test were averaged for reporting.

The clinical testing was conducted as follows. The subjects were given soap formulation A, the control soap, and were instructed to use this soap for all bathing for a preliminary period of approximately five days.

Next, each subject underwent a first supervised wash with soap formulation A, the control soap. In such supervised wash, a wet six-inch square of new white terry cloth was rubbed on a bar of the control soap for about fifteen seconds. This cloth was then used to scrub one axillary area for a period of about one minute. A fresh terry cloth squ'are was then used to wipe away the lather and the area was dried with a disposable towel. The procedure was repeated for the other axillary area. Such supervised washings were under the direction of a skilled technician who had the additional responsibility of assuring that the proper soap formulation was used.

Twenty-four hours following the supervised wash as described above, each axilla of each subject was evaluated for axillary odor and the average of the scores in each group of subjects was recorded. No intervening washes were permitted during this twenty-four hour period. The odor was evaluated by two judges using a rating scale ranging from zero, indicating no detectable body odor, up to ten indicating a very strong and disagreeable body odor. This evaluation technique was used throughout the clinical tests. The odor rating of the two axillae of each subject was separately noted so that subsequent comparison test ratings could be weighted to compensate for any differences between the axillae of a subject.

For the next three days, each of the subjects bathed with soap formulation A, the control soap.

On the next two succeeding days, the fifth and sixth days following the initial supervised wash, there were supervised washes at about 7 a.m. and 4 p.m. During these two days of supervised washes, one soap formulation was used for one axilla of a subject and a second soap formulation was used for the other axilla of the same subject.

On the seventh day, there was a supervised wash at about 7 am, with the axillae of each subject being bathed with the soap formulations in the manner utilized on the fifth and sixth days. At 4 p.m. on the seventh day, nine hours after the supervised wash, the subject was evaluated for odor by the judges, utilizing the rating scale set forth above. Each axillary area was separately rated and the rating noted. Following the above odor rating, there was a final supervised wash again using the same soap formulations as used previously.

A final odor evaluation was made on the eighth day, about twenty-four hours after the final supervised wash.

The subjects were instructed not to smoke or eat for at least one hour prior to those supervised washes which were followed immediately by an odor evaluation. The subjects were instructed not to use any shaving lotion or the like on such days. During the entire period of the tests, the subjects were instructed to use no anti-perspirants or deodorants. Other than these restrictions, the subjects were permitted their normal daily activity and personal hygiene.

The odor evaluations were analyzed as follows: First, arithmetic averages were computed based on the numerical evaluations of the judges scores on each of the nine or more subjects using the soaps referred to in Table I. Then the differentials were computed between the initial odor evaluation and the evaluations on the seventh day, nine hours after a supervised wash, and on the eighth day, 24 hours after the final supervised wash. The standard deviation (normally represented by sigma, a) was determined statistically to be 0.06. The aforesaid differentials were then divided by 2 sigma and the resulting quotients tabulated in Table II. In such table, any positive number represents a reduction in odor, and any number of unity or greater indicates a statistically significant result at the confidence level.

Analyzing the data in Table II, it can be seen that the use of 2% styrenated phenols in formulation B results in an odor improvement over that provided by the control soap, formulation A. However, increasing the amount of styrenated phenols to 4% in soap formulation C resulted in a decrease in deodorant effectiveness, as shown by a comparison of formulations A and C. It is believed that this adverse result is caused by the residual odor of the antioxidant itself. Of course, it is to be appreciated that the odor of the antioxidant must be taken into account in odor evaluation ratings since the ultimate objective is to provide complete absence of any odor.

In the comparison of formulations A and D, the expected deodorant advantage of the use of the skinsubstantive sodium bithionolate is evidenced.

In the list of the camparisons involving the control formulation as one of the soaps, it can be seen that the combination of antioxidant and bacteriostat of formulation E is a substantial improvement over the control, in the evaluation conducted after the sixth day wash.

The last three comparisons in Table II involve the rating of one test soap formulation as against another. In the comparison of formulations C and D, formulation D is indicated to be superior. This may be attributed to the odor of the antioxidant itself, as was evident from a comparison of soap formulations A and C.

The comparison of formulations D and E indicate that there is an advantage in the addition of an antioxidant to the bacteriostat.

Likewise, the advantage shown by formulation E over that of formulation D also shows that the combination of an antioxidant with a bacteriostat is superior to the antioxidant alone.

In view of the improvement of 2% of the antioxidant formulation B over that of the 4% antioxidant formulation C, it is evident that a combination of 2% styrenated phenols and 2% sodium bithionolate would represent a substantial improvement in deodorant properties over any of the other combinations tested.

In another test, in which a soap formulation containing 1% styrenated phenols was compared with control soap formulation A, it was determined that there was no odor improvement. A level of 1% of this antioxidant was insufficient to improve odor.

Anionic or nonionic detergents may be substituted effectively for part or all of the toilet soap used in the foregoing description.

The following test is suitable for use in determining the skin-substantivity.

A button of animal hide is soaked for five minutes in an 8% aqueous solution of a neutral high grade white toilet soap or of an anionic or nonionic detergent, having incorporated therein 1% by weight of the soap or detergent of the constituent being tested, e.g., a bacteriostat and/or an antioxidant. The hide button is then rinsed four times with distilled water.

A tryptone glucose yeast agar is seeded with an 18- hour nutrient broth culture of a bacterium such as Escherichia coli, Staphylococcus aureus, Bacillus subtilis or Salmonella typhosa at the rate of 20 milliliters of the broth culture per liter of agar. The agar solution comprises per liter, grams of tryptone, 2.5 grams of yeast extract, 1 gram of glucose, 15 grams of agar and sufficient water to make one liter. A sufficient amount of the indicator 2,3,5-triphenyl ZH-tetrazolium is then added to achieve a 0.1% concentration of the latter in the seeded culture. Thereafter, the seeded agar is added to a sterile Petri dish and allowed to harden.

The button of animal hide is then placed on the hardened agar and sufiicient of the above described seeded agar is added to completely cover the hide button. The Petri dish containing the hide button is then incubated at about 37 C. for about 18 hours. At this time, the culture is observed to determine the presence or absence of the formation of color in the media surrounding the button. The absence of color indicates that the antioxidant was skin-substantive to the hide button.

The foregoing test depends on the sensitivity of the indicator in the presence of oxygen released by certain growing bacteria. A red color exhibited by the indicator indicates the presence of such oxygen. If any measurable antioxidant is present in the vicinity of the hide button, it prevents absorption by the indicator of the small amount of oxygen released by the bacteria and in this area there will be no color formation.

Using the foregoing test, it has been determined that the styrenated phenols referred to herein were skin-substantive in neutral white toilet soap and in anionic and nonionic detergents, such as sodium lauryl sulfate, doclecyl-benzene sodium sulfonate and octyl phenoxy polyethoxy ethanol. In addition, other phenol-type antioxidants found to be skin-substantive in such soaps and detergent include 2,2'-ditertiary-butyl-4,4' isopropylidene diphenol (para-nonyl or octyl phenyl) phosphites, trialkylated phenyl phosphites, and 2,2'-methylenebis [6-(1- methylcyclohexyl -para-cresol] In addition to the sodium bithionolate utilized in the odor evaluating tests set forth above, other skinsubstantive bacteriostats are suitable for use in the present invention in combination with a skin-substantive antioxidant. Such skin-substantive bacteriostats include, for example, bithionol, other metal salts of bithionol, such as zinc bithionolate, hexachlorophene, the Zinc salt of lhydroxy-2-pyridinethione, tribomosalicylanilide and trichlorocarbanilide.

The amount of the bacteriostats used in the compositions of the present invention may be from about by weight to 3% and preferably from about /2% to 2%. The lower limit in this respect is set by the fact that at least this minimum is necessary in achieving antibacterial action. The upper limit is not critical, although effectiveness is not proportionately increased with increased concentrations above about 3%.

As indicated by the test results set forth above, it is seen that an amount greater than about 1% by Weight of antioxidant is necessary in compositions of the present invention. According to the data, concentrations of about 2% are preferred. It can be seen that 4% represents a practical upper limit in view of the problem encountered of the undesirable odor of the antioxidant itself. When used in combination, it is desirable to use about 2% of antioxidant and 2% of bacteriostat.

The styrenated phenols referred to in Table I and utilized in the odor evaluation tests set forth above was a 6 mixture of mono-, di-, and tri-styrenated phenols, the formula for which is set forth below:

acs

where n is an integer from 1 to 3, inclusive. Such a mixture is sold as AgeRite Spar (Reg. T.M., the B. F. Goodrich Company) and comprises about 15% mono-,

55% di-, and 30 tri-styrenated phenols. Kehes U.S..

Patent No. 2,670,340 describes at col. 1, lines 45 et seq.

a process of making such mixtures of styrenated phenols.

The tri-[(intermediate-alkyl) phenyl] phosphites referred to herein have the general structure:

wherein R is an intermediate-length alkyl radical, e.g., heptyl, octyl, nonyl or decyl. Trinonylated phenyl phosphites are preferred. Mixtures of tri-alkylated phenyl phosphites may be used.

The 2,2'-ditertiary butyl-4,4-isopropylidene diphenol (para intermediate-alkyl phenyl) phosphites as referred to herein have the structure:

' x and y will be fractional numbers intermediate between 1 and 2. Illustrative examples of such phosphites include (2,2' di tertiary-butyl-4,4'-isopropylidenedjphenol)bis (p-octylphenyl) phosphite, bis(2,2-di-tertiary-butyl-4,4- isopropylidenediphenol) (p-octylphenyl) phosphite and their mixtures, and (2,2'-di-tertiary-butyl-4,4-isopropylidenediphenol) bis (p-nonylphenyl phosphite, bis (2,2-ditertiary butyl 4,4 isopropylidenediphenol) (p-nonylphenyl) phosphite and their mixtures.

The structure of 2,2-methylenebis [6-(l-methylcyclohexyl)-para-cresol] is:

OH HO CH3! i CH3 y co l CH3 CH3 Not all antioxidants are skin-substantive. For instance, ortho-tolyl biguanide (Sopanox, Reg. T.M., Monsanto Chemical Co.) is not. This compound is believed to be the most widely used antioxidant to prevent rancidity in toilet soaps. When so used, it comprises 0.04 to 0.1% of the soap. Also, 2,6-ditertiary butyl-6-methyl phenol is not skin-substantive. Such phenol is referred to in Taylors U.S. Patent No. 2,977,316.

As used herein, soap refers to water-soluble alkali metal, ammonium, and amine soaps suitable for cleansing the human body, such as the sodium, potassium, ammonium, or triethanolamine salts of the higher fatty acids derived from naturally occurring plant or animal fats or oils, such as coconut oil, tallow, palm oil, lard, soybean oil, babassu oil, castor oil, whale or fish oils and the like, and mixtures thereof.

The term detengent refers to anionic and nonionic detergents suitable for cleansing the body. Anionic detergents are generally derived from fatty matters or their derivatives by sulfonation. Illustrative examples include the sodium salts of sulfonation products of higher alcohols, e.g. sodium lauryl sulfate; sodium salts of alkyl aryl sulfonates, e.g., dodecylbenzene sodium sulfonate; alkyl aryl snlfonates; the product of chlorosulfonation of paraffin hydrocarbons, e.g., octadecenyl sulfonate; and the condensate of a fatty acid chloride with an amine.

Nonionic detergents include surface active agents which do not form ions, such as those obtained by condensation of ethylene oxide with fatty substances and their derivatives. Illustrative examples of nonionic detergents include the condensation products of propylene glycol (mol. wt. 900) with fatty acid derivatives; the condensation products of ethylene oxide with fatty alcohols such as lauryl alcohol; the condensation products of fatty acids with diethanolamine; the condensation products of ethylene oxide with alkyl phenols; and fatty acid cyclo-imides.

The cleansing compositions to which this invention is directed consist essentially of one or more of such soaps or such detergents or mixtures thereof as the predominant cleansing constituents, such being referred to herein as the detergent base; the skin-substantive antioxidants, optionally together with skin-substantive bacteriostats, as herein described; and optionally other conventional constituents of cleansing compositions, such as, by way of illustration, emollients, fillers, mild abrasives, neutral salts, perfumes or a major proportion of solvent, and which are used in amounts which do not materially affeet in an adverse manner the body-odor inhibiting characteristics of the total composition.

The compositions may be prepared as pastes, bars, liquids (e.g., shampoos), flakes or granules.

The specific embodiments described herein are intended as merely illustrative of the present invention and variations may be made therein by one skilled in the art without departing from the spirit and scope of the invention.

What is claimed is:

1. A composition consisting essentially of a detergent base selected from the class consisting of at least one of water soluble soaps, nonionic detergents, anionic detergents and mixtures thereof, and a skin-substantive antioxidant selected from the class consisting of mono-, di-, and tri-styrenated phenols, tri-[(intermediate-alkyl) phenyl] phosphites, 2,2'ditertiary buty1-4,4'-isopropylidene diphenol (para intermediate-alkyl phenyl) phosphites, and 2,2'-methylenebis [6-(1-methyl-cyclohexyl)- para-cresol], said antioxidant being present in said composition in an amount in the range of at least about 1% to about 4% by weight and sufiicient to inhibit the formation of body odor from an area of the human body cleansed with said composition.

2. A composition in accordance with claim 1 wherein said detergent base is a water soluble toilet soap and wherein said antioxidant is a mixture of the styrenated phenols.

3. A composition in accordance with claim 1 wherein said detergent base is an anionic detergent and said antioxidant is a trinonylated phenyl phosphite.

4. A composition consisting essentially of a detergent base selected from the class consisting of at least one of water soluble soaps, nonionic detergents, anionic detergents and mixtures thereof, a skin-substantive antioxidant selected from the class consisting of mono-, di-, and tristyrenated phenols, tri[(intermediate alkyl) phenyl] phosphites, 2,2'-ditertiary butyl-4,4-isopropylidene diphenol (para intermediate-alkyl phenyl) phosphites, and 2,2-methylenebis [6-(l-methyl-cyclohexyl)-para-cresol], said antioxidant being present in an amount at least about 1% up to about 4% by weight, and a skin-substantive bacteriostat selected from the class consisting of bithionol, sodium or zinc salts of bithionol, hexachlorophene, the zinc salt of 1-hydroxy-2-pyridinethione, tribromosalicylanilide and trichlorocarbanilide, and mixtures thereof, in an amount in the range of from about to about 3%, said antioxidant and said bacteriostat retaining their respective activities and substantivities in said composition.

5. A composition in accordance with claim 4 wherein said detergent base is a water soluble toilet soap, said bacteriostat is a sodium or zinc salt of bithionol and said antioxidant is a mixture of styrenated phenols.

References Cited UNITED STATES PATENTS 1,987,288 1/1935 Brunson 260-3985 2,112,381 3/1938 Solyberg 252-404 2,234,379 3/1941 Martin 252-404 2,467,295 4/1949 Cook 252-108 2,734,924 2/1956 Lambert 260-619 2,814,597 11/1957 Wenneis et al. 252-107 2,977,316 3/1961 Taylor 252-107 3,024,163 3/1962 Harvey et al. 252-106 3,152,039 10/1964 Mattson 252-107 3,172,871 3/1965 Maly et al. 260-967 FOREIGN PATENTS 215,821 6/195'8 Australia.

792,538 3/1958 Great Britain.

671,117 9/1963 Canada.

LEON D. ROSDOL, Primary Examiner.

W. SCHULZ, Assistant Examiner.

Claims (1)

1. A COMPOSITION CONSISTING ESSENTIALLY OF A DETERGENT BASE SELECTED FROM THE CLASS CONSISTING OF AT LEAST ONE OF WATER SOLUBLE SOAPS, NOMIONIC DETERGENTS, ANIONIC DETERGENTS AND MIXTURES THEREOF, AND SKIN-SUBSTANTIVE ANTIOXIDANT SELECTED FROM THE CLASS CONSISTING OF MONO-, DIAND TRI-STYRENATED PHENOLS, TRI((INTERMEDIATE-ALKYL) PHENYL) PHOSPHITES, 2,2''DITERTIARY BUTYL-4,4''-ISOPROPYLIDENE DIPHENOL (PARA INTERMEDIATE-ALKYL PHENYL) PHOSPHITES, AND 2,2''-METHYLENEBIS (6-(1-METHYL-CYCLOHEXYL) PARA-CRESOL), SAID ANTIOXIDANT BEING PRESENT IN SAID COMPOSITION IN AN AMOUNT IN THE RANGE OF AT LEAST ABOUT 1% TO ABOUT 4% BY WEIGHT AND SUFFICIENT TO INHIBIT THE FORMATION OF BODY ODOR FROM AN AREA OF THE HUMAN BODY CLEANSED WITH SAID COMPOSITION.