US 3574821 A
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United States Patent Ofice 3,574,821 FEMININE HYGIENE SPRAY DEODORANT COMPOSITIONS Rolf Wilhelm Pfirrmann and Peter Geistlich, Lucerne, Switzerland, assignors to Mediline A.G., Wolhusen, Lucerne, Switzerland No Drawing. Continnation-in-part of application Ser. No. 370,111, May 25, 1964. This application Oct. 23, 1967, Ser. No. 677,018 Claims priority, application Great Britain, May 31, 1963, 21,976/ 63 Int. Cl. A61k 9/00; A61l 23/00 US. Cl. 424-45 10 Claims ABSTRACT OF THE DISCLOSURE An article of toiletry in the form of an aerosol spray unit for use in feminine hygiene is prepared by filling a suitable aerosol container with a composition including an organic aerosol propellant substantially at least as volatile as dichlorodifluoromethane, from 0.01%-10% by weight of at least one cosmetically acceptable bactericide and from 0.01%10% by weight of at least one emollient substance which may be a fat, oil or oily or fatty nonionic emulsifying agent, the composition containing less than 10% by weight of undissolved solid material.
This application is a continuation-in-part of copending US. application Ser. No. 370,111, filed May 25, 1964, now abandoned.
It is often difiicult for females to maintain a high order of personal cleanliness after urination and other elimination, particularly where facilities are not available for washing the lower pelvic region. Toilet tissue is often irritant to the skin and mucous membrane of this region and ineffective in complete removal of metabolic prod ucts. The resulting undesirable body odor has been recognized by us to be caused by the presence of microorganisms which by breaking down these unremoved metabolic products, liberate malodorous substances.
It is thus the object of the present invention to provide a toilet or cosmetic preparation which can be quickly and conveniently employed to overcome the above difficulties.
We have found that a particularly convenient method of reducing the above-described body odor is to spray an antibacterial composition, formulated in an organic aerosol propellant, onto the area concerned, particularly the external vaginal area, whereby unwanted bacterial activity is reduced or prevented. Spraying is especially effective since it facilitates direct application of the bactericidal substances without the use of toilet tissues and the like and enables any particular area to be readily treated Without substantial irritation of the skin or mucous membrane. Further, a spray container is easily carried, for example, in a hand-bag, and does not have to be frequently replaced as is the case with medicated toilet tissues etc.
However, because of the particularly sensitive nature of the mucous membrane present in the area being treated, We encountered difficult problems which had to be solved before there could be formulated an effective composition which was at the same time highly acceptable to the user. In particular, as distinct from the aerosol spray formulations conventionally employed to apply deodorants, antiperspirants and cosmetics to less sensitive areas of the body, the propellant employed should be as highly volatile as possible to reduce the quantity of unevaporated spray reaching the skin. dichlorodifluoromethane being especially suitable in this respect. Thus in other words, the propellant used should be substantially at least 3,574,821 Patented Apr. 13, 1971 as volatile as dichlorodifiuoromethane and by this means the propellant completely or nearly completely evaporates before the composition contacts the target area. Otherwise, a pronounced so-called burning or chilling sensation results which causes discomfort to the user and discourages use of the preparation. Also, the composition must be dry and contain no water or other material such that the product when used would leave Wet and/or messy deposits which would soil the clothing. Moreover, the product should have no astringent or irritant properties as are caused by astringents customarily used in deodorant preparations. For similar reasons substantial amounts of ethanol, also customarily used in cosmetic spray formulations, must be avoided, although minor amounts may be present to promote solubility of the bactericide in the liquified propellant.
The antibacterial substance or substances used as active material in the compositions should, of course, be substantially non-irritant to the skin and mucous membrane. In spraying with an organic aerosol propellant, even one which is highly volatile, small quantities of the liquid propellant may be deposited on the skin and mucous membrane and cause irritation. We have found that such irritation can be reduced or avoided completely by including in the aerosol composition one or more emollient substances. Such emollient substances may be oils or fats or may be non-toxic oily or fatty emulsifying agents. In the case of the emulsifying agents, the emollient effect is accompanied by improved dispersion of the bactericide in the propellant and it has also been found that the emollient helps in holding the bactericide in place, and hence prolongs its duration of action. Products based upon dichlorodifluoromethane without an emollient have been found to have a comparatively short duration of action, a problem which was not encountered when prior customarily used propellants were present.
By the terms fat and oil as used herein, we mean substances exerting an emollient action upon human skin and mucous membrane and being of a fatty or oily physical character. The terms thus include not only triglycerides but also substances such as long chain fatty alcohols and long chain fatty acid esters having similar physical and emollient properties to the natural fats and oils. Essential oils, however, such as perfume oils, cannot be classed as emollient substances and are not included within the term oil as used herein, it being understood that perfume oils may additionally be included in the compositions according to the invention purely for their odoriferous properties.
Fluoro-aliphatic hydrocarbons are especially suitable propellants, but, as indicated, the propellant should have a volatility substantially at least that of dichloro-difluoromethane which has a vapor pressure of five atmospheres (absolute) at 16.l 0, this being necessary in order to insure that little, if any, liquid propellant reaches the skin to cause burning upon application of the composition. The required volatility can be assured by selecting a single propellant having the requisite low boiling point, or by a suitable mixture of propellants, one of which can have a relatively high boiling point. Fluoro-hydrocarbon derivatives are preferred, for example, trichlorofluoromethane, dichloromonofluoromethane, dichlorodifiuoromethane, difluoromonochloromethane, monochlorotrifluoromethane, dichlorotetrafluoroethane, difluoroethane, monochlorodifluoroethane, monofluorodichloroethane, or octafiuorocyclo butane, it being understood that the fluoro-hydrocarbons of relatively high boiling point will be used only in admixture with at least one propellant of high volatility. Lower paratfins such as propane and butane are also useful propellants, particularly when employed in admixture with the preferred propellants of the invention. In general,
as stated, the propellant should be sufiiciently volatile to reduce to a minimum the quantity of liquid spray reaching the skin, dichlorodifluoromethane, of itself, being especially suitable in this respect.
The bactericidal substance must be one acceptable for use in a cosmetic or toilet preparation as distinct to sub stances which are prescription items or in any other way unsuitable for a purely cosmetic preparation. The bactericide must further be compatible with the skin and mucous membrane. Examples of these include certain halogenophenyl bactericides, such as 2,4-dichloro-3,S-xylenol, 3,4, 6-trichlorophenol, 4-chloro-3,5-xylenol, tribromo-salicylanilide 4-chloro-2-cyclopentylphenol, 2-hydroxy-2',4,4'- trichlorodiphenyloxide, 2,2 dihydroxy 3,3',5,5'-tetrachlorodiphenylsulfide, 2,2 thiobis (4-bromophenol), 2,2 thiobis-(4,6 dichlorophenol), chlorophenylglycerly ethers and 3,5-dibromo-3'-trifluoromethylsalicylanilide and the especially preferred bactericides bis-p chlorophenyl-diguanidinohexane and its acid addition salts, such as the diacetate, dichloride and digluconate, and 2,2'-methylene-bis-(3,4,6-trichlorophenol). Other useful bactericides include long-chain quaternary ammonium compounds, such as cetyl-trimethyl-ammonium bromide, lauryl isoquinolinium bromide and saccharinates of quaternaries, nitrofuran derivatives, such as N-(S- nito-2-furfurylidene)-1-an1inohydantoin and N-(S-nitro-Z- furfurylidene)-3-amino-2-oxazolidone etc. bactericidal urea-formaldehyde condensation products (as described for example in US. Pat. No. 3,102,108) hydroxymethylene derivatives of thiourea, such as N-hydroxymethyl-N- methyl-thiourea, trichlorocarbanilide, trishydroxymethyl, nitromethoxy (3 chlorallyl) 3,5,7-t1'iaza 1 azonioadamantane chloride, salts of 1-hydroxy-pyridine-2-thione, tetramethyl thiuram disulfide, N-trichloromethylthio-l' cyclohexane 1,2 dicarboximide, 1,6 bis(4-ethylmercaptophenylbiguanide)-hexane and its salts, amyl-meta cresol, alkyl parahydroxybenzoates and 3-trifluoromethyl- 4,4-dichlorocarbanilide.
It is advantageous for the bactericidal spectrum of the material to be broad and to include activity against both Gram-positive and Gram-negative bacteria. It is often desirable, therefore to use two or more bactericidal compounds to ensure a broad range of activity. It is especially useful to combine the halogeno-phenyl bactericides with the long-chain quaternary ammonium compounds since the latter also possess a useful cleansing action in assisting removal of undesirable malodorous substances, flakes of skin etc. from the surface.
The halogeno-phenyl bactericide preferably predominates in such compositions and one useful combination is hexachlorophene, i.e. 2,2-methylene bis-(3,4,6-trichlorophenol) or bis-p-chlorophenyl-diguanidino hexane with a quaternary ammonium compound, such as cetyltrimethyl ammonium bromide, with the ratio of halogenophenyl bactericide to quaternary ammonium compound being about 10:1 by weight.
The choice of the emollient substance which may be used in the compositions will depend on the bactericidal substance and on the carrier liquid. Examples of nonionic emulsifying agents include sorbitan mono-fatty acid esters and their polyoxyethylene derivatives, such as sorbitan mono-oleate, mono-laureate or mono-stearate and their polyoxyethylene derivatives, oxyethylated long chain alcohols, ethers thereof and esters thereof, such as oxyethylated lanolin, oxyethylated oleyl alcohol and ethers of such alcohols, oxyethylated phosphoric acid esters of long chain fatty alcohols, such as oleyl, lauryl or woolfat alcohol e.g. the substance sold under the name Hostaphat KO 280 by Farbwerke Hoechst A.G.; monoand di-ethanolamides of long chain fatty acids such as coco acid poly-diethanolamide, stearic acid mono-ethanolamide, myristic acid mono-ethanolamide etc.
One class of compounds especially suitable as emollient substance and also well suited to assist solution or suspension of halogeno-phenyl bactericides is the saturated and unsaturated long chain alcohols, such as cetyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, oleylcetyl alcohol and octyldodecanol. Emollients derived from such alcohols can also be used, for example ethers thereof, as well as esters of higher fatty acids, such as adipic acid, caproic capric and caprylic acids, stearic acid, myristic acid, palmitic, linoleic or linolenic acid, e.g., the ethyl, isopropyl, glyceryl, polyoxyethylated glyceryl, or polyglycol esters. for example, isopropyl myristate, isopropylpalmitate, purceline oil, sesame oil, almond oil and polyethylene glycol stearate (e.g. the substances sold under the name Chremophor A by Badische Anilin und Soda-fabrik). One particularly useful fat is hydrogenated and refined fat from animal skins; this fat is relatively hard and such hard fats are preferably used in combination with a softer fat or oil, e.g. purceline oil or isopropylmyristate.
It is especially preferred to use an oil or fat in combination with a non-ionic emulsifying agent. For such combinations, preferred non-ionic emulsifying agents, especially when used in combination with oils such as isopropyl myristate or purceline oil, are polyethylene glycol stearate and oxyethylated orthophosphoric acid esters of long chain alcohols. All of the above substances not only aid solution or suspension of the active bactericide but also exert an emollient or soothing effect and, furthermore, assist retention of the bactericide on the surface.
The concentration of the bactericidal material in the spray liquid is as stated above between 0.01% by Weight and 10% by weight depending on the type of liquid carrier used and the activity of the bactericide. Concentrations of the bactericide in the liquefied propellant of between 0.05% and 2.0%, e.g. about 0.1% by weight, are especially convenient, having regard to bactericidal activity. The concentration of surface active material or emollient is preferably of approximately the same order as the active bactericide, namely between 0.01% and 10% by weight, but the concentration of such material is most preferably about twice to four times, that of the bactericide, i.e. preferably 0.1% to 8.0%.
Where the bactericidal substance is insoluble in the aerosol propellant, the material may be formulated as a suspension in the propellant, e.g. by grinding to a very fine powder, for example, of a particle size below 101w.
Such a suspension can be sprayed from an aerosol container without requiring a surface active agent to maintain the material in suspension. It will be apparent from the above, however, that there should be less than about 10% by weight of undissolved solid material in the pack aged composition.
A lower aliphatic alcohol, such as ethanol or isopropanol, may advantageously be present in the compositions. In general, lower alcohols reduce the rate of evaporation of the propellant and reduce the tendency ofthe dissolved components to precipitate at the low temperatures generated by rapid evaporation. The concentration of lower alcohol in the compositions is preferably between 0.2% and 2.0% by weight. As pointed out earlier, no more than minor amounts of lower alcohols, such as ethanol, can be present, since excessive quantities will no longer fulfill the requirement that the composition must be nonirritant to the skin and mucous membrane.
According to the invention we also provide aerosol spray units containing a composition according to the invention. Such spray units will be provided with a nozzle having a valve to allow ejection of spray liquid to take place only when the valve is opened by the user and a dip tube leading from the nozzle to the bottom of the vessel to carry liquid under pressure up to the nozzle.
The body of the aerosol container is preferably cylindrical and the walls and bottom advantageously consti tute a single sheet of metal or plastic to avoid joints which would weaken the construction. Where metal is used, the
inner side is preferably treated to avoid corrosion, e.g. by varnishing. f 1 l The nozzle aperture is preferably below 0.8 mm. to ensure a fine uniform spray and in the case ofthe more volatile propellants, where the spray velocity would normally be very high and; the spray thus reach the skin in liquid form before evaporation could take place. it is preferred to use a nozzle adapted to reduce the spray velocity.
In order that the invention may be well understood we give the following examples by way of illustration only. The perfume on used in theseexamples was a mixture of Eroica 3739/2 sold by Dragoco of Holzminden, Germany and IFF 1 239, sold by International Flavors and Fragrances, Holland:
EXAMPLE 1 0.1 g. cetyl-trimethylammonium bromide 0.4 g. polyoxyethylene-sorbitan monolaurate 0.2 g. ethanol a 0.1 g. perfume oil are stirred together and added to 70 g. dichlorodifiuormethane in an aerosol container.
EXAMPLE 2 EXAMPLE, 3
0.1 2,2-methylene-bis- 3,4,6-trichlorophenol) 0.5% isopropyl myristate 0.1% perfumeoil and 2.0% ethanol (96% of volume)v are mixed together and added to 20.0% propane-butane and 77.3 difluorodichloromethane in an aerosol container. 1
EXAMPLE 4 0.1 g. 2,2-methylene-bis(3,4,6-trichlorophenol) 0.3 g. oxyethylated oleyl alcohol 0.2 g. oxyethylated orthophosphoric acid ester Of oleyl alcohol (C18H35O 8P0 0.2 g. perfume oil are stirred together and added to 70 g. difluorodichloromethane in an aerasol container.
EXAMPLE 5 0.07 g. bis-p-chlorophenyl diguanidohexane acetate 0.07 g. perfume 0.1 g. cetyl alcohol and 0.06 g. octyldodecanol are stirred together and added to 70 g. difluorodichloromethane in an aerosol container.
If desired, the difluorodichloromethane may be replaced by other fluoro-chloro methane or ethane propellants alone or in admixture provided that the total propellant is substantially at least as volatile as dichlorodifluoromethane.
EXAMPLE 6 0.07 g. 2,2-methylene-bis-(3,4,6-trichlorophenol) were dissolved in 1.00 g. ethanol (96% by volume) and lightly warmed with 0.5 g. isopropyl myristate (pure) and 0.07 g. perfume oil to give an oily liquid. The liquid was then filledinto a 2.5 ounce aerosol container by the conventional vacuumcrimping method with the valve closed and the container filled with difiuorodichloromethane to make up to 70 g.
EXAMPLE 7 EXAMPLE 8 0.07 g. Bis(p-chlorophenyldiguanidohexane acetate) 1.00 g. isopropanol 0.5 g. isopropyl myristate 0.2 g. hydrogenated hide fat and 0.07 g. perfume oil are mixed and difiuorodichloromethane added in an aerosol container up to a total of 70 g.
EXAMPLE 9 70 mg. bis-(p-chlorophenyldiguanidohexane) diacetate (particle size under 1 mp) 300 mg. sesame oil 70 mg. perfume oil were stirred together and added to 70 g. difluorodichloromethane in an aerosol container.
EXAMPLE 10 70 g. dichlorodifluorotmethane 100 mg. hexachlorophene '2 g. hexyl laurate 0.1 g. perfume oil If desired this formulation may also contain 0.2 g. of ethanol.
EXAMPLE 11 2 g. of hexyl laurate, 0.1 g. of perfume oil, 100 mg. of hexachlorophene were mixed together and incorporated with 70 g. of a propellant mixture consisting of dichlorodifluoromethane and 20% of tetrafluorodichloroethane.
1 'EXAMPLE 12 G. Dichlorodifluoromethane 70 Bis-(p-chlorophenyldiguanidohexane)dichloride 0.07
The propellant in this example consists of a mixture of dichlorodifluoromethane:butane in the proportion of 80% to 20% by weight.
EXAMPLE 14' 70 mg. hexachlorophene 70 mg. perfume oil 700 mg. emollient 35 mg. Dow Corning fluid F-157 (Stearyl ester of dimethylpolysiloxane) 70 g. dichlorodifluoromethane In this example the emollient component has the followmg composition:
Percent by wt. Isopropyl myristate 40 Purcellin Oil (Dragoco, Holzminden, Germany) 40 Hide fat (hydrogenated) 20 In this example instead of Dow Corning fluid F-157 other Dow Corning Silicon fluids which may be used are 225 Fluid, 420 fluid and 471 fluid.
EXAMPLE 15 In this example the propellant is a mixture of dichlorodifluoromethane and monofluorotrichloromethane in the ratio by weight of 90: 10.
EXAMPLE 16 1000 mg. Polynoxylin 1000 mg. Dow Corning Medical fluid 200 70 mg. dichlorodifluoromethane 100 mg. perfume oil Polynoxylin is a bactericidal urea-formaldehyde polycondensation product marketed by Ed. Geistlich Sohne A.G. fur Chemische 'Industrie, Wolhusen, Lucerne, Switzerland.
1. A non-irritant anhydrous aerosol spray composition in an aerosol container for use on the female external vaginal area consisting essentially of an organic aerosol propellant having a vapor pressure of at least the order of five atmospheres at 161 C., from 0.0l%% by weight of a cosmetic bactericide substantially non-irritant to the skin and mucous membrane and active against odor-producing bacteria infesting said vaginal area, and from 0.01%10% by weight of an emollient substance of a fatty or oily physical character soothing the skin and mucous membrane and counteracting irritation of said vaginal area and containing less than 10% by weight of undissolved solid material.
2. A composition as claimed in claim 1 in which there is present an amount of said emollient substance from two to four times the amount of said bactericide.
3. A composition as claimed in claim 1 in which the concentration of said bactericide in said propellant is within the range of about 0.05% to 2.0% by weight and the concentration of said emollient substance in said propellant is within the range of 0.1% to 8.0% by weight.
4. A composition as claimed in claim 3 in which said propellant is dichlorodifluoromethane and said bactericide is 2,2 methylenebis (3,4,6 trichlorophenol, bis p a chlorophenyldiquanidohexane or its acid addition salts, or cetyl-trimethylammonium bromide. I p 5. A composition as claimed in claim 4 in which said bactericide is 2,2-methylene-bis-(3,4,6-trichlorophenol).
6. A composition as claimed in claim 4 in which said bactericide is bis-p-chlorophenyldiguanidohexane or its acid addition salts.
7. A composition as claimed in claim 4 in which said bactericide is cetyl-trimethylammonium bromide.
8. A composition as claimed in claim 3 in which said emollient substance is cetyl, lauryl, mristyl, stearyl, oleyl, oleylcetyl or octyldodecyl alcohol.
9. A composition as claimed in claim 3 in which said emollient substance is a mixture of isopropyl myristate and hydrogenated hide fat.
10. A composition as claimed in claim 3 containing from about 0.2% to about 2.0 by weight of an alcohol selected from the group consisting of ethanol and isopropanol.
References Cited UNITED STATES PATENTS 2,684,924 7/1954 Rose et al. 424-326 3,227,614 1/ 1966 Schever 424-263 FOREIGN PATENTS 59,548 8/ 1947 Argentina.
. OTHER REFERENCES Merck Index, 1960, 7th Ed., P. 423, 675-67 6.
Remingtons Practice of Pharmacy, 12th 'Ed., 1961, p. 246.
Barr, M. JAPA vol. 19, No. 11, 1958, p. 675-678.
ALBERT T. MEYERS, Primary Examiner V. D. YTURNER, Assistant Examiner mg UNITED STA'IES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,574,821 Dated April 13, 1971 Inventor) Rolf Wilhelm Pfirrmann and Peter Geistlich It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 3, line 13,
"anilide 4-chloro-2-cycl0pentylphenol, should read anilide, 4-c hloro2-cyclopentylphenol,;
Column 3, line 17,
"erly" should read -eryl-,-
. Column 3, line 26,
"nito" should read --nitro-.
Column 4, line 7,
"caproic capric" should read caproic, capric.
Column 7, line 9, "70 mg. propellant" should read --70 g propellant-;
Column- 7, line 16, "70 mg. dichlorodifluoromethane"should re --70 g dichlorodifluoromethane--;
Column 7, line 35, soothing the" should read soothing to the-.
Column 8, line 6, trichlorophenol, should read -trichlorophenol) Signed and sealed this 21st day of September 1971.
, EDWARD MEIETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Acting Commissioner of Paton