CA1050891A - Anti-perspirant sprays - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

An anti-perspirant composition suitable for spray application which contains, as an emollient, at least two members of the group consisting of an alkoxylated higher fatty alcohol, an alkoxylated lower alcohol, and lower aliphatic alcohol esters of higher fatty acids, isopropyl, the composition having a reduced tendency to stain clothing.

Description

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The present invention relates to a dry anti-perspirant spray having a reduced tendency to stain clothing.
Conventional emollients used in known compositions are partially or wholly replaced in the present invention with a combination of materials to maintain the character and performance of the dry anti-perspirant spray while reducing staining.
The composition preferably in a pressuri~ed container for the production of a mild but effective dry spray, compr.ises a po~dered anti-perspirant material in an amount sufficient to have an effective anti- -perspirant action, a propellant fluid for maintaining pressure in the container and aiding in the discharge of the anti-perspirant composition therefrom, a vehicle as described herein and a suspending agent capable of ;~ ` maintaining the powder component of the composition in suspension. ;
According to the present invention there is provided a dry anti-perspirant composition suitable for spray application whi~h contains a powdered astringent anti-perspirant material and, as an emollient system.
(i) polypropoxylated cetyl alcohol and at least one member of th~ two groups (ii) poly - C2---C3 alkoxylated Cl - - C8 fatty alcohols and Cl - C~ fatty ~' alcohol esters of C14 - C18 fatty acids, such as isopropyl myristate.
Compositions according to the present invention preferably contain a mixture of an alkoxylated higher fatty alcohol and an alkoxylated lower alcohol. The alkoxylated higher fatty alcohol may be a propoxylated , ',, ~ ' ;;, ~' :
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cetyl alcohol and the alkoxylated lower alcohol may be ~n ethoxylated and/or propoxylated lowar alcohol such as butanol.
The poly-lower alkoxylated higher fatty alcohol '; will be formed from an alcohol having 12-18 carbon atoms, preferably cetyl alcohol. The poly-lower alkoxylated higher fatty alcohol is usually alkoxylated by propylene oxide but may have ethylene oxide present, too. The extent o~ alkoxylatlon will generally be within the range o~ 3 to 100 lower alkoxy groups per mole (lower meaning 2- to 3- carbon alkoxy groups) and of these, 10 to 100~ will normally be propoxy, rather than ethoxy. The propoxy may b~ n-propoxy or isopropoxy, with the latter being more c~mmon. Preferred poly-lower alkoxylated higher ~atty alcohols will be completely water soluble and will contain from 3 to 20 alkoxy groups per mole, o~ten 5 to 15 and most preferably about 10 propoxy groups per mole.
However, a balance can be struck between the proportion o~ ethoxy and propoxy groups and the length of the poly-lower alkoxy chain to produce a product of the mo~t desired hydrophilic~ water soluble, counter-irritant, detersive and vehicle properties.
The alkoxylated lower alcohol of this invention is: a propellant soluble polyalkylene oxide adduct of a monohydric alcohol. These adducts are prepared by the ~-- addition of an alkylene oxide to a monohydric aliphaticalcohol. The reaction which takes place between ~he alcohol and the alkylene oxide is a chain addition ~3S~891 wherein the alkylene oxide mol~cules undergo con~er ion to the corresponding oxyalk~lene radical. Preferred adducts for use in the formulations of` the present inven-tlon are those formed ~rom a lower alkylene oxide of 3-~
carbon atoms or a mixture of alkylene oxides of 2-5 carbon atoms. Useful adducts are p~opellant-soluble and preferably contain an average of at least 5 ~lkylene oxide ~roups in the molecule. Particularly useful poly-alkylene oxide adducts are the polypropylene oxicle adducts of monohydric aliphatic alcohols which contain ~1 average of at least 5 propylene oxide groups ln the molecule.
~ny lower monohydric aliphatic alcohol may be employed Ln the reaction. Pre~erably~ alcohols containing from 1 to 8 carbon atoms including both normal and branched ~ chain alcohols are used. Thus, suitable alcohols which can be used include methanoI, ethanol, isopropanol, n-propanol, n-butanol, 2-ethylbutanol, n-hexanol, 2-ethyl-hexanol and n-octanol, etc. Most pre~erred of these compounds for use in the present invention are the propylen~
oxide adducks of n-butanoI having a vlscosity range of from 2.5 to 55 centistokes at 210F.
The lower aliphatic alcohol esters o~' higher .~ .
fatty acids are formed ~rom a lower aliphatic ~lcohols of 1 to 4 carbon atoms and a higher ~atty acids o~ 12 to 1~ carbon atoms. More preferably, the alcohols will be of 2 to 3 carbon atoms and the higher fatty acid~ will be .
of 14 to 18 carbon atoms. Most perferablyj the alcohol is i~opropanol and the fatty acid is myristlc acid.
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The combination of vehicles is an essential ingredient o~ the com~ositions of the invention. Such compounds must, however, be employecl in quantities which (lo not impa:ir the dry powder property o~ the sub~ect ~ .
'j composition. In order to maintain/c~esirable ~omposition the vehicles æhould be used in total ~mount of about 0.5 7 pre~erably9 1-4~. The use o~ amount~ greater than about 6 percent results in the deposi*ion o~ an undesirable greasy film.
In general, two types Or products are possible, namely, one having a relatively "low" emollie~t level, i.e., a low level of t~ key ingredients of the present invention. Such "low" emollient level products are pre~erred as giving a particularly dry deposit which ls .
not powdery. Alternatively, "high" emollient products ~ can also be :prepared from the present key ingredients.
i A cvmbination o~ two of the three types of ~ vehicles disclosed herein~will be used together to form -!
: the products of the invention. The two vehlcles will be i 20 used in the ratio of 1:5 to 5:I, preferably 1:2.5 to 2.5:1. ;
The pre~erred combination of vehicles is an alko~ylated ~ higher fatty alcohol and an alkoxylated lower alcohol in .; a ratio of~about 1:2 to 1:3.
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~ The active anti-perspirant ingredient i8 any one . ~ .
.~: 25 or more o~ the known salts having astringent properties .
~ ~ such as alumlnum, zinc, irvn, or zirconium salt~ or : complexes, which salt should also be:incoluble in the .
~ propellant and vehicle. For example, such compounds ~:

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8gl include, but are not limited to~ zirconium salt~ such as:
zirconium chloride~ zirconium ox~chloride, ~irconyl hydroxychloride, and zlrconium sulfate; zine ~alts such as:
zinc hydroxychloride, zinc hydroxybromide, zinc sul~ate, and zinc phosphate; aluminum salts such as: aluminum basic chloride, aluminum chloride, a~luminum bromide, aluminum su].fate, aluminum oxychloride, aluminum oxy-sul~ate~ and hydrates o~ the aluminum ~alt~, such as ali~in~m chloride hexahydrate, and iron salts such as ferric sul~ate and ferrous sulfate. Ma~y inorganic-organic astringent salt complexes and mixtures o~ astringent salts can also be used as long as they remain lnsoluble in both alcohol and the propellant.
As used herein~ the te~m "aluminum basic chloride"
: 15 refers to those compounds having~the empiric~l ~ormula:
A12(0H)(6_X)C1x, wherein x is a positive num~Pr o~ ~rom 1 to 5. Similar considerations apply with respect to : aluminum basic iodide and aluminum basic bromide.
: Particularly use~ul results are obt~ined when an aluminum basic chloride having an aluminu~ to ~hlorine mol ratio of ~rom about 2:5 ~p to about 2.1 to 1, advantage-ously between about 1:1 to about 2:1. One desirable ~alt is actually a mixture of aluminum salts having an apparent atomic ratio o~ all~inum to chlorine of about 2:1, e.g., an average o~ about 2.1 to 1.9:1, and an empirical formula .~ of A12(0H)5Cl in aqueous solu~ion.
. The actlve anti-perspir~nt material should be present in the composition as a powder and in an amount of about 0.5 to 15~ by wei~ht, preferably an ~mount of about 1 to 6~.

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~ nother component of the subject composition is a suspending agent. It is important that the powder be adequately suspended in the container. Por this purpose it is necessary to use an effective suspending agent. Useful suspending agents include known bulking agents such as a colloidal silica. For example, "Cab-O-Sil" which is a trade mark for a pyrogenic silica having a particle diameter between about 0.001 and 0.03 microns as ;
disclosed in British Patent No. 987,301; colloidal (fumed) ~ -alumina; and finely divided hydrophobically treated clays ~ such as a reaction product of a clay such as bentonite or ;~ hectorite with, for example, dimethyldistearyl ammonium chloride. These suspending agents are the hydrophobically treated montmorillonite or hectorite clays available under the trademark "Bentone" which are prepared by reacting a ;
clay such as bentonite or hectorite in a cation exchange system with a variety of amines. Different amines are re-acted to obtain different "Bentone" suspending agents which ;~
; may also differ in proportions of SiO2, MgO and A1203.
Examples of useful "Bentone" suspending agents are "Bentone-27", which is stearaluminum hectorite, "Bentone-34", which is quaternium 18 bentonite, "Bentone-38", which is quaternium .
18 hectorite, and "Bentone-14", which is a clay extended quaternium 18 hectorite, all of which have a particle size ;
of below about 5 microns and are commercially available from the NL Industries, Inc.
The hydrophobic clays should be thoroughly dispersed. Three forms of energy which aid in such dis-persion are temperature ~ncrease, chemical energy and :

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mechanical she~ring action. Chemical energy can be supplied in the ~orm of a polar additive such as alcohol ~ -or a high boiling organic llquld such as propylene carbo-nate. Propylene carbonate. usually in an amount of about 0.05~ to about 0.5~, is also particularly helpful ~hen the organic liquid has poor wetting propertie~s~ or when dis-persion is unusually difficult. As taught by NL Industrie~
in their Data Sheet B-33 of April 1970, high mechanical shearing action is also an important factor. Equipment such as homogenizers, shear pumps, and colloid ~ills will give positive results. Examples of useful mixers include, among others, the Cowles Dissolver and the Eppenbach Homogenizer.
The suspending agent is employed in amounts of from about 0.1 about 3~, desirably about 0.1 to l~, and preferably from about 0.25 to about 0.75~ thereo~.
The ~ropellant used in connection with th~
subject invention may be any non toxic, liquifiable pro- ~
pellant suitable for use in connection with the dispensing ~ ;
o~ the solid material. That is to say, any non-toxic, volatile, organic material which exlsts as a gas at the temperature of use (and ambient or atmospheric pressure~
and which exists as a liquid at the same temperature under superatmospheric pressures can be used as the ga~-producing agent. Especially suitable are the C3-C4 aliphatic hydro-carbons~ namely liquefied propant, n-butane, and isobutane;
halogenated aliphatic hydrocarbons which contain from I to

2 carbon atoms and include, by way of example, ~inyl chloride, methylene chloride, "F~eons" such as dichlorodi~luorometh~ne, monochlorodifluoromethane, dichlorotetrafluoroethane, trl~
chlorofluoromethane~ trichlorofluoroethane, difluoroethane~ -difluoromonochloro0thane, trichlorotrifluoroethane, mont~
fluorodichloromethane, monofluorodichloroethane, penta-:
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rluoromonochLoroethane; cyc~ic hexafluorodichlorobutane;
octafluoropropane; ar.d cyclic octafluorobutane; and mixture~
of two or more thereof. Pre~erably the saturated hydro-carbons and halogenated saturated a}iphatic hydrocarbons '~ are employed in the sub~ect cQmposition. The boiling point of said propellant, or of the mixture o~ propellants, : used in the final product should ~all within the range Or about -30C. to about 60C. at atmospheric pre~sure. A
: highly desirable propellant ~or use in connection with the LO sub~ect composition is a mixture of dichlorodi~luoromethane and dichlorotetrafluoroethane in a 25:75 blendO
The propellant will normal~y constitute from about 65 to 97 percent of the ~inal composition, pre~er-ably from about 80 to 93 percent by weight thereo~.
~lthough not essential for this i~vention~ it is desirable to add a non-irritating, non-toxic germicide or bactericide in amounts of about 0.02 to .5% by weight of the total composition. Suitable antiseptic agents include dichlorophene, 3, 4', 5 tribromosalicylanilide;
2, 2~, 3, 4-tetrabromosalicylanilideJ and other bacterio-stats commonly known in the market as well as mixtures thereof. ~ :
In addition to the foregoing components of the sub~ect composition one may also include therein components such as per~umes, colorings, and the like, so as to improv0 the aesthetic value and consumer acceptability thereo~.
One may also incorporate talc or other powdered compounds to improve the properties of the product. Other compounds !
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such as fatty amide, dipropylene glycol, antioxidants, leci~hin, and/or vitc~mins, eith~r separately or in combination may also be incorporated into the subject composition. Such compounds should not, however, be employed in quantities which impair the dry powder property of subject composition.
The following examples will serve to illus-trate the new composition of the subject convention. In the examples as well as throughout the specificati all ~.
parts and percentages are by weight. Trade marks are in - quotation marks.

Dry aerosol anti-perspirants were prepared utilizing the basic ingredients of the present com~osition.

~, Table 1, below, sets forth the compositions of said dry .j .
spray anti-perspirants.

; Table 1 -Example 1 2 3 4 ~-Ingredients Wt % Wt % Wt % Wt %

-~ 20 Isopropyl Myristate 1.0 2.0 - - -~ "Fluid AP" ~Union Carbide) 2.0 - 2.0 4.95 -~

; i'Procetyl AWS" (Croda) - 1.0 1.0 1.65 ;~ Aerosil 200 0.1 0.1 0.1 0.2 ~ Aluminium Chlorhydroxide* 3.0 3.0 3.0 3.0 ~: :,,, ~; ~ Trichlorhydroxy Diphenyl Ether ("Iragasan DP 300") 0.06 0.06 0.06 0.06 ;
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Tribromosalicylanilide 0.015 0.015 0.015 0.015 ~ Perfume 0.2 0.2 0.2 0.2 -~ ;;

- Propellant 11/12 as a 60/40 Mixture to 100% to 100% to 100% to 100% ~

*AIuminum basic chloride as defined herein having the formula ~ i Al2(OH)5Cl.

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As used in the above examples, the ~ollowlng terms denote the indicated material~:
"Procetyl AWS" is propoxylated cetyl alcoholD
In particular "Procetyl AWS" is manufactured by Croda International and is a pale straw~ oily liquid with a faint characteristic odor. Its molecular weight is about 1200 and its specifications are as follo~:
Color (Gardner 3 Max.
Acid ~alue 2.0 T~droxyl Value 40 - 50 pH (3a~0 Solutio~) 6.0 - 7.5 "Fluid AP" is available ~rom the Unlon Carbide Corporation and is ethoxylated, propoxylated butanol.
"Aerosil 200" i8 finely dlvided sil:Lca.
Propellant "11" is trichlorofluorom~thane.
Propellant "12" is dichloroai~luoromekhane~
The above composition~ were ~ub~ected to in ~ivo testing on human sub~ects to determine the degree of :~ staining to clothing of the dry anti-perspirant spray - 20 thereby obtained. It was ~ound that the above formulas :~
gave stains o~ only about 30a~ of thoce caused by a similar product not employing the combinatlon o~ the pre~ent invention.
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Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A dry anti-perspirant composition suitable for spray application which contains a powdered astringent anti-perspirant material and, as an emollient system; (i) polypropoxylated cetyl alcohol and at least one member of the two groups (ii) poly - C2-C3 alkoxylated C1-C8 fatty alcohols and (iii) C1-C4 fatty alcohol esters of C14-C18 fatty acids.

2. A dry anti-perspirant aerosol composition comprising a powdered astrigent anti-perspirant material; a suspending agent; a liquefied normally gaseous propellant; and, as an emollient system, (i) polypropoxylated cetyl alcohol and at least one member of the two groups (ii) poly - C2-C3 alkoxylated C1-C8 fatty alcohols and (iii) C1-C4 fatty alcohol esters of C14-C18 fatty acids.

3. A composition as claimed in claim 1 or claim 2 wherein the C1-C4 fatty alcohol ester of a C14-C18 fatty acid, when present, is isopropyl myristate.

4. A composition as claimed in claim 1 or 2 wherein the astringent anti-perspirant material is an aluminium basic chloride as hereinbefore defined.

5. A composition as claimed in claim 1, or in claim 2 wherein the suspending agent is a hydrophobically treated montmorillonite clay dispersed therein.

6. A composition as claimed in claim 1 or 2 wherein the emollient system is present in an amount of 1 - 4% by weight.