US2586288A - Aluminum sulfamate antiperspirant - Google Patents

Description

Patented Feb. 19, 1952 ALUMINUM SULFAMATE ANTIPERSPIRANT Lester D. Apperson, Convent Station, and Earl Leroy Richardson, Bound Brook, N. J assignors to Colgate-Palmolive-Peet Company, Jersey City, N. J., a corporation of Delaware No Drawing. Application December 11, 1948, Serial No. 64,905

This invention relates to cosmetic astringent compositions and more particularly to improvements in anti-perspirant preparations.

Among the many anti-perspirants described as having the property of retarding or inhibiting the flow of perspiration the most effective have been found heretofore to be those containing aluminum salts of strong inorganic acids, e. g. hydrochloric, sulfuric, etc. Cosmetic preparations containing salts of these strong acids, however, have the very serious disadvantage of corroding or tendering clothing fabric, e. g., portions of garments which come in contact with areas of the body on which the preparation is applied. This corrosive action is especially noticeable on fabrics containing cellulosic materials such as cotton, rayon and the like. The corrosive effect that is detrimental to fabrics manifests itself particularly where the clothing portion carrying some of the anti-perspirant material is ironed or otherwise subjected to a relatively high temperature before removal of the anti-perspirant preparation. Even long continued contact at ordinary temperatures of cosmetic preparations containing aluminum salts of these mineral acids cause weakening or deterioration of the clothing fabric.

Of the many salts which have been used or described as useful anti-perspirants, aluminum chloride and aluminum sulfate are by far the most commonly used and have heretofore been considered to be the most effective. However, both salts show high corrosive action on cotton fabrics. This corrosive action is so severe that considerable research and investigation has been directed to a satisfactory reduction of the corrosive action without simultaneously reducing the anti-perspirant effectiveness of the salts. Because of its less corrosive action, aluminum sulfate is generally preferred over aluminum chloride.

It has now been discovered that the aluminum salt of sulfamic acid is a very efficacious perspiration retardant, having been found by, tests to be definitely superior to the aluminum salt of sulfuric acid in this respect; and, of more importance, it has beenobserved that aluminum sulfamate is practically non-tendering to clothing fabrics. Under certain severe conditions, however, aluminum sulfamate may cause some discoloration of cellulosic fibers. The discoloration appears as a yellowish to light brown cast when an aluminum sulfamate-containing preparation is applied to and dried by heat on white fabrics made of cotton, linen or regenerated 9 Claims. (01. 167-90) cellulosic fibers. Therefore, in order to use aluminum sulfamate in cosmetic preparations, it became necessary to eliminate or reduce to a satisfactory degree its property of causing discoloration of fabrics.

Extensive research 'was carried out with the object of finding a way to overcome this undesirable discoloration effect without impairing the eificiency of the aluminum sulfamate as an antiperspirant. It was discovered that the discoloration tendency could be prevented or satisfactorily lessened by incorporating in the anti-perspirant preparation certain organic compounds in suificient concentration. Compounds found to aid in preventing this discoloration, for convenience, may be classified into four general groups, as follows:

GROUP I Amides which are neutral and contain the functional group ("3NHz o and are soluble in aqueous aluminum sulfamate and which do not precipitate therefrom a compound containing aluminum. for example: urea, ethyl carbamate, formamide, and acetamide. The word neutraPis used herein to mean that the compounds are practically unionized in aqueous solution.

GROUP II Amino carboXylic acids which contain the func- -tional group ECNH2 and are soluble in aqueous aluminum sulfamate and which do not precipitate therefrom a compound containing aluminum, for example: glycine, a-alanine and )8- alanine.

- GROUP III Compounds which contain the functional group 56-5-41 and are soluble in aqueous aluminum sulfamate and which do not precipitate therefrom a compound containing aluminum, for example: sodium mercaptopropanesulfonate (1,2), sodium 2-mercaptoethane-l-sulfonate, ammonium Z-mercaptoethane-l-sulfonate, ammonium thioglycola'te, thioglycolic acid, thiourea and ethylene thiourea.

The extent of solubility of the substance used as a discoloration inhibitor in the aqueous sulfamate solution may vary with the var-ious compounds and it is essential only that a sufficient quantity of the substance used. go into solution 'to suitably inhibit the discoloration. In-some cases the substance may be present in the composition in amounts greater than the limit of -solubility without disadvantage. Further, the inhibiting substance used should not reduce the :rflllti" perspirant property of the aluminum sulfamate, nor should it cause the finished preparation "to have an objectionable odor, color or other undesirable characteristics such as cause irritation.

It is, of course, recognized that a fewof 'the compounds listed above and manyothers which are inoperative in the present invention have been proposed for use in anti-perspirant preparations containing aluminum chloride or aluminum sulfate to prevent serious weakening or the destruction of fabric due to the corrosive action of these salts. In such preparations, however, the

"problem was solely to prevent tendering of the fabric since aluminum chloride and sulfate cause no discoloration and there was no reason to-sug- 'gest that'anyknown anti-tendering agent would "be useful in preparations employing aluminum *sulfamate-forthe-entirely different function of preventing discoloration, particularly since tests had demonstrated that no anti-tendering agent was necessary in aluminum sulfamate prepara- =tions,znor-was there anything to guide the search for anti-discoloring agents.

Test data have further-indicated that aluminum sulfamate, either with or without the addition of a discoloration inhibitor from the above described :"groups produces definitely superior results in'inhibiting' perspiration when'compared with likerpreparations'which contain aluminum sulfate.

.Tosecure such data, specific areas of skinof --a number-'of' human subjects were-treated daily over a definite period and the perspiration inhibiting effects for aluminum sulfate and aluminum sulfamatewere evaluated. The perspirationfrom .twoequal, comparable areas of skin with and without. anti-perspirant treatment was periodically collected and weighed. For each measurement a per cent of perspiration-lessening effect was calculated as follows: Where..-X= weight of perspiration on untreated area and Y=weight of perspiration on like area treated with anti-perspirant material, then, the perspiration-lessening e'ffect, as representedby (Z), expressed in-per cent, is as follows:

The results =obtainedfrom the testsshowed that aluminum sulfamate was from three tofsix or more times as effective as aluminum sulfate whencomparable concentrations were used. :In

4 agents. Furthermore, where the cosmetic or other prepartion does not come in contact with cotton, muslin, rayon or the like substance whose chief ingredient is cellulose, the discoloration inhibitor may be omitted. For example, wool ffibers do not give any discoloration when treated with solutions containing aluminum sulfamate. Where, however, the aluminum sulfamate-containing preparation is to be used for general purposes during which some discoloration may occur which would be objectionable, it is necessary'toincorporate a suitable amount of an inhibitorsuch asdescribed hereinbefore.

*The'proportion of inhibitor required to revent discoloration varies with the particular inzhlbitOI. :In-general, it has been found that when employing Grou 1, Group II and Group III compounds at least an equal rnolai' proportion of the discoloration inhibitor to thatof aluminum sulfamate should be used, and preferably about twotothree mols of those inhibitors for each mol of aluminum sulfamate in solution is employed. -With Group IV compounds about /4 mol ermol of aluminum sulfamate is suificient.

Greater "or less quantities of the discoloration inhibitor, or mixtures of difierent inhibitor compounds may of course be used so long as enough is incorporated to prevent discoloration where the same is objectionable.

In accordance with the present invention, novel anti-perspirant compositions containing alumi- 'num'sulfamate may be prepared and marketed inany desired form, e. g, as emulsions,- suspensionsysolutions, salves, creams, lotions and the like. Suchpreparations may comprise the usual ingredients including pigments, fillers, perfumes,

etc., andthey may be compounded in any suit- Satisfactory results may be obtained in com-- positions in which the proportionate quantity of aluminum sulfamate incorporated ranges between about.5'% and 50% by weight of the antiperspirant preparation, and a preferred range liesbetween', about 10% to 30% by weight.

Aluminum sulfamate may be incorporatedinto creambases of widely varying composition either with or .without a discoloration inhibitor.- Generally speaking, such a cream includes an oily phase held in dispersion in an aqueous phase Cor taining the anti-perspirant by one or more suitable emulsifying agents. The oily phase may include such materials as natural and synthetic oils, fats and waxes, e. g. spermaceti, palmityl .palmitate, polymerized ethylene oxide (Carbowax), .paraflin, sterols, mineral oils, vegetable oils and. other. esters of fatty acids, etc. Glycer- 'ine,.propylene ,glycol, sorbitol and the like emol-- lients may also be present.

Any suitable emulsifying agent may be em-- ployed which is sufficiently stable in acid media. Examplesof emulsifying agents which have been "found .useful preparing creams are: partial.

.esters of fatty acids with glycerine, glycol or other polyhydric alcohol, preferably in combination with a stabilizer such as sodium monosulfate monoglyceride of coconut oil fatty acids, diethyloleylamid phosphate, sodium lauryl sulfate, sodium alkyl aromatic sulfonate, etc.

As specific examples of preparations embodying the principles of this invention the following are given without intending to be limited thereby. The parts indicated are by weight.

Example 1 Parts Acid stabilized glyceryl monos'tearate 1 16.0 Spermaceti wax 5.0 Sodium lauryl sulfate 1.5 Titanium dioxide 0.5 Aluminum sulfamate 18.0 Urea 5.0 Water 54.0

Acid stabilized glyceryl monostearate comprises glyceryl monostearate and a small amount (2 to 5% by Acid stabilized glyceryl monostearate 15.0

Glycerine 3.0 Spermaceti wax 5.0 Titanium dioxide 0.5 Aluminum sulfamate 18.0 Formamide 7.7 Water 50.8

Example 4 Parts Acid stabilized glyceryl monostearate 15.0 Glycerine 3.0 Spermaceti wax 4.0 Sodium lauryl sulfate 1.0 Titanium dioxide 0.5 Aluminum sulfamate 18.0 Acetamide 10.1 Water 48.4

Example 5 Parts Glyceryl palmitate 15.0 Palmityl palmitate 3.0 Glycerine 2.0 Sodium salt of sulfated monoglyceride of coconut oil fatty acids 3.0, Titanium dioxide 0.5 Aluminum sulfamate 18.0 Glycine 12.8 Water 45.7

Example 6' Parts Glyceryl monostearate 16.0 Spermaceti wax 3.0 Glycerine 3.0 Sodium salt of sulfated monoglycerideof coconut oil fatty acids 3.0 Titanium dioxide 1.0 Aluminum sulfamate 18.0 Diammonium malonate .1..'.'.. 11.9

Water 44.1

6 Example 7 Parts Glyceryl monostearate 15.0 Spermaceti wax 4.0 Sodium salt of sulfated monoglyceride of coconut oil fatty acids 3.0 Titanium dioxide 0.5 Aluminum sulfamate 18.0 Ammonium acetate 13.2 Water 46.3

' Example 8 Parts Acid stabilized glyceryl monostearate 15.0 Spermaceti wax 5.0 Sodium salt of sulfated monoglyceride of coconut oil fatty acids 3.0 Glycerine 2.0 Titanium dioxide 0.5 Aluminum sulfamate 13.0 Triethanolamine acetate 12.9 Water 48.6

' Example 9 Parts Glyceryl monostearate 13.00 Spermaceti wax 3.00 Stearyl alcohol 3.00 Mineral oil 1.00 Igepon T (sodium p-oleylethane-amidsulfonate) 2.50 Titanium dioxide 0.50 Aluminum sulfamate 13.00 Ammonium 2-mercaptoethane-1-sulfonate 1.64 Water 63.36

Example 10 Parts Glyceryl monostearate 1 15.00 Spermaceti wax 3.00 Mineral oil 2.00 Glycerine 2.00 Titanium dioxide 0.40 Sodium salt of sulfated monoglyceride of coconut oil fatty acids 3.00 Aluminum sulfamate 18.00 Sodium mercaptopropanesulfonate (1,2) 2.54 Water 54.06

Example 11 v Parts Acid stabilized glyceryl monostearate 13.00 Spermaceti wax 3.00 Stearyl alcohol 2.00 Igepon T (sodium p-oleylethane-amidsulfonate) 3.00 Glycerine 2.50 Aluminum sulfamate 22.50 Ammonium thioglycolate 2.34 Water 51.66

Example 12 Parts Acid stabilized glyceryl monostearate 10.00 Glyceryl monostearate L. 4.00 Spermacetiwax 4.00 Mineral oil 2.00 Igepon T (sodium B-oleylethane-amidsulfonate) 2.50 Titanium dioxide 0.50 Aluminum sulfamate c 18.00 Thio'glycolic acid 1.59 Water 57.41

{Titanium dioxide v. -Aluminum sulfa-mate 20.0 :Ethylene thiourea Eaample; 13

1 Sodium salt. of ,sulfatedumonoglyceride of coconut oil fattyacids A 2.3 0.3

I 1.6 Water 57.8

The aluminum sulfamatecream preparations -of-'2Examples 1 through 13 were tested to deter- I mine the. effectiveness: of the jvarious inhibitors in lessening .thediscoloration tendency on fabrics.

In carryingsoutthe testsathe cream-was smeared -over.a cotton. swatch. .(2 ""X1.4' strip) l until all of "the fabric .was .covered..evenly..with fine-excess cream.on thesurface. .On. the reverse side of the strip. three .drops oLwaterwere added to moisten the cloth, and.thereafter-' thestripwas placed in nan oven .and baked .atabout 214 Rim-thirty minutes. These swatches were tested alongside a cotton swatch smeared..with a like aluminum sulfamate cream preparation which contained no rdiscoloration inhibitor. --conditions of this test, the strip treated with the Even .under the severe uninhibited cream was discolordto a greater ex- ;tent than any of the strips treated with creams of Examplesllto l3,,and. inl the case of Examples 1,; 2, 3, 5, 6, 7, 9, 10 and 12, there was practically no discoloration. Furthe'rfit has been ascertained from tests of the cream, containing the in- ;hibitor- ,giving the least effect under the severe ;:conditions of the above test' that even this substance was efiective in inhibiting this undesirable coloring effect on iabric when tested under conditions comparable to those encountered during .the normal use of the anti-perspirant.

'jExamples-of suitable-aluminum sulfamate anti- ,perspirant solutions which-may be used in liquid form or asthe-waterphase in acream or:emul- ,sion-type-preparation,-such as'described in'Examples 1-- to-13,- are-as follows, the parts beinghy weight:

ExamplejA Parts Aluminum sulfamate 24.9 Urea 14.2 Water 60.9

Example B Parts Aluminumsulfamate 24:9 Ethyl. carbamate (urethanelg 14;.1 Water A --61.0

..Ea:ample...C

Parts 'A-.lum-inumsuliamate 24,9 Thiourea 66.0 Water 69 1 Example D rt Aluminum sulfamate -2510 Glycine H M V .173 .Water f57.2

-Emmrlefi Pal'f/S Aluminum. suliamate ':-25.0 il-alanine i 21.2 Water 53:8

E$ p Parts Aluminum sulfamate 25.0 Diammoniumoxalate 17.0 5 Water. A 58.0

Example G Parts Aluminum sulfamate 25.0 Monoethanolamine acetate 25.0 I Water 50.0

Example H Parts :Aluminum sulfamate 24.9 15 .-Sodium Z-mercaptoethane-l-sulfonate 3.1 Water 72.0

Example I Parts Aluminum sulfamate 25.0 Sodium mercaptopropanesulfonate (1,2) 3.4 Water 71.6

Example J Parts Aluminum sulfamate 25.0 a-Alanine 21.2 NVater A 53.8

The eifectiveness of the various. discoloration inhibitors in Examples A to J inclusive was tested by dipping a cotton swatch into each solution and hetaing in an oven at about 214 F. for thirty minutes. In each case the discoloration of a similarly treated swatoh'whichhas been dipped into a; solution of aluminum sulfamate containing no "inhibitor was much greater than any of the swatches dipped, in the solutions of ExamplesA throug J.

Aqueous solutions of aluminum sulfamatesuitable for usein compounding theanti-perspirant compositions of theinvention may be prepared -=by;any appropriate method, such as by reaction of a theoretical amount of sulfamic acid with aluminum hydroxide geltogive a clear solution of'aluminum sulfamate. Another method which maybe used'comprises the reaction of barium sulfamate in an aqueous medium with a theoreti- .cal amount ofaluminum sulfate to form insoluble -barium sulfatewhich maybe removed to leave a *clearsolution of aluminum sulfamate.

'Althoughthe invention has been described in detail. andexemplified by numerous examples, it -wi'll .be. understood thatthe principles of the invention may be made use of by utilizing aluminum sulfamate with modified formulae such as will occur to those skilled in the art.

'What is claimed is: 1. A perspirant inhibiting or retarding preparation comprisingan aluminum salt of sulfamic -acid in an effective amount from about 5 to about .50% by weight, 'said'aluminum salt having a tendency'to discolor cellulosic fibers, and in an amount' suflicient to inhibit said discoloration an organic "nitrogen'compound selected from the class consisting of (a) amides which are neutral and contain the functional'group pound.containing,aluminum.

2. A perspirant inhibiting or retarding preparation comprising a water-containingvehicle, aluminum sulfamate in an eifective amount from about to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and a neutral amide containing the function group which is soluble in aqueous aluminum sulfamate and which does not precipitate therefrom a compound containing aluminum, the amount of said amide being at least in about equal molar proportion to that of said aluminum sulfamate and sufficient to inhibit said discoloration. I

3. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an efiective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and an ammonium salt of a non-hydroxy non-mercaptosaturated carboxylic acid and which is soluble in aqueous aluminum sulfamate and does not precipitate therefrom a compound containing aluminum, the amount of said ammonium salt being at least in about equal molar proportion to that of said aluminum sulfamate and sufiicient toinhibit said discoloration.

4. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an eifective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and an amino carboxylic acid compound containing the functional group ECNH2 and which compound is soluble in aqueous aluminum sulfamate and does not precipitate therefrom a compound containing aluminum, the amount of said amino carboxylic acid compound being at least in about equal molar proportion to that of said aluminum sulfamate and sufficient to inhibit said discoloration.

5. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an efiective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and urea in an amount suflicient to inhibit said discoloration.

6. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an effective amount from about 5 to about 50 %by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and diammonium malonate in an amount suflicient to inhibit said discoloration.

7. A perspirant inhibiting or retarding preparation comprising a water-containing vehicle, aluminum sulfamate in an effective amount from about 5 to about by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and, and glycine in an amount sufficient to inhibit said discoloration.

8. A perspirant inhibiting or retarding preparation in the form of a cream comprising fatty material emulsified with a Water-containing phase, aluminum sulfamate in an efiective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and urea in an amount suii'icient to inhibit said discoloration.

9. A cosmetic preparation for inhibiting or retarding perspiration comprising an oily phase held in dispersion in an aqueous phase, said aqueous phase containing aluminum sulfamate in an effective amount from about 5 to about 50% by weight, said aluminum sulfamate having a tendency to discolor cellulosic fibers, and in an amount suificient to inhibit said discoloration an organic nitrogen compound selected from the class consisting of (a) amides which are neutral and contain the functional group (b) amino carboxylic acids which contain the functional group ECNH2, and (c) compounds which are salts of non-hydroxy non-mercapto saturated "carboxylic acids and ammonia bases, said compound being soluble in aqueous aluminum sulfamate and not precipitating therefrom a compound containing aluminum.

LESTER D. APPERSON.

EARL LEROY RICHARDSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,621,528 Ellis Mar. 22, 1927 2,165,870 McQueen July 11, 1939 2,210,014 Teller Aug. 6, 1940 2,236,387 Wallace Mar. 25, 1941 2,504,107 Christian Apr. 18, 1950 OTHER REFERENCES Oberhauser: Chem. Abstracts, vol. 41, April 10,

Claims (1)

1. A PERSPIRANT INHIBITING OR RETARDING PREPARATION COMPRISING AN ALUMINUM SALT OF SULFAMIC ACID IN AN EFFECTIVE AMOUNT FROM ABOUT 5 TO ABOUT 50% BY WEIGHT, SAID ALUMINUM SALT HAVING A TENDENCY TO DISCOLOR CELLULOSIC FIBERS, AND IN AN AMOUNT SUFFICIENT TO INHIBIT SAID DISCOLORATION AN ORGANIC NITROGEN COMPOUND SELECTED FROM THE CLASS CONSISTING OF (A) AMIDES WHICH ARE NEUTRAL AND CONTAIN THE FUNCTIONAL GROUP