Patented Dec. ‘10, 1946 2,412,535 , UNITED STATES PATENT ‘OFFICE’ 1 2,412,535 ’ an'rrrnasrmam mamas-non Earl Leroy Richardson, Bound Brook, and Kenneth Lyman Russell, Nutley, N. J., assign‘ors to Colgate-Palmolive-Peet Company, Jersey City, N. J ., a corporation of Delaware No Drawing. Application November 29, ‘1944, Serial No.v 565,810 ‘ 6 Claims. (Cl. 167-90) 1 f ' The present invention relates to‘ improved preparations for retarding or inhibitingv perspira tion. 2 antl-perspirant agent on fabrics, but also is itself an anti-perspirant agent. . It is an object of this invention, therefore, to‘ ' Certain chemical compounds have the property ‘of retarding, eliminating or inhibiting the flow provide preparations which inhibit or retard per spiration and which do not have a corrosive ef of perspiration, and vmany of them are now. fect on fabrics. ' _ widely employed in preparations for that purpose. Of these compounds, the most commonly used v preparations which possess the full perspiration are aluminum salts, such as aluminumv chloride, retarding effect of the agents incorporated there It is another object of this invention to provide aluminum sulphate, and the like, but other com pounds, such as zinc, iron, tin and bismuth salts, in for that purpose, and which do not exhibit un desirable corrosive effect on fabrics. have also been proposed for the same purpose. Other objects will be apparent from the dis Such compounds are termed anti-perspirant closures herein. compounds or agents. 7 . . The objects of this invention are achieved by An undesirable consequence of the use of anti 15 providing preparations suitable for use as per perspirant compounds to stop the flow of pere spiration-inhibiting or retarding compositions, spiration has been found to be the corrosive ef containing aluminum salts now recognized as possessing that property, and also containing cer - fect of the composition on clothing. When a preparation containing these agents is applied to ‘ tain salts of acids of phosphorus which have the that area of the skin where retarding of the-per 20 effect of reducing or eliminating the corrosive ef spiration is desired, a portion» of the preparation ' fect of the perspiration-retarding agents upon may come into contact with and adhere to the These preparations may contain, as , fabrics. agents for inhibiting, retarding or eliminating clothing of the user. If the garment is ironed, perspiration in localized areas of the skin to pressed or otherwise heat-treated before the anti- ' perspirant agent is removed by laundering or 25 which they are applied, water-soluble astringent ‘salts of aluminum. The aluminum salts found _ cleaning, the corrosive effect of the composition ' is immediately manifested by a reduction in the strength of that portion of the garment withv which it has come into contact, sometimes even‘ resulting in holes, that is, a complete 100% de 80 terioration of the garment in speci?c areas. Long continued contact of the anti-perspirant agent with a garment, even at ordinary temperatures, may cause deterioration or reduction in strength . of the garment. The corrosive action of perspira tion-retarding compounds is particularly notice able on fabrics containing cellulosic materials, ‘such as cotton, rayon, and other synthetic ?bers; however, it is not limited thereto, and may be Obi»? served on other types of fabrics. most suitable for this purpose are aluminum sul phate and aluminum chloride, but other alumi num salts recognized by the art will serve the same purpose. The salts which have the effect of inhibiting or preventing the corrosive action or the anti-per spirant agents on fabrics are neutralized salts of acids of phosphorus, which are stable in solution, 35 asv illustrated by tertiary orthophosphates. Meta phosphates are not’suitable since'they are not stable in solution but gradually hydrolyze to form primary orthophosphates; and the primary and secondary orthophosphates, the so-called acid 40 salts, are not suitable to achieve the purposes de sired. Y Many methods have been proposed to reduce this undesirable effect of the perspiration-re The inhibiting salt may be selected to serve also as additional anti-perspirant agent in prepara tarding agents on fabrics, including the incor poration in the preparation containing the anti tions in which it is used. In such preparations, perspirant agent of such addition agents as urea 45 the cation of the inhibiting salt should be alumi num ion or the cation of some other perspiration and other amides, and oxides, hydroxides and inhibiting agent. A highly desirable preparation carbonates of aluminum, magnesium and zinc, and other compounds. Some of these addition may contain aluminum sulphate or chloride and agents do reduce or neutralize the corrosive ef aluminum orthophosphate or aluminum pyro fect of the anti-perspirant compound, but some 50 phosphate. In the making of these preparations of them also reduce the amount of anti-perspir or compositions, the aluminum phosphates are ant agent which has been incorporated in the added as such. preparation for thepurpose of retarding per If an increase in anti-perspirant agent is not spiration. No compound has yet been proposed desired, the inhibiting compounds may be pro which not only reduces the corrosive effect of the duced in situ. If it is desired to produce these 2,419,585 4 compounds in situ, that is, admixed with the anti perspirant agent, a suitable soluble'salt of an acid of phosphorus is added'to a solution containing _ . salt to one mol of thevinhibiting agent, or even less. sodium pyrophosphate or trisodium orthophos phate may be added to‘ a solution of aluminum sulphate, which results in the formation of It is appreciated that the cosmetic formulator cannot determine all the usesto which his Prep arations are to be directed. However, the fore going instructions will enable the manufacturer to select the proportion most suitable to his prod aluminum pyro- ' or orthophosphate. uct and, in cases of doubt, to include a safe pro- ' the anti-perspirant agent. For'example, tetra Likewise, the corrosive effect of the anti-rperspirant com portion of the ‘corrosion-inhibiting compound. It appears that aluminum phosphate in solu tion is itself an anti-perspirant agent, and that. when added as such (that is, not formed by the These novel‘ compositions may be made as reaction of the anti-perspirant compound with emulsions, solutions, creams, salves, and the like. a suitable soluble phosphate), it increases the and may contain any other ingredients which do not effect a chemical change in the perspiration ~15 potential anti-perspirant action of the prepara tion. inhibiting agent or in the fabric-protecting com The maximum proportion of the protective pounds and which are not irritating or otherwise aluminum phosphate that may be used is depend- ‘ unsuited for such preparations. That is, the nov ent upon the type of preparation to be made; el preparations may contain common cosmetic ingredients, coloring bodies, perfumes, and the 20 there is, in fact, no maximum within practical limits. If a clear anti-perspirant solution is de like. i _ sired, the maximum quantity of the corrosion-in The usual methods of compounding these prep hibiting aluminum phosphate'which may be in arations, such as are suitable for the preparation corporated therein, that is, in the aluminum sul of emulsions, solutions, extracts, selves, and the phate or aluminum chloride solution, is the great like, may be employed. est quantity of phosphate which may be dissolved The proportion of the anti-perspirant agent to in the solution. (Aluminum orthophosphate is the total composition may be widely varied and soluble only to a negligible degree in water, but is in?uenced by the type of preparation, the fre it readily dissolves to a considerable degree in a quency of use, and other like factors, but is gen erally a matter of choice. As has been disclosed 80 solution of aluminum sulphate.) In creams, emulsions and other non-transpar in the prior art, any proportion within the range ent preparations, the quantity of aluminum phos of 10% to 30% of hydrated aluminum sulphate phate may exceed that which will dissolve, par " makes a satisfactory preparation. In general, ticularly when the excess phosphate has no un the same proportions of aluminum chloride have desirable influence on the stability, appearance, been found suitable. or other characteristics of the preparation. , The proportion of phosphate salt to the anti When the inhibiting compound is formed' in perspirant agent‘ is dictated by the requirements situ, as by the addition of sodium or potassium or uses of the preparation. In those cases where orthophosphate or pyrophosphate to a solution garments which have come into contact with the of aluminum sulphate, the effect, if any, of the preparation are heat-pressed, or otherwise sub 40 by-product‘ sodium or potassium sulphate on the jected to high temperatures, without first being preparation should be considered. If this by laundered, a greater proportion of the corrosion product salt is undesirable for any reason in the inhibiting compound is required than otherwise, preparation, the inhibiting compound should not -a proportion of two to three mols of aluminum be formed in situ. 45 orthophosphate to one moi of aluminum sulphate _Thus, it will be seen that the limits of the being necessary for complete or substantially proportions of the aluminum phosphate corro complete protectionfrom corrosion. It will be sion-inhibiting compound may vary over a wide understood that even in those instances the tem range, and may be any desirable proportion that perature of the iron or pressing device has a di reduce or eliminate the corrosive action of rect relationship to the inhibiting power of the 50 will the anti-perspirant agent as a minimum and will phosphate salt. For example, when the tempera dissolve or not undesirably affect the preparation position may ‘be inhibited .by using tricalcium or 10 trimagnesium. orthophosphate. ture of the iron is no more than 250° to 275° F., two mols of aluminum orthophosphate to one mol - as a maximum. .In order to determine the corrosive effect, if of aluminum sulphate will afford substantially any, of the novel preparations on fabrics, certain complete protection from corrosion. However, 55 solutions and preparations were compounded. ap another factor to be- considered is the length of plied to fabrics, and the effect thereof upon the time during which the area containing the anti tensile strength of the fabric determined. perspirant agent is subjected to the ironing proc , In testing anti-perspirant creams, 21/2 grams ess. For the average time of ironing or pressing of the. preparation were applied evenly along a at 250° to 275° F., i. e., ?ve to ten seconds, the one-inch wide band, in the direction of the ?ll proportion speci?ed of two mols of aluminum or ing threads, in the center of a desized cotton thophosphate to one mol of aluminum sulphate muslin strip 24 inches long (in the direction of is satisfactory. Should the garment be such that the ?lling threads) and 6 inches wide (in the a higher temperature and/or a longer period of 65 direction of the warp‘ threads) . 'The treated fab- ’ pressing is required, the proportion should be ric was incubated at about 80° F. and 85-90% higher. relative humidity for twenty-four hours. The In view of the general method of laundering entire strip was then pressed for ?ve seconds and ironing garments, in which the cleaning . with the cream side down against the pad of a process removes the anti-perspirant agent or sub 70 G. E. flat bed ironer. The temperature of the stantially all of it, a smaller proportion of alumi ironer, which had been calibrated, was 293-305‘ num orthophosphate or pyrophosphate to the F. The ends of the strip were reversed, and the anti-perspirant agent is satisfactory. Prepara fabric was again pressed for ?ve seconds. The tions to be used under conditions of careful laun test fabric was then returned to the humidity dering may contain one mol of the phosphate 75 chamber and reconditioned for three hours. after . . 8,418,585 6 5 which time it was broken in the warp direction in a tensile strength testing machine by the 4" x 6" grab method, as outlined by A. S. T. M. Example V Parts Al2(SO4)a.18H-.~O ______________________ __ 25 (American Society for Testing Materials), Desig AIPO; _'_______________________ -__ ______ __ nation D39-39. As a control, a similar piece of 3.25 H20 ________________ __. ________________ __ 45.75 - the same cotton fabric (with no cream applied) Tensile strength loss of 54%. was treated in the same way along with the test strip. The diil'erence between the average tensile - Example VI strength of the control and test pieces was the . ' > Parts loss (or gain) in tensile strength due to the ef 10 A 34% solution of A1013 _________________ __ 22.4 fect oi’ the cream on the fabric. In’the case of anti-perspirant solutions, the muslin strip was folded along its width, and the folded edge was ‘immersed in the anti-perspirant H2O ___________________________________ __ 52.6 Tensile strength loss of ‘72.6%. Example VI‘I _ solution until there was a one-inch band of so AlPO4 _______________ __' _______________ _____ 14.0 Tensile strength loss of 34%. The following examples are formulae of prep arations which serve to illustrate the invention, Example VIII 7 NaaPO4J2I-IaO ___________________________ __.. 10 ples of this invention may contain the following 25 ingredients and percentages: mo , _ ________ __ Tensile strength loss of 1.7%. 40 ' Example IX Example I . Parts A12(SO4)3.18H2O ___;___'_ _________________ __ 25 and are not limiting in any sense thereon. - A suitable preparation embodying the princi Part I: Parts H20 __________________________ __,_-__'____- 38.6 - 20 . . A 34% solution of A101: ____________ __'_____ 22.4 lution along the center of the fabric. The ex cess solution was gently squeezed out, and the fabric was‘ allowed to hang, _to dry partially, for ?ve minutes. It was immediately pressed under the same conditions as outlined for creams. . Y . 1' Parts vAcid stabilized glycerol monostearate-___ 16 Spermaceti wax ______________________ __ 30 5 -Part II: H2O --__ _ Parts A1:|(S(__)4)3.18H20 _________ __. ______________ __ 25 Ca:(P04)z'_ ‘ 4 ' 46 Tensile strength loss of 22% . A12(SO4)3.18H2O _____________________ _- 19 A1PO4 ______________________________ __ Example X 7 Water ____________________________ __'__ 53 ' , Parts A12(SO4):I.18H2O __________ __. ___________ __ 25, The cream given in Example I caused a 32% reduction of the tensile strength of cotton fabric M83(PO4)2.5H2O _______________________ .._ H20 when subjected to the test previously described. Using no inhibitor, that is, substituting water 40 for the aluminum phosphate, the same test gave an 84% loss in tensile strength. The oil phase (part I) can be varied to suit the consistency ______________ __.“, _______________ __ 5.5 44.5 Tensile strength gain of 5.2%. The corrosive e?ect of the preparations given in the foregoing examples was determined ac cording to the tests. described hereinbefore. It is unlikely that any garment which might come. desired, as can the water phase (part II), but the ingredients of part II are the important agents 45 into contact with these preparations during use wouldbe subjected to such drastic conditions as in controlling‘ the anti-perspirant effectiveness those represented by these tests. Under less and the corrosiveness of the preparation. Ac drastic conditions, particularly where fabrics are cordingly, the use of 10 parts of aluminum phos washed or otherwise cleansed after contact with phate with a subsequent reduction of water gives an anti-perspirant solution which shows no. col‘.-_ 50 the anti-perspirant preparation and prior to pressing or other heat treatment, preparations rosive effect upon cotton fabrics. In fact, the such as illustrated by Examples 1, V, VII and IX test (see Example II) showed a slight increase would have av much less corrosive e?ect thereon. in tensile strength of cotton fabric. This solu It will be understood by chemists skilled in the tlon and other anti-perspirant solutions and their ‘ art that a solution made by dissolving aluminum effect on cotton fabric are noted herewith: 55 sulphate or aluminum chloride in water, and then dissolving aluminum phosphate therein, probably Example I! . Parts Alz(SO4)a.18HaO _________________________ __. 19 AIPO; __________________________________ -_ 10 H2O __- _____ __ __ 60 when sodium phosphate is dissolved in a solution Parts of aluminum sulphate, the solution contains alu minum, sulphate, phosphate and sodium ions. A similar condition obtains by the addition of the ‘other salts which have been referred to hereinbe Example III Al2(SO4)a.1BH2O _________________________ ..> 16 __.‘ _____ __. ________________________ __ 4 H2O _______________________________ __,____; 55 Tensile strength loss of 2.5%. phosphate in situ. Therefore, in view of the diiliculty of determin ing the nature of the various substances in the formed therein, the solution will be designated Parts A12(SO4)a.18H2O _________________________ -_ 18 AlP04 _____________________________ __'_____ 6 H2O ____________________________________ -_ 51 Tensile strength loss of 1.3% . 65 fore as suitable for formation of the aluminum solution, whether added as such or presumably‘ Example IV ‘ contains aluminum, sulphate - (or chloride) and phosphate ions, and possibly complex ions. Also, 45 _-_ Tensile strength gain of ‘6.3%. .AlPO4 does. not contain these compounds as such, but as a solution of the aluminum sulphate or alumi num chloride, or other astringent aluminum-salt, and the aluminum phosphate, whether added as aluminum phosphate or formed therein by the 75 addition of the salt, such as sodium, calcium, 2,412,586 , 8 magnesium. etc., phosphate, referred to herein? and an aluminum salt from the group consisting before. . 01' aluminum orthophosphate and aluminum py-jv We claim: 1. A perspirant inhibiting or retarding com position comprising a\ water-containing vehicle, rophosphate. the mol ratio of the aluminum phos phate to the aluminum salt or the ?rst group be Cl sisting oi’ aluminum sulphate and aluminum chloride, ‘and a corrosion inhibiting compound prising aluminum sulphate and aluminum ortho phosphate, the aluminum sulphate comprising selected from the group consisting of aluminum orthophosphate and aluminumv pyrophosphate, ing at least one to one. 4. A perspiration inhibiting preparation com an aluminum salt selected from the group con at least 10% or the total preparation and the mol 10 ratio of aluminum orthophosphate to aluminum the mol ratio of the phosphate to the salt of the first group being at least one to one. 2. Aperspiration ‘inhibiting or retarding com position comprising a water-containing vehicle, an aluminum salt selected from the group con sisting of aluminum sulphate . and aluminum sulphate being at least one to one. . 5. A perspiration inhibiting preparation com prising aluminum sulphate and aluminum pyro phosphate, the aluminum sulphate comprising at least 10% or the total preparation and the mol ratio or aluminum pyrophosphate to aluminum chloride in amount equal to from 10% to 30% ' sulphate being at least one to one. of the composition, and a corrosion inhibiting 6. A perspiration inhibiting preparation com compound selected from the group consisting of prising aluminum chloride and aluminum ortho aluminum orthophosphate and aluminum pyro 20 phosphate, the aluminum chloride comprising at phosphate, the mol ratio of the phosphate to the least 10% of the total preparation and the mol salt or the ?rst group being at least one to one. ratio 01’ aluminum orthophosphate to aluminum 3. A perspiration inhibiting cosmetic cream chloride being at least one‘to one. containing water, 10% to 30% of a substance selected from the group consisting of aluminum 25 sulphate and aluminum chloride, an oil phase, EARL LEROY RICHARDSON. KENNETH LYMAN RUSSELL.