US2854382A - Zirconyl hydroxy chloride antiperspirant compositions - Google Patents

Zirconyl hydroxy chloride antiperspirant compositions Download PDF

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US2854382A
US2854382A US66774057A US2854382A US 2854382 A US2854382 A US 2854382A US 66774057 A US66774057 A US 66774057A US 2854382 A US2854382 A US 2854382A
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antiperspirant
chloride
zirconium
aluminum
compositions
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Grad Martin
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Procter and Gamble Co
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q15/00Anti-perspirants or body deodorants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/19Cosmetics or similar toilet preparations characterised by the composition containing inorganic ingredients
    • A61K8/28Zirconium; Compounds thereof

Description

Sept. 30, 1958 M. GRAD ZIRcoNYL HYDRoxY cHLoR 1DE ANTIPERSPIRANT coMPosITIoNs Filed June 25, l1957 IIILII 'Inl Z if cany/ Hydroxy CoriQ/e' ATTORNEYS ZIRCONYL HYDRXY CIERIDE ANTI- PERSPT COMPSITONS Martin Grad, Cincinnati, Ohio, assigner to The Procter & Gamble Company, Cincinnati, hio, a corporation of Ohio Application June 25, 1957, Serial No. 667,740

6 Claims. (Cl. 167-96) This invention relates to antiperspirant compositions. More particularly, this invention relates to highly effective antiperspirant compositions which lare non-irritating to the skin and non-corrosive to textiles.

Cosmetic preparations which have a perspiration inhibiting or re'tarding elfect are well known. Many chemical compounds capable of preventing or retarding the exudation of perspiration have been used or suggested for use in such compositions. 'The aluminum saltsof strong acids, and especially the chloride and sulfate, have been considered to be the most efficacious and for a time found the most widespread use. Recently the milder compositions of aluminum and zinc such as salts of weak acids or highly buered formulations have come into wide use. Even more recently, various derivatives of zirconium have been suggested for eficient antiperspirant application. n

The aluminum and zirconium salts which are the most effective antiperspirants, usually in the form of strong acid salts, have the disadvantage of forming strongly acid solutions and thus the use of these materials in antiperspirant preparations can result in irritation to the skin and damage to clothing. Moreover, the use of the salts of weak acids, especially organic acids, offers no solution to this problem since such compounds are relatively ineffective in inhibiting the flow of perspiration. It has been found that, as a general rule, decreasing acidity of the antiperspirant compounds is accompanied by decreasing antiperspirant eicacy.

The problem of high acidity of these antiperspirant compounds has been met to some extent by their formulation in compositions with buffering agents which decrease the acidity. Buifering agents drastically'reduce the efcacy of strongly acid salts of aluminum such as the chloride and sulfate, but strongly acid salts of zirconium can be buffered with certain agents withoutout substantially decreasing the antiperspirant efficacy. Many problems have been encountered by this technique, however, especially with the strongly acid zirconium salts such as zirconium oxychloride, a compound which has been found to be a highly effective antiperspirant.

Zirrnonium oxychloride (ZrOC12) is so strongly acidic .States Patent() ice that in order to formulate it into an antiperspirant composition, substantial quantities of buffering agents `are required to make it safe for use. These buffering agents are often expensive and their presence in substantial quantities reduces the amounts of formulating agents which can be used to make the antiperspirant composition into a cream or lotion, forms which are highly desirable. Moreover, because of the lengthy and complicated hydrolysis reaction characteristics of zirconium oxychloride in the various aqueous compositions, pH stability of the compositions is diliicult to obtain and complicates their formation.

It is an obiect of the invention to provide compositions which are highly elfective in inhibiting or retarding the exudation of perspiration and yet which are non-irritating to the skin and non-corrosive to textiles.v

2,854,382 Patented Sept. 3,0, 1958 A further object of the invention is the provision of highly eiective, non-irritating, and non-corrosive antiperspirant compositions which can easily be formulated into liquids, lotions, creams and other forms for application.

It has been found that the'disadvantages associated with prior art compositions containing aluminum and zirconium salts can be`overcome and the objects of this invention can be realized by providing an antiperspirant composition comprising in combination, an aqueous solution of zirconyl hydroxy chloride (ZrOOHCl), an aluminum chlorhydroxide complex which acts as a buffer and an amino Iacid in which `the number of Aamino groups is equal to the number of carboxyl groups in the molecule which, if required, acts as an additional buifer and an anti-gelling agent.` Forfconvenience, such amino acids will be referred to herein as neutralamino acids.

The drawing is a graph showing the range of the ratios of the ingredients suitable for the antiperspirant compositions of l this invention as hereinafter more completely described.

As mentioned hereinbefore, various zirconium derivativesl have been suggested as antiperspirant agents. The most ecacious of theseare the salts of the strong acids lwhich form such "strongly acid solutions that there is danger-'iny their use. ln general it has been recognized that most mineral acid salts of zirconium, if soluble in water; are relatively highly acid and cannot therefore safely be used alone in contact with the skin. For example, zirconium tetrachloride reactsvigorously with waterl to form zirconium `oxychloride and hydrochloric acid; 'Even this hydrolysis product, zirconium oxychloride,`, has a pH of about 0.8 in unbu'iered solution and is therefore uniit for general antiperspirant use.

Advantage has been taken of the excellent antiperspirant properties of zirconium oxychloride by rendering it usable in yaqueous solution by combination with an aluminum chlorhydroxide vcomplex and neutral amino acids; The aluminum chlorhydroxide complex and the amino actas buffering agents tobring the pH of the solution of the zirconium oxychloride to a value which renders it safe for antiperspirant usage, i. e. about 3 to about 5.` This buffering action takes place with substantially n'o loss in the antiperspirant eiiectiveness as compared to unbuered zirconium oxychloride. This was unexpected 4with zirconium-oxychloride since experience with the various aluminum salts commonly used in antiperspirants has shown decreased ei'cacy with buffering. The effectiveness of buifered zirconium oxychloride compositions is aptly illustratedin an articley in the Proceedings of the Scientiiic'Section ofthe Toilet Goods Association, December "1956,: page '27; That article shows Vthat vbuffered zirconium oxychloride `compositions are safe and that they have greater antiperspirant eicacy than aluminum sulfate,`aluminu'm chloride and aluminum chlorhydroxide complex antiperspirant compositions, such aluniinum= compounds having found the greatest practicalconnnercial use. t

However, it has lbeen found that zirconium oxychloride (ZrOClZ). has certain disadvantages .when used in appropriately bufferedl .antiperspirant compositions. Since zirconium oxychloride is so strongly acidic,:the quantity of buiering agents lneeded .to render it safe in a composition is larger than isdesirable. It would, therefore, be advantageousy to use a zirconium saltwhich is -less acidic and whichwould v require a lesseramount of buffering agents, but'would be equal in antiperspirant eicacy to zirconium oxychloride' for use in antiperspirant compositions. However, experience with a number of less Iacidic zirconiur'nl saltsj 4such as `zirconium carbonate, zirconium lactate,`lzirrconium 'glycolate and zirconiumy acetate has shown that they are very inferor to zirconium oxychloride 3'; in nniipofsoifnni oiiionoyf Diniioonioin irionyolilorioo (Zr2O3Cl3), which can be formed by reacting zirconium oxychloride with an alkali metal carbonate, is less acidic (pH of about 1.4 in solution) than zirconium .oxychloride, but alsoy has vsubstantially decreased, antiperspirant efficacy.

Since it was found` that z irconyl hydroxy.v chloride (ZrOOHCl) is less acidic (pH of about 1.2 in solution) than zirconiumv oxychloride` it was expected thatjtlwould likewise. be less evcacious. However, it wasmand-.that nrconyl hyhroxy. chloricl whencompared withzirconium oxychloride on anequal molar basis, h as. substantiglly oqonl. or honor nntipoispirant oiiioooyf'wlion bniorodzto tho. .Soins-.Pliin ontiorsnirnni compositions.

nioloonlnr.- Weight. of zitoonyl hydroxy Chloride is los* illnnnhnt of: niioonioni.. onvolilofidsand. itwns fonnd hat onion-equal. molar.. basis... about loss oi liioonvlfliydroy ohloridsyrwoisht is. nooslod for oqoivnlont; ooiinoisoiinnt oni. .oy-

psrrnitsf tho ioinl nmoontiof. noooosary Solitiglnsrodionts.' n n. antiperspironi Composition .iogbo losa Sinon ziroonyl hydroxy ohloriofis, loss it. was

found that tho total ninollni of boiorins agonia ospeoiolly f the neutral amino acids, required'A to Vo lgtaiulK al desirable oli isA Substantially 'loss thon.- iilot .rsaoirodf to. ,ronslorf liroonionn onlfolnliorisio Snioinfo Composition. In addition io. ihoooonotnioodvanioso.. of. thoflosso fninonni of: bofforinaasonlo. roaoiroofin tho oonirtosifionsy offhis invonl tion. 'iiio anioont of nooossnry. Solidinsiodients. is forihof. rodoooit. This` Permits. lhonildiiion of greater anionnts ofioiniolatinsnsonts-to tho; Composition when Grooms. or. lotions. nro. dosiroo. The. oosinolio vorintilitv with which omino-.finiront Compositions. can .be .produced is nfvoiy iniporinntooninioroiol novanta.

'Ihealuminum chlorhydroxide complexwith which. the zirconyl hydroxy chloride is preferably combinedffor butering..purposes. has the general empirical formula A12( OH ),6 ,!C ln where vn has an average-valuefrom about 0.8 to. about 1.2. It has been found that the aluminum chlorhydroxide complex of theformula A1,(OH) gCLxHgO where x is about 2Vnds ready application in the-practice of/theinvention in combination withthe 'zirconylhydijoxyV chloride although it is to be` appleciatedsthatthis basic aluminum compound itself hasantiperspirant Proportion.-A

In ih o Piopnration of thonishod products-from compta Siiions` oiihis invention, tho oonoontrationotthe zirconyl hydroxy chloride and the. aluminum, chlorhydrox'idecomplex can vary from about-5% toV about 30%, pgeferablyfrom about.8% to .about theseranges beingL on an. anhydrous basis.the.. relative permissible proportionsof each being more fullyhereinafter described.

Itwisno't known. precisely why the combinations of zirconyl hydroxy chloride theV alunztinum` chlorhydrpgixideY complex act as, such. elfectiveand safe` antiporspirnnts- It is probablethat-the aluminum. 4chlorhydroxide complex possesses-a characteristic other than that of :a mere buffer to` safe. the. n'rconylzhydrox-y chloride. in4 the composition.. It has. been.` found that :in order .to achievethe objects of thiszinvention, i. e. a safe, yet very effective, stable antiperspirant Aconvipositiomthe ratio of the.aluminumchlorhydroxidecomplex andthe zirconyll hydroxy chloride should be controlledfwithin certain limits. Ithas been foundthat these ratio limits of aluminum chlorhydroxide complex to basic zirconyl chloride shouldxbe in the rangevof from about."0.5l:l to 3;l, on amolesbasis, in order for the antiperspirantvcom; Positions to` have .the outstanding. Safety. 'versatility and. emacy characteristic of this invention. lnall cases, however'. the proportions of al1-the1constitu entsA of `the tion from s the standpoint of skin irritation and fabric damage.

Although, theoretically, any neutral amino acid, as hereinbefore defined, can be used to accomplish the objects of the invention, it is to be appreciated that as a practical matter only those` neutral amino acids which are suciently soluble in the aqueous solutions are usable, forexample glycine, DL-valine, B-alanine, DL- methionine, DL-tryptophane and DL-B phenyl-alanine. Suicient neutral amino acid shouldl be added.A inl the preparation of the compositions of the inventionso that the composition will not gel and the proper pHis obtained. Gelling of the composition is due to the fact that zirconium andaluminum are multivalent and tend to form complexes. Certain concentrations of these salts in aqueous solutions tend to interact and form gels within a very short time (1 to 2 weeks) and become practicarlly useless as antiperspirantcompositions; The neutral aminov acids ad... to prevent this gelling. One of the advantages of this-inventionpas compared ,with zirconium oxychloride compositions istliat.aV lesser amount ofamino acid is required to prevent thisgelling. In factrwhen the ratio of aluminum chiot-hydroxide complex to zirconyl hydroxy chloride is greater than about 1.5 :1 and theconceutration of these-salts is about 10% or less, no neutral ac idispneeded to prevent gelling and, in the; stated pIjL range, a ,s afe non-irritating, effective. antiperspirnnt oompositionoonbeobtnined.

The shaded portions of the graph in the drawing-illustrates Iii-nits.witl1iu,whi ch it'y has been found that the safe, versatile, eective antiperspirant compositions of this inyention substantially. in the pH range of about 3.25 to about 4.2 5 .can be obtained. The abscissa values are the mole ratios of the aluminum chlorhydroxide complex to the zirconyllhydroxy` chloride and these mole-ratios range from about 0.521 to about 3:1. The ordinate values are the mole ratios of neutralamino acid-to the zirconyl hydroxy chloride required and canrange from 0 to about 4.5 :1, according to the curves Von thegraph. All cornpositions within theshaded portions of ,the graph are substantially non-irritatingto the skin. Thosc` composititnnnl falling in Area` A show a tendency toward fabric` damage, but in-any casethe damage is not signifi'- cantv audiisnmarkedly less thanthat experienced. with comparable zirconium oxychloride, aluminum chloride or aluminum sulfate antiperspirant.compositions. 'lhose compositions falling on the.curve. separating Area A and Area Ban,d, falling.A in Area Bare substantially -completelyssafeI to.- fabric:s.A It mustA be appreciated that the amount-,ofmeutral amino acid used with compositions in AreaB isin ,excessofthat required toy prevent gelling of the composition and'to` render thev compositions completelysafe. for fabrics. However, it often may be desirable in; commercial practiceto. use an excessl oE-neutral amino aidyto allow llexibilityin the proportions ofthe aluminum and..zirconium salts and las a safety factor to ensure .prevention of vfabric damage.

Thefmaximum amount-of neutral amino-acid vuseful in thecompositionis limitedfonly--by practical or economic considerations, and `according to the graph, is about 17.5%.by weightof the composition if the total concentration.. ofzirconyl hydroxy chloride and aluminum chlorhydroxide complex is1as high as 30% and,l is about 11.5% if 'the total concentration lof these salts is about 20%. The, minimumamount of neutral amino, acid useful inthe compositions of this invention is that required to preyentlgelling of the composition within the pHrange-of 3.25 to 4.25. This minimum amount can bedetermined by usingtherat-ios of.neut ral aminotacid to zirconyl hydroxy chloride found in thelowcst portion offAreaA of the V,graphfor aparticular. ratio of aluminum chlorhydroxidecomplex. to. zirconyl hydroxy chloride. II igh; total..concentnations of..zirconyl hydroxy chloride and aluminum chlorhydroxide complex require slightly It has been also found that the neutral amino acidsV alone, without any aluminum chlorhydroxide complex being present, will buffer a zirconyl hydroxy chloride. The quantity of amino acid necessary to raise the pH of the zirconyl hydroxy chloride to a level which is considered safe from the standpoint of skin irritation and corrosion of textiles is, however, prohibitively large when compared with that necessary when the aluminum chlorhydroxide complex is also present. For example, a 7.5% solution of zirconyl hydroxy chloride on an anhydrous basis required glycine to provide a solution pH of 3.7. Also, the antiperspirant efcacy of such composiu tions, i. e. those bufered solely with a neutral amino acid, is rather poor when compared with those compositions -buffered with an amino acid and aluminum chlorhydroxide complex or only aluminum chlorhydroxide complex, and is, in fact, poorer than the eicacy displayed by the well-known aluminum chloride antiperspirants. `Consequently, it is not considered that those zirconyl hydroxy chloride containing antiperspirant compounds buifered with a neutral amino acid alone fall within the scope of the present invention.

The antiperspirant compositions of the invention can be formulated into cosmetic preparations which are in liquid7 semi-liquid or other forms, the water in the cosmetic preparation comprising from about 25% to 95% by weight thereof. Representative formulas for a cream type, a lotion type, and a liquid antiperspirant 'utilizing zirconyl hydroxy chloride and aluminum chlorhydroxide complex as the active antiperspirant constituents are set forth below. e'

Cream: Parts by Weight Zirconyl hydroxy chloride (ZrOOHCl-3H2O) 5.0 Aluminum chlorhydroxide (A12(OH)5Cl-2H2O) 7.5 Glycine 2.0 Water 59.1 Perfume 0.2 Glyceryl monostearate 10.0 Spermaceti wax Ll-.fl Mineral oil (about 70 S. S. U. at 100 F.).. 4.0 Polyoxyethylene 50 stearato, Myrj 53 5.0 Glycerine 3.0 Titanium dioxide 0.2

Lotion:

Zirconyl hydroxy chloride (ZrOOHCl-3I-I2O) 5.0 Aluminum chlorhydroxide (A12(OH)5Cl-2H2O) 7.5 Glycine 2.0 Water 75.8 Veegum 1.0 Glyceryl monostearate 2.0 Mineral oil (about 70 S. S. U. at 100 F.) 1.0 Spermaceti wax 0.5 Polyoxyethylene 100 stearate, Myrj 59 V 2.0 Glycerine 3.0 Perfume 0.2

Liquid:

Zirconyl hydroxy chloride (ZrGGHCl'3H2O) 5.0

Aluminum chlorhydroxide (A12(OH)5Cl-2H2O) 7.5 Glycine 2.0 Polyoxyethylene sorbitan monooleate,

Tween 80 2.0 Ethanol 2.0 Perfume 0.2

Water 81.3

it is to be understood that in the above compositions the ingredients other than the zirconium salts and aluminum salts and glycine have been added, not for their antiperspirant characteristics, but to obtain a product having properties which are desirable from a purely cos- `6" metic aspect. Also, if desired, various bacteriostatic, germicidal and/ or deodorizing agents such as hexachlorophene (2,2dihydroxy 3,5,6-3,56hexachlorodiphenyl methane or the quaternary ammonium salts such as para diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride mono-hydrates, Vcan be added in lthe preparation of these antiperspirant cosmetic preparations. The use of these and otheradditives is optional and while contemplated in the kcommercial practice of the invention is not claimed as essential to the -antiperspirant function of the compositions.

The antiperspirant composition off the prior art containing zirconium oxychloride were characterized by a pH which rose to an equilibrium value as the composition aged. When the zirconium oxychloride is dissolved in water the hydrolysis and hydration of `the molecules and ions proceed slowly. As hydration proceeds, the nature and extent of hydrolysis change. During the period in which these changes occur, the chemical properties of the solution change, and therefore, the pH does not reach equilibrium until these changes are substantially complete. Often the pH of a zirconium oxychloride, aluminum chlorhydroxide complex composition was observed to have changed substantially in pH particularly in the rst week after formulation. `It has been found that zirconyl hydroxy chloride is apparently inV a more stable form and appears to hydrate and hydrolyze to a much lesser extent and therefore tends to reachan equilibrium pH in a shorter time than the compositions containing zirconium oxychloride. A shorter time to reach equilibrium pH is a great advantage in the formulation of antiperspirant compositions since the determination of the proper pH is important. While an equilibrium 'pH which takes time to reach may be predictable with experience, `for testing and packaging purposes a shorter time is very desirable.

In the following examples, which are by vway of illustration only, the eiicacy of the various antiperspirant compounds was determinedby the following methods.

The back of human subjectsuwere Washed with soap and water and a number of cotton disks, about 11/2 inches in diameter, saturated with a solution of the antiperspirant to be testedwas placed on each back. The saturated patches were left in place for ve minutes, then removed and each test area was blotted dry with a towel.

After about six hours the back was coated with an indicating cream made up of sodium carbonate, phenolphthalein and an anhydrous oleaginous base, and sweating was induced by either exposing the subjects to heat and high humidity or through vigorous exercise. This indicating cream turns a bright red whenever a droplet of perspiration appears. Thus, in areas where eective antiperspirants had been applied only a few drops of perspiration appeared, the resultant few bright red droplets contrasting these areas withlthe surrounding untreated areas which showed a high! proportion of the red droplets.

After the sweat pattern was fully developed a photograph of the subjects back was made. 8 x 10 inch prints of these photographs were obtained so that the test areas on the prints were about one inch in diameter. The

.number of sweat droplets appearing in a square one-half inch `on a side were counted on each test area and a count of the number of sweat droplets in an equal-sized but untreated adjacent area was also made. The percentage reduction in sweating was then determined by a comparison of the count lfor the untreated area with the count for a treated area.

In addition to the above-described back testing method, another method involving direct measurement in the axillae is Very significant in that that area is of the most practical importance in the inhibition of perspiration. The axillae method used a gravimetric measure of the amount of perspiration produced in the axillae to determine antiperspirant effect. Sweating was induced by 7 either exposing the subjects to heat and high humidity orthrough vigorous exercise. A fter the sweat-induction period, tared Webril p ads were placed under each arm for a given period, usually ten minutes. These pads were weighed after the sweating period, and the amount of perspiration produced determined.

While the amounts of perspiration produced in the left and right axillae of a subject are usually not the same, a given subject will have a reasonably consistent ratio of output between the two sites. A normal ratio for a subject was established by making four or five control runs before any treatment was applied. When the antiperspirant to be tested was applied to one arm the normal ratio was significantly altered. The reductionV in sweating produced by the antiperspirant was obtained by fitting the results from this method into the formula antiperspirant test. ratio X 1(1) average untreated `ratio Example I.-Antiperspirantcompositions were formulated by dissolving the following-ingredients in the water shown:

Peroentfreduction== 100- It is to be noted vthat the amounts of zirconium saltin the above compositions are approximately` on an equal mole basis. Six parts of glycine were required in Composition B to `prevent gelling and to obtain a pH of 3.8 in conjunction with the 7.5 parts aluminum chlorhydroxide complex. ,It is toV be noted that Composition A, the zirconyl hydroxy chloride composition, required only two parts of glycine, i. e. one-third as much, in order to prevent gelling and to .obtain approximately the same pH as Composition B using the same amount of aluminum chlorhydroxide complex. Y

These two compositionsV and solutions of other antiperspirant compounds were compared for antiperspirant c Theecacy by means of the axilla testing technique. subjects were treated and tested with the-composition each day for four days.

It is apparent that the zirconyl hydroxy chloride antiperspirant Vcompositions are equal to, if not superior to, the zirconium oxychloride compositions in antiperspirant etlicacy. Moreover, the zirconyl hydroxy chloride compositions are markedly superior in eflicacy to the other solutions of antiperspirant compounds.

Composition C was formulated by dissolving the following ingredients in the water shown:

Parts by weight Zirconium oxychloride (ZrOCla-SHzO) 8.0

Aluminum chlorhydroxide (Al2(OH)5Cl-2H,O) 7.0 Glycine 2.5 Water 82.5 pH-3.5

A series of tests was made to determine the effects of various antiperspirants on the tensile strength of textiles. The procedure was as follows:

Cotton muslin was washed, rinsed thoroughly and ironed dry. It was then cut into strips measuring 6 inches by 21 inches. An area one inch wide was marked lengthwise down the center of each strip and the area was saturated with the antiperspirant to be tested. An identical strip containing no antiperspirant was carried through the treatment along with the antiperspirant-containing' strips to serve as ay control. All strips were stored for 24 hours at about 80 F. and 80% relative humidity, were then ironed at 275 F. and again stored under the same conditionsV for three hours. At the end of this period the strips were tested for tensile strength using a Scott tensile strength machine with one inch jaws.

Percent loss in strength It is apparent that the zirconium oxychloride composition required much more glycine to obtain a safe composition from the point of fabric damage. The zirconyl hydroxy chloride compositions of this invention are very mild with respect to skin irritation and fabric damage as compared to other common, less eicacious antiperspirant compositions.

The water-soluble, neutral amino acids DL-valine, B- alanine, DL-methionine, DL-tryptophane and DL-B phenyl-alanine can be substituted for the glycine in Composition A in this example on an equal mole basis to give substantially equivalent results.

Any of the aluminum chlorohydroxide complexes having the formula A12(OH), C1 where n ranges from about 0.8 to about 1.2 can be substituted in composition A with substantially equivalent results and only slight variation in pH.

The aluminum chlorhydroxide compleses and zirconyl hydroxy chloride salts described in this invention ordinarily exist as hydrated salts in the dry state. The amount of the water of hydration in these salts in their dry state does not affect their properties when used in the aqueous antiperspirant compositions of this invention; in fact anhydrous salts could be used if they were available.

Example II.-Antiperspirant compositions were formulated by dissolving the following ingredients in the water shown:

It is to be noted that the above three solutions have approximately equal zirconium content. It has been found that zirconium content is the best basis for comparison of the zirconium chloride salts. These salts were buffered with equal quantities of aluminum chlorhydroxide and the pH of each solution Was approximately equalized with glycine in suiiicient amount also to prevent gelling.

The solutions were then tested for antiperspirant efticacy by using the back testing method on seven male subjects.

Percent reduction in sweating Solution A 59 Solution R 21 Solution C- 39 It is apparent that the antiperspirant ecacy of the zirconyl hydroxy chloride solutions is outstandiugly superior to those of dizirconium trioxychloride.

It is to be pointed out that zirconium and hafnium have a chemical similarity greater than that existing between any other pair of elements. This is a reection of the similar arrangement of the electrons of their two outermost major quantum groups and the closeness of their atomic radii. Zirconium and hafnium are always found associated in nature and nearly all zirconium compounds contain more or less of hafnium. 'I'.herefore, if hafnyl hydroxy chloride exists as a compound, its properties should be so similar to zirconyl hydroxy chloride as to be substantially equivalent.

The term consisting assentially of as usedv in the definition of the ingredients present in the composition claimed is intended to exclude the presence of other materials in such amounts as to interfere substantially 10 with the properties and characteristics possessed by the composition set forth but to permit the presence of other materials in such amounts as not substantially to affect said properties and characteristics adversely.

Having described the invention, what is 'claimed is:

1. An aqueous perspiration inhibiting composition consisting essentially of 1) zirconyl hydroxy chloride having the general empirical formula ZrOOHCl; (2) an aluminum chlorhydroxide complex having the general empirical formula Al2(OH)6 Cln where n has an average value from about 0.8 to about 1.2; (3) from 0% to about 17.5% by weight of a Water-soluble amino acid, in which the number of amino groups is equal to the number of carboxyl groups in the molecule, in an amount suiicient to prevent gelling of the composition, the minimum amount being determined by using the ratios of neutral amino acid to zirconyl hydroxy chloride found in the lowest portion of Area A of the graph in the drawing and (4) about 25% to about 95% water, the concentration of constituents (1), (2) and (3) being on an anhydrous basis, the total concentration of lconstituents (l) and (2) being from about 5% to about 30% by weight of the composition and the proportions of constituents (2) and (1) being so related that their mole ratio is between 0.5:1 and 3:1 and the proportions of constituents (l), (2) and (3) being so related as to fall within the shaded portions on the graph in the drawing and the proportions of all constituents being so related that the pH of the composition is in the range of from about 3.25 to about 4.25.

2. The composition of claim l wherein the concentration of constituents 1) and (2) are from about 8% to about 20% by weight and the concentration of constituent (3) is from 0% to about 11.5% by Weight.

3. The composition of claim l wherein the amino acid is glycine.

4. The composition of claim 2 wherein the amino acid is glycine.

5. An aqueous perspiration inhibiting composition consisting essentially of (l) about 5 parts by Weight zirconyl hydroxy chloride trihydrate; (2) about 7.5 parts by weight aluminum chlorhydroxi'de complex dihydrate;

v(3) about 2 parts by weight glycine; and (4) .from about 59 parts to about 85.5 parts water.

6. An aqueous perspiration inhibiting composition consisting essentially of (1) about 5% by weight zirconyl hydroxy chloride trihydrate; (2) about 7.5% by weight aluminum chlorhydroxide complex dihydrate; (3) about 2% by weight glycine; and (4) about 85.5% of a mixture of water and cosmetic ingredients.

No references cited.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,854,382 Septemberao, 195s Martin Grad It is hereby certed that error appears in the printed specification of the above v numbered patent requiring correction and that the `said Letters Patent should read as corrected below.

Column 1,1nes 50 and 51, for Without-out read without; line 56, for Zirmonium read Zz'rcom'um; column 3, line 40, for A12(OH) 501.001-120 read AZOH) 5UZ-wH20; column 8, line 50, for chlorohydroxde read chZoTLg/drom'de; line 55, for compleses read oomplees; line 66, Jfor (ZrOOHC1.3H2O) read (ZTOOHUZ-HgO) line 68, for (A12 Q Cln-QHZO read @..nZn QHQO- Signed and sealed this 27th day of January 1959.

[SEAL] Attest: KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Oyicer. owmz'ssz'oner of Patents.

Claims (1)

1. AN AQUEOUS PERSPIRATION INHIBITING COMPOSITION CONSISTING ESSENTIALLY OF (1) ZIRCONYL HYDROXY CHLORIDE HAVING THE GENERAL EMPIRICAL FORMULA ZROOHC1; (2) AN ALUMINUM CHLORHYDROXIDE COMPLEX HAVING THE GENERAL EMPIRICAL FORMULA A12(OH)6-NC1N WHERE N HAS AN AVERAGE VALUE FROM ABOUT 0.8 TO ABOUT 1.2; (3) FROM 0% TO ABOUT 17.5% BY WEIGHT OF A WATER-SOLUBLE AMINO ACID, IN WHICH THE NUMBER OF AMINO GROUPS IS EQUAL TO THE NUMBER OF CARBOXYL GROUPS IN THE MOLECULE, IN AN AMOUNT SUFFICENT TO PREKVENT GELLING OF THE COMPOSITION, THE MINIMUM AMOUNT BEING DETERMINED BY USING THE RATIOS OF NEUTRA AMINO ACID TO ZIRCONYL HYDROXY CHLORIDE FOUND IN THE LOWEST PORTION OF AREA A OF THE GRAPH IN THE DRAWING AND (4) ANOUT 25% TO ABOUT 95% WATER, THE CONCENTRATION OF CONSTITUENTS (1), (2) AND (3) BEING ON AN ANHYDROUS BASIS, THE TOTAL CONCENTRATION OF CONSSITUENTS (1) AND (2) BEING FROM ABOUT 5% TO ABOUT 30% BY WEIGHT OF THE COMPOSITION AND THE PROPORTIONS OF CONSTITUENTS (2) AND (1) BEING SO RELATED THAT THEIR MOLE RATIO IS BETWEEN 0.5:1 AND 3:1 AND THE PROPORTIONS OF CONSTITUENTS (1), (2) AND (3) BEING SO RELATED AS TO FALL WITHIN THE SHADED PORTIONS ON THE GRAPH IN THE DRAWING AND THE PROPORTIONS OF ALL CONSTITUTENTS BEING SO RELATED THAT THE PH OF THE COMPOSITION IS IN THE RANGE OF FROM ABOUT 3.25 TO ABOUT 4.25.
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Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009769A (en) * 1960-06-02 1961-11-21 Chattanooga Medicine Co Method of preparing zirconiumaluminum-chloro complexes
DE1164600B (en) * 1958-10-21 1964-03-05 Chattanooga Medicine Co Using Zirkonyltrichloraluminat or its hydrate as a transpiration and perspiration odor inhibitory agent
US3198708A (en) * 1960-06-14 1965-08-03 Colgate Paimolive Company Antiperspirant-deodorant composition
US3235458A (en) * 1962-08-22 1966-02-15 Colgate Palmolive Co Process for preparing an aluminum sulfate-aluminum chlorhydrate antiperspirant cream
FR2099688A1 (en) * 1970-07-30 1972-03-17 Procter & Gamble
US3927188A (en) * 1971-07-20 1975-12-16 Armour Pharma Zirconium complexes of basic aluminum bromides and methods of making same
US3928545A (en) * 1971-07-20 1975-12-23 Armour Pharma Zirconium complexes of basic aluminum chlorides and methods of making same
US3928557A (en) * 1970-10-28 1975-12-23 Exxon Research Engineering Co Deodorant formulations and antiperspirant formulations containing particular aliphatic diols and their esters
US3947556A (en) * 1971-07-20 1976-03-30 Armour Pharmaceutical Company Zinc complexes of basic aluminum chlorides and methods of making same
US3947557A (en) * 1971-07-20 1976-03-30 Armour Pharmaceutical Company Zinc complexes of basic aluminum bromides and methods of making same
US3981986A (en) * 1973-11-23 1976-09-21 Armour Pharmaceutical Company Zirconium-aluminum-polyol buffered anti-perspirant complexes
DE2605386A1 (en) * 1975-03-26 1976-10-07 Armour Pharma Basic zirconium complexes and methods for making and using same in antiperspirants
US4017599A (en) * 1973-11-23 1977-04-12 Armour Pharmaceutical Company Aluminum-zirconium anti-perspirant systems with salts of amino acids
US4021536A (en) * 1975-04-18 1977-05-03 Armour Pharmaceutical Company Magnesium-zirconium complexes useful as antiperspirants
US4025615A (en) * 1975-02-25 1977-05-24 Armour Pharmaceutical Company Antiperspirant complexes formed with alkali metal and ammonium zirconyl carbonates
US4120948A (en) * 1976-11-29 1978-10-17 The Procter & Gamble Company Two phase antiperspirant compositions
US4331609A (en) * 1980-09-08 1982-05-25 The Procter & Gamble Company Antiperspirant composition
US4369173A (en) * 1974-11-27 1983-01-18 Wickhen Products, Inc. Antiperspirant compositions
US4775528A (en) * 1983-08-16 1988-10-04 The Gillette Company Antiperspirant composition
US4871525A (en) * 1986-10-24 1989-10-03 Westwood Chemical Corporation Antiperspirant composition and method of preparation
US5098698A (en) * 1989-03-16 1992-03-24 The Gillette Company Novel antiperspirant adduct compositions and process for making same
US5114705A (en) * 1983-08-16 1992-05-19 The Gillette Company Antiperspirant composition
US5225187A (en) * 1991-02-15 1993-07-06 Somerville Technology Group, Inc. Process for preparing concentrated aluminum-zirconium solutions
US5298640A (en) * 1983-08-16 1994-03-29 The Gillette Company Antiperspirant composition
US5486347A (en) * 1983-08-16 1996-01-23 The Gillette Company Antiperspirant composition
US5601809A (en) * 1986-09-26 1997-02-11 The Gillette Company Axillary malodor neutralization
US6436381B1 (en) 2000-10-25 2002-08-20 The Gillette Company Aluminum-zirconium antiperspirant salts with high peak 5 al content
US6663854B1 (en) 2002-06-19 2003-12-16 Yan-Fei Shen Aluminum-zirconium antiperspirant salts made with zirconium salts having low Zr:Cl ratio
US6726901B2 (en) 2002-05-09 2004-04-27 The Gillette Company Stabilized antiperspirant compositions containing aluminum-zirconium salts with low M:Cl ratio
US20050019287A1 (en) * 2003-07-22 2005-01-27 Zijun Li Stable aluminum / zirconium antiperspirant solution free of amino acid and polyhydric alcohol
US20050191256A1 (en) * 2003-04-04 2005-09-01 Colgate-Palmolive Company Glycine-free antiperspirant salts with betaine for enhanced cosmetic products
US20050276773A1 (en) * 2004-06-10 2005-12-15 Parekh Jawahar C Fragrance friendly and cost effective antiperspirant actives and method of making the same
US20060008435A1 (en) * 2004-07-07 2006-01-12 Somerville Technology Group, Inc. D/B/A Summit Research Labs Stabilized aqueous aluminum zirconium solutions
US20070187256A1 (en) * 2006-01-06 2007-08-16 Pratt Willam E Polyaluminum Chloride and Aluminum Chlorohydrate, Processes and Compositions: High-Basicity and Ultra High-Basicity Products
US20070196302A1 (en) * 2006-01-06 2007-08-23 Pratt William E Polymetal Hydroxychloride Processes and Compositions: Enhanced Efficacy Antiperspirant Salt Compositions
EP3192491A1 (en) 2016-01-15 2017-07-19 Evonik Degussa GmbH Composition comprising polyglycerol esters and hydroxy-alkyl modified guar

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1164600B (en) * 1958-10-21 1964-03-05 Chattanooga Medicine Co Using Zirkonyltrichloraluminat or its hydrate as a transpiration and perspiration odor inhibitory agent
US3009769A (en) * 1960-06-02 1961-11-21 Chattanooga Medicine Co Method of preparing zirconiumaluminum-chloro complexes
US3198708A (en) * 1960-06-14 1965-08-03 Colgate Paimolive Company Antiperspirant-deodorant composition
US3235458A (en) * 1962-08-22 1966-02-15 Colgate Palmolive Co Process for preparing an aluminum sulfate-aluminum chlorhydrate antiperspirant cream
FR2099688A1 (en) * 1970-07-30 1972-03-17 Procter & Gamble
US3928557A (en) * 1970-10-28 1975-12-23 Exxon Research Engineering Co Deodorant formulations and antiperspirant formulations containing particular aliphatic diols and their esters
US3927188A (en) * 1971-07-20 1975-12-16 Armour Pharma Zirconium complexes of basic aluminum bromides and methods of making same
US3928545A (en) * 1971-07-20 1975-12-23 Armour Pharma Zirconium complexes of basic aluminum chlorides and methods of making same
US3947556A (en) * 1971-07-20 1976-03-30 Armour Pharmaceutical Company Zinc complexes of basic aluminum chlorides and methods of making same
US3947557A (en) * 1971-07-20 1976-03-30 Armour Pharmaceutical Company Zinc complexes of basic aluminum bromides and methods of making same
US3981986A (en) * 1973-11-23 1976-09-21 Armour Pharmaceutical Company Zirconium-aluminum-polyol buffered anti-perspirant complexes
US4017599A (en) * 1973-11-23 1977-04-12 Armour Pharmaceutical Company Aluminum-zirconium anti-perspirant systems with salts of amino acids
US4369173A (en) * 1974-11-27 1983-01-18 Wickhen Products, Inc. Antiperspirant compositions
US4025615A (en) * 1975-02-25 1977-05-24 Armour Pharmaceutical Company Antiperspirant complexes formed with alkali metal and ammonium zirconyl carbonates
US4028390A (en) * 1975-03-26 1977-06-07 Armour Pharmaceutical Company Methods of making basic zirconium complexes
DE2605386A1 (en) * 1975-03-26 1976-10-07 Armour Pharma Basic zirconium complexes and methods for making and using same in antiperspirants
US4021536A (en) * 1975-04-18 1977-05-03 Armour Pharmaceutical Company Magnesium-zirconium complexes useful as antiperspirants
US4120948A (en) * 1976-11-29 1978-10-17 The Procter & Gamble Company Two phase antiperspirant compositions
US4331609A (en) * 1980-09-08 1982-05-25 The Procter & Gamble Company Antiperspirant composition
US4775528A (en) * 1983-08-16 1988-10-04 The Gillette Company Antiperspirant composition
US5770186A (en) * 1983-08-16 1998-06-23 The Gillette Company Antiperspirant composition
US5589196A (en) * 1983-08-16 1996-12-31 The Gillette Company Antiperspirant composition
US5114705A (en) * 1983-08-16 1992-05-19 The Gillette Company Antiperspirant composition
US5486347A (en) * 1983-08-16 1996-01-23 The Gillette Company Antiperspirant composition
US5298640A (en) * 1983-08-16 1994-03-29 The Gillette Company Antiperspirant composition
US5601809A (en) * 1986-09-26 1997-02-11 The Gillette Company Axillary malodor neutralization
US4871525A (en) * 1986-10-24 1989-10-03 Westwood Chemical Corporation Antiperspirant composition and method of preparation
US5098698A (en) * 1989-03-16 1992-03-24 The Gillette Company Novel antiperspirant adduct compositions and process for making same
US5225187A (en) * 1991-02-15 1993-07-06 Somerville Technology Group, Inc. Process for preparing concentrated aluminum-zirconium solutions
US6436381B1 (en) 2000-10-25 2002-08-20 The Gillette Company Aluminum-zirconium antiperspirant salts with high peak 5 al content
US6649152B2 (en) 2000-10-25 2003-11-18 The Gillette Company Aluminum-zirconium antiperspirant salts with high peak 5 Al content
US20040136934A1 (en) * 2000-10-25 2004-07-15 The Gillette Company Aluminum-zirconium antiperspirant salts with low M:Cl ratio
US6991780B2 (en) 2000-10-25 2006-01-31 The Gillette Company Aluminum-zirconium antiperspirant salts with low M:CI ratio
US6726901B2 (en) 2002-05-09 2004-04-27 The Gillette Company Stabilized antiperspirant compositions containing aluminum-zirconium salts with low M:Cl ratio
US6663854B1 (en) 2002-06-19 2003-12-16 Yan-Fei Shen Aluminum-zirconium antiperspirant salts made with zirconium salts having low Zr:Cl ratio
US20050191256A1 (en) * 2003-04-04 2005-09-01 Colgate-Palmolive Company Glycine-free antiperspirant salts with betaine for enhanced cosmetic products
US20050019287A1 (en) * 2003-07-22 2005-01-27 Zijun Li Stable aluminum / zirconium antiperspirant solution free of amino acid and polyhydric alcohol
US7074394B2 (en) 2003-07-22 2006-07-11 Reheis, Inc. Stable aluminum/zirconium antiperspirant solution free of amino acid and polyhydric alcohol
US7153495B2 (en) 2004-06-10 2006-12-26 Reheis, Inc. Fragrance friendly and cost effective antiperspirant actives and method of making the same
US20050276773A1 (en) * 2004-06-10 2005-12-15 Parekh Jawahar C Fragrance friendly and cost effective antiperspirant actives and method of making the same
US20060008435A1 (en) * 2004-07-07 2006-01-12 Somerville Technology Group, Inc. D/B/A Summit Research Labs Stabilized aqueous aluminum zirconium solutions
US7731943B2 (en) * 2004-07-07 2010-06-08 Summit Research Labs, Inc. Stabilized aqueous aluminum zirconium solutions
US20070187256A1 (en) * 2006-01-06 2007-08-16 Pratt Willam E Polyaluminum Chloride and Aluminum Chlorohydrate, Processes and Compositions: High-Basicity and Ultra High-Basicity Products
US20070196302A1 (en) * 2006-01-06 2007-08-23 Pratt William E Polymetal Hydroxychloride Processes and Compositions: Enhanced Efficacy Antiperspirant Salt Compositions
US7846318B2 (en) 2006-01-06 2010-12-07 Nextchem, Llc Polyaluminum chloride and aluminum chlorohydrate, processes and compositions: high-basicity and ultra high-basicity products
EP2418171A1 (en) 2006-01-06 2012-02-15 Nextchem Method for increasing the hydroxide content of polymetal hydroxychlorides used as antiperspirant salt compositions with enhanced efficacy
US8801909B2 (en) 2006-01-06 2014-08-12 Nextchem, Llc Polymetal hydroxychloride processes and compositions: enhanced efficacy antiperspirant salt compositions
EP3192491A1 (en) 2016-01-15 2017-07-19 Evonik Degussa GmbH Composition comprising polyglycerol esters and hydroxy-alkyl modified guar

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