IT8149876A1 - ANTIPERSPIRANT COMPOSITION CONTAINING ALUMINUM CHLOROIDATE, ALUMINUM CHLORIDE AND AN ALUMINUM ZIRCONIUM POLYCHLOROHYDRATE COMPLEX - Google Patents

Description

DESCRIPTION

in support of a patent application for an invention entitled:

"Antiperspirant composition containing aluminum chlorohydrate, aluminum chloride and a compound_aluminum zirconium polychloride II

SUMMARY

The antiperspirant composition buffered to a pH of approximately 2.5 to approximately 4.5 contains a combination of aluminum chlorohydrate, aluminum chloride, and an aluminum zirconium polychloride complex as the active ingredient; an additional buffering agent, preferably glycine, may be incorporated into the composition.

The present invention relates to antiperspirant compositions. More particularly, it concerns antiperspirant compositions incorporating aluminum chlorohydrate, aluminum chloride, an aluminum zirconium polychlorohydrate complex, and a buffering agent, such as gliein.

Aluminum chlorohydrate (ACH) has been known for many years to be an effective and safe antiperspirant. This is nevertheless true.

There is room for improvement and research into effective antiperspirants is constantly underway. It has also been known in the field for some time that aluminum chloride and zirconium salts provide exceptionally effective antiperspirants. However, solutions of aluminum chloride hexahydrate, zirconium oxide, or zirconium oxide are extremely acidic and are therefore not widely used alone because of their

potential for irritation and because of the great damage they cause to tissue. Therefore, various attempts have been made to raise the pH to "3-41" by using less acidic aluminum salts and incorporating compounds containing organic nitrogen. Daley (U.S. Patent Nos. 2,814,534 and 2,14,5d5) and Grad (U.S. Patent 2,654,362) have shown that when zirconium oxy- or zirconium hydroxide are buffered with ACH and glycine, the pH is greater than when ^ ?si .i.mpie "ga" il~lo system ?ema "ACH. Since then the j!_ combination of aluminum chlorohydrates, zirconium hydroxychloride and gliein has been used widely as the most effective active antiperspirant system. _

Luedders et al. in U.S. Pat. No. 3?_7112*_96?_suggest a process for the preparation of breathable materials which process involves spray-drying a solution containing, for example, ACH, zirconyl hydroxychloride, and glycine. This combination is claimed to have superior characteristics not possessed when the components are dried separately and combined by simple physical mixing.

Shin et al. British Patent No. 1,347,950 discloses the use of a combination of ACH and aluminium chloride as an effective antiperspirant. This combination has been shown to be particularly useful in an aerosol composition. However, as with other antiperspirants known in the art, there is still scope for improvement.

Other antiperspirant systems containing aluminum and zirconium salts have been reported, for example, by Beekman (U.S. Patent 2,906,668), Rubino (U.S. Patents 2,979,510; 13,981,896; and 4,017,599); Siegei et al. (U.S. Patent 3,407,254), Mecca (U.S. Patent 3,977,748); Shelton (U.S. Patent 4,202,879), etc. The antiperspirant activity of all these products in these patients has not been clearly stated to be superior to systems containing zirconium hydroxychloride, ACH, and glycine.

Although aluminum chloride, aluminum chlorhydrate, zirconyl hydroxy chloride, and certain aluminum zirconium chlorhydrate-type complexes have been suggested individually for use as antiperspirant substances in the prior art, and the combination of aluminum chloride and aluminum chlorhydrate on the one hand and the combination of aluminum chlorhydrate and zirconyl hydroxychloride on the other have been suggested for use as an active antiperspirant substance, an unexpectedly active compound has been found in the PK section of aluminum chloride, aluminum chlorhydrate, an aluminum zirconium polychloride complex, as defined above. particularly subsequently, they act synergistically and at the same concentration level of active substances show a higher degree of antiperspirant activity than would be expected from the level of activity of the individual ingredients or from a given combination of ingredients that are known in the previous art. In combination with a buffering agent, for example glycerin, these substances provide a high antiperspirant performance that presents a base.

there is irritation to the skin and/(L?a little damage to the tissue.

Accordingly, it is an object of the present invention to provide highly effective antiperspirant compositions.

It is also an object of this invention to provide a method for inhibiting perspiration on the skin of individuals by applying to the skin surface the above-mentioned compositions.

_ __ Other and more particular objects of this invention will become apparent from the following description and claims.

In the second description, unless otherwise indicated, percentages are expressed as a percentage by weight of the total weight of the composition.

The aluminum chloride which is incorporated in the compositions of the present invention may be hydrated aluminum chloride at various degrees of hydration. However, aluminum chloride hexahydrate (A1C1- .

6H 0) has been shown to be more effective and is therefore preferred for the purposes of this invention.

The amount of aluminum chloride that may be incorporated into the composition of the present invention may vary somewhat. Generally, aluminum chloride will be incorporated into these compositions at a rate of about 0.5 to about 6% by weight as anhydrous substance based on the total weight of the composition. As the hexahydrate (AlCl. 6H0) it will be incorporated at a concentration ranging from about 0.9 to about 1% by weight based on the total weight of the composition, with the preferred range being from about 2 to about 6% based on the total weight of the composition.

Aluminum chloride hexahydrate will normally be incorporated into this composition as a 50% aqueous solution. When employed in this form, from about 1/2 to about 2/3 of this composition by weight will be used based on the total weight of the composition.

Aluminum chlorohydrate (sometimes referred to as aluminum chlorohydroxide) may also be incorporated into the composition of this invention in varying amounts. Typically, this compound will be used at a concentration ranging from about 1% to about 17% by weight as anhydrous substance based on the total weight of the composition, with the preferred concentration being in the range from about 2% to about 10% by weight based on the total weight of the composition. Aluminum chlorohydrate is also supplied as a 50% aqueous solution. When employed in this form, it will be used at a concentration ranging from 2.6% to about 38% by weight based on the total weight of the composition.

ACH may be added to this composition in whole or in part as a polymerized mixture as described in Shin et al.'s British Patent No. 1,347,950. This may be prepared by drying an aqueous solution of aluminum chloride hexahydrate and ACH using common drying techniques such as oven drying, vacuum oven drying, spray drying, or freeze drying. These compositions are characterized in that the mole ratio of aluminum to chloride will be in the range

-ranges from about 0.7:? to about 1.95:1? the preferred range being about 1.2:1 to about 1.5:1. When the mole ratio of aluminum to chloride is less than 1, the addition of larger amounts of a buffering agent such as gliein may be necessary to reduce the potential for irritation and tissue damage.

The aluminum zirconium polychloride complexes that can be incorporated into the composition of the present invention can be described by the following formula:

CD Al Zr(OH) Cl_ . nCH^COOH

x Y ? | 2 . inHgO

NH

in which

_ (a) x is a number ranging from 2 to 1.0;_ _ (b) Z is a number ranging from 1 to 8;_

(c) y ? equal (3x 4) - Z;_ _

(a) the sum of y_+_Z is a number ranging from 10 to j(4;

(e) m h a number ranging from .0__to_.12;

(f) n is a number ranging from 0 to 3.

y will normally have a value ranging from about 5 up to about 29._ _

As will be evident from Formula I, gliein may be combined in the complex or it may be absent. The presence or absence of gliein in the complex will determine the amount of uncombined gliein or high buffer that can be incorporated into the composition to raise the pH to a level ranging from about 2.5 to about 4.5 or to a preferred pH ranging from about 2.5 to about 3.5.

_ A number of aluminum zirconium poly-i-chlorohydrate complexes are known in the prior art which are useful for the purposes of the present invention. By way of example, the following complexes may be cited together with their empirical formulae: aluminum zirconium tetrachlorohydrate (Al Zr

(OHj-.Cl.); aluminum zirconium tetrachlorohydrate glycine (Wickenol ^JE-369M Al^Zr(OH) ^,,01^ . NH^CH^COOH); aluminum zirconium trichlorohydrate (-A.l.^ZriOH);V,j-)C1j?; j; aluminum zirconium trichlorohydrate glycine (Al.Zr(OH).

CI . mi2CH2C00H); aluminum zirconium pentachlorohydrate (Al^ ZrCOHK-Cl,.); aluminum zirconium pentachlorohydrate-- - - 2y? -?-1-to gliein (Al^0Zr(0H)2gCl^. . NH2CH2C00H); aluminum ?

-zirconium octachlorohydrate (Al^-Zr(OH)1.4.C?lo^-); aluminum;? -zirconium octachlorohydrate gE?-liein (Al5^?Zr-(OH)1.4.C?low-NH^CH^COOH). The aluminum zirconium polychlorohydrate complex can be mixed individually with ACH and

AlCl^ ? 6H20 in solution or in powder form?

of various combinations.

The Food and Drug Administration's OTC Antiperspirant Panel has adopted a specific and definitive nomenclature for various aluminum zirconium polychlorides that are

not useful in the present invention. These are listed in Table A below:

TABLE A

adopted classification Ratio range Ratio range to the metal-halide group ??/Zr [

ro

Aluminum zirconium from 2.1:1 up to 1.5: from 2.0:1 up to 6.0: T hydrochloride but not included but not included

TABLE A (continued)

aluminum zirconium 1.5:1 up to 0.9:1 2.0:1 up to 6.0:1 tetrachlorohydrate included but not included Lllivnninium zirconium 2.1:1 up to 1.5:1 6.0:1 up to 10.0:1 tetrachlorohydrate _ but not included_ j_ included

.aluminium zirconium from_1.5_:_1_ up to_0.9:1 from 6.0:l,..finp._a.._1.0,0:1 ittahydrochloride included included

A number of .aluminium zirconium polychloride type complexes that are useful in the

This invention is commercially available*_Reheis

Chemical Company promotes a number of substances that

they are marketed under the trade name _ _

TM REZAL . The following table describes a certain nu? _

of these products together with their specifications: _

TABLE I

1 REZAL 360 Aluminum zirconium tetrachlorohydrate (powder) 2 REZAL 36 ^Aluminum zirconium trichlorohydrate (powder) __ _

|3 REZAL 67 Aluminum_ zirconium pentachlorohydrate (solution)._

[4 REZAL 67 Aluminum zirconium pentachlorohydrate (powder)

Approximate Al/Zr ratio 3.6:1 3.6:1 6.7:1 6.7:1 [approximate metal/Cl contribution 1.4:1 1.6:1 J_,70. J ,7:1 concentration of

?dry residue 10Ofo 10C$ ,aluminium(Al) 5 ,0#>-5,H0 16,3#-17 ,7$ ' 7,6#-8,4?i 19,0^-21 y?fo _ TABLE I (continued)_

?rconium(Zr) _ l_3,^-15,2f0_ 3.7$-4.3$ __ 9,2f0-lO,Sf0 .icma 3.6$ -4.7$_ ? _ ^- - -Loride _(Cl) I 5>9$-6.7$ _ 16.0$-19.0$ _ 6.5$-7.2$ 16.2$-i?,0$ ?rro (Fe) NMT 50 ppm NMT 10Oppm NMT 5Oppa NMT 1OOppm_ ?talliheavy

?ome lead) NMT 10 ppm NMT 20ppm NMT 10ppm NMT 20ppm ?grain size

through a

(Leglio di^325 ma-.ie) >97$ min >97$ min

Similar products are marketed by Wickhsn Products, Inc., and Comet Chemical Corporation.

The amount of any type-aluminium-zirconium polychloride complex that will be incorporated in the composition of the present invention may be;

I

can also be quite variable. Typically, a concentration of about 5 to about 16% by weight of the anhydrous substance will be used.

total weight of the composition? In the preferred forms of this invention, concentrations will range from about 1/4 to about 1/4 by weight as anhydrous substance based on the total weight of the composition.

The aluminum zirconium polychloride complex of the present invention is aluminum

Zirconium tetrachloride glycine. This isolite complex is used at concentrations ranging from about 100% to about 16% by weight as an anhydrous substance with respect to the total weight of the composition, with the preferred concentration ranging from about 100% to about 14% by weight. The aluminum-zirconium tetrachloride-glycine complex is supplied as a 35% aqueous solution...When used in this split formulation, it is incorporated into the composition of this invention and has a contraction ranging from about 1% to about 11.60% by weight of the total weight of the composition.

Glycine, which is the preferred buffering agent, is a major component of the composition of the present invention. This substance may be incorporated as free gliein, as part of the titration aluminum zirconium polychloride complex, or as a combination of both. In general, the total gliein incorporated in these compositions (i.e., as free gliein, complexed gliein, or a combination of both) will be incorporated in an amount ranging from about 0.5% to about 5% by weight based on the total weight of the composition. The preferred range of total glycine, however, is from about 1.5% to about 3% on the same weight basis.

Other buffering agents or complexing agents besides gliein may also be employed in this invention. For example, other amino acids and their salts (e.g., sodium glycinate, dihydroxyaluminum glieinate), urea, organic nitrogen-containing base, metal hydroxide, carbonate, and oxides of alkali metals and alkaline earth metals (Mg(-OH)O), Na(-CO), Zn-O, etc.) may be employed. These buffering agents may be used alone or in combination with gliein to give the composition a pH ranging from 2.5 to 4.5 (preferably from 2.8 to 3.8).

These complexing and buffering agents serve to reduce the potential for skin irritation and tissue damage. They also function to stabilize the antiperspirant system. The compositions of the present invention can be in a variety of dosage forms. Thus, they can be produced as "roll-on" emulsions or clear hydroalcoholic products or aqueous "roll-on" products. Aqueous solutions of aluminum chloride, ACH4 aluminum zirconium polychloride complex type and a buffering agent such as glycine can be spray dried to a fine powder. This can be used as such or incorporated into sticks, suspensions, powders or "roll-on" products.

While the compositions of the present invention may take various forms, they are shown to be most effective in a system containing a relatively high water content. These compositions may be in the form of solutions or emulsions in which the active ingredients (i.e., aluminum chloride, ACH, an aluminum zirconium hydrochloride complex, and buffer) are contained in the aqueous phase. Aqueous emulsion systems are preferred because they provide more organoleptically elegant compositions. These emulsion systems will usually be of the oil-in-water type in which the active ingredients are contained in the continuous aqueous phase.

The amount of water that can be included in these compositions can vary somewhat. Typically, this amount will range from about 40 to about 1 oz of water by weight of the total weight of the composition, with the preferred range being from about 6 to about 75 oz of water on the same weight basis.

The emulsion-type products of the present invention may also contain other ingredients commonly found in lotion- or emulsion-type roll-on antiperspirants. These will include, for example, emollients, surfactants, sequestering agents, perfumes, colorants, etc. Examples of emollients that may be used include fatty acid esters (isopropyl myristate, isopropyl palmitate); dicarboxylic acid diesters (diisopropyl adipate); polyoxyalkylene glycol esters (polypropylene glycol 2000 monooleate); propylene glycol diesters; short-chain fatty acids (CH-C1n) (Neobee M-20); polyoxypropylene fatty series ethers (pr?cetyl, Arlamol E, Wilconol APS, Witconol APM, etc.); propoxylated monohydric alcohol with a molecular weight of 1000 930 (Fluid AP), fatty alcohols (hexadecyl alcohol), silicone oils (dimethyl polysiloxane, 10-2000 centistokes), cyclomethicones (volatile silicone 7207 and 715h - Union Carbide), fatty ether of polyoxyethylene polyoxypropylene (Procetyl A\vs Modified, Witconol APES). The above non-polar liquids alone or in mixtures are equally suitable for

1The objects of the invention. Generally the above emollients are organic oily liquids which are of the non-polar type and have (a) a boiling point under atmospheric pressure not lower than about

!1200C; (b) a density between about 0.7 and 1.6, preferably between 0.7 and 1.2.

The amount of boiling agent used will vary somewhat and the concentration will usually be in the range of about 1 to about 100 by weight of the total weight of the composition. Preferably, this amount will range from about 2 to about 15 by weight of the total weight of the composition.

A variety of surfactants and combinations of surfactants are also useful in the preparation of the lotion or emulsion-type products of the present invention. These surfactants include those generally of the non-ionic, cationic, and amphoteric types which may be used in emulsion systems having antiperspirant action. Examples are as follows:

Non-ionic surfactants

1. Polyoxyethylene fatty seat ethers-J3i_- _Brij_30f__Brij 35.,JBriJ 72, Brij 78, etc_ j_ 1_ L_ 2. Polyoxypropyl fatty seat ethers Procetyl AWS, Witconol APEM, Wl t?Conol APES,_etc.

3. Polyoxyethylene alkyl..phenyl ethers! Igepal_CO_..5.3p etc...

|_ _ ._ _4._Polyoxyethylene fatty acid ester Sorbitan - Tween 20, Twee.dO, etc.. ... _

5. Sorbitan fatty acid ester - Span 60, Span ?5, etc.

6. Lanolin ethers - laneto 50, Solulan 9 6 , and c c . .

7. Fatty alcohols and polyoxyethylene fatty ethers - Promulgen G. Polawax, etc.

II. Cationic surfactants

N(lauryl cholaminoformyl methyl)pyridinium chloride (Emcol E607L)

III Amphoteric surfactants Coconut imidazoline (Monateric CA-35^). I IV. Auxiliary surfactants 1. Fatty acid glyceryl esters - ceryl monostearate.

2. Fatty acid amides Witcamide 70 (Witco Chem. Co.).

3. Fatty alcohols - stearic alcohol

As with emollients, the amount employed may vary somewhat. For the most part, this will range from about 1/4 to about 10% by weight as anhydrous substance based on the total weight of the composition, the preferred range being from about 2% to about 6% on the same weight basis. The "popular" antiperspirant used in the prior art is an aluminum zirconium trichlorohydrate complex. The system of the present invention has the following advantages over that "popular" system:

1. Low cost of goods. The aforementioned accessible or "popular" external system is much more expensive than Alci. 6H.0 or ACH

2. Improved emulsion stability and ease of production. Straight-line α-catein Al/Zr polypyrohydrate glycine systems are difficult to stabilize and produce as emulsions.

3. Low tissue staining potential. Generally, the straight-structured Al/Zr hypoglycemic polychloride salts stain more than the aluminum salts.

The following examples are provided to further illustrate the present invention. It is understood, however, that the invention is not limited by this example,

EXAMPLE 1

Formula 1906

Ingredients by weight Stearyl ether PPG-11 2.25 Polyoxyethylene( 2)stearyl

1,65 Polyoxyethylene(20)stearyl ether

ether 0.6Q Perfume 0.30 Disodium edetate, dihydrate 0.10 Deionized water 35.40

?i-Aluminum chlorhydroxide, 5Of0 10.00

! ^ Aluminum chloride hexahydrate ? in 50% solution _ 6.00 Aminoacetic acid (Crystal

Glycine USP) 0.50 Aluminum zirconium tetrachloride solution to-glycine, 35$ J.5.00. Dye FD&C Blue No. 1 (solution

aqueous 0.1$) 0.2?

100.00 Appearance: homogeneous opaque solution

Color: pale blue _ _

pH: 3.3 ? 0.3_

Viscosity: Spindle No. 3 at 20 rpm 15 seconds Overnight output: 500-500 centipoise._ ;

Procedure:

1. In a suitable stainless steel vessel, melt together polyoxypropylene fatty alcohol ethers, polyoxyethylene (2) stearyl ether, and polyoxyethylene (20) stearyl ether, heating to 140?F (60?C). Add perfume and mix together immediately before step 3. 2. In a separate stainless steel vessel, dissolve disodium edetate in water and heat to 140?F (60?C).

3? Slowly add the oil phase to the water phase (both at 140?P (60?C)) using a Lightnin mixer with low speed stirring.

Maintain temperature at 1400F (60?G) for 15 minutes.

4. At 140?P (60?C) slowly add to the charge, using gentle stirring, a solution consisting of aluminum chlorhydroxide, aluminum chloride hexahydrate, gliein, and aluminum zirconium tetrachlorohydride solution, which has been preheated to 120?P (40.9?C). Continue stirring and cool the charge to 125?P (51.7?C). Stir for 45 minutes, maintaining the charge temperature at 120-125?P (40.9-51.7?C).

5. Cool the batch to 105?C (40.6?C ) add the dye solution and continue stirring and cooling.

6. When the charge temperature reaches 0-5 F (26.7-29.4 C) stop agitation and adjust water loss if necessary.

EXAMPLE 2

The procedure and composition of Example 1 are followed except that instead of PPG-11 stearyl ether, Arlamol ESP (PPG-15 stearyl ether) is used.

EXAMPLE 3

Formula 1956

Following the procedure in example 1, the following composition is prepared:

Ingredients $ by weight PPG-11 stearyl 2.25 . Polyoxyethylene i(2)stearyl ether 1.65^ Polyoxyethylene( 20)stearyl ether 0.60 ? . Perfume 0.32 ? i r? Disodium edetate, dihydrate 0.1?

XT

>. Deionized water 35, ?3 Butylated hydroxytoluene 0.05 i ? Aluminum chlorohydrox 18.00 c ido 50$

Aluminum chloride hexahydrate solution, $50.00 6j?0 Aminoacetic acid (Glycine Cryo from the United States Pharmacopoeia) $0.50 Aluminum chloride hexahydrate solution, $35.00 . 2-iron tetrachlorohydride-glycine $35.00

i Red D&C No.19|.(0.1$ aqueous solution) 0.03 Yellow D&C No.10 (0.1$ aqueous solution) 0.32

100.00 Appearance: smooth matte lotion

Color: pink

pH: 3.3 ? 0.3

Viscosity: No. 3 spindle at 20 rpm 15 seconds Overnight viscosity: 500-1500 centipoise.

EXAMPLE 4

The procedure and composition of example 3 are followed except that instead of ?

??-1 1.slearyl ether yes.,Arlamol.ESP.(PPG-15j) is used

stearyl ether_._ _

EXAMPLE 5

The procedure in example 1 is followed and the following composition is prepared:

Ingredients _ oi I -in reso? 'PPG-11 stearyl ether 2.25 Polyoxyethylene(2)stearyl ether 1.65 Polyoxyethylene(20)stearyl ether 0.60 [Fragrance 0.30 ; Disodium edetate dihydrate 0.10 Deionized water 31.40 ! Aluminum chloride hydroxide 50$ 12.00 . Aluminum chloride hexahydrate solution 50$ 6.00 l Aminoacetic acid (Glycine Crystal pharmacopoeia

(American) 0.50 Aluminum zirconium tetrachlorohydrex-glycine solution

35$ 45.00 PD&C Blue No.1 (aqueous solution 0.1$) 0.20

100.00 Appearance: smooth matte lotion

Color: pale blue

pH: 3.3 0?3.._

.[Viscosity: shaft No. 3..at 20.rpm, per minute 15 seconds Viscosity for the whole night: 500-1500 centipoise EXAMPLE 6

Do you follow the procedure and composition?

? stodel PPG-11 stearyl

(PPG-15 stearyl ether).

EXAMPLE 7

Formula 1979

It is performed

and the following composition is prepared:

Ingredients: PPG-11 stearyl ether 2.25 Polyoxyethylene(2)stearyl ether J_*65_ Polyoxyethylene(20)stearyl ether 0.60 Perfume 0.30 Disodium edetate, dihydrate 0.10 Deionized water 35.40 Uranium chloride hydroxide 50$ 15.50 Aluminum chloride hexahydrate solution 50$ 8.00 Aminoacetic acid (Glycine Crystal, U.S. Pharmacopoeia) 1.00 Aluminum zirconium tetrachlorohydride-glycine solution 35$ 35.00 31u FD&C N0.1 (aqueous solution 0.1$ )_ 0.20

100.00 Appearance: lotion, smooth and opaque

Pain: pale blue

pH: 2.3 ?P,3

[viscosity: shaft No^ at 20_revolutions per^rain.15_seconds_

!Viscosity?-overnight: 5Q0-2000__centipois.e.._ !_ ..

EXAMPLE t?_

We follow... the. procedure, and .the .composition. ;of !_exampleJ7.with.the.exception..for.the.fact.that.instead._ !_

.del.PPG-11_ stearyl_ether_is_used_Arlamol. ESP _

-1.5...stearic alcohol)._ _

.EXAMPLE 9

Formula 1991

_ Follow the procedure in example 1.e.

the following composition is prepared:.

Ingredients _ ? m weight PPG-11 stearyl ether_ ?_ ?2.25 Polyoxyethylene(2)stearyl ether_ 1 .65 Polyoxyethylene(20)stearyl ether_ 0.60 ..perfume .....0.30 .Disodium edetate dihydrate -0.10 Deionized water. -31.40 _ 'Aluminum chloride hydroxide 50$ a 0.00 'Aluminum chloride hexahydrate solution 50$_ -.8.00 Aminoacetic acid (Glycine Crystal pharmacopoeia

0.50 Aluminum zirconium tetrachlorohydrexglycine solution $35 ^5 ?00 FD&C Blue No.1 (aqueous solution $0.10) 0.20

100.00 Smooth matte lotion appearance

Color: pale blue

P_H*_3,3_?_q,3_

Viscosity? Spindle No. 3 at 20 rpm 1-5 seconds Viscosity? Overnight: 500-1500 centipoise.

EXAMPLE 10

We follow the composition and procedure of example 9 with the exception of the fact that instead

! Arlamol ESP (PPG-15 stearyl ether) is used instead of PPG-11 stearyl ether. ??

EXAMPLE 11?

Z N

Formula 1955 tc We follow the procedure in example 1 and c* !we prepare the following composition:

Ingredients ? by weight PPG-11 stearyl ether 2.25 Polyoxyethylene(2)stearyl ether 1.6 5 Polyoxyethylene(20)stearyl ether 60 Perfume_ 0.30 Disodium edetate dihydrate 0.1 0 Deionized water 35 .60 Aluminum chloride hydroxide 50$ 6.00 Aluminum chloride hexahydrate solution __50$_ .6.00. Aminoacetic acid (Glycine Crystal. Pharmacopoeia,

US) _ _ P,5.0 Solution _allm inium zirconium tetraciorqidrex-glycine .35#. -35 ??

100.00 .. Appearance: smooth matte lotion.

Cjp1orea:Jbianco

pH: 3.3 -4- 0.3

Viscosity: No. 3 shaft at 20 rpm 1.5 seconds. Viscosity overnight: 5.00-1500 centipoise.

EXAMPLE 12 ?_

_ The procedure and composition of example 11 are followed with the exception that at the po- ._

;sto of PPG-11 stearyl ether_ Arlamol ESP is used

(PPG-15 stearyl ether)._

_ ....EXAMPLE 13_ ._

_ Formula BA 1?10-64

_ Aluminum zirconium trichlorohydrate powder 31 is used. The number following the term "tri- _

"[hydrochloride]" in this example and in the other examples indicates the mole ratio of Al/Zr in the compound. Thus, _

for example, 31 indicates a mole ratio of Al/Zr.

3:1. _

xmiuxsione prm cn:>axe A <f0 by weight PPG-11 stearyl et;ere . . _ _ , 5.56

.

Polyoxyethylene(2!)stearyl ether A.07_ Polyoxyethylene(2>0)stearyl ether 1.48 Perfume C.74 Disodium edetate hydroxide C.25 FD&C No. 1 (0.1$ aqueous solution) cj.49

?

Deionized water 87.41

10J.00 Ingredient $ I!in p "eso | Powder Al/Zr ti?hydrochloride 31 10,00

I

^Solution ACH_.5(rfo 18,00 _So.lution A1C1^_. 6H 0, 50g 6I,00

2

Glycine 11.50 Water, deionized 24.00

j _Main emulsion A as much as 100.00

pH: 3.4 0.3

Whole night output: 500-1500 centipoise.

EXAMPLE 14

Formula BA 1810-65

The trichlorohydrate aluminum zirconium powder 21 is used (mole ratio Al/Zr = 2:1): !

j Ingredients $0 by weight ! ' Powder Al/Zr trihydrochloride 21 lOiOO

! - I ACH 50 Solution? 10.00

- ?A

? ooi.uzione

3 2 - 6.00 Glycine 1 ,^0 Deionized water ?4.00 Main emulsion As much as "suffices" to 100.00 pH : 3.5 0.3 <

Viscosity: Whole night: 500-1500 centipoise. <

0 ? EXAMPLE 15 tXL 1? ?

?v Formula BA 1010-56 Rtuc?T z Aluminium zirconium powder < -I M <> n octachlorohydrex-glycine 81 is used (mole ratio Al/Zr = 1 ? '9 ? a" fl/1): tu ta Ingredients $ in iffeso Al/Zr powder octachlorohydrex-glycine 81 15,000 ACH Solution 50<fo 10r00

? AlCl^ solution. 6??0 8.00

3 2

Gucina 0.50 Ldeionized water 26.00 Main emulsion As needed at 100.00 pH: 3.2 0.3

Voscist? All night: 500-1500 centipoise.

EXAMPLE 16

Formula BA 1810-57

A solution of aluminum ziri is used

conium pentachlorohydrate (mole ratio Al/Zr = 10/1):

'

% by weight Al/Zr pentahydrochloride solution 30$ ? 35,Q0_

r ACH Solution 5(yfo'? ? . r __10,00_

! AlCl^ solution,'6H2050$ __8.?0. _ KLicine 2.00.

Deionized water .4.50

! ?main emulsion As required at 100.00_< CL vi pH: 3.4 0.3 ,<L~-Viscosity? Whole night: 450-1^500_centimeters. O KJ OS I? EXAMPLE 17 OoS o < o Formula BQ-1056-63

? * > -A different Rampone agent is used such as ? .or ? 5-o sodium carbonate as a sup- ? buffering agent.

< i ta supplementary in this example. Oi ! c ?main emulsion B $ in neso PG-11 stearyl ether 6;,43 oxyethylene(2)stearyl ether _ 4,71_ oxyethylene(20)stearyl ether rji

i

I

perfume 0.86 isodium edetate dihydrate 0.29 lu FD&C No. 1 (aqueous solution 0.1$) 0.57

?

deionized water 8.5143.

100.00 Ingredients % m weight Al/Zr tetrachlorohydrex-glycine solution 35$ ACH solution 50$ - 10.00 AlCl^ solution . 6H2050$ --8.00-Glycine ? 1.20

Sodium carbonate monohydrate -0.50_ Deionized water_ -0-?30?

Main emulsion B as needed to__ J.0Q.,00_

PH ; 3.4+0.3

Viscosity overnight: 500-1500 centipoise,

EXAMPLE 18

Formula BQ 1056-83

Magnesium hydroxide is used as an agent

additional buffer.

cn Ingredients -$_in p?so J Solution _A1/ZrJ etrachlorohydrex-glycine 35$ - 45.00 Solution ACH_50$ _ JUX,.00 Solution

A1C1 -, . 6H 0, 50$

- 3- 2? -- .8.,00. rlicine ? 0.-50 flagnesium hydroxide ? 0.50 Deionized water _ 1_.00 Main emulsion B as required to _100.0.0_ sH s 3.4 0.3*

1/iscosity? whole night: 500-1500 cetiooise.

EXAMPLE 19

Formula 1509-61

(formula follows)

Ingredients $ by weight i

PPG-11 stearyl ether 2.25 Polyoxyethylene (2)stearyl ether 1.6.5 Polyoxyethylene (20)stearyl ether 0.60 Perfume 0.30 Deionized water 41.2P

I

Disodium edetate dihydrate __Ot?O_ Antifoam AF DC 25$ 0.1 0

T

Al/Zr tetrachlorohydrex-glycine solution 35$ 35 ,'?? i ACH solution 50$ A3 ,!qo A1C1 solution _6? 050$ .3.00 Glycine 0.60 FD&C Blue No. 1 (aqueous solution 0.1$) 0.20

100.00 pH: 3.4 0.3

Viscosity overnight: 400-1200 centipoise.

To demonstrate that the combination of alumin-' . :? minium^chloride, ACH, aluminum zirconium polychloride and glycine acts synergistically, _ !

jun a number of formulas identified in Table II below. Formula ITo._ 1903 is representative of the present invention.

(table follows)

TABLE III. 1

! fi in weight compared to the

I I | total weight Commercial emulsion Ingredients FNo.jt052 F No.1676 F NO.1908! F No.1341 ;"Roll-on"(BR-4504)

ACH(# substance|anhydrous) 18.3 7.5 16.2

AICI3 6H20 j |

($ anhydrous substance) 1.7 2.0

Al/Zr tetrachloride

(anhydrous substance) ??;? Al/Zr trihydrochloride {f

1I anhydrous substance) 19.7

I

Glyine? | j .2;8 1.9! Glyein 4,2

PPG-11?stearyljether 3.0 2;o 2.25 ?3.5

Polyoxyethylene?(2)stearyl ether 1.9 1.5 j1.65 3 PEG-40 stearate, glyceryl I ! I I i

Ji2' stearate, glycerin,

refined paraffin, Polyoxyethylene(20)steril ether 1,1 0^6 j h.z isopropyl palmitate,

! ; I ! I | ! ! Mg/Al silicate and perfume ? i

Disodium edetate dihydrate! I ojl 0.1! '0.1

Perfume and water color; how much?

enough at 100! J

Total active substances; j : i;8.3 i |18.6 18.5: 18.2 19.7'total active substances Total glycine ! 0 : 2.6 1.9 -1*0. 4.2 total glycine

As you may have noticed, each of these formulas is similar except for the active ingredients that will be used. Furthermore, each formula contains the total active ingredients at essentially the same concentration, i.e., approximately 1% of the dry substance.

Each of these compositions was tested for antiperspirant activity. The general procedure used is as described in the Federal Journal, Vol. 43, Number 196, October 10, 1976. It is called the gravimetric axillary antiperspirant test. Paired comparison studies (treated versus untreated subjects) were performed.

i about the antiperspirant efficacy of the antiperspirant emulsion.

Details of the test procedure are provided below.

Test procedure

A type of statistical test provided by statistical services is used. For example, if a certain test substance is being evaluated, half of the test group receives the test substance under their left armpit while the remaining half receives test substances under their right armpit. The opposite armpit serves as a control. If two test substances are being evaluated, half of the group has applied product A to the left armpit and product B to the right armpit while the remaining group members have different locations, product/armpit.

The test is carried out over a period of 5 days (from Monday to Friday). Perspiration is induced in environmental conditions of 100°C.

2? (37.8 l, l?C) and at a humidity? relative of 40$ 2$.

First day: control determination followed by application of the product,

The group members wait half an hour at room temperature (about 65-80°F - 18.2-26.7°C) after which they return to the testing room. They then place uncalibrated Webril swabs (which have been folded in half to a size of 4 x 2 inches) in their armpits. The subjects sit in the testing room for a 40-minute warm-up period. At the end of this period,

-? j-do the heated swabs are removed_ by the group members and discarded.

Group members remove the plastic bags containing the calibrated swabs, which are collected from the manila bags. Subjects insert the swabs under the instructions of a technician. The swabs remain in the armpit for a period of 20 minutes. After this period of time, group members are instructed to remove the swabs and place them in the designated plastic bags, which are then returned to the manila bags. Group members exit the testing room with their hands in their bags, then wash their armpits with warm water using gauze pads and dry them. Approximately 1-3 minutes later, the swabs are removed and the group members exit. The plastic bags are removed from the manila wrappers and weighed by a technician. Group members must exhale at least 200 mg/armpit to continue participating in the test group.

Day 2: Product application only - Group members wait half an hour at room temperature after which they wash their armpits with clean water using gauze pads and dry them. Approximately 1-1 minutes

|later the material under examination is applied and the members of the group leave._ ? _

Day 3? Product application and collection. Group members wait half an hour at room temperature, after which they wash their armpits as previously described. Approximately 15 minutes.

[later the material under test is applied*..The members of the group then wait one hour at room temperature.. They then enter the "test room" for a 40-minute warm-up period and place the uncalibrated crampons in their armpits._ j At the end of this period the warm-up pads are removed and discarded.

The members of the group remove .insac-

. plastic bags that contain the swabs, which are then removed from the manila envelopes. They insert the swabs according to the instructions of a technician.!...

The swabs remain in the armpits for a period of 20 minutes. Then the group members are instructed to remove the swabs and place them in designated plastic bags, which are then returned to the manila bags. The group members exit the testing room, hand in their manila bags, and leave. The plastic bags are removed from the manila bags and weighed by a technician.

Day 4: Product application only As per day 2._ _

Day 5; Product Application and Harvesting Same as Day 3*

t?

The test results are summarized as follows:_

I. Formula No.1908 compared to formula No.1052 Results:

JL_data from this study with 11iraplego of

47 female subjects are submitted to the Department of Statistical Services for evaluation.

In short, their analysis indicates that the antiperspirant formula "Roll-on" No. 1908 is naturally more effective than the formula No. 1052 at the j_

.

concentration 0.01*

,

This conclusion is supported by the report.

. .

A/B__(amount of sweat collected from the armpit treated with A compared to the armpit treated with B) for the 1st day of collection-final treatment (adjusted by control) with a mean of 0.819 which is significantly different from the equality 1.0.

The above data indicate that formula No. 1908 is approximately 18% more effective than formula No. 1.

II. Formula No. 1908 versus formula No. 1676 Results

The data from this study using

46 female subjects are submitted to the Department of Statistical Services for 1st evaluation.

In short, their analysis indicates that Formula No. 190 is significantly more effective than

to formula No._167_6_at a concentration of 0.01...i?

This conclusion is supported by the A/B ratio for the final harvest-treatment day.

(control adjustment) cpn_mean of 0.883_notably different from the equality 1.0.

_ The above data indicate that formula No.

190# is approximately 12$ more effective than the-_ ....

iI formula No. 1676._ _ _ _ _ III? Formula No. 190# compared to the emulsion._ ! _ __ of the trade "Roll-on" formula No. BR 4504 _ Results: _ __ L_ _ The data of this study with the use of_ _

I

44 female subjects were submitted to the Department of Statistical Services for evaluation. ! _ In short, their analysis indicates that the formula No. 190# is significantly more effective than the commercial emulsion "Roll-on" at a concentration of 0.01._ _

_ _ This conclusion is supported by the A/B ratio for the harvest-treatment day (final f-rJ-adjustment for control) with mean of 0.##1 which is significantly different from the equality 1.0._

_ The above data indicate that formula No.

1908 is approximately 12$ more effective than formula No. BR 4504*

IV. Formula No. 1341 (see table 1?) which contains as the antiperspirant active substance a combination of ACH and A1C1. 6H2O_(at a concentration of approximately 1b,2) has been shown in a s-i-I manner

It was found to be on average 9.6% less effective than the commercial roll-on emulsion (BR 4504) which contains 19.7% of Al/Zr trihydrochloride as a breathable activator (see Table II). However, this intimate hygiene product was also shown to be less effective than the formula No. 1908 presented here.

-rte invention i.e. formula No. 1906 is approximately 12$ more effective than formula No. BR_ 14505 (see paragraph III). _ _ _ _ _ _ _ _ V. formula No. 1991 (see example 9) has similarly been shown to be approximately 15$ more effective than a commercially discontinued "Roll-on" product identified as formula No. BR_ 4751. This^jAltimo has the following

ite composition:

Formula No. BR 4751

Ingredients by weight Aluminum zirconium tetrachloride

(anhydrous substance) 13.0 Slicerin 2.0

?A

Claims (1)

1 Anti-rasp_irante tamponatal composition at a pH ranging from about 2.5 to about 4.5 is the composition in which the active ingredients are incorporated: aluminum chloride, aluminum hydrochloride and a complex of aluminum zirconium polychloride, called aluminum zirconium polychloride complex. having the formula: the) Al__Zr(OH) CI . nCH^COOH . mH_0 x y z j 2 2 NH? in which (a) x is a number from 2 to 10: (b)Z ? a number from 3 to ?; (c) x ? equals (3x 4) - Zi (d) the sum of y and Z is a number that goes from 10 to 34; (e) n is a number from 0 to 3; (f) n is a number ranging from 0 to said active ingredients being incorporated into said composition in the following percentages by weight ? with respect to the total weight of said composition and as an anhydrous substance: ! (1) aluminum chloride from about 0.-5$ to about (2) aluminum chlorohydrate from about $1 to about $15 (3) aluminum zirconium polychloride complex from about $5 to about $16. 2. How do you position yourself according to the claim? f 1 which includes a buffering agent added in a supplementary manner, 3. The composition of claim 2 wherein the additionally added buffering agent is gliein. 4. The composition of claim 3 wherein the total amount of gliein in the combined and/or uncombined form is present in said composition at a concentration ranging from about 0.5% to 1.5%. ja about 5$ in weight compared to the total weight of the composition 5. Composition according to claim 1 wherein the aluminium chloride is incorporated with the aluminium chloride hexahydrate. i 6_. Composition according to claim 1 | 1 wherein the aluminium zirconium polychlorohydrate complex is aluminium zirconium tetrachlorohydrate glycine. ..]._ _ 7.?.Cpmpposition_.according to claim i I . 1 in which the aluminum zirconium polychlorohydrate complex to ? chosen from the group which consists of aluminum zirconia aluminum zirconium tetrachloride; aluminum zirconium tetrachloride glycine; aluminum zirconium trichloride.; aluminum zirconium trichloride glycine; aluminum zirconium trichloride i conium pentachlorohydrate; aluminum, zirconium pentachlor- Gliein hydrate; aluminum zirconium octachloride;_al-^ aluminum zirconium octachloride gliein and related ! I . . ? mixtures,_ _ 6, Composition according to_.the...claim 7 in which aluminum chloride is incorporated as_hexa- hydrate . 9. Antiperspirant composition...tamponatal at a pH ranging from approximately 2.? to 1r? _called c.orap.o_sizione_ ? j containing incorporated as active ingredients_aluminum-1 I. . . ? ! minium chloride, aluminum hydrochloride, a complex gl- aluminum zirconium polychloride and containing gliningi? ! said complex aluminum zirconium polychloride having- I I give the formula: (I) Al Zr(OH) Cl, . nCH^?OOH . mH^O x y ? ?| 2 NH? (a) x is a number from 2 to 10; - -- . (b) Z is a number from 3 to 10; (c) x = (3x 4) - Z; (d) the sum of y and Z is a number from 10 to 34; (e) m ? a number from 0 to 12; (f) n is a number from 0 to 3 said active ingredient being incorporated in said composition in the following percentages by weight - with respect to the total weight of said composition and as an anhydrous substance: (1) Aluminum chloride from about $1.5 to about $3.3 | (2.) Aluminum chlorohydrate from about $2 to about $10 | <3, from about $b to about $14 the total weight percentage of glycine form < | combined and/or non-combined being the one that goes from j about 1.5$ to about 3$ of the total weight j of the composition. 10. Composition according to claim 9 wherein aluminum chloride is incorporated as aluminum chloride hexahydrate. 10 wherein the aluminum zirconium polychloride complex and aluminum zirconium tetrachloride are glycine. '[_ ._ _ 12. Composition according to claim 10 wherein the aluminum zirconium polychloride complex % dr-ate and selected from the group consisting of aluminum, zirconium tetrachloride; aluminum zirconium tetra- 1 _ hydrochloride gliein; aluminum zirconium trichlorochloride;_ _ aluminum zirconium trichlorochloride gliein; aluminum_ zirconium pentachlorochloride; aluminumz irconium pentachlorohydrate gliein; aluminum zirconium octachlorochloride; aluminum zirconium octachlorochloride gliein and mixtures thereof. j 13? Composition according to claim J12 wherein the aluminum chloride incorporated as hexahydra- j. 14. Composition according to claims jl, 2, 3, 4, 5, 6,J7, d, 9,J0, 11, 12__q_13_in the form of an oil-in-water emulsion wherein at least one major component of the active ingredients and the gliein are contained in the aqueous phase. 15. A method for inhibiting perspiration in a subject which comprises applying to the skin of said subject an effective amount of the composition of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13.