NZ198966A

NZ198966A - Antiperspirant composition containing an aluminium zirconium polychlorohydrate complex

Info

Publication number: NZ198966A
Application number: NZ198966A
Authority: NZ
Inventors: C T Shin; M S Slade; A Nersesian
Original assignee: Bristol Myers Co
Priority date: 1980-12-15
Filing date: 1981-11-13
Publication date: 1985-04-30
Also published as: DE3149649A1; ES507961A0; FR2495933B1; IT8149876A0; CH649707A5; CA1153313A; ES8303085A1; IT1172144B; BE891488A; DE3149649C2; JPH0239486B2; JPS57131715A; PT74127A; SE8107512L; PT74127B; SE452108B; GB2091099A; GB2091099B; ZA817173B; AU7653381A

Description

New Zealand Paient Spedficaiion for Paient Number 1 98966 198966 - id ~S<=> NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION ANTIPERSPIRANT COMPOSITION CONTAINING ALUMINUM CHLOROHYDRATE, ALUMINUM CHLORIDE AND AN ALUMINUM ZIRCONIUM POLYCHLOROHYDRATE GOMPIEX AND METHOD OF USE ^ We, BRISTOL-MYERS COMPANY, a State of Delaware corporation having offices at 345 Park Avenue, New York, New York, United States of America, hereby declare the invention for which K/ we pray that a patent may be granted toxHSt/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- 1 f-FollnwPfl hv la) 198966 ANTIPERSPIRANT COMPOSITION CONTAINING ALUMINUM CHLOROHYDRATE, ALUMINUM CHLORIDE AND AN ALUMINUM ZIRCONIUM POLYCHLOROHYDRATE. COMPLEX AND METHOD OF USE This invention relates to antiperspirant compositions. More particularly, it concerns antiperspirant compositions having incorporated therein aluminum chlorohydrate, aluminum chloride, an aluminum zirconium polychlorohydrate complex and a buffering agent e.g. glycine.

Aluminum chlorhydrate (ACH) has been known for many years to be an effective and safe antiperspirant. Nevertheless, there is room for improvement and the search to find more effective antiperspirant materials is constantly going on. It has also been known in the art for sometime that aluminum chloride and zirconium salts provide exceptionally effective antiperspirants. However, solutions of aluminum chloride hexahydrate and zirconium oxy- or hydroxychloride are very acidic and therefore, they are not widely used alone because of their irritation potential and high fabric damage. Therefore, various efforts have been centered on raising the pH to 3 to 4 by using less acidic aluminum salts and incorporating organic nitrogen containing compounds.

Daley (U.S. Patents 2,814,584 and 2,814,585) and Grad (U.S. Patent 2,854,382) showed that when zirconium oxy- or zirconium hydroxychloride are buffered with ACH and glycine, the antiperspirant efficacy is greater than an ACH system alone. Since then, the combination of aluminum chlorohydrate, zirconium hydroxychloride and glycine has been used widely as a most effective antiperspirant active system.

Luedders et al in U.S. Patent 3,792,068 suggest a process for preparing an antiperspirant which comprises spray drying a solution containing, for example, ACH, zirconyl hydroxychloride and glycine. It is claimed that 198966 this combination has superior characteristics not possessed when the components are dried separately and combined by simple physical mixing.

The British patent to Shin et al 1,347,950 discloses the use of a combination of ACH and alumintim chloride as an effective antiperspirant material. This combination was found to be particularly useful in an aerosol composition. However, as in the case with other antiperspirant materials known in the prior art, it still left room for improvement.

Other antiperspirant systems containing aluminum and zirconium salts have been reported, for example, Beekman (U.S. Patent 2,906,668), Rubino (U.S. Patents 3,979,510; 3,981,896 and 4,017,599), Siegel et al (U.S. Patent 3,407,254), Mecca (U.S. Patent 3,970,748), Shelton (U.S. Patent 4,202,879), etc. The antiperspirant activity of all these salts in these patents has not been clearly claimed as having superiority over systems containing zirconium hydroxychloride, ACH and glycine.

Although aluminum chloride, aluminum chlorohydrate, zirconyl hydroxychloride and certain aluminum zirconium chlorohydrate complexes, individually have been suggested for use as antiperspirant materials in the prior art and the combination of aluminum chloride and aluminum chlorohydrate on the one hand, and the combination of aluminum chlorohydrate and zirconyl hydroxychloride on the other hand, have also been suggested for use as an active antiperspirant, it has been unexpectedly found that combination of aluminum chloride, aluminum chlorohydrate, an aluminum zirconium polychloro-hydrate complex as defined more particularly below act synergistically and at the same level of concentration of actives show a higher degree of antiperspirant activity than would be expected from the level of activity of the individual ingredients or certain combination of ingredients which are shown in the prior art. In combination with a buffering agent e.g. glycine, these materials provide a high 198966 performance antiperspirant having a low potential for skin irritation and/or fabric damage.

It is accordingly an object of the present invention to provide highly effective antiperspirant compositions .

It is also an object of this invention to provide a process for inhibiting perspiration on the skin of individuals by application to the skin area of the aforesaid antiperspirant compositions .

The present invention provides an antiperspirant canpositcn buffered to a pH in the range of frcm substantially 2.5 to substantially 4.5 having incorporated therein as active ingredients a combination of aluminum chlorohydrate, aluminum chloride and an aluminum zirconium polychlorohydrate complex. An additionally added buffering agent, preferably glycine, may be incorporated in the composition.

In the following description, unless otherwise specified, the percentages are expresssed as percentages by weight based on the total weight of the composition.

The aluminum chloride that is incorporated in the compositions of the present invention may be aluminum chloride hyd-rated to various degrees. However, aluminum chloride hexahydrate (AlCl^. 6H2O) has been found to be most effective and is therefore preferred for the purposes of the present invention.

The quantity of aluminum chloride that may be incorporated in the present composition may vary somewhat. Generally, the aluminum chloride will be incorporated in these compositions at a level of frcm substantially 0.5% to substantially 6% by weight on an anhydrous basis based on the total weight of the composition with the preferred level being in the range of frcm substantially 1.5% to substantially 3.3% by weight on the same basis. As the hexahydrate (AlCl^.6H20) it will be incorporated at a concentration of frcm substantially 0.9% to substantially 11% by veight based on the total weight of the composition with the preferred range being frcm substantially 2% to substantially 6% on the same basis.

^ The aluminum chloride hexahydrate will usually be (incorporated in the present composition as a 50% aqueous /^/solution. When employed in this form, from substantially 1.8% ^ to substantially 22% by weight of this composition based on the total 198966 weight of the composition will be used.

The aluminum chlorohydrate (sometimes referred to as aluminum chlorhydroxide) may also be incorporated in the composition of this invention in varying amounts. Usually, this will be used at a level in the range of from substantially 5 1% to substantially 15% by weight on an anhydrous basis based on the total weight of the composition with the preferred level falling in the range of frcm substantially 2% to substantially 10% by weight on the same weight basis. Aluminum chlorohydrate is also supplied as a 50% aqueous solution. When employed in this 10 form, it will toe used at a concentration of frcm substantially 2.6% to substantially 38% by weight based on the total weight of the ccrnposition.

The ACH and aluminum chloride may be added to this canposition in whole or in part as a powdered mixture as described in the British patent to Shin et al 1,347,950. This may be prepared by 15 drying an aqueous solution of aluminum chloride hexahydrate and ACH using conventional drying techniques such as oven drying, vacuum oven drying, spray drying or freeze drying. These compositions are characterized by the fact that the molar ratio of aluminum to chloride will fall within the range of 20 from about 0.78:1 to about 1.95:1 with the preferred range being about 1.2:1 to about 1.5:1. When the molar ratio of alumintim to chloride is less than 1, the addition of larger amounts of buffering agent e.g. glycine may be necessary to reduce irritation potential and fabric damage.

The aluminum zirconium polychlorohydrate complexes that may be incorporated in the composition Of the present invention may be described by the general formula: (I) Al Zr(OH) Cl„ . nCH-COOH . mH„0 x y Z | 2 2 nh2 wherein: (a) x is a number from 2 to 10; \ (b) Z is a number from 3 to 8; 198966 (c) y equals (3x + 4) - Z; (d) the sum of y + Z is a number from 10 to 34; (e) m is a number from 0 to 12; (f) n is a number from 0 to 3 y ordinarily will have a value of from about 5 to about 29.

As will be clear from Formula I, the glycine may be bound in the complex or it may be absent. The presence or absence of the glycine in the complex will determine the amount of unbound glycine or other buffer that may be incorporated in the composition to increase the pH to a level of frcm substantially 2.5 to substantially 4.5 or the preferred pH of from substantially 2.8 to substantially 3.8.

A number of aluminum zirconium polychlorohydrate complexes are known in the prior art which are useful for the present purposes. By way of example, the following may be mentioned along with their empirical formulas: aluminum zirconium tetrachlorohydrate (Al^Zr(OH); aluminum zirconium tetrachlorohydrate glycine (Wickenol #E-369) (Al^Zr (OH) ^2C^"4 * NH2CH2COOH^ ' a^um^-iuim zirconium trichloro-hydrate (Al^Zr(OH)^3^13; alumintim zirconium trichlorohydrate glycine (Al^Zr (OH) • N^C^COOH) ; aluminum zirconium pentachlorohydrate (Al^Zr (OH) ^gCl^) ; aluminum zirconium pentachlorohydrate glycine (Al^QZr (OH) ^gCl,. . NH^^COOH) ; aluminum zirconium octachlorohydrate (AlgZr(OH) j^Clg) ; ;aluminum zirconium octachlorohydrate glycine (AlgZr(OH)^^Cl^ . NH^CH^COOH) . The aluminum zirconium polychlorohydrate complex can be mixed individually with the ACH and AlCl^ • 6^0 in solution or powder form or in various combinations thereof. ;The OTC Panel on antiperspirants of the Food and Drug Administration has adopted certain nomenclature and specifications for various aluminum zirconium polychloro-hydrates that are useful in the present invention. These are set out in Table A below: ;- 6 - ;»1 9 8 9 6 6 ;Table A ;Panel Adopted ;Nomenclature ;Aluminum zirconium trichlorohydrate ;Aluminum zirconium tetrachlorohydrate ;Aluminum zirconium pentachlorohydrate ;Aluminum zirconium octachlorohydrate ;Metal-Halide Ratio Range ;2.1 down to but not including 1.5:1 ;1.5 down to and including 0. 9; l ;2.1 down to but not including 1.5:1 ;1.5 down to and including 0.9:1 ;Al/Zr ;Ratio Range ;2.0 up to but not including 6.0:1 ;2.0 up to but not including 6.0:1 ;6.0 up to and including 10.0:1 ;6.0 up to and including 10.0:1 ;A number of the aluminum zirconium polychlorohydrate complexes that are useful in the present invention are available commerically. Reheis Chemical Company promotes a series ;TM ;or materials under the general trademark REZAL . The follow-ing Table describes a number of these products together with their specifications: ;Table I ;1 REZAL 3£G ;2 REZAL 36 ;3 REZAL 67 ;4 REZAL 67 ;Aluminum zirconium tetrachlorohydrex Gly (soln.) ;Aluminum zirconium trichlorohydrate (pdr.) ;Aluminum zirconium pentachlorohydrate (soln.) ;Aluminum zirconium pentachlorohydrate (pdr.) ;Approx. Al/Zr ratio ;3.6:1 ;3.6:1 ;6.7:1 ;6.7:1 ;Approx. ;metal/Cl ratio ;1.4:1 ;1.6:1 ;1.7:1 ;1.7:1 ;Concentration of solids ;^35% ;100% ;~-40% ;100% ;Alumintim (Al) ;5.0%-5.7% ;16.3%-17.7% ;7.6%-8.4% ;19.0%-21.0% ;Zirconium (Zr) ;4.4%-5.7% ;13.8%-15.2% ;3.7%-4.3% ;9.2%-10.8% ;Glycine ;3.6%-4.7% ;Chloride(CI) ;5.9%-6.7% ;16.0%-19.0% ;6.5%-7.2% ;16.2%-18.0% ;Iron(Fe) ;NMT 50ppm ;NMT lOOppm ;NMT 50ppm ;NMT lOOppm ;Heavy metals (as Pb) ;NMT lOppm ;NMT 20ppm ;NMT lOppm ;NMT 20ppm ;Particle size (thru 325. mesh) ;7 97% min. ;-it n, — ;797% min. ;- 7 - ;198966 ;Similar products are marketed by Wickhen Products, Inc. and-the Comet Chemical Corporation. ;The quantity of any aluminum zirconium polychlorohydrate complex that will be incorporated in the composition of the present invention may also vary somewhat. Usually, it will be used at a concentration level in the range of from substantially 5% to substantially 16% by wsight on an anhydrous basis based on the total weight of the composition. In the preferred forms of this invention, the levels will be in the range of from substantially 8% to substantially 14% by weight on an anhydrous basis based on the total weight of the composition. ;The aluminum zirconium polychlorohydrate complex of choice in the present invention is aluminum zirconium tetrachlorohydrate glycine complex. This is usually used at a level of frcm substantially 5% to substantially 16% by weight on an anhydrous basis based on the total weight of the composition with the preferred level being in the range of frcm substantially 8% to substantially 14% based on the same weight basis. The aluminum zirconium tetrachlorohydrate glycine complex is supplied as a 35% ;aqueous solution. When employed in this form, it is usually incorporated in the present composition at a level in the range of from substantially 18% to substantially 60% by weight based on the total weight of the composition. ;/ ;Glycine, the preferred buffering agent, is an important component of the present composition. This may be incorporated as free glycine or as part of the aluminum zirconium polychlorohydrate complex or as a combination of the both. In general, the total glycine incorporated in these compositions (i.e. as free glycine, complexed glycine or a combination of both) ;will fall in the range of frcm substantially 0.5% to substantially 5% by weight based on the total weight of the composition. The preferred range of total glycine, however, is from substantially 1.5% to substantially 3% on the same weight basis. ;Other buffering or complexing agents besides glycine ;- 8 - ;19 8966 ;acids or their salts (e.g. sodium glycinate, dihydroxy aluminum glycinate), urea, organic base containing nitrogen, metal hydroxide, carbonate, and oxide including alkaline and alkaline earth metal (MgfOH^/ Na2C0^, ZnO, etc.). These buffering agents can be used alone or in combination with glycine to give the composition a pH in the range of from 2.5 to 4.5 (preferably 2.8 to 3.8). ;These complexing and buffering agents serve to reduce irritation potential 'and fabric damage. They also function to stabilize the antiperspirant system. ;The compositions of the present invention may take a variety of dosage forms. Thus, they might be emulsion roll-on products or a clear hydro-alcoholic or aqueous roll-on products. Aqueous solutions of the aluminum chloride, ACH, aluminum zirconium polychlorohydrate complex and buffering agent e.g. glycine may be spray dried into an impalpable powder. This can be used as such or incorporated into sticks, suspensions, powders or roll-on products. ;- 9 - 19 8966 ;Although the compositions of the present invention may take a variety of forms, they appear very effective in system that contain a relatively high water content. These may take the form of solution or emulsion in which the active ingredients (i.e. the aluminum chloride, ACH, aluminum zirconium polychlorohydrate complex and buffer) are contained in the aqueous phase. The aqueous emulsion systems are preferred since they give more organoleptically elegant compositions. These emulsion systems will usually be of the oil-in-water type in which the active ingredients will be contained in the continuous aqueous phase. ;The quantity of water that may be contained in these compositions may vary somewhat. Usually, it will comprise from about 40% to about 80% by weight based on the total weight of the composition, the preferred range being from about 60% to about 75% on the same weight basis. ;The emulsion type products of the present invention may also contain other ingredients that are commonly found in roll-on antiperspirant of the lotion or emulsion type. ;These will include such things as emollients, surfactants, sequestering agents, perfumes, coloring agents, etc. ;By way of illustrating the emollients that may be employed herein, mention may be made of fatty acid esters (isopropyl myristate , isopropyl palmitate);diesters of dicarboxylic acids (diisopropyl adipate), polyoxyalkylene glycol esters (polypropylene glycol 2000 monooleate); propylene glycol diesters of short chain fatty acids (Cq-C^q) (Neobee M-20); polyoxypropylene fatty ethers (Procetyl, Arlamol E, Witconol APS, Witconol APM, etc.), propoxylated monohydric alcohol M.W. 880-930 (Fluid AP), fatty alcohol (hexadecyl alcohol), silicone oils (dimethyl polysiloxane, 10-2000 centistokes), cyclomethicones (volatile silicone 7207 and 7158-Union Carbide), polyoxyethylene polyoxypropylene fatty ether (Procetyl AWS Modified, Witconol APES). Alone or mixtures of the above non-polar liquids are equally suitable for the purposes of this invention. Generally, the above emollients are organic oily liquids which are non-polar in character ;198966 ;and have (a) a boiling point under atmospheric pressure not lower than about 120°C; (b) a specific gravity between about 0.7 and 1.6, preferably between 0.7 and 1.2. ;The quantity of emollient employed will vary somewhat, the level usually being within the range of from about 1% to about 30% by weight based on the total weight of the composition. Preferably, this will fall in the range of from about 2% to about 15% on the same weight basis. ;A variety of surfactants and combinations of surfactants are also useful in preparing the present lotion or emulsion type products. These include such materials as generally nonionic, cationic and amphoteric surfactants which can be used in antiperspirant emulsion systems. Examples are as follows: ;I. Nonionic Surfactants ;1. Polyoxyethylene fatty ethers - Brij 30, Brij 35, ;Brij 72, Brij 78, etc. ;2. Polyoxypropylene polyoxyethylene fatty ethers -Procetyl AWS, Witconol APEM, Witconol APES, etc. ;3. Polyoxyethylene alkyl phenyl ethers - Igepal CO 530, etc. ;4. Polyoxyethylene sorbitan fatty acid esters -Tween 20, Tween 80, etc. ;5. Sorbitan fatty acid esters - Span 60, Span 85, etc. ;6. Lanolin ethers - Laneto 50, Solulan 98, etc. ;7. Fatty .alcohols and polyoxyethylene fatty ethers - Proiaulgen G, Polawax, etc. ;II. Cationic Surfactants ;N(Lauryl colamino formyl methyl)pyridinium chloride (Emcol E607L) ;III. Amphoteric Surfactants ;Coconut imidazoline (Monateric CA-35%) ;IV. Auxiliary Surfactants ;1. Glyceryl fatty acid esters - Glyceryl monostearate ;19 8966 ;2. Patty acid amides - Witcamide'70 (Witco Chem. Co.) ;3. Fatty alcohols - Stearyl alcohol ;As in the case with the emollients, the quantity employed can vary somewhat. For the most part, this will be in the range of from about 1% to about 10% by weight on an anhydrous basis based on the total weight of the composition with the preferred range being from about 2% to about 6% on the same weight basis. ;As indicated above, one of the popular antiperspirant systems employed in the prior art is an aluminum zirconium trichlorohydrate glycine complex .. The present system has the following advantages over said popular system: ;1. Low cost of goods. The above popular system is much more expensive than either A1C1 . 6H O or ACH. ;J M ;2. Better emulsion stability and more ease to manufacture. Straight Al/Zr polychlorohydrate glycine systems are difficult to stabilize and to manufacture as emulsions. ;3. Low fabric staining potential. Generally, straight ;Al/Zr polychlorohydrate glycine salts stain more than aluminum salts. ;The following Examples are given to further illustrate the present invention. It is to be understood, however, ;that the invention is not limited thereto. ;EXAMPLE 1 ;Formula 1908 ;Ingredients % by Wt. ;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 ;Water, deionized 35.40 ;Aluminum chlorhydroxide, 50% 18.00 ;- 12 - ;19 8966 ;Aluminum chloride hexahydrate solution, 50% ;6.00 ;Aminoacetic acid (Glycine Crystal USP) ;0.50 ;Alumintim zirconium tetrachloro- ;hydrex-glycine solution, 35% Color FD&C Blue #1 (0.1% Aq. Sol.) ;35.00 0.20 ;100.00 ;Appearance: Smooth, opaque lotion Color: Pale blue pH: 3.3 + 0.3 ;Viscosity: #3 spindle at 20 RPM 15 seconds Overnight viscosity: 500-150X) cps ;Procedure: ;1. In a suitable stainless steel kettle, melt together polyoxypropylene fatty alcohol ethers, polyoxyethylene(2)stearyl ether and polyoxyethylene(20)stearyl ether by heating to 140°F. Add the perfume and mix together just prior to Step 3. ;2. In a separate stainless steel kettle, dissolve the disodium edetate in the water and heat to 140°F. ;3. Slowly add the oil phase to the water phase (both at 140°F) using a Lightnin' mixer at slow agitation. Maintain the temperature of 140°F for 15 minutes. ;4. At 140°F, slowly add to the batch, using slow agitation, a solution consisting of the aluminum chlorhydroxide, aluminum chloride hexahydrate, glycine and aluminum zirconium tetrachlorohydrex-glycine solution which has been preheated to 120°F. Continue agitation and cool the batch to 125°F. Mix for 15 minutes, maintaining the batch temperature at 120°F-125°F. ;5. Cool the batch to 105°F, add the dye solution and continue agitation and cooling. ;6. When the batch temperature reaches 80°-85°F, ;stop agitation and adjust for water loss, if necessary. ;19 8966 ;EXAMPLE 2 ;The composition and procedure of Example 1 is followed except that in place of the PPOll stearyl ether, Arlamol ESP (PPG-15 stearyl ether) is- employed. ;EXAMPLE 3 Formula 1956 ;Following the procedure of Example 1, the following composition is prepared: ;Ingredients % by Wt. ;PPG-11 stearyl ether . 2.25 ;Polyoxyethylene(2)stearyl ether 1.65 ;Polyoxyethylene(20)stearyl ether 0.60 ;Perfume 0.32 ;Disodium edetate, dihydrate 0.10 ;Water, deionized 35.13 ;Butylated hydroxytoluene ~ 0.05 ;Aluminum chlorhydroxide,50% 18.00 ;Aluminum chloride hexahydrate solution, 50% 6.00 ;Aminoacetic acid (Glycine Crystal ;USP) 0.50 ;Alumintim zirconium tetrachlorohydrex- ;glycine solution, 35% 35.00 ;DSC Red #19 (0.1% Aq. Sol.) 0.08 ;D&C Yellow #10 (0.1% Aq. Sol.) 0.32 ;100.00 ;Appearance: Smooth, opaque lotion Color; Pink pH: 3.3 + 0.3 ;Viscosity: #3 spindle at 20 RPM 15 seconds Overnight viscosity: 500-1500 cps ;1 9896 ;EXAMPLE 4 ;The composition and procedure of Example 3 is followed excepting that in place of the PPG-11 stearyl ether, Arlamol ESP (PPG-15 Stearyl Ether) is used. ;EXAMPLE 5 ;The procedure of Example 1 is followed and the following composition is prepared: ;Ingredients % by Wt. ;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 ;Water, deionized 31.40 ;Aluminum chlorhydroxide, 50% 12.00 ;Aluminum chloride hexahydrate solution, ;50% 6.00 ;Aminoacetic acid (Glycine Crystal ;USP) 0.50 ;Aluminum zirconium tetrachlorohydrex-glycine solution, 35% ;45.00 ;FD&C Blue #1 (0.1% Aq. Sol.) 0.20 ;100.00 ;Appearance: Smooth, opaque lotion Color: Pale blue pH: 3.3 + 0.3 ;Viscosity: #3 spindle at 20 RPM 15 seconds Overnight viscosity: 500-1500 cps ;EXAMPLE 6 ;The procedure and composition of Example 5 is followed excepting that in place of the PPG-11 stearyl ether, Arlamol ESP (PPG-15 Stearyl Ether) is employed. ;19 8966 ;EXAMPLE 7 ;Formula 1979 ;The procedure of Example 1 is followed and the following composition is prepared: ;Ingredients % by Wt. ;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 ;Water, deionized 35.40 ;Aluminum chlorhydroxide, 50% 15.50 ;Aluminum chloride hexahydrate solution, ;50% 8.00 ;Aminoacetic acid (Glycine Crystal ;USP) 1.00 ;Aluminum zirconium tetrachlorohydrex-glycine solution, 35% ;35.00 ;FD&C Blue #1 (0.1% Aq. Sol.) 0.20 ;100.00 ;Appearance: Smooth, opaque lotion Color: Pale blue pH: 3.3 + 0.3 ;Viscosity: #3 spindle at 20 RPM 15 seconds Overnight viscosity: 500-2000 cps ;EXAMPLE 8 ;The composition and procedure of Example 7 is followed excepting that in place of the PPG-11 stearyl ether, Arlamol ESP (PPG-15 Stearyl Alcohol) is employed. ;- 16 - ;19 8966 ;EXAMPLE 9 Formula 1991 ;The procedure of Example 1 is followed and the following composition is prepared: ;Ingredients PPG-11 stearyl ether Polyoxyethylene(2)stearyl ether Polyoxyethylene(20)stearyl ether Perfume ;Disodium edetate, dihydrate ;Water, deionized ;Aluminum chlorhydroxide, 50% ;Aluminum chloride hexahydrate solution, 50% ;Aminoacetic acid (Glycine Crystal USP) ;Aluminum zirconium tetrachlorohydrex-glycine solution, 35% ;FD&C Blue #1 (0.1% Aq. Sol.) ;Appearance: Smooth, opaque lotion Color: Pale blue pH: 3.3 + 0.3 ;Viscosity: #3 spindle at 20 RPM 15 seconds Overnight viscosity: 500-1500 cps ;EXAMPLE 10 ;The composition and procedure of Example 9 is followed excepting that in place of the PPG-11 stearyl ether, Arlamol ESP (PPG-15 Stearyl Ether) is employed. ;% by Wt. 2.25 1.65 0.60 0.30 0.10 31.40 10.00 ;8.00 ;0.50 ;45.00 0.20 100.00 ;19 8966 ;EXAMPLE 11 ;Formula 1955 ;The procedure of Example 1 is followed and the following composition is prepared: ;Ingredients % by Wt. ;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 ;Water, deionized 35.60 ;Aluminum chlorhydroxide, 50%„ 18.00 ;Aluminum chloride hexahydrate solution, 50% 6.00 ;Aminoacetic acid (Glycine Crystal ;USP) 0.50 ;Aluminum zirconium tetrachlorohydrex- ;glycine solution, 35% 35.00 ;100.00 ;Appearance: Smooth, opaque lotion Color: White pH: 3.3 + 0.3 ;Viscosity: #3 spindle at 20 RPM 15 seconds Overnight viscosity: 500-1500 cps ;EXAMPLE 12 ;The composition and procedure of Example 11 is followed excepting that in place of the PPG-11. stearyl ether, Arlamol ESP (PPG-15 Stearyl Ether) is employed. ;198966 ;EXAMPLE 13 ;Formula BA 1810-64 ;Aluminum zirconium trichlorohydrate 31 powder was employed. The number following the term "trichlorohydrate" in this and other Examples designates the Al/Zr molar ratio in the compound. Thus, for example, 31 designates an Al/Zr molar ratio of 3/1. ;Primary Emulsion A % by Wt. ;PPG-11 stearyl ether 5.56 ;Polyoxyethylene(2)stearyl ;SEhisr 4.07 ;Polyoxyethylene(20)stearyl ether 1.48 ;Perfume 0.74 ;Disodium edetate, dihydrate 0.25 ;FD&C Blue #1 (0.1% Aq. Sol.) 0.49 ;Water, deionized 87.41 ;100.00 ;Ingredients % by Wt. ;Al/Zr trichlorohydrate 31 powder 10.00 ;ACH 50% solution 18.00 ;A1C13 . 6H20, 50% solution 6.00 ;Glycine 1.50 ;Water, deionized 24.00 ;Primary Emulsion A q.s. to 100.00 ;pH: 3.4 + 0.3 ;Overnight viscosity: 500-1500 cps ;- 19 - ;.198966 ;EXAMPLE 14 Formula BA 1810-65 Aluminum zirconium trichlorohydrate 21 powder (Al/Zr molar ratio = 2/1) was used: ;Ingredients % by Wt. ;Al/Zr trichlorohydrate 21 powder 10.00 ;ACH 50% solution 18.00 ;AlCl^ • 6^0 ,50% solution 6.00 ;Glycine 1.50 ;Water, deionized 24.00 ;Primary Emulsion A q.s. to " 100.00 ;pH: 3.5 + 0.3 ;Overnight viscosity: 500-1500 cps ;EXAMPLE 15 Formula BA 1810-56 ;Aluminum zirconium octachlorohydrex-glycine powder 81 (Al/Zr molar ratio = 8/1) was used: ;Ingredients % by Wt. ;Al/Zr octachlorohydrex-glycine powder 81 15.00 ;ACH 50% solution 10.00 ;A1C13 . 6H20 solution 8.00 ;Glycine 0.50 ;Water, deionized 26.00 ;Primary Emulsion A q.s. to 100.00 ;pH: 3.2 + 0.3 ;Overnight viscosity: 500-1500 cps ;- 20 - ;19 8966 ;EXAMPLE 16 ;Formula BA 1810-57 ;Aluminum, zirconium pentachlorohydrate solution (Al/Zr molar ratio = 10/1) was used: ;Ingredients % by Wt. ;Al/Zr pentachlorohydrate solution, 30% 35.00 ;ACH 50% solution 10.00 ;AlCl^ • 6^0 50% solution 8.00 ;Glycine 2.00 ;Water, deionized , 4.50 ;Primary Emulsion A q.s. to 100.00 ;pH: 3.4 + 0.3 ;Overnight viscosity: 450-1500 cps ;EXAMPLE 17 Formula BQ 1856-83 Different buffering agent such as sodium carbonate is used as an additional buffering agent in this Example. ;Primary Emulsion B % by Wt. ;PPG-11 stearyl ether 6.43 ;Polyoxyethylene(2)stearyl ether 4.71 ;Polyoxyethylene(20)stearyl ether 1.71 ;Perfume 0.86 ;Disodium edetate, dihydrate 0.29 ;FD&C Blue #1 (0.1% aq. sol.) 0.57 ;Water, deionized 85.43 ;100.00 ;- 21 - ;1 98966 ;Ingredients % by Wt. ;Al/Zr tetrachlorohydrex-glycine solution, 35% 45.00 ;ACH, 50% solution 10.00 ;AlCl^ • ^H^O, 50% solution 8.00 ;Glycine 1.20 ;Sodium carbonate raonohydrate 0.50 ;Water, deionized 0.30 ;Primary Emulsion B q.s. to 100.00 ;pH: 3.4+0.3 ;Overnight viscosity: 500-1500 cps ;EXAMPLE 18 Formula BQ 1856-83 ;Magnesium hydroxide was used as an additional buffering agent. ;Ingredients % by Wt. ;Al/Zr tetrachlorohydrex-glycine solution, 35% 45.00 ;ACH, 50% solution 10.00 ;AlCl^ • 6^0, 50% solution 8.00 ;Glycine 0.50 ;Magnesium hydroxide 0.50 ;Water, deionized 1.00 ;Primary Emulsion B q.s. to 100.00 ;pH:. 3.4 + 0.3 ;Overnight viscosity: 500-1500 cps ;- 22 - ;198966 ;EXAMPLE 19 ;Formula 1509-61 ;Ingredients % by Wt. ;PPG-11 stearyl ether 2.25 ;Polyoxyethylene(2)stearyl ether 1.65 ;Polyoxyethylene(20)stearyl ether 0.60 ;Perfume 0.30 ;Water, deionized 41.20 ;Disodium edetate, dihydrate 0.10 ;DC Antifoam AF, 25% 0.10 ;Al/Zr tetrachlorohydrex-glycine solution, 35% 35.00 ;ACH, 50% solution 15.00 ;A1C13 . 6H20, 50% solution 3.00 ;Glycine 0.60 ;FD&C Blue #1 (0.1% aq. sol.) 0.20 ;100.00 ;pH: 3.4 + 0.3 ;overnight viscosity; 400-1200 cps ;To demonstrate that the combination of aluminum chloride, ACH, aluminum zirconium polychlorohydrate and glycine act synergistically, a number of formulas identified in Table II below were prepared. Formula # 1908 is representative of the present invention. ;TABLE II ;n ;<N ;Ingredients ;F #1052 ;ACH(% anhydrous basis) ;18.3 ;A1C1 . 6H 0 ;(% anhydrous basis) ;Al/Zr tetrachlorohydrate ($ anhydrous basis) ;Glycine ;PPG-11 stearyl ether ;Polyoxyethylene(2) stearyl ether ;Polyoxyethylene(20) stearyl ether ;3.0 ;1.9 ;1.1 ;Disodium edetate, dihydrate ;Perfume & Color Water q.s. to 100 ;Total Actives ;Total Glycine i ;18.3 0 ;% by Wt. based on Total Weight ;F #1676 ;F #1908 F #1341 ;Commercial Emulsion Roll-On (BR-4504) ;18.6 2.8 ;2.0 ;1.5 ;0.6 ;0.1 ;18.6 2.8 ;7.5 ;1.7 ;9.3 1.9 ;2.25 ;1.65 ;0.6 ;0.1 ;18.5 1.9 ;16.2 2.0 ;2.0 3.5 2.3 1.2 0.1 ;18.2 2.0 ;Al/Zr trichlorohydrate (% anhy. basis) 19.7 ;Glycine 4.2 ;PEG-40 stearate, Glyceryl stearate, Glycerin, Refined paraffin, Isopropyl palmitate, ;Mg/Al silicate and Fragrance to ;U> ;19.7 Total actives 4.2 Total Glycine ;NO ;198966 ;As will be noted, each of these formulas is similar excepting for the active ingredients that are employed. Further, each contains the total active ingredients at essentially the same concentration i.e. about 18% on an anhydrous basis. ;Each of these compositions was tested for antiperspirant activity. The general procedure employed was as described in Federal Register, Vol. 43, Number 196, ;October 10, 1978. It is called the gravimetric axillary antiperspirant test. Paired comparison (treated vs. ;treated) studies of the antiperspirant effectiveness of antiperspirant emulsion. ;The details of the test procedure are given below. ;Test Procedure ;A random test pattern supplied by Statistical Services is employed, e.g. if one test material is evaluated, half of the panelists receives the test material under the left axilla while the remaining half receives it tinder the right. The opposite axilla serves as a control. If two test materials are evaluated, half the panel has product A applied to the left axilla and product B to the right while the remaining panelists have the reverse product/axilla allocations. ;The test is conducted during a five-day period (Monday through Friday). Sweating is induced under environmental conditions of 100°F ± 2° and 40% relative humidity ± 2%. ;Day 1; Control measurement followed by product application ;Panelists wait one-half hour at room temperature (approximately 65°-80°F) after which time they enter the test room. They then place the untared Webril Pads (which are folded in half to a size of 4nx2") in their axillae. Subjects sit in the test room for a 40 minute warm-up period. At the end of this period, the warm-up pads are removed by the panelists and are discarded. ;198966 ;The panelists remove the plastic bags containing the tared collection pads from the manila envelopes. The subjects insert the pads as directed by a technician. ;The pads remain in the axilla for a period of 20 minutes. ;After such time, the panelists are instructed to remove the pads and to place them into the designated plastic bags which are then returned to the manila envelopes. ;The panelists exit the test room, hand in their envelopes, and then wash their axillae with tepid water with the aid of gauze pads and towel dry them. Approximately one to three minutes later, the test material is applied and the panelists leave. The plastic bags are removed from the manila envelopes and are weighed by a technician. Panelists must perspire at least 200 mg/axilla to continue participation on the panel. ;Day 2: Product application only ;Panelists wait one-half hour at room temperature, ;after which time they wash their axillae with tepid water with the aid of gauze pads and towel dry them. Approximately one to three minutes later, the test material is applied and the panelists leave. ;Day 3: Product application and collection ;Panelists wait one-half hour at room temperature, ;after which time they wash their axillae as described above. Approximately one to five minutes later the test material is applied. The panelists then wait one hour at room temperature. Then they enter the test room for a 40-minute warm-up and place the untared pads in their axillae. At the end of this period, the warm-up pads are removed and discarded. ;The panelists remove the plastic bags containing the tared collection pads from the manila envelopes. They insert the pads as directed by a technician. The pads remain in the axillae for a period of 20 minutes. Then the panelists are instructed to remove the pads and to place them into the ;t 9 8966 ;designated plastic bags which are then returned to the manila envelopes. The panelists exit the test room, hand in their envelopes, and leave. The plastic bags are removed from the manila envelopes and are weighed by a technician. ;Day 4: Product application only ;Same as Day 2. ;Day 5 : Product application and collection ;Same as Day 3. ;The results of the test are summarized as follows: I_. Formula #1908 vs. Formula #1052 ;Results: ;The data from this study, employing 47 female subjects, were submitted to the Statistical Services Department for evaluation. ;• Briefly, their analysis indicated that Antiperspirant Roll-on Formula #1908 was significantly more effective than Formula #1052 at the 0.01 level. ;This conclusion is supported by the A/B ratio (amount of sweat collected from A treated axilla over B treated axilla) for the final treatment-collection day (adjusted by control) averaging 0.819 which is significantly different from 1.0 equality. ;The above data indicates that Formula #1908 is about 18% more effective than Formula #1052. ;II. Formula #1908 vs. Formula #1676 ;Results: ;The data from this study, employing 46 female subjects, were submitted to the Statistical Services Department for evaluation. ;Briefly, their analysis indicated that Formula #1908 was significantly more effective than Formula #1676 at the 0.01 level. ;t 98966 ;This conclusion is supported by the A/B ratio for the final treatment-collection day (adjusted for control) averaging 0.883 which is significantly different from 1.0 equality. ;The above data indicates that Formula #190 8 is about 12% more effective than Formula #1676. ;III. Formula #1908 vs. Commercial Emulsion Roll-On Formula # BR 4504 ;Results: . ;The data from*this study, employing 48 female subjects, were submitted to the Statistical Services Department for evaluation.

Briefly, their analysis indicates that Formula #1908 was significantly more effective than Commercial Emulsion Roll-On at the 0.01 level.

This conclusion is supported by the A/B ratio for the final treatment-collection day (adjusted for control) averaging 0.881 which is significantly different from 1.0 equality.

The above data indicates that Formula #1908 is about 12% more effective than Formula #BR 4504.

IV. Formula #1341 (see Table II ) which contains as antiperspirant actives a combination of ACH and AlCl^ • SI^O (at a level of about 18.2) in a similar manner was shown to be on the average 9.6% less effective than the Commercial Emulsion Roll-on (BR 4504) which contains 19.7% Al/Zr trichlorohydrate as the antiperspirant active (see Table II). The latter, however, has also been shown to be less effective than Formula #1908 embodied in the present invention i.e. Formula #1908 was about 12% more effective than Formula #BR 4505 (see Paragraph III). 19 8966 V. Formula #1991 (See Example 9) in a similar manner was shown to be 15% more effective than a commercial suspension roll-on product identified as Formula #BR 4751. The latter has the following composition: Formula # BR 4751 Ingredients % by Wt.

Aluminum zirconium tetrachlorohydrate (anhydrous basis) 13.8 Glycine 2.0 Bentone 38 * 3.25 Cyclomethicone and Perfume q.s. to 100.00 Although the invention has been described with reference to specific forms thereof, it will be understood that many changes and modifications may be made without departing from the spirit of this invention. 98966

Claims

WHAT WE CLAIM IS: \

!• An antiperspirant composition buffered to a pH in the range of frcm substantially 2.5 to substantially 4.5, said composition having incorporated therein as active ingredients aluminum chloride, aluminum chlorohydrate, and an aluminum zirconium polychlorohydrate complex, said aluminum zirconium polychlorohydrate complex having the formula: (I) Al Zr(OH) CI . nCH COOH . mH^O X y 2 , 2 2 NH 10 2 wherein: (a) x is a number from 2 to 10; (b) Z is a number from 3 to 8; (c) y equals (3x + 4) - Z; 15 (d) the sum of y + Z is a number from 10 to. 34; (e) m is a number from 0 to 12; (f) n is a number from 0 to 3 said active ingredients being incorporated in said composition in the following weight percentages based on the total weight 20 of said composition and on an anhydrous basis: (1) aluminum chloride frcm substantially 0.5% to substantially 6% (2) aluminum chlorohydrate frcm substantially 1% to substantially 15% (3) aluminum zirconium polychlorohydrate complex frcm substantially 5% to substantially 16%. 25
2. A composition according to Claim 1 including an additionally added buffering agent-
3. A composition accordina^feo^laim 2 in which the additionally added buffering ac^e$% is g^^sine. - 30 - 198966 \
4. A composition according to Claim 3 in which the total amount of glycine in bound and/or unbound form is present in said composition at a level in the range of from substantially 0.5% to substantially 5% by weight based on the total weight of said composition.
5. A composition according to any one of Claims 1 to 4 wherein the aluminum chloride is incorporated as the aluminum chloride hexahydrate.
6. A composition according to any one of Claims 1 10 to 5 in which the aluminum zirconium polychlorohydrate complex is aluminum zirconium tetrachlorohydrate glycine.
7. A composition according to any one of Claims 1 to 5 wherein the aluminum zirconium polychlorohydrate complex is selected from the group consisting of aluminum zirconium tetrachloro- 15 hydrate; aluminum zirconium tetrachlorohydrate glycine; aluminum zirconium trichlorohydrate; aluminum zirconium trichlorohydrate glycine; aluminum zirconium pentachlorohydrate; aluminum zirconium pentachlorohydrate glycine; alumintim zirconium octachlorohydrate; aluminum zirconium 20 octachlorohydrate glycine and mixtures thereof.
8. A composition according to Claim 7 wherein the aluminum chloride is incorporated as the hexahydrate.
9. An. antiperspirant composition buffered to a pH in the range of from substantially 2.8 to 3.8, said ccmposi-r 25 tion having incorporated therein as active ingredients aluminum chloride, aluminum chlorohydrate,and an aluminum zirconium polychlorohydrate complex; and containing glycine, said aluminum zirconium polychlorohydrate complex having the formula: 3D (1) Al Zr (OH) Clz . nCH2COOH . mH20 J " I NH wherein: (a) x is a number from 2 to 10; ^Ui- - 31 - (b) Z is a number from. 3 to 8; (c) y equals (3x + 4) - Z; (d). the sum of y + Z is a number from 10 to 34; (e) m is a number from 0 to 12; (f) n is a number from 0 to 3 said active ingredients being incorporated in said composition in the following weight percentages based on the total weight of said composition and on an anhydrous basis: (1) aluminum chloride frcm substantially 1.5% to substantially 3.3% (2) aluminum chlorohydrate frcm substantially 2% to substantially 10% (3) aluminum zirconium polychlorohydrate complex frcm substantially 8% to substantially 14%. the total weight percent of glycine in bound and/or unbound form being frcm substantially 1.5% to substantially 3% based on the total weight of the ccmpo-sition.
10. A composition according to Claim 9 wherein the aluminum chloride is incorporated as the aluminum chloride hexahydrate.
11. A composition according to Claim 9 or Claim 10 in which the aluminum zirconium polychlorohydrate comnlex is aluminum zirconium tetrachlorohydrate glycine.
12. A composition according to Claim 9 or Claim 10 wherein the aluminum zirconium polychlorohydrate complex is selected from the group consisting of aluminum zirconium tetrachlorohydrate; aluminum zirconium tetrachlorohydrate glycine; aluminum zirconium trichlorohydrate; aluminum iirconium trichlorohydrate glycine; aluminum zirconium pentachlorohydrate; aluminum zirconium pentachlorohydrate glycine; aluminum zirconium octachlorohydrate; aluminum zirconium octachlorohydrate glycine and mixtures thereof. - 32 - 198966
13. A composition according to Claim 12 wherein the aluminum chloride is incorporated as the hexahydrate.
14. A composition according to any one of Claims 1 to 13 in the form of an oil-in-water emulsion in which at least the major proportion of the active ingredients and the glycine are contained in the water phase.
15. A composition according to Claim 1, substantially as hereinbefore described with particular reference to any one of the foregoing Examples 1 to 19. GATED THIS / DAY OF i9?V A. J. PARK & SON PER tft ■ S . AGENTS FOR THE APPLICANTS