GB2091099A - Antiperspirant composition containing aluminum chlorohydrate, aluminum chloride and an aluminum zirconium polychlorohydrate complex - Google Patents
Antiperspirant composition containing aluminum chlorohydrate, aluminum chloride and an aluminum zirconium polychlorohydrate complex Download PDFInfo
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- GB2091099A GB2091099A GB8137597A GB8137597A GB2091099A GB 2091099 A GB2091099 A GB 2091099A GB 8137597 A GB8137597 A GB 8137597A GB 8137597 A GB8137597 A GB 8137597A GB 2091099 A GB2091099 A GB 2091099A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/28—Zirconium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/58—Metal complex; Coordination compounds
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Abstract
An antiperspirant composition buffered to a pH in the range of from about 2.5 to about 4.5 having incorporated therein as active ingredients a mixture of aluminum chlorohydrate, aluminum chloride and an aluminum zirconium polychlorohydrate complex; an additionally added buffering agent, preferably glycine, may be incorporated in the composition.
Description
SPECIFICATION
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 oxyor 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 pI- 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-orzirconium 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 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 aluminum 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 petal (U.S. Patent3,407,254),
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 anti perspicant 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 a combination of aluminum chloride, aluminum chlorohydrate, and an aluminum zirconium polychlorohydrate complex as defined more particularly below acts synergistically and at the same level of concentration of actives shows 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 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 slain of individuals by application to the skin area the afonsaid antiperspirant compositions.
Other and more detailed objects of this invention will be apparent from the following description and claims.
n the following description, unless otherwise specified, the percentages are expressed 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 hydrated to various degrees.
However, aluminum chloride hexahydrate (AlCl3.6HO) 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 between about 0.5% and about 6% by weight on an anhydrous basis based on the total weight of the composition. As the hexahydrate (AICl3.6H2O) it will be incorporated at a concentration of from about 0.9% to about 11% by weight based on the total weight of the composition with the preferred range being from about 2% to about 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 about 1.8% to about 22% by weight of this composition based on the total 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 about 1%to about 15% by weight on an anhydrous basis based on the total weight of the composition with the preferred level falling in the range of from about 2% to about 10% by weight on the same weight basis. Aluminum chlorohydrate is also supplied as a 50% aqueous solution. When employed in this form, it will be used at a concentration of from 2.6% to about 38% by weight based on the total weight of the composition.
The ACH and aluminum chloride may be added to this composition 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 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 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 aluminum to chloride is less than 1, the addition of larger amounts of buffering agent e.g. glycine may be necessaryto 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)yCIz.nH2NCH2COOH.mH20 *e wherein:
(a) xisa numberfrom2to 10;
(b) Z is a number from 3 to 8;
(c) yequals(3x+4) -Z; (d) the sum ofy + Z is a number from 10 to 34;
(e) mis a numberfrom Oto 12; (f) nisa 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 from about 2.5 to about 4.5 or the preferred pH of from about 2.8 to about 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 tetrach- lorohydrate (Al4Zr(OH)12Cl4); aluminum zirconium tetrachlorohydrate glycine (Wickenol #E-369) (Al4Zr(OH)12Cl4. NH2CH2COOH); aluminum zirconium trichlorohydrate (Al7r(OH)13Cl3 aluminum zirconium trichlorohydrate glycine (Al4Zr(OH)13Cl.
NH2CH2COOH); aluminum zirconium pentachlorohydrate (Al10Zr(OH)29Cl5); aluminum zirconium pentachlorohydrate glycine (Al10Zr(OH)29Cl5.
NH2CH2COOH); aluminum zirconium octachlorohydrate (AlEZr(OHh4CI8); aluminum zirconium octach
lorohydrate glycine (Al6Zr(OH)14CI8. NH2CH2COOH).
The aluminum zirconium polychlorohydrate com
plex can be mixed individually with the ACH and AICI3. 6H2O 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 zir
conium polychlorohydrates that are useful in the
present invention. These are set out in Table A
below:
Table A
PanelAdopted Metal-Halide AllZr Nomenclature Ratio Range Ratio Range
Aluminum zirconium 2.1 down to but not 2.0 up to but not
trichlorohydrate including 1.5:1 including 6.0:1
Aluminum zirconium 1.5 down to and 2.0 up to but not
tetrachlorohydrate including 0.9:1 including 6.0:1
Aluminum zirconium 2.1 down to but not 6.0 up to and
pentachlorohydrate including 1.5:1 including 10.0:1
Aluminum zirconium 1.5 down to and 6.0 up to and
octachlorohydrate including 0.9:1 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 of materials under the general trademark REZALTM. The following Table describes a number of these products together with their specifications:
Table I 1 REZAL 36G Aluminum zirconium tetrachlorohydrex Gly (soln.) 2 REZAL 36 Aluminum zirconium trichlorohydrate (pdr.) 3 REZAL 67 Aluminum zirconium pentachlorohydrate (soln.) 4 REZAL 67 Aluminum zirconium pentachlorohydrate (pdr.) 1 2 3 4
Approx.
Al/Zr ratio 3.6:1 3.6:1 6.7:1 6.7:1
Approx.
metal/CI ratio 1.4:1 1.6:1 1.7:1 1.7:1
Concentration of solids ~35% 100% ~40% 100%
Aluminum (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 (Cl) 5.9%-6.7% 16.0%-19.0% 6.5%-7.2% 16.2%-18.0% Iron (Fe) NMT50ppm NMT100ppm NMT50ppm NMT 100 ppm
Heavy metals (as Pb) NMT10ppm NMT20ppm NMT10ppm NMT20ppm
Particle size (thru 325 mesh) - > 97% min. - > 97% min.
Similar products are marketed by Wickhen Products, Inc. and the Comet Chemical Corporation.
The quantity of any aluminum zirconium polych- lorohydrate 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 about 5% to about 16% by weight 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 about 8% to about 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 from about 5% to about 16% by weight on an an hydrous basis based on the total weight of the composition, with the preferred level being in the range of from about 8% to about 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 about 18% to about 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 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 or complexing agents besides glycine can also be used in this invention. For example, other amino acids or their salts (e.g. sodium glydnate, dihydrnxy aluminum glycinate), urea, organic base containing nitrogen, metal hydroxide, carbonate, and oxide including alkaline and alkaline earth metal (Mg(OH)2, Na2CO3, 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.
Although the compositions of the present invention may take a variety of forms, they appear very effective in systems 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 inven tion may also contain other ingredients that are commonlyfound in roll-on antiperspirantofthe 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 (dilsopropyl adipate), polyox yalkylene glycol esters (polypropylene glycol 2000 monooleate); propylene glycol diesters of short chain fatty acids (C8-C,O) (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 (hex adecy. 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 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 su rfactants are also useful in preparing the present
lotion or emulsion type products. These include such
materials as generally nonionic, cations and
amphoteric surfactants which can be used in anti
perspirant emulsion systems. Examples are as fol
lows:
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 - Promulgen G, Polaviax, etc.
II. Cationic Surfactants
N(Lauryl colaminoformyl methyl)pyridinium chloride (Emcol E607L) Ill. Amphoteric Surfactants
Coconut imidazoline (Monateric CA-35%)
IV. Auxiliary Surfactants
1. Glyceryl fatty acid esters-Glyceryl monostearate
2. Fatty acid amides-Witcamide70 (Witco Chem.
3. Fattyalcohols-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 AICI3. 6H2O or
ACH.
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 %byWt.
PPG-1 1 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
Aluminum chloride hexahydrate solution, 50% 6.00
Aminoacetic acid (Glycine Crystal USP) 0.50
Aluminum zirconium tetrachlorohydrex glycine solution, 35% 35.00 ColorFD & Blue #1 (0.1% Aq. Sol.) 0.20
100.00
Appearance: Smooth, opaque lotion
Color: Pale blue pH: 3.3 i 0.3
Viscosity: #3 spindle at 20 RPM 15 seconds
Overnight viscosity: 500-1500 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 1200F. Continue agitation and cool the batch to 125"F. Mix for 15 minutes, maintaining the batch temperature at 1 20"F-1 25"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.
EXAMPLE2
The composition and procedure of Example 1 is followed except that in place of the PPG-11 stearyl ether, Arlamol ESP (PPG-15 stearyl ether) is employed.
EXAMPLE3
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
Aluminum zirconium tetrachlorohydrex glycine solution, 35% 35.00
D & Red #19 (0.1% Aq.Sol.) 0.08
D & 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
EXAMPLE 4
The composition and procedure of Example 3 is followed excepting that in place of the PPG-1 1 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 %byWt.
PPG-11 stearyl ether 2.25
Polyoxyethylene(2)stearyl ether 1.65 Polyoxyethylene(20)stearyl ether . 0.60 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 & IBlue #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-1 1 stearyl ether, Arlamol ESP (PPG-15 Stearyl Ether) is employed.
EXAMPLE 7
Formula 1979
The procedure of Example 1 is followed and the following composition is prepared:
Ingredients %byWt.
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 & 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 at20 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.
EXAMPLE9
Formula 1991
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 1.66
Polyoxyethylene(20)stearyl ether 0.60
Perfume 0.30
Disodium edetate, dihydrate 0.10
Water, deionized 31.4û Aluminum chlorhydroxide, 50% 10.00
Aluminum chloride hexahydrate solution, 50% 8.00
Aminoaoetic acid (Glycine Crystal USP) 0.50
Aluminum zirconium tetrachlorohyorexglycine solution, 35% 45.00
FD & Blue #1 (0.1% Aq.Sol.) 0.20
100.00
Appearance: Smooth, opaque lotion
Color: Pale blue pH: 3.3 + 0.3
Viscosity: #1 spindle at 20 RPM 15 seconds
Ovenight viscoslty: 500-1500 cps
EXAMPLE 10
The composition and procedure of Example 9 is followed excepting that in place of the PPG-1 i stearyl ether, Arlamol ESP (PPG-15 Stearyl Ether) is employed.
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
Polyonyethylene(2)stearyl ether 1.65
Polyonyethylene(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 tetrachlorohydrexglycine 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.
EXAMPLE 13 Formula BA 1810-64
Aluminum zirconium trichlorohydrate 31 powder
was employed. The number following the term
"richlorohydrate" 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 ether 4.07
Polyoxyethylene(20)stearylether 1.42
Perfume 0.74
Disodium edetate, dihydrate 0.25
FD & Blue #1 (0.1% Aq. Sol.) 0.49
Water, deionized 87.41 100.00 lngredients % by Wt.
AVZrtrichlorohydrate 31 powder 10.00 ACH 50% solution 13.00 Al Cl3. 6H2O, 50% solution 6.00 Giycine 1.50 Water, deionized 24.00 Prinmary Ermulsion A q.s. to 100.00 pH:3.4 # 0.3
Overnight viscosity: 500-1500 cpa EXAMPLE 14
Formula BA 1810-65
Aluminium zirconium trichlorohydrate 21 powder (Al/Zr molar ratio = 2/1) ) was used: lngredients % by VVt.
Al/Zr trlchlorohydrate 21 powder 10.00
ACH 50% solution 18.00
AlCl3.6H2O,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: lngredients % by Wt.
Al/Zr octachlorohydrex-glycine powder 81 15.00 ASH 50% solution 10.00 AICI3. GH2O solution 8.00
Glycine 0.50
Water, deionized 26.00 Primary Emulsion A q.s. to 100.00 pH: 3.2 i 0.3
Overnight viscosity: 500-1500 cps EXAMPLE 16
Formula Ba 1810-57
Aluminum zirconium pentachlorohydrate solution (Al/Zr molar ratio = 10/1) was used:
Ingredients %byWt.
Al/Zr pentachlorohydrate solution, 30% 35.00
ACH 50% solution 10.0û AICI3. 6H3O 50% solution 8.00
Glycine 2.00
Water, deionized 4.50
PrimaryEmulsionA q.s.to 100.00 pH: 3.4 i 0.3 Overnight viscosity: 450-1500 cps
EXAMPLE 17
Formula BO 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 & Blue # (0.1% aq. sol.) 0.57
Water, deionized 85.43
100.00
Ingredients %by Wt.
Al/Zr tetrachlorohydrex - glycine solution, 35% 45.00
ACH, 50% solution 10.00 AICI3. 6H2O, 50% solution 8.00
Glycine 1.20
Sodium carbonate monohydrate 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 BO 1856-83
Magnesium hydroxide was used as an additional buffering agent.
Ingredients %byWt.
Al/Zr tetrachlorohydrex - glycine solution, 35% 45.00
ACH, 50% solution 10.00 AICI3. 6H2O, 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
EXAMPLE 19
Formula 1509-61
Ingredients %byWt.
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
AICI3. 6H3O, 50% solution 3.00
Glycine 0.60
FD & Blue #1 (0.1%aq.sol.) 0.20
100.00 pH: 3.4 t 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 IT
% byWt. based on Commercial Emulsion Total Weight Roll-On (BR4504) Ingredients F #1052 F #1676 F #1908 F #1341 ACH (%anhydrousbasis) 18.3 - 7.5 16.2 AICI3. 6H2O (% anhydrous basis) - - 1.7 2.0 Al/Zr tetrachlorohydrate Al/Zr trichlorohydrate (% anhydrous basis) - 18.6 9.3 - (% anhy. basis) 19.7 Glycine - 2.8 1.9 2.0 Glycine 4.2 PPG-11 stearyl ether 3.0 2.0 2.25 3.5 Polyoxyethylene(2) stearyl ether 1.9 1.5 1.65 2.3 PEG40 stearate, Glyceryl stearate, Glycerin, Polyoxyethylene(20) Refined paraffin, stearyl ether 1.1 0.6 0.6 1.2 Isopropyl palmitate, Mg/AI silicate Disodium edetate, and Fragrance dihydrate 0 0.1 0.1 0.1 Perfume & Color Water q.s. to 100J Total Actives 18.3 18.6 18.5 18.2 19.7 Total actives Total Glycine 0 2.8 1.9 2.0 4.2 Total Glycine 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 anti
perspirant activity. The general procedure employed
was as described in Federal Register, Vol.43,
Number 196, October 1978. It is called the
gravimetric axillary antiperspirant test. Paired com
parison (treated vs. treated) studies of the antipers
pirant effectiveness of antiperspirant emulsion.
The details of the test procedure are given below.
Test Procedure
A random test pattern supplied by Statistical Services isemployed, 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 under 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 t 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 4" x 2") in their axillae. Subjects sit in the test room for a 40 minute warm-up period. Atthe end of this period, the warm-up pads are removed by the panelists and are discarded.
The panelists remove the plastic bags containing a:h-- 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 appllcation 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 enterthe 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 insertthe 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 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 #190S was significantly more effec tire 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 Servlces
Department for evaluation.
Briefly, their analysis indicated that Formula #1908 was significantly more effective than Formula #1676 at the 0.01 level.
This conclusion is supported by the A/B ratio fo the final treatment-collection day 5adjusted for c3n- trol) averaging 0.883 which is significantly different from 1.0 equality.
The above data indicates that Formula #1908 is about 12% more effective than Formula #1676.
lll. Formula #1908 vs. Commercial Emulsion Roll- On Formula #BR45W 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 11) which contains as antiperspirant actives a combination of ACH ancl AICI3. 6H2O (at a level of about 18.2) in a similar manner ways 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 Ill).
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 #BR4751 Ingredients %byWt.
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 ambit of this invention.
Claims (16)
1. An antiperspirant composition buffered to a pH in the range of from about 2.5 to about 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:
(1) Al2Zr(OH)yCl2.nH2NCH2COOH.mH2O
-NH+Ewherein::
(a) as is a numberfrom 2 to 10;
(b) Zis a number from 3 to 8, (c) y equals (3x + 4) -
(d) the sum ofy y + + Z is a number from 10 O to 34; (e) m is a number from 0 to 12;
(f) n is a numberfrom 0to3 said active ingredienis being incorporated in said composition in the following weight pereentages based on the total weight of said composition and on an anhydrous basis:
(1) aluminum chloride from about 0.5% to
about 6%
(2) aluminum chlorohydrate from about 1% to
about 15%
(3) aluminum zirconium polychlorohydrate
complex from albout 5% to about 16%.
2. A composition according to Claim 1 including an additionally added buffering agent.
3. A composition according to Claim 2 in which the additionally added buffering agent is glycine.
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 about 0.5% to about 5% by weight based on the total weight of the composition.
5. A composition according to any preceding
Claim wherein the aluminum chloride is incorporated as the aluminum chloride hexahydrate.
6. A composition according to any preceding
Claim in which the aluminum zirconium polychlorohydrate complex is aluminum zirconium tetrach
lorohydrate glycine.
7. A composition according to any of Claims 1 to
5 wherein the aluminum zirconium polychlorohy- drate complex is selected from the group consisting
of aluminum zirconium tetrachlorohydrate;
aluminum zirconium tetrachlorohydrate glycine;
aluminum zirconium trichlornhvdrate; luminum zirconium trichlorohydrate glycine; aluminum zirconium pentachlorohydrate; aluminum zirconium pentachlcrohydrate glycine; aluminum zirconium
octachlorohydrate; aluminum zirconium octach
lorohydrate 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 about 2.8 to 3.8, said composition having incorporated therein as active ingredients aluminum chloride, aluminum chlorohydrate, an aluminum zirconium polychlorohydrate complex and containing glycine, said aluminum zirconium polychlorohydrate complex having the formula:
(I) Al"Zr(OH)yCIz.nH2NCH2COOH . mH2O wherein::
(a) xisanumberfrom2to 10; (b) Zisa numberfrom3to8;
(c) y equals (3x + 4)
(d) the sum ofy + Z is a number from 10 to 34;
(e) m is a number from 0 to 12;
(f) nisa 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 from about 1.5% to
about 3.3%
(2) aluminum chlorohydrate from about 2% to
about 10
(3) aluminum zirconium polychlorohydrate
complex from about 8% to about 14% the total weight percent of glycine in bound andlor unbound form being from about 1.5% to about 3% based on the total weight of the composition.
10. A composition according to Claim 9 wherein the aluminum chloride is incorporated as the aluminum chloride hexahydrate.
11. Acomposition according to Claim 9 or lOin which the aluminum zirconium polychlorohydrate complex is aluminum zirconium tetrachlorohydrate glycine.
12. A composition according to Claim 9 or 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 zirconium trichlorohydrate glycine; aluminum zirconium pentachlorohydrate; aluminum zirconium pentachlorohy drate glycine; aluminum zirconium octachlorohy
ate; aluminum zirconium octachlorohydrate glycine and mixtures thereof.
13. A composition according to Claim 12 wherein the aluminum chloride is incorporated as the hexahydrate.
14. A composition according to Claims 1,2,3,4, 5,6,k7,8,9,10,11,12 or 13 in the form of a oil-inwater emulsion in which at least a large component of the active ingredients and the glycine are contained in the water 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 Claims1,2,3,4,5,6,7,8,9,10,11,12Or13.
16. A composition as claimed in claim 1 or9, substantially as described in any of the foregoing
Examples.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21641380A | 1980-12-15 | 1980-12-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2091099A true GB2091099A (en) | 1982-07-28 |
GB2091099B GB2091099B (en) | 1985-05-01 |
Family
ID=22806970
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8137597A Expired GB2091099B (en) | 1980-12-15 | 1981-12-14 | Antiperspirant composition containing aluminum chlorohydrate aluminum chloride and an aluminum zirconium polychlorohydrate complex |
Country Status (15)
Country | Link |
---|---|
JP (1) | JPS57131715A (en) |
AU (1) | AU547985B2 (en) |
BE (1) | BE891488A (en) |
CA (1) | CA1153313A (en) |
CH (1) | CH649707A5 (en) |
DE (1) | DE3149649A1 (en) |
ES (1) | ES8303085A1 (en) |
FR (1) | FR2495933A1 (en) |
GB (1) | GB2091099B (en) |
GR (1) | GR76682B (en) |
IT (1) | IT1172144B (en) |
NZ (1) | NZ198966A (en) |
PT (1) | PT74127B (en) |
SE (1) | SE452108B (en) |
ZA (1) | ZA817173B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775528A (en) * | 1983-08-16 | 1988-10-04 | The Gillette Company | Antiperspirant composition |
US5486347A (en) * | 1983-08-16 | 1996-01-23 | The Gillette Company | Antiperspirant composition |
US5593663A (en) * | 1991-11-12 | 1997-01-14 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Antiperspirant materials and compositions |
US6893630B2 (en) | 2000-01-18 | 2005-05-17 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Anti-microbial antiperspirant products |
WO2023280755A1 (en) * | 2021-07-07 | 2023-01-12 | Unilever Ip Holdings B.V. | Method of manufacture of antiperspirant salts |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ241567A (en) * | 1991-02-13 | 1994-08-26 | Bristol Myers Squibb Co | Zirconium-aluminium-amino acid salts, and antiperspirant compositions thereof |
US6042816A (en) * | 1998-08-19 | 2000-03-28 | The Gillette Company | Enhanced antiperspirant salts stabilized with calcium and concentrated aqueous solutions of such salts |
US6375937B1 (en) | 2000-10-20 | 2002-04-23 | Colgate-Palmolive Company | Antiperspirant salts for enhanced cosmetic products |
US6436381B1 (en) | 2000-10-25 | 2002-08-20 | The Gillette Company | Aluminum-zirconium antiperspirant salts with high peak 5 al content |
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 |
US20040109833A1 (en) | 2002-12-09 | 2004-06-10 | Xiaozhong Tang | High efficacy, low irritation aluminum salts and related products |
JP7009088B2 (en) * | 2017-06-07 | 2022-01-25 | ライオン株式会社 | Antiperspirant composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA958338A (en) * | 1971-03-08 | 1974-11-26 | Chung T. Shin | Antiperspirant powder aerosol compositions containing aluminum chloride and water soluble aluminum compounds and methods of preparation |
US4049792A (en) * | 1973-06-26 | 1977-09-20 | The Procter & Gamble Company | Antiperspirant stick |
DE2608123B2 (en) * | 1975-03-12 | 1981-07-23 | Colgate-Palmolive Co., 10022 New York, N.Y. | Antiperspirant in aerosol form |
US4083956A (en) * | 1976-04-29 | 1978-04-11 | The Procter & Gamble Company | Anhydrous antiperspirant creams |
US4120948A (en) * | 1976-11-29 | 1978-10-17 | The Procter & Gamble Company | Two phase antiperspirant compositions |
CA1140470A (en) * | 1980-05-27 | 1983-02-01 | Leonard Mackles | Aluminum chloride and aluminum zirconium hydroxychloride as antiperspirant |
-
1981
- 1981-03-23 CA CA000373677A patent/CA1153313A/en not_active Expired
- 1981-10-16 ZA ZA817173A patent/ZA817173B/en unknown
- 1981-10-16 AU AU76533/81A patent/AU547985B2/en not_active Ceased
- 1981-11-13 NZ NZ198966A patent/NZ198966A/en unknown
- 1981-11-27 GR GR66635A patent/GR76682B/el unknown
- 1981-12-10 IT IT49876/81A patent/IT1172144B/en active
- 1981-12-11 FR FR8123189A patent/FR2495933A1/en active Granted
- 1981-12-11 JP JP56198733A patent/JPS57131715A/en active Granted
- 1981-12-14 CH CH7981/81A patent/CH649707A5/en not_active IP Right Cessation
- 1981-12-14 PT PT74127A patent/PT74127B/en unknown
- 1981-12-14 ES ES507961A patent/ES8303085A1/en not_active Expired
- 1981-12-14 GB GB8137597A patent/GB2091099B/en not_active Expired
- 1981-12-15 DE DE19813149649 patent/DE3149649A1/en active Granted
- 1981-12-15 SE SE8107512A patent/SE452108B/en not_active IP Right Cessation
- 1981-12-15 BE BE0/206844A patent/BE891488A/en not_active IP Right Cessation
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775528A (en) * | 1983-08-16 | 1988-10-04 | The Gillette Company | Antiperspirant composition |
US5486347A (en) * | 1983-08-16 | 1996-01-23 | The Gillette Company | Antiperspirant composition |
US5770186A (en) * | 1983-08-16 | 1998-06-23 | The Gillette Company | Antiperspirant composition |
US5593663A (en) * | 1991-11-12 | 1997-01-14 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Antiperspirant materials and compositions |
US6893630B2 (en) | 2000-01-18 | 2005-05-17 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Anti-microbial antiperspirant products |
WO2023280755A1 (en) * | 2021-07-07 | 2023-01-12 | Unilever Ip Holdings B.V. | Method of manufacture of antiperspirant salts |
Also Published As
Publication number | Publication date |
---|---|
SE8107512L (en) | 1982-06-16 |
BE891488A (en) | 1982-06-15 |
ES507961A0 (en) | 1983-02-01 |
PT74127A (en) | 1982-01-01 |
DE3149649A1 (en) | 1982-09-02 |
CA1153313A (en) | 1983-09-06 |
DE3149649C2 (en) | 1991-08-08 |
ES8303085A1 (en) | 1983-02-01 |
NZ198966A (en) | 1985-04-30 |
JPS57131715A (en) | 1982-08-14 |
IT8149876A0 (en) | 1981-12-10 |
FR2495933B1 (en) | 1985-04-19 |
AU7653381A (en) | 1982-08-12 |
GR76682B (en) | 1984-08-24 |
FR2495933A1 (en) | 1982-06-18 |
GB2091099B (en) | 1985-05-01 |
AU547985B2 (en) | 1985-11-14 |
CH649707A5 (en) | 1985-06-14 |
JPH0239486B2 (en) | 1990-09-05 |
IT1172144B (en) | 1987-06-18 |
PT74127B (en) | 1984-01-05 |
ZA817173B (en) | 1982-10-27 |
SE452108B (en) | 1987-11-16 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19921214 |