CA1146073A - Aluminum salt glycine complex in anhydrous alcohol - Google Patents
Aluminum salt glycine complex in anhydrous alcoholInfo
- Publication number
- CA1146073A CA1146073A CA000359369A CA359369A CA1146073A CA 1146073 A CA1146073 A CA 1146073A CA 000359369 A CA000359369 A CA 000359369A CA 359369 A CA359369 A CA 359369A CA 1146073 A CA1146073 A CA 1146073A
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- Prior art keywords
- emollient
- composition according
- glycine
- aluminum
- volatile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- A61K8/26—Aluminium; Compounds thereof
-
- 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
-
- 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
-
- 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
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
- A61K2800/31—Anhydrous
-
- 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
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An antiperspirant composition of the suspension type comprising an anhydrous alcoholic vehicle having suspended wherein one or more of the following astringent salt glycine complexes and a suspending agent: aluminum/zirconium/
tetrachlorohydrate glycine complexes; aluminum/zirconium/
trichlorohydrate glycine complexes; aluminum/zirconium/
pentachlorohydrate glycine complexes; aluminum/zirconium/
octachlorohydrate glycine complexes, and aluminum/sesqui-chlorohydrate glycine complexes. Composition may also contain a non-staining hydrophilic emollient and/or a non-polar emollient and/or a volatile emollient.
An antiperspirant composition of the suspension type comprising an anhydrous alcoholic vehicle having suspended wherein one or more of the following astringent salt glycine complexes and a suspending agent: aluminum/zirconium/
tetrachlorohydrate glycine complexes; aluminum/zirconium/
trichlorohydrate glycine complexes; aluminum/zirconium/
pentachlorohydrate glycine complexes; aluminum/zirconium/
octachlorohydrate glycine complexes, and aluminum/sesqui-chlorohydrate glycine complexes. Composition may also contain a non-staining hydrophilic emollient and/or a non-polar emollient and/or a volatile emollient.
Description
~146~3!73 A~HYDROUS ALCOHOLIC ANTIPERSP~RANT SUSPENSI~N
COMPOSITION CONTAINI~G CERTAIN ALUMINUM OR ALUMINUM/
- ZIRCONIUM SALT GLYCINE COr~PLEXES
/This invention relates to antiperspirant suspen-sion compositions. Mbre particularly, it concerns anti-perspirant compositions in which the active antiperspirant materials are present in the form of essentially insoluble particles suspended in an essentially anhydrous liquid vehicle. This invention especially concerns antiperspirant suspension compositions of the so-called "roll-on" type;
that is, compositions that are designed particularly for application by a roll-on dispenser.
A number of astringent salts are known in the prior art which are said to be effective antiperspirant materials.
Ho~ever, the degree of effectiveness, the long-lasting efficacy and the organoleptic qualities of the astringent salts are to a large extent dependent upon the form of the composition from which they are dispensed.
It has been suggested, for example, to prepare anti-perspirant compositions for pump spray or roll-on application in which the active antiperspirant is present in solution in a vehicle which is primarily alcoholic vehicle (see U.S. Patent 4,073,880). For this purpose, an alcohol soluble aluminum salt and/or complex is suggested as the active antiperspirant. Although solutions of the active antiperspirant materials are inclined to have effective antiperspirant activity, they are disadvantageous from other aspects. Thus, for example, they do not have the same long-lasting effect that is characteristic of suspension type products. Suspension type products are therefore to be preferred because of their long-lasting effect. Moreover, the alcohol solution type products also tend to be organo-leptically unsatisfactory in that they are inclined to be tac~y when applied.
:1146~73 Antiperspirant roll-on preparations in the form of an oil-in-water emulsion or an aqueous alcoholic liquid that uses a variety of astringent salts as antiperspirant materials are also known in the prior art. These, however, have the disadvantage in that they go on wet and therefore, cause some discomfort.
It is also known in the prior art to prepare anti-perspirant compositions of the suspension type which contain aluminum chlorohydrate as the active antiperspirant material.
In addition, these compositions are known to contain a volatile silicone (cyclomethicone), alcohol, octyl palmitate, isopropyl palmitate, stearalkonium hectorite, propylene carbonate and fragrance. These products, however, have a high staining potential that, to a lar~e extent, is probably due to the presence of the fatty acid ester emollients i.e.
octyl palmitate and isopropyl myristate which are contained in these compositions in significant quantities. When an effort is made to reduce the staining potential of these products by removing the fatty acid esters, the suspension becomes unstable and the aluminum chlorohydrate becomes a gel.
It has now been found that an antiperspirant composi-tion of the suspension type (and therefore of the long-lasting type) can ~e provided having the appropriate organoleptic properties which can be provided by combining in an essentially anhydrous alcoholic vehicle, certain specific aluminum salt-glycine complexes or aluminum zirconium salt-glycine complexes and a suspending agent. Moreover, these products are stable and quick drying and have a low potential for staining.
It is accordingly an object of this invention to prepare an antiperspirant composition of the suspension type useful as a roll-on preparation that is stable and long-lasting.
1146~3 It is a further object of the present invention to provide an antiperspirant composition of the above type that is further characterized as not being tacky when applied and as beinq quick drying.
Although, according to the present invention, certain specific aluminum salt glycine complexes or certain aluminum zirconium salt glycine complexes form stable suspensions in an anhydrou~ alcoholic vehicle containing a suspending agent, some of these compositions are inclined to have an undesirable staining potential. It has been found that this can be eliminated by also incorporating in the composition a non-staining hydrophilic emollient described in more detail below.
It is accordingly still a further object of this invention to provide an antiperspirant composition of the type set out in the above objects that is further character-ized as having a low staining potential.
It i~ another object of this in~ention to provide a method for inhibiting perspiration in subjects by applying the compositions set out in the above objects.
Other and more detailed objects of this invention will be apparent from the following description and claims.
As previously mentioned, the benefits of the present invention are obtained through the use of certain specific complexes formed between certain aluminum salts and glycine, on the one hand, ôr certain aluminum/zirconium salts and glycine. The complexing of these salts with glycine alters the solubility of these salts in the essentially anhydrous alcoholic vehicle rendering the salts less soluble and therefore, more readily suspendible therein. By being more suspendible and therefore, less likely to go into solution in the liquid vehicle, the active materials are available for long-lasting activity.
Although Applicants do not want to be bound by any theory, it is their belief that the longer lasting action 114ti~73 exhibited by its suspension products can be explained as a t,ype of "sustained release" activity. At any one time,~ a small portion of the active material is dissolved in the ', alcohol vehicle and is ready for acting immediately. The suspension active material which is the bulk of material is in a sense held in reserve and becomes active upon moisturiza-tion of the underarm area.
The particular astringent salt glycine complexes that may be employed in the present invention are selected from the group consisting of aluminum/zirconium/tetrachloro-hydrate glycine complexes (e.g. Wickenol ~ E-369, Wickenol E-1363), aluminum/zirconium/trichlorohydrate glycine com~lexes ~e.g. Reheis*type 410 Micronized Powder), aluminum/zirconium/
pentachlorohydrate glycine complexes, aluminum/zirconium/
octachl,orohydrate glycine complexes and aluminum/sesqui-chlorohydrate glycine complexes and mixtures thereof. The alumlnum/zirconium chlorohydrates that are used in preparing the aforesaid mentioned glycine complexes can be prepared by mixing aluminum chlorohydrate with zirconium hydroxychloride.
The glycine is then incorporated into these mixtures. In some cases, Al/Zr chlorohydrate also can be prepared by reacting aluminum and zirconium carbonate with hydrochloric acid. The glycine is then incorporated into these mixtures.
In a typical process, Al/Zr chlorohydrate glycine complex solution is spray dried. In a preferred form of this invention, the molar ratio of Al/Zr in the aluminum/zirconium tetrachlorohydrate glycine com~lexes employed is from about 3:1 to about 4.5:1. In the case of the aluminum/zirconium trichlorohydrate glycine complex, the molar ratio of Al/Zr is also preferably about 3:1 to 4.5:1. The U.S. Patent to Luedders 3,792,068 describes the preparation of Al/Zr chlorohydrate glycine complexes which may also can be used in the present invention.
The aluminum sesquichlorohydrate glycine complex that is employed in the present invention can be prepared by mixing *Trademark ~ .~
aluminum chloride (e.g. aluminum chloride hexahydrate) with aluminum chlorhydroxide and then incorporating glycine in the mixture. In a typical process, aluminum chloride hexa-hydrate is added to a solution of aluminum chlorohydrate solution and the solution is mixed until clear. The glycine is added and then this solution is spray dried.
The aluminum sesquichlorohydrate glycine complexes that are useful for the purposes of the present invention are characterized by the fact that the molar ratio of aluminum to chloride will fall within the range o~ from about 0.78:1 to about 1.95:1 with the preferred range being in the range of from about 1.33:1 to about 1.79:1. The optimum results are obtained with all~m;num sesquichlorohydrate glycine complexes in which the molar ratio of aluminum to chloride is in the range of from 1.39:1 to about 1.5:1.
The quantity of glycine that will be complexed with the astringent salts used herein will vary somewhat. Usually, this will be in the range of from about 5~ to about 20% by weight based on the total weight of the astringent salt.
The preferred range, however, is from about 7% to about 15~ by weight of glycine based on the total weight of the astringent salt.
The following are the specifications of various glycine complexes that are useful for the present purposes:
Aluminum/Zirconium/Tetrachlorohydrate Glycine (Wickenol ~ E-369) A14ZrO(OH)10 C14 . NH2CH2CH
il'~6~73 Test Range Preferred Form @ 25COff White PowderOff White Powder # Aluminum as Al 14.5 - 15.5% 15.1 - 15.2%
% Zirconium as Zr 14.49 max 13.9 - 14.4%
Al:Zr atomic ratio 3.4:1 - 3.8:1 3.66:1 - 3.57:1 % Chloride17.0 - 18.5% 17.5 - 17.6~
% Glycine 10.5 - 13.5% 11.8 - 13.0%
pH (15% aq.)3.7 - 4.1 3.8 - 3.95 Metal:Chloride Atomic Ratio0.9:1 - 1.5:1 1.44:1 Loss on Heating 16 Hrs. @ 105C 6.0 - 9.0 7.8 - 8.6 Particle Size100% thru 270 mesh100%
98.5% Max. thru 325 mesh 99+%
Aluminum/Zirconium/Tetrachlorohydrate Glycine low moisture (Wickenol E-1363) Test Analysis Form ~ 25C Lt. Yellow Powder % Aluminum as Al 15.6%
% Zirconium as Zr 14.8%
Al:Zr atomic ratio 3.56:1 % Chloride 17.9%
% Glycine 12.1%
Iron as Fe 43 ppm Loss on H~ating 16 Hrs. ~ 105C 5.3%
pH (15% aq.) 3.75 Particle size 100% thru 325 mesh -Aluminum/Zirconium/Trichlorohydrate Glycine Complex (Reheis Chemical Type 410 Micronized Powder Regular A14ZrO(OH)llcl3 IH2 . nH20 NH2 Analysis Sample Resul*s .
% Aluminum as Al 14.8%
% Zirconium as Zr 14.0%
Al:Zr atomic ratio 0.95:1 % Chloride 15.7%
% Glycine 13.9%
pH (25% aq.~ 4.02 Particle Size Residue on 325 mesh 0.2%
Residue on 200 mesh o.o%
H20 105C for 16 hrs. 8.2%
Aluminum/Sesquichlorohydrate Glycine Complex A12(OH)4 5 Cl 1.5 ~CH2 Test _ Range % Aluminum as Al 20.1 - 22.1%
% Chloride 18.5 - 19.8%
Aluminum/Chloride Atomic Ratio 1.39/1 - 1.50/1 Glycine 9.0 - 11.0 pH (5% w/w suspension)3.9 - 4.3 Particle Size % remaining on US 270 mesh None % remaining on US 325 mesh 0.5% max.
Wt. loss at 105C for 16 hrs. 9 - 15%
-The quantity of astringent salt complex that may be contained in the compositions of this invention may vary some-what depending upon the results desired and other components contained in the composition. For the most part, this will be in the range of from about 14% to about 34% by weight based on 1146q~73 the total weight of the composition.
Essenti~lly anhydrous ethyl alcohol will usually be the major component of the liquid vehicle of the compositions of this invention. Alcohol SD 40 (anhydrous) that is commercially available will be quite suitable for this purpo3e. The amount of alcohol present may vary somewhat depending on the concentration of the various components as well as the particular materials selected. Ordinarily, however, it will constitute between about 10% to about 65%
by weight based on the total weight of the composition, the preferred range being between about 20% to about 40%.
A third important component of these compositions are the suspending agents. A number of suspending agents well known in this art may be employed herein. The preferred agents in this class are the powdered silicon containing compounds that include such materials as the hydrated aluminum silicate clays, silica, hydrated silica, etc.
A number of suspending agents of this type are available commercially. These include the so-called Bentone Clays (e.g. Bentone 27, Bentone 38; Bentone 34, NL Industries), fumed silicon dioxide (e.g. Cab-O-Sil M-5 Cabot), hydrated silica (Syloid).
The quantity of suspending agent that will be incor-porated in the present composition will vary somewhat.
Usually, this will fall within the range of from about 2%
to about 5% by weight based on the total weight of the composition.
Not all suspending agents are of equal usefulness from the point of view of potential for staining. Thus, Bentone 38 and/or Cab-O-Sil M-5 are superior to Bentone 27.
Furthermore, when high levels of alcohol are employed, more satisfactory products are obtained when the suspending agents are used in conjunction with both non-staining hydrophilic emollients and non-polar emollients described in more detail below.
*Trademark 1146~73 g As indicated above, in some instances, it is desirable to employ a non-staining hydrophilic emollient in the present compositions. A class of non-staining hydrophilic emollients that are especially useful herein are the polyoxypropylene, polyoxyethylene ethers of the aliphatic alcohols that can be described by the formula:
R-(OIHC~2)x - (OCH2CH2)yOH
in which x and y are whole numbers. R is an aliphatic alcohol moiety having from 4 to 20 C atoms (e.g. butyl, cetyl, myristyl, stearyl). The value of x can range from 3 to 15 and the value of y can range from 2 to 50. The preferred range in the case of x it is 3 to 5 and for y it is 2 to 25. A material that is particularly suitable for the purposes of the present inven-tion is a material of Formula II in which x has an averagevalue of 5 and y has an average value of 20 and R is cetyl.
A material of this type that is sold commercially is sold under the trade designation Procetyl AWS (Croda). Other commercially available materials which are suitable are Witconol AP~ (PPG-3 Myreth-3), Witconol APES (PPG-9 Stearth-3), Standamul OXL (PPG-10 Cetearth-20), Procetyl AWS Modified (~PG-8 Ceteth-2), Ucon 50-HB-660 (PPG-12 Buteth-16), etc.
In general, non-staining hydrophilic emollients which are soluble and/or dispersible in wa~er and soluble in alcohol are suitable. Aside from counteracting the staining potential of the non-polar emollient when employed, they also tend to improve the suspension stability and uniformity of viscosity over a variable temperature range.
The quantity of non-staining hydrophilic emollients that may be contained in the present composition may also vary " over a range. Generally, it will constitute between 0 to about 25% by weight based on the total weight of the composition, with the preferred range being from about 3% to about 15% by weight on the same basis.
*Trademark - 1146~73 As an optional ingredient, the present compositions may contain a volatile emollient. This imparts superior organoleptic properties to the composition and is therefore used to advantage. The most widely known emollient of this character are the volatile ~ilicones and are exemplified by Cyclomethicone* This is a cyclic dimethyl polysiloxane described in the CTFA Cosmetic Ingredient Dictionary, 2nd Edition, 1977, p. 71.
The quantity of volatile emollient that will be incor-porated in the com~ositions of this invention will vary from 0 to about 40% by weight of the composition, the preferred upper range being about 25%. When the volatile emollient is used, it will be present in the range of from about 5%
to 40% by weight based on the total weight of the composition and in the preferred range of from about 5~ to about 25 by weight based on the total weight of the composition.
Another class of optional ingredients of the present composition is the non-polar emollients which are often employed herein as suspension stabilizers. The quantity of non-polar emollients that will be used will be in the range of from 0 to about 30~ by weight based on the total weiqht of the composition. 8est results are obtained when the non-polar emollient is used at a le~el in the range of from about 3% to about 25% by weight based on the total weight of the composition.
A variety of non-polar emollients may be used for the purposes of this invention. By way of example, mention may be made of fatty acid monoesters (isopropyl myristate), fatty acid diesters (Neobee M-20, dibutyl phthalate), branched fatty acid esters (2-ethyl hexyl pelargonate, 2-ethyl hexyl palmitate, 2-ethyl hexyl stearate, etc.), polyoxypropylene fatty (C4-C18) ethers (Witconol APS, Fluid AP), polysiloxanes, fatty alcohols (hexadecyl alcohol), etc. Suitable non-polar emollients that can be used herein are described in U.S.
Patent 3,968,203 column 3, lines 48 to 63.
*Trademark , .
1146~73 -- 11 -- .
When the non-polar emollients are employed, the potential for staining may tend to increase. To counteract this, it is advantageous to also incorporate in the compo-~itions containing a non-polar emollient a non-staining hydrophilic emollient described above.
In addition to the components mentioned above, the present compositions may also include other ingredients that are conventionally contained in compositions of this character, these include things such as talc, Oat-Pro, DRY FLO, anti-bacterial agents, perfumes, coloring materials, etc.
As pointed out above, the selection of the particular astringent salt is very important in obtaining a satisfactory product according to the present invention. Thus, for example, if an attempt is made to employ aluminum chlorohydrate, severe product gellation is encountered in high alcohol content ~olatile silicone systems which contain Bentones or Cab-O-Sil M-5 as suspending agents. This is particularly true when the alcohol level exceeds a le~el of 20%.
Another interesting observation along these lines is the behavior of alu~inum/zirconium/trichlorohydrate as compared with the corresponding glycine complex employed in the present invention. In the absence of glycine, the aluminum/zirconium/trichlorohydrate becomes exceedingly soluble in alcohol and discolors. This results in a gellation of the product which is obviously unacceptable. On the other hand, the aluminum/zirconiu~/trichlorohydrate in the presence of glycine (e.g. about 10% to about 15%) exhibited a diminished alcohol solubility with the consequent improvement in the stability profile of the products.
The moisture content of the astringent salt complexes employed in the present invention also appears to have a bearinq on the overall susPension stability of the product.
The lower "moisture content" complexes have a lower solu-bility in alcohol and demonstrate a better suspension stability. -11~6~73 .',`
Furthermore, the products containing low moisture ccmplexes also exhibit lower fabric staining potential.
The moisture content of the astringent salt complexes employed in the invention is best expressed in terms o~ the ~ 1088 in weight of the complex when heated at 105C for 16 hours. It has been found that good results are obtained when this percentage falls in the range of from about 4% to about 15%. In the table below, the preferred moisture ranaes are given for the particular types of astringent complexes.
TABLE I
Wt. loss at 105C
16 hours Actives Range Al/Zr tetrachlorohydrate glycine (WickenoS E-369) 6 --9 Aluminum sesquichlorohydrate glycine 9 - 15 Al/Zr tetrachlorohydrate glycine ~Wiakenol E-1363) 4 - 6 Al/Zr trichlorohydrate glycine4 - 9 The following Examples are to further illustrate the present invontion. It is to be understood, however, that the invention is not limited thereto.
Preparation of Aluminum Sesquichlorohydrate Glycine Ingredients % by Wt.
Aluminum chloride hexahydrate (50% aq. soll 16.32 Aluminum chlorhydroxide (50~ aq. sol) 73 43 Glycine 10.00 Magnesium stearate 0.25 100. 00 Procedure -A. The aluminum chloride hexahydrate is added to the 50% ~luminum chlorhydroxide solution and mixed until clear, ~146~73 then the glycine and magnesium stearate are added and mixed into the solution.
B. The resulting mixture is spray dried, using a 30wen flat bottom drier having a diameter of 18 feet, under the following conditions:
Inlet temperature 350F
Outlet temperature 140F
Feeding rate 85 + 5 gal/hr The resulting spray dried powder mix had a moisture content of 1.0%. This was determined by extracting the moistuEe using acetone from a sample of the dried product and then analyzing the water content of the extract using gas chromatography.
C. The dried powder is then ground in a jet mill and the resulting fine powder is screened through a 325 mesh sieve (44 microns) from which an active antiperspirant mix having uniform particle size is obtained.
Followin~ the Procedure of Example 1, dried antiper-spirant powder mixes can be prepared from aqueous solutions containing Al/Cl molar ratios as follows:
Ex. lA Ex. lB Ex. lC
Molar ratio Al/Cl 1:1 l.S:l 1.79:1 % by wt. aluminum chloride hexahydrate19.097.67 2.51 % by wt. aluminum-chlorhydroxide (50% aq. sol) 70.9187.33 95.49 % by wt. glycine 9.59 4.50 1.50 % by wt. magnesium stearate 0.50 0.50 0.50 Staining Test The following laboratory staining test was used to evaluate staining potential of various formulations described below.
114~73 ~ 14 -Procedure "Hanes" white T-shirts were-cut into 6" x 8" swatches.
~est material was applied by pipetting one gram of liquid product and spreading the product onto each of two 1" x 6"
~trips across the fabric. The product was spread evenly to cover the entire 1" x 6" area. Swatches were placed at 100F and 80-85% R.H. for 18-24 hours and laundered in a Sears Kenmore Heavy Duty Washer, Model 29921 set at Warm Wash/
Warm Rinse (105F water), wash and second rinse, cotton white settings. The detergent manufacturer's directions were followed as closely as possible, which were consistent with AATCC
test method 124-1978. On the average, 50 grams (3/4 cup) of TIDE detergent were added to a 1.0 to 1.5 Kg load and 11.5 gallons (Ex. low setting) of water. Depending on load size, the amount of water (machine setting) and amount of detergent used was varied to insure AATCC test conditions (4.4 - 4.7 g. detergent/gallon of water, 42-54 g. detergent/
Kg load).
Swatches were dried in a Sears Xenmore Automatic Dryer set at automatic cycle, cotton sturdy setting.
~ en test cycles were run for the suspension roll-on products.
Samples were e~aluated visually for stains by at least two judges. The coding system for degree of stain in this study was as fol}ows:
Degree of Stain Comments None No stain observable Very slight Barely perceptible Very slight to slight Average of very slight & slight Slight Obvious, undesirable;
acceptable Slight to moderate Borderline, acceptable Moderate Unacceptable Moderate to heavy Unacceptable Heavy Unacceptable ExAMæLE 3 Formula BA 1746-24 % w/w Bentone 38 1.50 Cab-O-Sil M-51 1.00 Alcohol SD 40, anhydrous 49.05 Cyclomethicone 7207 20.65 Al/Zr tetrachlorohydrate glycine E-1363 12.00 ACH BMS II 12.00 Dibutyl phthalate 3.80 100.00 after 10 applications & washings - slight staining 1 Pumed silicon dioxide Aluminum sesquichlorohydrate glycine complex Ex. 4 . Ex. 5 Ex. 6 Ingredients % w/w % w/w % w/w Bentone 38 1.50 1.50 1.50 Cab-O-Sil ~-5 1.00 1.00 1.00 Alcohol SD 40 anhydrous 49.05 49.05 49.05 Cyclomethicone 7207 21.15 21.15 21.15 PPG-8 Ceteth-2 3.00 -- --25. PPG-5 Ceteth-20 -- -- 3.00 ACH BMS II 14.00 14.00 14.00 A1/Zr tetrachloro-hydrate glycine E-1363 10.00 10.00 10.00 Perfume 0.30 0.30 0.30 Ucon 50 HB 660 -- 3.00 --100.00 100.00 100.00 after 10 applications & washings - no staining ~146~73 Ex. 7 Ex. 8 Ex~ 9 Ingredients % w/w % w/w % w/w Bentone 38 2.50 2.50 2.50 Bentone 27 1.00 1.00 1.00 Cab-O-Sil M-5 1.50 1.50 1.50 Alcohol SD 40 anhydrous 51.42 55.92 55.92 PPG-5 Ceteth-20 3.00 -- --PPG-8 Ceteth-2 1.50 - --PPG-14 Butyl ether15.00 15.00 15.00 Al/Zr tetrachloro-hydrate glycine E 1363 (low moisture) 10.00 10.00 10.00 ACH BMS II 14.00 14.00 --Perfume 0.08 0.08 0.08 100.00 100.00 100.00 After 10 appli-cations no staining sli~ht stainin~ moderate staining Ex. 10 Ex. 11 Ex. 12 Formula 1939 BQ 1809-24 BQ 1809-25 Ingredients % w/w % w/w % w/w Bentone 38 1.30 1.30 1.30 Bentone 27 0.50 0.50 0.50 Cab-O-Sil M-5 1.00 1.00 1.00 Alcohol SD 40 anhydrous 47.96 44.96 44.96 Cyclomethicone 7207 24.94 24.94 24.94 PPG-8 Ceteth-2 -- 3.00 --PPG-5 Ceteth-20 -- -- 3.00 Al/Zr tetrachloro-hydrate glycine E-1363 (low moisture) 10.00 10.00 10.00 ACH BMS II 14.00 14.00 14.00 Perfume .30 .30 .30 100.00 100.00 100.00 1~46Q73 EX~PLE 13 % TA7/W
Bentone 38 1.50 Cab-O-Sil M-5 1.50 Alcohol SD 40, anhydrous 48.55 Cyclomethicone 7207 17.35 PPG-8 Ceteth-2 3.00 Dibutyl phthalate 3.80 AC~ BMS II 24.00 Perfume 0.30 100. 00 Ex. 14 Ex. 15 Ingredients % w/w % w/w Bentone 38 2.50 2.50 Bentone 27 1.00 1.00 Cab-O-Sil M-5 1.50 1.50 Alcohol SD 40, anhydrous 51.42 52.92 PPG-5 Ceteth-20 3.00 3.00 PPG-8 Ceteth-2 1.50 --Fluid AP 3 15.00 15.00 Al/Zr tetrachloro-hydrate glycine E-1363 24.00 24.00 Perfume 0.08 0.08 100 . 00 100. 00 3 Fluid AP - PPG-14 Butyl Ether 1146~)73 Ex. 16 Ex. 17 Ingredients % w/w % w/w Bentone 27 1.20 1.20 ACH BMS II 24.00 24.00 Ucon 50 HB 66022.50 --Procetyl AWS -- 22.50 Fluid AP 7.50 . . 7.50 Alcohol SD 40, anhydrous 25.84 . 20.84 Cyclomethicone 7207 18.76 23.76 Perfume 0.20 0.20 100. 00 loo . 00 Ingredients % w/w Bentone 38 2.50 3entone 27 1.00 Cab-O-Sil M-5 1.50 Fluid AP 25.00 Cyclomethicone 7207 20.00 Procetyl AWS 6.00 Alcohol SD 40, anhydrous 19.92 Wickenol E-1363 10.00 ACH BMS II 14.00 Perfume 0.08 - 100. 00 EX~PLE 19 Ingredients % w/w Bentone 38 2.50 Bentone 27 1-.00 Cab-O-Sil M-5 1.50 Fluid AP 25.00 Cyclomethicone 7207 20.00 Procetyl AWS 6.00 Alcohol SD 40, anhydrous 19.92 Al/Zr trichlorohydrate glycine type 410 10.00 1146~73 EXAMPLE 19 (Cont'd) -ACH BMS II 14.00 Perfume 0.08 100. 00 ExAMæLE 20 Formula 1901 Ingredients % w/w Bentone 27 2.10 Wickenol E-369 24.00 Cab-O-Sil M-5 1.50 Cyclomethicone 7207 24.85 Alcohol SD 40, anhydrous 47.47 Perfume 08 100.00 It ha~ been found that high alcoholic suspension roll-on such as Formula 1901 showed significantly higher staining-potential than low or non-alcoholic suspension roll-on.
However, addition of polyoxyethylene polyoxypropylene fatty alcohol ether reduced significant staining potential.
It has also been found that aluminum sesquichloro-hydrate glycine showed significantly lower staining potential than Al/Zr tetrahydrate glycine formula. For example, BA 1746-38 containing 24% Al/Zr salt E-1363 showed moderate staining, but addition of 14% ACH BMS II replacing Al/Zr salt E-1363 made formula BA 1746-88 slight staining. ~3A
1746-78 containing non-staining emollients PPG-5 Ceteth-20 and PPG-8 Ceteth-2 eliminated staining potential.
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.
COMPOSITION CONTAINI~G CERTAIN ALUMINUM OR ALUMINUM/
- ZIRCONIUM SALT GLYCINE COr~PLEXES
/This invention relates to antiperspirant suspen-sion compositions. Mbre particularly, it concerns anti-perspirant compositions in which the active antiperspirant materials are present in the form of essentially insoluble particles suspended in an essentially anhydrous liquid vehicle. This invention especially concerns antiperspirant suspension compositions of the so-called "roll-on" type;
that is, compositions that are designed particularly for application by a roll-on dispenser.
A number of astringent salts are known in the prior art which are said to be effective antiperspirant materials.
Ho~ever, the degree of effectiveness, the long-lasting efficacy and the organoleptic qualities of the astringent salts are to a large extent dependent upon the form of the composition from which they are dispensed.
It has been suggested, for example, to prepare anti-perspirant compositions for pump spray or roll-on application in which the active antiperspirant is present in solution in a vehicle which is primarily alcoholic vehicle (see U.S. Patent 4,073,880). For this purpose, an alcohol soluble aluminum salt and/or complex is suggested as the active antiperspirant. Although solutions of the active antiperspirant materials are inclined to have effective antiperspirant activity, they are disadvantageous from other aspects. Thus, for example, they do not have the same long-lasting effect that is characteristic of suspension type products. Suspension type products are therefore to be preferred because of their long-lasting effect. Moreover, the alcohol solution type products also tend to be organo-leptically unsatisfactory in that they are inclined to be tac~y when applied.
:1146~73 Antiperspirant roll-on preparations in the form of an oil-in-water emulsion or an aqueous alcoholic liquid that uses a variety of astringent salts as antiperspirant materials are also known in the prior art. These, however, have the disadvantage in that they go on wet and therefore, cause some discomfort.
It is also known in the prior art to prepare anti-perspirant compositions of the suspension type which contain aluminum chlorohydrate as the active antiperspirant material.
In addition, these compositions are known to contain a volatile silicone (cyclomethicone), alcohol, octyl palmitate, isopropyl palmitate, stearalkonium hectorite, propylene carbonate and fragrance. These products, however, have a high staining potential that, to a lar~e extent, is probably due to the presence of the fatty acid ester emollients i.e.
octyl palmitate and isopropyl myristate which are contained in these compositions in significant quantities. When an effort is made to reduce the staining potential of these products by removing the fatty acid esters, the suspension becomes unstable and the aluminum chlorohydrate becomes a gel.
It has now been found that an antiperspirant composi-tion of the suspension type (and therefore of the long-lasting type) can ~e provided having the appropriate organoleptic properties which can be provided by combining in an essentially anhydrous alcoholic vehicle, certain specific aluminum salt-glycine complexes or aluminum zirconium salt-glycine complexes and a suspending agent. Moreover, these products are stable and quick drying and have a low potential for staining.
It is accordingly an object of this invention to prepare an antiperspirant composition of the suspension type useful as a roll-on preparation that is stable and long-lasting.
1146~3 It is a further object of the present invention to provide an antiperspirant composition of the above type that is further characterized as not being tacky when applied and as beinq quick drying.
Although, according to the present invention, certain specific aluminum salt glycine complexes or certain aluminum zirconium salt glycine complexes form stable suspensions in an anhydrou~ alcoholic vehicle containing a suspending agent, some of these compositions are inclined to have an undesirable staining potential. It has been found that this can be eliminated by also incorporating in the composition a non-staining hydrophilic emollient described in more detail below.
It is accordingly still a further object of this invention to provide an antiperspirant composition of the type set out in the above objects that is further character-ized as having a low staining potential.
It i~ another object of this in~ention to provide a method for inhibiting perspiration in subjects by applying the compositions set out in the above objects.
Other and more detailed objects of this invention will be apparent from the following description and claims.
As previously mentioned, the benefits of the present invention are obtained through the use of certain specific complexes formed between certain aluminum salts and glycine, on the one hand, ôr certain aluminum/zirconium salts and glycine. The complexing of these salts with glycine alters the solubility of these salts in the essentially anhydrous alcoholic vehicle rendering the salts less soluble and therefore, more readily suspendible therein. By being more suspendible and therefore, less likely to go into solution in the liquid vehicle, the active materials are available for long-lasting activity.
Although Applicants do not want to be bound by any theory, it is their belief that the longer lasting action 114ti~73 exhibited by its suspension products can be explained as a t,ype of "sustained release" activity. At any one time,~ a small portion of the active material is dissolved in the ', alcohol vehicle and is ready for acting immediately. The suspension active material which is the bulk of material is in a sense held in reserve and becomes active upon moisturiza-tion of the underarm area.
The particular astringent salt glycine complexes that may be employed in the present invention are selected from the group consisting of aluminum/zirconium/tetrachloro-hydrate glycine complexes (e.g. Wickenol ~ E-369, Wickenol E-1363), aluminum/zirconium/trichlorohydrate glycine com~lexes ~e.g. Reheis*type 410 Micronized Powder), aluminum/zirconium/
pentachlorohydrate glycine complexes, aluminum/zirconium/
octachl,orohydrate glycine complexes and aluminum/sesqui-chlorohydrate glycine complexes and mixtures thereof. The alumlnum/zirconium chlorohydrates that are used in preparing the aforesaid mentioned glycine complexes can be prepared by mixing aluminum chlorohydrate with zirconium hydroxychloride.
The glycine is then incorporated into these mixtures. In some cases, Al/Zr chlorohydrate also can be prepared by reacting aluminum and zirconium carbonate with hydrochloric acid. The glycine is then incorporated into these mixtures.
In a typical process, Al/Zr chlorohydrate glycine complex solution is spray dried. In a preferred form of this invention, the molar ratio of Al/Zr in the aluminum/zirconium tetrachlorohydrate glycine com~lexes employed is from about 3:1 to about 4.5:1. In the case of the aluminum/zirconium trichlorohydrate glycine complex, the molar ratio of Al/Zr is also preferably about 3:1 to 4.5:1. The U.S. Patent to Luedders 3,792,068 describes the preparation of Al/Zr chlorohydrate glycine complexes which may also can be used in the present invention.
The aluminum sesquichlorohydrate glycine complex that is employed in the present invention can be prepared by mixing *Trademark ~ .~
aluminum chloride (e.g. aluminum chloride hexahydrate) with aluminum chlorhydroxide and then incorporating glycine in the mixture. In a typical process, aluminum chloride hexa-hydrate is added to a solution of aluminum chlorohydrate solution and the solution is mixed until clear. The glycine is added and then this solution is spray dried.
The aluminum sesquichlorohydrate glycine complexes that are useful for the purposes of the present invention are characterized by the fact that the molar ratio of aluminum to chloride will fall within the range o~ from about 0.78:1 to about 1.95:1 with the preferred range being in the range of from about 1.33:1 to about 1.79:1. The optimum results are obtained with all~m;num sesquichlorohydrate glycine complexes in which the molar ratio of aluminum to chloride is in the range of from 1.39:1 to about 1.5:1.
The quantity of glycine that will be complexed with the astringent salts used herein will vary somewhat. Usually, this will be in the range of from about 5~ to about 20% by weight based on the total weight of the astringent salt.
The preferred range, however, is from about 7% to about 15~ by weight of glycine based on the total weight of the astringent salt.
The following are the specifications of various glycine complexes that are useful for the present purposes:
Aluminum/Zirconium/Tetrachlorohydrate Glycine (Wickenol ~ E-369) A14ZrO(OH)10 C14 . NH2CH2CH
il'~6~73 Test Range Preferred Form @ 25COff White PowderOff White Powder # Aluminum as Al 14.5 - 15.5% 15.1 - 15.2%
% Zirconium as Zr 14.49 max 13.9 - 14.4%
Al:Zr atomic ratio 3.4:1 - 3.8:1 3.66:1 - 3.57:1 % Chloride17.0 - 18.5% 17.5 - 17.6~
% Glycine 10.5 - 13.5% 11.8 - 13.0%
pH (15% aq.)3.7 - 4.1 3.8 - 3.95 Metal:Chloride Atomic Ratio0.9:1 - 1.5:1 1.44:1 Loss on Heating 16 Hrs. @ 105C 6.0 - 9.0 7.8 - 8.6 Particle Size100% thru 270 mesh100%
98.5% Max. thru 325 mesh 99+%
Aluminum/Zirconium/Tetrachlorohydrate Glycine low moisture (Wickenol E-1363) Test Analysis Form ~ 25C Lt. Yellow Powder % Aluminum as Al 15.6%
% Zirconium as Zr 14.8%
Al:Zr atomic ratio 3.56:1 % Chloride 17.9%
% Glycine 12.1%
Iron as Fe 43 ppm Loss on H~ating 16 Hrs. ~ 105C 5.3%
pH (15% aq.) 3.75 Particle size 100% thru 325 mesh -Aluminum/Zirconium/Trichlorohydrate Glycine Complex (Reheis Chemical Type 410 Micronized Powder Regular A14ZrO(OH)llcl3 IH2 . nH20 NH2 Analysis Sample Resul*s .
% Aluminum as Al 14.8%
% Zirconium as Zr 14.0%
Al:Zr atomic ratio 0.95:1 % Chloride 15.7%
% Glycine 13.9%
pH (25% aq.~ 4.02 Particle Size Residue on 325 mesh 0.2%
Residue on 200 mesh o.o%
H20 105C for 16 hrs. 8.2%
Aluminum/Sesquichlorohydrate Glycine Complex A12(OH)4 5 Cl 1.5 ~CH2 Test _ Range % Aluminum as Al 20.1 - 22.1%
% Chloride 18.5 - 19.8%
Aluminum/Chloride Atomic Ratio 1.39/1 - 1.50/1 Glycine 9.0 - 11.0 pH (5% w/w suspension)3.9 - 4.3 Particle Size % remaining on US 270 mesh None % remaining on US 325 mesh 0.5% max.
Wt. loss at 105C for 16 hrs. 9 - 15%
-The quantity of astringent salt complex that may be contained in the compositions of this invention may vary some-what depending upon the results desired and other components contained in the composition. For the most part, this will be in the range of from about 14% to about 34% by weight based on 1146q~73 the total weight of the composition.
Essenti~lly anhydrous ethyl alcohol will usually be the major component of the liquid vehicle of the compositions of this invention. Alcohol SD 40 (anhydrous) that is commercially available will be quite suitable for this purpo3e. The amount of alcohol present may vary somewhat depending on the concentration of the various components as well as the particular materials selected. Ordinarily, however, it will constitute between about 10% to about 65%
by weight based on the total weight of the composition, the preferred range being between about 20% to about 40%.
A third important component of these compositions are the suspending agents. A number of suspending agents well known in this art may be employed herein. The preferred agents in this class are the powdered silicon containing compounds that include such materials as the hydrated aluminum silicate clays, silica, hydrated silica, etc.
A number of suspending agents of this type are available commercially. These include the so-called Bentone Clays (e.g. Bentone 27, Bentone 38; Bentone 34, NL Industries), fumed silicon dioxide (e.g. Cab-O-Sil M-5 Cabot), hydrated silica (Syloid).
The quantity of suspending agent that will be incor-porated in the present composition will vary somewhat.
Usually, this will fall within the range of from about 2%
to about 5% by weight based on the total weight of the composition.
Not all suspending agents are of equal usefulness from the point of view of potential for staining. Thus, Bentone 38 and/or Cab-O-Sil M-5 are superior to Bentone 27.
Furthermore, when high levels of alcohol are employed, more satisfactory products are obtained when the suspending agents are used in conjunction with both non-staining hydrophilic emollients and non-polar emollients described in more detail below.
*Trademark 1146~73 g As indicated above, in some instances, it is desirable to employ a non-staining hydrophilic emollient in the present compositions. A class of non-staining hydrophilic emollients that are especially useful herein are the polyoxypropylene, polyoxyethylene ethers of the aliphatic alcohols that can be described by the formula:
R-(OIHC~2)x - (OCH2CH2)yOH
in which x and y are whole numbers. R is an aliphatic alcohol moiety having from 4 to 20 C atoms (e.g. butyl, cetyl, myristyl, stearyl). The value of x can range from 3 to 15 and the value of y can range from 2 to 50. The preferred range in the case of x it is 3 to 5 and for y it is 2 to 25. A material that is particularly suitable for the purposes of the present inven-tion is a material of Formula II in which x has an averagevalue of 5 and y has an average value of 20 and R is cetyl.
A material of this type that is sold commercially is sold under the trade designation Procetyl AWS (Croda). Other commercially available materials which are suitable are Witconol AP~ (PPG-3 Myreth-3), Witconol APES (PPG-9 Stearth-3), Standamul OXL (PPG-10 Cetearth-20), Procetyl AWS Modified (~PG-8 Ceteth-2), Ucon 50-HB-660 (PPG-12 Buteth-16), etc.
In general, non-staining hydrophilic emollients which are soluble and/or dispersible in wa~er and soluble in alcohol are suitable. Aside from counteracting the staining potential of the non-polar emollient when employed, they also tend to improve the suspension stability and uniformity of viscosity over a variable temperature range.
The quantity of non-staining hydrophilic emollients that may be contained in the present composition may also vary " over a range. Generally, it will constitute between 0 to about 25% by weight based on the total weight of the composition, with the preferred range being from about 3% to about 15% by weight on the same basis.
*Trademark - 1146~73 As an optional ingredient, the present compositions may contain a volatile emollient. This imparts superior organoleptic properties to the composition and is therefore used to advantage. The most widely known emollient of this character are the volatile ~ilicones and are exemplified by Cyclomethicone* This is a cyclic dimethyl polysiloxane described in the CTFA Cosmetic Ingredient Dictionary, 2nd Edition, 1977, p. 71.
The quantity of volatile emollient that will be incor-porated in the com~ositions of this invention will vary from 0 to about 40% by weight of the composition, the preferred upper range being about 25%. When the volatile emollient is used, it will be present in the range of from about 5%
to 40% by weight based on the total weight of the composition and in the preferred range of from about 5~ to about 25 by weight based on the total weight of the composition.
Another class of optional ingredients of the present composition is the non-polar emollients which are often employed herein as suspension stabilizers. The quantity of non-polar emollients that will be used will be in the range of from 0 to about 30~ by weight based on the total weiqht of the composition. 8est results are obtained when the non-polar emollient is used at a le~el in the range of from about 3% to about 25% by weight based on the total weight of the composition.
A variety of non-polar emollients may be used for the purposes of this invention. By way of example, mention may be made of fatty acid monoesters (isopropyl myristate), fatty acid diesters (Neobee M-20, dibutyl phthalate), branched fatty acid esters (2-ethyl hexyl pelargonate, 2-ethyl hexyl palmitate, 2-ethyl hexyl stearate, etc.), polyoxypropylene fatty (C4-C18) ethers (Witconol APS, Fluid AP), polysiloxanes, fatty alcohols (hexadecyl alcohol), etc. Suitable non-polar emollients that can be used herein are described in U.S.
Patent 3,968,203 column 3, lines 48 to 63.
*Trademark , .
1146~73 -- 11 -- .
When the non-polar emollients are employed, the potential for staining may tend to increase. To counteract this, it is advantageous to also incorporate in the compo-~itions containing a non-polar emollient a non-staining hydrophilic emollient described above.
In addition to the components mentioned above, the present compositions may also include other ingredients that are conventionally contained in compositions of this character, these include things such as talc, Oat-Pro, DRY FLO, anti-bacterial agents, perfumes, coloring materials, etc.
As pointed out above, the selection of the particular astringent salt is very important in obtaining a satisfactory product according to the present invention. Thus, for example, if an attempt is made to employ aluminum chlorohydrate, severe product gellation is encountered in high alcohol content ~olatile silicone systems which contain Bentones or Cab-O-Sil M-5 as suspending agents. This is particularly true when the alcohol level exceeds a le~el of 20%.
Another interesting observation along these lines is the behavior of alu~inum/zirconium/trichlorohydrate as compared with the corresponding glycine complex employed in the present invention. In the absence of glycine, the aluminum/zirconium/trichlorohydrate becomes exceedingly soluble in alcohol and discolors. This results in a gellation of the product which is obviously unacceptable. On the other hand, the aluminum/zirconiu~/trichlorohydrate in the presence of glycine (e.g. about 10% to about 15%) exhibited a diminished alcohol solubility with the consequent improvement in the stability profile of the products.
The moisture content of the astringent salt complexes employed in the present invention also appears to have a bearinq on the overall susPension stability of the product.
The lower "moisture content" complexes have a lower solu-bility in alcohol and demonstrate a better suspension stability. -11~6~73 .',`
Furthermore, the products containing low moisture ccmplexes also exhibit lower fabric staining potential.
The moisture content of the astringent salt complexes employed in the invention is best expressed in terms o~ the ~ 1088 in weight of the complex when heated at 105C for 16 hours. It has been found that good results are obtained when this percentage falls in the range of from about 4% to about 15%. In the table below, the preferred moisture ranaes are given for the particular types of astringent complexes.
TABLE I
Wt. loss at 105C
16 hours Actives Range Al/Zr tetrachlorohydrate glycine (WickenoS E-369) 6 --9 Aluminum sesquichlorohydrate glycine 9 - 15 Al/Zr tetrachlorohydrate glycine ~Wiakenol E-1363) 4 - 6 Al/Zr trichlorohydrate glycine4 - 9 The following Examples are to further illustrate the present invontion. It is to be understood, however, that the invention is not limited thereto.
Preparation of Aluminum Sesquichlorohydrate Glycine Ingredients % by Wt.
Aluminum chloride hexahydrate (50% aq. soll 16.32 Aluminum chlorhydroxide (50~ aq. sol) 73 43 Glycine 10.00 Magnesium stearate 0.25 100. 00 Procedure -A. The aluminum chloride hexahydrate is added to the 50% ~luminum chlorhydroxide solution and mixed until clear, ~146~73 then the glycine and magnesium stearate are added and mixed into the solution.
B. The resulting mixture is spray dried, using a 30wen flat bottom drier having a diameter of 18 feet, under the following conditions:
Inlet temperature 350F
Outlet temperature 140F
Feeding rate 85 + 5 gal/hr The resulting spray dried powder mix had a moisture content of 1.0%. This was determined by extracting the moistuEe using acetone from a sample of the dried product and then analyzing the water content of the extract using gas chromatography.
C. The dried powder is then ground in a jet mill and the resulting fine powder is screened through a 325 mesh sieve (44 microns) from which an active antiperspirant mix having uniform particle size is obtained.
Followin~ the Procedure of Example 1, dried antiper-spirant powder mixes can be prepared from aqueous solutions containing Al/Cl molar ratios as follows:
Ex. lA Ex. lB Ex. lC
Molar ratio Al/Cl 1:1 l.S:l 1.79:1 % by wt. aluminum chloride hexahydrate19.097.67 2.51 % by wt. aluminum-chlorhydroxide (50% aq. sol) 70.9187.33 95.49 % by wt. glycine 9.59 4.50 1.50 % by wt. magnesium stearate 0.50 0.50 0.50 Staining Test The following laboratory staining test was used to evaluate staining potential of various formulations described below.
114~73 ~ 14 -Procedure "Hanes" white T-shirts were-cut into 6" x 8" swatches.
~est material was applied by pipetting one gram of liquid product and spreading the product onto each of two 1" x 6"
~trips across the fabric. The product was spread evenly to cover the entire 1" x 6" area. Swatches were placed at 100F and 80-85% R.H. for 18-24 hours and laundered in a Sears Kenmore Heavy Duty Washer, Model 29921 set at Warm Wash/
Warm Rinse (105F water), wash and second rinse, cotton white settings. The detergent manufacturer's directions were followed as closely as possible, which were consistent with AATCC
test method 124-1978. On the average, 50 grams (3/4 cup) of TIDE detergent were added to a 1.0 to 1.5 Kg load and 11.5 gallons (Ex. low setting) of water. Depending on load size, the amount of water (machine setting) and amount of detergent used was varied to insure AATCC test conditions (4.4 - 4.7 g. detergent/gallon of water, 42-54 g. detergent/
Kg load).
Swatches were dried in a Sears Xenmore Automatic Dryer set at automatic cycle, cotton sturdy setting.
~ en test cycles were run for the suspension roll-on products.
Samples were e~aluated visually for stains by at least two judges. The coding system for degree of stain in this study was as fol}ows:
Degree of Stain Comments None No stain observable Very slight Barely perceptible Very slight to slight Average of very slight & slight Slight Obvious, undesirable;
acceptable Slight to moderate Borderline, acceptable Moderate Unacceptable Moderate to heavy Unacceptable Heavy Unacceptable ExAMæLE 3 Formula BA 1746-24 % w/w Bentone 38 1.50 Cab-O-Sil M-51 1.00 Alcohol SD 40, anhydrous 49.05 Cyclomethicone 7207 20.65 Al/Zr tetrachlorohydrate glycine E-1363 12.00 ACH BMS II 12.00 Dibutyl phthalate 3.80 100.00 after 10 applications & washings - slight staining 1 Pumed silicon dioxide Aluminum sesquichlorohydrate glycine complex Ex. 4 . Ex. 5 Ex. 6 Ingredients % w/w % w/w % w/w Bentone 38 1.50 1.50 1.50 Cab-O-Sil ~-5 1.00 1.00 1.00 Alcohol SD 40 anhydrous 49.05 49.05 49.05 Cyclomethicone 7207 21.15 21.15 21.15 PPG-8 Ceteth-2 3.00 -- --25. PPG-5 Ceteth-20 -- -- 3.00 ACH BMS II 14.00 14.00 14.00 A1/Zr tetrachloro-hydrate glycine E-1363 10.00 10.00 10.00 Perfume 0.30 0.30 0.30 Ucon 50 HB 660 -- 3.00 --100.00 100.00 100.00 after 10 applications & washings - no staining ~146~73 Ex. 7 Ex. 8 Ex~ 9 Ingredients % w/w % w/w % w/w Bentone 38 2.50 2.50 2.50 Bentone 27 1.00 1.00 1.00 Cab-O-Sil M-5 1.50 1.50 1.50 Alcohol SD 40 anhydrous 51.42 55.92 55.92 PPG-5 Ceteth-20 3.00 -- --PPG-8 Ceteth-2 1.50 - --PPG-14 Butyl ether15.00 15.00 15.00 Al/Zr tetrachloro-hydrate glycine E 1363 (low moisture) 10.00 10.00 10.00 ACH BMS II 14.00 14.00 --Perfume 0.08 0.08 0.08 100.00 100.00 100.00 After 10 appli-cations no staining sli~ht stainin~ moderate staining Ex. 10 Ex. 11 Ex. 12 Formula 1939 BQ 1809-24 BQ 1809-25 Ingredients % w/w % w/w % w/w Bentone 38 1.30 1.30 1.30 Bentone 27 0.50 0.50 0.50 Cab-O-Sil M-5 1.00 1.00 1.00 Alcohol SD 40 anhydrous 47.96 44.96 44.96 Cyclomethicone 7207 24.94 24.94 24.94 PPG-8 Ceteth-2 -- 3.00 --PPG-5 Ceteth-20 -- -- 3.00 Al/Zr tetrachloro-hydrate glycine E-1363 (low moisture) 10.00 10.00 10.00 ACH BMS II 14.00 14.00 14.00 Perfume .30 .30 .30 100.00 100.00 100.00 1~46Q73 EX~PLE 13 % TA7/W
Bentone 38 1.50 Cab-O-Sil M-5 1.50 Alcohol SD 40, anhydrous 48.55 Cyclomethicone 7207 17.35 PPG-8 Ceteth-2 3.00 Dibutyl phthalate 3.80 AC~ BMS II 24.00 Perfume 0.30 100. 00 Ex. 14 Ex. 15 Ingredients % w/w % w/w Bentone 38 2.50 2.50 Bentone 27 1.00 1.00 Cab-O-Sil M-5 1.50 1.50 Alcohol SD 40, anhydrous 51.42 52.92 PPG-5 Ceteth-20 3.00 3.00 PPG-8 Ceteth-2 1.50 --Fluid AP 3 15.00 15.00 Al/Zr tetrachloro-hydrate glycine E-1363 24.00 24.00 Perfume 0.08 0.08 100 . 00 100. 00 3 Fluid AP - PPG-14 Butyl Ether 1146~)73 Ex. 16 Ex. 17 Ingredients % w/w % w/w Bentone 27 1.20 1.20 ACH BMS II 24.00 24.00 Ucon 50 HB 66022.50 --Procetyl AWS -- 22.50 Fluid AP 7.50 . . 7.50 Alcohol SD 40, anhydrous 25.84 . 20.84 Cyclomethicone 7207 18.76 23.76 Perfume 0.20 0.20 100. 00 loo . 00 Ingredients % w/w Bentone 38 2.50 3entone 27 1.00 Cab-O-Sil M-5 1.50 Fluid AP 25.00 Cyclomethicone 7207 20.00 Procetyl AWS 6.00 Alcohol SD 40, anhydrous 19.92 Wickenol E-1363 10.00 ACH BMS II 14.00 Perfume 0.08 - 100. 00 EX~PLE 19 Ingredients % w/w Bentone 38 2.50 Bentone 27 1-.00 Cab-O-Sil M-5 1.50 Fluid AP 25.00 Cyclomethicone 7207 20.00 Procetyl AWS 6.00 Alcohol SD 40, anhydrous 19.92 Al/Zr trichlorohydrate glycine type 410 10.00 1146~73 EXAMPLE 19 (Cont'd) -ACH BMS II 14.00 Perfume 0.08 100. 00 ExAMæLE 20 Formula 1901 Ingredients % w/w Bentone 27 2.10 Wickenol E-369 24.00 Cab-O-Sil M-5 1.50 Cyclomethicone 7207 24.85 Alcohol SD 40, anhydrous 47.47 Perfume 08 100.00 It ha~ been found that high alcoholic suspension roll-on such as Formula 1901 showed significantly higher staining-potential than low or non-alcoholic suspension roll-on.
However, addition of polyoxyethylene polyoxypropylene fatty alcohol ether reduced significant staining potential.
It has also been found that aluminum sesquichloro-hydrate glycine showed significantly lower staining potential than Al/Zr tetrahydrate glycine formula. For example, BA 1746-38 containing 24% Al/Zr salt E-1363 showed moderate staining, but addition of 14% ACH BMS II replacing Al/Zr salt E-1363 made formula BA 1746-88 slight staining. ~3A
1746-78 containing non-staining emollients PPG-5 Ceteth-20 and PPG-8 Ceteth-2 eliminated staining potential.
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.
Claims (20)
1, An antiperspirant suspension composition com-prising an anhydrous alcoholic vehicle containing an effective amount of a suspending agent and an antiperspirant effective amount of an astringent salt glycine complex suspended in said alcoholic vehicle, said complex being selected from the group consisting of aluminum/zirconium/tetrachlorohydrate glycine complexes; aluminum/zirconium/trichlorohydrate glycine complexes aluminum/zirconium/pentachlorohydrate glycine complexes; aluminum/zirconium/octachlorohydrate glycine complexes, and aluminum/sesquichlorohydrate glycine complexes and mixtures of said complexes.
2. A composition according to Claim 1 also including a non-staining hydrophilic emollient.
3. A composition according to Claim 2 in which said non-staining hydrophilic emollient is a polyoxypropylene, polyoxyethylene ether of an aliphatic alcohol of the formula:
in which x and y are whole numbers; R is an aliphatic alcohol moiety having from 4 to 20 C atoms; x has a value in the range of from 3 to about 15 and y has a value in the range of from about 2 to about 50.
in which x and y are whole numbers; R is an aliphatic alcohol moiety having from 4 to 20 C atoms; x has a value in the range of from 3 to about 15 and y has a value in the range of from about 2 to about 50.
4. A composition according to Claim 2 also including a non-polar emollient.
5. A composition according to Claim 3 also including a non-polar emollient.
6. A composition according to Claim 5 wherein said non-polar emollient is selected from the group consisting of fatty acid monoesters, fatty acid diesters, branched fatty acid esters and polyoxypropylene fatty (C4-C18) ethers, poly-siloxanes, fatty alcohols and mixtures thereof.
7. A composition according to Claim 1 including a volatile emollient.
8. A composition according to Claim 7 in which said volatile emollient is a volatile silicone.
9. A composition according to Claim 2 also including a volatile emollient.
10. A composition according to Claim 9 in which the volatile emollient is a volatile silicone.
11. A composition according to Claim 5 also containing a volatile emollient.
12. A composition according to Claim 11 in which said volatile emollient is a volatile silicone.
13. A composition according to Claim 6 also contain-ing a volatile emollient.
14. A composition according to Claim 13 in which said volatile emollient is a volatile silicone.
15. A composition according to Claims 1, 2, or 7 in which the various ingredients are present within the following ranges:
% by weight (a) astringent salt from about 14 to about 34 glycine complex (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 0 to about 25 (e) non-polar emollient from about 0 to about 30 (f) volatile emollient from about 0 to about 25
% by weight (a) astringent salt from about 14 to about 34 glycine complex (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 0 to about 25 (e) non-polar emollient from about 0 to about 30 (f) volatile emollient from about 0 to about 25
16. A composition according to Claims 2 or 3 in which the various ingredients are present within the following ranges:
% by weight (a) astringent salt from about 14 to about 34 glycine complex (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25
% by weight (a) astringent salt from about 14 to about 34 glycine complex (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25
17. A composition according to Claims 4, 5, or 6 in which the various ingredients are present within the following ranges:
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25 (e) non-polar emollient from about 3 to about 25
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25 (e) non-polar emollient from about 3 to about 25
18. A composition according to Claims 7 or 8 in which the various ingredients are present within the following ranges:
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) volatile emollient from about 5 to about 40
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) volatile emollient from about 5 to about 40
19. A composition according to Claims 9 or 10 in which the various ingredients are present within the following ranges:
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25 (e) volatile emollient from about 5 to about 40
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25 (e) volatile emollient from about 5 to about 40
20. A composition according to Claims 11, 12, or 13 in which the various ingredients are present within the following ranges:
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25 (e) non-polar emollient from about 3 to about 25 (f) volatile emollient from about 5 to about 40
% by weight (a) astringent salt glycine complex from about 14 to about 34 (b) ethyl alcohol (anhy.) from about 20 to about 65 (c) suspending agent from about 2 to about 5 (d) non-staining hydro-philic emollient from about 3 to about 25 (e) non-polar emollient from about 3 to about 25 (f) volatile emollient from about 5 to about 40
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/168,925 US4435382A (en) | 1980-07-14 | 1980-07-14 | Anhydrous alcoholic antiperspirant suspension composition containing certain aluminum or aluminum/zirconium salt glycine complexes |
| US168,925 | 1980-07-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1146073A true CA1146073A (en) | 1983-05-10 |
Family
ID=22613522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000359369A Expired CA1146073A (en) | 1980-07-14 | 1980-08-29 | Aluminum salt glycine complex in anhydrous alcohol |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4435382A (en) |
| CA (1) | CA1146073A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135741A (en) * | 1984-04-24 | 1992-08-04 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Antiperspirant product |
| US5518714A (en) * | 1984-04-24 | 1996-05-21 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Method for inhibiting the dissolution of antiperspirant compounds in alcohols |
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| US4775528A (en) * | 1983-08-16 | 1988-10-04 | The Gillette Company | Antiperspirant composition |
| US5589196A (en) * | 1983-08-16 | 1996-12-31 | The Gillette Company | Antiperspirant composition |
| US5114705A (en) * | 1983-08-16 | 1992-05-19 | The Gillette Company | Antiperspirant composition |
| GB2144992A (en) * | 1983-08-16 | 1985-03-20 | Gillette Co | Antiperspirants |
| US4678663A (en) * | 1984-02-06 | 1987-07-07 | Nuetrogena Corporation | Hydroquinone composition having enhanced bio-availability and percutaneous adsorption |
| US4944937A (en) * | 1984-12-19 | 1990-07-31 | The Procter & Gamble Company | Cosmetic sticks |
| US4673570A (en) * | 1985-03-20 | 1987-06-16 | Carter-Wallace, Inc. | Gelled antiperspirant compositions |
| GB8519426D0 (en) * | 1985-08-01 | 1985-09-04 | Ici Plc | Composition for personal care products |
| US4871525A (en) * | 1986-10-24 | 1989-10-03 | Westwood Chemical Corporation | Antiperspirant composition and method of preparation |
| GB8619553D0 (en) * | 1986-08-11 | 1986-09-24 | Unilever Plc | Antiperspirants |
| ES2028791T3 (en) * | 1986-12-23 | 1992-07-16 | Unilever Nv | ANTI-BREATHING PRODUCT. |
| GB8630724D0 (en) * | 1986-12-23 | 1987-02-04 | Unilever Plc | Cosmetic product |
| US4944938A (en) * | 1988-12-16 | 1990-07-31 | Colgate-Palmolive Company | Antiperspirant and deodorant |
| US5202123A (en) * | 1990-04-20 | 1993-04-13 | Somerville Technology Group, Inc. | Surface modified aluminum and aluminum-zirconium salts |
| BR9106483A (en) * | 1990-05-30 | 1993-05-25 | Procter & Gamble | LIQUID ANTIPERSPIRANT COMPOSITES |
| CA2082823A1 (en) * | 1990-05-30 | 1991-12-01 | Alejandro Cedeno | Liquid antiperspirant compositions |
| BR9206290A (en) * | 1991-07-18 | 1994-09-27 | Procter & Gamble | Liquid deodorant compositions. |
| GB9604341D0 (en) * | 1996-02-29 | 1996-05-01 | Unilever Plc | Antiperspirant composition |
| US5919437A (en) * | 1996-05-24 | 1999-07-06 | Colgate-Palmolive Company | Cosmetic cream composition containing silicone gel material |
| US5997850C1 (en) * | 1997-10-29 | 2001-11-27 | Colgate Palmolive Co | Antiperspirant actives and formulations made therefrom |
| US6399049B1 (en) | 1999-08-24 | 2002-06-04 | The Procter & Gamble Company | Compositions containing solubilized antiperspirant active |
| US6126928A (en) * | 1999-08-24 | 2000-10-03 | The Procter & Gamble Company | Compositions containing solubilized, acid-enhanced antiperspirant active |
| US6096298A (en) * | 1999-08-24 | 2000-08-01 | The Procter & Gamble Company | Deodorant compositions containing isopropyl glycerol ether |
| US6083493A (en) * | 1999-08-24 | 2000-07-04 | The Procter & Gamble Company | Antiperspirant compositions containing isopropyl glycerol ether |
| US6149897A (en) * | 1999-08-24 | 2000-11-21 | The Procter & Gamble Company | Process for making anhydrous compositions containing solubilized, enhanced antiperspirant active |
| US6436381B1 (en) * | 2000-10-25 | 2002-08-20 | The Gillette Company | Aluminum-zirconium antiperspirant salts with high peak 5 al content |
| US6663854B1 (en) * | 2002-06-19 | 2003-12-16 | Yan-Fei Shen | Aluminum-zirconium antiperspirant salts made with zirconium salts having low Zr:Cl ratio |
| US20040109833A1 (en) * | 2002-12-09 | 2004-06-10 | Xiaozhong Tang | High efficacy, low irritation aluminum salts and related products |
| US7704531B2 (en) | 2005-02-18 | 2010-04-27 | Colgate-Palmolive Company | Enhanced efficacy aluminum or aluminum-zirconium antiperspirant salt compositions containing calcium salt(s) and betaine |
| CL2006003116A1 (en) * | 2005-11-16 | 2008-02-29 | Colgate Palmolive Co | ANTI-TRANSPIRING COMPOSITION THAT INCLUDES AT LEAST ONE CHOSEN ALUMINUM SALT, ZIRCONY ALUMINUM, A COMPLEX ALUMINUM SALT OR A COMPLEX ALUMINUM-ZIRCONY SALT, A HYDROXIACIDE AND AN ACID COMPOUND OF QUATERNARY AMMONIUM; PROCESS TO PREPARE |
| AU2006331192B2 (en) * | 2005-12-29 | 2010-08-05 | Riemann Trading Aps | Alcohol-in-oil type emulsion comprising a multivalent metal salt |
| US20110038902A1 (en) * | 2009-08-13 | 2011-02-17 | The Dial Corporation | Antiperspirant compositions and products and methods for manufacturing antiperspirant compositions and products |
| WO2014187685A1 (en) * | 2013-05-20 | 2014-11-27 | Unilever Plc | Antiperspirant compositions |
| ES2658682T5 (en) * | 2013-05-20 | 2021-10-26 | Unilever Nv | Antiperspirant compositions |
| MX2015016073A (en) | 2013-05-20 | 2016-03-21 | Unilever Nv | Method of manufacture of antiperspirant salts. |
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| AU2015340798B2 (en) | 2014-10-27 | 2018-11-29 | Unilever Global Ip Limited | Anhydrous antiperspirant aerosol compositions |
| US10098821B2 (en) | 2014-11-19 | 2018-10-16 | Conopco, Inc. | Process of manufacture of an antiperspirant composition |
| US9867765B2 (en) * | 2014-11-19 | 2018-01-16 | Conopco, Inc. | Antiperspirant compositions |
| AU2016349244B2 (en) | 2015-11-06 | 2018-12-20 | Unilever Global Ip Limited | Antiperspirant compositions |
| WO2017076840A1 (en) | 2015-11-06 | 2017-05-11 | Unilever Plc | Aerosol antiperspirant product |
| EA036617B1 (en) | 2015-11-06 | 2020-11-30 | Юнилевер Н.В. | Antiperspirant aerosol product |
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| US2814584A (en) | 1954-04-30 | 1957-11-26 | Procter & Gamble | Buffered antiperspirant compositions |
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| US3395214A (en) | 1964-01-09 | 1968-07-30 | Scholl Mfg Co Inc | Antiperspirant composition providing a readily collapsible sprayable foam |
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| US4017599A (en) | 1973-11-23 | 1977-04-12 | Armour Pharmaceutical Company | Aluminum-zirconium anti-perspirant systems with salts of amino acids |
| GB1487812A (en) | 1974-02-04 | 1977-10-05 | Procter & Gamble | Antiperspirant complexes |
| US4028390A (en) | 1975-03-26 | 1977-06-07 | Armour Pharmaceutical Company | Methods of making basic zirconium complexes |
| US4053581A (en) | 1975-08-15 | 1977-10-11 | Lever Brothers Company | Antiperspirant solution containing a mixture of substantially volatile and substantially non-volatile siloxane liquids |
| US4065564A (en) | 1975-08-15 | 1977-12-27 | Lever Brothers Company | Antiperspirant solution containing a substantially non-volatile siloxane liquid |
| US4073880A (en) | 1975-08-15 | 1978-02-14 | Lever Brothers Company | Antiperspirant solution containing a substantially volatile polydimethyl siloxane liquid |
-
1980
- 1980-07-14 US US06/168,925 patent/US4435382A/en not_active Expired - Lifetime
- 1980-08-29 CA CA000359369A patent/CA1146073A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135741A (en) * | 1984-04-24 | 1992-08-04 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Antiperspirant product |
| US5518714A (en) * | 1984-04-24 | 1996-05-21 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Method for inhibiting the dissolution of antiperspirant compounds in alcohols |
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| Publication number | Publication date |
|---|---|
| US4435382A (en) | 1984-03-06 |
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