DE2148160C3 - Antiperspirant - Google Patents

Description

ners and other complexes or mixtures around- The basic used according to the invention

should eat, where the formula given as through-aluminum bromide can be used in a manner analogous to

Average value of the overall composition and / or the conventional production of basic aluminum

, on fractions is to be understood. nium chlorides by converting aluminum

Although basic aluminum bromides are in themselves metalized with hydrobromic acid in aqueous solution

Already known for a long time, was only now over or by reaction of aluminum metal with a

surprisingly found that this obtained in contrast to the aqueous solution of aluminum bromide

Chlorides in used for cosmetic purposes. Additionally, they can look through implementation

Solvents such as anhydrous ethanol readily soluble the elements bromine and aluminum in aqueous

and with the commonly used fluorocarbon media.

fuel propellants are highly compatible. Regardless of whether HBr, AlBr ₃ or Br _{2 is used} as the output

Even more surprising, however, is to find that material is used, the first step is

the basic aluminum bromide far better anti-producing the equivalent to a 15- to

Perspirants are available as the currently commercially available 20% bromide solution in a glass-lined

basic aluminum chlorides: ₁₅ deten or other inert containers with a stirrer

The antiperspirants according to the invention are systematic. When using HBr, there is a leg up significant technical progress on the quest process in getting enough water Deodorant field: add 48% commercial HBr. When

(1) The good solubility of the starting ^one ba- invention ^{of A1Br} 3, the anhydrous form is most convenient in alcoholic solu- ²⁰ at the Cartesian Aluminiumbromide. It is then first in solid solvents that are used for cosmetic purposes ^{in the form in the Behal} ter and carefully set with, for example, in anhydrous water until the reaction subsides. Hydrati-ethanol or propylene glycol, made possible by de-aerated aluminum bromide can also be obtained by converting antiperspirants ^{from HBr with bauxite} . If the alcohol-based liquid, which is highly effective with ^{bromine as the} starting material, is used as the starting material, the aluminum will dry at a much higher rate than nium powder, first in the required amount in the case of aqueous compositions and slurried water. The bromine is then added sorgzugleich next adjustability of cheaper con- ^fäUi S, after the reaction vessel for consistency enables a simpler incorporation of lipophilic prevent evaporation losses with ingredients such as fragrances or perfumes ³ ° reflux condenser was provided.

lj _cnen For example, if you use HBr, the

(2) ^should be heated Water freedom of supply ^Lösun S invention ^{to about 70} ° ^C and Aluminiumsammensetzungen has added a number of reasons for P ^{ulver la} "GSAM to the solution. The basic technical progress comparable ^Be 8 ⁱⁿⁿ sufficient aluminum powder added responsible · ^{35 are} "the exothermic reaction, a Losungs-from a chemical point of view is characterized hydrolysis temperature of about 95 ° C yields After reaching the active ingredient avoided, which is a significant desired temperature should the aluminum powder increase the shelf life of the final products ^derarl m small portions may be added that allows no effect change. B ^{esamte to} f ^abe at a 1-1-neck in about 45 micro

40 grooves is finished. For a 2-1 approach, increases

From a technological point of view, the water time can last for around 60 to 90 minutes, with even larger ones

freedom of the corrosive influence of the active ingredient on loading approaches, however, the time is no longer proportional

container and packaging materials extraordinarily tional. If necessary, the reaction speed can

can be greatly reduced, which for the first time reduces the practicality and temperature by heating or cooling.

Utilization of the very slow 45 according to the invention can be trolled.

Hydrolysis without additional stabilizing additives The total amount of bromine for the given bromine

by specifying a correspondingly longer usable amount of hydrochloric acid of the aluminum added to the solution

times and also in the application should be slightly greater than the stoichiometric for the

the previously required Al / Br ratio in the product in the form of spray cans, d. H. in the

Corrosion protection treatment, for example by applying 5 ° of the basic aluminum bromide to be produced,

makes protective coatings superfluous, thereby creating a large amount. When all the powder is added it should

the temperature of the reaction mixture as quickly as when preparing the corresponding container

Process step can be saved. it allows the foam level increased to about 10O ⁰ C

will. When the heat of reaction decreases, will

(3) The considerably lower viscosity of the invention requires an external supply of heat to complete the appropriate antiperspirants.
Technological progress, for example, if the heat development of the reaction after the application in spray cans, since the spraying begins, the pH reading should be slightly improved and lighter and faster (25 ⁰ C) should be started. When the pH value 3.0 allows for dosing. 6o, further readings should be taken every 15 minutes.

(4) The basic aluminum grooves according to the invention are made until a pH end point bromides are reached with all common propellants from 3.45 is reached. When an Al / Br ratio of drawn compatible. about 1.9 to 2.0 is desired, the reactor should be

(5) The Aluminiumbromide invention are not longer than be continued for about 10 to 15 minutes to the well in non-aqueous alcoholic solutions of pH 6 ₅ endpoint addition before said filtration soluble, cause no skin irritation and. If higher or lower Al / Br ratios are desired, correspondingly with excellent dermatological properties, a correspondingly higher or Bischer compatibility is required. lower pH endpoint used.

The reaction mixture is then passed through an Ertel filter pack under a pressure of about 1.4 atm No. 5 «filtered. This filtration takes about 10 to 15 minutes, and the clear, water-white filtrate has a specific gravity of about 1.46 or becomes adjusted to it. Typical values for this product are:

11.1 to 11.9% aluminum,

16.9 to 17.8% bromide,

Al / Br ratio = 1.9 to 2.0 (molar ratio).

Finally, the aqueous solution of the basic aluminum bromide must be dried to form a solid. Although drying is the most important part of the preparation, the particular manner in which drying is undertaken does not seem particularly critical. For example, products with high alcohol solubility and good compatibility with fluorocarbons have been obtained by air drying at room temperature or spray drying. However, excellent results are obtained with rapid vacuum drying, for example using a rotary vacuum dryer at a pressure of about 20 torr and a maximum outside temperature of about 35 ° C. With this procedure, the normal drying time is about 3.5 to 4 hours.

Although those in the basic aluminum bromide end product The amount of water contained, as with the basic aluminum chlorides, should not be critical Care must be taken not to overdry the product to the point where it appears becomes insoluble in alcohol is avoided. Solid basic aluminum bromides with a calculated water content in the range of about 14 to 22% by weight and preferably about 16 to 18% by weight have been used as found to be extremely satisfactory. A typical product should be pale white and have a composition have within the following areas:

19.0 to 21.0% aluminum, 28.0 to 32.0% bromide,

Al / Br ratio = 1.7 to 2.2 (molar ratio),

19 to 25% water according to Karl Fischer,

14 to 22% water according to calculation *).

*) The theoretical amount of free and coordinated water was calculated based on the following equation

Moles [OHl + moles [Br] = 3 moles [Al]

and determining the difference in the wt .-% OH, Br and Al to 100% charged. 5 «

Since with the water content determinations by Karl Fischer titration large discrepancies and somewhat inconsistent results are generally used theoretically calculated water content indicated, to which reference is made below.

All percentages in the context of this description are based on weight, if nothing other is indicated.

The antiperspirant according to the invention is produced by using a basic aluminum bromide the formula

AI ₂ (OHXrBr ₁ , · X H ₂ O

in which .v is between 4.8 and 5.1 and y between 0.9 and 1.2 with .ν + y - = 6 and X between 2.0 and 3.4, in a non-toxic, dermatologically acceptable aqueous solvent, in particular anhydrous ethanol, to a content of the resulting solution of at least about 10 wt .-% contains bromide. The preparation of the basic aluminum bromides used according to the invention can be seen in detail from the following Examples I to VIl.

Example I.

To a 4-1 glass-lined vessel with a stirrer was added 505 grams of 48% reagent grade hydrobromic acid and 830 grams of deionized water. The solution was heated to about 70 ⁰ C and treated with aluminum powder so that the temperature rose to 95 C. A total of 172 g of aluminum powder was added in small portions during manufacture so that the reaction would not become too violent. ^{The temperature was then increased to KlO 0} C to accelerate the dissolution of the aluminum and the reaction was continued up to a pH end point (25 ⁰ C) of 3.45, the net weight of the reaction mixture being adjusted to about 1500 g.

The reaction mixture was filtered from the end point within 15 minutes. The filtrate was then subjected to rotary vacuum drying to about 50% of its weight to obtain solids of the composition: 19.5% Al, 28.3% Br, 24.8% H ₂ O according to Karl Fischer (21.4% calculated) and an Al / Br ratio of 2.05 (molar ratio). The solids were soluble to a level of 30% in anhydrous ethanol in less than half an hour and had a carbon tetrachloride tolerance (defined as the amount (ml) of the carbon tetrachloride to be added to 60 g of a 30% solution of the product in anhydrous ethanol to effect a permanent turbidity) of about 111 ml.

Example II

To 830 g of water was added 505 g of 48% hydrobromic acid (HBr). The hydrobromic acid was reacted as in Example I with 172 g of aluminum powder. A pH end point of 3.5 was reached in 3.25 hours. The following was found for the filtrate: 10.75% Al and 15.9% Br; a viscosity of 12.5 cP; a specific gravity of 1.415 and a pH of 3.55. A 1000 g sample of the filtrate was air dried at room temperature to a constant weight of 540 g. The resulting solids were readily soluble in anhydrous ethanol, and had a CCl ₄ tolerability of 149 ml The composition analysis revealed. 20.42% Al, 29.5 ⁿ "Br, 17.8% H ₂ O (calculated) and an Al / Br ratio of 2.05.

Example III

Another sample was prepared in the same way as in Example II, but using more Al powder; A sample of the filtrate was spray dried at 65.6 "C. The resulting solids were readily soluble in anhydrous ethanol, had a CCl ,, tolerance of 115 ml and resulted in 20.3% Al, 27.2% Br, an Al / Br ratio of 2.21 and 19.9 ", HoO (calculated).

Example IV

_{430 g of H 2} O and 320 g of 48% strength HBr were added to a reaction vessel with 715 g of Al pellets (99.9%). The mixture was reacted for a total of 12 hours and allowed to stand for two nights, reaching an endpoint pH of about 3.6. Analysis of the solution showed 11.5% Al, 16.1% Br and an Al / Br ratio of 2.11. A 100 g sample was dried to a constant weight of 57.1 g at room temperature and yielded 20.1% Al, 28.1% Br and 19.8% H ₂ O (calculated). The solids had a CCl ₄ tolerance of 127 ml.

Example V

15th

To a reaction vessel containing 97 g of anhydrous AlBr ₃ , water was added dropwise until conversion to the hydrate was complete. The total water content was then increased to 650 g. The aqueous bromide solution was then reacted with 47 g of aluminum powder as in Example I. To ensure a complete reaction, an additional 5 g of aluminum powder were added and the mixture was filtered after 15 minutes. A portion of the clear filtrate was rotary vacuum dried at ambient temperature and about 10 torr pressure to give a pale white solid containing 20.5% Al, 31.2% Br and an Al / Br ratio of 1.95 which works well in anhydrous ethanol was soluble.

Example VI

54 g of aluminum powder and 650 g of deionized water were placed in a 1 -! Glass reaction vessel equipped with a stirrer and reflux condenser. To the stirred slurry, maintained at ambient temperature, was added 84 grams of liquid bromine over 30 minutes. The reaction mixture was brought to about 95 ° C and held at that temperature for 2 hours after which time the reaction appeared to be complete. To ensure a complete reaction, an additional 5 g of aluminum powder were added and the reaction mixture was nitrated after 15 minutes. The clear filtrate was dried to a friable solid in a rotary vacuum dryer. This solid was readily soluble in anhydrous ethanol and gave 20.7% Al, 30.9% Br, 15.9% H ₂ O (calculated) and an Al / Br ratio of 1.98.

B e i s ρ i e 1 VlI

Another product was made as in Example II, but using less aluminum powder. A sample of the filtrate was rotary vacuum dried at ambient temperature to give a solid with the following analytical results: 18.9% Al, 32.0% Br, Al / Br = 1.75 and 20.2% H ₂ O (calculated). At least 30% of the product was readily soluble in anhydrous ethanol and had a CCU tolerance of 207 ml.

The basic aluminum bromides used in the present invention have quite favorable and unexpected dissolving properties compared to aluminum compounds which are currently or have been used in antiperspirant compositions. For example, the solid produced according to Example I is 30% soluble in anhydrous ethanol in less than 0.5 hours, and its compatibility with CCl ₄ is 111 ml. These two values are comparable to those obtained for glycol complexes of basic aluminum halides described in US Pat. No. 3,420,932.

A spray-dried alcohol-soluble basic aluminum chloride used for comparison, which was prepared according to DT-OS 21 52 509 of the applicant (alcohol-soluble basic aluminum chlorides and process for the preparation of the same) and shows the following analysis results: 24.6% Al, 17.04% CI, 22 , 5% Karl Fischer water (20.0% calculated) and an Al / Cl ratio of 1.90 (molar ratio), requires about 6 hours to dissolve up to 30% in anhydrous ethanol; it also has a CCl ₄ tolerance of only 74 ml. According to another interesting comparison, a 56% alcoholic solution of basic aluminum bromide has a viscosity of about 200 cP, while a 40% solution of the alcohol-soluble basic aluminum chloride has a viscosity of about 300 cP has. The basic aluminum bromide is also superior to both the alcohol-soluble basic aluminum chloride and the glycol complexes of basic aluminum halides in terms of cosmetic acceptability and dry skin characteristics (ie adhesion or stickiness). The basic aluminum bromides are further characterized by the following solvent solubilities:

Solubility% (g / 100 g sol.)

Ethanol anhydrous 56

Propylene glycol 47.5

Isopropyl alcohol 3.3

Dioxane 1.3

n-butanol 0.66

Isopropyl myristal 0.0

Dimethyl sulfoxide 0.0

Hexadecyl alcohol 0.0

In the manufacture of the astringent for antiperspirant compositions According to the invention, solutions of the basic aluminum bromides can be used in non-toxic, dermatologically acceptable non-aqueous Solvents with any conventional aerosol propellants including commercially available Fluorocarbon compounds combined who the. Examples of suitable propellants are trichlor monofluoromethane, dichlorotetrafluoroethane, mono chlorodifluoromethane, trichlorotrifluoroethane, octafluoro cyclobutane, pentafluononochloroethane, dimethyl ether, vinyl chloride, nitrogen oxide, nitrogen unc 1,1,1-chlorodifluoroethane. It should be noted that sthi 3 ml of the for the compatibility tests ii Examples above used carbon tetrachloride: one milliliter of a 60/40 mixture of trichloro monofluoromethane and dichlorotetrafluoroethane are equivalent.

To test the aerosol compositions gemäl the invention in terms of corrosion resistance and clogging of valves was a number of experiments carried out according to the following examples.

709613/161

'

Example VIII

A solid basic aluminum bromide similar to that prepared in Example I was made with the following ingredients mixed together:

Basic aluminum bromide (BAB) 210 g

Hexadecyl alcohol 90 g

Silicon-Fluid 1066 (General

Electric) *) 30 g

Stearic acid 30 g

Perfume 9 g

Anhydrous ethanol (SDA-40) 1130 g

·) Trade name for a copolymer of surface-active organosilicon compounds and dimethyl polyoxyalkylene ethers; nominal viscosity 1200-150OcSt at 25 ⁰ C.

The above composition was the same

Made as in Example VIII and canned

or bottles with the same amount of propellant

for the production of 10% aerosols together

Settlements of basic aluminum bromide mixed

In the bottles stored ^{at 40.6 0 C a}

easy excretion found and the trace one:

Precipitation in the at ambient conditions

stored bottles. After a month and a half, "

ίο no failure observed in the spray tests. Be:

over a month in ambient conditions

The concentrate was clear yellow and in stored cans

Can and valve in excellent condition. Similar

Results were seen at doses that were one

Had been stored for month at 40.6 ^{0 C, only}

that in this case the lining was discolored and

a can of peeling off the bottom and a soft one

Lining showed.

A composition was prepared from the above components as follows: Hexadecyl alcohol, silicone fluid, stearic acid and perfume were added to the anhydrous ethanol and mixed until a clear solution was obtained. The 2; basic aluminum bromide was added to the solution and mixed again until a clear solution was obtained. The above 14% solution of basic aluminum bromide was then mixed with a 60/40 mixture of trichloromonofluoromethane 3c and dichlorotetrafluoroethane to produce an approximately 7% aerosol composition of basic aluminum bromide. American Miraspra aerosol cans (DX20, J4 liner, BX4 LSC with OEL 500 TSS valves) were then filled with 75.5 g of the 14% solution and 55.4 ml of propellant mixture. Similarly, (spray) bottles were filled with 25 g of the 14% solution and 18.1 ml of propellant mixture. After one and a half months of spray testing, no impairment of the spray function as a result of gelling of the composition or clogging of the valves was found. The composition according to one month's storage of the cans at 40.6 ⁰ C "was cloudy" and yellowish green, and can and valve showed excellent corrosion resistance with only slight discoloration of the can liner. Similar results were obtained when the cans were stored at ambient conditions for a month, except that no discoloration was observed. In the bottle a slight excretion was found in the samples stored at 40.6 ⁰ C 50 samples and only the trace of a precipitate in stored samples under ambient conditions.

bromide

Example X

^{Of basic}

and Durctoic to Tiaren

Example XI 10% aerosol total

from ba-

only one semester

Example LX

A 20% solution of basic aluminum bromide was prepared from the following ingredients:

BAB (basic aluminum bromineJd

according to Example I) 300 g

Hexadecyl alcohol 90 g

Silicone fluid SF1066 (see Example VIII) 30 g

Stearic acid 30 g

Perfume ._. 9 g

Anhydrous ethanol 1041 g

55 ^{'J edoch} the spray ^8ε · ^{The BehäI} * r showed ^νο11ι> η emptying.

^{d those in the above examples} ^ ¹¹

^ ^{Ungen not} exhaustive, and T ° ^{Ut find or more D} ° ** »which in produced? ^lk * ™ ^ η, were actually

^{ago corrosive} effects g 'cloudiness, light training ** »^ occur above,

effectiveness

changes ASL ^{? Umbromide} ™ ^Va & * »SenStilf ■ ^ans P ^iranten was tested by an independent i, ^em ^ tnmspiranstest with the 10 in

The Mfif ^mn ^ ™ carried out. One at ^{1 was accomplished by} applying the? ready ^ ^{er of the armpit tei} 36 women from the area of Miamiville, Ohio, who spent a week

were not allowed to use any other antiperspirants before or during the exams. The investigations were in four periods of 1 week duration starting on February 23, March 16, Conducted April 6 and April 27, 1970. Each test subject received in the individual test weeks administered different samples, of which sample A was a control sample that was used in all 36 test subjects was applied in one of the 4 weeks.

The samples were applied by technical staff to one of the test subject's armpits after rinsing with lukewarm water to remove any soap residue. Aerosol samples D and G to J were achieved by spraying the armpits for 2 seconds from a distance of about 15 to 20 cm upset. The stick sample E was spread over the entire surface of the Ach by rubbing. The applied Amount of aerosol or stick sample was determined by weighing the respective container before and after each Application determined. The solution samples A, C and F were in Spread 0.6 ml portions over the entire armpit area by rubbing in. Sample B (gel) was made applied in a 0.6 ml portion with a spatula by rubbing over the entire armpit area. It can be assumed that the above servings of the individual samples in terms of quantity of the active ingredients applied were approximately equivalent.

The subjects were in a at about 37.8'C and a relative humidity of about 35% held room to sweat. Sweat was collected using weighed »Webril packs«, that were pressed against the armpit.

Sample applications and sweat accumulations were carried out every week according to the following scheme: As a control, no sample was applied on Monday, and sweat accumulation took place in three consecutive collection periods of 20 minutes each immediately after the test subject entered the sweat room. The first sample applications took place on Tuesday, which was immediately followed by three sweat collection periods of 20 minutes each, as on Monday. A second sample application followed the last sweat collection on Tuesday. The third and fourth sample applications were performed on Wednesday and Thursday, and the sweat build-up occurred one hour after each application. The fifth sample was applied on Thursday after the last sweat sample, and the last sample was made on Friday 22 hours after the fifth sample was applied.

In all cases, the "sweat ratio" was calculated by dividing the amount of sweat collected under the test axilla by that obtained under the control axilla. The mean “control sweat ratios” were calculated using all the results from the control days. Corrected ratios were then calculated for each test subject by dividing the individual ratios by the mean control ratio.These corrected ratios were converted into the percentage decrease in perspiration using the following formula:

100 · (1 - corrected ratio).

The percentage reductions observed after 1, 3, 4 and 5 applications of the test materials of the sweat flow are shown in Table II. The limits for 95% probability are omitted for these values, but they range from about 4 to 15%.

The mean values determined after 3 and 4 as well as after 5 applications were based on the relative response of 3 test groups to the antiperspirant effect of sample A corrected. This Means were obtained using the ratios of mean reductions observed in each group calculated for the mean reduction in all 36 test subjects. The resulting corrected mean values are given in Table III.

As can be seen from Tables II and III, Sample F with basic aluminum bromide was sizeable more effective than any of the samples (A, C, and D) with basic aluminum chloride. Further the sample with basic aluminum bromide showed an antiperspirant effect that - apart from the corrected mean of sample H - was superior to that of all other samples. Next is to note that there was no noticeable in any subject or sample during the test period Armpit irritation was observed.

In the following Table IV results of test series are listed, which with the invention Substance in alcohol as a solvent. Also from this table goes the superior effect of the substance according to the invention clearly emerges.

Table I.

A 20% strength by weight aqueous solution of a basic aluminum chloride ("Chlorhydrol"),

B gel containing basic aluminum chloride,

C 20% by weight solution of alcohol-soluble »Chlorhydrol« in anhydrous ethanol,

D aerosol composition of 3.5% powdered dried basic aluminum chloride, 6.2% isopropyl myristate, 0.3% »Bentone 34« *) and 90% propellant,

E Antitranspiransstifte based on "Chlorhydrol®"

F 20% strength by weight aqueous solution of basic aluminum bromide,

G — J Antiperspirant aerosols from 4 different manufacturers **)

*) Trade name of Baroid Div. of National Lead Company for Dimethyldioctadecylammonium Bentonite, a light cream colored, finely divided powder.

· *) Relevant active ingredients not known

969

13th

Table II

Test subject

Applications:

Hours ·): V ₃

-12-24 25-36-12-12 1-12-24-24 - 24 - 36 - 36 - 36

18.1

11.0

2.5

15.2

28.7

0.8

6.7

24.1

9.3

1.2

12.2

15.8

13.4

12.4

11.8

20.9

29.9

(5.1)

10.9

23.2

6.1

8.5

9.7

17.1

15.1 42.8 10.4 39.7 4.0 25.4 19.4 28.2 14.6 39.7 (6.1) .16.7 4.8 8.2 16.0 56.2 6.1 21.9 12.3 34.2 5.5 19.6 9.1 26.2

Sample test subject applications:

Means means

3 and 4

Hours *): 1

-12-24-36-12-12-12-24 - 24 - 24 - 36 - 36 - 36

43.8 45.2 25.9 35.3 39.0 22.0 7.0 59.6 21.0 40.2 24.0 23.8

43.3 42.5 25.6 31.7 39.4 19.4 7.6 57.6 21.5 37.2 21.8 25.1

49.8 51.0 31.8 31.5 42.2 26.1 11.6 63.3 32.6 50.8 17.5 27.9

Λ B C D

A E F G

A H I

sample

30th

A B C D

A E F G

35 14th

Table III

Sample test applications 3 and 4

people incorrectly corrected

Means means

1 - 12 43.3 1-12 31.7 1-12 39.4 1 - 12 19.4 13 - 24 42.5 13 - 24 7.6 13 - 24 57.6 13 - 24 21.5 25-36 25.6 25-36 27.3 25-36 21.8 25-36 25.1

Test subjects

36.8 26.9 33.5 16.5

37.0

6.6

50.1

18.7

36.9 53.6 31.4 36.1

Applications 5

uncorrected

medium

corrected mean

\ 12th 49.8 1 - 12th 31.5 } 12th 42.2 1 - 12th 26.1 • j β 24 51.0 13 - 24 11.6 13 - 24 63.3 13 - 24 32.6 25 - 36 31.8 25 - 36 50.8 25 - 36 17.5 25 - 36 27.9

43.8

27.7 37.1 23.0

43.9 10.0 54.4 28.0

43.9 70.1

24.2 38.5

*) Time in hours between the use of the antiperspirant and the start of the sweating treatment.

() percentage increase in sweat production.

The specific ways in which the invention can be carried out as explained above can be used can be modified in numerous ways without thereby departing from the scope of the invention.

Table VI

Percentage reduction in sweat (values for BAB in alcohol)

Conc. tries Test location Applications 2 7.8 3 8.0 4th 4th 5 Date of receipt 1 (1 H.) (1 H.) (1 H.) (22 hours) (22 hours) Wt% (1 H.) 7.2 33.5 ± 8.4 33.9 ± 11.2 34.6 ± 9, i 24.5 V-1052 Miamiville, 19.0-10.2 (March 29, 1972) Ohio 17.4 ± 16.6 ± 10.8 16.5 ± 8.6 12.5 72-680-70 Miamiville, - (March 26, 1973) Ohio 32.7 ± 34.2 ± 18.4 ± 10.6 20.0 73-522-G-I *) Anderson - (February 15, 1974) Hanover, Germany

*) Distributed with a hand pump.

Claims (10)

2i 48 160 Generally 40 to 60% propellant in total. holds that are eliminated immediately upon application, so that an initially 5% composition becomes an antiperspirant with a content of at least 10 °). at least 5% by weight of basic aluminum 5 One of the best currently available antiperspiran bromides, characterized, tien is basic aluminum chloride (commercially available that there is an aluminum bromide generally available under the name "CHLORHYDROL" Formula Reheis Chemical Company, a subsidiary of Al ₂ (OHJsBr ₁ , • JfH-O Armor Pharmaceutical Company). Unfortunately this has ίο product has the disadvantage that it is in non-aqueous media in the χ between 4.8 and 5.1 and y between 0. 9 like 95% ethanol, 100% propylene glycol or and 1,2 with χ + y = 6 and X between 2.0 and 100% glycerol is insoluble, and for the formation it is 3.4, dissolved in an alcoholic solution - highly viscous gelled masses which do not contain agents. aqueous alcoholic solvent is known. 15 Also known are hydrated forms of basic aluminum chloride in general with Fluorocarbon propellants, such as those used in aerosol cans, incompatible, causing gelling The subject of the invention is a new anti-basic aluminum chloride leads,
transpirans. ao In US-PS 34 76 509 the production of ba- Aluminum compounds have been around for some time as sic aluminum halides of the formula
useful active ingredients for astringent Means or antiperspirants as well as other cosme- Al ₂ (OH) _n Xe-Ji table products. To achieve an astrine The aluminum compound * 5 with X = F, Cl, Br or J and η equal to 1 to 5 inside an antiperspirant composition must give the same effect, and its usability as astrinic ionic character is retained, since only the yawing body deodorants are mentioned. The US-PS ionogenic, but not the covalent form of the Alumi- 34 76 509 but contains no reference to the Lösniums shows antiperspirant effects. Unfortunately, the corresponding products are now available in non-aqueous aluminum compounds that are readily soluble in alcohol systems or the cosmetic applicability of such solutions and are compatible with fluorocarbons. are, in general, the aluminum in covalent From GB-PS 7 70 00 ⁷ is also an antitrans- Form and are therefore known as antiperspirants relatively pirans, which are unusable as an antiperspirant, constituent in addition to a chloride, bromide, iodide or among the many antiperspirants, 35 of which are oxysalt of zirconium or hafnium or their are stated that they exhale and perspiration mixtures Inhibit or prevent 2 to 20% of a basic aluminum flow, those as a compound of the empirical formula
most effective are the aluminum salts of strong inorganic acids such as hydrochloric acid, sulfur- Al ₂ (0H) _e - _w X _n acid, sulfamic acid, etc. Such salts 40 Cosmetic preparations containing them have the disadvantage, however, with X = Cl, Br, I or nitrate and η equal to 0.8 to 2, that they contain irritation or inflammation and have a pH of 3 to 5.
the human skin and damage to the skin. However, the composition is based exclusively on Clothing near the skin. To be borrowed on an aqueous basis and contains 25 to 90% water, the damage to skin and clothing is practically 45. The object of the invention is accordingly to eliminate aluminum, the product should have a pH (in minium compound with high solubility in alcohols Water) of at least about 3.0, but at the same time or other organic solvents and prematurely a sufficient amount of aluminum, preferably with good compatibility with conventional ones Ionic form contain aerosol propellants as well as suitable effectiveness as antiperspirants to be effective. 5 ° to indicate antiperspirant, which is little additional For very widespread use in aerosol treatment or pre-injection modification Aerosol cans must have usable antiperspirants in an antiperspirant composition, tel also with the halogenated carbon- This goal is achieved by the inventive anti- Hydrogen compatible, which is usually achieved as transpirans, which is characterized by propellants used in spray cans. 55 further has a content of at least 5 wt .-% of a Bahin should contain only a minimal rectangular aluminum bromide of the general formula male amount of water, such compositions so that corrosion problems avoided, and impurities of Al ₂ (CH) ₁ FRY · X H ₂ O
spraying products due to corrosion products of metal valves and containers in aqueous media 60 in which χ between 4.8 and 5.1 and y between 0.9 and are switched off. 1.2 with χ + y = 6 and X is between 2.0 and 3.4, Finally, the active ingredient must be in non-aqueous and that in a non-aqueous, alcoholic solution Media is dissolved in concentrations of at least solvent. 10% by weight soluble in what is commonly considered to be minimally the approximately 5/6 basic aluminum bromides concentration required for effective use of the above formula have an Al / Br ratio of Twist is considered an antiperspirant (at about 1.7 to 2.2, and preferably about 1.9 to 2.0. Application in an aerosol can increase the concentration. It is clear that the above formula is greatly simplified reduced to 5%, since the composition is and in practice simple hydrated salts, poly-