DK146212C - Process for producing a highly effective antiperspirant product - Google Patents

Description

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The present invention relates to a process for the preparation of a highly effective antiperspirant product in the form of an aqueous liquid or hydrated powder and consisting of a basic aluminum compound which is an aluminum chloride, bromide, iodide or nitrate with a molar ratio of aluminum to chloride, bromide, iodide or nitrate between 6.5: 1 and 1.3: 1.

For the prevention of perspiration or transpiration, the literature has described the application to the skin of many different antiperspirant active compounds; but the compounds most commonly used in commercial products at present are basic aluminum halides, especially aluminum chlorohydrate, having an Al / Cl molar ratio of approx. 2. These active compounds are applied to the skin from many different applicator types including aerosol sprays, pump sprays, squeeze gaskets, roller applicators and pins, and e.g. Thus, aluminum chlorohydrate is used as an active ingredient in various antiperspirant preparations in the form of liquids, creams, sticks or dry powders. However, despite the popularity of 20 aluminum chlorohydrate, the currently available products are only capable of providing a limited reduction in transpiration.

From Danish Patent Specification No. 129,433 it is known to prepare solid basic aluminum bromides which exhibit some solubility in non-aqueous solvents. These compounds, like the corresponding chlorides, form polymeric ions in aqueous solution. In the Examples of the present invention, the preparation of the solid basic aluminum bromide is illustrated by drying concentrated (about 50%) aqueous solutions from which powdery substances are obtained upon drying.

It is therefore the object of the present invention to provide a process for the preparation of a more effective antiperspirant product.

The invention is based on the recognition that by using certain basic aluminum chloride, bromide, iodide 35

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o and nitrate compounds, an improvement in antiperspirant efficiency is obtained by using the forms which contain in aqueous solution polymeric types having a size greater than 100 Angstroms (Å), in which types 5 are contained at least 2% by weight of the total aluminum. Since the halide or nitrate in aqueous solutions of the basic aluminum compounds is in ionic form, the polymeric types present are hydroxy aluminum types.

It has now been found that such polymeric forms are formed in aqueous media at temperatures from 80 to 140 ° C and concentrations from 7 to 35% by weight, thereby obtaining, after a sufficient time, basic aluminum compounds having an effective diameter of over 100 Angstroms. which comprises from 2 to 80 and preferably 5-60% of the total aluminum content of this polymeric form, which - quite unexpectedly, exhibits increased activity over the aforementioned common basic aluminum compounds obtained either as aqueous liquids or as aqueous liquids. powders traditionally produced by spray drying or drum drying. Here, there is no actual heat treatment of these solutions of basic aluminum halides, thereby increasing their activity, and as the comparative example below shows, even a prolonged heat treatment at 120 ° C for 24 hours of such a concentrated solution as 50% basic aluminum chloride, cf. the above-mentioned Danish presentation letter, nor do the formation of polymers greater than 100 Å. Accordingly, the process of the invention is characterized in that the basic aluminum compound is dissolved in water at a concentration of 7-35% by weight and heated to a temperature of 80-140 ° C for a period of time sufficient to allow the solution forms polymeric forms having a size greater than 100 Å containing 2-80% of the total aluminum, after which the aqueous antiperspirant product is cooled to ambient temperature and, if desired, concentrated or dried to give the product in the form of a hydrated powder.

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It is preferred according to the invention that the basic aluminum compound be dissolved at a concentration of 10-20% by weight. Furthermore, according to the invention, it is preferred that the polymeric forms contain 5-60% of the total aluminum. The formation of the desired forms depends on the proper selection of the reaction conditions which are interrelated. The solutions are heated to temperatures of 80-140 ° C, and the heating time may be shorter at higher temperatures, e.g. from 1/2 hour to 30 days. Of particular importance is the concentration of the basic aluminum compound, since at the above temperatures, virtually no formation of the higher polymeric types of the basic aluminum compound has been observed with solutions in which the concentration is above ca. 40% by weight. Therefore, at these temperatures, the concentration of the solution should not be more than about 10 35% by weight. The conditions described above for the heat treatment have been found to be the cause of the improved basic aluminum compound in amorphous form, and in particular, the formation of boehmite as observed by X-ray diffraction has not been observed. Formation of a substantial amount of boehmite or other crystalline forms of alumina must be considered disadvantageous. In the process of the invention, the aqueous solution of the more active antiperspirant compound comprising the higher polymeric forms as defined above can be evaporated, if desired, to concentrate the solution or it can be dried to give the compound in the form of a solid hydrate. Drying conditions leading to loss of both condensation water should be avoided between the hydroxy groups in the compound and hydrochloric acid, as these can cause an irreversible degradation of the basic aluminum compound. Any suitable drying method may be used, but spray drying is particularly suitable and the spray drying method disclosed in U.S. Patent No. 3,887,692 can be used. The solid material can then be ground if desired.

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The solutions of polymeric basic aluminum compounds mentioned herein are intended to include not only true solutions but also colloidal solutions or dispersions. Such solutions may contain large colloidal polymeric forms, the upper limit of size being not critical; but it must be required that the polymeric forms can be dissolved or dispersed stably in water to form a colloidal solution. Usually, however, there will be no significant amount of polymeric forms greater than 1,000 Å in effective diameter, although the appearance of the aqueous solutions may be foggy or unclear.

The basic aluminum compound has by process. preferably according to the invention, the empirical formula "2" (OH> 6-a Xa where X represents Cl, Br, I or NO 2, and a is from 0.4 to 1.5, the formula being in the case of the compound being The solid aluminum compound has a molar ratio of aluminum to chloride, bromide, iodide or nitrate of 4-1.6: 1 and more preferably 2.5-1.6: first

The antiperspirant product produced by the process of the invention is suitably used in finished uses comprising the active antiperspirant product thus produced in combination with suitable carriers and placed in a desired application means as a package for use on the skin.

The packaged product may be one in which the applicator is a container equipped with a valve for discharging liquid in aerosol form, and the antiperspirant preparation consists of a suspension of the antiperspirant active compound in particulate form in a liquid carrier which may be mixed with a propellant. In addition, the packaged product may be a product wherein the applicator is a container equipped with a valve for discharging liquid in aerosol form, and anti-liquid.

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the perspirant composition consists of an aqueous or aqueous / alcoholic solution of the antiperspirant active compound. In this case, the aqueous solution may be discharged by means of a propellant gas or a finger operated pumping mechanism or by the composition being contained in a container of a flexible material so that the composition is ejected through the spray valve by squeezing the container. A third form of a packaged product is a product in which the applicator is an application roller and the antiperspirant composition consists of an aqueous or aqueous / alcoholic solution of the antiperspirant active compound. Finally, the packaged product may also be a product wherein the applicator is designed to discharge a powdered material and the antiper spirant composition is a powdered composition containing the antiperspirant active compound in powder form. The applicator may also be in the form of a pin or rod containing the antiperspirant preparation in the same form, or it may be a napkin or piece of fabric impregnated with the antiperspirant active material.

A suitable antiperspirant composition comprises an aqueous solution of an antiperspirant active compound prepared by the process of the invention together with an additive such as a perfume, a thickening agent, an alcohol or propellant.

The antiperspirant composition may take the form of a lotion consisting of an aqueous or aqueous / alcoholic solution of the basic aluminum compound at a concentration of 1-30% by weight and 0.1-5% by weight of a thickening agent. Suitable thickening agents for antiperspirant lotions are well known and include e.g. magnesium aluminum silicates, but thickened. the latter may also be obtained by emulsifying an oil or the like in the composition. In addition, the composition may consist of an aqueous or aqueous / alcoholic solution of the basic aluminum compound at a concentration of 1-30% by weight and 0.1-1% by weight perfume.

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The composition may comprise an aqueous / alcoholic solution of the basic aluminum compound containing from 1 to 60% by weight of an alcohol. These aqueous / alcoholic preparations preferably contain ethanol or isopropanol as the alcohol, and it is preferably present in an amount of between 1 and approx. 30% by weight of the composition. The antiperspirant compositions comprising an aqueous solution of the active compound may contain from about 1 to approx. 80% by weight of a propellant.

The antiperspirant composition may also comprise a powdered antiperspirant active compound prepared by the method of the invention combined with a powdery, inert solid diluent or an organic liquid carrier. The composition may take the form of a powder aerosol comprising a suspension of the basic aluminum compound in particulate form in a liquid baser and then also contains a propellant. In particular, the composition may take the form of a powder aerosol composition which contains A. from about 1 to about 12% by weight of the basic aluminum compound in powder form, B. from ca. 0.1 to approx. 5% by weight of a suspending agent, C. from ca. 1 to approx. About 15% by weight of a carrier liquid and D. from ca. 70 to approx. 96% by weight of a propellant.

The carrier liquid may e.g. be a non-volatile, non-hygroscopic liquid as mentioned in U.S. Patent No. 3,968,203, but particularly useful are liquids having skin-softening properties, a number of which are mentioned in British Patent No. 1,393,860, and in particular that preferred are fatty acid esters such as isopropyl meristate and the esters mentioned in British Patent No. 1,353,914 such as dibutyl phthalate and diisopropyl adipate.

Various other carrier liquids for powder suspension aerosols are disclosed in United States Patent Nos. 3,833,721, 3,833,720, 3,920,807, 3,949,066 and 3,974,270, and in British Patent Nos. 1,341,748, 1,300,260, 1,369. .872 and 1,411,547. Volatile carrier liquids may also be used, thus 7

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eg. ethanol as described in South African Patent No. 75/3576, and volatile silicones. The ratio of total solids content of the compositions to the carrier liquid may vary within wide limits, e.g. from 0.01 to 3 parts by weight of the powder for each part by weight of the carrier liquid.

The propellant may be liquefied hydrocarbons or halogenated hydrocarbons or mixtures thereof. Examples of materials useful for use as propellants are found in the above-mentioned patents and include trichlorofluoromethane, dichloro-difluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, trichlorotrifluoroethane, propane, butane, 1,1-difluoroethane, 1,1-difluoroethane chloroethane, dichloromonofluoromethane, methylene chloride, isopentane and isobutane, used separately or mixed. Trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane and isobutane, used separately or mixed, are preferred.

Examples of materials suitable for use as permanent gas propellants are nitrogen, carbon dioxide and nitric oxide.

It is common practice in aerosol powder spray preparations to incorporate a material which contributes to suspending the powder in the liquid carrier. These materials prevent baking of the powder and may also act as thickening or gelatinizing agents for the liquid carrier. Particularly preferred are hydrophobic clays and colloidal silicas. Hydrophobic clays are commercially available under the designation "Bentone" ®, e.g. "Bentone 34" ® or "Bentone 38" ®, and their use as suspending agents are described in several patents, e.g. U.S. Patent No. 3,773,683. Suitable colloidal silicas include "Aerosil 200" ® and "Cab-O-Sil M-5" ® as well as other qualities.

However, the antiperspirant composition may also simply comprise from 5 to 40% of said basic alumina.

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powdered nium compound with the residue consisting essentially of an inert powdered material such as e.g. talc or starch.

Below, the test methods for examining the antiperspirant efficacy of various antiperspirant preparations will be described, as discussed in the examples given below.

Test Methods for Evaluating Antiperspirant Effectiveness 10 In the following examples, five test methods are referred to assess the various antiperspirant active agents disclosed therein. Details of these test methods are listed below.

Test methods I-IV for assessing the antiperspirant-15 efficacy are based on the voluntary stress and gravimetric determination of sweat in the armpits of volunteers.

Test method I

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subjects

A panel of up to 18 women who did not use any antiperspirant for 14 days before the trial or in the 16-day interval between the two halves of the trial.

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Warm room

Temperature 37 -1 ° C, relative humidity approx. 35%.

Products 30

2-4 products are tested, one of which is referred to as the control. Each subject receives a different treatment for each armpit and, as far as possible, an equal number of left and right armpits each treatment.

Product application Spray over 2 seconds.

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9 Sweat collection Absorbent cotton pads are used to collect the sweat. Upon entering the warm room, each subject placed in the armpits a pair of pillows, which after 40 minutes were removed and discarded. Sweat is then collected for two consecutive periods of 20 minutes, using freshly cushioned pads for each collection and the sweat weight is then determined. Experimental Pattern On the first day of the experiment, the subjects are treated with the experimental products, but they do not sit still for some time in the warm room. Each of the next four days, they sit for a while in the warm room with treatment immediately before each sitting and after washing. The final treatment is omitted on the fifth day. After an interval of 16 days, the subjects return and the whole procedure is repeated with the two products received by each subject, used for the opposite tea armpit. Analysis of data The statistical processing includes a variant analysis that takes into account the subject, page and product. Efficiency is calculated from the average geometric weight of sweat collected from the armpits treated with each product. The percentage decrease is determined by% reduction = 100 - where C is the geometric mean value

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5 10 15 20 weight from armpits treated with the control product, and T is the geometric mean sweat weight from armpits treated with the test product. The percentage reduction is usually calculated for each day individually and for the entire trial. Significance is calculated using Duncan's Multiple Range Test for the logarithmically transformed weights.

Test Method II

Subjects A panel of up to 54 women who did not use antiperspirant for 14 days prior to the trial.

Products Two aerosol powder spray products, one of which is referred to as the control. The panel is divided into two equal groups, of which one group receives the experimental treatment in the left armpit and the control treatment in the right, while the other group is treated the opposite.

Experimental Pattern The subjects participate daily over three consecutive days and are treated once with the products each time. On the third day, treatment is immediately followed by a stent in the protected room as indicated under test method I and sweat collection.

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Analysis of data This is done as in test method I, except that the significance is calculated using Student's t-test for the logarithmically transformed weights.

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The products used in test methods I and II had the following composition: 10

Ingredients_ beh. or discomfort. aluminum chlorohydrate isopropyl myristate pyrogen silica ("Aerosil 200" ®) perfume propellant 1}

Experimental Product I (%) - 3.50 3,250.10 0.44 to 100.00

Experimental Product II (%) - 4,506.00 0.45 0.44 to 100.00 15 ^ CCl ^ FiCC ^ i ^ 65:35 by weight 50:50 by weight (product I) (product II)

Test Method III

This method is like Method II with the following differences: 20 Test product A 10% s solution of treated aluminum chlorohydrate (unless otherwise stated) in water.

Control product 25

A 10% solution of untreated aluminum chlorohydrate (unless otherwise stated) in water.

Application method Each armpit is applied approx. 0.5 g of the solution with a cotton swab.

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Test Method IV

This method is carried out as method III with the following difference Application method Each armpit is applied approx. 0.5 g of the solution with a pump spray applicator.

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Test method V

This method is that of Wada & Tokayaki in J. Exp. Med., 49, 284, 1948, described "Forearm Starch Iodine Patch Test" performed as follows:

A panel of volunteer subjects was selected, each of whom received a number of test solutions applied at different locations on the palm side of the forearm. The solutions (12 drops) were placed under semi-occlusive cushions and allowed to sit for 6 hours, after which multiple coatings of the forearm were applied to several coatings of a 1% solution of iodine in alcohol. After evaporation of the alcohol, the coated area was covered with a 50% suspension of starch powder in oil and the subject was then placed in a heated room (40 -2 ° c) until he started to sweat. The effectiveness of the various treatments was then assessed on the basis of the number and size of blue spots that arose from the reaction between starch, iodine and sweat.

Determination of the% content of aluminum in polymeric forms with a size greater than 100 Å

All of the present heat-treated basic aluminum compounds are characterized by molecular year-end chromatography. For this purpose, a 1.2 m long and 6.0 mm wide column packed with spherical porous silica beads with a particle size of 75-125 microns, a surface area of 350-500 m / g and a maximum pore size of 100 Å was used. . The used silica commercially available as "Porasil AX" ® was activated to eliminate adsorption by molecular sieve separations. The use of "Porasil" silica beads as column packing by chromatography is discussed in "Gel Permeation Chroma-tography" by K.H. Altgelt and L. Segan, 1971, pages 16-18. The silica was conditioned prior to use by passing a single large sample (e.g., 0.5 ml of a 2% (w / w) solution) of a heat-treated aluminum chlorohydrate. The samples to be examined were dissolved in deionized water for a concentration 13

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tration of approx. 0.2 M aluminum and thoroughly dispersed by treatment (for 4 minutes) with a sonic probe. Samples of approximately Ο, ca. ml of approx. 0.2 M aluminum solutions using a system of sample loops and eluted with a 10 M aqueous hydrochloric acid solution using a peristaltic pump. A differential refractive index monitor associated with a printer was used to track fractions as they eluted. These fractions were collected and analyzed for aluminum by atomic absorption.

Complete elution of all aluminum used in each sample was verified by direct analysis of another sample of the same volume. The percent of the total aluminum that appeared in the fraction eluted at the column void volume was considered to be that derived from polymeric material having a size greater than 100 Å in effective diameter. None of this polymeric material was found in any of the untreated aluminum chlorohydrate solutions.

Determination of water content in powdered materials 20 The water content in powdered materials was assessed by thermogravimetric analysis (TGA). Upon heating to 1,000 ° C, aluminum chlorohydrate undergoes the following reaction A12 (OH) 5C1 (H2O) x-5 * A1203 + HCl * + (x + 2) H2Of 25 from knowledge of the Al / Cl ratio in the material (and thus the empirical weight of the anhydrous Al0 (OH) c ..Cl), it is possible to calculate the number of moles of water (x) associated with each anhydrous unit, based on an accurate determination of the weight loss by heating a known weight amount of the sample 30 to 1,000 ° C. The method of calculation is shown in the equation weight of solid before heating. \ .., n :) _ emp. weight of anhydrous \ weight of solid after recovery Jx [Al2 (OH) g_aCl &] x = -—--- - ---- 18 35 14

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The percentage content of water is then given at _1.800x_ emp. weight of anhydrous Al0 (OH)> - Cl + 18x Zé D ™ d 3.

The following examples are intended to further illustrate the invention.

Example 1

Aluminum chlorohydrate powder with an Al / Cl molar ratio of 2.04 and a water content of 18.5% was dissolved in deionized water to form a 10% * s (w / w) solution and this solution was heated in 1 liter glass bottles and with screw cap to 96 ° C over 9 hours and then kept at this temperature for another 39 hours. The resulting solution was cooled to room temperature and found to contain 27.3% of the total aluminum as polymers with an effective diameter of over 100 Å. The treated solution was spray dried in a co-stream spray dryer using inlet and outlet temperatures of 250 and 95 ° C, respectively. The powder thus obtained had an Al / Cl molar ratio of 2, 10 and a water content of 14.2%, and it was aimed at obtaining a fraction of between 30 and 50 microns, which is a normal particle size for powder for use in aerosolsprøjtepræparater. This constitutes the main fraction, since the powder is made precisely for this purpose, but fractions outside this range can be very well used in other formulations.

The spray-dried powder was tested for antiperspirant efficacy in two experiments using test method I.

Experiment # 1

This trial included 17 people.

Experimental Products Experimental Product I made with the treated aluminum chlorohydrate. Two test products I made with untreated aluminum chlorohydrate taken from two different production batches.

Control Product 5 Results 10

An alcohol-based deodorant.

The percent reductions for the experimental products compared to the control product are listed in Table I, where e.g. "2nd day" refers to the total results for the second day of each of the two weeks, etc. The table shows the average of the results with the two products containing untreated aluminum chlorohydrate.

Table I

Experimental product 2nd day 3rd day 4th day 5th day total with discomfort. aluminum 7 15 22 22 17 chlorohydrate m. beh. aluminum 32 42 47 56 45 20 chlorohydrate

The differences between the treated and untreated aluminum chlorohydrate antiperspirants were significant at 1% level one.

Experiment No. ♦ 2

This experiment was a repeat of Experiment # 1 using the same products for 14 other people. Results The percentage reductions for the experimental products compared to the control product are given in Table II, where the headings have the same meanings as above.

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Table II

Experimental product 2nd day 3rd day 4th day 5th day total with discomfort. aluminum chlorohydrate 22 16 29 28 24 5 m. aluminum aluminum 37 37 44 44 40 chlorohydrate

The differences between the treated and untreated aluminum chlorohydrate antiperspirants were also significant here at the 10 1% level.

Example 2

A portion of "Reheis" ® aluminum chlorohydrate "Microdry, Ultrafine grade" ® with an Al / Cl molar ratio of 2.04 and a water content of 18.5% was dissolved in deionized water to form a 10% ( w / w) solution which in a 1 liter glass bottle and with screw cap was heated to 97-100 ° C over 10 hours and then kept at this temperature for an additional 38 hours. The resulting solution was cooled to room temperature and found to contain 23.9% of the total aluminum as polymers with an effective diameter greater than 100 Å. The obtained solution was tested for antiperspirant efficacy according to test method III using a sample of 46 subjects. The test solution was found to give a reduction of 22% of the sweat collected compared to the control sample (a 10% solution of untreated aluminum chlorohydrate solution), which was statistically significant at 0.1% levels.

The treated solution was then spray dried, and the resulting powder was screened as described in Example 1 to give a material having an Al / Cl mole ratio of 2.14 and a water content of 14.3%. This powder was tested according to test method II (with 43 persons) using an aerosol application. suspension type of suspension type as test product I. The product containing the treated aluminum chlorohydrate gave a 17

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a 25% reduction in sweating compared to the control product containing the untreated aluminum chlorohydrate, which was significant at the 0.1% level.

Example 3

A 5.0 kg aliquot of "Reheis" aluminum chlorohydrate having an Al / Cl molar ratio of 2.15 and a water content of 16.1% was dissolved in 45 liters of deionized water of 50-60 ° C in a stainless steel reaction vessel. 50-liter steel, which was syringe-coated with polytetrafluoroethylene and additionally equipped with a propeller stirrer and partial vapor cap. The solution was stirred and heated to 100 ° C in the closed reaction vessel over 10 minutes, then kept at this temperature with stirring for 48 hours. The solution was then cooled to ambient temperature and homogenized to disperse any gel formed.

This solution contained 43.3% of the total aluminum as polymers with an effective diameter of more than 100 Å.

Tested for antiperspirant efficacy according to test method III with a panel of 19 persons and using the 10% solution of aluminum chlorohydrate described in Example 2 also prepared by the process of the invention, which controlled this solution a 10% reduction of the total sweat, and the difference was statistically significant at the 10% level. This shows that increasing the overall aluminum content in the polymeric form (over 100 Å) from 23.9% to 43.3% makes the product more active.

Example 4

A 5.0 kg portion of aluminum chlorohydrate (marketed as "Reheis Aluminum Chlorohydrate Microdry, Ultrafine grade") ^ with an Al / Cl molar ratio of 2.15 and a water content of 16.1% was dissolved in 45 liters of deionized water of 50 60 ° C in the reaction vessel described in Example 3. The solution was stirred and heated to 120 ° C in the closed reaction vessel in solution 18

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bake for 15 minutes and then kept at this temperature with stirring for 6 hours. Then, the solution was cooled to 90 ° C over 15 minutes, then poured into a storage vessel and allowed to cool to ambient temperature. Before further treatment, the solution was passed through a homogenizer. This solution contained 40.8% of the total aluminum as polymers with an effective diameter greater than 100 Å. When tested for antiperspirance according to test method III with a panel of 42 persons and using the 10% solution of the treated aluminum chlorohydrate described in Example 3 as a control, this solution gave a reduction of 1% of the sweat collected. The difference was not statistically significant at the 5% level. This shows an activity decrease in moving a portion of the total minimum content away from the polymeric form (over 100 Å). A portion of the treated solution was then spray dried in the manner described in Example 1. The resulting powder had an Al / Cl ratio of 2.23 and a water content of 11.2%. The powder was sieved to obtain a fraction of between 30 and 50 microns, which was incorporated into a suspension type aerosol tip (test product II) and, following test method II (with a panel of 51 persons), was compared with a control product consisting of a commercially available , highly effective powder spray product based on a zirconium / aluminum complex, thereby providing a reduction of 7% of the sweat collected. This was not statistically significant at the 5% level.

When a sample of the spray-dried powder was heated to 120 ° C for 24 hours, the dried product obtained had the empirical composition Al 2 (OH) 2 C 2 q gg * The solution obtained by dissolving the anhydrous powder in water was found to contain 45.4% by weight of the total aluminum in polymers having an effective diameter greater than 100 Å.

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Example 5 A 10 kg portion of a 50% (w / w) solution of aluminum chlorohydrate commercially available as Reheis ® "Chlorohydrol" having an Al / Cl mole ratio of 2.09 was added to 40 liters of deionized water, whereupon the solution is stirred and heated to 120 ° C for 6 hours in the closed reaction vessel as described in Example 3. The treated solution contained 32.9% of the total aluminum as polymers with an effective diameter of over 100 Å and by test method III with a panel of 45 people, when compared to the 10% solution of treated aluminum chlorohydrate as control described in Example 4, it gave an increase of 2% of the sweat collected, but this was not statistically significant at 5% * s the level. Part of the treated solution was concentrated in vacuo in a rotary evaporator at 40 ° C to give a solution which was 1.62 molar with respect to aluminum corresponding to 17.1% treated aluminum chlorohydrate. Another portion of the solution was spray dried in the manner described in Example 1 to form a powder having an Al / Cl molar ratio of 2.05 and a water content of 12.7%. A sample of this powder was redissolved in deionized water and found to contain 32.4% of the total aluminum as polymers with a size greater than 100 Å. This powder was screened to produce a 30-50 micron fraction which was worked up to a suspension type aerosol antiperspirant (test product II) and compared to test method II (with 48 persons), this was compared to the powder spray control used in Example 4 showed a decrease of 14% of the sweat collected, which was statistically significant at the 5% level.

Example 6 A solution of aluminum chlorohydrate was prepared as described in Example 3 and stirred and heated to 120 ° C in the closed reaction vessel over 15 minutes. Stirring 30 20

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and heating to this temperature was continued and, after 1, 6 and 25 hours, samples were taken from the reactor for approx. 2 kg of the solution which was cooled rapidly to room temperature and homogenized. These solutions, respectively, contained 19.4, 45.1 and 78.4% of their total aluminum as polymers having an effective diameter greater than 100 Å. The results of antiperspirant trials of these materials according to test method IV are listed in Table III.

Example 7

Aluminum chlorohydrate (Reheis, Microdry, Ultrafine grade®) having an Al / Cl molar ratio of 1.31 and a water content of 18.8% was dissolved in ionized water to form a 10% (w / w) solution which placed in 25 ml Pyrex glass with screw cap and equipped with polytetrafluoroethylene packing rings and heated to 115 ° C in an oil bath for 2 hours. Then the solutions were cooled to ambient temperature and found to contain 5.3% of the total aluminum as polymers with an effective diameter of more than 100 A. The results of antiperspirant experiments with this solution according to test method IV are listed in Table III.

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Example 8

A 70 kg portion of a Reheis ® aluminum chloride hydrate having an Al / Cl molar ratio of 1.91 and a water content of 18.8% was dissolved in 630 kg of deionized water of 45 ° C and stirred and heated to 120 ° C. in a stainless steel reaction vessel over 3 3/4 hours. Stirring and heating to this temperature was continued for an additional 5 1/2 hours, then cooled rapidly to 70 ° C and more slowly to ambient temperature. The solution obtained contained 41.0% of the total aluminum as polymers with an effective diameter greater than 100 A.

Example 9

A 140 kg portion of a Reheis ® "Chlorohydro1" solution with an Al / Cl ratio of 2.09 was diluted with 560 liters of ionized water of 45 ° C and treated in the same manner in the reactor as described for the solution of Example 8 The resulting solution was found to contain 30.6% of the total aluminum as polymers with an effective diameter of more than 100 Å.

Example 10 in 30%, 20% * and 15% (w / w) solutions of Reheis ® aluminum chlorohydrate having an Al / Cl ratio of 1.91 and a water content of 18.8 were prepared. % and they were heated to 120 ° C in 25 ml screw-cap Pyrex glass and equipped with polytetrafluoroethylene packing rings in an air circulation oven for 6 hours. The solutions thus obtained contained 0, 6.3 and 20.8% of the total aluminum, respectively, as polymers with an effective diameter greater than 100 Å.

Example 11

A more acidic aluminum chlorohydrate was prepared by admixing 19.0 g of an aluminum chlorhydrate with an Al / Cl molar ratio of 1.91 and a water content of 18.8%, 2.25 g of aluminum chloride hexahydrate and sufficient deionized water to give 1 kg of solution. Some of this solution was placed in 25 ml screw screw Pyrex glass and equipped with polytetrafluoroethylene packing rings and heated to 120 ° € for 24 1/2 hours in an air circulation oven. The solutions were cooled to ambient temperature and found to have an Al / Cl ratio of 1.6, and 40.5% of the total aluminum in this solution was found in polymers with an effective diameter of more than 100 Å.

Example 12

A more basic aluminum chlorohydrate solution was prepared by heating a solution of 36.3 g of aluminum chloride hexahydrate in 150 g of deionized water in the presence of 145 g of a 0.5 mm thick aluminum foil, divided into squares of approx. 6 mm, to 90 ° C for 31 hours. After cooling to room temperature, the solution was decanted from excess aluminum and then found to have an Al / Cl molar ratio of 2.5 and containing 0% of the total aluminum as polymeric forms with an effective diameter greater than 100 Å.

This solution was diluted to an aluminiuro concentration of 0.95 M and part of the diluted solution was heated to 120 ° C for 8 hours in 25 ml Pyrex glass with screw cap and polytetrafluoroethylene packing rings in an air circulation oven. The cooled solution contained 37.6% of the total aluminum as polymeric forms with an effective diameter greater than 100 Å. Compared to Sample Method IV (a panel of 20 people) with the non-heat-treated, diluted solution as a control, it reduced 36% of the total sweat, which was significant at the 0.1% level.

Example 13

A 10% (w / w) solution of a basic aluminum bromide having an Al / Br mole ratio of 2 and a water content of approx. 22% and heated to 100 ° C in a glass 24

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Λ 1 liter flask with screw cap for 62 hours in a ventilated oven. The resulting solution was immediately cooled to room temperature and found to contain 46.4% of the total aluminum as polymers with an effective diameter greater than 100 Å. When tested for antiperspirance according to test method V, this solution proved to be appreciably more effective than an untreated solution of the basic aluminum bromide of the same concentration.

Example 14

A basic aluminum nitrate was prepared by dissolving 37.4 g of aluminum nitrate nonanhydrate in deionized water to give 200 g of solution. This solution was heated to 90 ° C under a reflux condenser and 13.45 g of aluminum powder was added in small portions over 5 hours. The heating was then continued with stirring for a further 24 hours. After this time, the solution was cooled to room temperature and filtered to remove excess aluminum, and it was then found to have an Al / nitrate molar ratio of 2.9. It was found that 41.9% of the total aluminum in this solution was found in polymeric forms with an effective diameter of more than 100 Å. Some of this solution was diluted to 0.1 M with aluminum and tested for antiperspirance according to test method V, thereby proving to have the same efficiency as the solution prepared in Example 2 with the same aluminum concentration.

comparison Example

A 50% (w / w) solution of a Reheis ® aluminum chlorohydrate having an Al / Cl molar ratio of 1.91 and a water content of 18.8% was prepared and heated to 120 ° C in Pyrex glass. of 25 ml with screw cap and polytetrafluoroethylene packing rings in a ventilation oven for 24 hours. The solution thus obtained contained 0% of the aluminum in polymers with an effective diameter greater than 100 Å. When testing for another 25

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tipirpans as a 10% by weight solution according to Test Method IV with a panel of 46 persons gave this solution a 2% increase in the sweat collected compared to an untreated solution of aluminum chlorohydrate of the same concentration. This result was not statistically significant at the 5% level.

In the following Examples 15-25 various compositions are provided which can be prepared from the treated basic aluminum compounds described in the preceding Examples. All percentages indicated are by weight, and for convenience, the treated aluminum antiperspirant in powder and solution form is designated "treated powder" and "treated solution" respectively.

Examples 15-20 illustrate suspension-type aerosol spray products used with an aerosol applicator.

Example 15%

Beh. powder Isopropyl myristate "Aerosil

200 "(pyrogen silica) Perfume 3.50 3.50 0.10 0.44

100.00 CCl2F: CCl2F2 65:35 by weight.

Example 16% 4.50 6.00 0.45 0.44 200 "(pyrogen silica)

Beh. powder Isopropyl myristate "Aerosil ® 200" (

to 100.00

Propellant CC13F: CC12F2 50:50 by weight.

26

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Example 17%

Beh. Powder 3.50 Isopropyl myristate 8.00 "Bentone® 38" (hydrophobic) 0.60

Ethyl alcohol (95%) 0.27

Parf urn 0.40

Propeller Loan ^ to 100.00 ^ Propellant CCl ^ F: 'CCIF2-CCIF ^: n-butane, 20: 10: 50: 20 by weight.

Example 18 15% Beh. Powder 3.50 Dibutyl Phthalate 8.00 S Tearoyl Monoethanolamide 0.60 Perfume 0.40 20 Propellant ^ to 100.00 ^ Propellant CCl2F: CCl2F2: Cutaneous, Weight 40: 30: 3 (25 Example 19% 4.00 Treat Powder Isopropylmyristate 6.00 Methylene chloride 25.00 1: 1: 1 trichloroethane 5.00 "Aerosil ^ 200" (pyrogen silica) 0.45 "Butane 40" 59.55 µS * 27 o

Example 20 s% Beh. powder 4.00 "Bentone ^ 38" (hydrophobic) 0.40 Isopropyl myristate 6.00 Perfume 0.50 Propellant 1 '89.10 Chloro-difluoromethyl-methane 10

Example 21

This example discloses an antiperspirant lotion suitable for use with a roller applicator.

% Beh. Powder 5.00 Urea 5.00 Ethano1 50.00 Water 35.00 / n \ "Tween ^ 80" (polyoxyethylene 5.00 sorbitan monooleate)

Example 22

This example discloses an antiperspirant lotion suitable for application with a roller applicator.

% 25 Beh. solution 80.00

Glyceryl Monostearate 10.00 ("Arlacel 165" ®) 10.00

Distilled water

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Example 23 This example discloses an antiperspirant lotion suitable for application with roller or pump spray applicator.

% Beh. Powder 12.50 Ethanol 30.00 Glycine / TV 5.00 "Tween ^ 20" (Polyoxyethylene 2.50 Sorbitan Monolaurate) Water 50.00 Example 24 ...

This example indicates the composition of a product in the form of a pin or rod. 15 '% Beh. Powder 20.00 Volatile Silicon 7158 ^ "48.00 (Union Carbide)" Spandes "(sorbitan trioleate) 2.00 20

Decamethylcyclopentasiloxane.

25

Example 25 This example indicates an antiperspirant cream.

Beh. solution (17.5%) Glyceryl monostearate ("Arlacel 165") 85.70

Water £ 10.00 £ 4.30

Claims (3)

A process for preparing a highly effective antiperspirant product in the form of an aqueous liquid or hydrated powder and consisting of a basic aluminum compound which is an aluminum chloride, bromide, iodide or nitrate having an aluminum to chloride molar ratio, bromide, iodide or nitrate between 6.5: 1 and 1.3: 1, ke n-denoted by dissolving the basic aluminum compound in water at a concentration of 7-35 wt% and heating to a temperature of 80-140 ° C for a time sufficient to form in the solution polymeric forms having a size greater than 100 Å containing 2-80% of the total aluminum, after which the aqueous antiperspirant product is cooled to ambient temperature and The desired is concentrated or dried to obtain the product in the form of a hydrated powder. Process according to claim 1, characterized in that the basic aluminum compound is dissolved in a concentration of 10-20% by weight. 3. A process according to claim 1 or 2, wherein the polymeric forms contain 5-60% of the total aluminum.