DE2531831A1 - ALUMINUM-ZIRCONIUM-ANTITRANSPIRANE SYSTEMS WITH TRACE QUANTITIES OF EARTH ALCOHOLIC METALS AND THEIR USE - Google Patents

Description

Armor Pharmaceutical Company

a corporation of the State of Delaware, Greyhound Tower,

Phoenix, Arizona. 85O77

V. St. A.

Aluminum-zirconium antiperspirant systems with trace amounts on alkaline earth metals and their uses

The invention relates to aluminum-zirconium antiperspirant systems with trace amounts of alkaline earth metals, especially unusually effective aluminum-zirconium-antiperspirant complexes, which are fortified with salts of alkaline earth metals such as magnesium and calcium, and their use ·

509886/1057

2 5 3 18

It has been known for some time that zirconium salts have exceptionally effective antiperspirant properties exhibit. Such zirconium salts include, in particular, the acidic zirconium salts, such as zirconium oxychloride or Zirconyl chloride, zirconium hydroxychloride and other halide and sulfate derivatives of these salts.

So far, the most effective and acceptable antiperspirant systems have been which contained zircon, those in which the zircon salts in numerous forms with basic aluminum compounds were combined, either in solutions or complexes of the salts. Examples of such aluminum-zirconium antiperspirant systems are in U.S. Patents 2,814,534 and 2,814,585, 2,854,382, 2,906,668, 3,405,153 and 3 792 06Π. More recently, they became one Number of new buffered aluminum-zirconium antiperspirant complexes in DT-PS ......... (patent application P 24 49 880.4) and US patent applications 431 639, 433 931 and 477 5 ^ 4.

Despite the effectiveness of zirconia compounds in antiperspirant systems, the most effective antiperspirant systems found to date (which are not too acidic to apply to the skin) have only been in the range of about 30 to 45 % antiperspirant effectiveness. Therefore, there has been a constant effort in the antiperspirant art to obtain more effective antiperspirant agents.

Surprisingly, it has now been found that exceptionally effective antiperspirant agents by strengthening the aluminum-zirconium-antiperspirant complexes can be formed with trace amounts of salts of an alkaline earth metal. Such complexes are generally made from a basic aluminum compound,

ORJGJNAL INSPECTED

fi 0 9 8 8 6/1 Π Γ> 7th

a zirconium compound from the group of zirconium oxy salts, zirconium hydroxy salts and their mixtures and traces of one Salt of an alkaline earth metal from the group of magnesium, calcium and their mixtures. The aluminum and Zirconium compounds are present in amounts such that an Al / Zr molar ratio of about 10: 1 to 1; 10, preferred about 4: 1 to 1: 1 is achieved. So become unusually effective anti-stress inhalants by forming one astringent complex of a basic aluminum compound, a zirconium compound and a trace of an alkaline earth metal salt provided. The alkaline earth metal salt can be either calcium and / or magnesium, preferably but magnesium, and can be used as any of the common salts such as halides, carbonates, oxides, hydroxides etc. can be added. The basic aluminum compounds can be any basic antiperspirant aluminum salt , especially basic aluminum halides, and the zirconium compound can be a zirconium oxy salt and / or zirconium hydroxy salt be. The pH of an aqueous, 5 to 15 percent by weight of the complex (based on the oxides of aluminum and zirconium) containing solution should be at least about. The complexes can be in the form of conventional anti-stress inhalants are used, including aqueous solutions, aerosol sprays (including powder-in-oil aerosol sprays), as well as creams, lotions and sticks.

The alkaline earth metal, preferably magnesium, need not be in an amount greater than about 1 part by weight to 30 parts by weight of aluminum and zircon are present. In other words, a 10 percent solids solution of the antiperspirant complex must be used contain no more than about 0.1 weight percent of the alkaline earth metal.

The presence of magnesium and / or calcium salts in Antiperspirant systems isn't entirely new. So beats

η <ί R fl Π / 1 η

- I ₁ _

e.g. US-PS 2,350 0 ^ 7 the use of magnesium oxide, -hydroxide or carbonate in small amounts (about 1 to 3%) in antiperspirant solutions or creams, which are certain Contain astringent aluminum salts. After that, the magnesium compounds should be the worsening ones or reduce the adverse effects of the aluminum compounds on fabrics. Similarly, U.S. Patent No. 2,571,030 proposed Formation of double complexes between aluminum chloride and Calcium or magnesium chloride containing antiperspirant creams containing antiperspirant creams to prevent the corrosive effects on tissues To reduce aluminum chloride. This patent recommends the use of about 0.2 to 15 parts by weight Magnesium or calcium halide per 100 parts of aluminum.

More recently, the DT-PS (patent application

P) basic aluminum antiperspirants described, in which magnesium salts were partially substituted for aluminum salts in order to achieve synergistic aluminum-magnesium-antiperspirant systems of comparable effectiveness. The magnesium salts are present in such amounts that the Al ₂ O_ / MgO ratio is in the range from about 4: 1 to 1: 4. In addition, some of the other four German patents mentioned above, including in particular the DT-PS ··. ····· "(patent application P), describe the use of various

Magnesium and calcium compounds and complexes as buffers in aluminum-zirconium antiperspirant systems.

However, as far as is known, it has never before been found or recognized that trace amounts of salts of alkaline earth metals such as e.g. Magnesium and calcium, the antiperspirant effectiveness of aluminum-zirconium antiperspirant systems are crucial can improve. This synergistic effect of the alkaline earth metals on aluminum-zirconium complexes was complete unexpectedly.

⁺⁾ USSN 4ll 995
⁺⁺ ' USSN 477 544

B 0 9 fl Π Π / 1 M ^r . 7th

i 3 1 8 3

The basic aluminum compounds that can be used to form the complexes of the invention include the conventional basic aluminum salts that have been in the field of antiperspirants for quite some time are known and already have a certain degree of antiperspirant effectiveness as a result the presence of the active aluminum ion. These basic aluminum salts can be determined by the following general empirical Formula can be represented:

^A V ^0H > 6-nx ^A x '

where χ is greater than 0 and less than 6, 6-nx is greater than or equal to zero, η is the valence of A and A Halides, nitrate, sulfamate, sulfate and their mixtures is selected.

It will of course be understood that the above formula is greatly simplified and are basic aluminum compounds and are intended to include coordinated and / or bound molecules of water, as well as polymers, complexes and mixtures of the above basic formula.

Particularly preferred basic aluminum compounds of the above formula are 2/3 to 5/6 basic aluminum chlorides, where A is chloride and χ is between about 1 and 2 and need not be an integer. So can such basic aluminum chlorides through the formulas

Al ₂ (OH) ₅ Cl and Al ₂ (OH) ₄ Cl ₂ are represented.
The basic aluminum chlorides are also called aluminum

509886/10 Π 7

£ 5 3 183 I.

chlorohydroxides or aluminum chlorohydrates or aluminum hydroxychlorides and are commercially available (e.g. under "Chlorhydrol").

In addition to the simple basic aluminum salts given above complexes or derivatives of the basic aluminum salts can likewise advantageously be incorporated into the inventive Complexes are used. Examples of such derivatives or complexes include those in U.S. Patent 3 634 48Θ described phenolsulfonate derivatives. Such complexes are made by reacting 5/6 basic aluminum chloride with Phenolsulfone Mure, zinc - »phenol sulfonate or Aluminum phenol sulfonate is formed. Other suitable derivatives and complexes of basic aluminum salts which can be used in the complexes of the invention will be readily apparent to those skilled in the art from the description of the invention .

The zirconium compounds useful in forming the complexes of the present invention include both the zirconium oxy salts also the zirconium hydroxy salts, also known as zirconyl salts and zirconyl hydroxy salts. These connections can by the general empirical formula

^{Zr0 (0H)} ₂ -nz ^B e.g.

where ζ can be between about 0.9 and 2 and need not be an integer, η is the valence of B, 2-nz is greater than or equal to zero, and B can be equal to A in the preceding formula. That is, B may be any of halides, nitrate, SuIfamat, sulfate, and a mixture thereof _o If only zirconium compounds are exemplified in this specification, it should be understood however, that other metals of Group IV a, including hafnium, to form the according to the invention

SO9B86 / 1057

253 183

Complexes can be used.

As with the basic aluminum compounds, it goes without saying that the above formula is greatly simplified and represents and comprises compounds with coordinated and / or bound water in various amounts, as well as Polymers, mixtures and complexes thereof. As can be seen from the above formula, represent the zirconium hydroxy salts actually a range of compounds with different proportions of hydroxyl groups, in one range from about 1.1 to only slightly more than 0 groups per zirconium atom.

Particularly preferred zirconium compounds for use according to the invention include zirconyl chloride (also as basic Zirconium chloride or zirconium oxychloride) and zirconyl hydroxychloride, represented by the simple formulas ZrOCIp or ZrO (OH) Cl can be represented. These connections are commercially available in the form of solutions. Alternatively, the zirconium compounds can be removed by loosening commercial zirconium carbonate paste (carbonized, water-containing Zirconium oxide) in the appropriate amount of the acid of the anion to be used, e.g. hydrochloric acid. Other useful zirconium salts are available to those skilled in the art, such as trioxodizirconium hydroxyhalides and salts similar to those described, for example, in U.S. Patent 2,837,400 are.

The salt of an alkaline earth metal can be a salt of either magnesium or calcium, but preferably magnesium. The anion of the metal salt is not particularly critical and may be any halide, such as _o chloride or bromide, nitrate, carbonate, hydroxide, oxide, SuIfamat, phenolsulfonate, inter alia, be _o the anion, however, the alkaline earth metal in solution should not enclose or _c, shield, but the salt

η q R ρ. π / inn?

rather, it should be such that in an acidic solution it provides a strongly ionized alkaline earth metal.

The alkaline earth metal must be in the complexes according to the invention only be present in trace amounts. The exact limits of the trace amounts are not critical. The term "trace amounts" As used here, covers approximately the range between 1% by weight of alkaline earth metal to 1000 parts by weight Aluminum plus zirconium and about 1 part by weight of alkaline earth metal to about 30 parts by weight of aluminum plus zirconium. In other words, one of the complexes contains about 5 to 15 percent by weight aluminum plus Containing zirconium (calculated as oxides ΑΙ ,, Ο and ZrO) Solution only about 0.001 to 0.1 percent by weight magnesium or another alkaline earth metal.

The relative amounts of basic aluminum compound and zirconium compound added to form the complexes of the invention should be such that there is an Al / Zr molar ratio between about 10: 1 and 1:10, preferably about 4: 1 to 1: 1. Albeit higher proportions of zirconium in the complex would be desirable from the standpoint of antiperspirant effectiveness, it should be borne in mind that zirconium is considerably more expensive than aluminum. Furthermore, if higher proportions of zirconium are complexed, the acidity will decrease of the antiperspirant is problematic and it becomes necessary to add buffer in order to obtain a satisfactory one Maintain pH. That is, it is generally accepted that an antiperspirant agent in order for application to the human skin must have a pH of at least 3, and preferably between about 3 and 5 got to.

Even if the alkaline earth metal salts are generally used as buffers

S η 9 η R π / 1 η r. ?

2 5 3 10 3 1

for aluminum-zirconium antiperspirant systems are satisfactory, so are those in the inventive Complex trace amounts present inadequate to significantly affect the pH of the antiperspirant agent. In the event that a buffer is required, a number of buffers are available for aluminum-zirconium antiperspirant systems available to the professional. For example, the agents disclosed in U.S. Patents 2,814,584, 2,814,585 and 2,854,382 with urea or water soluble amino acids be buffered. More effective and sophisticated buffers for aluminum-zirconium systems are also in the DT-PS ........ (Patent application P 24 49 880.4), the US patent applications 431 639, 433 931 and 477 544. Additionally, if desired, the pH of the antiperspirant agent can be adjusted increased by adding additional aluminum compounds to the reaction mixture in the formation of the complexes according to the invention or be lowered. E.g. aluminum chloride (AlCl-) can be added to lower the pH, or aluminum hydroxide (Al (OH) -) can be used to increase the pH.

The process for forming the complexes of the invention is not particularly critical. In general, the complexes can be made simply by adding the various components to one another in aqueous solution and then, if desired, by drying the solution to a dry powder. the different components are preferably added together at the same time with stirring or agitation or shaking. Moderate Heating, for example to a maximum temperature of about 75 or 85 C for a period of up to half an hour can be advantageous after adding certain ingredients, in particular when an insoluble compound is added or when a precipitate is formed after adding an ingredient.

5 Π R R R 6/1 Π 5 7

2 5 3 13 3

The drying step is not particularly critical and can be carried out in a number of ways, including Vacuum drying, oven drying, spray drying or freeze drying. Of course, drying doesn't mean that all the water is removed because a certain amount of water is in the complex as coordinated and / or bound Water should remain. So drying is just past the point where the solution becomes crumbly solid mass becomes sufficient. If the complex is too dried, so that part of the coordinated and / or bound Water is removed, this can affect the stability and / or activity of the complex, and the complex may not be easily soluble again in solvents, especially aqueous / alcoholic Solvents.

Even if it has been stated that the method of implementation is not to be regarded as particularly critical, understand it turns out that sufficient time, heat and agitation are required for the reaction of the salts to form the to enable new complexes according to the invention.

The complexes of the invention will be discussed in more detail below with reference to the following specific ones limiting examples illustrates:

100 grams of a 0.5 weight percent slurry of basic magnesium carbonates was prepared. To this slurry was added 200 g of a 25 weight percent solution of aluminum chlorohydrate (5/6 basic aluminum chloride) with stirring. The resulting solution was stirred until it was clear and then heated to 80 ° C. before 73 g of a zirconyl chloride solution (14.4 percent by weight zirconium) were added. After cooling, this solution was oven dried at 55 C under a vacuum of 45 ctn Hg. The dried

naohtrg -rfich

r, 7

'j γ') 1 O "} i - 11 -

The analysis of the neat material showed 15.3 % Al, 13.5 % Zr and 0.08% Mg. An aqueous solution containing 10% by weight of this dried complex had a pH of 4.0.

The antiperspirant effectiveness of the above astringent By means of an independent test laboratory by applying it to the axles of a number of female test persons from the Miamiville, Ohio area. The test procedure used to determine the antiperspirant effectiveness is a standard procedure, as it is in the professional world is known and is described in detail in US patent applications 411,995 and 88,206 (9/11/1970). The tests were made at the same time for comparison purposes with four different antiperspirant agents as follows:

Sample A - a 10 w / w -% aqueous solution of an aluminum chlorohydrate (5/6 basic aluminum chloride) / zirconium hydroxychloride complex.

Sample B - a 10 w / w -% aqueous solution of an aluminum chlorohydrate (5/6 basic aluminum chloride) / zirconyl chloride complex.

Sample C - a 10 w / w -% aqueous solution of a complex, which was formed according to the specific example above, namely a complex of aluminum chlorohydrate (5/6 basic aluminum chloride), zirconyl chloride and a trace of magnesium carbonate

Sample D - a 10 w / w -% aqueous solution of 5/6 basic aluminum chloride.

C ₁ π q P, p, r / ι μ r, -7 ORIGINAL INSPECTED

2 531Ö31

All samples were applied at a rate of 0.5 ml per application. The test is carried out so that as far as possible equal conditions can be created for all samples examined. The results of the tests are as follows shown in Table I.

Table I.

Sample wt .-% Al / Zr- % welding assessment metals molar reduction limit (%) ratio

A. Al = I, 20
Zr = 2, 14 2, 0 * 7. β * 7.8 B. Al = 1.63
Zr = 1.39 4, 0 46, 6th ¹ 9.2 C. Al = 1.53
Zr = 1.35
Mg = 0.008 4, 0 59, 1 ± 8.2 D. Al = 2.5 - 31, 6th ^t 15.4

The antiperspirant effectiveness is shown in Table I as a percentage the reduction in sweat or perspiration. The assessment limits of this effectiveness are shown in the last column of Table I. As from the percentages by weight of the metals and The Al / Zr molar ratios are samples B and C practically identical except for the presence of a trace of magnesium in sample C, which is the invention Represents antiperspirant complexes. Nevertheless, Sample C showed a greatly improved increase in antiperspirant effectiveness due to the presence of the trace of an alkaline earth metal is returned.

η η π R π / 1 η π 7

ORIGINAL INSPECTED

"t r -ι ι η ο ι __ jj IuJI

Without wishing to be bound by any particular theory, it is believed that the highly ionized alkaline earth metal the zirconium in the formation of larger and more highly charged complexes with the aluminum compounds supports. That is, at times the theory of antiperspirants the antiperspirant effectiveness with a high positive charge of the complexes or polymers of the active ingredients associated. With very acidic or low pH values (e.g. 1 to 4), zirconium becomes masked by oxide and hydroxyl groups of the water of the aqueous solution. This masking effect, like that is believed to lead to steric problems that a prevent effective complexation of the zirconium with aluminum.

At the aforementioned low pH values, however, polyvalent alkaline earth metals, such as calcium and magnesium, highly ionized and can easily collide with the aluminum. It is believed that these metals are reversed Form a bond with the zirconium forming large, highly charged antiperspirant complexes.

As indicated above, the complexes of the invention can be used in a variety of conventional antiperspirant porms applied to the human armpit to effectively prevent perspiration. In in such formulations the complex should be present in amounts such that the total aluminum plus zirconium content of the formulation between about 1.5 and 15 percent by weight (depending on the type of formulation used), calculated as oxides of aluminum and zirconium ·

Aqueous solutions of the complexes e.g. can be used in lotions, oil / water creams and co-dispensed aerosols

ORIGINAL INSPECTED

5 09886/10 8 7

I 5 3 λ 8 3!

the. The complexes of the invention are not a rule Soluble in pure alcoholic solvent systems. However, the complexes can be used in aqueous-alcoholic Solvents should be considered. The complexes of the invention should be in the above Antiperspirant Fortnen be present in such quantities, that the total aluminum plus zirconium content in the formulation is on the order of about 5 to 15 weight percent (calculated as oxides of aluminum and zirconium) or 10 to 30 percent by weight of the active ingredient (calculated on a solids basis).

The complexes according to the invention can also be used in the now popular powder-in-oil aerosol sprays. The powder-in-oil systems include the dispersion of a finely divided Antiperspirant powder, e.g., the dried complexes of the invention, in a non-solubilizing agent polar organic solvent, such as an ester, which acts as both a dispersing agent and a plasticizing agent Means serving. The organic liquid coats or wets the powder particles so that they become heavier and close the armpit region better and more permanently. This powder-in-oil primary suspension, known as "concentrate", may also contain a suspending agent, i.e. an agent that counteracts compactness, such as Cab-O-Sil or Benton 3 ^ to prevent the disperse Phase settles and irreversibly condenses. The so-called "extra dry" formulations use less emollient Medium and higher amounts of dry powder, such as talc. Finally, after vigorous stirring, the viscous one becomes Concentrate generally mixed at about 9 times its weight of a standard propellant mixture.

Are the complexes according to the invention in the powder-in-oil aerosol sprays used, they should be in the finished form

R09986 / 1 η57 or: c! Times inspected

Mulation up to about 1 to 6 percent by weight, preferably about 1.5 to 3 percent by weight, namely aluminum plus zirconium total, calculated as oxides. A typical powder-in-oil aerosol suspension is about 5 w / w. -% of the active ingredient (dried complex) or about 2.5 % total oxides.

B 0 9 R R 6/1 η 5 7

Claims (20)

PATENT CLAIMS I) / Antiperspirant agent containing a water-soluble Complex of a basic aluminum compound, a zirconium compound from the group of zirconium oxy salts and / or zirconium hydroxy salts and a trace amount of a salt of an alkaline earth metal from the group of magnesium and / or calcium with a content of the compounds corresponding to an Al / Zr molar ratio of about 10: 1 to 1:10. 2) means according to claim 1, characterized in that the Complex in an aqueous solution in an amount corresponding to a total amount of aluminum plus zirconium in of the solution, calculated as oxides, from about 5 to 15 percent by weight is dissolved and the pH of the solution is at least about 3. 3) Composition according to claim 1 or 2, characterized in that the alkaline earth metal is magnesium. k) Agent according to claim 3ι, characterized in that the alkaline earth metal salt is a salt from the group consisting of magnesium halides, magnesium nitrate, magnesium sulfamate, magnesium phenolsulfonate, magnesium carbonate, magnesium hydroxide and / or magnesium oxide. 5) means according to one of claims 1 to 4, characterized in that that the alkaline earth metal is present in the solution in an amount of about 0.1 percent by weight or less is. ORIGINAL INSPECTED S09fiRR / in ^r , 7 6) means according to one of claims 1 to 5t, characterized in that that the basic aluminum compound is a compound of the general empirical formula: ^A1 2 ^(OTl) 6-nx ^A x is, where χ can be greater than 0 and smaller than 6, 6-nx is greater than or equal to 0, η is the valence of A and A from the group of halides, nitrate, sulfamate and / or sulfate is selected. 7) Means according to claim 6, characterized in that χ is between about 1 and about 2. 0) means according to claim 6 or 7 »characterized in that A is chloride or bromide. 9) means according to one of claims 1 to o, characterized in that that the connection is a connection of the general empirical formula ZrO (OHl B
^x S-nz ζ where ζ varies between 0.9 and 2, η is the valence of B is 2-nz greater than or equal to 0 and B is selected from the group of the halides, nitrate, sulfamate and / or sulfate is. 10) means according to claim 9 _t, characterized in that B is chloride and ζ is about 1. 11) means according to claim 9 »characterized in that B Bromide and ζ is about 1. B 0 q ß R R / 1 η π 7 12) means according to one of claims 1 to 11, characterized in that that the Al / Zr molar ratio is about 4 I 1 to 1: 1 is. 13) means according to any one of claims 1 to 12, characterized in that that the complex also contains aluminum chloride. 14) means according to claim 1, characterized in that the Complex is in powder form. 15) Composition according to claim l4, characterized in that the complex is included in a powder-in-oil astringent system an aerosol propellant is present in suspension in an amount of about 1 to 6 percent by weight of the system. 16) Agent according to one of Claims 1 to 13, characterized in that that the complex also contains a buffer compound in a to maintain the pH of the complex in aqueous solution contains between about 3 and 5 sufficient amounts. 17) Antiperspirant agent containing an aqueous solution containing about 10 percent by weight of a complex with 5/6 basic aluminum chloride, zirconyl chloride and a trace of magnesium carbonate, a pH of about 4 and an analysis of about 1.5 percent by weight aluminum, 1.4 percent by weight zirconium and 0.01 percent by weight magnesium. 18) Use of the agent according to claim 2 for inhibiting perspiration by applying the agent to the human Armpit. OrV.ClMAL ittSPCCTED 509886 / inr, 7 2531331 19) Use of the agent according to claim 1.7 for inhibiting perspiration by applying the remedy to the human armpit, 20) Use of the agent according to claim 1 for inhibiting of perspiration by suspending the dried complex in an aerosol propellant to about 1 to 6 Percentage by weight of the complex in the propellant and spraying of the suspension obtained on the human armpit. r.nqnpr./i “r. ₇ 509886/1057