JPS6323169B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to antiperspirant actives. Many different compounds have been described in the literature as antiperspirant active compounds that are applied to the skin to prevent sweating. However, the most widely used compounds in current commercial products are basic aluminum halides, particularly aluminum chlorohydrate, whose Al/Cl molar ratio is approximately 2. Active compounds of this type are applied to the skin from a variety of applicators, such as aerosol sprays, pump sprays, compression packs, roll-on and stick applicators. Thus, aluminum chlorohydrate is used, for example, as an active ingredient in a variety of liquid, cream, stick or dry powder antiperspirant compositions. Aluminum chlorohydrate is commonly used, but currently commercially available products provide only limited sweat reduction. Pending Patent Application No. 5368 of 1972 discloses basic chloride in which the molar ratio of aluminum and chlorine, bromine, iodine or nitrate ions is 6.5 to 1.3:1;
consisting of aluminum bromide, iodide or aluminum nitrate;
A method for making an improved antiperspirant is described in which the compound forms a solution in water containing at least 2% by weight of the total aluminum as a polymer having a size of 100 angstroms or more. In aqueous solutions of basic aluminum compounds, the halide or nitrate is in ionic form and therefore the polymeric species present (hereinafter referred to as polymers) is a hydroxy-aluminum material. This antiperspirant active compound can be used in the form of an aqueous solution. As described in the above-mentioned pending patent application, this special form of basic aluminum, which is a solution in which at least 2% by weight of the total aluminum is present as a polymer of 100 angstroms or more in size, It can be produced by heating an aqueous solution of the compound to a high temperature. In order to produce the desired polymer, a combination of reaction conditions is appropriately selected. The temperature is preferably 80°C to 140°C. The higher the temperature, the shorter the heating time may be, for example, from 0.5 hours to 30 days. What is most important is the concentration of the basic aluminum compound starting material. The higher the concentration of the solution, the more
The rate of formation of high polymers of basic aluminum compounds is reduced and the concentration must be below about 35% by weight at the above temperatures. The present invention relates to improvements in the antiperspirants described in this co-pending patent application. The present invention provides an antiperspirant comprising an aqueous solution of basic chloride, bromide, iodide or aluminum nitrate in which the molar ratio of aluminum to chlorine, bromine, iodine or nitrate ions is 6.5 to 1.3:1. or 80% by weight is present in the solution as a polymer with a size of 100 angstroms or more,
Further provided are antiperspirant actives containing neutral amino acids. The term neutral amino acid refers to an amino acid having an equal number of non-neutralizing amino and acid groups. Preferred amino acids are those having 2 to 10 carbon atoms, such as glycine, sarcosine, alanine, phenylalanine, valine, leucine, methionine, taurine, ornithine-hydrochloride and glutamic acid monomethyl ester. Addition of neutral amino acids reduces the viscosity of the solution and suppresses gelation. This amino acid increases the pH of the solution, reducing skin irritation and metal corrosion of its container. In the powder obtained from this solution, the amino acids prevent corrosion of metal containers. The amount of amino acid is preferably such that the molar ratio of aluminum to amino acid is 20:1 to 1:1. The basic aluminum compound preferably has a molar ratio of aluminum to chlorine, bromine, iodine or nitrate ions of 4 to 1.3:1, particularly 2.5 to 1.6:1. The weight of aluminum in the polymer having an effective diameter of 100 angstroms or more is preferably 5 to 60% of the total aluminum. An aqueous solution of an active antiperspirant consisting of a highly polymeric material as defined may optionally be evaporated to concentrate the solution. The compositions of the present invention can be prepared by dissolving the amino acids in a solution of a basic aluminum compound containing polymers of 100 angstroms or more, prepared as described in the above-mentioned patent application. Alternatively, the amino acids may be added to a solution prepared from a powder obtained by drying a solution prepared according to the above patent application. The antiperspirant active agent of the present invention can also be manufactured by the method described in the patent application (title of the invention: antiperspirant) filed on the same day by the present applicant. This method involves heating an aqueous solution of a mixture of basic chloride, bromide, iodide or aluminum nitrate and an amino acid in which the molar ratio of aluminum and chlorine, bromine, iodine or nitrate ions is 6.5 to 1.3:1. It is a method of manufacturing substances. In this case, the concentration of the basic aluminum compound and the heating temperature and time of the solution are such that a polymer with a size of 100 angstroms or more is formed in the solution and 2 to 80% by weight of the total aluminum is contained in the polymer. The conditions shall be as follows. The antiperspirant of the present invention can be used directly as a solution as an antiperspirant composition. Various examples of suitable antiperspirant compositions are described in the above-mentioned co-pending patent applications. That is, one aspect of the present invention provides an antiperspirant composition comprising an aqueous solution of the basic aluminum compound and amino acid according to the present invention and an auxiliary agent such as a fragrance, a thickener, an alcohol, or a propellant. . The antiperspirant composition may be in the form of a lotion consisting of an aqueous or hydroalcoholic solution containing a concentration of 1 to 30% by weight of a basic aluminum compound and a thickening agent of 0.1 to 5% by weight. Suitable thickeners for antiperspirant lotions are well known in the art and include, for example, magnesium aluminum silicate.
Thickening can also be achieved by emulsifying oils and the like in the composition. Furthermore, the composition may be a water or hydroalcoholic solution of a basic aluminum compound at a concentration of 1 to 30% by weight, an amino acid and a fragrance of 0.1 to 2% by weight. The composition can also be a hydroalcoholic solution of a basic aluminum compound and a neutral amino acid containing up to 75% by weight of _C1 - _C3 aliphatic alcohol. Hydroalcoholic compositions of this type preferably contain ethanol, propanol, isopropanol or mixtures thereof as alcohol. The use of amino acids is particularly useful in hydroalcoholic solutions of basic aluminum compounds, since hydroalcoholic solutions tend to gel much more easily than simple aqueous solutions. An antiperspirant composition comprising an aqueous solution of a basic aluminum compound and an amino acid may contain from about 1 to 80% by weight of a propellant. The invention also encompasses packaging that combines an antiperspirant composition comprising an antiperspirant active of the invention and an applicator for applying the antiperspirant composition to the skin. The applicator of the package is a container with a valve that discharges the liquid in the form of an aerosol, and the antiperspirant composition can be a water or hydroalcoholic solution of a basic aluminum compound and an amino acid.
In this case, the aqueous solution may be evacuated by propellant gas or by a hand pump, or the composition may be placed in a flexible container and the composition may be forced out of the spray valve by compressing the container. It can also be discharged. Other packaging formulations include those in which the applicator is a roll-on applicator and the antiperspirant composition is a water or hydroalcoholic solution of the antiperspirant active and amino acids. Method for measuring aluminum content in a polymer having a size of 100 angstroms or more The heat-treated basic aluminum compound described herein is quantified by molecular sieve chromatography. For this ^purpose , a 1.2 m
Use a ×6.0mm column. The silica, commercially available as Porasil AX, is previously deactivated to eliminate adsorption in molecular size separations. For information on using Porasil silica beads as column packing in chromatography, see KHAltget and L. Segan: “Gel
Permeation Chromatography”, 1971, 16−18
There is a description on the page. Heat treated aluminum before use
Large samples of chlorohydrate (e.g. 2
% W/W solution) in one pass.
The sample to be treated was dissolved in deionized water to approximately 0.2 M aluminum and sonicated (4
Disperse completely by 1 minute). Approximately 0.1 ml of sample of approximately 0.2M aluminum solution was applied to the column via a sampling ring and using a peristaltic pump.
Elute with 10 ^-2 M aqueous hydrochloric acid. A refractive index monitor device connected to a pen recorder is used to examine the eluting fraction. The eluting fractions are collected and aluminum is quantified by atomic absorption spectrometry. Directly quantify other samples of the same volume to determine the value when all aluminum in each sample is completely eluted. The proportion of total aluminum appearing in the fraction eluted in the interstitial volume of the column gives the proportion derived from polymers with an effective diameter of 100 angstroms or more. This polymerization is not observed in the untreated aluminum chlorohydrate solution. Determination of Moisture Content in Powdered Materials The moisture content in powdered materials is determined by thermogravimetric analysis (TGA). When heated to 1000℃, aluminum
Chlorohydrate causes the following reaction. Al ₂ (OH) ₅ Cl (H ₂ O) _x →Al ₂ O ₃ +HCl↑+(X+2
) H ₂ O↑ Since the Al/Cl ratio in the substance is known (also,
From the weight of experimental anhydrous Al ₂ (OH) _6-a Cla), we determined the amount of water incorporated into each anhydride unit by accurately measuring the weight loss when a known amount of sample was heated to 1000 °C. The number of molecules (X) can be calculated. The calculation formula is as follows. X = (solid weight before heating / solid weight after heating x 102)
−Experimental molecular weight of anhydrous Al ₂ (OH) _6-a Cl _a /18 The water content is
1800X/Experimental molecular weight of anhydrous Al ₂ (OH) _6-a Cl _a + 18X. Next, the present invention will be explained in more detail with reference to Examples. In the examples, parts are parts by weight. Example 1 Aluminum chlorohydrate 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% solution. The solution was heated to 97-100 DEG C. for 10 hours in a screw cap glass bottle and then kept at this temperature for 38 hours. When the resulting solution is cooled to room temperature, the total aluminum becomes a polymer with an effective diameter of 100 angstroms or more.
It was found that 23.9% of The solution was then spray dried and the powder was sieved to obtain a 30-50 micron fraction. Moisture content is 14.3%
It was hot. A solution with antiperspirant activity was prepared by adding deionized water to contain 17.5% of the spray-dried powder described above and 5% glycine. Glycine prevented gelation of the solution. Example 2-19 A number of hydroalcoholic solutions were prepared from a neutral amino acid and the powder obtained as described in Example 1. Ethanol (30%) was mixed with powder (15%) to form a slurry, to which neutral amino acids (5%) were added, followed by water to a total volume of 100%. The neutral amino acids used are as shown below. Examples Neutral amino acids 2 Glycine 3 α-alanine 4 β-alanine 5 Taurine 6 Serine 7 Sarcosine 8 Valine 9 Leucine 10 Proline 11 Methionine 12 Threonine 13 Lysine-hydrochloride 14 Ornithine-hydrochloride 15 Glutamic acid α-methyl ester 16 α-amino -n-butyric acid 17 γ-amino-n-butyric acid 18 5-aminocaproic acid 19 ω-aminocaprylic acid In both cases, the neutral amino acid prevents gelation of the solution, and the effectiveness is independent of the isomeric form of the acid. It was hot. Omitting the amino acids resulted in gelation when left standing. Using the same concentrations of lysine, arginine, aspartic acid and glutamic acid was ineffective, and amino acids other than neutral amino acids did not prevent gelation. Examples 20-22 The following examples demonstrate the use of neutral amino acids in solutions containing high concentrations of ethanol. The solution was prepared by adding ethanol, antiperspirant powder (15%), and neutral amino acids (5%) to 100% with water as described above. The concentrations of ethanol and the neutral amino acids used are shown below. Example % Ethanol Neutral Amino Acids 20 40 Ornithine-HCl 21 50 Leucine 22 60 Valine In each case, the neutral amino acids prevented gelation of the solution. Example 23 70 kg of aluminum chloride with an Al/Cl molar ratio of 1.91 and a water content of 18.8% is dissolved in 630 kg of deionized water at 45°C.
Heated to 120° C. for 3.75 hours under stirring in a stainless steel reactor. Stirring and heating at this temperature were continued for an additional 5.5 hours, then rapidly cooled to 70°C and then gradually cooled to room temperature. The resulting solution contained 41.0% of the total aluminum as polymers with an effective diameter of 100 angstroms or more. Glycine was added to this solution so that the glycine concentration was 7% and the molar ratio of aluminum:glycine was 1. The resulting solution was spray dried at inlet and outlet temperatures of 250°C and 95°C, respectively. 17.5% from this powder
An aqueous solution was prepared, but no gelation occurred.
A 17.5% solution obtained from the powder prepared as described above without the addition of glycine gelled. Example 24 An aluminum chlorohydrate solution (50% solids) with an Al/Cl molar ratio of 2.0 was diluted to 10% with water, stirred and heated in a pressurized stainless steel reactor for 2 hours.
It was heated to 120°C. This temperature was maintained for an additional 3 hours and then cooled to room temperature. One batch of this solution was spray dried at an introduction and ejection temperature of 350°C and 110°C, respectively.
A powder with a total aluminum content of 8% was obtained as a polymer with an effective diameter greater than Å. The empirical formula of this powder was as follows. Al ₂ (OH) _5.06 Cl _0.94 1.7H ₂ O To another batch of the solution prepared above was added enough glycine to give an aluminum:glycine molar ratio of 4.0. The resulting solution was spray dried at inlet and jet temperatures of 250°C and 95°C, respectively. Analysis of the solid gave the following empirical formula: Al ₂ (OH) _5.06 Cl _0.94 1.2H ₂ O (glycine) _0.4
8 In the gelation test, a 20% by weight aqueous solution was prepared from each powder. The powder without glycine gelled within 3 days, while the powder with glycine gelled within 17 days.
After several days, the stock remained liquid. Example 25 Two solutions A and B with the following compositions were prepared using aluminum chlorohydrate powder containing 15% total aluminum in the polymer with an effective diameter greater than 100 Å.

[Table] When those solutions were examined after the first 10 days, solution B
had gelled, whereas solution A was still a fluid liquid. I checked again 14 days later and found that Solution A had not changed. Example 26 Two solutions C and D with the following compositions were prepared using aluminum chlorohydrate powder containing 21% total aluminum in a polymer with an effective diameter greater than 100 Å.

[Table] When those solutions were examined after the first 10 days, solution D
had gelled, but Solution C was still a fluid liquid. When checked again 14 days later, Solution C remained unchanged.

Claims (1)

[Scope of Claims] 1. Consisting of an aqueous solution of basic chloride, bromide, iodide or aluminum nitrate in which the molar ratio of aluminum to chlorine, bromine, iodine or nitrate ions is 6.5 to 1.3:1, and the total amount of aluminum is 2 to 1. 80% by weight
An antiperspirant present in the solution as a polymer having a size of 100 angstroms or more, characterized in that the solution further contains a neutral amino acid. 2. The antiperspirant of claim 1, wherein the amino acid has 2 to 10 carbon atoms. 3. The antiperspirant according to claim 1, wherein the amino acid is glycine, sarcosine, alanine, phenylalanine, valine, leucine, methionine, taurine, ornithine hydrochloride or glutamic acid monomethyl ester. 4 Molar ratio of aluminum and amino acids is 20:1 ~
The antiperspirant according to any one of claims 1 to 3, wherein the ratio is 1:1. 5 The amount of aluminum in the polymer with a size of 100 angstroms or more is between 5 and 60 of the total aluminum.
The antiperspirant according to any one of claims 1 to 4, which is % by weight. 6. The antiperspirant according to any one of claims 1 to 5, wherein the solution further contains a _C1 - _C3 aliphatic alcohol.