CH627367A5 - Product which inhibits the microbial breakdown of lipoid materials to fatty acids - Google Patents

Description

The present invention relates to a product which has the property of inhibiting the degradation of lipoid materials to fatty acids with up to 18 carbon atoms per molecule by microorganisms of the genus Corynebacterium.

Body secretions, for example sweat and menstrual secretions, contain lipoid materials which, when exposed to microorganisms, for example microorganisms of the genus Corynebacterium, are broken down into malodorous fatty acids with up to 18 carbon atoms.

It has now surprisingly been found that products can be produced which contain an active ingredient in such a concentration that the undesired degradation of lipoid materials by microorganisms of the genus Corynebacterium is prevented, but that bacteria continue to maintain their viability.

One of the long-standing problems is that of the unpleasant smell of the menstrual fluid.

The menstrual fluid contains a variety of substances, including proteins and lipids. There is usually a large number of gram-negative and gram-positive organisms in the menstrual fluid that can act on these natural products. It has been recognized that an unpleasant amine odor is released due to the action of bacteria on proteins. When the bacteria act on lipids, unpleasant smelling materials can be formed, which are fatty acids.

The smell of the forearm or the smell of the armpits is also a long-standing problem. The armpit sweat consists of secretions from the apocrine and eccrine sweat glands, which are found in the armpit area. Although the eccrine sweat mainly consists of water and salt, the apocrine sweat contains a large number of substances, including protein, carbohydrates and lipids. A large number of microorganisms, including staphylococci and corynebacteria, are present on the skin surfaces in the armpit area. The microbiological decomposition of the lipids of the apocrine sweat, which leads to the formation of low-molecular fatty acids, has been found to be one of the main reasons for unpleasant armpit odors (Borick et al., Antimicrobial Agents Annual 1960, pages 647-651, Plenum Press , Inc. New York).

Germicides and antibiotics have been used to combat the unpleasant smells of body products such as sweat and menstrual fluid. For example, hexachlorophene was once a popular component of preparations to combat the smell of sweat. However, these results of the action of germicides and antibiotics were achieved by killing the organisms, which leads to a disturbance in the normal balance of the microorganisms. As is well known, killing non-pathogenic organisms favors the establishment of opportunistic organisms such as pathogenic bacteria, yeast or fungi, the presence of which can manifest itself in fever, inflammation, dermatitis or other undesirable phenomena. It is therefore desirable to combat the undesirable body odors caused by the action of microorganisms on lipids in such a way that the non-pathogenic microbial flora is not substantially destroyed. Furthermore, it is desirable to achieve the results without affecting the human patient.

Other methods to combat the appearance of undesirable odors have used products that act on the causative agent after it is formed. This method is generally unsatisfactory because it requires the use of relatively large amounts of the treatment agent and / or long treatment times. Furthermore, the results have not been completely satisfactory in all cases, both in terms of the completeness of the control and the avoidance of side reactions.

The aim of the present invention was to develop a product which inhibits the degradation of lipoid materials into unpleasant smelling fatty acids with up to 18 carbon atoms per molecule by microorganisms, but does not kill the microorganisms which cause this degradation. With the help of these products, the natural microorganism flora appearing on the skin should remain essentially unaffected.

Surprisingly, it has been shown that the desired goals can be achieved by products which contain a salt of ethylenediaminetetraacetic acid as the only active ingredient.

The present invention therefore relates to a product which has the property of inhibiting the degradation of lipoid materials to fatty acids having up to 18 carbon atoms per molecule by microorganisms of the genus Corynebacterium, which is characterized in that this product is the only active ingredient of a salt of ethylenediaminetetraacetic acid contains.

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Preferred salts of ethylenediaminetetraacetic acid contained in the products according to the invention are alkali metal salts or alkanolamine salts of this acid. Of the salts mentioned, particular preference is given to the sodium salts, in particular the disodium salt, the trisodium salt, the tetrasodium salt, or a mixture of the disodium salt and the tetrasodium salt of ethylenediaminetetraacetic acid.

Another preferred salt contained in the products according to the invention is the trialkanolamine salt, specifically preferably the triethanolamine salt of ethylenediaminetetraacetic acid.

The product according to the invention can be a cosmetic composition in solid, liquid, semi-solid form or in the form of an aerosol, this cosmetic composition containing the salt of ethylenediaminetetraacetic acid as an active ingredient. A particularly preferred cosmetic composition according to the invention is a deodorant. Another preferred product according to the invention is a monthly hygiene product which has an absorbent core and a liquid-permeable sheath arranged around the core, the salt of ethylenediaminetetraacetic acid being present on at least those areas of the surface which first come into contact with the menstrual fluid during use is contained, preferably in a concentration of at least 0.0002 g / cm2.

Such monthly hygiene products can be, for example, a sanitary napkin or a tampon. The monthly hygiene product preferably contains the salt of ethylenediaminetetraacetic acid in a concentration of 0.0006 to 0.0155 g / cm 2.

The degradation of lipoid materials in body secretions with the formation of undesired fatty acids is effectively inhibited by the products according to the invention. The term “lipoid materials in body secretions” encompasses lipids or lipids that are present in body fluids, which in turn are secreted, excreted or exuded as secretions. The term “secretions” therefore also stands for waste liquids. Typical secretions are sebum, sweat, menstrual fluid, etc.

In the case of lipids or lipoids, whose degradation by microorganisms leads to the undesirable smelling fatty acids with up to 18 carbon atoms, not only triglycerides but also phosphorus lipids belong.

The triglycerides can be represented by the following general formula I

0

CH ~ -0-C-R

I 2

CH-0-C-R (I)

I 0

I II

CH2-0-C-R

are illustrated, in which the radicals R are identical to or different from one another and come from fatty acids which have the formula R — COOH and which contain a total of up to 18 carbon atoms per molecule.

The phosphorus lipids, the degradation of which can be prevented with the aid of the products according to the invention, include phosphorus triglycerides, which are represented by the following formula II

0

CH2-0-C-R

CH — 0 — C — R (II)

0

H

CH -0-P-0-B

1

0

can be reproduced, in which formula R has the meaning given above and B stands for the remainder of an alcoholamine compound, for example an amino alcohol, a quaternary hydroxyammonium base or a hydroxyamino acid.

When microorganisms act on lipoid materials, products can be formed which are similar to those which are formed in the corresponding chemical hydrolysis. As can be seen from the following equation, glycerol and fatty acids are formed from the triglycerides of the general formula I:

CH "0H

! ^ ch5h + 3 RCOOH

ch2oh

As already mentioned, the three fatty acids are often different from one another in the triglycerides, so that generally different fatty acids are formed. These fatty acids also include low molar, unpleasant smelling fatty acids, such as butyric acid, isobutyric acid, isovaleric acid and the like, which cause the unpleasant smell of sweat and the smell of menstruation. With this degradation of the lipoids, however, higher molecular fatty acids with up to 18 carbon atoms are also formed, and their formation is also inhibited by the products according to the invention.

The undesired fatty acids mentioned can also be formed from the phosphorus lipids of the formula II given above by microorganisms, and the formation is explained using the following reaction scheme:

CH-, 0H t <■

II> CHOH + 2 RCOOH + H-jPO, + BOH

l 3

CH2OH

It can be seen from this reaction scheme that phosphorus lipids can also be a starting material for the formation of the unpleasant smelling fatty acids.

It should be pointed out that the products according to the invention generally have the property of inhibiting the degradation of lipoid materials with the formation of the undesired fatty acids with up to 18 carbon atoms per molecule. Although it is believed that mining is primarily

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Lies according to the above-mentioned reaction schemes, the subject of the invention should not be restricted in any way by the above explanations, because other ways of formation for the fatty acids mentioned from lipoid materials are also conceivable.

As can be seen from the explanations given above, with the help of the products according to the invention the lipid degradation with the formation of the undesired fatty acids should expediently be prevented at the points where the lipoid materials emerge and are subjected to the action of microorganisms. Normally the most important areas of formation are the body surface or the skin surface as well as the vagina, and the undesired lipid degradation should therefore be prevented at these locations or in materials that are in the vicinity of these locations, for example materials that are used for Absorption of body fluids are suitable, such as menstrual pads, clothing, bed pillows and the like.

As already mentioned, the products according to the invention contain a salt of ethylenediaminetetraacetic acid as the only active ingredient which prevents the formation of the undesired fatty acids from lipoid materials by microorganisms.

As already mentioned, preferred salts are alkali metal salts and in particular sodium salts thereof, and alkanolamine salts and thereof in particular ethanolamine salts. However, potassium salts of ethylenediaminetetraacetic acid can also be advantageous for certain applications.

As already mentioned, mixtures of salts of ethylenediaminetetraacetic acid can also be present in the products according to the invention. When they come into contact with water, these salts should preferably provide a pH which is at least 4.0 and particularly preferably in the vicinity of the neutral range, that is to say in the range from about 6.2 to about 8.5, lies.

In general, it is advantageous to use the salts of ethylenediaminetetraacetic acid in the products according to the invention in such amounts that, when the products come into contact with the body secretions, a final concentration of the salts in question of at least 0.01% by weight is ensured. The upper limit is mainly determined by practical circumstances. In general, no further benefit is obtained by adding an amount that results in a concentration greater than about 0.5% by weight based on body secretions. The preferred amounts depend on the purpose, location, type of application and the particular connection. If the microorganism population is large, as in the case of menstrual fluid, larger amounts are preferably used. Thus, to control menstrual odor, at least about 0.04% by weight based on the menstrual fluid is generally desirable, and 0.10% by weight or more is preferred. The preferred ranges lying within the broad range result from the following description of the particular use of the products according to the invention.

As already mentioned, preferred products according to the invention are those for monthly hygiene, which have an absorbent core and a liquid-permeable sleeve arranged around the core. These products contain the salt of ethylenediaminetetraacetic acid at least on those areas of the surface that first come into contact with the menstrual fluid during use. Examples of such products are sanitary towels, tampons or other products used to absorb the menstrual fluid, such as pillows lying between the labia. The liquid-permeable casing of these products can be a soft, knitted, woven or non-woven casing. The absorbent core of this

Products usually consist of layers of fiber, such as carded cotton fleece, air-laid cellulose fiber fleece, cotton wool made from shredded wood pulp or similar materials, but can also consist of newer synthetic materials, such as synthetic polymer foams and fibers.

The salts of ethylenediaminetetraacetic acid can be evenly distributed in the products for monthly hygiene, but it is essential that they are available at least in those areas of the surface that are the first to come into contact with the menstrual fluid. Preferably, these salts of ethylenediaminetetraacetic acid are therefore on the surface of the absorbent core or the liquid-permeable casing of the materials for 15-month hygiene, in particular in such amounts that they are present on these surfaces in an amount of at least 0.0002 g per cm 2 (and especially the upper limit of the concentration is preferably 0.02 g / cm 2). A very particularly preferred range of the salts of ethylenediaminetetraacetic-20 acid in the surfaces in question is the range from 0.0006 to 0.0155 g / cm2 and even more preferably the range from 0.006 to 0.009 g / cm2. It has been shown that if the concentrations of ethylenediaminetetraacetic acid on the surfaces in question of the products for monthly hygiene in the specified ranges are adhered to, it is ensured that when the menstrual fluid is absorbed by the products in question in this body secretion the necessary concentration of the salt of ethylenediaminetetraacetic acid is reached in order to inhibit the undesired degradation of lipoid materials by microorganisms.

The monthly hygiene materials can be marketed in such a way that they already contain the salts of ethylenediaminetetraacetic acid. These salts can also be applied in materials of the permeable casing or the absorbent cores, for example the surface thereof, for example by padding.

However, the products according to the invention can also be formulated in such a way that they represent products which are suitable for application to a product for monthly hygiene immediately before its use. For example, they can be in the form of aqueous solutions, aerosol sprays or dustable powders which contain the salt of ethylenediaminetetraacetic acid as the only active ingredient. 45 Such products are sprayed onto the monthly hygiene products immediately before use in the form of an aqueous spray solution or an aerosol spray, or they are dusted on or applied by any other method. In aerosol sprays, blowing agents such as dichlorodifluoromethane or trichlorofluoromethane can be used, while generally inert solvents, such as isopropanol, are generally used to form the solvent spray. The use of a blowing agent or an inert organic solvent is preferred in comparison to an aqueous solution or a suspension in order to facilitate the drying of the products for monthly hygiene after the application.

However, the products according to the invention can also be in the form of cosmetic compositions which can be applied to the body surface or to places where body secretions can escape, preferably before they emerge. If the products according to the invention are cosmetic products which are applied to the skin surface, such as cosmetic compositions in solid, liquid or semi-solid form or in the form of an aerosol, then these products should expediently be the salt of ethylenediaminetetraacetic acid in such a concentration included that after the on

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It is guaranteed that the products are carried on the surface of the skin so that exuding body secretions absorb this salt in a concentration of at least 0.01% by weight, based on the weight of the body secretions. Such products, such as a deodorant, are preferably applied to the body surface before the body fluid has leaked out. However, it is also possible to apply cosmetic products of this type after the release of body secretions, in which case the degradation of lipoid materials by microorganisms in the body secretions is effectively inhibited. Examples of inert carrier materials which may be contained in such cosmetic products for external use are those which enable the formulation of solid, semi-solid or sprayable products, including lotions, ointments, aerosol spray solutions, aqueous solutions, creams, powder mixtures, Gel pens and the like

Examples of additives and diluents which may be contained in such products are ointment additives such as polysorbate 80 (polyoxyethylene sorbitan monooleate), polyoxyethylene sorbitan trioleate; surfactants and emulsifiers, such as lauryl sulfate, sodium cetyl sulfate, glycerol monostearate, diethylaminoethyl alkyl amide phosphate, isopropyl myristate, octyl alcohol, glycerol and glycol esters of stearic acids; Glycols such as propylene glycol; other polyhydroxy compounds such as glycerin and sorbitol; Alcohols such as ethanol or isopropanol; Witch hazel water; Fragrances; essential oils; Blowing agents, such as halogenated hydrocarbons, for example dichlorodifluoromethane, dichlorofluoroethane, etc., carbon dioxide and nitrogen; solid diluents such as calcium carbonate, starch, bentonite and talc; and silicone-like liquids such as polysiloxane liquids. The choice of special carrier materials depends on the intended use.

In the case of cosmetic products which are intended for application to the skin, that is to say for topical use, the salt of ethylenediaminetetraacetic acid is generally used in a concentration of at least 0.05% by weight, based on the total weight of the cosmetic product. The remainder to 100% will generally consist of an inert carrier material for the main part. However, it is also possible to use the salt of ethylenediaminetetraacetic acid as the main constituent in cosmetic products, although this is generally not desirable for practical reasons. In such cosmetic compositions, the corresponding alkanolamine salts are particularly preferred as salts of ethylenediaminetetraacetic acid.

If such a cosmetic preparation contains an aqueous diluent or carrier material, the salt of ethylenediaminetetraacetic acid can be generated in situ in the preparation of this agent by mixing the free ethylenediaminetetraacetic acid with a corresponding base, for example an alkanolamine, in the aqueous carrier material. In corresponding aqueous cosmetic products, the salt of ethylenediaminetetraacetic acid can be present, for example, in an amount of 2 to 15% by weight, calculated as free acid, based on the total weight of the aqueous cosmetic product.

If the cosmetic product is a lotion, a cream or an aerosol preparation, it is generally advantageous to add the salt of ethylenediaminetetraacetic acid in the form of a solution in a suitable solvent, for example in water, glycerol, propylene glycol, in the preparation of these cosmetic products , Tripropylengly-col, methyl ether, ethanol or similar solvents. However, it is also possible to add the salt of ethylenediaminetetraacetic acid to the otherwise finished cosmetic product and to mix it intimately with it. Such one

Addition is particularly advantageous in the case of dustable cosmetic products, such as dusting powders, or cosmetic products based on aqueous solutions.

The cosmetic products, for example deodorants, can be applied directly to the point at which the undesirable fatty acids can be formed in lipoid materials of body secretions by microorganisms.

Both gram-negative and gram-positive organisms belong to the microorganisms that can decompose lipoid materials with the formation of fatty acids with up to 18 carbon atoms per molecule and which therefore lead to an undesirable development of odor. Examples of microorganisms that can cause the unpleasant smell of menstruation are Gram-negative organisms such as Proteus mirabilis, Klebsiella pneumoniae, Aerobacter aerogenes, Escherichia coli, Pseudomonas aeruginosa etc., gram-positive organisms such as Staphylococcus aureus, Streptococcus faecalis etc. such as Candida Albicans, etc. The microorganisms that lead to the formation of substances that cause armpit sweat odor are those that are normally present on the surface of the skin, of which the bacteria of the genera Corynebacterium and Staphylococcus are the most important.

By using the products according to the invention, the action of the microorganisms, which leads to the formation of the undesired acid, is inhibited or changed to a certain extent. It is believed that the salts of ethylenediaminetetraacetic acid act by removing the necessary metallic cofactor for the enzymatic formation of the fatty acids from the microorganisms. However, the invention is not to be restricted by theoretical considerations, it being noted that the suppression of fatty acid production can be achieved without having a deleterious effect on the microbial flora.

The effectiveness of the salts of ethylenediaminetetraacetic acid in inhibiting the formation of undesirable fatty acids from the lipids is examined by means of gas chromatographic analyzes, and the effectiveness of the odor control can also be assessed by means of organoleptic methods.

In the gas chromatographic analysis, a comparison is made with known acids. The method used is the following:

The fatty acids are extracted from the acidified test samples with the aid of diethyl ether and determined by gas chromatography using a gas chromatograph (Hewlett-Packard 7620A) equipped with a glass column which is 1.83 m (6 feet) long Has an inner diameter of 2 mm and is filled with Porapak QS 80 / particle diameter 0.149 mm (100 mesh). The instrument is programmed from 135 ° to an upper limit of 235 ° and at a heating speed of 40 ° C / min and holds the upper temperature limit for 6 minutes. Helium is used as the carrier gas at a pressure of 4.22 kg / cm2 (60 psi) and a flow rate of 40 ml / min. used.

A quantitative organoleptic evaluation method, which is called the organoleptic evaluation method with a modified evaluation scale, is used to evaluate the effectiveness of the sanitary napkins against odors and is carried out as follows:

Organoleptic evaluation method with modified evaluation scale

This method is structured in such a way that the values obtained from an organoleptic evaluation group enable the sample to be evaluated with an absolute value for the odor intensity. Thus, not only can there be the difference between two samples one in a different environment5

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the odorant (for example on a pillow with or without deodorant), but the evaluation also indicates in a quantitative manner whether the odor intensities of the samples are strong or weak. For example, one sample may contain a deodorant that is significantly more effective than that contained in a second sample. Irrespective of this, however, the two deodorants can only cause a slight reduction in the odor intensity, which can be assessed using the present evaluation method.

The first step in this method is to determine the threshold concentration of the odorant. The method used has been described by Fred H. Steiger in Chemical Technology, Volume 1, page 225, April 1971, in relation to the odor threshold concentration for ethylamine and uses the Weibull distribution function. More generally, organoleptic values are determined in this procedure with the help of a group of subjects who are confronted with a series of samples in which the odorant contains increasing concentrations in order to determine the concentration at which an arbitrarily fixed percentage of the subjects can detect the smell. For the purposes of the present evaluation, this arbitrary percentage is selected as a cumulative percentage of 50%. The threshold concentration of the odorant determined in this way is specific for the odorant and the conditions of sampling and sample presentation.

The method used in accordance with the invention is to provide each subject with a series of samples in a sample device that includes an opaque 0.5 liter (1 pint) Mason polyethylene bottle with a polyethylene screw cap. The inside of the bottle is lined with a polyethylene bag and the lid is fitted with a Büchner funnel, the narrow outlet of which lies below the filter plate and extends through the cap and into the lined bottle. A sample is then placed in the bottle, the hatch closed with the Büchner funnel, after which a watch glass is placed on the wide inlet area of the funnel. Then the sample is allowed to equilibrate for one hour under room conditions. Samples containing an aqueous solution of the fragrance with a specific fragrance concentration are used to determine the threshold concentration, a total of 3 ml of the solution being introduced into the bottle. A group of about 30 women is then given a series of equilibrium samples of increasing concentration and the subjects are asked to start with the zero concentration sample, which contains only water, to indicate the first sample that has a detectable odor . The subjects are then instructed to smell each sample in turn, with a 30 second pause between each sample and the next sample. The values obtained are used to determine the cumulative percentage of subjects who smell. The values determined in this way are applied to the Wei-Bull probability paper described in the Steiger article mentioned above, by plotting the concentration on the abscissa and the cumulative percentage of the test group on the ordinate. The concentration at 50% is then taken as the threshold concentration.

After the determination of the threshold value, the method with the modified evaluation scale is applied by creating a calibration curve. Using the same test device, a series of samples are prepared and made available to the experimental group who performed the

Contain odorant in concentrations that correspond to multiples of the threshold concentration or odor units. One of these samples contains 20 times the threshold concentration (20 odor units). In accordance with the standard method of ratio evaluation, each subject is asked to evaluate the group of samples available to them and to assign each sample a value in terms of the odor intensity in relation to the intensity of the other samples. The test subjects can use any scale. For example, a test person can assign the highest number to the evaluation number 10. A sample that has half the intensity when evaluating this test person is then assigned the evaluation number 5. The values determined then comprise a series of evaluation figures for each test subject, each series being based on the individual scale of the test subject. An arbitrary score of 100 is then arbitrarily assigned to the sample with a concentration that corresponds to 20 times the threshold concentration. The evaluations of each individual test subject are then converted in such a way that the basis 100 for the 20-fold threshold concentration is obtained for the individual standards. For example, the evaluation of the test subject who has given the evaluation number 10 to a first sample with a concentration which corresponds to the 20-fold threshold concentration is converted such that the first sample receives a value of 100 and the second sample receives a value of 50. The values are then grouped in such a way that for each sample that corresponds to a certain multiple of the threshold concentration, there is a specific evaluation number (the 20-fold threshold concentration = 100), which is based on the same scale for all test subjects and corresponds to the assessment of the test subject. The geometric mean of the ratio values of each sample is then calculated and the value is defined as the ratio value for this multiple of the threshold concentration.

If the logarithm of the ratio on the ordinate is plotted against the logarithm of the multiple of the threshold concentration, a straight line attached to the points of the stings up to 20 times the threshold concentration gives an excellent correlation.

It has been shown that regardless of the amine odor substance investigated, when determining the threshold concentration for the particular odor substance and determining the calibration curve in the above manner, calibration curves are obtained which can be superimposed between multiples of the threshold concentration of approximately 3 to approximately 20.

The curve determined in this way for isobutyric acid, a chemically dissimilar material, is also in agreement with the calibration curves of the amines. Thus, the comparative odorant used in any investigation need not be chemically dissimilar to the investigated odor component or components.

The calibration curve can now be used to assess the odor intensity of any odorant when placed in any environment, such as a pillow made of untreated cellulose fibers or a pillow made of fibers containing a deodorant material, so that in addition to a comparison of the relative intensities of the examined samples an absolute measure of the intensity of each sample can be obtained. For this purpose, the test group is provided with a series of samples, including a standard sample, which contains the investigated odorant in known concentration in an environment which is identical to the environment used to determine the calibration curve. This standard sample preferably has a 20-fold threshold concentration and thus a ratio of 100 on the calibration curve.

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Subjects are again asked to rate the series of samples using any scale. Based on the value assigned to each subject's intensity of the standard sample, all other subjects' values are converted accordingly so that they are consistent with the evaluation of the standard sample. For example, the values of a test subject who has assigned the evaluation number 50 to the standard sample and the evaluation number 5 to a second sample of unknown intensity are converted in such a way that the standard receives the ratio value of 100 and the unknown sample receives a ratio value of 10. By comparison with the calibration curve, it can be determined that the ratio value 10 of the second sample determined by the test subject is equivalent to an odor intensity of a certain multiple of the threshold concentration for which it can be read from the calibration curve 1, 2, which means that the odor intensity of the sample unknown intensity in the applied test environment is equal to the intensity of a sample containing the odorant in a concentration that corresponds to 1.2 times the threshold concentration in the standard environment.

Preliminary investigations into the smell of the menstrual fluid are carried out to detect the presence of phospholipids in the menstrual fluid and the formation of malodorous fatty acids by the microbial flora normally present in the menstrual fluid.

The presence of substantial amounts of phospholipid in the menstrual fluid is determined using a method which consists in heating the phospholipids with perchloric acid to oxidize the organic part of the molecule and convert the phosphorus to a blue phosphoromolybdate, which is determined colorimetrically can.

A detailed description of this procedure can be found on pages 375 to 376 of "Bray's Clinical Laboratory Methods", by Bauer et al., 17th Edition, C.W. Mosby Co., 1969. Ten samples of menstrual fluid are collected in beakers and subjected to phospholipid analyzes. The analyzes show the presence of phospholipids in an amount of 2250 to 4140 ppm, which corresponds to 0.225 to 0.4% of the liquid.

In order to determine the ability of the microorganisms normally present in the menstrual fluid to form malodorous fatty acids, separate samples of sterile human blood are inoculated with various organisms which have previously been isolated from the menstrual fluid. The material is then incubated and a gas chromatographic analysis is carried out in the manner described below. Blood is used in the determination instead of menstrual fluid because sterile blood is available and a sterile substrate is required to identify the fatty acid formation caused by the microorganism with which the blood was inoculated. The suitability of the blood as a substitute is based on the known fact that triglycerides are present in both the blood and the menstrual fluid, and previous tests on six samples of human blood and menstrual fluid have shown that these materials average 2807 ppm and 2771, respectively ppm total phospholipids included. The methods used and the results obtained are the following:

In each case 2.5 ml of test samples of sterile whole human blood are inoculated with 0.2 ml of a suspension of bacterial cells from various test organisms, which were previously isolated from the menstrual fluid in the usual way. The test samples and the non-inoculated control sample are in 24 hours at 37 ° C. incubated in a constant temperature bath with constant shaking at 200 rpm. All samples are then analyzed by gas chromatography. The results obtained are summarized in Table 15 below.

Table A

existing fatty acid (ppm)

20th

Isobutter- Butter- Isovalerian-

acid acid noninoculated control

0

0

3.5

gram-negative bacteria

Proteus mirabilis

59.5

9

111.7

Klebsiella pneumoniae

0

0

11.3

Aerobacter aerogenes

0

8.7

15.0

Escherichia coli

0

0

0

Pseudomonas aeruginosa

0

0

0

gram positive bacteria

Staphylococcus aureus

13.7

0

50.5

Streptococcus faecalis

0

0

39.1

yeast

Candida albicans

12th

0

38.5

The following examples serve to further explain the invention.

example 1

Two samples of menstrual fluid are collected, after which the untreated and non-incubated fluid is first analyzed for fatty acid by gas chromatography, namely isobutyric acid, butyric acid and iso-45 valeric acid. Test samples are then prepared, each containing about 2 ml of the respective menstrual fluid. Then two groups, each containing two different samples of the menstrual fluid, are treated as follows: One group is treated with disodium 50 ethylenediaminetetraacetate to a final concentration of 0.2% by weight, based on the menstrual fluid, while the other group leaves untreated. The treated and the untreated samples are then incubated for 24 hours at 37 ° C. and then gas chromato-55 graphically analyzed for the above-mentioned fatty acids. The results obtained are summarized in Table I below.

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Table I

Fatty acids (ppm)

Isobutter- Butter- Isovalerian-acidic acid

Sample 1 fresh, non-inoculated, untreated control sample incubated, untreated incubated, Na2EDTA treated

0

685.7 0

36 1014.0 16.6

0

857.1 14.3

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Table I (continued)

Fatty acids (ppm)

Isobutter- Butter- Isovalerian-acidic acid

Sample 2 fresh, non-incubated, untreated control sample 0 0 0

incubated, untreated 475.0 307.0 336.0

incubated, treated with Na2EDTA 4.0 13.0 9.0

Example 2

Five samples, each containing 2.5 ml of sterile human blood, are inoculated with 0.2 ml of a suspension of Proteus mirabilis. Disodium ethylenediaminetetraacetate is added to four of the samples in amounts corresponding to 0.04 to 0.2%. A sample is an inoculated control sample that contains no ethylenediaminetetraacetic acid compound. In addition, a non-inoculated control sample is prepared which contains 2.5 ml of the blood to which 0.2 ml of sterile distilled water has been added. The treated and untreated inoculated samples and the non-inoculated control sample are then incubated for 24 hours at 37 ° C in a constant temperature water bath, shaking the samples at 200 rpm. After the end of the treatment period, aliquots are examined by gas chromatography for the presence of acids. The results obtained are shown in Table II below.

Table II

treatment

Fatty acids (ppm)

% Na2 EDTA

Isobutyric acid

Isovaleric acid

Proteus + no Na2 EDTA

102.7

98.2

Proteus + 0.04% Na2 EDTA

28.4

52.3

Proteus + 0.1% Na2 EDTA

6.6

17.5

Proteus + 0.2% Na2 EDTA

7.9

17.6

untreated sterile blood

0

0

Example 3

Sterile blood inoculated with Proteus mirabilis is applied to treated and untreated samples of fluffy kisses and sanitary napkins. To prepare the treated samples, first apply a 14% aqueous solution of a mixture of disodium ethylenediaminetetraacetate and tetra sodium ethylenediaminetetraacetate (pH = 7) at different locations and in different concentrations 20 to samples from down pillows or samples from sanitary napkins, what this is done by impregnating the shell with the material, spraying or padding the material. The samples are then dried and the amount of ethylene diamine tetraacetate salts 25 dispersed in the samples is determined by weighing. Then the blood previously inoculated with Proteus mirabilis is applied to the various treated samples as well as to an untreated sample and to a sample containing dimethylamine as a reference fragrance. (3 ml is used for the down pillows and 5 ml for the 30 month sanitary napkins). The samples are then incubated at 37 ° C. for 24 hours and then sent to the organoleptic examination in the manner described above. The results show a significant reduction in odor, which is shown in Table III below.

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Table III

Percentage reduction of odor1 with different application4 of EDTA

I.

II

III

IV

V

VI

Concentration in that

Paper as

Nonwoven cover

Cotton on the EDTAS

entire

Filters over on the fabric as

Surface embossed g / gdes

Fluff that

Sanitary napkin

Filters over the down

Dispersed area of the investigated

Down pillow

the

Sanitary napkin

Inoculum

Down pillow

0.00052

3rd

46

__

_

_

0.0016

-

-

48

_

-

_

0.0050

-

-

-

52

_

24th

0.0060

-

-

-

-

46

0.0084

-

-

-

-

50

42

0.0100

-

-

_

-

40

0.0140

68

-

_

_

0.0200

-

-

- -

58

0.0330

-

-

-

-

-

1 Compared to the untreated control sample, as a detected smell.

2 Estimated based on the concentration of the EDTA solution that was applied during spraying during fabric fabrication.

3 The dashed lines mean that no examination has been carried out.

4 The methods used to disperse EDTA are: 1) soaking in a 14% aqueous solution, 2) spraying with an aqueous solution, 3) padding (insert into the solution and then squeeze with the help of rollers), 4) padding, 5) spraying with an aqueous solution, 6) spraying with an aqueous solution.

5 The neutral (pH = 7) ethylenediaminetetraacetate solution is obtained by dissolving 10.0 g of tetrasodium ethylenediaminetetraacetate and 11.4 g of disodium ethylenediaminetetraacetate in 125 ml of distilled water. The solution formed has a concentration of about 14% by weight.

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Example 4

In a six-month study, a group of different test subjects was used to wear the sanitary napkins for a minimum of 4 hours or until the menstrual fluid pent up necessitated a change of the sanitary napkin. Within 30 minutes of changing the bandage, the bandages are examined and physical characteristics such as weight, physical appearance and stain area are determined. The bandages are then incubated for 1 hour at 30 ° C. and then examined for their smell. *

This procedure is repeated by each subject with a treated and an untreated (control) bandage used on alternating months. In some cases, the values are determined over the entire duration of six months, while in other cases only values for 2 months or for 4 months are available. The selection of a product for a specific test subject is carried out statistically, so that factors such as the climate or the change in activity have a minimal influence.

The bandages used were made by removing the nonwoven cover of a commercially available sanitary napkin (MODESS Sanitary Napkin from JOHNSON & JOHNSON), passing the absorbent tissue of the inner filling through a solution containing a mixture of disodium ethylenediaminetetraacetate and tetrasodium. contains ethylenediaminetetraacetate (and which has been prepared according to Example 3), the material dries and the liquid-permeable casing is fixed in place again. The concentration of the salt after drying is 0.0006 g / cm2 (0.004 g per square inch) of the fabric.

The odor values of all test subjects who were used during this period are collected and the odor intensity of the test products is compared with that of a control sample. The odor intensity of 25 treated and 25 untreated bandages is reproduced with the help of odor units that range from 0 to 21 (maximum). The untreated bandages show odor units from 3 to 21, with five bandages having odor units above 15. Ten of the bandages treated have odor units less than 3 and there is no treated bandage with an odor unit greater than 11.

Example 5

2 ml samples of diluted human plasma (1 part plasma and 2 parts sterile distilled water) are inoculated with Cory-nebacterium. To three of the samples, disodium ethylene diamine tetraacetate is added in such an amount that concentrations of 0.1, 0.2 and 0.5% result. A sample containing no sodium ethylenediaminetetraacetate serves as an untreated control sample. In addition, a non-inoculated control sample with unmodified diluted human plasma is prepared. The test samples and the control samples are incubated for 24 hours at 37 ° C., shaking at about 200 rpm. After the time has elapsed, the samples are examined by gas chromatography for the content of free fatty acids. The results obtained are as follows.

Table IV

Treatment of fatty acids (ppm)

Isobutyric acid Isovaleric acid untreated sterile plasma 0 0

Corynebacterium inoculum - no Na2EDTA 155 564

Table IV (continued)

Treatment of fatty acids (ppm)

Isobutyric acid isovaleric acid

Corynebacterium inoculum

+ 0.5% Na2EDTA 12 22

Corynebacterium inoculum

+ 0.2% Na2EDTA 25 49

Corynebacterium inoculum

+ 0.1% Na2EDTA 22 41

Example 6

Disodium-ethylenediamine-traacetate is added to a final concentration of 0.5 wt. . A further 2 ml sample of the inoculated broth is not mixed with disodium ethylenediaminetetraacetate. In addition, a 2 ml sample of the sterile brain-heart infusion broth is used as the non-inoculated control sample. The test sample and the control sample are incubated for 24 hours at 37 ° C. with shaking at 200 rpm. After the time has elapsed, the samples are examined by gas chromatography for the free fatty acids. The results obtained are summarized in Table V below.

Table V

Treatment of fatty acids (ppm)

Isobutyric acid isovaleric acid

Sterile BHI broth 0 0

BWI broth inoculated with the forearm bacteria 32 57 BHI broth inoculated with the forearm flora

+ 0.5% Na2EDTA 0 0

Example 7

An aqueous solution containing 0.45% by weight of a mixture of Na2EDTA and Na4EDTA (and which was prepared as in Example 3) is applied to the armpit of a test person using a sterile gauze cushion which has been wetted with the solution. Sterile distilled water is applied in the same way to the other armpit, which serves as an untreated control. Then both armpits are examined by smelling twice a day to determine the odor development and the odor intensity by comparison. The treated armpit shows a very important deodorized effect.

Example 8

A cream which is used to suppress the sweat odor and is to be applied to the skin is prepared by (1) heating the component A specified below to 70 ° C, (2) heating the component B specified below to 75 ° C, (3) adding the Component B with stirring to component A and (4) adjusting the pH to 5.5 with dilute sodium hydroxide solution.

Ingredient A wt% cetyl alcohol 2.5 stearyl alcohol 5.0 isopropyl myristate 2.0 light silicone oil 1.0

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Sodium salt of the reaction product of lactic acid and stearic acid 1.5 (Emplex, Patco Products, Kansas City, Missouri)

Methyl hydroxybenzoate (methyl paraben) 0.15

Propyl hydroxybenzoate (propyl paraben) 0.05 component B

deionized water 78.8

Disodium salt of EDTA 4.0

Propylene glycol 5.0

Example 9

A lotion suitable as a skin lotion for suppressing the smell of sweat is prepared by heating

(1) of component A described below at 72 ° C,

(2) heating component B below to 75 ° C,

(3) Add component B while stirring to component A and

(4) Adjust the pH to 5.3 with dilute sodium hydroxide solution.

deionized water ingredient C fragrance

Component A Cetyl alcohol Stearyl alcohol Isopropyl myristate light silicone oil

% By weight 1.9 3.0 1.3 0.8

Sodium salt of the reaction product of lactic acid and stearic acid 1.1 (Emplex, Patco Products, Kansans City, Missouri)

Methyl hydroxybenzoate (methyl paraben) 0.15

Propyl hydroxybenzoate (propyl paraben) 0.05 component B

deionized water 81.7

Propylene glycol 3.0

Disodium salt of EDTA 7.0

Example 10

The preparations described in Examples 8 and 9 can be applied to the skin surfaces in order to prevent the formation of fatty acids which are formed by the action of co-ryne bacteria on the excreted sebum.

Example 11

A hand or body lotion suitable for odor control is prepared by (1) heating component A below to 82 ° C, (2) heating component B below to 78 ° C, (3) adding component ( A) with stirring to component B and (4) cooling to 46 ° C and adding component C.

Component A% by weight

Mineral oil 3.00

Glyceryl monostearate 5.00

Isopropyl palmitate 3.00

Sterolatum (Amerchol-H-9, Amerchol Products, Inc.) 1.00

Stearic acid 1.50

Propyl hydroxybenzoate (propyl paraben) 0.05

Component B

Methyl hydroxybenzoate (methyl paraben 0.15

2-bromo-2-nitropropane-1,3-diol (Onyxide 500 from Onyx Co.) 0.20

Propylene Glycol - USP 4.00

Glycerin 96% -USP 3.00

Sulfosuccinate half ester (Standapol SHC-301,

Henkel Co.) 2.50

Disodium salt of EDTA 5.0

71.35 0.25

Example 12

By vigorously mixing the following ingredients together, a body powder that is suitable for topical application and fights the smell of sweat is produced:

(Trisodium ethylenediaminetetraacetate talc perfume

10 g 787 g 3 g

Example 13

The preparation described in Example 12 can be applied to the skin surfaces in order to prevent the formation of malodorous fatty acids by the action of co-ryne bacteria on the sebum deposited.

20 Example 14

A menstrual tampon is prepared which has an absorbent compressed cylindrical core made of tissue pulp and short rayon fibers. A neutral mixture of disodium ethylenediaminetetraacetate and tetranetrium ethylenediaminetetraacetate is applied to the front half of the core in an amount of 0.233 mg / cm2 (1.5 mg per square inch). The salt is applied to the surface of the core in the dry state with the aid of an aerosol spray solution which contains dichlorodifluoromethane as the blowing agent. Then you cover the core with a nonwoven cover and fasten a tape at the front end to pull out the tampon by knotting.

Example 15

35 A tampon similar to the menstrual tampon described in Example 14 is made which is coated on two thirds of the front surface of the absorbent core and the liquid permeable sheath with 0.155 mg / cm 2 (1.0 mg per square inch) of trisodium ethylenediaminetetraacetate.

40

Example 16

A cream stick is prepared by mixing the following materials in the appropriate proportions at about 60 ° C:

45 components ozokerite wax carnauba wax candellila wax alkoxylated alcohol

Weight in g 48.0 32.0 64.0 42.0

see above (Emcol 249-3K, Witco Chemical Company)

a mixture of 20% butylated hydroxy anisole, 20% butylated hydroxytoluene and 60% corn oil (Tenox 4 from Eastman Chemical

Products Inc.) 0.8 55 modified bentonite (Benton M-20, National

Lead Company) 80.0

Talc 120.0

Propyl hydroxybenzoate (propyl paraben) 0.8

neutral mixture of Na2EDTA + Na4EDTA 40.0 60 (preparation see footnote 5) of Table III)

The mixture is then poured into cooled molds and a final product in pencil form is obtained by cooling.

Subjects are then provided with two cream sticks labeled Kodenum-65 mers to be used as armpit deodorants, one stick having the above composition and the other stick having a similar composition but not the mixture

11

627 367

contains from the two sodium ethylenediaminetetraacetate salts. The test subjects are not informed which stick contains the EDTA salts.

The subjects treat one armpit with one pin and the other armpit with the other pin, after which qualitative assessments of the odor intensity are carried out. The test results are summarized in Table VI below.

Table VI

Noise intensity through self-assessment

Experimental control armpit Examination armpit person

A

strong no smell

B

very strong no smell

C.

very strong no smell

D

strong no smell

E

strong no smell

F

very bad smell

G

very bad smell

H

very low smell

I.

very bad smell

J

very bad smell

K

very low smell

L

very low smell

M

very bad smell

Example 17

An aerosol preparation is prepared by first mixing the following materials in the stated proportions:

Parts by weight

Micropulverized talc 2.50

Micropulverized Na3EDTA 2.50

Perfume 0.16

anhydrous ethanol 0.20

Isopropyl meristat 0.60

The mixture is then introduced into pressure vessels (spray cans) and the following blowing agents are used in the proportions given: trichloromonofluoromethane (Freon 11,

EGG. duPont de Nemours & Co.) 47.02

Dichlorodifluoromethane (Freon 12,

EGG. duPont de Nemours & Co.) 47.20

Example 18

In an experiment similar to that described in Example 5, test samples are prepared by adding one of the following aminopolycarboxylic acid compounds to sterile plasma inoculated with Corynebacterium: disodium ethylenediamine tetraacetate (Na2EDTA), and one Triethanolamine salt of ethylenediaminetetraacetic acid (TEDTA), which is obtained by adding triethanolamine to aqueous ethylenediaminetetraacetic acid up to a pH of 6.3. The amount in which the two salts are added to the samples is so large that the test medium contains 0.2% by weight of the salt (calculated as free acid). In addition, two control samples are prepared, one from unmodified sterile plasma (not inoculated and containing no aminopolycarboxylic acid compound) and a second control sample, which is an inoculated sample that contains no salt and serves as an untreated control. The samples are incubated and examined for free fatty acids as previously described. The results obtained are as follows:

Table VII

Fatty acids formed (ppm) Isobutyric acid Isovaleric acid untreated sterile plasma

0

0

Corynebacterium inoculum

no EDTA connection

105

187

Corynebacterium inoculum

+ 0.1% Na2EDTA

0

0

Corynebacterium inoculum

+ 0.1% TEDTA

0

0

Example 19

In the manner described in Example 16, a cream stick is prepared by mixing the following materials in the proportions indicated:

Component weight in grams

Ozokerite wax 48.0

Carnauba wax 32.0

Candle purple wax 64.0

alkoxylated alcohol 42.0 (Emcol 249-3K, Witco Chemical Co.)

Mixture of 20% butylated hydroxy anisole, 20% butylated hydroxytoluene and 60% corn oil (Tenox 4, Eastman

Chemical Products Inc.) 0.8 modified bentonite

(Benton M-20, National Lead Co.) 80.0

Talc 120.0

Propyl hydroxybenzoate (propyl paraben) 0.8 triethanolamine salt of

Ethylenediaminetetraacetic acid 50.0

The stick can be applied to the skin surface of the armpit to prevent the formation of smelling fatty acids due to the action of Corynebacterium on lipoid materials.

Example 20

Preparations for topical application, with which the formation of fatty acids from lipoid materials can be inhibited by the corynebacteria, can be prepared by intimately mixing the constituents indicated below in the amounts indicated.

Preparation of ethylenediaminetetraacetic acid 10 triisopropanolamine 17.7 witch hazel water 72.3

Example 21

A mixture suitable for application to the skin tissue is prepared by intimately mixing the following ingredients:

Ethylenediaminetetraacetic acid 10 parts by weight of triethanolamine 13.8 parts by weight of witch hazel water 76.2 parts by weight

This aqueous preparation can be applied to the skin tissue in order to prevent the formation of such fatty acids from the excreted lipoid materials which lead to bad odor, in particular sweat odor. It was found that when the desired area, for example the armpit, was rubbed in, the decomposition of the lipoid materials and thus the development of the sweat odor, which would otherwise arise, for example, due to the action of Corynebacteria on the excreted lipoid materials, can be prevented. Used for use

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a daily job by rubbing in, and this job was repeated as soon as the first hint of odor occurred.

Although in the past the undesirable products formed by the action of the microorganisms on the body secretions were inhibited by the killing of the microorganisms, it has now been found that the desired inhibitory effects can be achieved according to the invention without the necessary killing of the organisms. This results, for example, from the fact that when Proteus mirabilis is grown in heparinized blood at 37 ° C. in the presence or in the absence of disodium ethylenediamine tetraacetate for 24 hours, no harmful effect on the growth of the organisms can be determined, as can be seen from the following table results.

Blood inoculated with Prozeus mirabilis

Bacterial enumeration

0 hours io no Na2EDTA 2% Na2EDTA

lOOxlO4 lOOxlO4

24 hours

182X107 231X107

s

Claims (9)

627 367 2nd PATENT CLAIMS 1. Product which has the property of inhibiting the degradation of lipoid materials to fatty acids with up to 18 carbon atoms per molecule by microorganisms of the genus Corynebacterium, characterized in that the product contains a salt of ethylenediaminetetraacetic acid as the only active ingredient. 2. Product according to claim 1, characterized in that it contains an alkali metal salt or an alkanolamine salt of ethylenediaminetetraacetic acid. 3. Product according to claim 2, characterized in that it contains a sodium salt of ethylenediaminetetraacetic acid, preferably the disodium salt, the trisodium salt, the tetrasodium salt or a mixture of the disodium salt and tetrasodium salt of ethylenediaminetetraacetic acid. 4. Product according to claim 2, characterized in that it contains a trialkanolamine salt, preferably a triethanolamine salt of ethylenediaminetetraacetic acid. 5. Product according to any one of claims 1 to 4, characterized in that it is a cosmetic composition in solid, liquid, semi-solid form or in the form of an aerosol which contains the salt of ethylenediaminetetraacetic acid as an active ingredient. 6. Product according to claim 5, characterized in that it is a deodorant. 7. Product according to one of claims 1 to 4, characterized in that it is a monthly hygiene product which has an absorbent core and a liquid-permeable sheath arranged around the core, at least on those areas of the surface which are first used during use come into contact with the menstrual fluid containing the salt of ethylenediaminetetraacetic acid, preferably in a concentration of at least 0.0002 g per cm2. 8. Product according to claim 7, characterized in that it is a sanitary napkin or a tampon. 9. Product according to claim 7, characterized in that it contains the salt of ethylenediaminetetraacetic acid in a concentration of 0.0006 to 0.0155 g per cm2.