WO1996003971A1

WO1996003971A1 - Active compositions against foot smell with a fatty acid oligoglycerine ester content

Info

Publication number: WO1996003971A1
Application number: PCT/EP1995/002766
Authority: WO
Inventors: Manfred Klier; Bernd Traupe; Florian Wolf
Original assignee: Beiersdorf Ag
Priority date: 1994-07-30
Filing date: 1995-07-14
Publication date: 1996-02-15
Also published as: JPH10503498A; EP0772433A1; DE4427075A1

Abstract

Oligoglycerides of branched and/or linear saturated and/or unsaturated monocarboxylic acids with 8 to 14 carbon atoms are used to prevent or control foot smell caused by the decomposition of human foot sweat by Brevi bacteria.

Description

description

Anti-odor preparations containing oligoglycerol esters of fatty acids

The present invention relates to active substances and preparations containing active substances which are effective against foot odor.

Microorganisms in general, but also bacteria in particular, are practically omnipresent. For example, mycobacteria, streptococci, staphylococci and propionibacteria are mainly found on healthy human skin.

Coryneform bacteria also occurring on the skin have recently been made responsible for the development of unpleasant body odor through the decomposition of apocrine sweat.

The typical cheese-like smell of sweaty feet is caused by Brevibacterium spec.

Brevibacteria are also coryneform bacteria. They are facultative anaerobic, gram-positive, cylindrical bacteria. The fact that Brevibacterium spec. The "cheesy" smell caused is no coincidence, as some cheeses, especially when ripening Soft cheese, Brevibacteria play a role (e.g. Brevibacterium linens).

Foot odor is usually combated with conventional deodorants or antiperspirants, analogous to the armpit smell, or simply with water and soap.

In antiperspirants, the development of sweat can be prevented by astringents - primarily aluminum salts such as aluminum hydroxychloride (aluminum chlorohydrate). Apart from denaturing the skin proteins, the substances used for this, depending on their dosage, have a drastic effect on the heat balance of the foot region and should only be used in exceptional cases.

By using antimicrobial substances, the bacterial flora on the skin can be reduced. Ideally, only the odor-causing microorganisms should be effectively reduced. In practice, however, it has been found that the entire microflora of the skin can be impaired.

The sweat flow itself is not affected by this, in the ideal case only the microbial decomposition of the sweat is temporarily stopped.

The combination of astringents with antimicrobial 1 active substances in one and the same composition is also common. However, the disadvantages of both classes of active ingredient cannot be completely eliminated in this way.

Finally, foot odor can also be covered by fragrances, a method that least meets the aesthetic needs of the consumer, since the mixture of foot odor and perfume smells rather unpleasant. However, most cosmetics are perfumed, even if they contain antimicrobial1 substances. Perfuming can also serve to increase the consumer acceptance of a cosmetic product or to give a product a certain flair.

There is an abundance of antimicrobially active substances, in particular also substances which are active “in vitro” against brevibacteria. "In vivo", ie on the human foot, however, brevibacteria colonize deeper layers of the skin, which are far from being attained by the vast majority of antimicrobial substances.

It is therefore generally not sufficient to apply a physiologically compatible, antimicrobial substance to the skin of the feet affected by Brevibacteria.

It was therefore the object of the present invention to provide preparations which, when used, make it possible to combat the foot odor caused by the decomposition of human foot sweat by Brevibacteria "in vivo" or to prevent its formation.

The solution to the problem is

Use of oligoglycerides of branched and / or unbranched saturated and / or unsaturated monocarboxylic acids with 8 - 14 carbon atoms for the prophylaxis or control of the foot odor caused by the decomposition of human foot sweat by Brevibacteria.

Surprisingly, the 01 iogoglycerides according to the invention penetrate into the skin of the foot and selectively combat the Brevibacteria responsible for the foot odor. It is known that fatty acid esters of glycerol have certain antimicrobial effects. It is also known to use glycerol fatty acid esters in deodorising cosmetics. However, the only fatty acid ester that was really considered to be practical is the glycerol onolaurate.

Furthermore, JP-OS Sho-48/019940 describes Taiyo Kagaku Kogyo Co. Ltd. a cosmetic with antiseptic properties is known which is characterized by a content of caprylic acid monoglyceride.

Finally, EP-OS 530 861 describes topical antimicrobial pharmaceutical combinations comprising, in addition to glycerol monocaprylate and glycerol monocaprinate, a mixture of saturated fatty acids.

According to the invention, the 01 igoglycerides are preferably selected from the group of the di- and triglycerides, the di- and triglycerol units of the monocarboxylic acid esters according to the invention being linear, unbranched molecules, ie via the respective OH groups in 1- or 3- Etherified "monoglycerol molecules" are present.

3 2 1 H ₂ C-CH-CH ₂ (glycerin = "monoglycerin") HO OH OH

A small proportion of cyclic di- or triglycerol units and glycerol molecules etherified via the OH groups in the 2-position can be tolerated. However, it is advantageous to keep such impurities as low as possible.

The monocarboxylic acid esters of diglycerol according to the invention are preferably monocarboxylic acid onoesters and are preferred characterized by the following structure (substitution positions indicated):

3'2 '1'

H ₂ C-CH-CH ₂ -0-CH ₂ -CH-CH ₂ -0-CR

HO OH OH

where R 'is a hydrocarbon radical, advantageously a branched or unbranched alkyl or alkenyl radical of 7 to 13 carbon atoms.

The monocarboxylic acid esters of triglycerol according to the invention are preferably monocarboxylic acid onoesters and are preferably characterized by the following structure (substitution positions indicated):

3 "2" 1 2 '1'

H ₂ C-CH-CH ₂ -0-CH ₂ -CH-CH ₂ -0-CH ₂ -CH-CH ₂

HO OH 0 OH OH

C = 0 R "

where R "is a hydrocarbon radical, advantageously a branched or unbranched alkyl or alkenyl radical, alkyl radical of 7 to 13 carbon atoms.

The acids on which these esters are based are

Octanoic acid (caprylic acid) (R 'or R "= -C ₇ H ₁₅ ), nonanoic acid (pelargonic acid) (R' or R" = -C ₈ H ₁₇ ), decanoic acid (capric acid) (R ¹ or R "= -C ₈ H ₁₉ ) undecanoic acid (R ¹ or R "= ^{" C} 10 ^H 21

10-undecenoic acid (undecylenic acid) (R 'or R "= ^{" C} 10 ^H 19

Dodecanoic acid (lauric acid) (R ¹ or R "= ^{" C} 11 ^H 23

Tridecanoic acid (R 'or R "= ~ ^C 12 ^H 25

Tetradecanoic acid (myristic acid) (R ¹ or R "= ^{" C} 13 ^H 27 lo

R 'and R "are selected particularly favorably from the group of unbranched alkyl radicals with odd C numbers, in particular with 9, 11 and 13 C atoms.

In general, the esters of diglycerol are preferred to those of triglycerol.

Are very particularly cheap

Diglycerol monocaprinate (DMC) R '= 9

Triglycerol onolaurate (TML) R "= 11

Diglycerol monolaurate (DML) R '= 11

Triglycerol Monomyristate (TMM) R "= 13.

Diglycerol monocaprinate (DMC) has proven to be the preferred monocarboxylic acid ester according to the invention.

The monofatty acid esters of diglycerol according to the invention are preferably in the 1-position, the monofatty acid esters of triglycerol according to the invention are preferably esterified in the 2'-position.

In the case of the glycerol esters esterified in the 1-position of the glycerol, the 2-position is a center of asymmetry. The 2S and 2R configurations are active and equally advantageous according to the invention.

It has proven advantageous to use racemic mixtures of the stereoisomers.

According to an advantageous embodiment of the present invention, an additional portion of di- or triglycerol esterified in other places is used, as is a portion of the various diesters of di- or triglycerol. Those monocarboxylic acid esters which can be obtained by a process as described in DE-OS 38 18 293 are particularly advantageous.

The diglycerol esters, which are distinguished by two, and the triglycerol esters, which are distinguished by three centers of asymmetry, are effective according to the invention in all their configurations. The diglycerol esters have four, the triglycerol esters eight stereoisomers.

In the diglycerol esters are the 2 and 2 'positions

Asymmetry centers. The 2S2'S, the 2R2'S, the 2S2'R and the 2R2'R configurations are active and equally advantageous according to the invention.

In the triglycerol esters, the 2-, the 2 'and the 2 "-positions are asymmetry centers. According to the invention, the 2S2'S2" S-, the 2R2'S2 "S-, the 2S2'R2" S-, the 2R2'R2 "S, the 2S2'S2" R, the 2R2'S2 "R, the 2S2'R2" R, and the 2R2 'R2 "R configuration.

It has proven advantageous to use racemic mixtures of the stereoisomers.

According to an advantageous embodiment of the present invention, mixtures of one or more monocarboxylic acid esters of diglycerol with one or more monocarboxylic acid esters of triglycerol are used.

According to a further advantageous embodiment of the present invention, one or more monocarboxylic acid esters of diglycerol and / or one or more monocarboxylic acid esters of triglycerol are used in combination with other active ingredients (substitute active ingredients), auxiliaries, blends and / or Additives used. The blends and / or replacement active ingredients are then advantageously present in a concentration of up to 50 parts by weight, preferably up to 35 parts by weight, based on the 100 parts by weight of the total amount resulting from the monocarboxylic acid ester or the monocarboxylic acid esters of diglycerol and / or triglycerol and these substitute active ingredients and / or blends.

According to a further advantageous embodiment of the present invention, one or more monocarboxylic acid esters of diglycerol and / or one or more monocarboxylic acid esters of triglycerol are used in combination with other substances which inhibit the growth of Brevibacteria or kill Brevibacteria.

According to yet another advantageous embodiment of the present invention, one or more monocarboxylic acid esters of diglycerol and / or one or more monocarboxylic acid esters of triglycerol are used in combination with monocarboxylic acid esters of glycerol (ie the "monoglycerol"). These monocarboxylic acid esters of glycerol take on the role of blending agents and / or substitute active ingredients and are preferably used in a concentration of up to 50 parts by weight, preferably up to 35 parts by weight, based on 100 parts by weight of the total amount. which is composed of the monocarboxylic acid ester or the monocarboxylic acid esters of diglycerol and / or triglycerol and these monocarboxylic acid esters of glycerol.

The cosmetic preparations according to the invention against foot odor are particularly advantageously characterized in that the mono- or oligoglycerol esters according to the invention are present in concentrations of 0.05-10.00% by weight, preferably 0.1-5.0 % By weight are present, in each case based on the total weight of the preparations.

The preparations according to the invention which are effective against impure skin can be in the form of liquid compositions which can be applied by means of brushes or scrapers or roll-on devices, as pens and in the form of W / O or O / W water which can be applied from normal bottles and containers. Emulsions, e.g. Creams or lotions.

In addition to water, ethanol and isopropanol, glycerol and propylene glycol, skin-caring fat or fat-like substances such as oleic acid decyl ester, cetyl alcohol, cetyl stearyl alcohol and 2-0ctyldodecanol can be used as customary carriers for the preparation of the preparations according to the invention against impure skin in addition to water, ethanol and isopropanol, glycerol and propylene glycol usual proportions are used as well as slime-forming substances and thickeners, for example Hydroxyethyl or hydroxypropyl cellulose, polyacrylic acid, polyvinylpyrrole idone, but also in small quantities also cyclic silicone oils (polydimethylsiloxanes) and liquid polymethylphenylsiloxanes of low viscosity.

As emulsifiers for the preparation of the preparations according to the invention effective against foot odor, which should advantageously be applied to the feet as liquid preparations, advantageously by means of a cotton ball, and which are present in the preparations in small amounts, for example 2 to 5 weights. %, based on the total composition, can be used as non-ionic types, such as polyoxyethylene fatty alcohol ethers, for example cetylstearyl alcohol polyethyleneglycol ether with 12 or 20 added ethylene oxide units per molecule, cetylstearyl alcohol and sorbitan esters and sorbitan esters. Etiylene oxide compounds (e.g. sorbitan monostearate and polyoxyethylene sorbitan onostearate) and long-chain, high molecular weight waxy polyglycol ethers have been found to be suitable.

In addition to the ingredients mentioned, the preparations according to the invention, the pH of which is preferably e.g. is adjusted to 4.0 to 9.0, in particular 5.0 to 6.5, by customary buffer mixtures, perfume, dyes, antioxidants (for example .alpha.-tocopherol and its derivatives or butylated hydroxytoluene (BHT = 2,6-di tert -butyl-4-methylphenol) in amounts of 0.01 to 0.03%, based on the total composition), suspending agents, buffer mixtures or other customary cosmetic basic substances.

The pH of the preparations according to the invention is advantageously adjusted in the weakly acidic to neutral range, preferably from 4.0 to 7.0, particularly preferably from 5.0 to 6.5.

Depending on the type of product, the amounts of carrier substances to be used can easily be determined by a person skilled in the art by simply trying them out.

The preparations according to the invention are prepared in the customary manner, apart from special preparations which are noted separately in the examples, mostly by simply mixing with stirring, if appropriate with gentle heating. It offers no difficulties. For emulsions fat phase and water phase e.g. prepared separately, optionally with heating and then emulsified.

Otherwise, the usual measures for the composition of galenical formulations, which are known to the person skilled in the art, must be observed. //

Advantageous exemplary embodiments of the present invention follow.

example 1

Aerosol spray

(a) Liquid phase

Wt .- «octyldodecanol 0.50

DMC 0.30

Perfume q.s.

Ethyl alcohol ad 100.00

(b) The liquid phase obtained under (a) is filled into an aerosol container together with a propane / butane 2.7 mixture in a ratio of 39:61.

Example 2

Pump spray

(a)

% By weight

Ethyl alcohol 60.00

Glycerin 1.00

PEG-40 hydrogenated castor oil 2.00

DMC 0.70

Perfume q.s.

(b)

Water to 100.00

The components mentioned under (a) are processed to a homogeneous solution, then slowly with the 11

Water phase (b) filled up. The finished pump spray can then be filled into pump atomizers.

Example 3

Roll on gel

% By weight (a)

1,3-butylene glycol 2.00 hydroxyethyl cellulose 0.50 (e.g. Tylose 4000, Hoechst)

(b)

Ethyl alcohol 60.00

PEG-40 hydrogenated castor oil 2.00 DMC 0.80 perfume q.s.

(c)

Water ad 100.00

The constituents mentioned under (a) are dispersed, water (c) is added, left to swell at room temperature, a solution of the constituents mentioned under (b) is added after about 15 minutes. The resulting mixture is homogenized and can be filled. J3

Example 5

Crayon

% By weight

Hydrogenated castor oil 5.00

Beeswax 6.00

Ceresin (hard ozokerite) 30.00

C ₁₂ _ ₁₅ alcohol benzoates 17.00

DMC 0.70

Perfume q.s.

Octyldodecanol ad 100.00

The ingredients are melted at approx. 75 ° C, mixed well and poured into suitable molds.

Example 6

Roll on emulsion

(a)

% By weight

Triceteareth phosphate 0.30

Octyldodecanol 2.00

C ₁₂ _ ₁₅ alcohol benzoates 2.00

DMC 0.90

C ₁₀ _ _3Q alkyl _acrylates 0.15

(b)

Ethyl alcohol 10.00 perfume q.s.

(c) NaOH 0.05

Water ad 100.00

The constituents mentioned under (a) and (c) are each heated to 75 ° C. with stirring. The components (a) are then added to (c). The mixture is cooled to 35 ° C. A solution is prepared from the components (b), which is heated to 35 ° C. and added to the mixture of (a) and (c) with stirring.

Example 7

Aerosol spray

(a) Liquid phase

% By weight

Octyldodecanol 0.50

TMM 0.65

Perfume q.s.

Ethyl alcohol ad 100.00

(b) The liquid phase obtained under (a) is filled into an aerosol container together with a propane / butane 2.7 mixture in the ratio 39 61.

Example 9

Pump spray

(a)

% By weight

Ethyl alcohol 60.00 Glycerin 1.00 / r

PEG-40 hydrogenated castor oil 2.00

TMM 0.70

Perfume q.s.

(b)

Water to 100.00

The constituents mentioned under (a) are processed to a homogeneous solution, then slowly filled up with the water phase (b). The finished pump spray can then be filled into pump atomizers.

Example 10

Roll on gel

% By weight (a)

(b)

Ethyl alcohol 60.00

PEG-40 hydrogenated castor oil 2.00 TMM 0.90 perfume q.s.

(c)

Water ad 100.00 The constituents mentioned under (a) are dispersed, water (c) is added, left to swell at room temperature, a solution of the constituents mentioned under (b) is added after about 15 minutes. The resulting mixture is homogenized and can be filled.

Example 11

Crayon

% By weight

Hydrogenated castor oil 5.00

Beeswax 6.00

Ceresin (hard ozokerite) 30.00

C _{12 15} alcohol benzoates 17.00

TMM 1, 25

Perfume q.s.

Octyldodecanol ad 100.00

Example 12

Roll on emulsion

(a)

Gew.-X

Triceteareth phosphate 0.30

Octyldodecanol 2.00

^C 12 i5 ^{_All <ono} l- ^Benzo ate 2.00

TMM 1.10

C ₁₀ _ ₃₀ -alkyl 0.15 IT

(b)

Ethyl alcohol 10.00

Perfume q.s.

(c)

NaOH 0.05

Water ad 100.00

Claims

19 patent claims

1. Use of oligoglycerides of branched and / or unbranched saturated and / or unsaturated monocarboxylic acids with 8 - 14 carbon atoms for the prophylaxis or control of the foot odor caused by the decomposition of human foot sweat by Brevibacteria.

2. Use according to claim 1, characterized in that as 01 igoglyceride monocarboxylic acid esters of diglycerol and are characterized by the following structure:

3 '2' 1 '3 2 1

H ₂ , CC - CCHH - CCHH ₂₂ --00 - CCHH ₂₂ --CCHH - CH ₂ -0-CR 'H0 OH OH

3 Use according to claim 1, characterized in that the oligoglycerides are monocarboxylic acid esters of triglycerol and are characterized by the following structure:

3 "2" 1 "3 '2' 1 1

H ₂ C-CH-CH ₂ -0-CH ₂ -CH-CH ₂ -0-CH ₂ -CH-CH ₂

HO OH 0 OH OH

C = 0 R "