DE102017215323A1 - Polyethyleneimine of low molecular weight as Antitrasnpirant active ingredient as a spray - Google Patents

Abstract

The present application relates to cosmetic products in the form of aerosols which contain a water-in-oil emulsion with a defined homo-polyethyleneimine as an antiperspirant active ingredient. The homo-polyethylenimine is present in the aqueous phase along with selected anions and the water-in-oil emulsion has an acidic to neutral pH. The water-in-oil emulsion containing such homo-polyethylenimine makes it possible to provide sprayable antiperspirant cosmetic products in the form of aerosols which contain no aluminum salts and / or zirconium salts yet are highly effective and have less staining on textiles.

Description

The present application relates to cosmetic products in the form of aerosols which contain a water-in-oil emulsion with a defined homo-polyethyleneimine as an antiperspirant active ingredient. The homo-polyethylenimine (hereinafter also sometimes referred to as "PEI") is present in the aqueous phase along with selected anions and the water-in-oil emulsion has an acidic to neutral pH. The PEI-containing water-in-oil emulsion of the present invention provides for the provision of antiperspirant cosmetic products in the form of aerosols which contain no aluminum salts and / or zirconium salts yet are highly effective and have less staining on textiles.

Furthermore, the present invention relates to a non-therapeutic cosmetic method for preventing and / or reducing transpiration of the body, in which an inventive antiperspirant cosmetic product by means of an aerosol dispenser on the skin, especially on the skin of the armpits, is applied and for at least 1 hour, preferably for at least 2 hours, preferably for at least 4 hours, in particular for at least 6 hours, remains on the skin of the armpits.

An aerosol is a disperse system in which a solid or liquid is very finely dispersed in a gas. The aerosol is usually only when using a suitable spray system by spraying solutions, emulsions or suspensions itself generated, including, for example, spray cans can be used, in which a liquefied compressed gas serves as a propellant gas. When the pressure valve is opened, the propellant-preparation mixture escapes through a fine nozzle, the propellant evaporates and leaves the finely distributed spray material as an aerosol.

Washing, cleansing and caring for one's own body is a basic human need, and modern industry is constantly trying to meet these needs of man in a variety of ways. Especially important for daily hygiene is the permanent elimination or at least reduction of body odor and underarm wetness. Numerous specific deodorant or antiperspirant personal care products are known in the art which have been developed for use in body regions having a high density of sweat glands, especially in the underarm area. These are packaged in a wide variety of dosage forms, for example as powder, in stick form, as aerosol spray, pump spray, liquid and gel-like roll-on application, cream, gel and as impregnated flexible substrates (handkerchiefs).

Prior art cosmetic antiperspirants contain, in addition to at least one oil or a wax and a fragrance component or perfume, at least one antiperspirant compound in the form of aluminum salts and / or aluminum-zirconium salts, in particular in the form of halides and / or hydroxyhalides of aluminum and or zirconium. These antiperspirant compounds reduce sweat secretion of the body by temporarily narrowing and / or obstructing the excretory ducts of the sweat glands, so that the amount of sweat can be reduced by about 20 to 60 percent. On the other hand, they have an additional deodorizing effect due to their antimicrobial effect.

Halides and / or hydroxy halides of aluminum and / or zirconium, combined with the acidic pH of these antiperspirants, can cause unpleasant skin reactions in some users. In addition, the use of the aforementioned antiperspirant compounds can lead to staining on clothing.

A technically important area for the application of cosmetic Aersolsprays is the field of antiperspirant or deodorant cosmetic products. Common antiperspirant spray compositions are frequently known as anhydrous suspensions of the powdered antiperspirant active, usually an aluminum salt, in a liquid carrier, for example a relatively volatile oil such as cyclomethicone. Before spraying, the suspension must be shaken in the propellant gas. A disadvantage of these suspension aerosols is that the valve or nozzle bores can clog at higher concentrations of the active ingredient. In addition, such products cause white spots on the clothes, which are perceived by the consumer to be particularly unpleasant on dark clothing. There have therefore been attempts to spray the antiperspirant salt in dissolved form. However, the formulation of aqueous antiperspirant salt solutions in propellant-containing metal cans causes corrosion problems in the aerosol packaging, so that even with painted spray cans in many cases Corrosion phenomena occur on the can and thus the storage and application periods of such aerosols are significantly reduced.

As a further alternative form of preparation in the prior art water-in-oil emulsions (W / O emulsions) are known which do not lead to corrosion phenomena. However, such W / O emulsions often show a slower release of the antiperspirant drug on the skin so that the antiperspirant performance of these W / O emulsions is not always satisfactory.

The WO 2006/018073 A1 discloses various polyamines, including polyethyleneimines, as alternatives to halides and / or hydroxy halides of aluminum and / or zirconium antiperspirants. These antiperspirant agents are in the WO 2006/018073 A1 described as flocculant, meaning that the light transmission of natural sweat upon contact with the antiperspirant is reduced by at least 10%. The WO 2006/018073 A1 further discloses that the flocculating water-soluble polymers are partially or completely quaternized at a pH of 4 to 8. It will be in the WO 2006/018073 A1 suspected that the antiperspirant effect is due to the fact that the resulting flocculations clog the exits of sweat glands. The formation of flocculations is often perceived by consumers as visually unpleasant, and the flocculations can also get into the clothing and cause stains there.

Object of the present invention was to provide antiperspirant products without halides and / or hydroxy halides of aluminum and / or zirconium, which are formulated as a spray. The antiperspirant active contained in the cosmetic should have an improved or very good antiperspirant effect and less staining on textiles. In addition, it is necessary that corrosion resistance is given to the containers in which the aerosol is stored and sold.

It has now surprisingly been found that the use of certain polyethyleneimines, which are contained in a set to an acidic to neutral pH sprayable water-in-oil emulsion containing certain anions, have an antiperspirant effect which is comparable to the antiperspirant effect of formulations with aluminum salts and / or aluminum-zirconium salts. The antiperspirant products according to the invention contain no antiperspirant halides and / or hydroxy halides of aluminum and / or zirconium. It has also been found in the context of the present invention that the specific homo-polyethyleneimines in the form of a sprayable emulsion can only be formulated as a water-in-oil emulsion. The formulation as a water-in-oil emulsion can also ensure a good skin feel and excellent corrosion resistance compared to the respective storage container in which the sprayable emulsion we stored or traded, guaranteed.

Quantities refer to the propellant-free composition before bottling.

1. 1. Ein schweißhemmendes kosmetisches Produkt, enthaltend:
   • - eine Wasser-in-Öl-Emulsion, umfassend:
     1. a. mindestens ein verzweigtes Homo-Polyethylenimin mit einem Molekulargewicht von 300 bis 10000 g/mol in einer Gesamtmenge von 0,1 bis 20 Gew.-%, wobei das Polyethlenimin einen Anteil von Aminogruppen mit drei Nicht-Wasserstoffatomresten von 20 Mol-% bis 35 Mol-% aufweist, bezogen auf die Molmenge aller Aminogruppen in dem Homo-Polyethylenimin,
     2. b. mindestens einen Wasser-in-Öl Emulgator in einer Gesamtmenge von 0,05 bis 10 Gew.-%,
     3. c. mindestens eine Ölkomponente, die kein Riechstoff und kein ätherisches Öl ist, in einer Gesamtmenge von 1,0 bis 50 Gew.-%, wobei:
        • - sich die Mengenangaben jeweils auf die Gesamtmenge der Wasser-in-Öl-Emulsion beziehen,
        • - die Wasser-in-Öl-Emulsion bzw. die wässrige Phase einen bei 22 °C bestimmten pH-Wert von 2,5 bis 7,5 aufweist und das Polyethylenimin polykationisch vorliegt,
        • - die Wasser-in-Öl-Emulsion bzw. die wässrige Phase mindestens ein Anion enthält, das aus der Gruppe ausgewählt ist, die aus Chlorid, Phosphaten und Sulfat besteht, und
        • - die Wasser-in-Öl-Emulsion keine Halogenide und/oder Hydroxyhalogenide von Aluminium und/oder Zirconium enthält,
   • - mindestens in Treibmittel, und
   • - eine Aerosol-Abgabevorrichtung.
2. 2. Kosmetisches Produkt nach Punkt 1, dadurch gekennzeichnet, dass die Wasser-in-Öl-Emulsion 0,5 bis 10 Gew.-%, bevorzugt 1,0 bis 7,0 Gew.-%, weiter bevorzugt 2,0 bis 5,0 Gew.-% des Homo-Polyethylenimins enthält.
3. 3. Kosmetisches Produkt nach Punkt 1 oder 2, dadurch gekennzeichnet, dass in der Wasser-in-Öl-Emulsion 10%, 30%, 50%, 95,0 Gew.-% oder mehr, bevorzugter 99,0 Gew.-% bis 100 Gew.-%, der enthaltenen Anionen Chloridionen sind.
4. 4. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass die Wasser-in-Öl-Emulsion einen bei 22 °C bestimmten pH-Wert von 2,5 bis 7,0 aufweist, bevorzugt 3,0 bis 5,5, noch bevorzugter 3,3 bis 4,5.
5. 5. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass das Homo-Polyethylenimin ein Molekulargewicht von 500 bis 3000 g/mol, bevorzugt von 1000 bis 2000 g/mol, aufweist.
6. 6. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass der Anteil von Aminogruppen mit einem Nicht-Wasserstoffrest (entsprechend primären Aminogruppen bei alkalischem pH-Wert) 30 bis 45 Mol-% beträgt, bevorzugt 35 bis 42 Mol-%, jeweils bezogen auf die Molmenge aller Aminogruppen in dem Homo-Polyethylenimin.
7. 7. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass der Anteil von Aminogruppen mit zwei Nicht-Wasserstoffresten (entsprechend sekundären Aminogruppen bei alkalischem pH-Wert) 30 bis 45 Mol-% beträgt, bevorzugt 32 bis 40 Mol-%, weiter bevorzugt 34 bis 38 Mol-%, jeweils bezogen auf die Molmenge aller Aminogruppen in dem Homo-Polyethylenimin.
8. 8. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass der Anteil von Aminogruppen mit einem Nicht-Wasserstoffrest 35 bis 42 Mol-% beträgt, der Anteil von Aminogruppen mit zwei Nicht-Wasserstoffresten 34 bis 38 Mol-% beträgt und der Anteil von Aminogruppen mit drei Nicht-Wasserstoffresten 22 bis 30 Mol-% beträgt, jeweils bezogen auf die Molmenge aller Aminogruppen in dem Homo-Polyethylenimin.
9. 9. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass die Gesamtmenge des mindestens einen Wasser-in-Öl-Emulgators 0,2 bis 10,0 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Wasser-in-Öl-Emulsion.
10. 10. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass die Gesamtmenge der mindestens einen Ölkomponente 5,0 bis 45 Gew.-% ist, bevorzugt 10,0 bis 25,0, bezogen auf das Gesamtgewicht der Wasser-in-Öl-Emulsion.
11. 11. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass die Wasser-in-Öl-Emulsion mindestens einen Deodorantwirkstoff in einer Gesamtmenge von 0,0001 bis 15 Gew.-% enthält, bevorzugt 0,5 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Wasser-in-Öl-Emulsion.
12. 12. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass die Wasser-in-Öl-Emulsion weiterhin mindestens ein Anion enthält, das aus der Gruppe ausgewählt ist, bestehend aus Citrat, Lactat, Tartrat und Malat.
13. 13. Kosmetisches Produkt nach einem der vorhergehenden Punkte, dadurch gekennzeichnet, dass die Wasser-in-Öl-Emulsion mindestens einen Riechstoff und/oder mindestens ein Antioxidationsmittel und/oder mindestens ein Konservierungsmittel und/oder mindestens einen Komplexbildner und/oder mindestens ein wasserlösliches mehrwertiges C₂-C₉-Alkanol mit 2 bis 6 Hydroxylgruppen oder ein beliebiges Gemisch dieser enthält.
14. 14. Kosmetisches Produkt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Gewichtsverhältnis zwischen Ölphase, einschließlich ggf. vorhandenen Riechstoffen und ätherischen Ölen, und Wasserphase, einschließlich des Homo-Polyethylenimins, im Bereich von 15 bis 70 (Ölphase) zu 30 bis 85 (Wasserphase) ist.
15. 15. Nicht-therapeutisches kosmetisches Verfahren zur Verhinderung und/oder Reduzierung des Körpergeruchs und/oder der Transpiration des Körpers, bei welchem ein kosmetisches Produkt nach einem der vorhergehenden Punkte mittels einer Aerosol-Abgabevorrichtung auf die Haut, insbesondere auf die Haut der Achselhöhlen, aufgetragen wird und für mindestens 1 Stunde, vorzugsweise für mindestens 2 Stunden, bevorzugt für mindestens 4 Stunden, insbesondere für mindestens 6 Stunden, auf der Haut verbleibt.

The present invention is characterized in particular by the following points:

1. 1. An antiperspirant cosmetic product containing:
   • a water-in-oil emulsion comprising:
     1. a. at least one branched homo-polyethyleneimine having a molecular weight of 300 to 10,000 g / mol in a total amount of 0.1 to 20 wt .-%, wherein the Polyethlenimin a proportion of amino groups with three non-hydrogen atom radicals from 20 mol% to 35 mol %, based on the molar amount of all amino groups in the homo-polyethylenimine,
     2. b. at least one water-in-oil emulsifier in a total amount of from 0.05 to 10% by weight,
     3. c. at least one oil component that is not a fragrance and no essential oil, in a total amount of 1.0 to 50 wt .-%, wherein:
        • - the quantities given refer to the total amount of the water-in-oil emulsion,
        • - the water-in-oil emulsion or the aqueous phase has a pH of 2.5 to 7.5, determined at 22 ° C., and the polyethylenimine is polycationic,
        • the water-in-oil emulsion or aqueous phase contains at least one anion selected from the group consisting of chloride, phosphates and sulphate, and
        • the water-in-oil emulsion contains no halides and / or hydroxy halides of aluminum and / or zirconium,
   • - at least in propellants, and
   • an aerosol dispenser.
2. 2. Cosmetic product according to item 1, characterized in that the water-in-oil emulsion 0.5 to 10 wt .-%, preferably 1.0 to 7.0 wt .-%, more preferably 2.0 to 5 Contains 0 wt .-% of homo-polyethyleneimine.
3. 3. Cosmetic product according to item 1 or 2, characterized in that in the water-in-oil emulsion 10%, 30%, 50%, 95.0 wt .-% or more, more preferably 99.0 wt .-% to 100 wt .-%, of the anions contained are chloride ions.
4. 4. Cosmetic product according to one of the preceding points, characterized in that the water-in-oil emulsion has a pH determined at 22 ° C of 2.5 to 7.0, preferably 3.0 to 5.5, Still more preferably 3.3 to 4.5.
5. 5. Cosmetic product according to one of the preceding points, characterized in that the homo-polyethylenimine has a molecular weight of 500 to 3000 g / mol, preferably from 1000 to 2000 g / mol.
6. 6. Cosmetic product according to one of the preceding points, characterized in that the proportion of amino groups with a non-hydrogen radical (corresponding to primary amino groups at alkaline pH) is 30 to 45 mol%, preferably 35 to 42 mol%, respectively based on the molar amount of all amino groups in the homo-polyethyleneimine.
7. 7. Cosmetic product according to one of the preceding points, characterized in that the proportion of amino groups with two non-hydrogen radicals (corresponding to secondary amino groups at alkaline pH) is 30 to 45 mol%, preferably 32 to 40 mol%, further preferably 34 to 38 mol%, in each case based on the molar amount of all amino groups in the homo-polyethyleneimine.
8. 8. Cosmetic product according to one of the preceding points, characterized in that the proportion of amino groups with a non-hydrogen radical is 35 to 42 mol%, the proportion of amino groups with two non-hydrogen radicals 34 to 38 mol% and the proportion of amino groups with three non-hydrogen radicals 22 to 30 mol%, in each case based on the molar amount of all amino groups in the homo-polyethylenimine.
9. 9. Cosmetic product according to one of the preceding points, characterized in that the total amount of the at least one water-in-oil emulsifier is 0.2 to 10.0 wt .-%, based on the total weight of the water-in-oil Emulsion.
10. 10. Cosmetic product according to one of the preceding points, characterized in that the total amount of the at least one oil component is 5.0 to 45 wt .-%, preferably 10.0 to 25.0, based on the total weight of the water-in-oil -Emulsion.
11. 11. Cosmetic product according to one of the preceding points, characterized in that the water-in-oil emulsion contains at least one deodorant active ingredient in a total amount of 0.0001 to 15 wt .-%, preferably 0.5 to 10 wt .-% , in each case based on the total weight of the water-in-oil emulsion.
12. 12. A cosmetic product according to any one of the preceding points, characterized in that the water-in-oil emulsion further contains at least one anion selected from the group consisting of citrate, lactate, tartrate and malate.
13. 13. Cosmetic product according to one of the preceding points, characterized in that the water-in-oil emulsion at least one fragrance and / or at least one antioxidant and / or at least one preservative and / or at least one complexing agent and / or at least one water-soluble polyvalent C ₂ -C ₉ alkanol having 2 to 6 hydroxyl groups or any mixture thereof.
14. 14. Cosmetic product according to one of the preceding claims, characterized in that the weight ratio between the oil phase, including any existing fragrances and ethereal Oils, and water phase, including the homo-polyethyleneimine, in the range of 15 to 70 (oil phase) to 30 to 85 (water phase).
15. 15. A non-therapeutic cosmetic method for preventing and / or reducing body odor and / or perspiration of the body, wherein a cosmetic product according to one of the preceding points by means of an aerosol dispenser on the skin, in particular on the skin of the armpits applied and remains on the skin for at least 1 hour, preferably for at least 2 hours, preferably for at least 4 hours, especially for at least 6 hours.

The term "antiperspirant" is understood according to the invention to reduce or reduce the perspiration of the sweat glands of the body.

The term "halides and / or hydroxy halides of aluminum and / or zirconium" in the context of the present invention, in particular chlorides, bromides and iodides of aluminum and zirconium and compounds of the formulas Al (OH) _y X and Zr (OH) _z X understood where X in the aforementioned formulas is a halide ion. The invention does not contain halides and / or hydroxy halides of aluminum and / or zirconium in the water-in-oil emulsion, meaning that their content is less than 0.5% by weight, preferably less than 0.1% by weight. , more preferably 0 wt .-%.

Unless indicated otherwise, percentages by weight in the present invention refer to the total amount of the cosmetic agent, without any propellant present.

Essential for the present invention is the presence of at least one branched homo-polyethyleneimine ("PEI"). Homo-polyethyleneimines are generally composed of the following structural units and may be linear or branched.

Branched polyethylenimines can be described by the following schematic partial structural formula, ie a section of the entire structure without illustrated ends, and can have different ratios of primary, secondary and tertiary amino groups.

The polyethyleneimines may also be star-branched.

Branched and unbranched homo-polyethyleneimines have an alkaline pH in aqueous solution. In the acidic pH range, the quaternizable amino groups are present partially to completely quaternized.

It has now surprisingly been found in the context of the present invention that certain branched homo-polyethyleneimines in an acidic to neutral pH range and in combination with certain anions, in particular chloride ions, showed an excellent antiperspirant effect. In particular, when adjusting an acidic pH by means of hydrochloric acid, so that chloride ions are present as anions, an excellent antiperspirant effect could be observed. Even at low Use concentrations of such PEI of about 3 wt .-% could be achieved a comparable antiperspirant effect as with a 10 wt .-% Aluminiumchlorohydratlösung.

The homo-polyethylenimines used according to the invention are branched polyethylenimines which are unmodified, ie have no substituents on the nitrogen atoms apart from hydrogen radicals. According to the invention, homo-polyethyleneimines are furthermore to be understood as meaning that they are composed only of ethyleneimine as the structural unit and have no other comonomers, such as, for example, other alkyleneimine units.

As mentioned above, branched homo-polyethyleneimines may have different ratios of primary, secondary and tertiary amino groups. The homo-polyethyleneimines used in the present invention are those having an amount of tertiary amino groups in an alkaline pH range of 20 mol% to 35 mol% relative to the total amount of the amino groups of the homo-polyethyleneimine. Since the homo-polyethyleneimines according to the invention are present in an acidic pH range, the amino groups are partially or completely quaternized. Therefore, in the present invention, not the proportion of tertiary amino groups is defined in the homo-polyethylenimine, but defines the proportion of amino groups having three non-hydrogen atom radicals as 20 mol% to 35 mol%, based on the molar amount of all amino groups, ie quaternized and non-quaternized amino groups in which homo-polyethyleneimine (ie, based on the sum of all groups having one, two, and three non-hydrogen radicals). The proportion of amino groups with three non-hydrogen atom radicals is according to the invention preferably 21 to 32 mol%, more preferably 22 to 30 mol%, in each case based on the molar amount of all amino groups in the homo-polyethylenimine.

The proportion of amino groups with a non-hydrogen radical (corresponding to primary amino groups at alkaline pH) is according to the invention preferably 30 to 45 mol%, more preferably 35 to 42 mol%, in each case based on the molar amount of all amino groups in the homo-polyethylenimine.

The proportion of amino groups with two non-hydrogen radicals (corresponding to secondary amino groups at alkaline pH) is according to the invention preferably 30 to 45 mol%, more preferably 32 to 40 mol%, more preferably 34 to 38 mol%, in each case based on the molar amount all amino groups in the homo-polyethyleneimine.

In particularly preferred cosmetic compositions according to the invention, the proportion of amino groups with a non-hydrogen radical (corresponding to primary amino groups at alkaline pH) is 35 to 42 mol%, the proportion of amino groups with two non-hydrogen radicals (corresponding to secondary amino groups at alkaline pH). Value) 34 to 38 mol% and the proportion of amino groups with three non-hydrogen radicals 22 to 30 mol%, each based on the molar amount of all amino groups in the homo-polyethyleneimine.

The proportion of primary, secondary and tertiary amino groups, based on the molar amount of all amino groups in the homo-polyethyleneimine can be determined by NMR spectroscopy.

Due to the water solubility of the homo-polyethyleneimine, it can be assumed that the homo-polyethylenimine is in the aqueous phase of the water-in-oil emulsion.

Essential for the present invention is that the water-in-oil emulsion or the aqueous phase has an acidic pH of 2.5 to 7.5 (determined at 22 ° C). The pH of the water-in-oil emulsion is preferably adjusted to a range of from 2.5 to 7.0, more preferably from 3.0 to 5.5, even more preferably from 3.3 to 4.5. As already mentioned, aqueous solutions of unmodified homo-polyethyleneimines have an alkaline pH. In order to bring the pH into the claimed range according to the invention, a pH adjusting agent is used.

According to the invention, the preparation of the water-in-oil emulsion can be carried out so that first a water-in-oil emulsion with the specific homo-polyethyleneimine is prepared, and then the water-in-oil emulsion with an acid of acidic pH Value is set. According to the invention, in particular inorganic acids such as hydrochloric acid, phosphoric acid and / or sulfuric acid are suitable for this purpose. According to the invention, the water-in-oil emulsion or the aqueous phase accordingly contains chloride ions, sulfate ions and / or phosphate ions as inorganic anions, with chloride ions being particularly preferred. With chloride ions the best antiperspirant effect was observed. In preferred embodiments, chloride is therefore included as the inorganic anion. Preferably, the proportion of chloride ions is 10%, 30%, 50%, 95.0% by weight or more, more preferably 99.0% by weight to 100% by weight, of all the anions contained. According to the invention to count sulfate ions also hydrogen sulfates. According to the invention, the phosphates also include hydrogen phosphates and dihydrogen phosphates.

In embodiments of the invention, at least one further anion may be present in addition to chloride, sulfate ions and / or phosphate ions. Further anions may be inorganic anions or organic anions. The organic anions may be, for example, phosphonates, citrate, lactate, tartrate and / or malate. It has been found in the context of the present invention that with the exclusive use of organic anions such as lactate and / or citrate no or only a weak antiperspirant effect was achieved. In preferred embodiments, the water-in-oil emulsion therefore contains lactate and / or citrate in a total amount of less than 0.5 wt%, more preferably 0.1 wt% or less, more preferably or 0 wt. %, based on the total amount of the water-in-oil emulsion.

In preferred embodiments of the invention, apart from chloride ions, sulfate ions and / or phosphate ions, no further anions are contained.

In the present invention, the homo-polyethyleneimines contained in the water-in-oil emulsion have a weight average molecular weight Mw of 300 to 10,000 g / mol, preferably 500 to 3,000 g / mol, more preferably 1,000 to 2,000 g / mol. The average molecular weight Mw can be determined, for example, by gel permeation chromatography (GPC) ( Andrews P: "Estimation of the Molecular Weights of Proteins by Sephadex Gel Filtration"; Biochem. J., 1964, 91, pages 222 to 233 ).

The water-in-oil emulsion according to the invention contains at least one homo-polyethyleneimine in a total amount of 0.1 to 20 wt .-%, based on the total amount of the water-in-oil emulsion. More preferably, the at least one homo-polyethylenimine is contained in a total amount of 0.5 to 10% by weight, more preferably 2.0 to 7.0% by weight, still more preferably 2.5 to 5.0% by weight. %. Due to the excellent antiperspirant effect of homo-polyethyleneimine in the acidic pH range as chloride, sulfate and / or phosphate, in particular as chloride, an excellent antiperspirancy can be obtained even with relatively low use concentrations.

The antiperspirant effect is based on an influence on the sweat gland (s). By influencing the sweat gland (s), the influencing of the sweat gland (s) according to the invention is to be understood as meaning that the secretion of sweat from the excretory duct is avoided or reduced.

The sprayable by means of a blowing agent according to the invention is present in the form of a water-in-oil emulsion. The cosmetic agent according to the invention accordingly contains at least one water-in-oil emulsifier.

The at least one emulsifier is contained in a total amount of 0.05 to 10.0 wt%, more preferably 0.2 to 8.0 wt%, still more preferably 1.0 to 6.0 wt%, more preferably 1.5 to 3.0 wt .-%.

Emulsifiers suitable according to the invention may be selected from anionic, cationic, nonionic, amphoteric, in particular ampholytic and zwitterionic, emulsifiers. However, since the homo-polyethyleneimine according to the invention together with certain anions, in particular chloride, is present and could disturb other ionic constituents, nonionic emulsifiers are particularly preferred according to the invention. In preferred embodiments, the cosmetic agent according to the invention therefore contains only nonionic emulsifiers as emulsifiers.

Water-in-oil emulsifier:

The water-in-oil emulsion according to the invention contains at least one nonionic water-in-oil emulsifier, preferably with an HLB value greater than 1.0 and less than or equal to 7.0, selected from the mono- and diesters of ethylene glycol and the Mono-, di-, tri- and tetra-esters of pentaerythritol with linear saturated fatty acids having 12-30, in particular 14-22 carbon atoms, which may be hydroxylated, and mixtures thereof, as consistency regulator and / or water binder. According to the invention, the mono- and diesters are preferred. C ₁₂ -C ₃₀ fatty acid radicals preferred according to the invention are selected from lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid radicals; particularly preferred is the stearic acid residue. Particularly preferred nonionic water-in-oil emulsifiers according to the invention having an HLB value greater than 1.0 and less than or equal to 7.0 are selected from pentaerythrityl monostearate, pentaerythrityl distearate, pentaerythrityl tristearate, pentaerythrityl tetrastearate, ethylene glycol monostearate, Ethylene glycol distearate and mixtures thereof. Water-in-oil emulsifiers which are particularly preferred according to the invention and have an HLB value of greater than 1.0 and less than or equal to 7.0 are available, for example, as commercial products Cutina® PES (INCI: pentaerythrityl distearate), Cutina® AGS (INCI: glycol distearate) or Cutina® EGMS (INCI: Glycol stearate). These commercial products are already mixtures of mono- and diesters (in the pentaerythrityl esters are also tri- and tetraester contained). According to the invention it may be preferable to use only a single water-in-oil emulsifier. In another preferred embodiment, the compositions according to the invention comprise mixtures, in particular technical mixtures, of at least two water-in-oil emulsifiers. A technical mixture is understood, for example, as a commercial product such as Cutina® PES. In addition to the stated water-in-oil emulsifiers based on the ethylene glycol or pentaerythrityl esters, in a preferred embodiment, at least one further nonionic water-in-oil emulsifier having an HLB value greater than 1.0 and less than or equal to 7, 0 should be included, the proportion of the total weight of nonionic water-in-oil emulsifiers with an HLB value greater than 1.0 and less than or equal to 7.0, but preferably should not be greater than 80%. In a particularly preferred embodiment, the compositions according to the invention contain the at least one additional water-in-oil emulsifier having an HLB value greater than 1.0 and less than or equal to 7.0 only in a proportion by weight of not more than 5% or are free of additional water -in-oil emulsifiers.

• - lineare gesättigte Alkanole mit 12-30 Kohlenstoffatomen, insbesondere mit 16-22 Kohlenstoffatomen, insbesondere Cetylalkohol, Stearylalkohol, Arachidylalkohol, Behenylalkohol und Lanolinalkohol oder Gemische dieser Alkohole, wie sie bei der technischen Hydrierung von pflanzlichen und tierischen Fettsäuren erhältlich sind,
• - Ester und insbesondere Partialester aus einem Polyol mit 3-6 C-Atomen und linearen gesättigten und ungesättigten Fettsäuren mit 12-30, insbesondere 14-22 C-Atomen, die verzweigt und oder hydroxyliert sein können. Solche Ester oder Partialester sind z. B. die Mono- und Diester von Glycerin oder die Monoester von Propylenglycol mit linearen oder verzweigten, gesättigten und ungesättigten C-C-Carbonsäuren, die hydroxyliert sein können, insbesondere diejenigen mit Palmitin-, Isostearin und Stearinsäure, die Sorbitanmono-, -di- oder -triester von linearen gesättigten und ungesättigten C-C-Carbonsäuren, die hydroxyliert sein können, insbesondere diejenigen von Myristinsäure, Palmitinsäure, Stearinsäure oder von Mischungen dieser Fettsäuren und die Methylglucosemono- und -diester von linearen gesättigten und ungesättigten C-C-Carbonsäuren, die hydroxyliert sein können;
• - Sterine, also Steroide, die am C3-Atom des Steroid-Gerüstes eine Hydroxylgruppe tragen und sowohl aus tierischem Gewebe (Zoosterine, z. B. Cholesterin, Lanosterin) wie auch aus Pflanzen (Phytosterine, z. B. Ergosterin, Stigmasterin, Sitosterin) und aus Pilzen und Hefen (Mykosterine) isoliert werden und die niedrig ethoxyliert (1-5 EO) sein können;
• -Alkanole und Carbonsäuren mit jeweils 8-24 C-Atomen, insbesondere mit 16-22 C-Atomen, in der Alkylgruppe und 1-4 Ethylenoxid-Einheiten pro Molekül, die einen HLB-Wert größer 1,0 und kleiner/gleich 7,0 aufweisen,
• - Glycerinmonoether gesättigter und/oder ungesättigter, verzweigter und/oder unverzweigter Alkohole einer Kettenlänge von 8-30, insbesondere 12-18 Kohlenstoffatomen.
• - Partialester von Polyglycerinen mit n = 2 bis 10 Glycerineinheiten und mit 1 bis 5 gesättigten oder ungesättigten, linearen oder verzweigten, gegebenenfalls hydroxylierten C-C-Fettsäureresten verestert, sofern sie einen HLB-Wert von kleiner/gleich 7 aufweisen,
• -sowie Mischungen der vorgenannten Substanzen.

Preferred water-in-oil emulsifiers are:

• linear saturated alkanols with 12-30 carbon atoms, in particular with 16-22 carbon atoms, in particular cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolin alcohol or mixtures of these alcohols, as obtainable in the industrial hydrogenation of vegetable and animal fatty acids,
• - Esters and in particular partial esters of a polyol having 3-6 C-atoms and linear saturated and unsaturated fatty acids having 12-30, in particular 14-22 C-atoms, which may be branched and or hydroxylated. Such esters or partial esters are, for. The mono- and diesters of glycerine or the monoesters of propylene glycol with linear or branched, saturated and unsaturated C 2 -C 4 -carboxylic acids which may be hydroxylated, in particular those with palmitic, isostearic and stearic acid, the sorbitan mono-, -di- or triesters of linear saturated and unsaturated CC carboxylic acids which may be hydroxylated, in particular those of myristic acid, palmitic acid, stearic acid or mixtures of these fatty acids and the methyl glucose mono- and diesters of linear saturated and unsaturated CC carboxylic acids which may be hydroxylated;
• Sterols, ie steroids, which carry a hydroxyl group at the C3 atom of the steroid skeleton and both from animal tissue (zoosterols, eg cholesterol, lanosterol) as well as from plants (phytosterols, eg ergosterol, stigmasterol, sitosterol ) and from fungi and yeasts (mycosterols) which may be low ethoxylated (1-5 EO);
• Alkanols and carboxylic acids having in each case 8-24 C atoms, in particular having 16-22 C atoms, in the alkyl group and 1-4 ethylene oxide units per molecule which have an HLB value greater than 1.0 and less than or equal to 7, Have 0,
• - Glycerinmonoether of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8-30, in particular 12-18 carbon atoms.
• Esterified partial esters of polyglycerols with n = 2 to 10 glycerol units and with 1 to 5 saturated or unsaturated, linear or branched, optionally hydroxylated CC fatty acid residues, if they have an HLB value of less than or equal to 7,
• and mixtures of the aforementioned substances.

According to the invention, it may be preferable to use only a single water-in-oil emulsifier. In another preferred embodiment, the compositions according to the invention comprise mixtures, in particular technical mixtures, of at least two water-in-oil emulsifiers. A technical mixture is understood, for example, as a commercial product such as Cutina® GMS, which is a mixture of glyceryl monostearate and glyceryl distearate. Particularly advantageous additional water-in-oil emulsifiers are stearyl alcohol, cetyl alcohol, glyceryl monostearate, especially in the form of the commercial products Cutina® GMS and Cutina® MD (ex Cognis), glyceryl distearate, glyceryl monocaprate, glyceryl monocaprylate, glyceryl monolaurate, glyceryl monomyristate, glyceryl monopalmitate, glyceryl monohydroxystearate, glyceryl monooleate , Glycerylmonolanolat, Glyceryldimyristat, Glyceryldipalmitat, glyceryl dioleate, propylene glycol monostearate, propylene glycol monolaurate, sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, Sorbitansesquistearat, sorbitan distearate, sorbitan dioleate, sorbitan sesquioleate, sucrose distearate, arachidyl alcohol, behenyl alcohol, Polyethylene glycol (2) stearyl ether (steareth-2), steareth-5, oleth-2, diglycerol monostearate, diglycerol monoisostearate, diglycerol monooleate, Diglycerindihydroxystearat, diglycerol distearate, diglyceryl, Triglycerindistearat, tetraglycerol monostearate, Tetraglycerindistearat, Tetraglycerintristearat, Decaglycerinpentastearat, Decaglycerinpentahydroxystearat, Decaglycerinpentaisostearat, Decaglycerinpentaoleat, Soy Sterol, PEG-1 soy sterol, PEG-5 soy sterol, PEG-2 monolaurate and PEG-2 monostearate.

Preferred cosmetic products according to the invention are characterized in that at least one water-in-oil emulsifier is present in a total amount of 0.1-10% by weight, preferably 0.2-8.0% by weight, and particularly preferably 0, 5-5 wt .-%, based on the total composition, are included. Furthermore, amounts of from 1.0 to 3.0% by weight, based on the total weight of the composition, may also be preferred according to the invention. The HLB values can be calculated according to Griffin. If there are different details in the literature about the HLB value of a substance, that HLB value should be used for the teaching according to the invention which comes closest to the value calculated according to Griffin. If no definite HLB value can be determined in this way, the HLB value which the manufacturer of the emulsifier specifies must be used for the teaching according to the invention. If this is not possible, the HLB value must be determined experimentally.

A particularly preferred group of water-in-oil emulsifiers according to the invention are the poly (C ₂ -C ₃ ) alkylene glycol-modified silicones whose previous INCI name was Dimethicone Copolyol, with the current INCI names PEG-x Dimethicone (with x = 2-20, preferably 3-17, more preferably 11-12), bis-PEG-y dimethicones (with y = 3-25, preferably 4-20), PEG / PPG a / b dimethicones (where a and b independently of one another represent numbers of 2-30, preferably 3-30 and particularly preferred 12-20, in particular 14-18,), bis-PEG / PPG-c / d dimethicones (where c and d independently of one another represent numbers of 10) 25, preferably 14-20 and more preferably 14-16) and bis-PEG / PPG-e / f PEG / PPG g / h dimethicones (where e, f, g and h independently of one another represent numbers of 10-20, preferably 14-18 and more preferably 16, stand). Particularly preferred are PEG / PPG-18/18 Dimethicone, which is commercially available in a 1: 9 mixture with Cyclomethicone as DC 3225 C or DC 5225 C, or as a mixture with dimethicone as DC ES-5227 DM, or PEG / PPG-18/18 dimethicones DC 5227 C, PEG / PPG-4/12 dimethicones, available under the name Abil B 8852, and bis-PEG / PPG-14/14 dimethicones, mixed in a mixture with cyclomethicones Abil EM 97 (Goldschmidt) is commercially available, Bis-PEG / PPG-20/20 dimethicone, which is available under the name Abil B 8832, PEG / PPG-5/3 trisiloxanes (Silsoft 305), and PEG / PPG 20/23 Dimethicone (Silsoft 430 and Silsoft 440). Further preferred W / O emulsifiers according to the invention are poly (C ₂ -C 3) alkylene glycol-modified silicones which are hydrophobically modified with C ₄ -C ₁₈ -alkyl groups, particularly preferably cetyl PEG / PPG-10/1 dimethicone (formerly: cetyl dimethicone Copolyol, available as Abil EM 90 or in a mixture of polyglyceryl-4-isostearate, cetyl PEG / PPG-10/1 dimethicone and hexyl laurate under the trade name Abil WE 09), furthermore alkyl methicone copolyols. These may be used alone or as a mixture of two or more thereof.

Oil-in-water emulsifiers:

The water-in-oil emulsion according to the invention may additionally contain a nonionic oil-in-water emulsifier having an HLB value of more than 7 to 20. These are emulsifiers which are generally known to the person skilled in the art. For ethoxylated products, the HLB value is calculated according to the formula HLB = (100-L): 5, where L is the weight fraction of the lipophilic groups, that is the fatty alkyl or fatty acyl groups, in the ethylene oxide adducts, expressed in weight percent. In selecting nonionic oil-in-water emulsifiers which are suitable according to the invention, it is particularly preferable to use a mixture of nonionic oil-in-water emulsifiers in order to optimally adjust the stability of the water-in-oil emulsions. The individual emulsifier components thereby deliver a proportion to the total HLB value or average HLB value of the oil-in-water emulsifier mixture in accordance with their proportion of the total amount of the oil-in-water emulsifiers. n. However, in another preferred embodiment, the cosmetic products according to the invention may also contain only a single oil-in-water emulsifier having an HLB value in the range from 10 to 19. According to the invention, the water-in-oil emulsions preferably comprise at least one nonionic oil-in-water emulsifier selected from ethoxylated C ₈ -C ₂₄ -alkanols with an average of 10-100 moles of ethylene oxide per mole of ethoxylated C ₈ -C ₂₄ Carboxylic acids with an average of 10-100 moles of ethylene oxide per mole, silicone copolyols with ethylene oxide units or with ethylene oxide and propylene oxide units, alkyl mono- and oligoglycosides having 8-22 carbon atoms in the alkyl radical and their ethoxylated analogs, ethoxylated sterols, partial esters of Polyglycerols having 2 to 10 glycerol units and esterified with 1-4 saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ -C ₃₀ fatty acid residues, provided that they have an HLB value of more than 7, and mixtures of the aforementioned substances. The ethoxylated C ₈ -C ₂₄ alkanols have the formula R ¹ O (CH ₂ CH ₂ O) _n H, where R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 8-24 carbon atoms and n, the average number of ethylene oxide units per molecule, for numbers of 10-100, preferably 10-30 moles of ethylene oxide to 1 mole of caprylic alcohol, 2-ethylhexyl alcohol, Capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical mixtures thereof. Adducts of 10-100 moles of ethylene oxide with technical fatty alcohols having 12-18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol, are suitable.

According to the invention, the water-in-oil emulsions preferably comprise a nonionic emulsifier from the group of the polyalkylene glycol ethers, preferably from the group of the alkoxylated C ₈ -C ₂₄ -alkanols with an average of 10-100 mol of alkylene oxide per mole, preferably from the group of the ethoxylated C ₁₂ -C ₁₈ -alkanols with an average of 10-30 moles of ethylene oxide per mole.

The ethoxylated C ₈ -C ₂₄ -carboxylic acids have the formula R ¹ (OCH ₂ CH ₂ ) _n OH, where R ^{1 is} a linear or branched saturated or unsaturated acyl radical having 8-24 carbon atoms and n, the average number of ethylene oxide Units per molecule, for numbers of 10-100, preferably 10-30 moles of ethylene oxide to 1 mole caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, cetylic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, arachidic acid, Gadoleic acid, behenic acid, erucic acid and brassidic acid and their technical mixtures. Also adducts of 10-100 moles of ethylene oxide with technical fatty acids having 12-18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty acid, are suitable. Particularly preferred are PEG-50 monostearate, PEG-100 monostearate, PEG-50 monooleate, PEG-100 monooleate, PEG-50 monolaurate and PEG-100 monolaurate. Particular preference is given to using the C ₁₂ -C ₁₈ -alkanols or the C ₁₂ -C ₁₈ -carboxylic acids with in each case 10-30 units of ethylene oxide per molecule and mixtures of these substances, in particular ceteth-12, ceteth-20, ceteth-30, steareth- 12, Steareth-20, Steareth-30, Laureth-12 and Beheneth-20. Furthermore, preference is given to using C 8 -C 22 -alkyl mono- and -oligoglycosides. C ₈ -C ₂₂ -alkyl mono- and -oligoglycosides are known, commercially available surfactants and emulsifiers. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8-22 carbon atoms. With regard to the glycoside radical, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of up to about 8, preferably 1-2, are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products. Products available under the name Plantacare® contain a glucosidically bonded C ₈ -C ₁₆ -alkyl group on an oligoglucoside radical whose average degree of oligomerization is 1-2, in particular 1.1-1.4. Particularly preferred C ₈ -C ₂₂ alkyl mono- and oligoglycosides are selected from octyl glucoside, decyl glucoside, lauryl glucoside, palmityl glucoside, isostearyl glucoside, stearyl glucoside, arachidyl glucoside and behenyl glucoside and mixtures thereof. The glucamine-derived acylglucamides are also suitable as non-ionic oil-in-water emulsifiers. Ethoxylated sterols, in particular ethoxylated soy sterols, are also oil-in-water emulsifiers which are suitable according to the invention. The degree of ethoxylation must be greater than 5, preferably at least 10, in order to have an HLB value greater than 7 to 20. Suitable commercial products are, for. PEG-10 Soy Sterol, PEG-16 Soy Sterol and PEG-25 Soy Sterol. Furthermore, partial esters of polyglycerols having 2 to 10 glycerol units and having 1 to 4, saturated or unsaturated, linear or branched, optionally hydroxylated C ₈ -C ₃₀ fatty acid residues are preferably esterified, provided that they have an HLB value in the range of more than 7 to 20 have. Particularly preferred are Diglycerinmonocaprylat, Diglycerinmonocaprat, diglycerol, Triglycerinmonocaprylat, Triglycerinmonocaprat, triglycerol, Tetraglycerinmonocaprylat, Tetraglycerinmonocaprat, Tetraglycerinmonolaurat, Pentaglycerinmonocaprylat, Pentaglycerinmonocaprat, Pentaglycerinmonolaurat, Hexaglycerinmonocaprylat, Hexaglycerinmonocaprat, Hexaglycerinmonolaurat, Hexaglycerinmonomyristat, Hexaglycerinmonostearat, Decaglycerinmonocaprylat, Decaglycerinmonocaprat, decaglyceryl monolaurate, decaglyceryl monomyristate, Decaglycerinmonoisostearat, decaglycerol monostearate, Decaglycerinmonooleat , Decaglycerinmonohydroxystearat, Decaglycerindicaprylat, Decaglycerindicaprat, Decaglycerindilaurat, Decaglycerindimyristat, Decaglycerindiisostearat, Decaglycerindistearat, Decaglycerindioleat, Decaglycerindihydroxystearat, Decaglycerintricaprylat, Decaglycerintricaprat, Decaglycerintrilaurat, Decaglycerintrimyristat, Decaglycerintriisostearat, Decaglycerintristearat, Decaglycer intrioleate and decaglycerol trihydroxystearate. Other particularly suitable oil-in-water emulsifiers are polyethylene glycol derivatives of hydrogenated castor oil (PEG-Hydrogenated Castor Oil). The nonionic oil-in-water emulsifier may according to the invention preferably in a total amount of 0.5-5 wt .-%, more preferably 1-4 wt .-% and exceptionally preferably 1.5-3 wt .-%, based on the total composition, be included.

The water-in-oil emulsion of the cosmetic product according to the invention further contain at least one oil component in a total amount of 1.0 to 50 wt .-%. Under oil component are to understand cosmetic oils according to the invention. For the purposes of the present invention, the term "cosmetic oil" means an oil which is suitable for cosmetic use and which is immiscible with water in all amounts. The cosmetic oil used according to the invention is neither fragrances nor essential oils.

The water-in-oil emulsion of the cosmetic product of the present invention contains as a cosmetic oil at least one substance selected from the group of cosmetic oils which are liquid at 20 ° C and 1013 hPa.

In the context of the present invention, the cosmetic oil which is liquid at 20 ° C. and 1013 hPa is selected from the group of (i) volatile cyclic silicone oils, in particular cyclic and linear silicone oils; (ii) volatile non-silicone oils, especially liquid paraffin oils and isoparaffin oils; (iii) nonvolatile silicone oils; (iv) non-volatile non-silicone oils; and (v) their mixtures.

According to the invention, the term "volatile oil" denotes oils which have a vapor pressure of 2.66 Pa to 40,000 Pa (0.02 to 300 mm Hg) at 20 ° C. and an ambient pressure of 1013 hPa, preferably 10 to 12,000 Pa (0, 1 to 90 mm Hg), more preferably from 13 to 3000 Pa (0.1 to 23 mm Hg), especially 15 to 500 Pa (0.1 to 4 mm Hg).

In addition, the term "nonvolatile oils" in the context of the present invention means oils which have a vapor pressure of less than 2.66 Pa (0.02 mm Hg) at 20 ° C. and an ambient pressure of 1.103 hPa.

It may be preferred according to the invention to use mixtures of volatile silicone oils and volatile non-silicone oils in the antiperspirant cosmetic products according to the invention, since this results in a drier skin feel. Furthermore, in the context of the present invention, it may be preferred for the antiperspirant cosmetic products to comprise a non-volatile silicone oil and / or a non-volatile non-silicone oil to mask insoluble constituents, such as talc or skin-dried ingredients.

Particularly preferred according to the invention is the use of mixtures of nonvolatile and volatile cosmetic oils, since in this way parameters such as skin feel, visibility of the residue and stability of the antiperspirant cosmetic agent according to the invention can be adjusted and the agent can thus be better adapted to the needs of the consumer.

Volatile cosmetic oils are usually selected from cyclic silicone oils having the INCI name Cyclomethicone. The INCI name cyclomethicones is understood to mean, in particular, cyclotrisiloxane (hexamethylcyclotrisiloxane), cyclotetrasiloxane (octamethylcyclotetrasiloxane), cyclopentasiloxane (decamethylcyclopentasiloxane) and cyclohexasiloxane (dodecamethylcyclohexasiloxane). These oils have a vapor pressure of about 13-15 Pa at 20 ° C. Cyclomethicones are known in the art as well-suited oils for cosmetic compositions, especially for deodorizing compositions such as sprays and sticks. Due to their persistence in the environment, it may be preferred according to the invention to dispense with the use of cyclomethicones. In a particularly preferred embodiment, the water-in-oil emulsions used according to the invention contain 0 to less than 1% by weight, preferably not more than 0.1% by weight, of cyclomethicone, based on the weight of the water-in-oil emulsion , where existing propellant is not taken into account. A cyclomethicone substitute preferred according to the invention is a mixture of C ₁₃ -C ₁₆ -lsoparaffins, C ₁₂ -C ₁₄ -isoparaffins and C ₁₃ -C ₁₅ -alkanes whose viscosity is in the range from 2 to 6 mPas at 25 ° C. and a vapor pressure at 20 ° C in the range of 10 to 150 Pa, preferably 100 to 150 Pa has. Such a mixture is z. B. under the name SiClone SR-5 from Presperse Inc. available. Further preferred volatile silicone oils are selected from volatile linear silicone oils, especially volatile linear silicone oils having 2-10 siloxane units, such as hexamethyldisiloxane (L2), octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), as described e.g. In the commercial products DC 2-1184, Dow Corning® 200 (0.65 cSt) and Dow Corning® 200 (1.5 cSt) from Dow Corning, and low molecular weight phenyl trimethicone having a vapor pressure at 20 ° C of about 2000 Pa as available, for example, from GE Bayer Silicones / Momentive under the name Baysilone Fluid PD 5. Preferably, according to the invention, the water-in-oil emulsion contains at least one volatile silicone oil, which may be cyclic or linear, because of the drier skin feel and the faster release of the active ingredient. More preferably, the water-in-oil emulsion according to the invention contains at least one volatile non-silicone oil because of the drier skin feel and the faster release of the active ingredient. Preferred volatile non-silicone oils are selected from C ₈ -C ₁₆ isoparaffins, in particular from isononane, isodecane, isoundecane, isododecane, isotridecane, Isotetradecane, isopentadecane and isohexadecane, and mixtures thereof. Preference is given to C ₁₀ -C ₁₃ isoparaffin mixtures, in particular those having a vapor pressure at 20 ° C. of 10-400 Pa, preferably 13-100 Pa. Furthermore, the water-in-oil emulsion according to the invention preferably contains at least one nonvolatile cosmetic oil selected from nonvolatile silicone oils and non-volatile non-silicone oils. Residues of components insoluble in the composition, such as antiperspirant actives (= antiperspirant aluminum salts) or talc, can be successfully masked with a nonvolatile oil. In addition, with a mixture of different oils, especially non-volatile and volatile oils, parameters such as skin feel, residue visibility and stability of the composition of the invention can be finely regulated and better adapted to consumer needs. Agents preferred according to the invention are characterized in that the cosmetic oil, which is not a perfume and an essential oil, at least a volatile oil having a vapor pressure of 10-3000 Pa at 20 ° C, which is no perfume and no essential oil, in a total amount from 0.1 to 100% by weight, more preferably from 10 to 90% by weight, based in each case on the total weight of the cosmetic oils.

Of course, it is also possible according to the invention to formulate the water-in-oil emulsion with a low proportion of volatile oils, based on the total weight of the medium - or even without volatile oils. Non-volatile oils which are particularly preferred according to the invention are esters of linear or branched saturated or unsaturated fatty alcohols having 2-30 carbon atoms with linear or branched saturated or unsaturated fatty acids having 2-30 carbon atoms which may be hydroxylated. It should be noted that some esters of linear or branched C ₁ -C ₂₂ -alkanols or C ₁₄ -C ₂₂ -alkenols and some triesters of glycerol with linear or branched C ₂ -C ₂₂ -carboxylic acids, which may be saturated or unsaturated, under normal conditions, such as cetyl stearate or glycerol tristearate (= stearin). According to the invention, these esters which are solid under normal conditions do not constitute cosmetic oils, since they do not fulfill the condition "liquid under normal conditions". The assignment of whether such an ester is liquid or solid under normal conditions is within the general knowledge of those skilled in the art. Preferred are esters of the linear or branched saturated fatty alcohols having 2-18 carbon atoms with linear or branched saturated or unsaturated fatty acids having 3-18 carbon atoms which may be hydroxylated. Preferred examples thereof are isopropyl palmitate, isopropyl stearate, isopropyl myristate, 2-hexyldecyl stearate, 2-hexyldecyl laurate, isodecyl neopentanoate, isononyl isononanoate, 2-ethylhexyl palmitate and 2-ethylhexyl stearate. Also preferred are isopropyl isostearate, isopropyl oleate, isooctyl stearate, isononyl stearate, isocetyl stearate, isononyl isononanoate, isotridecyl isononanoate, cetearyl isononanoate, 2-ethylhexyl laurate, 2-ethylhexyl isostearate, 2-ethylhexyl cocoate, 2-octyl dodecyl palmitate, butyloctanoic acid 2-butyl octanoate, diisotridecyl acetate, n-butyl stearate, n-hexyl laurate , n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, ethylene glycol dioleate, ethylene glycol dipalmitate, n-hexyl laurate, n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate, C ₁₂ -C ₁₅ alkyl lactate and di-C ₁₂ -C ₁₃ alkyl malate and the benzoic acid esters of linear or branched C _8-22 alkanols. Particularly preferred are benzoic acid C ₁₂ -C ₁₅ alkyl esters, for. B. available as a commercial product Further preferred oil components according to the invention are selected from the C ₈ -C ₂₂ fatty alcohol esters of monohydric or polyhydric C ₂ -C ₇ hydroxycarboxylic acids, in particular the esters of glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and salicylic acid. Such esters based on linear C14 / 15-alkanols, eg. B. C ₁₂ -C ₁₅ -alkyllactate, and of branched in 2-position C12 / 13-alkanols are under the trade name Cosmacol® Nordmann, Rassmann GmbH & Co., Hamburg, refer, in particular the commercial products Cosmacol® ESI, Cosmacol® EMI and Cosmacol® ETI, Finsolv® TN (C ₁₂ -C ₁₅ alkyl benzoate), and isostearyl benzoate, e.g. Available as Finsolv® SB, 2-ethylhexyl benzoate, e.g. B. available as Finsolv® EB, and benzoic acid 2-octyldodecylester, z. Available as Finsolv® BOD.

Particularly advantageous has been the use of isopropyl esters of C ₁₂ -C ₁₈ carboxylic acids, in particular the use of isopropyl myristate, and particularly preferred mixtures of isopropyl myristate with C ₁₀ -C ₁₃ isoparaffin mixtures and / or volatile silicone oils proven. Another particularly preferred ester oil is triethyl citrate.

The water-in-oil emulsion is preferably characterized in that it contains an ester of a C ₃ -C ₃₀ -carboxylic acid, preferably an ester from the group 2-ethylhexyl palmitate, isopropyl palmitate and triethyl citrate.

Products preferred according to the invention may contain branched saturated or unsaturated fatty alcohols having 6-30 carbon atoms. Further preferred products according to the invention include triethyl citrate and at least one C ₈ -C ₁₆ isoparaffin selected from isononane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane and isohexadecane and mixtures thereof Isoparaffins. Further inventively preferred products include triethyl citrate and at least one C ₈ -C ₁₆ isoparaffin selected from isononane, isodecane, isoundecane, isododecane, isotridecane and mixtures of these C ₈ -C ₁₆ isoparaffins. Further inventively preferred products include triethyl citrate and a mixture of isodecane, isoundecane, isododecane and isotridecane. Further non-volatile non-silicone oils which are preferred according to the invention are selected from branched saturated or unsaturated fatty alcohols having 6-30 carbon atoms. These alcohols are also often referred to as Guerbet alcohols, as they are obtainable by the Guerbet reaction. Preferred alcohol oils are 2-hexyldecanol, 2-octyldodecanol and 2-ethylhexyl alcohol. Also preferred is isostearyl alcohol. Other preferred nonvolatile oils are selected from mixtures of Guerbet alcohols and Guerbet alcohol esters, e.g. For example, 2-hexyldecanol and 2-hexyldecyl laurate. The term "triglyceride" used hereinafter means "glycerol triester". Further preferred nonvolatile oils according to the invention are selected from the triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated C8-30 fatty acids, provided that they are liquid under normal conditions. Particularly suitable may be the use of natural oils, eg soybean oil, cottonseed oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, castor oil, corn oil, rapeseed oil, olive oil, sesame oil, thistle oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil and the like. Particularly preferred are synthetic triglyceride oils, in particular Capric / Caprylic triglycerides, z. As the commercial products Myritol® 318 or Myritol® 331 (BASF / Cognis) with unbranched fatty acid residues and glyceryl triisostearin and glyceryl tri (2-ethylhexanoate) with branched fatty acid residues. Such triglyceride oils preferably account for less than 50% by weight of the total weight of all cosmetic oils in the composition of the invention. The total weight of triglyceride oils is particularly preferably 0.5-10% by weight, preferably 1-5% by weight, in each case based on the total composition, without taking into account any propellant present. Further non-volatile non-silicone oils which are particularly preferred according to the invention are selected from the dicarboxylic acid esters of linear or branched C ₂ -C ₁₀ -alkanols, in particular diisopropyl adipate, di-n-butyl adipate, di- (2-ethylhexyl) adipate, dioctyl adipate, diethyl / di-n- butyl / dioctyl sebacate, diisopropyl sebacate, dioctyl malate, dioctyl maleate, dicaprylyl maleate, diisooctyl succinate, di-2-ethylhexyl succinate and di- (2-hexyldecyl) succinate. Further according to the invention particularly preferred non-volatile non-silicone oils are chosen from the addition products of from 1 to 5 propylene oxide units onto mono- or polyhydric C _8-22 alkanols, such as octanol, decanol, decanediol, lauryl alcohol, myristyl alcohol and stearyl alcohol, eg. PPG-2 myristyl ether and PPG-3 myristyl ether. Further according to the invention particularly preferred non-volatile non-silicone oils are selected from the addition products of at least 6 ethylene oxide and / or propylene oxide units onto mono- or polyhydric C _3-22 alkanols such as glycerol, butanol, butanediol, myristyl alcohol and stearyl alcohol, which may optionally be esterified, z. PPG-14 butyl ether, PPG-9 butyl ether, PPG-10-butanediol and PPG-15 stearyl ether. Further non-volatile non-silicone oils which are particularly preferred according to the invention are selected from the symmetrical, unsymmetrical or cyclic esters of carbonic acid with C 6 -C 20 -alcohols, eg. Di-n-caprylyl carbonate (Cetiol® CC) or di (2-ethylhexyl) carbonate (Tegosoft DEC). Carbonic acid esters with C ₁ -C ₅ -alcohols, e.g. As glycerol carbonate or propylene carbonate, however, are not suitable as a cosmetic oil compounds. Further oils which may be preferred according to the invention are selected from the esters of dimers of unsaturated C ₁₂ -C ₂₂ -fatty acids (dimer fatty acids) with monovalent linear, branched or cyclic C ₂ -C ₁₈ -alkanols or with polyvalent linear or branched C ₂ - C ₆ alkanols. Other cosmetic oils which are particularly preferred according to the invention are selected from nonvolatile silicone oils. Preferred nonvolatile silicone oils according to the invention are selected from linear polyalkylsiloxanes having a kinematic viscosity at 25 ° C. of at least 5 cSt to 2000 cSt, in particular selected from linear polydimethylsiloxanes having a kinematic viscosity at 25 ° C. of from 5 cSt to 2000 cSt, preferably from 10 to 350 cSt , particularly preferably 50-100 cSt, as z. Available under the trade names Dow Corning® 200 and Xiameter PMX, respectively, from Dow Corning and Xiameter respectively. Further preferred nonvolatile silicone oils are phenyltrimethicones having a kinematic viscosity at 25 ° C. of from 10 to 100 cSt, preferably from 15 to 30 cSt, and also cetyldimethicones. Natural and synthetic hydrocarbons preferred according to the invention are selected from paraffin oils, isohexadecane, isoeicosane, polyisobutenes and polydecenes, which, for example, are disclosed in US Pat. B. under the name Emery® 3004, 3006, 3010 or under the name Ethylflo® Albemarle or Nexbase® 2004G are available from Nestle, and 1,3-di (2-ethylhexyl) cyclohexane.

The water-in-oil emulsions may according to the invention further contain at least one fragrance. For the purposes of the present invention, the term "fragrances" means substances having a molecular weight of 74 to 300 g / mol, which contain at least one osmophoric group in the molecule and have an odor and / or taste, ie they are capable of To excite receptors of the hair cells of the olfactory system. Osmophore groups are covalently bonded to the molecular skeleton groups in the form of hydroxyl groups, formyl groups, oxo groups, alkoxycarbonyl groups, nitrile groups, nitro groups, azide groups, etc. In this context, the term "fragrances" in the context of the present invention also at 20 ° C and 1013 hPa liquid perfume oils, perfumes, or perfume oil ingredients.
However, mixtures of different fragrances are preferably used, which together produce an appealing scent.

Particularly pleasing antiperspirant cosmetic agents according to the invention are obtained if the at least one perfume in a total amount of 0.05 to 10 wt .-%, preferably from 0.001 to 9 wt .-%, preferably from 0.01 to 8 wt .-% , more preferably from 0.1 to 7 wt .-%, even more preferably from 0.2 to 6 wt .-%, in particular from 0.2 to 4 wt .-%, based on the total weight of the water-in-oil -Emulsion, is included.
Perfume oils can be present as free oil and / or in encapsulated form.

According to the invention it is further preferred if the water-in-oil emulsion additionally contains at least one preservative. Preservatives which are preferred according to the invention are formaldehyde releasers iodopropinyl butylcarbamates, parabens, phenoxyethanol, ethanol, benzoic acid and salts thereof, dibromodicyanobutane, 2-bromo-2-nitro-propane-1,3-diol, imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazoline. 3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates. Further preservatives which can be used in the context of the present invention are the substances listed in Annex 6 of the Cosmetics Regulation, as well as cosmetic raw materials with preservative properties or raw materials which support or enhance the preservative action of the abovementioned preservatives. The preservatives are preferably in a total amount of 0.01 to 10 wt .-%, preferably from 0.1 to 7 wt .-%, preferably from 0.2 to 5 wt .-%, in particular from 0.3 to 2, 0 wt .-%, based on the total weight of the antiperspirant cosmetic agent included.

According to the invention, the antiperspirant cosmetic agent may preferably further contain at least one antioxidant, preferably in a total amount of 0.01 to 5.0 wt .-%, based on the total weight of the cosmetic composition. The antioxidant may be selected from ascorbic acid, ascorbyl palmitate, BHT, substituted hydroxyhydrocinnamic acid esters, substituted benzotriazoles, dialkyl thiodialkanoates, tocopherol and its esters (e.g., acetate), hydroxymethoxyphenyl decanones, paradox, and mixtures thereof, especially substituted hydroxyhydrocinnamates and mixtures thereof.

According to the invention, the antiperspirant cosmetic agent preferably contains at least one further adjuvant selected from the group of chelating agents; Deodorant agents; monohydric and / or polyhydric alcohols and / or polyethylene glycols; skin-cooling agents; pH adjusting agents; skin-care active substances, such as moisturizers, soothing substances, skin-whitening substances, skin-smoothing substances; as well as their mixtures.

It may be advantageous for the preparations according to the invention to comprise a chelating agent in a total amount of from 0.01 to 3.0% by weight, preferably from 0.02 to 1.0% by weight, in particular from 0.05 to 0.1 Wt .-%, based on the total weight of the water-in-oil emulsion, to add. In the context of the present invention, preferred chelating agents are selected from the group consisting of β-alaninediacetic acid, cyclodextrin, diethylenetriaminepentamethylenephosphonic acid, sodium, potassium, calcium disodium, ammonium and triethanolamine salts of ethylenediaminetetraacetic acid (EDTA), etidronic acid, hydroxyethylethylenediaminetetraacetic acid (HEDTA) and their sodium salts. sodium salts of nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid, phytic acid, hydroxypropyl cyclodextrin, methylcyclodextrin, Aminotrimethylenphosphonat pentasodium, ethylenediamine pentasodium, diethylenetriamine pentaacetate pentasodium, pentasodium triphosphate, potassium EDTMP, sodium EDTMP, Natriumdihydroxyethylglycinat, sodium phytate, Natriumpolydimethylglycinophenolsulfonat, tetrahydroxyethylethylenediamine, tetrahydroxypropylethylenediamine, Tetrakaliumetidronat , Tetrasodium tetidronate, tetrasodiumiminodisuccinate, trisodium ethylenediamine disuccinate, tetrasodium N, N-bis ( Carboxymethyl) glutamate, tetrasodium DL-alanine-N, N-diacetate and desferrioxamine.

In order to further improve the antiperspirant and odor-reducing effect of the products according to the invention, in a preferred embodiment the water-in-oil emulsion contains at least one deodorant active ingredient in a total amount of 0.0001 to 15% by weight, preferably 0.1 to 10 wt .-%, preferably 0.2-7 wt .-%, particularly preferably 0.3-5 wt .-% and most preferably 0.4-1.0 wt .-%, each based on the total weight of the active substance the deodorant active ingredient or the deodorant active ingredients in the water-in-oil emulsion. If ethanol is used in the compositions according to the invention, this does not apply in the context of the present invention as a deodorant active ingredient, but as a constituent of the carrier.

Deodorant active ingredients which are preferred according to the invention are odor absorbers, deodorizing ion exchangers, germ-inhibiting agents, prebiotic components and enzyme inhibitors or, with particular preference, combinations of the active substances mentioned.

Silicates serve as odor absorbers, which at the same time advantageously support the rheological properties of the composition according to the invention. Among the silicates which are particularly preferred according to the invention are, in particular, phyllosilicates and, among these, in particular montmorillonite, kaolinite, IIit, beidellite, nontronite, saponite, hectorite, bentonite, smectite and talcum.

Other preferred odor absorbers are, for example, zeolites, Zinkricinoleat, cyclodextrins, certain metal oxides, such as. As alumina, and chlorophyll.

Further inventively preferred odor absorbers are selected from perlite.

According to the invention, germ-inhibiting or antimicrobial active ingredients are understood as meaning those active substances which reduce the number of skin germs participating in the formation of the odor or inhibit their growth. These organisms include, among others, various species from the group of staphylococci, the group of Corynebacteria, anaerococci and micrococci.

Preferred antimicrobial or antimicrobial agents according to the invention are in particular organohalogen compounds and halides, quaternary ammonium compounds, a number of plant extracts and zinc compounds. These include triclosan, chlorhexidine and chlorhexidine gluconate, 3,4,4'-trichlorocarbanilide, bromochlorophene, dichlorophen, chlorothymol, chloroxylenol, hexachlorophene, dichloro-m-xylenol, dequalinium chloride, domiphenbromide, ammonium phenolsulfonate, benzalkonium halides, benzalkonium cetyl phosphate, benzalkonium saccharinates, benzethonium chloride, cetylpyridinium chloride, Laurylpyridinium chloride, laurylisoquinolinium bromide, methylbenzethonium chloride. Furthermore, phenol, phenoxyethanol, disodium dihydroxyethylsulfosuccinylundecylenate, sodium bicarbonate, zinc lactate, sodium phenolsulfonate and zinc phenolsulfonate, ketoglutaric acid, terpene alcohols such as. As farnesol, chlorophyllin copper complexes, α-monoalkyl glycerol ether with a branched or linear saturated or unsaturated, optionally hydroxylated C ₆ -C ₂₂ alkyl, particularly preferably α- (2-ethylhexyl) glycerol ether, commercially available as Sensiva® SC 50 (ex Schülke & Mayr), carboxylic esters of mono-, di- and. Triglycerin (eg, glycerol monolaurate, diglycerol monocaprate), lantibiotics and plant extracts (eg., Green tea and components of lime blossom oil) can be used.

Further preferred deodorant active substances are selected from so-called prebiotically active components, which according to the invention are to be understood as meaning those components which inhibit only or at least predominantly the odor-causing germs of the skin microflora, but not the desired ones, that is, the non-odor-forming germs that lead to a include healthy skin microflora. Explicit here are agents such as conifer extracts, especially from the group of Pinaceae, and plant extracts from the group of Sapindaceae, Araliaceae, Lamiaceae and Saxifragaceae, in particular extracts of Picea spp., Paullinia sp., Panax sp., Lamium album or Ribes nigrum and Mixtures of these substances, to name.

Further preferred deodorant active ingredients are selected from the germ-inhibiting perfume oils and the Deosafe® perfume oils, which are available from Symrise, formerly Haarmann and Reimer.

Further preferred deodorant active compounds are selected from silver salts, in particular silver citrate, dihydrogen silver citrate, silver lactate and silver sulfate, soluble complex salts of silver, colloidal silver and silver zeolites.

The enzyme inhibitors include substances which inhibit the enzymes responsible for the sweat decomposition, in particular arylsulfatase, β-glucuronidase, aminoacylase, esterases, lipases and / or lipoxigenase, e.g. B. trialkylcitric acid, in particular triethyl citrate, or zinc glycinate.

Preferred antiperspirant compositions according to the invention are characterized in that the at least one deodorant active ingredient is selected from arylsulfatase inhibitors, beta-glucuronidase inhibitors, aminoacylase inhibitors, esterase inhibitors, lipase inhibitors and lipoxygenase inhibitors, α-monoalkyl glycerol ethers having a branched or linear saturated or unsaturated, optionally hydroxylated C ₆ -C ₂₂ -alkyl radical, especially α- (2-ethylhexyl) glycerol ether, phenoxyethanol, benzylheptanol, cocamidopropyl PG-dimonium chlorides phosphates and butyloctanoic acid, polyglycerol-3-caprylates, germ-inhibiting perfume oils , Deosafe® perfume oils (Deosafe® is a registered trademark of the company Symrise, formerly Haarmann & Reimer), prebiotic active ingredients, Trialkylcitronensäureestem, especially triethyl citrate, active ingredients containing the number of skin microorganisms involved in the formation of odor from the group of staphylococci, Coryneba reduce the number of arteries, anerococci and micrococci or their growth inhibit zinc compounds, in particular zinc phenolsulfonate and Zinkricinoleat, organohalogen compounds, especially triclosan, chlorhexidine, Chlorhexidingluconat and Benzalkoniumhalogeniden, quaternary ammonium compounds, in particular Cetylpyridiniumchlorid, odor absorbers, in particular silicates and zeolites, sodium bicarbonate, lantibiotics, and mixtures of the aforementioned substances.

In a further particularly preferred embodiment, the compositions according to the invention contain both at least one deodorant and at least one antiperspirant active ingredient.

According to the invention, the water-in-oil emulsion preferably contains at least one water-soluble polyhydric C ₂ -C ₉ -alkanol having 2-6 hydroxyl groups and / or at least one water-soluble polyethylene glycol having 3-50, preferably 3-20 ethylene oxide units and mixtures thereof to further improve the stability of the compositions. Preferably, these components are selected from 1,2-propylene glycol, 2-methyl-1,3-propanediol, glycerol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, pentylene glycols such as 1,2-pentanediol and 1,5-pentanediol, hexanediols such as 1,6-hexanediol, hexanetriols such as 1,2,6-hexanetriol, 1,2-octanediol, 1,8-octanediol, dipropylene glycol, tripropylene glycol, diglycerol, triglycerol, erythritol, sorbitol and mixtures of aforementioned substances. Suitable water-soluble polyethylene glycols are selected from PEG-3, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18 and PEG-20 and mixtures thereof, with PEG-3 to PEG-8 being preferred. Preference is given to propylene glycol, dipropylene glycol or a mixture of these, more preferably only propylene glycol. Preferably, these are contained in a total amount of 0.1 to 50 wt .-%, more preferably 0.5 to 30 or 1 to 25 wt .-%.

According to another embodiment of the present invention, the water-in-oil emulsion according to the invention further contains at least one skin-cooling active ingredient. Skin-cooling active ingredients suitable according to the invention are, for example, menthol, isopulegol and menthol derivatives, eg. Menthyl lactate, menthyl glycolate, menthyl ethyl oxamate, menthyl pyrrolidone carboxylic acid, menthyl methyl ether, menthoxy propane diol, menthone glycerol acetal (9-methyl-6- (1-methylethyl) -1, 4-dioxaspiro (4.5) decane-2-methanol), monomethyl succinate, 2-hydroxymethyl -3,5,5-trimethylcyclohexanol and 5-methyl-2- (1-methylethyl) cyclohexyl-N-ethyloxamate. Preferred skin-cooling active ingredients are menthol, isopulegol, menthyl lactate, menthoxypropanediol, menthylpyrrolidonecarboxylic acid and 5-methyl-2- (1-methylethyl) cyclohexyl-N-ethyloxamate, as well as mixtures of these substances, in particular mixtures of menthol and menthyl lactate, menthol, menthol glycolate and menthyl lactate, menthol and menthoxypropanediol or menthol and isopulegol.

According to the invention, the water-in-oil emulsion contains free water preferably in an amount of 20 to 70 wt .-%, based on the total weight of the water-in-oil emulsion, more preferably 30 to 60 wt .-%, in particular of 40 to 60 wt .-%, based on the total weight of the water-in-oil emulsion. Part of the water may also be replaced by ethanol in embodiments of the invention, for example less than 10% by weight.

The water phase of the water-in-oil emulsion contains, in addition to water, the homo-polyethylenimine, and optionally further constituents. The oil phase contains, in addition to the oil component, water-in-oil emulsifier and optionally other ingredients such as fragrances. Preferably, the weight ratio between water phase and oil phase is in a range of 30 to 85 wt .-% (water phase) to 20 to 80 wt .-% (oil phase).

The antiperspirant products according to the invention are formulated as a propellant-driven aerosol and accordingly contain a propellant. The blowing agent is preferably in a total amount of 1 to 95 wt .-%, based on the total weight of the antiperspirant cosmetic product, preferably in a total amount of 40 to 90 wt .-%, more preferably from 45 to 85 wt .-%, in particular of Contain 50 to 70 wt .-%. Preferred propellants (propellants) are propane, propene, n-butane, isobutane, isobutene, n-pentane, pentene, isopentane, isopentene, methane, ethane, dimethyl ether, nitrogen, air, oxygen, nitrous oxide, 1,1, 1,3-tetrafluoroethane, heptafluoro-n-propane, perfluoroethane, monochlorodifluoromethane, 1,1-difluoroethane, tetrafluoropropenes both individually and in their mixtures. Also hydrophilic propellants, such. As carbon dioxide, can be used advantageously in the context of the present invention, when the proportion of hydrophilic gases is selected low and lipophilic propellant gas (eg., Propane / butane) is present in excess. Particularly preferred are propane, n-butane, isobutane and mixtures of these propellants. It has been found that the use of n-butane as the only propellant gas according to the invention can be particularly preferred.

The amounts of blowing agent and the amount of water-in-oil emulsion in the cosmetic product of the present invention add up to 100% by weight. Accordingly, the total amount of water-in-oil emulsion in the cosmetic product of the present invention is preferably 3 to 99% by weight, 5 to 70% by weight, more preferably 10 to 60% by weight, further preferably 15% to 55 wt .-% and in particular from 20 to 50 wt .-%.

The cosmetic product according to the invention is packaged as a spray application and has an aerosol delivery device. The spray application is carried out with a spray device which contains a filling of the water-in-oil emulsion and blowing agent in a container (compressed gas cans, compressed gas packages, aerosols). As pressure gas container come vessels made of metal (aluminum, tinplate, tin), protected or non-splitterndem plastic or glass, which is coated with plastic outside, in question, in their selection pressure and fracture resistance, corrosion resistance, easy fillability as well as aesthetic Aspects, handiness, printability etc. play a role. Special internal protective lacquers ensure corrosion resistance to the water-in-oil emulsion.

Despite the water phase in the aerosol container, the products according to the invention have a particularly high corrosion resistance, which represents a great advantage over the prior art. Furthermore, the water-in-oil emulsions used according to the invention have excellent storage stability and effectiveness. It is particularly advantageous that the sprayed products are characterized by a pleasant, non-sticky feel on the skin.

In a preferred embodiment of the invention, the valve has a coated with a paint or a polymeric plastic A valve disk and a similar flexible element with a return characteristic that the valve after completion of the operation in the closed position (= rest position of the valve) resets. Corresponding cosmetic products in which the aerosol dispenser comprises a valve having a poppet and / or a flexible element having a return characteristic coated with a lacquer or a polymeric plastic A are preferred according to the invention.

In a further preferred embodiment of the invention, the valve has a flexible element with a return characteristic and / or a valve disk of at least one plastic B, preferably an elastomeric plastic. Here too, cosmetic products according to the invention in which the valve has a flexible element with a return characteristic and / or a valve cone made from at least one plastic B are preferred, preferred plastics B being elastomeric plastics. Particularly preferred elastomeric plastics are selected from Buna, in particular Buna N, Buna 421, Buna 1602 and Buna KA 6712, neoprene, butyl and chlorobutyl.
In a further preferred embodiment of the invention, the flexible element with return characteristic can be formed as a spiral spring or helical compression spring. In a further preferred embodiment of the invention, the flexible element with return characteristic can be formed integrally with the valve cone and have flexible legs. This spring may be made of metal, preferably of highly tempered, corrosion-resistant stainless steel (eg grade AISI 316) or plastic.

All the valves used in the invention preferably have an internally painted valve disk, wherein paint and valve material are compatible with each other. If aluminum valves are used according to the invention, their valve disks can be internally z. B. be coated with Micoflex paint or other resistant protective coatings. If tinplate valves are used according to the invention, their valve disks can be internally z. B. be coated with PET (polyethylene terephthalate). The used containers, the z. B. tinplate or aluminum, with aluminum containers are preferred according to the invention, must also be painted or coated internally in view of the corrosivity of the invention used in water-in-oil emulsions. An inventively preferred inner protective lacquer is an epoxy phenolic lacquer, as it u. a. available under the names Hoba 7407 P and Hoba 7940.

Finally, another object of the present invention is a non-therapeutic cosmetic method for preventing and / or reducing the transpiration of the body, in which an inventive antiperspirant cosmetic product by means of the aerosol dispenser on the skin, in particular on the skin of the armpits, applied and remains on the skin of the armpits for at least 1 hour, preferably for at least 2 hours, preferably for at least 4 hours, especially for at least 6 hours.

With regard to the method according to the invention, what has been said about the antiperspirant cosmetic agents according to the invention applies mutatis mutandis.

Examples:

To prepare sprayable water-in-oil emulsions, the ingredients were mixed using an unmodified, branched homo-polyethylenimine having a weight average molecular weight of 1300 g / mol and a primary: secondary: tertiary amino = 40: 36: 24 ratio Starting product was used.

The oil phase contained DC 5227 (Dow Corning) as a W / O emulsifier and cyclopentasiloxane as an oil component. Isopropyl myristate as an oil component Furthermore, perfume oil, a Deowirkstoff and polypropylene glycol were included in the water-in-oil emulsion.

Then it was acidified with hydrochloric acid to a pH of 3.5-4.5. The water-in-oil emulsion was filled at a weight ratio of 30% by weight (water-in-oil emulsion) to 70% by weight (propane / butane / isobutane propellant mixture) in a container with aerosol dispenser ,

Specifically, the components and ranges given in the table below have been used. WO / Emulsion antiperspirant spray Quantities in% by weight polyethyleneimine 0.5-5.0 Demineralized water ad 100 Hydrochloric acid 20% 1.0-20.0 Adapt the amount of pH Propanediol-1,2 5.0-30.0 Cyclopentasiloxane 5.0 to 25.0 Isopropyl myristate 1.0-10.0 Dow Corning ES-5227 DM Formulation Aid 3.0 - 8.0 Perfume 1.0-6.0 phenoxyethanol 0.1 -1.0 Antioxidant 0.01 -2.0 pH = 2-7.5 Filling with propellant propane, butane, isobutane or mixture thereof Filling ratio: W / O emulsion 10.0 to 40.0 propellant 60.0 - 90.0

The products had a good perspiration inhibition, a pleasant skin feel and a low tendency to staining.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2006/018073 A1 [0009]

Cited non-patent literature

• Andrews P: "Estimation of the Molecular Weights of Proteins by Sephadex Gel Filtration"; Biochem. J., 1964, 91, pages 222 to 233 [0033]

Claims (10)

Antiperspirant cosmetic product containing: a water-in-oil emulsion comprising: a. at least one branched homo-polyethyleneimine having a molecular weight of 300 to 10,000 g / mol in a total amount of 0.1 to 20 wt .-%, wherein the Polyethlenimin a proportion of amino groups with three non-hydrogen atom radicals from 20 mol% to 35 mol %, based on the molar amount of all amino groups in the homo-polyethylenimine, b. at least one water-in-oil emulsifier in a total amount of from 0.05 to 10% by weight, c. at least one oil component which is not a fragrance and no essential oil, in a total amount of 1.0 to 50 wt .-%, in which: - the quantities given refer to the total amount of the water-in-oil emulsion, the water-in-oil emulsion has a pH of from 2.5 to 7.5, determined at 22 ° C., and the polyethylenimine is polycationic, the water-in-oil emulsion contains at least one anion selected from the group consisting of chloride, phosphates and sulphate, and the water-in-oil emulsion contains no halides and / or hydroxy halides of aluminum and / or zirconium, - at least in propellants, and an aerosol dispenser. Cosmetic product after Claim 1 , characterized in that the water-in-oil emulsion 0.5 to 10 wt .-%, preferably 1.0 to 7.0 wt .-%, more preferably 2.0 to 5.0 wt .-% of Homo polyethyleneimine contains. Cosmetic product after Claim 1 or 2 , characterized in that in the water-in-oil emulsion 10%, 30%, 50%, 95.0 wt .-% or more, more preferably 99.0 wt .-% to 100 wt .-%, of the contained Anions are chloride ions. Cosmetic product according to one of the preceding claims, characterized in that the water-in-oil emulsion has a pH of 2.5 to 7.0 determined at 22 ° C, preferably 3.0 to 5.5, more preferably 3.3 to 4.5. Cosmetic product according to one of the preceding claims, characterized in that the homo-polyethylenimine has a molecular weight of 500 to 3000 mol / g, preferably from 1000 to 2000 mol / g. Cosmetic product according to one of the preceding claims, characterized in that the total amount of the at least one water-in-oil emulsifier is from 0.2 to 10% by weight, based on the total weight of the water-in-oil emulsion. Cosmetic product according to one of the preceding claims, characterized in that the total amount of the at least one oil component is 5.0 to 45 wt .-%, preferably 10.0 to 25.0, based on the total weight of the water-in-oil emulsion , Cosmetic product according to one of the preceding claims, characterized in that the water-in-oil emulsion contains at least one deodorant active in a total amount of 0.0001 to 15 wt .-%, preferably 0.5 to 10 wt .-%, respectively based on the total weight of the water-in-oil emulsion. Cosmetic product according to one of the preceding claims, characterized in that the water-in-oil emulsion further contains at least one anion selected from the group consisting of citrate, lactate, tartrate and malate. Non-therapeutic cosmetic method for preventing and / or reducing body odor and / or perspiration of the body, wherein a cosmetic product according to any one of Claims 1 to 9 by means of an aerosol dispenser on the skin, in particular on the skin of Armpits, is applied and for at least 1 hour, preferably for at least 2 hours, preferably for at least 4 hours, in particular for at least 6 hours, remains on the skin.