WO2010145922A2 - Antiperspirant composition comprising silver citrate - Google Patents

Abstract

The invention relates to a water-free cosmetic or dermatological preparation comprising one or more silver citrate and citric acid complexes of formula (I) wherein x+y = 3, having a water content of up to 90 wt.%, based on the total mass of the complex, in combination with one or more passivation agents selected from the group of silicic acids, one or more antiperspirant substances and perfume, said preparation being characterised in that sheet silicate(s) is/are contained in a total amount of 0 to a maximum of 1,3 wt.%.

Description

 "Antiperspirant compositions with silver citrate"

The invention describes antiperspirant anhydrous cosmetic or dermatological preparations comprising water-soluble silver citrate-citric acid complexes in combination with passivating agents selected from the group of silicic acids.

The use of silver as a disinfectant in wound treatment, medical devices and in pharmaceutical and cosmetic preparations is known in the art. For cosmetic products, for example, a maximum content of 4% silver nitrate is allowed (KosmetikV, Appendix 3 to § 3, Part A).

In contrast to aqueous solutions of soluble silver salts (eg silver nitrate or silver acetate), aqueous colloidal silver solutions are either liquid dispersions of elemental silver or liquid dispersions of complex sparingly soluble silver compounds. The water-dispersible starting materials then contain silver ions only in traces. There is a need for non-colloidal silver for cosmetic preparations. WO 2006029213 A1 describes antimicrobial silver citrate compounds. These stabilized in aqueous citric acid silver compounds are commercially available under TINOSAN ^® SDC. The preparation of these compounds via an electrochemical process is described in EP 1 041 879 A1. TINOSAN ^® SDC contains electrolytically generated silver ions (Ag ⁺ ) and there is no colloidal silver in the mixture.

The TINOSAN described in the publications WO 2006029213 A1 and EP 1041879 A1 ^® SDC may be used in cosmetic, in aqueous and / or emulsion based composition and with various additives. In particular deodorants and antiperspirants in combination with TINOSAN ^® SDC in WO 2006029213 A1 describes. However, the use of silver compounds dissolved in water due to corrosion in metallic storage media, such as, for example, aerosol cans, presents a problem. This effect is enhanced by the presence of corrosion promoting compounds such as aluminum and / or aluminum / zirconium antiperspirant salts. In the aerosol, contact with water also frequently causes clogging of the valves and in other cosmetic application forms, clumping, instabilities and inhomogeneities. Another problem with aqueous mixtures can occur with the use of water-soluble encapsulated perfume. In the presence of water, these encapsulated perfumes can swell, stick together and react with dissolution.

DE 202008014407 U1 proposes to solve these problems using one or more passivating agents selected from the group of phyllosilicates and / or talc. On Thus, means may be provided, which may contain up to 10 wt .-% water (wt .-% of other sources than 5% by weight of the TINOSAN ^® SDC plus additional 5). There is also a need for ways to incorporate water-soluble silver compounds stably in cosmetic compositions, even if the water contents are well below 10 wt .-%. Even in systems with much less water, it should be possible to administer antimicrobial silver compounds dissolved in water from an actually water-hostile environment.

The problems are solved by an anhydrous cosmetic or dermatological preparation according to the invention comprising silver citrate-citric acid complexes having a water content of up to 90% by weight, based on the total mass of the complex, in combination with one or more passivating agents selected from the group of silicic acids. Furthermore, one or more antiperspirant active ingredients and perfume are preferably contained in the preparation.

Anhydrous preparation according to the invention means that in addition to the water contained in the silver complex, up to 90 wt .-% with respect to the total complex mass, only additional water up to a proportion of about 6 wt .-%, based on the total mass of the preparation can be. Anhydrous is preferably a proportion of not more than 2 wt .-%, in particular 0 wt .-%, based on the total mass of the preparation. In addition to the water introduced via the silver citrate-citric acid complex, the preparation therefore contains a maximum of 3% by weight of further water, based on the total mass of the preparation. In a preferred maximum proportion of silver citrate complex of about 5 wt .-% and contained therein water of max. 90% by weight, the preparation according to the invention preferably comprises a maximum of 4-5% by weight of water which can be introduced through the complex. In addition, at most 3% by weight of further water is accepted in the formulation without causing problems as known in the art. A maximum water content of 8% by weight, formed from water from the complex and water from other preparation constituents or extra added water, can therefore be contained in the preparation as a whole according to the invention without any loss in the below-described advantages of the preparation according to the invention comes.

Despite this proportion of possible water, the preparation according to the invention is understood to be anhydrous. The advantages are set out below.

The invention makes it possible to use this water-containing silver citrate with its antimicrobial effect in an environment which normally leads to instabilities and storage problems in the presence of water, as stated above. For example, the use of the aqueous silver citrate complex in aerosol formulations would be critical, as the water would damage the metal can or valve parts, e.g. As the spring can corrode. This effect is enhanced by the presence of corrosion promoting compounds, such as aluminum and / or aluminum / zirconium antiperspirant salts, as are common in antiperspirant or deodorant formulations. It is also known that as soon as the water is removed from the silver citrate complex, the silver precipitates and can not show the antimicrobial effect. This problem has now also been solved according to the invention in very low-water preparations.

According to the invention, the water present through the silver citrate complex, as well as any additional water (up to 3% by weight), is complexed and bound by the passivating agent. The water supplied through the complex is bound to the passivating agent and is therefore no longer available for damaging influence.

The passivating agents are preferably selected from the group of silicas. In this case, both hydrophilic silicas and hydrophobic silicas can be used. It is particularly preferred to use mixtures of at least one hydrophilic silica and at least one hydrophobic silica. In this case, it is particularly preferred if the hydrophobic silica (s) is present in excess of the hydrophilic silica (s). Weight ratios are preferably hydrophobic: hydrophilic from 0: 1 to 10: 1, preferably 2: 1 to 6: 1, particularly preferably 3: 1 to 4: 1.

Hydrophilic silicas used according to the invention are readily wettable with water. Preferred hydrophilic silicas, hydrophilic pyrogenic silicas, in particular non-alkylated commercial products of Aerosil ^® series from Evonik Degussa, in particular Aerosil ^® -130, Aerosil ^® -150, Aerosil ^® -200, Aerosil ^® -300, Aerosil ^® -380, besides also Cabot Cab-O-Sil products, especially Cab-O-Sil HS-5.

According to preferred spray compositions are characterized in that at least one hydrophilic silica in a total amount of 0.2 to 2 wt .-%, preferably 0.4 to 1, 5 wt .-%, particularly preferably 0.5 to 1, 0 Wt .-% and most preferably 0.6 to 0.8 wt .-%, each based on the total weight of the propellant-free composition according to the invention, is included.

According to preferred pen compositions are characterized in that at least one hydrophilic silica in a total amount of 0.1 to 1 wt .-%, preferably 0.2 to 0.8 wt .-%, particularly preferably 0.3 to 0.5 % By weight, based in each case on the total weight of the composition according to the invention.

Hydrophobic silicas used according to the invention are alkyl-modified at least on the surface of the silica particles. They preferably contain hydrophobic groups on the surface, such as (CH ₃ ) ₃ Si-O-, (-Si (CH ₃ ) ₂ O-) _n ,

O- O-

(CH ₃ ) ₂ Si (and C ₈ H ₁₇ Si ^ -O-

O- V

Preferred hydrophobic silicas are hydrophobic fumed silicas, particularly the alkylated commercial products of Aerosil ^® series of Degussa, in particular Aerosil ^® -R202, -R805 Aerosil ^®, Aerosil ^® -R812, -R972 Aerosil ^® and Aerosil ^® -R976, besides also products the Cab-O-Sil TS series by Cabot, especially Cab-O-Sil TS-530. Particularly preferred hydrophobic silicas are silica silylates and silica dimethyl silylates. Also particularly preferred is Aerosil ^® -R972, having a BET surface area of approximately 1 10 rrvYg and about 70% of the surface occupied with methylated hydroxyl groups. Spray compositions preferred according to the invention are characterized in that at least one hydrophobic silica in a total amount of 1-5 wt .-%, preferably 1, 5 - 4 wt .-%, particularly preferably 2 - 3.5 wt .-%, extraordinarily preferably 2.5 to 3 wt .-%, each based on the total weight of the propellant-free composition of the invention is included.

According to preferred pen compositions are characterized in that at least one hydrophobic silica in a total amount of 0.5 to 5 wt .-%, preferably 0.7 to 4 wt .-%, particularly preferably 0.8 to 3.5 wt. -%, most preferably 1 - 3 wt .-%, each based on the total weight of the composition according to the invention, is contained.

The compositions according to the invention are characterized in that they contain layer silicate (s) in a total amount of zero to at most 1.3% by weight, preferably zero to at most 1% by weight, more preferably zero to a maximum of 0.5% by weight. %, based on the total weight of the propellant-free composition (sprays) or based on the total weight of the composition (pencil, roll-on, etc.) included.

The term sheet silicates includes in particular talc, soapstone, clay minerals such as montmorillonites, nontronites, hectorites, bentonites, in particular disteardimonium hectorites and quaternium-18 hectorites, saponite, sauconite, beidellite, allevardite, illite, halloysite, attapulgite and sepiolite.

According to the invention, contrary to the expected findings, it has now been found that these passivating agents bind the water of the silver citrate complex only to the extent that there are no negative side effects such as corrosion, etc., and no precipitation of the dissolved silver salt occurs. Ie. the silver does not precipitate in spite of dehydration via the binding to the passivating agent and is still available as an antimicrobial agent. Surprisingly, the passivated in the formulation silver in the presence of additional water such as skin moisture or sweat is released again in aqueous solution and can develop its antimicrobial activity. Ie. if the preparation is dispensed from a metal can where water is bothering, a water additive, e.g. As by sweating, the fact that the silver can act freely.

The combination of silver citrate-citric acid complex and silicic acids as passivating agents makes it possible to produce cosmetic or dermatological preparations which develop the desired antimicrobial activity at the site of action only by external addition of water. Cosmetic antiperspirants or deodorants serve to eliminate body odor that results when the odorless fresh sweat is decomposed by microorganisms. The usual cosmetic deodorants are based on different active principles. In that way The antiperspirants (AT) mentioned may be used to reduce sweat formation (antiperspirant) by astringents - predominantly aluminum salts such as aluminum hydroxychloride (aluminum chlorohydrate, ACH or activated ACH - AACH) or aluminum zirconium salts (AZG). By using the antimicrobial silver citrate complex in cosmetic antiperspirants, the bacterial flora on the skin can be reduced. The odor-causing microorganisms are effectively reduced. The sweat flow itself is not affected, in the ideal case, only the microbial decomposition of the sweat is temporarily stopped.

The compositions according to the invention contain at least one antiperspirant active substance.

Preferred antiperspirant active ingredients are selected from the water-soluble astringent inorganic and organic salts of aluminum, zirconium and zinc or any desired mixtures of these salts.

A solubility of at least 5 wt .-% at 20 ⁰ C is understood according to the invention, solubility in water, that is, amounts of at least 5 g of the antiperspirant active ingredient in 95 g of water are soluble at 20 ⁰ C.

Particularly preferred antiperspirant active ingredients are selected from aluminum chlorohydrate, in particular aluminum chlorohydrate having the general formula [Al ₂ (OH) ₅ ^Cl. 1-6 H ₂ O] _n , preferably [Al ₂ (OH) ₅ ^Cl. 2-3 H ₂ O. ] _n , which may be in non-activated or in activated (depolymerized) form, and aluminum chlorohydrate having the general formula [Al ₂ (OH) ₄ Cl ₂ ^■ 1-6 H ₂ O] _n , preferably [Al ₂ (OH) ₄ CI ₂ ^■ 2-3 H ₂ O] _n , which may be in unactivated or activated (depolymerized) form.

The preparation of preferred antiperspirant agents is disclosed, for example, in US 3887692, US 3904741, US 4359456, GB 2048229 and GB 1347950.

Also preferred are aluminum sesquichlorohydrate, aluminum dichlorohydrate, aluminum chlorohydrex-propylene glycol (PG) or aluminum chlorohydrex polyethylene glycol (PEG), aluminum or aluminum zirconium glycol complexes, e.g. Aluminum or aluminum zirconium propylene glycol complexes, aluminum sesquichlorohydrex PG or aluminum sesquichlorohydrex PEG, aluminum PG dichlorohydrex or aluminum PEG dichlorohydrex, aluminum hydroxide further selected from the aluminum zirconium chlorohydrates such as aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate, aluminum zirconium octachlorohydrate, aluminum-zirconium chlorohydrate glycine complexes, such as Aluminiumzirco- niumtrichlorohydrexglycin, Aluminiumzirconiumtetrachlorohydrexglycin, Aluminiumzirconium- pentachlorohydrexglycin, Aluminiumzirconiumoctachlorohydrexglycin, potassium aluminum sulfate (KAI (SO _{4) 2} ^■ 12 H ₂ O, alum), Aluminiumundecylenoylcollagenaminosäure, Natriumaluminiumlactat + aluminum sulfate, sodium aluminum, Aluminum bromohydrate, aluminum chloride, the complexes of zinc and sodium salts, the complexes of lanthanum and cerium, the aluminum salts of lipoamino acids, aluminum sulfate, aluminum lactate, aluminum chlorohydrate allantoinate, sodium aluminum chlorohydroxactate, zinc chloride, zinc sulfocarbolate, zinc sulfate, zirconium oxyhalides, in particular zirconyl oxychlorides, zirconyl hydroxy halides, in particular zirconyl chlorohydrate (zirconium chlorohydrate).

Antiperspirant active ingredients which are particularly preferred according to the invention are selected from what are known as "activated" aluminum and aluminum zirconium salts, which are also referred to as "enhanced activity" as antiperspirant active ingredients. Such agents are known in the art and are also commercially available. Their preparation is disclosed, for example, in GB 2048229, US 4775528 and US 6010688. Activated aluminum and aluminum-zirconium salts are typically produced by heat-treating a relatively dilute solution of the salt (e.g., about 10% by weight of salt) to increase its HPLC peak 4-to-peak 3 area ratio. The activated salt can then be dried to a powder, in particular spray-dried. In addition to the spray drying z. B. also suitable for drum drying.

Activated aluminum and aluminum zirconium salts typically have an HPLC peak 4 to peak 3 area ratio of at least 0.4, preferably at least 0.7, more preferably at least 0.9, with at least 70% of the aluminum attributable to these peaks , Activated aluminum and aluminum zirconium salts do not necessarily have to be used as a spray-dried powder. Antiperspirant active ingredients which are likewise preferred according to the invention are nonaqueous solutions or solubilisates of an activated aluminum or aluminum zirconium antiperspirant salt, for example according to US 6010688, by adding an effective amount of a polyhydric alcohol having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups , preferably propylene glycol, sorbitol and pentaerythritol, are stabilized against the loss of activation against the rapid degradation of the HPLC Peak 4: Peak 3 area ratio of the salt. For example, preferred are compositions containing by weight (USP): 18-45% by weight of an activated aluminum or aluminum zirconium salt, 55-82% by weight of at least one anhydrous polyhydric alcohol of 3 to 6 carbon atoms and 3 to 6 Hydroxyl groups, preferably propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, glycerol, sorbitol and pentaerythritol, more preferably propylene glycol.

Also particularly preferred are complexes of activated antiperspirant aluminum or aluminum-zirconium salts with a polyhydric alcohol containing 20-50% by weight, more preferably 20-42% by weight, activated antiperspirant aluminum or aluminum zirconium salt and 2-16% by weight % molecularly bound water, the remainder to 100 wt .-% is at least one polyhydric alcohol having 3 to 6 carbon atoms and 3 to 6 hydroxyl groups. Propylene glycol, propylene glycol / sorbitol mixtures and propylene glycol / pentaerythritol mixtures are preferred such alcohols. Such inventively preferred complexes of an activated antiperspirant aluminum or aluminum zirconium salt with a polyhydric alcohol are, for. As disclosed in US 5643558 and US 6245325. Further preferred antiperspirant actives are basic calcium aluminate salts, as disclosed, for example, in US Pat. No. 2,577,030. These salts are prepared by reacting calcium carbonate with aluminum chlorhydroxide or aluminum chloride and aluminum powder or by adding calcium chloride dihydrate to aluminum chlorhydroxide. Other preferred antiperspirant actives are aluminum-zirconium complexes as disclosed, for example, in US Pat. No. 4,017,599, which are buffered with salts of amino acids, in particular with alkali metal and alkaline earth glycinates.

Other preferred antiperspirant actives are activated aluminum or aluminum zirconium salts such as disclosed in US 6,245,325 or US 6042816, containing 5-78% by weight (USP) of an activated antiperspirant aluminum or aluminum zirconium salt, an amino acid or hydroxyalkanoic acid in an amount to provide an (amino acid or hydroxyalkanoic acid) to (Al + Zr) weight ratio of 2: 1-1: 20 and preferably 1: 1 to 1:10 and a water-soluble calcium salt in such an amount as to provide Ca: (AI + Zr) weight ratio of 1: 1-1: 28 and preferably 1: 2-1: 25. Particularly preferred solid activated antiperspirant salt compositions, for example according to US 6245325 or US 6042816, contain 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum or aluminum zirconium salt and 1-16% by weight. %, preferably 4-13% by weight molecularly bound water (water of hydration), furthermore sufficient water-soluble calcium salt, that the Ca: (Al + Zr) weight ratio is 1: 1-1: 28, preferably 1: 2-1: 25, is and so much amino acid that the amino acid to (Al + Zr) - weight ratio 2: 1 - 1: 20, preferably 1: 1 - 1: 10, is.

Further particularly preferred solid antiperspirant activated salt compositions, for example according to US 6245325 or US 6042816, contain 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum or aluminum zirconium salt and 1-16% by weight. %, preferably 4-13% by weight molecularly bound water (water of hydration), furthermore so much water-soluble calcium salt, that the Ca: (Al + Zr) weight ratio is 1: 1-1: 28, preferably 1: 2-1: 25 is, and so much glycine, that the glycine to (Al + Zr) - weight ratio 2: 1 - 1: 20, preferably 1: 1 - 1: 10 ,.

Further particularly preferred solid antiperspirant activated salt compositions, for example according to US 6245325 or US 6042816, contain 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum or aluminum zirconium salt and 1-16% by weight. %, preferably 4-13% by weight of molecularly bound water, furthermore sufficient water-soluble calcium salt, that the Ca: (Al + Zr) weight ratio is 1: 1-1: 28, preferably 1: 2-1: 25, and so much hydroxyalkanoic acid that the hydroxyalkanoic acid to (Al + Zr) - weight ratio 2: 1 - 1: 20, preferably 1: 1 - 1: 10, is.

Water-soluble calcium salts preferred for the stabilization of the antiperspirant salts are selected from calcium chloride, calcium bromide, calcium nitrate, calcium citrate, calcium formate, Calcium acetate, calcium gluconate, calcium ascorbate, calcium lactate, calcium glycinate, calcium carbonate, calcium sulfate, calcium hydroxide, and mixtures thereof.

Preferred amino acids for the stabilization of the antiperspirant salts are selected from glycine, alanine, leucine, isoleucine, β-alanine, valine, cysteine, serine, tryptophan, phenylalanine, methionine, β-amino-n-butanoic acid and γ-amino-n-butanoic acid and the salts thereof, each in the d-form, the I-form and the dl-form; Glycine is particularly preferred.

Preferred hydroxyalkanoic acids for the stabilization of the antiperspirant salts are selected from glycolic acid and lactic acid.

Other preferred antiperspirant actives are activated aluminum or aluminum zirconium salts, such as disclosed in US 6902723, containing 5-78% by weight (USP) of an activated antiperspirant aluminum or aluminum zirconium salt, an amino acid or hydroxyalkanoic acid in one Amount to provide an (amino acid or hydroxyalkanoic acid) to (Al + Zr) weight ratio of 2: 1-1: 20 and preferably 1: 1 to 1:10, and a water-soluble strontium salt in such an amount as to provide a Sr : (Al + Zr) - weight ratio of 1: 1 - 1:28 and preferably 1: 2 - 1: 25 provide. Particularly preferred solid antiperspirant activated salt compositions, for example according to US 6902723, contain 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum or aluminum-zirconium salt and 1-16% by weight, preferably 4 - 13 wt .-% molecularly bound water, further enough so much water-soluble strontium salt that the Sr: (AI + Zr) weight ratio 1: 1 - 1: 28, preferably 1: 2 - 1: 25, and so much amino acid the amino acid to (Al + Zr) - weight ratio 2: 1 - 1: 20, preferably 1: 1 - 1: 10, is. Further particularly preferred solid antiperspirant activated salt compositions, for example according to US 6902723, contain 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum or aluminum-zirconium salt and 1-16% by weight, preferably 4 to 13% by weight of molecularly bound water, furthermore sufficient water-soluble strontium salt that the Sr: (Al + Zr) weight ratio is 1: 1 to 1:28, preferably 1: 2 to 1:25, and as much glycine, the glycine to (Al + Zr) - weight ratio 2: 1 - 1: 20, preferably 1: 1 - 1: 10, is. Further particularly preferred solid antiperspirant activated salt compositions, for example according to US 6902723, contain 48-78% by weight (USP), preferably 66-75% by weight of an activated aluminum or aluminum-zirconium salt and 1-16% by weight, preferably 4 to 13% by weight of molecularly bound water, furthermore sufficient water-soluble strontium salt that the Sr: (Al + Zr) weight ratio is 1: 1-1: 28, preferably 1: 2-1: 25, and as much hydroxyalkanoic acid, the hydroxyalkanoic acid is in the (Al + Zr) weight ratio 2: 1-1: 20, preferably 1: 1-1: 10.

Further preferred activated aluminum salts are those of the general formula Al ₂ (OH) ₆ . _a Xa, wherein X is Cl, Br, I or NO ₃ and "a" is a value of 0.3 to 5, preferably from 0.8 to 2.5 and particularly preferably 1 to 2, so that the molar ratio of Al X is 0.9: 1 to 2.1: 1, as disclosed, for example, in US 6074632. These salts are generally slightly hydrated. associatively bound, typically 1 to 6 moles of water per mole of salt. Particularly preferred is aluminum chlorohydrate (ie, X is Cl in the aforementioned formula) and especially 5/6 basic aluminum chlorohydrate wherein "a" is 1 such that the molar ratio of aluminum to chlorine is 1.9: 1 to 2.1: 1 ,

Preferred activated aluminum-zirconium salts are those which are mixtures or complexes of the aluminum salts described above with zirconium salts of the formula ZrO (OH) ₂ _ _{pb b} represent Y, wherein Y is Cl, Br, I, NO ₃ or SO _4, b is a rational number from 0.8 to 2 and p is the valence of Y, as disclosed, for example, in US 6074632. The zirconium salts also typically associate some hydration water associatively, typically 1 to 7 moles of water per mole of salt. Preferably, the zirconium salt is zirconyl hydroxychloride having the formula ZrO (OH) _{2 -b} Cl _b , wherein b is a rational number of from 0.8 to 2, preferably from 1.0 to 1.9. Preferred aluminum zirconium salts have a molar Al: Zr mole ratio of 2 to 10 and a metal: (X + Y) ratio of 0.73 to 2.1, preferably 0.9 to 1.5. A particularly preferred salt is aluminum-zirconium chlorohydrate (ie, X and Y are Cl), which has a molar Al: Zr ratio of 2 to 10 and a molar metal: Cl ratio of 0.9 to 2.1. The term aluminum-zirconium chlorohydrate includes the tri-, tetra-, penta- and octachlorohydrate forms.

Zirconium salts preferred according to the invention have the general formula ZrO (OH) ₂ - _a Cl _a ^.x H ₂ O where a = 1.5- 1.87; x = 1-7, where a and x are rational numbers. These zirconium salts are disclosed, for example, in the Belgian specification BE 825146.

Other preferred antiperspirant actives are disclosed in US 6663854 and US 20040009133.

The antiperspirant active ingredients can be present both in solubilized and in undissolved, suspended form.

If the antiperspirant active ingredients are suspended in a water-immiscible carrier, it is preferred for reasons of product stability that the active ingredient particles have a number average particle size of 0.1-200 .mu.m, preferably 1-50 .mu.m, particularly preferably 3-20 .mu.m and extraordinarily preferably 5 - 10 microns have. Preferred active substance particles have a volume-average particle size of 0.2-220 .mu.m, preferably 3-60 .mu.m, more preferably 4-25 .mu.m and most preferably 10-15.5 .mu.m.

Preferred aluminum salts and aluminum zirconium salts have a molar metal to chloride ratio of 0.9 to 2.0, preferably 1, 0 to 1, 51, more preferably 1, 1 to 1.5, most preferably 1.3 to 1, 4, up.

Preferred aluminum zirconium chlorohydrates have the empirical formula Al _n Zr (OH) _{[ 3n +} 4 _{-m (n +} i _)] (CI) _{[m (n +} i)] where n = 2.0-10.0, preferably 3.0-8 , .O, m = 0.77-1.1 (corresponding to a molar metal (Al + Zr) to chloride ratio of 1.3-3.0), preferably m = 0.91-1.1 ( corresponding to M: CI = 1, 1-0.9), and particularly preferably m = 1.00-1.11 (corresponding to M: CI = 1.0-0.9), furthermore very preferably m = 1.02 1, 11 (corresponding to M: CI = 0.98-0.9) and very preferably m = 1, 04-1.1 (corresponding to M: CI = 0.96-0.9). Further preferred aluminum zirconium trichlorohydrates have the empirical formula Al ₄ (OH) ₁₀ Cl ₂ ^.Zr (OH) Cl.

Further preferred Aluminiumzirconiumtetrachlorohydrate have the empirical formula Al ₄ (OH) ₁₀ Cl ₂ ZrCl ^■ _2nd

Further preferred Aluminiumzirconiumpentachlorohydrate have the empirical formula AI ₈ (OH) ₂₀ CI ₆ ^■ Zr (OH) Cl.

Further preferred Aluminiumzirconiumoctachlorohydrate have the empirical formula AI ₈ (OH) ₁₈ CI ₆ ^■ Zr (OH) Cl.

In general, some water of hydration is associatively bound to these salts, typically 1-6 moles of water per mole of salt, corresponding to 1-30% by weight, preferably 4-13% by weight of water of hydration.

Preferred antiperspirant salts are aluminum zirconium tetrachlorohydrates (molar ratio Al: Zr = 2-6, M: CI = 0.9-1.5, preferably 0.95: 1.3, more preferably 1.0: 1, 1), in particular salts with one molar metal to chloride ratio of 0.9-1.1, preferably 0.9-1.0.

Other preferred antiperspirant salts are aluminum chlorohydrates having a molar metal to chloride ratio of M: CI = 1.9- 2.1.

Usually, the preferred aluminum zirconium chlorohydrates are associated with an amino acid to prevent polymerization of the zirconium species during manufacture. Preferred stabilizing amino acids are selected from glycine, alanine, leucine, isoleucine, β-alanine, cysteine, valine, serine, tryptophan, phenylalanine, methionine, β-amino-n-butanoic acid and γ-amino-n-butanoic acid and the salts thereof, each in the d-form, the I-form and the dl-form; Glycine is particularly preferred. The amino acid is contained in the salt in an amount of 1 to 3 moles, preferably 1 to 3 to 1.8 moles, per mole of zirconium.

The aforementioned aluminum-zirconium trichlorohydrates, aluminum-zirconium tetrachlorohydrates, aluminum-zirconium pentachlorohydrates and aluminum-zirconium octachlorohydrates are preferably present both as activated and unactivated as complexes with glycine. Particularly preferred antiperspirant active substances are selected from activated aluminum-zirconium trichlorohydrex glycine, in particular activated aluminum-zirconium trichlorohydrex glycine with a water-free and glycine-free active substance (USP) of 69.5-88% by weight, preferably 72-85% by weight %, more preferably 77-80% by weight, in each case based on the raw material tel quel, of a molar metal: CI ratio of 0.9 to 1.5 and a molar Al: Zr ratio of 3.4. 3.8.

Further particularly preferred antiperspirant active substances are selected from non-activated aluminum-zirconium trichlorohydrex glycines, in particular non-activated aluminum zirconium trichlorohydrex glycines with anhydrous and glycine-free active substance (USP) of 69.5-88% by weight, preferably 72 85% by weight, particularly preferably 77-80% by weight, each based on the raw material tel quel, a molar metal: CI ratio of 0.9 to 1, 5 and a molar AI: Zr ratio of 3.4 to 3.8.

Further particularly preferred antiperspirant active substances are selected from activated aluminum-zirconium tetrachlorohydrex glycine, in particular activated aluminum-zirconium tetrachlorohydrex glycine with an anhydrous and glycine-free active substance (USP) of 72-88% by weight, preferably 77-85% by weight. , in each case based on the raw material tel quel, a molar metal: CI ratio of 0.9 to 1.5 and a molar Al: Zr ratio of 3.4-3.8.

Further particularly preferred antiperspirant active substances are selected from non-activated aluminum-zirconium tetrachlorohydrex glycine, in particular non-activated aluminum zirconium tetrachlorohydrex glycine with a water-free and glycine-free active substance (USP) of 72-88% by weight, preferably 77-85 Wt .-%, each based on the raw material tel quel, a molar metal: CI ratio of 0.9 to 1, 5 and a molar Al: Zr ratio of 3.4 to 3.8.

Further particularly preferred antiperspirant active substances are selected from activated aluminum zirconium pentachlorohydrex glycine, in particular activated aluminum zirconium pentachlorohydrex glycine with a water-free and glycine-free active substance (USP) of 72-88% by weight, preferably 77-86% by weight. , particularly preferably 78-81, 5 wt .-%, each based on the raw material tel quel, a molar metal: CI ratio of 1, 51 to 2.0 and a molar Al: Zr ratio of 9.2 to 9 ,8th.

Further particularly preferred antiperspirant active ingredients are selected from non-activated aluminum zirconium pentachlorohydrex glycine, in particular non-activated aluminum zirconium pentachlorohydrex glycine with a water-free and glycine-free active substance (USP) of 72-88 wt.%, Preferably 77-86 wt. %, more preferably 78-81.5% by weight, based in each case on the raw material tel quel, of a molar metal: CI ratio of 1.51 to 2.0 and a molar Al: Zr ratio of 9.2 - 9,8.

The water of crystallization content of the aforementioned activated as well as unactivated aluminum zirconium trichlorohydrex glycine, aluminum zirconium tetrachlorohydrex glycine, aluminum zirconium pentachlorohydrex glycine and aluminum zirconium octachlorohydrex glycine is 1.5 to 20% by weight, preferably 7 to 15% by weight, respectively based on the raw material tel quel. Further preferred aluminum zirconium trichlorohydrex glycines have the empirical formula [Al ₄ (OH) ₁₀ Cl ₂ ^.Zr (OH) Cl] ^.NH ₂ CH ₂ COOH.

Other preferred aluminum-zirconium tetrachlorohydrex glycine have the empirical formula [Al ₄ (OH) ₁₀ Cl ₂ ^■ ZrOCl _2] ^■ NH ₂ CH ₂ COOH.

Further preferred aluminum zirconium pentachlorohydrex glycines have the empirical formula [Al ₈ (OH) ₂₀ Cl ₄ ^.Zr (OH) Cl] ^.NH ₂ CH ₂ COOH.

Further preferred aluminum Zirconiumoctachlorohydrex Glycine have the empirical formula [Al ₈ (OH) ₁₈ Cl ₆ ^■ Zr (OH) CI] ^■ NH ₂ CH ₂ COOH or [Al ₈ (OH) ₁₈ Cl ₆ ^■ ZrOCl _2] ^■ NH ₂ CH ₂ COOH. Also preferred according to the invention are aluminum zirconium chlorohydrate-glycine salts which are stabilized with betaine ((CH ₃ ) _S N ⁺ -Cl-I ₂ -COO). Particularly preferred corresponding compounds have a total molar (betaine + glycine) / Zr ratio of (0.1-3.0): 1, preferably (0.7-1.5): 1, and a betaine molar ratio Glycine of at least 0.001: 1 on. Corresponding compounds are disclosed, for example, in US Pat. No. 7,105,691.

In a particularly preferred embodiment according to the invention, the particularly effective antiperspirant salt comprises a so-called "activated" salt, in particular one with a high HPLC peak 5-aluminum content, in particular with a peak 5 surface of at least 33%, particularly preferred at least 45%, based on the total area under peaks 2-5, as measured by HPLC of a 10% by weight aqueous solution of the active substance under conditions in which the aluminum species are resolved into at least 4 consecutive peaks (with peaks 2 - 5). Preferred aluminum zirconium salts having a high HPLC peak 5-aluminum content (also referred to as "E ⁵ AZCH") are disclosed, for example, in US 6436381 and US 6649152.

Furthermore, those activated "E ⁵ AZCH" salts whose HPLC peak has a 4-to-peak 3 area ratio of at least 0.4, preferably at least 0.7, particularly preferably at least 0.9, are preferred.

Further particularly preferred antiperspirant active ingredients are those aluminum zirconium salts having a high HPLC peak 5-aluminum content, which are additionally stabilized with a water-soluble strontium salt and / or with a water-soluble calcium salt. Corresponding salts are disclosed, for example, in US Pat. No. 6,923,952.

Other preferred antiperspirant actives are selected from astringent titanium salts such as disclosed in GB 2299506A.

The antiperspirant active compounds can be used as nonaqueous solutions or as glycolic solubilisates.

Particularly preferred compositions according to the invention are characterized in that the at least one antiperspirant active ingredient is present in an amount of 5 to 40% by weight, preferably 10 to 35% by weight, more preferably 11 to 28% by weight and most preferably 12%. 20 wt .-%, based on the total weight of the water-free and ligand-free active substance (USP) in the total composition.

In a particularly preferred embodiment, the composition contains an astringent aluminum salt, in particular aluminum chlorohydrate, more preferably aluminum chlorohydrate with an anhydrous active substance (USP) of 72-88 wt .-%, based on the raw material tel quel. Preferred non-activated aluminum chlorohydrates, for example, in powder form as Micro Dry ^®, Micro Dry ^® Ultrafine or Micro Dry ^® -323 from Summit Reheis, as Chlorhydrol ^® (powder) as well as in activated form as Reach ^® 101, Reach ^® 103, Reach ^® 501 Reheis / Summit or AACH-7171 is sold by Summit. Under the name Reach ^® 301, an aluminum sesquichlorohydrate from Reheis is also offered, which is also particularly preferred.

Especially preferred are aluminum-zirconium tetrachlorohydrex-glycine complexes, for example, from Summit Reheis under the name Rezal ^® 36 GP, Summit AZG-369, or Summit AZG-364, or, in activated quality than Summit Reach ^® AZP-908 , as powders are on the market.

Also particularly preferred are aluminum-zirconium-pentachlorohydrex-glycine complexes, which are commercially available, for example, in activated quality from Summit under the designations AAZG-3108 and AAZG-3110.

The antiperspirant active ingredients are in the formulations of the invention in an amount of 1 to 40 wt .-%, preferably from 3 to 15 wt .-%, based on the total mass of the preparation, d. H. Including possibly existing propellants used.

In stick formulations, the proportion of antiperspirant active ingredients is preferably in the range from 10 to 20% by weight, in each case based on the total mass of the preparation.

Vicinal diols can also be present as antiperspirant active ingredients in the compositions according to the invention. Preferred vicinal antiperspirant diols are selected from 1,2-propylene glycol, glycerol, 1,2-butylene glycol, 1,2-pentanediol, dipropylene glycol, tripropylene glycol, diglycerol and triglycerol. The total amount of vicinal diols is preferably 10 to 50 wt .-%, more preferably 15 to 30 wt .-%, most preferably 15 to 25 wt .-%, each based on the total mass of the preparation.

Optionally, the compositions according to the invention may contain further antiperspirant active ingredients and / or deodorant active ingredients.

The silver citrate complex, including water, is advantageously added to a proportion of at most 5% by weight, preferably 2% by weight, in particular 0.1 to 2% by weight, based on the total mass of the active compound mixture.

A preferred commercially available silver citrate complex, including water, contains a concentration of silver ions of 2280 to 2640 ppm, corresponding to 0.228 to 0.264% by weight of silver ions. Thus, the preparations according to the invention preferably contain not more than 114 to 132 ppm of silver ions, particularly preferably 45.6 to 52.8 ppm of silver ions, exceptionally preferably 0.1-45.6 ppm or also very preferably 0.1-52.8 ppm of silver ions. Further preferred compositions according to the invention are characterized in that silver ions in a total amount of 1-100 ppm, preferably 2-50 ppm, more preferably 5-20 ppm, most preferably 7-10 ppm, in each case based on the weight of the propellant-free composition of the invention are.

The active substance mixture is equal to the preparation, but if the preparation is an aerosol, the proportions refer to the active mixture without propellant gas. The spray formulations of the present invention are preferably presented from standard aerosol and pen packages. In particular, they are suitable for spraying by standard antiperspirant valves and spray heads, as they help prevent clogging disadvantages. Advantage of the preparations according to the invention is thus that can be dispensed with elaborate special packaging such as powder valves. Such valves are less sensitive to clogging due to their special design or geometry by larger particles. A disadvantage of the use of such powder valves is that the special form usually requires the use of adapted spray heads. This requires additional costs and a diversification of the packaging product range and thus additional logistical effort. These disadvantages are avoided according to the invention.

Another problem that is solved according to the invention is that with the simultaneous use of water-soluble encapsulated perfume, which react to the presence of water with swelling, sticking and dissolution, these disadvantages are not observed here, since the water is removed from the perfume. In spite of the presence of water (at most 8% by weight (see above)), any desired water-soluble capsule materials for perfume oils can be combined with aqueous silver solutions according to the invention. Thus, modified starch (INCI: Sodium Starch Octenylsuccinate or Modified Starch) may preferably be used as capsule material. Further particularly preferred deodorant or antiperspirant compositions according to the invention are characterized in that at least one perfume component is present in encapsulated form. A preferred embodiment is characterized in that the capsule material is water-soluble. A preferred water-soluble capsule material is sodium starch octenyl succinate. The perfume capsules are preferably composed of about 40% sodium starch octenyl succinate, 10% mannitol and about 50% perfume oil.

The amount of perfume capsules used is preferably in the range from 0.3 to 0.8% by weight, based on the total mass of the preparation. In addition, it is possible to contain 0.8-1.2% by weight of unencapsulated, that is to say free, perfume oil.

The cosmetic and dermatological preparations according to the invention may contain cosmetic adjuvants such as are conventionally used in such preparations, eg. As preservatives, bactericides, UV filters, antioxidants, vitamins, minerals, suspended solid particles, perfumes, substances to prevent foaming, dyes, pigments that have a coloring effect, thickeners, moisturizing and / or moisturizing substances or other common constituents of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers or silicone derivatives. If the compositions according to the invention be in the form of a pin, they preferably contain a lipid or wax matrix comprising at least one lipid or wax component with a melting point> 5O ⁰ C.

In general, waxes of solid to brittle hard consistency, coarse to fine crystalline, translucent to opaque, but not glassy, and melt above 50 ⁰ C without decomposition. she are already slightly above the melting point low viscosity and show a strong temperature-dependent consistency and solubility.

Preference according to the invention, for example, natural vegetable waxes, z. Candelilla wax, carnauba wax, Japan wax, sugarcane wax, ouricoury wax, cork wax, sunflower wax, fruit waxes such as orange waxes, lemon waxes, grapefruit wax, and animal waxes, e.g. Beeswax, shellac wax and spermaceti. For the purposes of the invention, it may be particularly preferred to use hydrogenated or hardened waxes. As a wax component and chemically modified waxes, especially the hard waxes, such as. As montan ester waxes, hydrogenated jojoba waxes and Sasol waxes used. Synthetic waxes, which are also preferable in the invention include, for example, polyalkylene waxes and polyethylene glycol waxes, C ₂ oC _4O dialkyl esters of dimer acids, C ₃₀ - ₅₀ alkyl and alkylaryl esters of -Alkylbienenwachs dinner as well as fatty acids.

A particularly preferred wax component is selected from at least one ester of a saturated monohydric C ₆ -C ₆ -alcohol and a saturated Cs-Csβ-monocarboxylic acid. Citrides, the cyclic double esters of alpha-hydroxy carboxylic acids of the corresponding chain length, also count according to the invention for this purpose. Esters of fatty acids and long-chain alcohols have been found to be particularly advantageous for the composition of the present invention because they give the antiperspirant preparation excellent sensory properties and overall high stability to the pin. The esters are composed of saturated branched or unbranched monocarboxylic acids and saturated branched or unbranched monohydric alcohols. Also, esters of aromatic carboxylic acids and hydroxycarboxylic acids (eg., 12-hydroxystearic acid) and saturated branched or unbranched alcohols are used according to the invention, provided that the wax component has a melting point> 5O ⁰ C. It is particularly preferred to select the wax components from the group of esters of saturated branched or unbranched alkanecarboxylic acids of a chain length of 12 to 24 carbon atoms and the saturated branched or unbranched alcohols of a chain length of 16 to 50 carbon atoms, which has a melting point > 5O ⁰ C have.

In particular, as the wax component C _6-36 alkyl stearates and C ₈ - ₃₈ stearate -Alkylhydroxystearoyl-, C ₂ o ₄ o-Alkylerucate and cetearyl be advantageous. The wax or the wax components have a melting point> 5O ⁰ C, preferably> 6O ⁰ C on.

A particularly preferred embodiment of the invention contains as wax component a C ₂ oC _4O alkyl stearate. This ester is known under the name Kester ^® K82H or Kesterwachs ^® K80H and is sold by Koster Keunen Inc.. It is the synthetic imitation of the monoester fraction of beeswax and is characterized by its hardness, oil gelability and broad compatibility with lipid components. This wax can be used as a stabilizer and consistency regulator for W / O and O / W emulsions. Kester wax has the advantage that it has an excellent oil gelability even at low concentrations and so does not make the pencil mass too heavy and a velvety abrasion allows. A further particularly preferred embodiment of the invention contains as wax component cetearyl behenate, ie mixtures of cetyl behenate and stearyl behenate. This ester is known under the name Kester ^® K62 and is sold by Koster Keunen Inc..

Other preferred lipid or wax components with a melting point> 5O ⁰ C are the triglycerides of saturated and optionally hydroxylated C ₁₂ - ₃ o-fatty acids such as hydrogenated triglyceride fats (hydrogenated palm oil, hydrogenated coconut oil, hydrogenated castor oil), glyceryl tribehenate (tribehenin), or glyceryl tri-12 Hydroxystearat, further synthetic full esters of fatty acids and glycols or polyols having 2 to 6 carbon atoms, as long as they have a melting point above 50 ⁰ C, for example, preferably Ci ₈ - C ₃₆ Acid triglycerides (Syncrowax ^® HGL-C). According to the hydrogenated castor oil as a wax component, available for example as a commercial product Cutina ^® HR, is particularly preferred.

Other preferred lipid or wax components with a melting point> 5O ⁰ C, the saturated linear C ₄ - C ₃₆ carboxylic acids, in particular myristic acid, palmitic acid, stearic acid and behenic acid, and mixtures of these compounds, for example. B. Syncrowax ^® AW 1C (C ₁₈ - C ₃₆ fatty acids) or Cutina ^® FS 45 (palmitic and stearic acid).

Preferred deodorant or antiperspirant sticks according to the invention are characterized in that the lipid or wax component a) is selected from esters of a saturated, monohydric C ₆ -C ₆ o-alkanol and a saturated C ₈ -C ₃₆ monocarboxylic acid, in particular cetyl behenate , stearyl behenate and C ₂ oC _4O alkyl stearate, glycerol triesters of saturated linear C _I2 - C ₃₀ carboxylic acids, which may be hydroxylated, candelilla wax, carnauba wax, beeswax, saturated linear C ₄ - C ₃₆ carboxylic acids and mixtures of the aforementioned substances. Particularly preferred lipid or wax component mixtures a) are selected from mixtures of cetyl behenate, stearyl behenate, hardened castor oil, palmitic acid and stearic acid. Further particularly preferred lipid or wax component mixtures a) are selected from mixtures of C ₂ -C ₄ -alkyl stearate, hardened castor oil, palmitic acid and stearic acid.

Further preferred deodorant or antiperspirant sticks according to the invention are characterized in that the lipid or wax component (s) is contained in total in amounts of 4 to 20% by weight, preferably 8 to 15% by weight, based on the total composition. In a particularly preferred embodiment, the ester (s) is / are a saturated monohydric C ₁₆ -C ₆ o alcohol and a saturated C ₈ -C ₃₆ monocarboxylic acid which is / are the lipid or wax component (s) Quantities of a total of 2 - 10 wt .-%, preferably 2 - 6 wt .-%, based on the total composition.

Preferred compositions of the present invention, which are in the form of a spray or stick, preferably further contain at least one oil which is liquid at 20 ° C. and which does not constitute a perfume component and does not represent an essential oil. Oils preferred according to the invention are selected from branched saturated or unsaturated fatty alcohols having 6 to 30 carbon atoms. These alcohols are often referred to as Guerbet alcohols, as they are available after the Guerbet reaction. Preferred oils are alcohol Hexyldecanol (Eutanol ^® G 16, Guerbitol ^® T 16) Octyldodecanol (Eutanol ^® G) and 2-ethylhexyl alcohol. Other preferred oil components are mixtures of Guerbet alcohols and Guerbet alcohol esters, for example the commercial product Cetiol ^® PGL (hexyldecanol and hexyldecyl laurate).

Further according to the invention preferred oils are selected from the triglycerides of linear or branched, saturated or unsaturated, optionally hydroxylated C ₈ - ₃ o-fatty acids. Particularly suitable may be the use of natural oils, for example soybean oil, cottonseed oil, sunflower oil, palm oil, palm kernel oil, linseed oil, almond oil, castor oil, corn oil, olive oil, rapeseed oil, sesame oil, thistle oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil and the like. But are also synthetic triglyceride oils, in particular Capric / Caprylic triglycerides, z. As the commercial products Myritol ^® 318, Myritol ^® 331 (Cognis) or Miglyol ^® 812 (Hüls) with unbranched fatty acid residues and glyceryl triisostearin and the commercial products Estol ^® GTEH 3609 (Uniqema) or Myritol ^® GTEH (Cognis) with branched fatty acid residues.

Further 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 oils are selected 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. B. PPG-2 myristyl ether and PPG-3 myristyl ether (Witconol APM ^®).

Further oil components preferred according to the invention are selected from the esters of linear or branched saturated or unsaturated fatty alcohols having 2 to 30 carbon atoms with linear or branched saturated or unsaturated fatty acids having 2 to 30 carbon atoms, which may be hydroxylated. These include, hexyldecyl stearate (Eutanol ^® G 16 S), hexyldecyl laurate, isodecyl neopentanoate, isononyl isononanoate, 2-ethylhexyl palmitate (Cegesoft ^® C 24) and 2-ethylhexyl stearate (Cetiol ^® 868). Also suitably suitable are isopropyl myristate, isopropyl palmitate, isopropyl stearate, 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. butyloctanoate, diisotridecyl acetate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, ethylene glycol dioleate and dipalmitate.

Further inventively preferred oil components are selected from the addition products of at least 6 ethylene oxide and / or propylene oxide units of mono- or polyhydric C ₃ - ₂₂ -alkanols such as butanol, butanediol, myristyl alcohol and stearyl alcohol, eg. For example, PPG-14-butyl ether (Ucon Fluid ^® AP), PPG-9-butyl ether (Breox B25 ^®), PPG-10 butanediol (Macol ^® 57) and PPG-15 stearyl ether (Arlamol ^® E).

Further oil components preferred according to the invention are selected from the C ₈ -C ₂₂ -fekalcohol esters of monohydric or polyhydric C ₂ -C ₇ -hydroxycarboxylic acids, in particular the esters of glycolic acid, citric acid, malic acid, tartaric acid, citric acid and salicylic acid. Such esters based on linear C _{14 /} -i ₅ alkanols, z. B. C ₁₂ -C ₅ alkyl citrate, and of branched in the 2-position C- _12/13 alkanols are under the trademark Cosmacol ^® by the company Nordmann, Rassmann GmbH & Co, Hamburg, refer, in particular the commercial products Cosmacol ^® ESI, Cosmacol® ^® EMI and Cosmacol® ^® EIT.

Further inventively preferred oil components are selected from the symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, eg. B. Glycerincarbo- nat, dicaprylyl carbonate (Cetiol ^® CC) or the esters of DE 197 56 454 A1.

Further preferred oil components according to the invention are selected from the esters of dimers of unsaturated C ₂ -C ₂₂ -fatty acids (dinner fatty acids) with monovalent linear, branched or cyclic C ₂ -C ₈ -alkanols or with polyvalent linear or branched C ₂ -C ₆ -alkanols. It may be extraordinarily preferred according to the invention to use mixtures of the abovementioned oils.

Further oil components preferred according to the invention are selected from silicone oils and hydrocarbon oils.

Silicone oils preferred according to the invention are selected from dialkyl and alkylaryl siloxanes, such as, for example, cyclopentasiloxane, cyclohexasiloxane, dimethylpolysiloxane and methylphenyl polysiloxane, but also include hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane. Further inventively preferred silicone oils are selected from volatile silicone oils which may be cyclic, such as. For example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane and mixtures thereof, as described for. B. in the commercial products DC 244, 245, 344 and 345 of Dow Corning, or linear, z. As hexamethyldisiloxane (L ₂ ), octamethyltrisiloxane (L ₃ ), decamethyltetrasiloxane (L ₄ ), any two and three mixtures of L ₂ , L ₃ and / or L ₄ , as described, for. B. in the commercial products DC 2-1184, Dow Corning ^® 200 (0, 65 cSt), and Dow Corning ^® 200 (1, 5 cSt) contained by Dow Corning. Further inventively preferred silicone oils are selected from non-volatile higher molecular weight linear dimethylpolysiloxanes, commercially available z. Example under the name Dow Corning ^® 190, Dow Corning ^® 200 fluid with viscosities ranging from 5 to 100 cSt, preferably of 5 - 50 cSt or 5 - 10 cSt, and Baysilon ^® 350 M.

According to the invention preferred natural and synthetic hydrocarbons are selected from paraffinic oils, isohexadecane, isoeicosane, polyisobutenes and polydecenes, for example, under the designation Emery ^® 3004, 3006, 3010 or under the name ^® Ethylflo of Albe- Marle or Nexbase ^® are available from Nestle 2004G, and 1, 3-di- (2-ethylhexyl) -cyclohexane (Cetiol ^® S).

Particularly preferred deodorant or antiperspirant compositions according to the invention are characterized in that the oil (s) liquid at 20 ^° C. in a total amount of 0.1-80% by weight, preferably 2-20% by weight, particularly preferably 3-15% by weight, in each case based on the total weight of the composition, is / are contained. Compositions which are particularly preferred according to the invention furthermore preferably contain at least one skin-cooling active substance. Skin-cooling active ingredients suitable according to the invention are, for example, menthol, isopulegol and menthol derivatives, eg. Menthyl citrate, menthylglycolate, menthylpyrrolidonecarboxylic acid, menthylmethyl ether, menthoxypropanediol, menthone-glycerol acetal (9-methyl-6- (1-methylethyl) -1, 4-dioxaspiro (4.5) decane-2-methanol), monomethylsuccinate and 2-hydroxymethyl -3,5,5-trimethylcyclohexanol. Preferred skin-cooling active ingredients are menthol, isopulegol, menthyl citrate, menthoxypropanediol and menthylpyrrolidonecarboxylic acid and mixtures of these substances, in particular mixtures of menthol and menthyl citrate, menthol, menthol glycolate and menthyl citrate, menthol and menthoxypropanediol or menthol and isopulegol.

It is particularly preferred according to the invention for at least one skin-cooling active ingredient to be present in a total amount of 0.01-1% by weight, more preferably 0.02-0.5% by weight and most preferably 0.05-0.2% by weight. %, in each case based on the total weight of the composition.

Particularly preferred compositions according to the invention, which are formulated as a propellant-driven aerosol, contain at least one propellant. 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, both individually and in combination. 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 amount of the blowing agent is preferably 20-80% by weight, more preferably 30-70% by weight and most preferably 40-50% by weight, in each case based on the total weight of the preparation, consisting of the composition according to the invention and the blowing agent , 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 the corrosion resistance compared with the composition according to the invention.

polyols

Preferred compositions according to the invention also comprise 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 3-20 ethylene oxide units and mixtures thereof. These components are preferably selected from 1,2-propylene glycol, 2-methyl-1,3-propanediol, glycerol, butylene glycols such as 1,2-butylene glycol, 1,3-butylene glycol and 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 the 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.

Preferred deodorant or antiperspirant compositions according to the invention are characterized in that the at least one water-soluble polyhydric C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol having 3 to 20 ethylene oxide units is selected from 1, 2 Propylene glycol, 2-methyl-1,3-propanediol, glycerin, butylene glycols such as 1,2-butylene glycol, 1,3-butylene glycol and 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 the aforementioned substances. Particularly preferred deodorant or antiperspirant compositions according to the invention are characterized in that the at least one water-soluble polyhydric C ₂ -C ₉ -alkanol having 2 to 6 hydroxyl groups and / or at least one water-soluble polyethylene glycol having 3 to 20 ethylene oxide units in total amounts of 3 - 30 wt .-%, preferably 8 - 25 wt .-%, particularly preferably 10-18 wt .-%, each based on the total composition, is included.

Particularly preferred according to the invention deodorant or antiperspirant compositions are characterized in that at least one lipid or wax component with a melting point in the range of 25 - <5O ⁰ C, selected from Kokosfettsäureglycerinmono- mono-, di- and triesters, Butyrospermum Parkii (Shea Butter ) and esters of saturated, monohydric C ₈ -C ₁₈ alcohols with saturated C ₁₂ -C ₁₈ monocarboxylic acids and mixtures of these substances. These lower melting lipid or wax components allow consistency optimization of stick-shaped or creamy products and minimization of visible residue on the skin. Especially preferred are products sold under the INCI name Cocoglycerides, in particular the commercial products Novata ^® (ex Cognis), particularly preferably Novata AB ^®, a mixture of C ₂ -C ₈ mono-, di- and triglycerides, which is in the range of 30 - 32 ° C to melt, and the products of Softisan series (Sasol Germany GmbH) with the INCI designation Hydrogenated Cocoglycerides, particularly Softisan 100, 133, 134, 138, 142. Other preferred esters of saturated, monohydric C ₂ -C ₈ alcohols having saturated Ci _Σ -C-is-monocarboxylic acids are stearyl laurate, cetearyl (z. B. Crodamol ^® CSS), cetyl palmitate (eg Cutina ^® CP) and myristyl myristate (eg Cetiol ^® MM).

Further particularly preferred deodorant or antiperspirant according to the invention cooperation ratios are characterized in that with a melting point in the range of 25 at least one lipid or wax component - <5O ⁰ C preferably in amounts of from 0.01 to 20 wt .-%, From 3 to 20% by weight, more preferably from 5 to 18% by weight, and most preferably from 6 to 15% by weight, based on the total composition.

Further preferred compositions according to the invention are characterized in that they contain at least one perfume. As fragrances or perfume oils, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. The phenolic fragrance compounds include z. B. carvacrol. Fragrance compounds of the ester type are known e.g. Benzyl acetate, methyl anthranilate, ortho-t-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, diethyl phthalate, nonanediol-1,3-diacetate, iso-nonylacetate, iso-nonylformate, phenylethylphenylacetate, phenoxyethylisobutyrate, linalylacetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate , Ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, ethylsalicylate, iso-amylsalicylate, hexylsalicylate and 4-nonanolide. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, e.g. 6-acetyl-1,1,1,4,4,6-hexamethyltetrahydronaphthalene, para-t-amylcyclohexanone, 2-n-heptylcyclopentanone, β-methylnaphthyl ketone and the ionones α-isomethyl-ionone and methyl cedryl ketone, to the alcohols cinnamyl alcohol, anethole , Citronellol, Dimyrcetol, Eugenol, Geraniol, Linalool, Phenylethylalcohol and Terpineol, the hydrocarbons include 1.SAΘJ.δ-Hexahydro ^ θ.θJ.δ.δ-hexamethylcyclopenta-a ^ -benzopyran, hydroxymethylisopropylcyclopentane, 3-a- Methyldodecahydro-6,6,9a-trimethylnaphtho-2 (2,1-b) furan, iso-butyl-quinone, and the terpenes and balsams. Preference is given to using mixtures of different fragrances which together produce an attractive fragrance.

Suitable perfume oils may also contain natural fragrance mixtures, such as those obtainable from vegetable or animal sources, for example pine, citrus, jasmine, rose, lily or ylang-ylang oil. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg sage oil, chamomile oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, laudanum oil, clove oil, iso-eugenol, thyme oil, bergamot oil , Geranium oil and rose oil. Preferred compositions according to the invention are characterized in that at least one perfume in a total amount of 0.1 to 10 wt .-%, preferably 0.2 to 7 wt .-%, particularly preferably 0.4 to 6 wt .-%, most preferably 1 to 5% by weight, furthermore very preferably 2 to 4% by weight, in each case based on the total weight of the blowing agent-free composition.

Advantageous constituents of the preparation according to the invention are silica, silica dimethyl silylates, aluminum chlorohydrate, perfume and silver citrate, advantageously as aerosol and advantageously with butane and / or propane as propellant gases.

A further subject of the present application is a non-therapeutic, cosmetic method for reducing and / or regulating perspiration and / or body odor, in which a composition according to the invention or a preferred composition according to the invention, in particular a composition according to one of claims 1, 2, 3 , 4, 5, 6, 7, 8, 9, 10, 11 or 12 are applied in an effective amount to the skin, preferably to the skin in the underarm area.

With respect to preferred embodiments of the method according to the invention mutatis mutandis applies to the compositions of the invention.

A further subject of the present application is the non-therapeutic, cosmetic use of a preferred or an inventively preferred antiperspirant composition according to the invention, in particular a composition according to one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 to reduce and / or regulate perspiration and / or body odor.

With regard to preferred embodiments of the use according to the invention, what has been said about the compositions according to the invention applies mutatis mutandis.

The following examples illustrate the preparations according to the invention. The proportions stated therein are based on the total mass of the preparation or active substance solution.

Examples:

With propellant gas preferably butane / isobutane / propane and filling ratio 5:95 to 30:70, preferably 10:90 to 20:80, preferably 15:85.

Antitranspirantaerosole:

All quantities are in wt .-%.

Antiperspirant suspension compositions (filling material) for packaging as aerosol spray with liquefied n-butane as blowing agent in a weight ratio of contents to blowing agent of 10:90 to 30:70, preferably from 14:86 to 25:75, particularly preferably from 18:82 to 23:77, more preferably 20:80.

Compositions Nos. 1 to 8 of the invention were applied to the skin in the underarm area.

Antitranspirantstick

No. 8

AZCH powder (Aluminum Zirconium 24.00 Chlorohydrate)

Silica dimethyl silylates

0.72

(Aerosil R972, hydrophobic silica)

Silica (Aerosil 300, hydrophilic silica) 0.18

Stearyl alcohol 20.00

MP70 castor wax 2.84

Myristyl myristate 1.92 PPG-14 Butyl ether 11.00 Perfume 0.85 Silver citrate 0,001 Cyclomethicone ad 100

List of raw materials used

Claims

claims An anhydrous cosmetic or dermatological composition comprising one or more silver citrate-citric acid complexes of the form

with x + y = 3 with a water content of up to 90% by weight, based on the total mass of the complex, in combination with one or more passivating agents selected from the group of silicic acids, one or more antiperspirant active ingredients and perfume, characterized in that phyllosilicate (e) in a total amount from zero to at most 1, 3 wt .-% are included. 2. Preparation according to claim 1, characterized in that the antiperspirant active ingredient is selected from the water-soluble astringent inorganic and organic salts of aluminum and zirconium and any mixtures of these salts. 3. Preparation according to one of the preceding claims, containing activated aluminum chlorohydrate. 4. A preparation according to any one of the preceding claims, containing encapsulated perfume, wherein the capsule material is water-soluble. 5. Preparation according to one of the preceding claims, characterized in that silver ions in a total amount of 1 - 100 ppm, preferably 2 - 50 ppm, more preferably 5 - 20 ppm, most preferably 7 - 10 ppm, each based on the weight of propellant-free Composition of the invention are included. 6. Preparation according to one of the preceding claims, characterized in that the passivation agent is a mixture of at least one hydrophilic silica and at least one hydrophobic silica. A composition according to any one of the preceding claims comprising silica and silica dimethyl silylates as passivating agents. 8. Preparation according to one of the preceding claims as an aerosol, characterized in that silica, silica dimethyl silylates, aluminum chlorohydrate, perfume and silver citrate are included. 9. Preparation according to one of the preceding claims, formulated as a spray composition, characterized in that at least one hydrophilic silica in a total amount of 0.2 to 2 wt .-%, preferably 0.4 to 1, 5 wt .-%, more preferably 0.5-1.0% by weight and most preferably 0.6-0.8% by weight, based in each case on the total weight of the blowing agent-free composition according to the invention. 10. Preparation according to one of the preceding claims, compounded as a stick composition, characterized in that at least one hydrophilic silica in a total amount of 0.1 to 1 wt .-%, preferably 0.2 to 0.8 wt .-%, more preferably 0.3-0.5% by weight, based in each case on the total weight of the composition according to the invention. 11. Preparation according to one of the preceding claims, compounded as a spray composition, characterized in that at least one hydrophobic silica in a total amount of 1 - 5 wt .-%, preferably 1, 5 - 4 wt .-%, particularly preferably 2 - 3.5 wt .-%, most preferably 2.5 to 3 wt .-%, each based on the total weight of the blowing agent-free composition of the invention is included. 12. Preparation according to one of the preceding claims, compounded as a stick composition, characterized in that at least one hydrophobic silica in a total amount of 0.5 to 5 wt .-%, preferably 0.7 to 4 wt .-%, particularly preferably 0.8 to 3.5 wt .-%, most preferably 1 to 3 wt .-%, each based on the total weight of the composition according to the invention is included. 13. A non-therapeutic, cosmetic method for reducing and / or regulating perspiration and / or body odor which comprises a preparation according to any of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 in an effective amount on the skin, preferably on the skin in the underarm area, is applied. A non-therapeutic, cosmetic use of an antiperspirant composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 for reducing and / or regulating transpiration and / or body odor.