Water-free, antiperspirant composition with improved stability

Abstract

Sprayable antiperspirant containing an antiperspirant composition for personal body care containing: a) at least one antiperspirant active ingredient in the form of spherical particles, which is present in suspended, non-dissolved form and is selected from aluminum salts in a total amount of 5 - 35 wt.%, b) 0.1 - 1% by weight of rice starch in the form of a powder treated with cationic surfactants, the proportion of cationic surfactants being 0.01 - 0.3% by weight, based on the weight of the rice starch, c) 1.5 - 3.5 wt.% hydrophobically modified clay mineral, d) at least one oil in a total amount of 20 - 94.8 wt.%, e) 0 to 7 wt% free water, where all weight percentages refer to the weight of the composition, without taking into account any blowing agents present, characterized in that the composition is in an aerosol can with a compressed gaseous propellant.

Description

[0001] The present invention relates to sprayable antiperspirants comprising an anhydrous antiperspirant composition having improved stability with respect to the oil suspensions of the antiperspirant active ingredients used therein, said antiperspirant composition being present in an aerosol can with a compressed gaseous propellant.

[0002] Commercially available antiperspirant compositions, also referred to as antiperspirants, contain at least one water-soluble, astringent, inorganic or organic aluminum salt as the antiperspirant active ingredient. These antiperspirant active ingredients do not directly influence the activity of the sweat glands, but rather minimize sweat secretion by constricting the sweat ducts. The aluminum salts inhibit sweating on the treated skin areas by superficially blocking the sweat gland ducts as a result of aluminum mucopolysaccharide deposits. Antiperspirant compositions are typically applied to the underarm area. Antiperspirant compositions are available in various dosage forms, for example, as a propellant-sprayable composition.Such compositions are usually packaged in aluminum or (less commonly) tinplate spray cans, which are protected against corrosion by an internal coating. Despite such a protective coating, corrosion damage can still occur. Another problem with such products is valve clogging. A corrosion-inhibiting and / or valve clogging-reducing composition would therefore be desirable for these special dosage forms.

[0003] DE10021056A1 discloses anhydrous, pasty or creamy antiperspirant compositions containing at least two particulate polysaccharides and / or polysaccharide derivatives, an antiperspirant aluminum salt, and a lipid component with a melting point of 30-150°C in a liquid, oil-containing carrier material. This gives these compositions good storage stability without syneresis of the oil components at room temperature, as well as high temperature stability. EP570085A2 discloses sprayable antiperspirants with the lowest possible proportion of volatile organic components and a high content of solid particles, preferably containing a mixture of aluminum salt and at least one filler selected from talc, chemically modified corn starch, non-reactive polymers such as micronized polyethylene, polyacrylates, or cross-linked polyurethanes, but also powders such as sodium bicarbonate, corn starch, or any other vegetable starches.

[0004] Propellant-sprayable compositions are usually based on suspensions of astringent salts such as aluminum chlorohydrate (ACH) in non-polar oils such as cyclomethicone. These suspensions must be stable for as long as possible. If the salt particles settle before or during filling, this leads to deviations in the composition. If the salt particles settle after filling, the effect can occur that, if the spray can is not shaken long enough, the antiperspirant composition sprayed by the consumer is uneven and has a poor antiperspirant effect. This poses a particular challenge for formulations with unmilled and therefore spherical ACH particles, because the round particles settle more easily than milled particles with irregular surfaces.

[0005] There is therefore a constant need for antiperspirant compositions that remain stable for a long time and do not sediment.

[0006] An object of the present invention was to provide antiperspirant compositions which form as stable as possible suspensions of powdered antiperspirant active ingredients, in particular aluminum chlorohydrate, in non-polar oils.

[0007] Surprisingly, it was found that the task is solved by antiperspirant active ingredients, in particular aluminum chlorohydrate, in the form of spherical particles in combination with rice starch and hydrophobically modified clay minerals, while no such pronounced stabilization is achieved with other types of starch.

[0008] An object of the present invention is therefore a sprayable antiperspirant containing an antiperspirant composition for personal body care, which contains: a) at least one antiperspirant active ingredient in the form of spherical particles, which is present in suspended, non-dissolved form and is selected from aluminum salts, in a total amount of 5 - 35 wt.%, b) 0.1 - 1 wt.% rice starch in the form of a powder treated with cationic surfactants, the proportion of cationic surfactants being 0.01 - 0.3 wt.%, based on the weight of the rice starch, c) 1.5 - 3.5 wt.% hydrophobically modified clay mineral, d) at least one oil in a total amount of 20 - 94.8 wt.%, e) 0 to 7 wt% free water, where all weight percentages refer to the weight of the composition, without taking into account any propellants that may be present, characterized in that the composition is in an aerosol can with a compressed gaseous propellant.

[0009] For the purposes of this application, "standard conditions" are a temperature of 20°C and a pressure of 1013.25 mbar. Melting points also refer to a pressure of 1013.25 mbar.

[0010] Unless otherwise stated, all quantities refer to the total weight of the antiperspirant composition according to the invention. Any added propellants are not included in the antiperspirant composition according to the invention; therefore, all quantities refer to the total weight of the propellant-free antiperspirant composition, unless otherwise stated.

[0011] According to the invention, “anhydrous” means a free water content of a maximum of 7% by weight, based on the total composition.

[0012] "Free water" within the meaning of the present application is water that is not present in the antiperspirant composition in the form of water of crystallization, water of hydration, or similarly molecularly bound water. The content of water of crystallization, water of hydration, or similarly molecularly bound water contained in the ingredients used, in particular in the antiperspirant active ingredients, does not constitute free water within the meaning of the present application. Free water is, for example, water that is added to the composition according to the invention as a solvent, as a gel activator, or as a solvent component of other active ingredients.

[0013] The antiperspirant compositions according to the invention contain, based on their total weight, 0 to 7 wt.% free water. Preferred antiperspirant compositions according to the invention contain, based on their total weight, 0 to 6 wt.% free water, preferably

[0014] 0-5% by weight, particularly preferably 0-4% by weight, extraordinarily preferably 0-3% by weight of free water. The antiperspirant compositions according to the invention are therefore to be considered essentially water-free.

[0015] The compositions according to the invention contain, in each case based on their weight, 0.1 - 1 wt.%, preferably 0.4 - 2 wt.% of rice starch, which is present as a powder treated with cationic surfactants, wherein the proportion of cationic surfactants is 0.01 - 0.3 wt.%, based on the weight of the rice starch.

[0016] The rice starch used according to the invention is obtained from rice. In preferred compositions according to the invention, the rice starch consists of 10-40 wt.%, preferably 20-30 wt.%, particularly preferably 22-28 wt.% amylose and 60-90 wt.%, preferably 70-80 wt.%, particularly preferably 72-78 wt.% amylopectin, based on the weight of the rice starch. Compositions according to the invention contain rice starch in a total amount of 0.1-1 wt.%, preferably 0.2-1 wt.%, particularly preferably 0.4-1 wt.%, based on the weight of the composition, as a powder treated with cationic surfactants, with a proportion of cationic surfactants of 0.01-3 wt.%, preferably 0.1-0.15 wt.%, based on the weight of the rice starch.

[0017] Preferred cationic surfactants are alkyltrimethylammonium chlorides, particularly preferably C 12 -C 22 -Alkyltrimethylammonium chlorides, preferably C 16-Alkyltrimethylammonium chloride (cetrimonium chloride).

[0018] The compositions according to the invention contain at least one hydrophobically modified clay mineral. Preferred hydrophobically modified clay minerals are selected from hydrophobically modified montmorillonites, hydrophobically modified hectorites, and hydrophobically modified bentonites, particularly preferably from disteardimonium hectorite, stearalkonium hectorite, quaternium-18 hectorite, and quaternium-18 bentonite. Compositions according to the invention are characterized in that they contain at least one hydrophobically modified clay mineral in a total amount of 1.5-3.5 wt. %, based on the total weight of the propellant-free composition according to the invention.

[0019] Hydrophobically modified clay minerals are clay minerals whose naturally occurring metal cations are completely or partially replaced by cations substituted by hydrophobic groups, preferably ammonium cations substituted by long-chain alkyl groups, wherein the long-chain alkyl groups preferably contain 5-30, particularly preferably 7-25, extremely preferably 10-20 carbon atoms.

[0020] The compositions according to the invention contain at least one antiperspirant active ingredient selected from aluminum salts. Preferred antiperspirant active ingredients are selected from the water-soluble astringent inorganic and organic salts of aluminum.

[0021] According to the invention, water solubility is understood to mean a solubility of at least 3% by weight at 20°C, i.e., amounts of at least 3 g of the antiperspirant active ingredient are soluble in 97 g of water at 20°C. According to the invention, water solubility is preferably understood to mean a solubility of at least 5% by weight at 20°C, i.e., amounts of at least 5 g of the antiperspirant active ingredient are soluble in 95 g of water at 20°C.

[0022] Particularly preferred antiperspirant active ingredients are selected from aluminum chlorohydrate, in particular aluminum chlorohydrate with the general formula [Al2(OH)5Cl · 1-6 H2O] n , preferably [Al2(OH)5Cl · 2-3 H2O] n , which can be in non-activated or activated (depolymerized) form, as well as aluminum chlorohydrate with the general formula [Al2(OH)4Cl2 · 1-6 H2O] n , preferably [Al2(OH)4Cl2 2-3 H2O] n, which can be in non-activated or activated (depolymerized) form.

[0023] In the compositions according to the invention, the antiperspirant active ingredient, preferably aluminum chlorohydrate, is in the form of spherical particles.

[0024] The term "spherical particles" refers to particles that are ellipsoidal in shape, preferably ellipsoidal with at least two axes of equal length, and most preferably spherical. The axial lengths of an ellipsoidal particle differ from each other by a maximum of 30%, preferably by a maximum of 20%, particularly preferably by a maximum of 10%, and most preferably by a maximum of 3%, based on the length of the longest axis.

[0025] "Ellipsoidal" and "spherical" mean that the particles appear as ellipsoids and spheres, respectively, when viewed under a microscope at approximately 1,000 times magnification. Ellipsoidal or spherical does not necessarily mean that the particles have a perfectly smooth surface.

[0026] In compositions according to the invention, preferably 70-95% by weight of the particles have a size greater than 10 µm, 80-100% by weight of the particles have a size up to 75 µm and 90-100% by weight of the particles have a size up to 125 µm, and extremely preferably 75-80% by weight of the particles have a size greater than 10 µm, 90-100% by weight of the particles have a size up to 75 µm and 99-100% by weight of the particles have a size up to 125 µm, in each case based on the weight of the antiperspirant active ingredient. “Size” is understood to mean the diameter for spherical particles and the length of at least two axes for ellipsoidal particles. According to the invention, the spherical particles are unmilled.

[0027] Also preferred are aluminum sesquichlorohydrate, aluminum dichlorohydrate, aluminum chlorohydrex-propylene glycol (PG) or aluminum chlorohydrex-polyethylene glycol (PEG), aluminum sesquichlorohydrex-PG or aluminum sesquichlorohydrex-PEG, aluminum-PG-dichlorohydrex or aluminum-PEG-dichlorohydrex, aluminum hydroxide, potassium aluminum sulfate (KAI(SO4)2 12 H2O, alum), dehydrated alum (KAI(SO4)2 with zero to 11 mol of crystal water), sodium aluminum chlorohydroxylactate, aluminum bromohydrate, aluminum chloride, aluminum sulfate, aluminum lactate, sodium aluminum chlorohydroxylactate. Antiperspirant active ingredients particularly preferred according to the invention are selected from so-called “activated” aluminum salts, which are also referred to as antiperspirant active ingredients “with enhanced activity”. Such active ingredients are known in the prior art and are also commercially available.Activated aluminum salts are typically produced by heat-treating a relatively dilute solution of the salt (e.g., approximately 10 wt.% salt) to increase its HPLC peak 4-to-peak 3 area ratio. The activated salt can then be dried to a powder, particularly by spray drying. In addition to spray drying, roller drying, for example, is also suitable.

[0028] Activated aluminum 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 being attributable to these peaks.

[0029] Other preferred antiperspirant active ingredients are basic calcium-aluminum salts. These salts are produced by reacting calcium carbonate with aluminum chlorohydroxide or aluminum chloride and aluminum powder, or by adding calcium chloride dihydrate to aluminum chlorohydroxide.

[0030] Other preferred activated aluminum salts are those of the general formula Al2(OH) 6-a Xa, wherein X is Cl, Br, I or NO3 and "a" is a value from 0.3 to 5, preferably from 0.8 to 2.5 and particularly preferably 1 to 2, such that the molar ratio of Al:X is 0.9:1 to 2.1:1, as disclosed, for example, in US 6074632. These salts generally have some water of hydration associatively bound, typically 1 to 6 moles of water per mole of salt. Particular preference is given to aluminum chlorohydrate (i.e., 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. Zirconium-free aluminum sesquichlorohydrates particularly preferred according to the invention have a molar metal to chloride ratio of 1.5:1-1.8:1.

[0031] Particularly preferred compositions according to the invention are characterized in that the at least one antiperspirant active ingredient is contained in a total amount of 5-35 wt.%, preferably 10-35 wt.%, particularly preferably 15-28 wt.% and extraordinarily preferably 23-27 wt.%, based on the total weight of the composition, without taking into account any propellants that may be present.

[0032] As further ingredients, the compositions according to the invention contain at least one oil which is liquid under normal conditions and which represents a carrier fluid or a suspending medium for the at least one antiperspirant active ingredient.

[0033] Cosmetic oils are divided into volatile and non-volatile oils. Non-volatile oils are those oils that have a vapor pressure of less than 2.66 Pa (0.02 mm Hg) at 20°C and an ambient pressure of 1013 hPa. Volatile oils are those oils that have a vapor pressure of 2.66 Pa - 40,000 Pa (0.02 mm - 300 mm Hg) at 20°C and an ambient pressure of 1013 hPa, preferably 12 - 12,000 Pa (0.1 - 90 mm Hg), particularly preferably 13 - 8,000 Pa, extraordinarily preferably 30 - 3,000 Pa, and furthermore preferably 100 - 400 Pa.

[0034] The at least one oil is preferably selected from volatile or non-volatile silicone oils; 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; dicarboxylic acid esters of linear or branched C2-C 10-alkanols; benzoic acid esters of linear or branched C 8-22 -Alkanols; single and multiple esters of lactic acid, citric acid, tartaric acid or adipic acid with a monohydric alcohol having 2 to 9 carbon atoms; single and multiple esters of lactic acid, citric acid, tartaric acid or adipic acid with a di-, tri- or tetrahydric alcohol having 2 to 9 carbon atoms; symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols; C8-C 30 -Isoparaffins; and branched saturated or unsaturated fatty alcohols with 6 - 30 carbon atoms.

[0035] The at least one oil is contained in the composition in a total amount of 20 - 94.8 wt.%, preferably 40 - 85 wt.%, particularly preferably 50 - 80 wt.%, extraordinarily preferably 60 - 75 wt.%, based on the weight of the composition, without taking into account any propellants that may be present.

[0036] Preferred volatile silicone oils are selected from dialkyl and alkylarylsiloxanes which have a vapor pressure of less than 2.66 Pa (0.02 mm Hg) at 20°C and an ambient pressure of 1013 hPa, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, dimethylpolysiloxane, low molecular weight phenyl trimethicone and methylphenylpolysiloxane, but also hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane. Particularly preferred are volatile silicone oils which are cyclic, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane and mixtures thereof, as contained, for example, in the commercial products DC 244, 245, 344 and 345 from Dow Corning (vapor pressure at 20°C approx. 13 - 15 Pa). Decamethylcyclopentasiloxane is extremely preferred.

[0037] Also particularly preferred are volatile linear silicone oils with 2 - 10 siloxane units, in particular hexamethyldisiloxane (L2), octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4) and any two- and three-component mixtures of L2, L3 and / or L4, preferably such mixtures as are used, for example, in the commercial products DC 2-1184, Dow Corning ® 200 (0.65 cSt) and Dow Corning ® 200 (1.5 cSt) from Dow Corning. Another preferred volatile silicone oil is a low-molecular-weight phenyl trimethicone with a vapor pressure at 20°C of approximately 2000 Pa, such as that available from GE Bayer Silicones / Momentive under the name Baysilone Fluid PD 5. Volatile silicone oils are excellently suited carrier oils for antiperspirant compositions according to the invention, as they impart a pleasant skin feel and low fabric soiling.

[0038] Preferred non-volatile silicone oils are selected from linear polydimethylsiloxanes with kinematic viscosities (25°C) in the range of 5 - 350 cSt, preferably 5 - 100 cSt or 10 - 50 cSt.

[0039] Preferred 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, are preferably selected from isopropyl palmitate, isopropyl stearate, isopropyl myristate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, 2-hexyldecyl stearate, 2-hexyldecyl laurate, isononyl isononanoate, isooctyl stearate, isononyl stearate, isocetyl stearate, isononyl isononanoate, isotridecyl isononanoate, cetearyl isononanoate, 2-ethylhexyl laurate, 2-ethylhexyl isostearate, 2-ethylhexyl cocoate, 2-octyldodecyl palmitate, Butyloctanoic acid 2-butyloctanoate, diisotridecyl acetate, n-hexyl laurate, n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate and erucyl erucate as well as mixtures of the aforementioned esters, particularly preferably isopropyl palmitate, isopropyl stearate, isopropyl myristate, 2-ethylhexyl palmitate and 2-ethylhexyl stearate.

[0040] Preferred dicarboxylic acid esters of linear or branched C2-C 10 -Alkanols are selected from 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 as well as mixtures of the aforementioned esters.

[0041] Preferred benzoic acid esters of linear or branched C 8-22 Alkanols are selected from dodecyl benzoate, tridecyl benzoate, tetradecyl benzoate, pentadecyl benzoate, hexadecyl benzoate, octdecyl benzoate, 2-methyl-heptadecyl benzoate, and octyldodecyl benzoate. Benzoic acid C12-C15 alkyl esters are particularly preferred, e.g., available as the commercial product Finsolv. ® TN, isostearyl benzoate, 2-ethylhexyl benzoate and 2-octyldocecyl benzoate, with C12-C15 alkyl benzoates being extremely preferred.

[0042] Among the mono- and polyesters of lactic acid, citric acid, tartaric acid, or adipic acid with a monohydric alcohol containing 2 to 9 carbon atoms, triethyl citrate is preferred. Triglyceride oils of linear or branched, saturated or unsaturated, optionally hydroxylated C 8-30 -Fatty acids, especially natural oils, e.g. 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, safflower oil, wheat germ oil, peach kernel oil and the liquid parts of coconut oil and the like, but also synthetic triglyceride oils, especially capric / caprylic triglycerides, e.g. the commercial products Myritol ® 318 or Myritol ®331 (BASF) with unbranched fatty acid residues and glyceryl triisostearin with branched fatty acid residues are also suitable as additional oils in principle, but are less preferred due to their less favorable residue behavior. Such triglyceride oils should preferably only be present in a total amount of 0 to 1 wt.%, particularly preferably 0 to 0.5 wt.%, based on the weight of the composition, without taking into account any propellants present.

[0043] Preferred symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols are selected from dicaprylyl carbonate (Cetiol ® CC), di-n-octyl carbonate, di-n-dodecyl carbonate, di-(2-ethylhexyl) carbonate or the esters according to the teaching of DE 19756454 A.

[0044] Preferred C8-C 16Isoparaffins are selected from isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, and isohexadecane, as well as mixtures thereof. Preferred are C 10 -C 13 -Isoparaffin mixtures, in particular those with a vapor pressure at 20°C of about 10 - 400 Pa, preferably 13 - 300 Pa,Preferred C 18 -C 30 -Isoparaffins are selected from isoeicosane, polyisobutenes or polydecenes, which are sold, for example, under the name Emery ® 3004, 3006, 3010 or under the name Ethylflo ® from Albemarle or Nexbase ® 2004G from Nestle, as well as 1,3-di-(2-ethylhexyl)-cyclohexane (available e.g. under the trade name Cetiol ® S from BASF).

[0045] Preferred branched saturated or unsaturated fatty alcohols with 6 - 30 carbon atoms are selected from 2-hexyldecanol, octyldodecanol (eutanol ® G) and 2-ethylhexyl alcohol.

[0046] Particularly preferred compositions according to the invention contain mixtures of at least two oils, wherein at least one volatile silicone oil, in a total amount of 10 to 40 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.%, furthermore at least one non-volatile oil in a total amount of 10 to 50 wt.%, preferably 20 to 45 wt.%, particularly preferably 25 to 40 wt.% and optionally a non-volatile silicone oil, preferably polydimethylsiloxane in a total amount of 0 - 20 wt.%, preferably 3 to 15 wt.%, particularly preferably 6 to 13 wt.%.

[0047] In compositions which are extraordinarily preferred according to the invention, the oil composition is a mixture of decamethylcyclopentasiloxane as volatile silicone oil, isopropyl myristate as non-volatile oil, polydimethylsiloxane with a viscosity of 5 cSt as non-volatile silicone oil and additionally ethylhexyl palmitate, in each case based on the weight of the composition, without taking into account any blowing agents which may be present.

[0048] According to the invention, fragrances and odoriferous substances are not considered oils d). The definition of a fragrance within the meaning of the present application corresponds to the definition commonly used by those skilled in the art, as can be found in the RÖMPP Chemical Dictionary, as of December 2007. According to this definition, a fragrance is a chemical compound with odor and / or taste that stimulates the receptors of the hair cells of the olfactory system (adequate stimulus). The necessary physical and chemical properties are a low molecular weight of a maximum of 300 g / mol, a high vapor pressure, minimal water and high lipid solubility, as well as weak polarity and the presence of at least one osmophoric group in the molecule. To avoid volatile, low-molecular substances, which are usually not considered and used as fragrances, but primarily as solvents, such as ethanol, propanol, isopropanol, and acetone,To distinguish them from fragrances according to the invention, fragrances according to the invention have a molecular mass of 74 to 300 g / mol, contain at least one osmophoric group in the molecule, and exhibit an odor and / or taste, i.e., they stimulate the receptors of the hair cells of the olfactory system. Examples of fragrance and odor compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate, and jasmecyclate. Examples of fragrance and odoriferous compounds of the ether type are benzyl ethyl ether and ambroxan, examples of fragrance and odoriferous compounds of the aldehyde type are the linear alkanals with 8 - 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal,Examples of fragrance and odor compounds of the ketone type are ionones, alpha-isomethyl ionone and methyl cedryl ketone. Examples of fragrance and odor compounds of the alcohol type are anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. Examples of fragrance and odor compounds of the terpene type are limonene and pinene. Examples of fragrance and odoriferous compounds are pine, citrus, jasmine, patchouli, rose, ylang-ylang oil, clary sage oil, chamomile oil, clove oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil, orange blossom oil, neroli oil, orange peel oil and sandalwood oil, as well as essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil,Iris oil, cajuput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, niaouli oil, orange oil, oregano oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, juniper berry oil, wormwood oil, wintergreen oil, hyssop oil, cinnamon oil, citronella oil, lemon oil and cypress oil. Other fragrance and odoriferous compounds are ambrettolide, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, alpha-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol,Eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methyl chavicol, p-methylquinoline, methyl β-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-Nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymen, thymol, γ-undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde,Cinnamyl alcohol, cinnamic acid, ethyl cinnamate and benzyl cinnamate.

[0049] Other (more volatile) fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral and citronellal.

[0050] It is preferable to use mixtures of different fragrances that together create an appealing scent.

[0051] Suitable perfume oils can also contain natural fragrance mixtures obtained from plant or animal sources, e.g., pine, citrus, jasmine, rose, lily, or ylang-ylang oil. Essential oils of lower volatility, which are usually used as aroma components, are also suitable as perfume oils, e.g., sage oil, chamomile oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, laudanum oil, clove oil, iso-eugenol, thyme oil, bergamot oil, geranium oil, and rose oil.

[0052] Preferred compositions according to the invention are characterized in that at least one fragrance is contained in a total amount of 0.1 - 15 wt.%, preferably 0.5 - 10 wt.%, particularly preferably 1 - 8 wt.%, extraordinarily preferably 2 - 7 wt.%, further extraordinarily preferably 3 - 6 wt.%, in each case based on the total weight of the propellant-free composition.

[0053] Further preferred compositions according to the invention are characterized by a content of at least one so-called "skin-cooling active ingredient." Skin-cooling active ingredients within the meaning of the present application are understood to be active ingredients that, when applied to the skin, produce a pleasant feeling of cooling as a result of surface anesthesia and irritation of the cold-sensitive nerves in migraines and the like, even when the treated skin areas actually exhibit a normal or elevated temperature. Skin-cooling active ingredients according to the invention are those compounds that, similar to I-menthol, stimulate the thermoreceptors in the skin and mucous membranes in such a way that a cool sensory impression is created. In particular, the CMR-1 receptor ("cold- and menthol-sensitive receptor"), which belongs to the TRP channel family, is stimulated by the cooling active ingredients, creating a cold sensation.

[0054] Preferred skin-cooling active ingredients are menthol, isopulegol, and menthol derivatives, e.g., menthyl lactate, menthylpyrrolidonecarboxylic acid, menthyl methyl ether, menthoxypropanediol, menthone glycerol acetal (9-methyl-6-(1-methylethyl)-1,4-dioxaspiro(4,5)decane-2-methanol), monomenthyl succinate, and 2-hydroxymethyl-3,5,5-trimethylcyclohexanol. Particularly preferred skin-cooling active ingredients are menthol, isopulegol, menthyl lactate, menthoxypropanediol, and menthylpyrrolidonecarboxylic acid. Preferred compositions according to the invention contain at least one skin-cooling active ingredient in a total amount of 0.01-1 wt.%, preferably 0.02-0.5 wt.%, and particularly preferably 0.05-0.2 wt.%, in each case based on the total weight of the (propellant-free) composition.

[0055] In a further preferred embodiment of the invention, the compositions according to the invention contain 0 to a maximum of 5 wt.% ethanol.

[0056] Furthermore, the compositions according to the invention can contain additional deodorant active ingredients. Antimicrobial, antibacterial, or germ-inhibiting substances, antioxidants, or odor adsorbents (e.g., zinc ricinoleate) can be used as deodorant active ingredients. Suitable antimicrobial, antibacterial, or germ-inhibiting substances are, in particular, organohalogen compounds and halides, quaternary ammonium compounds, a range of plant extracts, and zinc compounds. Halogenated phenol derivatives such as hexachlorophene or Irgasan DP 300 (triclosan, 2,4,4'-trichloro-2'-hydroxydiphenyl ether), 3,4,4'-trichlorocarbanilide, chlorhexidine (1,1'-hexamethylenebis[5-(4-chlorophenyl)]biguanide), chlorhexidine gluconate, benzalkonium halides, and cetylpyridinium chloride are preferred. Sodium bicarbonate, sodium phenolsulfonate and zinc phenolsulfonate as well as the components of linden blossom oil can also be used.Even less effective antimicrobial substances that have a specific effect against the gram-positive bacteria responsible for sweat decomposition can be used as deodorant active ingredients. Benzyl alcohol can also be used as a deodorant active ingredient. Other antibacterial deodorants include lantibiotics, glycoglycerolipids, sphingolipids (ceramides), sterols, and other active ingredients that inhibit bacterial adhesion to the skin, e.g., glycosidases, lipases, proteases, carbohydrates, di- and oligosaccharide fatty acid esters, and alkylated mono- and oligosaccharides. Preferred deodorant active ingredients are long-chain diols, e.g., 1,2-alkane-(C5-C. 18 )-diols, glycerol mono(C8-C 18 ) fatty acid esters or, particularly preferably, glycerol mono-(C6-C 16)-alkyl ethers, in particular 2-ethylhexylglycerol ethers, which are very well tolerated by skin and mucous membranes and effective against corynebacteria, as well as phenoxyethanol, phenoxyisopropanol (3-phenoxypropan-2-ol), anise alcohol, 2-methyl-5-phenyl-pentan-1-ol, 1,1-dimethyl-3-phenyl-propan-1-ol, benzyl alcohol, 2-phenylethan-1-ol, 3-phenylpropan-1-ol, 4-phenylbutan-1-ol, 5-phenylpentan-1-ol, 2-benzylheptan-1-ol, 2,2-dimethyl-3-phenylpropan-1-ol, 2,2-dimethyl-3-(3'-methylphenyl)-propan-1-ol, 2-ethyl-3-phenylpropan-1-ol, 2-Ethyl-3-(3'-methylphenyl)-propan-1-ol, 3-(3'-chlorophenyl)-2-ethylpropan-1-ol, 3-(2'-chlorophenyl)-2-ethylpro-pan-1-ol, 3-(4'-chlorophenyl)-2-ethylpropan-1-ol, 3-(3',4'-dichlorophenyl)-2-ethylpropan-1-ol, 2-Ethyl-3-(2'-methylphenyl)-propan-1-ol, 2-ethyl-3-(4'-methylphenyl)-propan-1-ol, 3-(3',4'-dimethylphenyl)-2-ethylpropan-1-ol, 2-ethyl-3-(4'-methoxyphenyl)-propan-1-ol, 3-(3',4'-Dimethoxyphenyl)-2-ethyl-propan-1-ol,2-Allyl-3-phenylpropan-1-ol and 2-n-pentyl-3-phenylpropan-1-ol.,

[0057] Complexing agents can also support the deodorizing effect by forming stable complexes with heavy metal ions (e.g., iron or copper) that act as oxidative catalytic agents. Suitable complexing agents include the salts of ethylenediaminetetraacetic acid or nitrilotriacetic acid, as well as the salts of 1-hydroxyethane-1,1-diphosphonic acid.

[0058] A further embodiment of the compositions according to the invention is characterized by containing at least one encapsulated active ingredient. The active ingredients that can advantageously be encapsulated are, in particular, deodorizing agents, fragrances, perfume oils, and / or skin-cooling agents, but also other skin-care active ingredients, such as vitamins, antioxidants, etc.

[0059] Preferred capsule materials are water-soluble polymers such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, or hydroxypropylmethylcellulose, carrageenans, alginates, maltodextrins, dextrins, plant gums, pectins, xanthan gums, polyvinyl acetate and polyvinyl alcohol, polyvinylpyrrolidine, polyamides, polyesters, and homo- and copolymers of monomers selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and the esters and salts of these acids, as well as any mixtures of these polymers. Suitable capsule materials are also described, for example, in WO 2010 / 009977 A2.

[0060] In a further particularly preferred embodiment, the compositions according to the invention may contain both at least one antiperspirant active ingredient and at least one deodorant active ingredient.

[0061] The formulation of the compositions according to the invention, which are applied as a spray, is preferably based on the requirements of the desired spray application. The compositions according to the invention are in the form of a suspension, i.e., the antiperspirant active ingredient and, if appropriate, other insoluble components are suspended in a liquid or solid carrier. Liquid-dispersed systems of this type, e.g., dispersions to be applied as a spray, should be shaken before use.

[0062] According to the invention, the composition is applied using a compressed or liquefied propellant. For this purpose, the composition according to the invention is packaged together with a propellant in a spray can. The propellant and the composition according to the invention can be present as a mixture. However, it is also possible for the propellant and the composition according to the invention to be present separately, e.g., in so-called bag-in-can spray cans.

[0063] Unless otherwise stated, all quantities refer to the weight of the propellant-free composition.

[0064] Packaging in a multi-chamber dispenser offers special technical advantages.

[0065] The multi-chamber dispenser can also be used in such a way that one chamber is filled with the composition according to the invention, while another chamber contains the compressed propellant. Such a multi-chamber dispenser is, for example, a so-called bag-in-can package.

[0066] However, both chambers can also be connected to one another in such a way that the composition according to the invention is separated into two partial compositions which can be dispensed from the packaging at the same time, for example from separate openings or from a single opening.

[0067] The compositions according to the invention are characterized in that they are packaged with at least one propellant in a suitable pressure container. Propellants (propellant gases) preferred according to the invention are selected from propane, propene, n-butane, iso-butane, iso-butene, n-pentane, pentene, iso-pentane, isopentene, methane, ethane, dimethyl ether, nitrogen, air, oxygen, nitrous oxide, dichlorofluoromethane, chlorodifluoromethane, chlorofluoromethane, 1,1,2,2-tetrachloro-1-fluoroethane, 1,1,1,2-tetrachloro-2-fluoroethane, 1,2,2-trichloro-1,1-difluoroethane, 1,1,2-trichloro-1,2-difluoroethane, 1,1,1-trichloro-2,2-difluoroethane, 2,2-dichloro-1,1,1-trifluoroethane, 1,2-dichloro-1,1,2-trifluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, 1-chloro-1,1,2,2-tetrafluoroethane, 1,1,2-trichloro-2-fluoroethane, 1,2-dichloro-1,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane, 1-chloro-1,2,2-trifluoroethane, 2-chloro-1,1,1-trifluoroethane, 1-chloro-1,1,2-trifluoroethane, 1,2-dichloro-1-fluoroethane, 1,1-dichloro-1-fluoroethane, 2-chloro-1,1-difluoroethane,1-Chloro-1,1-difluoroethane, 1-chloro-2-fluoroethane, 1-chloro-1-fluoroethane, 2-chloro-1,1-difluoroethene, 1,1,1,3-tetrafluoroethane, heptafluoro-n-propane, perfluoroethane, monochlorodifluoromethane, 1,1-difluoroethane, both individually and in combination.

[0068] Particular preference is given to propane, n-butane, isobutane, and, more preferably, mixtures of these propellants. Also further preferred are 1,1-difluoroethane, propane, n-butane, isobutane, and mixtures of these propellants, in particular mixtures of 1,1-difluoroethane and n-butane. Hydrophilic propellant gases, such as carbon dioxide, can also be used advantageously for the purposes of the present invention if the proportion of hydrophilic gases is selected to be low and lipophilic propellant gas (e.g. propane / butane) is present in excess. Particular preference is given to propane, n-butane, isobutane, and mixtures of these propellant gases. It has been shown that the use of n-butane as the sole propellant gas can be particularly preferred according to the invention.

[0069] The amount of propellant is preferably 10-95% by weight, particularly preferably 30-90% by weight and extraordinarily preferably 60-86% by weight, and further extraordinarily preferably 70, 72, 74, 76, 78, 82, 84 or 85% by weight, in each case based on the total weight of the preparation consisting of the composition according to the invention (suspension) and the propellant.

[0070] Suitable pressurised gas containers are vessels made of metal (aluminum, tinplate, tin), protected or non-splintering plastic, or glass coated on the outside with plastic. Pressure and fracture strength, corrosion resistance, ease of filling, as well as aesthetic aspects, handling, printability, etc., play a role in their selection. Special internal protective coatings ensure corrosion resistance to the suspension according to the invention. A preferred internal protective coating according to the invention is an epoxy-phenolic coating, such as that available under the name Hoba 7407 P. The valves used are particularly preferably provided with an internally coated valve disk, with the coating and valve material being compatible with each other. If aluminium valves are used, their valve disks can be coated on the inside, for example, with Micoflex varnish. If tinplate valves are used according to the invention, their valve disks can be coated on the inside, for example,be coated with PET (polyethylene terephthalate).

[0071] The cans are equipped with a suitable spray head. Depending on the spray head, discharge rates from 0.1 g / s to 2.0 g / s are possible, based on a fully filled can.

[0072] The invention is described in more detail by the following examples, without being limited thereto. Examples:

[0073] To prepare the antiperspirant suspensions, the ingredients (see table) were mixed and homogenized at 30°C. 100 mL of each batch was stored in cylinders at room temperature for 24 hours. The separation of the clear oil phase indicates the sedimentation of the ACH (aluminum chlorohydroxide) particles. Only the combination of rice starch with a hydrophobically modified clay mineral (Disteardimonium Hectorite (Bentone® 38 V CG)) produces the desired effect.

[0074] Table 1 shows four comparative formulations (V1), (V2), (V3), and (V4) as well as one formulation according to the invention (E), although the invention is not limited to these. Table 2 shows three compositions according to the invention (E1), (E2), and (E3), which are filled into aerosol cans in a weight ratio of 3:17 with the propellant propane / butane (15 / 85). Table 1 Four comparative formulations (V1), (V2), (V3) and (V4) and one formulation according to the invention (E), as well as the evaluation of the sedimentation of the individual formulations after 24 h V1 V2 V3 V4 E % by weight % by weight % by weight % by weight % by weight Octenylsuccinate of a hydrolyzed corn starch - 0,5 - - - Rice starch - - 0,5 - 0,5 Disteardimonium Hectorite - 2,5 - 2,5 2,5 Cyclopentasiloxane 29,5 26,5 29,0 28,0 26,5 Isopropyl myristate 30,0 30,0 30,0 30,0 30,0 Ethylhexyl palmitate 6,0 6,0 6,0 6,0 6,0 Dimethicone 5 cSt 10,0 10,0 10,0 10,0 10,0 Propylene carbonate 1,0 1,0 1,0 1,0 1,0 Aluminum Chlorohydrate (spherical particles) 23,5 23,5 23,5 23,5 23,5 Sedimentation after 24 h at room temperature Strong (6 cm clear oil) Strong (5 cm clear oil) Moderate (3cm clear oil) Weak (2cm clear oil) no Table 2 Three compositions according to the invention (E1), (E2) and (E3) filled into aerosol cans in a weight ratio of 3:17 with the propellant propane / butane (15 / 85) E1 E2 E3 % by weight % by weight % by weight Cyclopentasiloxane (Xiameter 0245 fluid) 21,5 21,1 21,7 Isopropyl palmitate (BASF) 30,0 30,0 30,0 Ethylhexyl palmitate (Cegesoft C24, BASF) 6,0 6,0 6,0 Rice starch (Rice starch DSA 7, Agrana AG) 0,5 0,9 0,3 Dimethicone (Xiameter PMX-200 Fluid 5CS) 10,0 10,0 10,0 Disteardimonium Hectorite 2,5 2,5 2,5 Propylene carbonate 1,0 1,0 1,0 Aluminum Chlorohydrate (AACH 7172, SummitReheis) 23,5 23,5 23,5 Perfume 5,0 5,0 5,0

Claims

[1] Sprayable antiperspirant containing an antiperspirant composition for personal body care containing: a) at least one antiperspirant active ingredient in the form of spherical particles, which is present in suspended, non-dissolved form and is selected from aluminum salts in a total amount of 5 - 35 wt.%, b) 0.1 - 1% by weight of rice starch in the form of a powder treated with cationic surfactants, the proportion of cationic surfactants being 0.01 - 0.3% by weight, based on the weight of the rice starch, c) 1.5 - 3.5 wt.% hydrophobically modified clay mineral, d) at least one oil in a total amount of 20 - 94.8 wt.%, e) 0 to 7 wt% free water, where all weight percentages refer to the weight of the composition, without taking into account any blowing agents present, characterized bythat the composition is in an aerosol can with a compressed gaseous propellant. [2] Sprayable antiperspirant according to claim 1, characterized by that the at least one antiperspirant active ingredient (a) is aluminum chlorohydrate. [3] Sprayable antiperspirant according to one of claims 1 or 2, characterized by that the hydrophobically modified clay mineral is selected from hydrophobically modified hectorites, hydrophobically modified bentonites and hydrophobically modified montmorillonites, [4] Sprayable antiperspirant according to claim 3, characterized by that the hydrophobically modified clay mineral is selected from Disteardimonium Hectorite, Stearalkonium Hectorite, Quaternium-18 Hectorite and Quaternium-18 Bentonite. [5] Sprayable antiperspirant according to any one of claims 1 to 4, characterized bythat 70-95 wt.% of the spherical particles have a size of more than 10 µm, 80-100 wt.% of the spherical particles have a size of up to 75 µm and 90-100 wt.% of the spherical particles have a size of up to 125 µm, in each case based on the weight of the antiperspirant active ingredient. [6] Sprayable antiperspirant according to any one of claims 1 to 5, characterized by that the at least one oil is a mixture of at least two oils, wherein at least one volatile silicone oil, in a total amount of 10 to 40 wt.%, and furthermore at least one non-volatile oil in a total amount of 10 to 50 wt.%, are contained therein. [7] Sprayable antiperspirant according to claim 6, characterized by that the at least one volatile silicone oil is selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane and mixtures thereof. [8] Sprayable antiperspirant according to claim 6 or 7, characterized by that the at least one non-volatile oil is selected from isopropyl myristate, isopropyl palmitate, isopropyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate and triethyl citrate and mixtures of the aforementioned esters. [9] Sprayable antiperspirant according to any one of claims 6 to 8, characterized by that polydimethylsiloxane with a viscosity of 5 cSt is included as a non-volatile silicone oil. [10] Sprayable antiperspirant according to any one of claims 1 to 9, characterized by that the at least one antiperspirant active ingredient (a) is contained in a total amount of 15 - 28 wt.%, based on the total weight of the composition, without taking into account any propellants present. [11] Sprayable antiperspirant according to any one of claims 1 to 10, characterized bythat at least one fragrance is contained in a total amount of 0.1 - 15 wt.% based on the total weight of the propellant-free composition.