Alum-based deodorant product and process for producing the same

WO 1997023197 A1

ABSTRACT
A solid shaped alum-based deodorant product containing fragrances or essential oils is produced by exposing to a sufficiently strong microwave radiation a mixture of 50-99 % by weight of a double salt of formula (I) M?IMIII(SO4)2.12H2O, in which MI stands for an alkali or ammonium ion and MIII stands for an aluminium, titanium, manganese, iron or chromium ion; 0.1-30 % by weight of auxiliary agents to improve the esthetic, cosmetic or processing properties, including 0.1-20 % by weight of a fragrance or essential oil, and optionally up to 40 % by weight of other water-soluble aluminium salts in a microwave-permeable form. Exposure to microwave radiation is continued until the mixture is heated and at least partially melted or sintered. It is then left to cool down and solidify.

CLAIMS
Claims 1) Solid shaped deodorant product containing 50-99 weight -% of a double salt of the formula (I) MV "(SO 4) 2 .12 H 2 O (I) in which M is an alkali metal or ammonium ion and M is aluminum, titanium.Manganese, iron or chromium ion, and optionally up to 40 wt -% of other water-soluble aluminum salts, characterized in that a fragrance, or an essential oil in an amount of 0.1 to 20 wt -%, and optionally up to 10 wt -% further additives are included. 2) deodorant product according to claim 1, characterized in that it comprises at least 80 weight -% of a double salt of the formula I wherein M is sodium, potassium, or NH 4
(+)

and M is aluminum.

3) deodorant product according to claim 1 or 2, characterized in that 1 to 10 weight -% of a fragrance is included. 4) A process for the preparation of solid, shaped, transparent, deodorantproducts, characterized in that a mixture of 50 - 99 wt -% of a double salt of the formula MV "(SO 4) 2 .12 H 2 O in a M Alkali metal or ammonium ion and M is aluminum, titanium, manganese, iron or chromium ion, 0.1 -30 wt -% auxiliaries for improving the esthetic, cosmetic or processing properties, and optionally up to 40 wt % of other water-soluble aluminum salts in the form of a microwave permeable by microwave irradiation having sufficient energy so long exposed until the mixture warms and at least partially melted or sintered and then, allowed to cool and solidify after the microwave irradiation.
1

5) Method according to claim 4, characterized in that the irradiation with a formulation-specific high-frequency power of at most 1500 W / kg h, preferably less than 1000 W / kg h, and most preferably is carried out under 500 watt / kg h.

DESCRIPTION
DEODORANT PRODUCT BASED ON ALUM AND METHOD FOR THE PRODUCTION The invention relates to a deodorant product based on alum, which has a content of fragrance or essential oils with the aid of microwave technology in the form of a substantially transparent and clear obtained molding. Alum is a collective term for a group of double salts, of which the potash alum KAl (SO 4) 2 .12 H 2 O is best known and is widely respected for its astringent and antiseptic properties use in medicine and pharmacy. It is also known that alumhas deodorant properties. As antiperspirant and deodorant you alums used in powder form or in the form of so-called alum stones. Alum has the characteristics of melting in the crystal water (at about 92 C potassium alum, ammonium alumat about 95 C, sodium alum at about 60 C). The melt is pourable and can be molded in this way as desired. From EP-A-157 736 a method is known to produce a one Kalialaunstein Alaunblock by cutting a cylindrical pin. Recipes for making hemostatic pins on the basis of alum can be found in various cosmetics handbooks, for example, "The Chemistry and Manufacture of Cosmetics" (Maison G. de Navarre, 2nd edition 1975), pages 707708, or "Cosmetics Science and Technology "(Edward Sagarin, 2nd edition, 1972), volume 2, pages 34-35 or" Textbook of Cosmetics "(Edmund shrink, 3rd edition, 1974), page 336 From the French patent FR 2 575 922 was a pasty deodorant composition based on a 50% solution of alum in water, and with a content of 5 wt -% known perfume. However, none of the previously known method enables the production of perfumes containing Anlaunstifte because the melting of alum in their own water of crystallization must be done very carefully and slowly by conventional procedures so that the crystal water not distilled off, and since this process to evaporate the volatile fragrances for the most part would . Delicate fragrance components would discolor or degrade due to the high temperature stress. In any case, unsightly, cloudy and little scented deodorant body shape would get. But a certain perfume content is intended for use as a deodorant very advantageous and therefore there was a strong interest in having a content to get Alaunstifte of fragrances that have an attractive appearance and develop not only an antiperspirant effect when applied to the skin, but simultaneously existing smells slightly overlap. It has now been found that these objects can be solved by the fact that such a deodorant is prepared using microwave technology. The invention therefore relates to a solid, and preferably transparent shaped deodorant product with a content of 50 to 99 weight -% of a double salt of the formula I

I M (SO 4) 2 .12 H 2 O
1 is

III

where M

an alkali metal or ammonium ion and M

an aluminum, titanium, manganese, iron or chromium ion,

and optionally up to 40 wt -% of other water-soluble aluminum salt and a fragrance or essential oil in an amount of 0.5 to 20 wt -%, based on the entire product, and optionally up to 10 wt -% of further excipients. Instead of the single double salts and mixtures of various double salts of the general formula I referred to in the group may be included. There may also be mixtures of the single salts from which the double salts composed used. For example, a mixture of 1 mole of K 2 OSO 4 and 1 mole of Al 2 (SO 4) 3 .18 H 2 O and 6 moles of H 2 O or 0.5 mole of Na 2 SO 4, 0.5 mol K 2 SO 4, 1 mole of Al 2 (SO 4) 3 .18 H 2 O and 6 mol H 2 O are used. From these mixtures, the double salts of formula I form by heating under the action of microwave radiation. Preferably, the deodorant product of the invention contains at least 80 weight -% of a double salt of the formula I sodium, potassium, or NH 4 and M aluminum in the M
+ first

Other, water-soluble aluminum salts in an amount up to

40 percent by weight in the deodorant product according to the invention -% may be contained, preferably, the previously known as astringents products such as aluminum sulphate (Al 2 (SO 4) 3 .18 H 2 O ), aluminum chloride (A1C1 3 6H 2 O), aluminum chlorohydrate (Al 2 (OH) 5 Cl 2-3 H 2 O), Aluminiumchlorat (AlClO 3) 3 .9 H 2 O), aluminum formate, Aluminiumlacetat.Aluminum potassium sulfophenylat, Aluminiumnaphtholsulfonat and aluminumsodium acetate. Preferably, these other aluminum salts are up to 20 weight only in minor amounts -% contained in the deodorant product of the invention. By the addition of one or more of aluminum salts to the products of the invention, the deodorant astringent and antiseptic properties of the products can be increased. As can Dufstoffe individual odorant compounds, such as linalool, geraniol. Acetophenone, lilial, geranonitrile, Dihydromyrcenol, O-tert. Butylcyclohexylacetate. Phenylethyl alcohol, benzophenone, rose oxide, methyl benzoate, -hexyl cinnamaldehyde, vetiveryl, -dodecalactone, AUylamylglycolat, hydroxycitronellal, benzyl or Amylbutyrat be used. Preferably, however, mixtures of different perfume compounds which, together, produce an agreeable fragrance. Such Parfurms may also contain natural odorant mixtures, as are obtainable from plant or animal sources. The amount of perfume blends depends on the intensity of the desired fragrance and on the volatility and the intensity of fragrance of the perfume. An amount of 1 to 10 weight -% should be sufficient as a rule. Essential oils, however, have usually a lower volatility, of an additional antimicrobial or skin care effect may be present in thedeodorant products according to the invention preferably instead or in addition to the actual fragrance. Suitable lse are essential, for example, chamomile oil, sage oil, clove oil, rose oil, melissa oil, mint oil, lime blossom oil or juniper berry oil. Other auxiliaries, in an amount up to 10 wt -% may be included in the deodorant product of the invention, serve to further thetischen and cosmetic features and their processing and durability.

Thus, it can be advantageous for clear and easy incorporation of fragrances or essential oils to dilute them with appropriate tools and make them dispersible or adsorbed on powdered carriers with high surface area and to make them better distributed in this way. Suitable auxiliaries for this purpose are, for example, monohydric or polyhydric alcohols having from 2 to 6 carbon atoms, for example isopropanol. Propylene glycol, glycerol, sorbitol, polyethylene glycol or surfactants such as ethoxylated sorbitan fatty acid esters, ethoxylated fatty acid partial glycerides, ethoxylated Rizenusl, fatty alcohol polyglycol ethers, alkyl (oligo) glycosides or mixtures of such products. Suitable carriers are, for example, powdered fumed silica (Aerosil ), talc, bentonite or other finely divided silicates. Other tools that serve to improve the appearance of deodorant products of the invention are dyes and pigments. For example, water-soluble dyes or pigments, preferably pearlescent, TiO 2-coated mica pigments can be added. To improve the cosmetic effect can entzngshemmende or skin care ingredients such as urea, allantoin, panthenol, antioxidants such as ascorbic acid, hydroxycarboxylic acids such as lactic acid, glycolic acid or citric acid or other cosmetically active substances such as phytic acid , amino acids are added, or tretinoin. Water-soluble polymers such as polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycols may be added to further enhance the effect deodorienden. Finally, lanolin, oil components such as almond oil, and silicone oils may be added in small amounts. Finally, it has been found advantageous to have a small amount of free, unbound water in alum grating educt. By such water is the dielectric loss factor - which is a measure of the energy, which receives the material under microwave irradiation - be increased and the time which is needed to produce a homogeneous melt, reduced further. In general, an amount of 0.5 to 5 weight is -% water is sufficient. This level of free water also causes small loss of water of crystallization which may occur during the melting process due to evaporation can be replaced again and the Alauen may crystallize with the full hydration shell is. However, the method described for the preparation of deodorant products of the invention on the basis of alum salts is not only the incorporation of volatile components such as fragrances but is more generally represents an advantageous opportunity, tools to improve the esthetic, cosmetic and technical processing homogeneous and gently incorporate features such as essential oils, dyes, pigments, skin care, dermatologically or cosmetically effective interesting materials, oil processing components or technically useful components in these products. This is mainly because that the microwave radiation, the mixture almost "inside" her heated as it excites the molecules according to their dipole moment, ie, in particular water-HNN for rotation therewith and for transmitting energy to neighboring molecules. A heat transfer by heating from the outside, in contrast, results in much slower and a much higher thermal loading of all the components, resulting in both the evaporation of volatile components and in the decomposition of labile active ingredients and leads to a reduction of color and odor of the final product. Another object of the invention is a method for manufacturing the solid shaped deodorant product, in which a mixture of 50 - 99 weight -% of a double salt of the formula I

I M, I

(SO 4) 2 .12 H 2 O (I) where M

1 is

an alkali metal or ammonium ion and

an aluminum, titanium, manganese, iron or chromium ion is 0.1 to 30 weight -% of adjuvants to enhance the
"cosmetic

aesthetics or

or processing properties, and optionally up to 40 wt -% of other water-soluble aluminum salts

with sufficient energy so long exposed in a form of a microwave transparent to microwave radiation until the mixture warms and at least partially melted or sintered and then, after completion of the microwave radiation, is cooled. In this method, the cosmetic auxiliaries, fragrances incorporated gently and homogeneously, for example, and a product of good transparency can be obtained. It is preferred, a small amount of about 0.5 to 5 weight -% of water add the mixture to the small amounts of water to evaporate through the process of melting or sintering, are compensated. The irradiation with microwaves takes place in a vessel which is transparent to microwaves, such as glass, ceramic or plastics. Particularly advantageous is allowed to the process of irradiating, melting and Erkaltens deodorant in the packaging of the product, carried for example in a pin sleeve. While each plastic is considered to be heat resistant, up to a temperature of from about 10 -, no softening or decomposition shows 20 C above the melting temperature of the deodorant product. The inner surface of the vessel or the form in which the microwave irradiation should be smooth, so that the product can be easily removed from the mold after cooling. The mixture of the double set, and the tools necessary to further water-soluble aluminum salts should be before melting under microwave irradiation relatively homogeneous and finely divided. This can be achieved, for example characterized in that one uses the solid components, so primarily the salts, in a finely ground form, fixed aid in powder form, liquid, low-viscosity form, and easily distributable solutions or emulsions or adsorbed on powdered carriers, and mixing together a homogeneous premix. The more homogeneous the mixture of components is already in front of the microwave irradiation, the more homogeneous and transparent to get the deodorant product according to the invention, after cooling the melt. When microwaves are to be understood within the scope of the invention electromagnetic wave radiation having a frequency in the range from 3 to 300,000 MHz. This range includes the frequency range of radio waves from 3 to 300 MHz, and the actual microwave 300-300000 MHz. Preferably carried out by irradiation with microwaves of a frequency of 2450 MHz. The formulation-specific highfrequency power is not more than 1500 W / kg h, preferably less than 500 W / kg h The duration of irradiation of microwaves is required to produce a homogeneous melt of the components depends on the set power of the microwave system, the amount, the homogeneity of the premix, and from the melting point and the dielectric loss value of the premix, and. provided that when the microwave system is a belt system, on the tape speed. It has been shown that when using a microwave oven at 2450 MHz with a power of 250 watts to produce a melt from a sample of approximately 50 g of potassium alum (with a content of about 2 wt -% of free water) only

irradiation time of 2 - 4 minutes is required to produce a homogeneous crystal melt. The following examples are intended to illustrate the subject of the invention in detail. Examples Production of Vormixchune Of perfume oil, propylene glycol, dye and water, a liquid mixture was prepared (Example 1 - 3 and 5). For Example 4, a powder premix was prepared from perfume oil, water and Aerosil. Preparation of deodorant product The finely crystalline alum (K Al (SO 4) 2 .12 H 2 O, particle size 0.01 to 0.5 mm) was mixed with the liquid premixture (in the case of Example 4, with the powdered premix), with stirring, until a homogeneous distribution of the components was achieved (approximately 3 Minunten). The resulting alum mixture was placed in a pen barrel with a capacity of 50 g, the lid screwed on and introduced the filled pen tube with the cap down in a microwave oven of the type MLS 1200 from MLS with a microwave frequency of 2450 MHz. There, the samples were irradiated for 2 minutes with an output of 250 watts. After cooling, the samples were inverted, and the lid is unscrewed. It was found that stable, clear or transparent, partially colored (Examples 2, 3 and 5), products were obtained with a smooth surface in the shape of the inside of the closure cap. The recipes are given in the following table (all values in wt -%):

There the following perfume oil compositions were used: A: AFF 7683 (fragrance mixture of Fa Azur Fragrances) B: 94-4754 (fragrance mixture of HENKEL KGaA) C: AF 947 649 (fragrance mixture of Fa Azur Fragrances)

There, the following dyes were used: (A) 0.3% Blue No. 1, 0.1% solution (B) Red 10 Williams B, no. 33, 0.1% solution.