WO1997023197A1

WO1997023197A1 - Alum-based deodorant product and process for producing the same

Info

Publication number: WO1997023197A1
Application number: PCT/EP1996/005553
Authority: WO
Inventors: Andreas PÖPPL; Sandra Witt; Birgit Zimmermann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-12-21
Filing date: 1996-12-12
Publication date: 1997-07-03
Also published as: EP0952814A1; DE19548067A1

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(SO¿4)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.

Description

DEODORANT PRODUCT BASED ON ALUMINUM AND METHOD FOR THE PRODUCTION THEREOF

The invention relates to a deodorant product based on alum, which contains fragrances or essential oils and is obtained with the aid of microwave technology in the form of a largely transparent to clear shaped body.

Alum is a collective name for a group of double salts, of which the potassium alum KAl (SO ₄ ) ₂ 12 H ₂ O is best known and has found application in medicine and pharmacy because of its astringent and antiseptic properties. Alum is also known to have deodorant properties. As antiperspirants and deodorants, alums have been used in powder form or in the form of the so-called alum stones. Alum has the properties of melting in crystal water (potassium alum at approx. 92 ° C, ammonium alum at approx. 95 ° C, sodium alum at approx. 60 ° C). The melts are pourable and can be shaped as desired.

From EP-A-157 736 a method is also known for producing a potassium alumina block from an alum block by cutting out a cylindrical pin. Recipes for the production of hemostatic sticks based on alum can be found in various cosmetic manuals, e.g. B. from "The Chemistry and Manufacture of Cosmetics" (Maison G. de Navarre, 2nd edition 1975) pages 707-708 or "Cosmetics, Science and Technology" (Edward Sagarin, 2nd edition, 1972), volume 2, Pages 34-35 or "Textbook of Cosmetics" (Edmund Schrumpf, 3rd ed., 1974), page 336. A paste-like deodorant composition based on a 50% solution of alum in water and containing 5% by weight of perfume was known from French patent FR 2 575 922.

None of the previously known methods, however, enables the production of scented pens, since the melting of the alum in its own crystal water has to be carried out very carefully and slowly by conventional methods so that the crystal water does not distill off and since the volatile fragrances would largely evaporate during this process . Sensitive fragrance components would discolor or decompose due to the high temperature load. In any case, unsightly, cloudy and less fragrant deodorant moldings would be obtained.

However, a certain fragrance content is very advantageous for use as a deodorant and there was therefore a great interest in obtaining alum pencils with a fragrance content which have an attractive appearance and not only have an antiperspirant effect when used on the skin, but also at the same time slightly cover up existing smells. It has now been found that these objects can be achieved by producing such a deodorant using microwave technology.

The invention therefore relates to a solid, shaped and preferably transparent deodorant product with a content of 50 to 99% by weight of a double salt of the formula I.

M ^l M ^III (SO ₄ ) ₂ 12 H ₂ O

in which M ^{1 is} an alkali or ammonium ion and M ^{ιπ is} an aluminum, titanium, manganese, iron or chromium ion and optionally up to 40% by weight of further water-soluble aluminum salts and with a fragrance or essential oil in an amount of 0.5 to 20% by weight, based on the entire product, and optionally up to 10% by weight of further auxiliaries. Instead of the uniform double salts, mixtures of different double salts of the group covered by general formula I can also be present. Mixtures of the simple salts from which the double salts are composed can also be used. So z. B. also a mixture of 1 mol K ₂ OSO ₄ and 1 mol Al ₂ (SO ₄ ) ₃ 18 H ₂ O and 6 mol H ₂ O or 0.5 mol Na ₂ SO ₄ , 0.5 mol K ₂ SO ₄ , 1 mol Al ₂ (SO ₄ ) ₃ 18 H ₂ O and 6 mol H ₂ O can be used. The double salts of the formula I are formed from these mixtures when heated under the action of microwave radiation.

The deodorant product according to the invention preferably contains at least 80% by weight of a double salt of the formula I. in which M ^{1 is} sodium, potassium or NH ₄ ⁺ and M is aluminum. Other water-soluble aluminum salts, which may be present in the deodorant products according to the invention in an amount of up to 40% by weight, are preferably the products already known as astringents, such as aluminum sulfate (Al ₂ (SO ₄ ) ₃ 18 H ₂ O) ), Aluminum chloride (A1C1 ₃ 6 H ₂ O), aluminum hydroxychloride (Al ₂ (OH) ₅ Cl 2-3 H ₂ O), aluminum chlorate (AlClO ₃ ) ₃ 9 H ₂ O), aluminum formate, aluminum acetate. Aluminum potassium sulfophenylate, aluminum naphthol sulfonate and aluminum sodium acetate. These further aluminum salts are preferably only present in small amounts of up to 20% by weight in the deodorant products according to the invention.

The astringent and antiseptic properties of the products can be increased further by adding one or more of these aluminum salts to the deodorant products according to the invention.

As fragrances, individual fragrance compounds, such as. B. Linalool, Geraniol. Acetophenol, lilial, geranonitrile, dihydromyrcenol, o-tert. Butylcyclohexyl acetate. Phenylethyl alcohol, benzophenone, rose oxide, methyl benzoate, α-hexyl cinnamaldehyde, vetiveryl acetate, δ-dodecalactone, AUylamylglycolat, hydroxycitronellal, benzyl acetate or amyl butyrate can be used. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such Parfurms can also contain natural fragrance mixtures, such as those obtained from plant or animal sources. The amount of fragrance contained depends on the intensity of the desired fragrance and the volatility and intensity of the perfume. An amount of 1 to 10% by weight should generally suffice.

Essential oils, which usually have a lower volatility but often have an additional antimicrobial or skin-care effect, can also be present in the deodorant products according to the invention instead of or preferably in addition to the actual fragrances. Suitable essential oils are e.g. B. chamomile oil, sage oil, clove oil, rose oil, lemon balm oil, mint oil, linden blossom oil or juniper berry oil.

Further auxiliaries, which can be contained in the deodorant product according to the invention in an amount of up to 10% by weight, serve for further aesthetic and cosmetic equipment, as well as their processing and durability.

For the clear and problem-free incorporation of the fragrances or the essential oils, it can be advantageous to dilute them with suitable auxiliaries and make them dispersible or to adsorb them on powdery carriers with a high surface area and thus make them more distributable. Suitable tools for this purpose are e.g. B. mono- or polyhydric alcohols with 2 to 6 carbon atoms, for. B. isopropanol. Propylene glycol, glycerin, sorbitol, polyethylene glycol or surfactants e.g. B. ethoxylated sorbitan fatty acid esters, ethoxylated fatty acid partial glycerides, ethoxylated castor oil, fatty alcohol polyglycol ether, alkyl (oligo) glycosides or mixtures of such products.

Suitable powdered carriers are e.g. B. fumed silica (Aerosil®), talc, bentonite or other finely divided silicates. Other auxiliaries which serve to improve the appearance of the deodorant products according to the invention are dyes and pigments. So z. B. water-soluble dyes or pigments, preferably pearlescent, coated with TiO ₂ mica pigments. To improve the cosmetic effect, skin care or anti-inflammatory agents such. As urea, allantoin, panthenol, antioxidants such. B. ascorbic acid, hydroxycarboxylic acids such as. B. lactic acid, glycolic acid or citric acid or other cosmetically active substances such. B. phytic acid, amino acids or tretinoin can be added.

Water-soluble polymers such as B. polyvinylpyrrolidone, polyvinyl alcohol or polyethylene glycols can be added to further improve the deodorant effect. Finally, lanolin, oil components such. B. almond oil and silicone oils can be added in small amounts.

Finally, it has proven advantageous to have a small amount of free water in the educt that is not bound in the alum grid. This water increases the dielectric loss factor - this is a measure of the energy that the material absorbs under microwave radiation - and further reduces the time required to produce a homogeneous melt. In general, an amount of 0.5 to 5% by weight of water is sufficient. This proportion of free water also serves to ensure that small losses of water of crystallization, which can occur during the melting process due to evaporation, are replaced again and the alum can crystallize out with the full hydrated water shell.

The process described for the production of the deodorant products based on alum salts is not only used to incorporate volatile components such as. B. of fragrances but generally represents an advantageous way to assist in improving the aesthetic, cosmetic and processing properties such. B. essential oils, dyes, pigments, skin-care, dermatologically effective or cosmetically interesting substances, oil components or processing-technically helpful components homogeneously and gently incorporated into these products. This is mainly due to the fact that the microwave radiation heats the mixture virtually "from the inside", since it stimulates the molecules to rotate and thus to transfer energy to the neighboring molecules according to their dipole moment, in particular water molecules.

In contrast, heat transfer by heating from the outside is considerably slower and leads to a significantly higher thermal load on all components, which is reflected in the evaporation of volatile components and in the decomposition of unstable active ingredients and leads to a color and odor reduction in the end product.

Another object of the invention is a process for producing the solid, shaped deodorant product, in which a mixture of 50-99 wt .-% of a double salt of formula I

M ^I M ^{l, I} (SO ₄ ) ₂ 12 H ₂ O (I) in which M ^{1 is} an alkali or ammonium ion and

M ^{ιπ is} an aluminum, titanium, manganese, iron or chromium ion, 0.1-30% by weight of auxiliaries for improving the aesthetic, ^" cosmetic or processing properties and optionally up to 40% by weight of further water-soluble aluminum salts in a microwave-permeable form of exposure to microwaves with sufficient energy until the mixture warms up and at least partially melts or sinters, and then cools down after the microwave irradiation has ended.

In this method, the cosmetic aids, e.g. B. Fragrances gently and homogeneously incorporated and get a product of good transparency. It is preferred to add a small amount of approximately 0.5-5% by weight of water to the batch so that the small amounts of water that evaporate through the melting or sintering process are compensated for.

Irradiation with microwaves takes place in a vessel which is permeable to microwaves, e.g. B. in glass, ceramics or plastics. The process of Irradiation, melting and cooling in the packaging of the deodorant product, e.g. B. done in a pen sleeve. Any plastic that does not show any softening or decomposition up to a temperature which is about 10 - 20 ° C above the melting temperature of the deodorant product can be regarded as heat-resistant. The inner surface of the vessel or the form in which the microwave radiation takes place should be smooth so that the product can be easily removed from the mold after cooling.

The mixture of the double set, the auxiliaries and possibly the other water-soluble aluminum salts should be relatively homogeneous and finely divided even before melting under microwave radiation. This can be done e.g. B. achieve that one uses the solid components, so primarily the salts, in finely ground form, solid auxiliaries in powder form, liquid in the form of low-viscosity and easily dispersible solutions or emulsions or adsorbed on powdered carrier and mixed together to form a homogeneous premix . The more homogeneous the mixture of the components before the microwave irradiation, the more homogeneous and transparent the deodorant product according to the invention is obtained after the melt has cooled. In the context of the invention, microwaves are to be understood as electromagnetic wave beams whose frequency is in the range between 3 and 300,000 MHz. This range covers the frequency range of the radio waves from 3 to 300 MHz and that of the actual microwaves from 300 to 300,000 MHz.

Irradiation is preferably carried out with microwaves at a frequency of 2450 MHz. The recipe-specific high-frequency output is a maximum of 1500 watts / kg h, preferably less than 500 watts / kg h.

The duration of the irradiation with microwaves, which is required to produce a homogeneous melt of the components, depends on the set power of the microwave system and on the amount, the homogeneity of the premix and the melting point and the dielectric loss value of the premix, and. if the microwave system is a belt system, depends on the belt speed.

However, it has been shown that when using a microwave device with 2450 MHz and an output of 250 watts to produce a melt from a sample of approximately 50 g of potassium alum (with a content of approximately 2% by weight of free water) only one Irradiation time of 2 - 4 minutes is required to produce a homogeneous crystal melt. The following examples are intended to explain the subject matter of the invention in more detail.

Examples

Production of the premix chune

A liquid mixture was prepared from perfume oil, propylene glycol, dyes and water (Examples 1-3 and 5).

For example 4, a powdery premix was made from perfume oil, water and Aerosil.

Production of the deodorant product

The finely crystalline alum (K Al (SO ₄ ) ₂ 12 H ₂ O, particle size 0.01-0.5 mm) was mixed with the liquid premix (in the case of Example 4 with the powdery premix) with stirring until a homogeneous distribution the components had been reached (approx. 3 minutes).

The alum mixture obtained was placed in a pencil case with a capacity of 50 g, the lid was screwed on and the filled pencil case with the sealing cap facing downwards was placed in a MLS 1200 microwave oven from MLS with a microwave frequency of 2450 MHz. There the samples were irradiated with a power of 250 watts for 2 minutes. After the samples had cooled, they were turned over and the lid unscrewed. It was found that solid, clear or transparent, e.g. T. colored (Examples 2, 3 and 5) products with a smooth surface in the shape of the inside of the cap were obtained.

The recipes can be found in the following table (all figures in% by weight):

The following perfume oil compositions were used: A: ÄFF 7683 (fragrance mixture from Azur Fragrances) B: 94-4754 (fragrance mixture from HENKEL KGaA) C: AF 947649 (fragrance mixture from Azur Fragrances)

The following dyes were used:

(a) 0.3% Blue No. 1, 0.1% solution

(b) Williams Red 10 B, No. 33, 0.1% solution.

Claims

1) Solid molded deodorant product containing 50-99% by weight of a double salt of formula (I)

MV "(SO ₄ ) ₂ 12 H ₂ O (I)

in the M an alkali or ammonium ion and M an aluminum, titanium. Manganese, iron or chromium ion and optionally up to 40% by weight of further water-soluble aluminum salts, characterized in that a fragrance or an essential oil in an amount of 0.1 to 20% by weight and optionally up to 10 % By weight of further auxiliaries are contained.

2) Deodorant product according to claim 1, characterized in that it contains at least 80 wt .-% of a double salt of formula I, in which M is sodium, potassium or NH ₄ ⁽⁺⁾ and M aluminum.

3) deodorant product according to claim 1 or 2, characterized in that 1 to 10 wt .-% of a fragrance are included.

4) Process for the production of solid, shaped, transparent deodorant products, characterized in that a mixture of

50-99% by weight of a double salt of the formula MV "(SO ₄ ) ₂ 12 H ₂ O in the M ¹

Alkali or ammonium ion and M is aluminum, titanium, manganese, iron or chromium ion,

0.1-30% by weight of auxiliaries for improving the aesthetic, cosmetic or processing properties and possibly up to 40% by weight of further water-soluble aluminum salts in a microwave-permeable form of radiation by microwaves with sufficient energy exposed for a long time until the mixture warms up and at least partially melts or sinters and then, after the microwave irradiation has ended, can cool and solidify.

5) Method according to claim 4, characterized in that one carries out the irradiation with a recipe-specific high-frequency power of at most 1500 watts / kg h, preferably less than 1000 watts / kg h and very particularly preferably less than 500 watts / kg h.