WO1996032923A2

WO1996032923A2 - Anti-transpirants

Info

Publication number: WO1996032923A2
Application number: PCT/EP1996/001511
Authority: WO
Inventors: Holger Tesmann; Heike Thomas; Armin Wadle; Thomas Förster; Marcus Claas; Bernhard Banowski; Claudia Weiler; Marion Zinken
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-04-15
Filing date: 1996-04-09
Publication date: 1996-10-24
Also published as: DE19514269A1; AU5500196A; WO1996032923A3

Abstract

The invention concerns anti-transpirants containing water-soluble inorganic astringent anti-perspirant substances, e.g. aluminum hydroxychloride. Such anti-perspirants can be produced as stable, fine oil-in-water emulsions with a droplet diameter of 100-300 nm and having a water content of 40-80 wt.% by emulsifying the oil component by the phase-inversion technique, using 0.1-0.3 parts by wt. of a non-ionic emulsifier with an HLB value of 10-15 plus 0.1-0.3 parts by wt. of a coemulsifier of the saturated fatty alcohol or polyol fatty-acid partial-ester type for each part by wt. of the oil component. The anti-perspirants proposed may also contain 1-20 wt.% of a water-soluble polyol with 2-8 C-atoms and 2-6 hydroxyl groups and are preferably free of lower alcohols having 2-3 C-atoms.

Description

"Antiperspirants"

The invention relates to antiperspirants based on a very finely divided, almost transparent oil-in-water emulsion of a cosmetic oil component and an inorganic, astringent deodorant active ingredient which is soluble in the aqueous phase.

The use of oil-in-water emulsions as carriers for cosmetic and dermatological active ingredients has long been known. One difficulty is that the nature of the active ingredients often adversely affects the stability of the carrier system. From German patent application P 43 37 041.1 it was already known that very finely divided emulsions, which are produced by the phase inversion process, are particularly suitable as carriers for deodorants, perfume oils and light protection factors. However, it has not yet been possible to conclude from this publication that such emulsions are also suitable as carriers for water-soluble, inorganic, astringent antiperspirant active ingredients.

The task was to improve the antiperspirants in their skin and mucous membrane compatibility by using an emulsion as a carrier for the astringent active ingredients, the oil components of which have a softening and anti-inflammatory effect on the skin. effect. The problem mainly consisted in the fact that conventional oil-in-water emulsions are not sufficiently stable in the presence of the inorganic active substances.

It has now surprisingly been found that the problem can be solved by using a very finely divided emulsion as the carrier, such as is used, for example, in can be produced by the phase inversion process.

The invention relates to an antiperspirant in the form of a finely divided oil-in-water emulsion with a droplet diameter of 100-300 nm and a content of 40-80% by weight of water and

(A) 1-20% by weight of a water-soluble, inorganic, astringent antiperspirant active ingredient and

(B) 3 to 30 parts by weight of an oil component, and the emulsion based on 1 part by weight of the oil component

(C) 0.1-0.3 parts by weight of a nonionic emulsifier with a

HLB value of 10-15 and

(D) 0.1-0.3 parts by weight of a saturated co-emulsifier

Fatty alcohols with 16-22 C atoms or the partial esters of polyols with 3-6 C atoms and saturated fatty acids with 14-22 C atoms

contains.

Such antiperspirant formulations according to the invention are notable for the fact that the astringent active ingredients are well tolerated even when used regularly on the skin. From Progr. Colloid & Polymer Sei. 73 (1987), 37-47, oil-in-water emulsions are known which were prepared with a combination of nonionic emulsifiers and coemulsifiers and were heated to phase inversion temperature during or after their preparation. Such emulsions are characterized by high stability, fine particle size and particularly low viscosity. DE 38 19 193 discloses an emulsifier system which enables the production of such emulsions even with polar oils which contain little or no hydrocarbon content.

The droplet diameter of such fine-particle emulsions - hereinafter referred to as PIT emulsions - is of the order of 100-300 nanometers (nm), i.e. they are not yet optically isotropic, single-phase systems such as are found in solubilizates and microemulsions, the particle diameter of which is far below 100 nm.

Rather, due to their droplet size, the PIT emulsions have a brown-red appearance when viewed through and bluish shimmering in reflected light, which is explained by the Tynda11 scattering on the emulsion droplets.

Particularly suitable as water-soluble, inorganic, astringent antiperspirant active ingredients (A) are salts of aluminum, Zi onium or zinc.

Such suitable antiperspirant active ingredients are, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds with propylene glycol 1,2. Aluminum Hydroxyallantoiπat, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate drat, aluminum-zirconium pentachlorohydrate and their complexes with amino acids, for example with glycine.

However, aluminum hydroxychlorides and their adducts with water-soluble glycols are preferred. Salts are understood to be water-soluble if they are at least 1% by weight soluble in water at 20 ° C.

All water-insoluble, skin-compatible oils and fatty substances and their mixtures with solid paraffins and waxes are suitable as cosmetic oil components. However, the melting point of the mixtures with solid paraffins and waxes which may be used should be as far as possible below the phase inversion range of the emulsion and preferably below 40 ° C.

Suitable skin-compatible oil components (B) are preferably still liquid hydrocarbons at 20 ° C., for example paraffin oils and synthetic hydrocarbons such as 1,3-di- (2-ethylhexyl) cyclohexane (cetiol ( ^R ) s). Another particularly suitable oil component are the di-n-alkyl ethers such as di-n-octyl ether, di- (2-ethylhexyl) ether, lauryl methyl ether or octyl butyl ether.

A particularly versatile group of cosmetic oil components is that of the fatty acid and Fettalkoholester, for example isopropyl myristate, n-butyl stearate, 2-ethylhexyl caprylate, cetyl oleate, glycerol trica- prylat, Kokosfettalkohol- (Ci2 ^_ CISS) -caprylat- / caprate and other . Also suitable are naturally occurring ester oils such as jojoba oil or liquid vegetable triglyceride oils such as olive oil, sunflower oil, soybean oil, rapeseed oil, almond oil, the liquid portions of coconut oil or beef tallow and synthetic triglceride oils.

Suitable dicarboxylic acid esters (II) are, for example, di-n-butyl adipate, di-n-butyl sebacate, di- (2-ethylhexyl) adipate, di- (2-hexyldecyl) succinate and di-isotridecyl acelaate. Suitable diol esters (III) are, for example, ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and neopentyl glycol - di-caprylate.

In a mixture with these liquid oil components, semi-solid and solid paraffins and waxes as well as solid triglyceride fats can also be used in smaller quantities.

As emulsifiers, the PIT emulsions contain a combination of a hydrophobic, nonionic emulsifier (C) with an HLB value of preferably 10-15 and a lipophilic coe ulgator (D). The HLB value is to be understood as a quantity that can be calculated from the structure of the emulsifier according to

HLB * 100 - * -

where L is the weight percentage l (in%) of the lipophilic groups, e.g. is the fatty alkyl or fatty acyl groups in the emulsifier.

The hydrophilic emulsifiers (C) are preferably ethylene oxide adducts on fatty alcohols with 16-22 C atoms or on partial esters of polyols with 3-6 C atoms and fatty acids with 14-22 C atoms. However, ethylene oxide addition products on fatty acids, on alkyl glucosides, on methyl glucoside fatty acid esters, on fatty acid alkanolamides, on fatty acid glucamides and other fatty substances with ethoxylatable substituents are also suitable. It can be particularly preferred to use alkyl polyglycosides of the formula R0 - (Z) _x as hydrophilic emulsifiers, in which R is a Cβ-C22-alkyl or alkenyl radical, Z is a monosaccharide, in particular glucose, and x is sen degree of oligomerization represents a number from 1.1 to 5, in particular from 1.2 to 1.4.

The lipophilic co-emulsifiers (D) are preferably saturated fatty alcohols with 16-22 C atoms, partial esters of polyols with 3-6 C atoms with saturated fatty acids with 14-22 C atoms, free fatty acids with 16- 22 carbon atoms, to glycol ono fatty acid esters, to fatty acid alkanolamides from Ci2-Cl8 ~ ^ ^et-t'aur '-' ^t mono- or dialkanolamines with 2 - 4 carbon atoms in the alkanol group or to glycerol mono-fatty alcohol ether.

The antiperspirant preparations according to the invention preferably additionally comprise 1 to 20% by weight of a water-soluble polyol having 2 to 8 carbon atoms and 2 to 6 hydroxyl groups. Such suitable polyols are e.g. Ethylene glycol, 1,2-propylene glycol, glycerin, erythritol, trimethylolpropane, sorbitol or methyl glucoside. Instead of these polyols, polyethylene glycols or adducts of ethylene oxide with such polyols can also be used.

Lower, volatile alcohols should only be present in the antiperspirants according to the invention in small amounts, but preferably not at all. the ethanol or isopropanol content does not exceed 2% by weight.

In addition, however, conventional oil-soluble and water-soluble auxiliaries can be present in smaller amounts in the antiperspirants according to the invention. Such oil soluble aids can e.g. his

anti-inflammatory, skin-protecting or fragrant essential oils synthetic skin-protecting agents

oil-soluble perfume oils.

Common water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH adjusting agents, e.g. Buffer mixtures, water soluble thickeners, e.g. water-soluble natural or synthetic polymers such as e.g. Xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.

To prepare the antiperspirants according to the invention, the mixture of oil component (B), emulsifier (C) and coemulsifier (D) is emulsified at a temperature above the melting point of this mixture with at least 1 part by weight of water (based on 1 part by weight of the oil component (B)), where the emulsion is heated during its production or thereafter to a temperature within or above the phase inversion temperature range and then cooled to a temperature below the phase inversion temperature range and optionally further diluted with water, and the deodorant active ingredient (D) , optionally in the form of an aqueous solution and optionally further water-soluble components.

The process according to the invention can be carried out by first determining the phase inversion temperature by heating a sample of the emulsion prepared in the customary manner using a conductivity meter and determining the temperature at which the Conductivity decreases sharply. The decrease in the specific conductivity of the oil-in-water emulsion initially present usually takes place over a temperature range from 2 to 8 ° C. from initially over 1 millisiemens per cm (mS / cm) to values below 0.1 mS / cm from. This temperature range is referred to as the phase inversion temperature range. }

After the phase inversion temperature range is known, the process according to the invention can either be carried out by subsequently heating the emulsion initially prepared in the customary manner to a temperature which is within or above the phase inversion temperature range, or in such a way that that a temperature which is within or above the phase inversion temperature range is already selected during the preparation of the emulsion.

The following examples were produced by the process according to the invention and are intended to describe the subject of the invention in more detail:

Examples

Antiperspirant preparations of the following composition were produced:

Example 1 2 3 4 5

Locron L (50%) (1) 10 20 10.0 30.0 10

Paraffin oil - 5 - - 1.7

Cetiol ( ^R ) s (2) 15.0 15 - - 5.0

Myritol ( ^R ) 318 (3) 5.0 - 5.0 2.5 -

Cetiol LC (4) - - 15.0 7.5 -

Cetyl palmitate 0.45 0.4 - - 0.13

Eumulgin Bl (5) 0.45 0.4 - - 0.14

Eumulgin B2 (6) 2.40 2.8 2.3 1.2 1.0

Cety stearyl alcohol 0.45 0.4 - - 0.13

Glycerol mono / di-stearate 2.25 2.0 3.7 1.9 0.7

1,2-propylene glycol 5.0 5.0 5.0 5.0 5.0

Perfume 1.0 1.0 1.0 1.0 1.0

Water 58.0 48.0 58.0 50.9 75.2

Claims

claims

1. Antiperspirant in the form of a finely divided oil-in-water emulsion with a droplet diameter of 100-300 nm and a content of 40-80% by weight of water and

(A) 1-20% by weight of a water-soluble, inorganic, stringent antiperspirant active ingredient,

(B) 3 to 30% by weight of an oil component, and the emulsion based on 1 part by weight of the oil component

(C) 0.1-0.3 parts by weight of a nonionic emulsifier with an HLB value of 10-15 and

(D) 0.1-0.3 parts by weight of a co-emulsifier of the type of saturated fatty alcohols with 16-22 carbon atoms or the partial esters of polyols with 3-6 carbon atoms and saturated fatty acids with 14-22 C atoms

contains.

2. Antiperspirant according to claim 1, characterized in that it additionally contains 1 to 20% by weight of a polyol having 2 to 8 carbon atoms and 2 to 6 hydroxyl groups.

3. Antiperspirant according to claim 1 or 2, characterized in that a hydrocarbon which is liquid at 20 ° C is contained as the oil component. 1 .

4. Antiperspirant according to one of claims 1 to 3, characterized in that an aluminum hydroxychloride is contained as the ..dstringierencier deodorant active ingredient.

5. A process for the preparation of an antiperspirant according to claim 1, characterized in that the mixture of oil component (B), emulsifier (C) and coemulsifier (D) at a temperature above the melting point of this mixture with at least 1 Part by weight of water, based on 1 part by weight of the oil component (B), emulsifies and the emulsion is heated during or after its preparation to a temperature within or above the phase inversion temperature range and then cooled to a temperature below the phase inversion temperature range and optionally with water further diluted and the deodorant active ingredient (D), optionally in the form of an aqueous solution, and optionally further water-soluble components are admixed.