WO2000032161A1

WO2000032161A1 - Preparations of aqueous-based cleaning agents which form vesicles and which contain active agents, method for their production and their utilisation

Info

Publication number: WO2000032161A1
Application number: PCT/EP1999/008595
Authority: WO
Inventors: Valentina Paspaleeva-Kühn; Silvia Schmandt; Rolf D. Beutler
Original assignee: Merz + Co. Gmbh & Co.
Priority date: 1998-11-27
Filing date: 1999-11-09
Publication date: 2000-06-08
Also published as: EP1133276A1; AU760248B2; AP2001002158A0; IL142877A0; NZ511785A; HRP20010400A2; EA003465B1; KR20010080615A; DE19854827A1; NO20012578L; NO20012578D0; BG105533A; CN1328444A; YU36101A; BR9915742A; EA200100594A1; JP2002531389A; HUP0104356A2; TR200101508T2; HUP0104356A3

Abstract

The present invention relates to preparations of aqueous-based cleaning agents, especially shower gels, foam bath preparations or shampoos. Said preparations contain active agents and well-known auxiliary agents and additives and a proprotion of at least one sterol. Said aqueous preparations containing active agents spontaneously form liposomal structures, especially when they are applied. The invention also relates to a method for producing such preparations containing active agents and to their utilisation as cleaning agents.

Description

Water-based vesicle-forming surfactant-containing cleaning preparations, process for their preparation and their use

The present invention relates to cleaning preparations on an aqueous basis, in particular shower baths. Foam bath compositions or shampoos, containing surfactants and conventional auxiliaries and additives and a proportion of one or more sterols. These aqueous surfactant-containing preparations spontaneously form liposomal structures, especially when used. The invention further relates to a method for producing such surfactant-containing preparations and the use of this preparation as a cleaning agent.

So far, water-based surfactant cleaning products as well as oil and cream preparations for showering or bathing with a more or less pronounced cleaning effect or regreasing are known.

Vesicular systems have found widespread use in cosmetics and pharmaceuticals as active ingredient carriers and skin care components. Cosmetic gels and emulsions containing liposomes or vesicles are already known, and dispersions containing liposomes or vesicles are already being produced in the pharmaceutical sector. Liposomal-based cleaning products have also been described. For example, "Mederma Regulativ-Waschlotion Plus" is a commercially available emulsion-based cleaning product with liposomes. This preparation contains O / W emulsifiers and a fat phase, but no washing-active substances.

Liposome formation in bath water from oil bath or oleogel preparations and bath tablets has also been described. For example, DE-OS 42 05 548 describes bath and shower additives with vesicle-forming properties, which contain fatty oils and / or apolar substances and also have a content of one or more oil-soluble surfactants together with a content of one or more vesicle-forming lipids. The oil-soluble surfactants have an HLB value of 6 to 13 and the vesicle-forming lipids have an HLB value of 2 to 6. DE 196 02 346 7 describes shower oleogels with vesicle-forming properties which contain more than 30% of one or more lipophilic components, 0.1 to 20% vesicle-forming substances and conventional auxiliaries and additives, and furthermore an emulsifier system composed of one or more W / O and one or more O / W emulsifiers, in a ratio of 1 2 to 1 0.2

Such hpid-containing cleaning agents, which are intended to compensate for the loss of skin lipids which occurs during the removal of dirt, are produced by incorporating prefabricated vesicle dispersions into the preparation or the liposomes, in particular when used as a bath additive, when used by contact with water from the preparation contained lipids arise

In the case of the products mentioned above, there are either no surfactants or, in the event that surfactants are present, special systems on those in combination with oils which are intended to prevent the interactions of the liposomal structures with surface-active substances in aqueous solutions in such a way that they are not dissolved. However, there are currently no preparations without a proportion of fatty oils or oil-containing components which form liposomal structures. Vesicle-forming lipids, such as phospholipids, sphingolides or ceramides, have also been used in the manufacture of liposomal structures in such cleaning products

RA Wächter et al describes in Parfumeπe and Cosmetics, 75 Volume, No. 11/94, pages 755 to 759, the use of naturally occurring phytosterols as herbal active ingredients in cosmetics. Phytosterols can be obtained from different oils and fats, such as corn germ, Rapeseed oil, soybean oil, olive oil etc and essentially consist of ß-sitosterol, campesterol and stigmasterol. The product name Generol ^® 122 is a soybean mixed product of the three phytosterol components mentioned with a predominant proportion of ß-sitosterol (58.1%) and 29.8% campesterol and 4.5% stigmasterol known In addition, there are also ethoxylated product variants of the phytosterols mentioned, in particular Generol ^® 122. Depending on the degree of ethoxylation, a number of products with different properties are obtained, such as Generol ^® 122 E5 ( 5 mol EO), which is predominantly hydrophobic, and such products with a degree of ethoxylation of 10 , 16 or 25 The latter products have the properties of a typical O / W emulsifier. As a result, the latter can be used as corresponding emulsifiers in O / W emulsions and as solubilizers, while the non-ethoxyethered product is suitable as a W / O emulsifier or co-emulsifier in addition to its emulsifying property Phytosterols can also be used positively on damaged or stressed skin, such as constitutional neurodermatitis or sunburn symptoms. Furthermore, in addition to the above-mentioned indication as emulsions, such products can also be used as hair conditioners. The use of generol-containing shampoos can help Wet combability and hair shine are improved in the cited literature parts accordingly W / O skin creams for dry skin are described, containing in addition to a conventional W / O emulsifier and various oil components as well as consistency agents and stabilizers a content of 1% of Generol ^® 1 22 as a co-emulsifier Furthermore, a hair conditioner is described there which, in addition to the cationic emulsion base and consistency enhancers and additives, contains an oil component, an O / W emulsifier and Generol ^® 122 in an amount of 1.0% found that Generol ^® 122 in combination with long-chain fatty acids, fatty alcohols or phosphides is able to build multiiameilar vesicles or layers. It is assumed that the phytosterols are deposited in the lamellar lipid layers. The ethoxylated generol products are in contrast to Generol ^® 122 in a layer arrangement before With water contents below 70%, lamellar phases are developed, but when the water content is increased to over 70%, a transition to multilamelar vesicles takes place, ie liposomes. However, no surfactants may be present

However, body cleansing agents contain a proportion of surfactants which are known (cf. DE-PS 42 05 548 and WO 92/04010) that they can have negative effects on the stability of liposomes, since liposomal structures are known to interact with surface-active substances in water Solutions are solubilized So far it has not been possible without special stabilization measures to formulate stable surfactant-containing aqueous systems, as are common for cleaning products, with liposomal components

US-A 5688752 describes cleaning and care compositions which, in addition to surfactants, have a lipid composition composed of three components A, B and C in very specific molar ratios, where A ceramides can be phospholipids, pseudoceramides, glycolipids or polyethylene glycol esters, component B long-chain hydrocarbons with polar head groups like fatty acids and component C is an auxiliary component for stabilizing any bilayers that may have formed component C can for example, 3-ß-sterol or cholesterol, sistosterol, stigmasterol or ergosterol. With such products, the loss of the skin of lipids and thus the dehydration should be reduced.

The object of the present invention is therefore to formulate an aqueous-based surfactant-containing cleaning system which does not contain any oil-containing components and yet has liposomal structures, in particular when used, which gives all the advantages of cleaning or skin care such as those for surfactant-containing and lipid-containing products are known can be achieved.

This object is achieved according to the invention by aqueous-based cleaning preparations containing 1 to 60% of one or more surfactants, which are selected in particular from anionic and / or nonionic and / or amphoteric and / or cationic surfactants, further 0 - 5%, in particular 0, 5 - 2% of one or more conditioning agents, 0 - 5%, in particular 1 - 3% of one or more stabilizers, 0 - 3%, in particular

0.1-1.5%, one or more preservatives, 0-5%, in particular 0.1-2%, one or more thickeners, and 0-20%, especially 0.5-3%, active ingredients, 0-1 %, in particular 0.0005-0.01% of dyes and 0-5%, in particular 0.5-2%, of one or more opacifiers or pearlescent agents, and which are characterized by a content of 0.001-15%, in particular 0 , 01-15%, very particularly preferably 0.5-10%, and in particular 0.5-5% of one or more sterols.

Surprisingly, it was possible to show that with such aqueous surfactant-containing preparations of the specific composition specified, liposomal structures arise spontaneously from the individual constituents in the course of production or use and remain as such during the cleaning process. This is in stark contrast to known oil-based cleaning compositions, from which, as described above, liposomes form when used in water. The loss of skin lipids caused by surfactants during dirt removal can be compensated for by the positive effects of sterols, which have been resolved above. In addition to the excellent cleaning effect, this can prevent the skin from drying out. Surprisingly, the use of oil components for this purpose could be dispensed with.

The cleaning preparation according to the invention preferably contains a mixture of anionic, nonionic and amphoteric, in particular anionic and amphoteric or anionic and nonionic surfactant (s). Anionic surfactants are known for the purpose described and can preferably be selected from alkyl sulfates (for example C10-C18) and / or the corresponding alkyl ether sulfates, in particular with 1-6 ethylene oxide groups in the molecule, sulfosuccinates, sulfosuccinamates, sarcosinates, isethionates, taurides , Ether carboxylic acids, protein-fatty acid condensates, alkyl sulfonates and alkyl benzene sulfonates, monoalkyl phosphates, monoglyceride sulfates, amide ether sulfates, alkyl sulfoacetates, α-olefin sulfonates. The alkyl chains in the surfactants mentioned can each comprise eight to eighteen carbon atoms.

Are particularly preferred alkyl ether sulfates derived from fatty alcohols containing 12 to 18 carbon atoms and a degree of ethoxylation of 2 to 6, such as lauryl / myristyl, Na salt (example Texapon ^® K 14 S Special IS, Elfan ^® NS 243 S), Ammoni - umlaurylethersulfat (Zetesol ^® LA-2) or Monoisopropanolammoniumlaurylethersulfat (Zetesol ^® 2056) or alkyl sulphates, eg sodium lauryl sulfate (Texapon ^® Z), ammonium lauryl sulfate (Texapon ^® ALS) or Monoisopropanolammoniumlaurylsulfat (Sulfetal ^® CJOT 60).

Also suitable are, in particular succinic acid derivatives, such as sulfosuccinates and sulfo succinamates having an alkyl group from 8 to 22 carbon atoms, for example WALLASOL ^® -L 29 (Disodi- to Laureth-3 Sulfosuccinate).

The amphoteric surfactant can in particular be selected from alkylaminopropionates, alkyl-, alkylamido- and sulfobetaines and alkylglycinates with a C chain length of C8 to C22. Most preferably, the known co camidopropylbetain under the trade name Dehyton ^® K.

The nonionic surfactant is particularly selected from alkanolamides, fatty reethoxylaten, fatty alcohol ethoxylates, alkyl polyglucosides, in particular with an alkyl group from 8 to 16 carbon atoms, such as Plantacare ^® 2000 UP (Decyl Glucoside), sorbitan esters, such as Tween ^® 20 (Polysorbate 20), amine oxides, in particular Fatty amine oxides with a C7 - C26 alkyl chain, e.g. Incromine Oxide ^® C30 (Cocamidopropylamine Oxide). Also suitable are sorbitan esters, alkylphenol oxyethylates (C8 - C22; possibly 4 - 20 ethylene oxide groups) or mixed condensates made of ethylene oxide and propylene oxide (eg Pluronics® types). Such surfactants suitable for cleaning agents are, for example, also in SÖFW-Journal, 120th year, 2-3 / 94, pp. 115 to 116, in issue 7/94, page 387 and in Cosmetics and Toiletries, vol. 108, 1993 , Pp. 83 - 89, as well as in SÖFW, 117 volume, No. 1 from 1991, pages 3 - 7 or in the monograph by K. Schrader, Basics and Recipes of Cosmetics, 2nd edition (1989, Hüthig Buchverlag), Pp. 683 - 691).

Suitable cationic surfactants are quaternary ammonium compounds with carbon chain lengths usually between 12 and 22, e.g. Steartrimonium chloride or pyridine salts, e.g. Cetylpyridinium chloride.

Particularly suitable sterols are phytosterols such as those derived from corn oil, rapeseed oil, soybean oil, olive oil etc. and mainly consisting of a mixture of ß-sitosterol, campesterol and stigmasterol in different weight proportions, as described, for example, by RA Wächter (cf. P. 4, paragraph 4 of this application). Cholesterol and its derivatives, for example dihydrocholesterol or cholesterol esters such as cholesteryl acetate, are also suitable. Particularly suitable as a phytosterol is a product with the trade name Genenerol ^® 122 N (refined soyasterol). Also preferred are ethoxylated sterols of the type mentioned with a degree of ethoxylation of 5 to 30, such as. B. Generol ^® 122 N E5D, E10, E16, E25D (ethoxylated soy sterols) or Nikkol ^® DHC-15 and -30 (ethoxyated dihydrocholesterol).

Quantities of 0.5 to 5%, in particular 0.5 to 3% and preferably 0.5 to 2%, of the sterols mentioned are particularly preferred. A mixture of non-ethoxylated phytosterol, for example Generol ^® 122 N and one with 5 units of ethoxylated phytosterol, such as, for example, is very particularly preferred. B. Generol ^® 122 N E5D. The proportion of ethoxylated sterol is preferably higher than or equal to the proportion of non-ethoxylated sterol, in particular in a ratio of 5: 1% by weight to 1: 1% by weight. A ratio of 3: 1% by weight is particularly preferred. Further preferably, the sole use of a non-ethoxylated sterol, such as Generol ^® is 122 N in the specified amounts, such as 1 wt.%.

Particularly suitable amounts of surfactant are 5 to 30%, in particular 7.5 to 25% and very particularly preferably 10 to 20% of surfactant or surfactants.

The composition according to the invention can furthermore contain customary auxiliaries and additives. These include cationic polymers as conditioning agents, such as polyquaters nium-22 (Merquat ^® 280), quaternized protein derivatives such as lauryldimonium hydroxypropyl hydrolized soy protein (part of Prota Flor ^® HSQ), silicone derivatives, e.g. Abil ^® B 8863, 8843 (Dimethicone Copolyol), protein hydrolyzates or water-soluble proteins.

One or more stabilizers can also be present in small amounts (0 to 5%). Here includes, for example complexing agents such as Trilon BD ^® (EDTA, sodium salt), agents for pH adjustment, eg citric acid, humectants such as Glycehn, inorganic salts such as sodium chloride as a viscosity regulator.

In addition, one or more preservatives and thickeners (0 to 5%) can optionally be present. Suitable preservatives are, for example, iodopropynyl butyl carbamate, phenoxyethanol and other common preservatives, such as e.g. p-hydroxybenzoic acid esters, formaldehyde and releasers, sorbic and dehydroacetic acid and their salts, isothiazolinones, 5-bromo-5-nitro-1, 3-dioxane, methyldibromoglutanonitrile, etc.

Suitable thickeners are, for example, Volpo ^® L 3 are (Laureth-3) or Antil ^® 208 (Laureth-3, propylene glycol, acrylates / steareth-50 copolymer) Glucamate DOE 120 ^® (PEG-120 Methyl Glu- cose Dioleate), Comperian ^® 100 (Cocamide MEA).

In particular, the cleaning preparation according to the invention can have one or more active ingredients in the amounts specified. These include, for example, perfume oils or essential oils, active ingredient extracts and / or vitamins.

These include, in particular, mint oil, lime oil, orange oil, juniper oil, valerian oil, eucalyptus oil, thyme oil, palmarosa oil, rosemary oil, lavender oil, menthol, ginger, linden blossom, marigold, algae, aloe vera, echinacea, ivy leaf extract and panthenol extract , Nicotinic acid ester. Depending on the intended effect, such as improving the hair or skin structure, increasing blood circulation, relaxation, aromatherapy and others, a suitable combination of active ingredients can be added. If necessary, further refatting agents such as fatty acid glycerides and their ethoxylates, for example PEG-6 Caprylic / Capric Glycerides (Softigen ^® 767) and / or dyes such as for example patent blue, amido blue, orange RGL, cochineal red, quinoline yellow can be used. In a preferred embodiment, the compositions according to the invention can also contain an additional proportion, for example 0.01 to 5%, of one or more vesicle-forming lipids. These include in particular lecithin, phospholipids, such as phosphatidylcholine dylcholin, and ceramides such as ceramide 2, -3, -6 and sphingolipids, such as Procera mide ^® L, Ceraderm ^® S, Ceraveg ^®.

Lecithin (e.g. soy lecithin), phosphatidylcholine, phosphatidylserine or diethanolamine or mixtures thereof are particularly preferred.

The cleaning preparations according to the invention are produced by melting the sterol or sterols in the aqueous surfactant solution. The preparation is then stirred cold. If necessary, active ingredients and other auxiliaries and additives are then incorporated in the course of production. Suitable temperatures for this are between 60 ° C and 25 ° C.

The products obtained with the compositions according to the invention spontaneously form liposomal structures, particularly when used. These can be detected by means of transmission electron microscopy (TEM) after freezing fracture.

With the cleaning preparations according to the invention, it is possible to use products with existing liposomes as cleaning and care agents. The preparations according to the invention are very easy to distribute. They have good cleaning and foaming properties, a pleasant feeling on the skin and favorable odor properties. So they meet the requirements for cosmetics.

The compositions according to the invention can be used in particular as a shower bath, foam bath or shampoo. Depending on the intended application, the individual components can be combined differently.

The products according to the invention also have very good stability and can be produced without the use of special and complex apparatus and production processes, as are usually required for the provision of liposomal articles. The consistency of the products can be adjusted as desired using small amounts of additives and auxiliary substances that do not change the feeling on the skin. Due to the special property of sterols, especially phytosterols, namely that they are plant-based In addition to the liposomal effect, raw materials that have a positive influence on hair and skin texture can also achieve a further care effect.

It was surprisingly found that the presence of surfactants in particular has no negative effect on the presence or formation of the liposomes. This could not be expected in view of the prior art already described, which found that conventional liposomal structures from e.g. B. phospholipids can be solubilized by such highly surface-active O / W emulsifiers or surfactants.

By incorporating one or more of the above active ingredients e.g. Indicative shower compositions can be prepared according to the desired purpose. For example, a hardening shower with eucalyptus oil, mint oil and echinacea extract; a stimulating shower with rosemary oil and lime oil or a muscle relaxation shower with ginger extract, methyl nicotinate, hydroxyethyl salicylate and juniper oil.

The invention is illustrated by the following examples. Following the examples, the transmission electron micrographs of the products produced according to the invention are attached. Here one can clearly see the liposomal structures (spherical structures) in the product produced according to the invention after dilution with water 1 T: 20 T at 37 ° C.

Preparation of the preparations according to the invention.

The products according to the following Examples 1 to 9 were prepared by melting the sterol (s) specified in the aqueous surfactant solution, ie the solution of demineralized water and the specified surfactants, at temperatures between 80 ° C. and 90 ° C. The mixture was then stirred cold and, if appropriate, the further additives, active ingredients and auxiliaries specified were incorporated in the order given at temperatures between 60 ° C. and 25 ° C.

example 1

Acrylates / Steareth-50 Copolymer + Propylene Glycol + Laureth-3

Example 2

Acrylates / Steareth-50 Copolymer + Propylene Glycol + Laureth-3

Example 3

Example 4

Example 5

Example 6

Acrylates / Steareth-50 Copolymer + Propylene Glycol + Laureth-3 Example 7

Acrylates / Steareth-50 Copolymer + Propylene Glycol + Laureth-3

Example 8

Acrylates / Steareth-50 Copolymer + Propylene Glycol + Laureth-3

Example 9

Acrylates / Steareth-50 Copolymer + Propylene Glycol + Laureth-3 Detection of the liposomal structures in the preparations according to the invention

The following Figures 1-9 show the liposomal structures (spherical structures) of the preparations according to Examples 1-9 by transmission electron microscopy after freeze fracture.

List of TEM recordings

Example 1 = No. 2778

Example 2 = No. 2831

Example 3 = No. 2841

Example 4 = No. 2726

Example 5 = No. 2922

Example 6 = No. 2928

Example 7 = No. 2925

Example e = No. 2913

Example 9 = No. 2952

Claims

claims

1. Water-based cleaning preparations containing 1 to 60% of one or more surfactants selected from anionic and / or nonionic and / or amphoteric and / or cationic surfactants, 0-5% of one or more conditioning agents, 0-5% of one or more Stabilizers, 0 - 3% of one or more preservatives, 0 - 5% of one or more thickeners and 0 - 20% active ingredients, 0 - 1% dyes and 0 - 5% of one or more opacifiers or pearlescent agents, characterized in that the cleaning preparation contains 0.001 -15% of one or more sterols.

2. Cleaning preparation according to claim 1, characterized in that it is a shower bath, a foam bath composition or a shampoo.

3. Cleaning preparation according to claim 1 or 2, characterized in that one or more phytosterols are contained as sterol.

4. Cleaning preparation according to claim 1 or 2, characterized in that the sterol is an ethoxylated sterol with a degree of ethoxylation of 5-30 (EO).

5. Cleaning preparation according to claim 1 or 2, characterized in that it contains a mixture of a sterol and an ethoxylated sterol.

6. Cleaning preparation according to claim 5, characterized in that the proportion of ethoxylated sterol is higher than or equal to the proportion of non-ethoxylated sterol.

7. Cleaning preparation according to one of claims 1 to 6, characterized in that a mixture of anionic and amphoteric or anionic and nonionic surfactants is contained.

8. Cleaning preparation according to one of claims 1 to 7, characterized in that the anionic surfactant is selected from an alkyl sulfate, alkyl ether sulfate, sulfosuccinate, sulfosuccinamate, sarcosinate, isethionate, tauride, ether carboxylic acid, protein fatty acid condensate, alkyl sulfonate and alkylbenzenesulfonate, monoalkyl phosphate, monoglyceride sulfate, amidether sulfate, alkyl sulfoacetate, α-olefin sulfonate, the amphoteric surfactant is selected from alkylaminopropionates, alkyl, alkylamido, sulfobetaines, alkylglycinates and the nonionic surfactant is selected from alkanolamides, fatty acid ethoxylates, fatty alcohol aminoxoxyidoxides, fatty alcohol aminoxoxyidoxides, fatty alcohol ethoxylates, fatty alcohol ethoxy ethoxides, fatty alcohol ethoxylates, fatty alcohol ethoxy ethoxides, fatty alcohol ethoxy ethoxides, Alkylphenol oxyethylates, mixed condensates made from ethylene oxide and propylene oxide.

9. Cleaning preparation according to one of claims 1 to 8, characterized in that it contains 10-25% of surfactant.

10. Cleaning preparation according to one of claims 1 to 9, characterized in that it has 0.5 to 5% of sterol and / or ethoxylated sterol.

11. Cleaning preparation according to one of claims 1 to 10, characterized in that 0.01 - 5% lecithin, phosphatidylcholine, sphingolipid and / or ceramide are contained.

12. A process for the preparation of a cleaning preparation according to any one of claims 1 to 11, characterized in that a solution of water and surfactants is prepared, heated to the melting temperature of the sterol or sterols, it melts therein, then the mixture is stirred cold and then, if necessary incorporates additional additives, auxiliaries and active ingredients at temperatures from 60 ° C to 25 ° C.

13. Use of cleaning preparations according to one of claims 1 to 11 as washing gels, shower baths, foam baths or shampoos.