DE19854827A1 - Water-based vesicle-forming surfactant-containing cleaning preparations, process for their preparation and their use - Google Patents

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

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

So far, water-based surfactant cleaning products as well as oil and cream have been known Preparations for showering or bathing with more or less pronounced Reini effect or regreasing.

Vesicular systems have a broad range of active ingredients and skin care components Found application in cosmetics and pharmacy. So cosmetic liposome or vesicle-containing gels and emulsions are known in the pharmaceutical field dispersions containing liposomes or vesicles have already been prepared. Even cleaning liposomal-based products have been described. For example, it is "Mederma Regulativ-Waschlotion Plus" is a commercially available cleaning product on Emul base with liposomes. This preparation contains O / W emulsifiers and a fat phase, however no detergent substances.

Liposome formation in bath water from oil bath or oleogel preparations and Badeta bletten has also been described. DE-OS 42 05 548 describes bathing and Shower additives with vesicle-forming properties, which are fatty oils and / or apolar sub contain punch and also contain 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 ones Lipids have an HLB between 2 and 6.  

DE 196 02 346.7 describes shower oleogels with vesicle-forming properties which more than 30% of one or more lipophilic components, 0.1 to 20% vesicle-forming Contains substances as well as usual auxiliaries and additives and also an emulsifier system comprises one or more W / O and one or more O / W emulsifiers, in Ratio from 1: 2 to 1: 0.2.

Such lipid-containing cleaning agents, which are the result of dirt removal To compensate for the loss of skin lipids are made by using pre-made vesicle Dispersions can be incorporated into the preparation or the liposomes, especially in the If used as a bath additive, when using water contact from the in The preparation contains lipids.

The products mentioned above either have no surfactants or, in the case, that surfactants are present, special systems on those in connection with oils that the Interactions of the liposomal structures with surface-active substances in aq prevent solutions in such a way that they are not resolved. Aqueous surfactant preparations without a proportion of fatty oils or oil-containing components which However, there are currently no liposomal structures. So far, have also been used Production of liposomal structures in such cleaning products in each case vesicle-forming Lipids used such. B. phospholipids, sphingolides or ceramides.

R. A. Wachter et al. describes in Perfumery and Cosmetics, Volume 75, No. 11/94, page 755 to 759, the use of naturally occurring phytosterols as a herbal active ingredient substances in cosmetics. Phytosterols can be made from different oils and fats be won, such as B. corn oil, rapeseed oil, soybean oil, olive oil etc. and exist in we mainly from β-sitosterol, campesterol and stigmasterol. Under the product name Generol®122 is a mixed product of the above three phytosterols obtained from soybean oil components with a predominant proportion of β-sitosterol (58.1%) and 29.8% campesterol and 4.5% stigmasterol known. There are also ethoxylated product variants of mentioned phytosterols, in particular from Generol®122. Depending on the ethoxylie degree of efficiency you get a number of products with different properties, such as e.g. B. Generol®122 E5 (5 mol EO), which is predominantly hydrophobic, and such Pro products with a degree of ethoxylation of 10, 16 or 25.  

The latter products have the properties of a typical O / W emulsifier. For that the latter can follow as corresponding emulsifiers in O / W emulsions and as solubilis Siermittel be used, while the non-ethoxylated product itself as a W / O emulsifier or co-emulsifier. In addition to their emulsifying properties, phytosterols can also can be used positively on damaged or stressed skin, such as e.g. B. in constitutional neurodermatitis or sunburn symptoms. Can also such products, in addition to the above indication as emulsions, also as hair rinses lungs are used. By using generol-containing shampoos, the Wet combability and hair shine can be improved. In the cited reference accordingly W / O skin creams for dry skin are described, containing one usual W / O emulsifier and various oil components as well as consistency agents and Stabilizers contain 1% of Generol®122 as a co-emulsifier. There will also be a Hair conditioner described, which in addition to the cationic emulsion base and Konsi additives and additives containing an oil component, an O / W emulsifier like Generol®122 in an amount of 1.0%. It is also noted that Generol®122 in combination with longer-chain fatty acids, fatty alcohols or phospholipi which is able to build multilamellar vesicles or layers. Here is of it assumed that the phytosterols are deposited in the lamellar lipid layers. The In contrast to Generol®122, ethoxylated Generol products are arranged in one layer ahead. With water contents below 70%, lamellar phases are developed, however when the water content is increased to over 70%, there is a transition to multilamellar Ve particles instead of liposomes. However, no surfactants may be present.

However, personal cleansers contain a proportion of surfactants that are known to exist (cf. DE-PS 42 05 548 and WO 92/04010) that they have negative effects on stability of liposomes, since liposomal structures are known to interact be solubilized with surface-active substances in aqueous solutions. Consequently So far it was not possible without special stabilization measures, stable surfactant ge aqueous systems, as are common for cleaning products, with liposomal loading formulate components.  

The object of the present invention is therefore to provide a cleaning system containing surfactants to formulate an aqueous base, which contains no oil-containing components, and yet has liposomal structures, especially when used, which gives all the advantages of Cleaning or skin care as known for products containing surfactants and lipids are can be achieved.

This object is achieved according to the invention by cleaning preparations on aqueous Base containing 1 to 60% of one or more surfactants, which are selected in particular are made of 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%, especially 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%, in particular 0.5-3%, active ingredients, 0-1%, in particular 0.0005-0.01% dyes and 0-5%, in particular 0.5-2% one or have several opacifiers or pearlescent agents, and which are characterized by a content of 0.001-15%, in particular 0.01-15%, very particularly preferred 0.5-10%, and especially 0.5-5% of one or more sterols.

Surprisingly, it could be shown that with such aqueous surfactant-containing additives Preparations of the specified composition in the course of production or the application of liposomal structures spontaneously arise from the individual components and remain as such during the cleaning process. There is a big difference to known oil-containing cleaning compositions, from which, as described above ben, liposomes form when used in water. The surfactants the dirt removal losses on skin lipids due to the positive above written effects of sterols can be balanced. This can in addition to the out the cleaning effect of drying out of the skin can be prevented. Overra Unfortunately, the use of oil components for this purpose could be dispensed with the.

The cleaning preparation according to the invention preferably contains a mixture of anio African, nonionic and amphoteric, especially from anionic and amphoteric or anionic and nonionic surfactant (s).  

Anionic surfactants are known for the purpose described and can preferably are selected from alkyl sulfates (e.g. C10-C18) and / or the corresponding alkyl ether sulfates, especially with 1-6 ethylene oxide groups in the molecule, sulfosuccinates, sul fosuccinamates, 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 contain eight to eighteen carbon atoms include.

Alkyl ether sulfates, which differ from fatty alcohols with 12 to 18 Koh lenstoffatomen and a degree of ethoxylation of 2 to 6 derived, such. B. Lauryl / Myristyl ether sulfate, sodium salt (e.g. Texapon® K 14 S special IS, Elfan® NS 243 S), ammoni umlauryl ether sulfate (Zetesol® LA-2) or monoisopropanolammonium lauryl ether sulfate (Zete sol® 2056) or alkyl sulfates, e.g. B. sodium lauryl sulfate (Texapon® Z), ammonium lauryl sulfate (Texapon® ALS) or monoisopropanolammonium lauryl sulfate (Sulfetal® CJOT 60).

Succinic acid derivatives such as sulfosuccinates and sulfo are also particularly suitable succinamate with an alkyl radical of 8-22 carbon atoms, e.g. B. Wallasol®-L 29 (Disodi around 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. The Co known under the trade name Dehyton® K is particularly preferred camidopropyl betaine.

The nonionic surfactant is especially selected from alkanolamides, fatty acids reethoxylates, fatty alcohol ethoxylates, alkyl polyglucosides, in particular with an alkyl radical from 8-16 carbon atoms, e.g. B. Plantacare®2000 UP (decyl glucoside), sorbitan esters, e.g. B. Tween®20 (Polysorbate 20), amine oxides, especially fatty amine oxides with a C7-C26 Alkyl chain, e.g. B. Incromine Oxide® C30 (Cocamidopropylamine Oxide).

Sorbitan esters, alkylphenol oxyethylates (C8-C22; optionally 4-20 ethylene) are also suitable oxide groups) or mixed condensates made of ethylene oxide and propylene oxide (e.g. Pluronics®- Types).  

Such surfactants suitable for cleaning agents are also described, for example, in the SÖFW Journal, 120th year, 2-3 / 94, pp. 115 to 116, in issue 7/94, page 387 and in Cosmetics and Toi letries, Vol. 108, 1993, pp. 83-89, as well as in SÖFW, 117 volume, No. 1 from 1991, pages 3-7 or in K. Schrader's monograph, Basics and Formulations of Cosmetics, 2. Ed. (1989, Hüthig Buchverlag), pp. 683-691).

Suitable cationic surfactants are quaternary ammonium compounds with carbon chain lengths usually between 12 and 22 such. B. steartrimonium chloride or pyridi nium salts, e.g. B. Cetylpyridinium chloride.

As a sterol are particularly phytosterols such. B. those made from corn oil, Rapeseed oil, soybean oil, olive oil etc. can be obtained and mainly from a mixture of β-sitosterol, campesterol and stigmasterol exist in different proportions by weight, such as B. described by R. A. Wachter (see p. 4, paragraph 4 of this application). Also suitable net is cholesterol and its derivatives, e.g. B. dihydrocholesterol or cholesterol esters such as Cholesteryl acetate. A product with the trade name Ge nerol®122 N (refined soy asterol) suitable. Ethoxylated sterols are also preferred 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 (ethoxylated dihy drocholesterol).

Amounts of 0.5 to 5%, in particular 0.5 to 3% and above are particularly preferred preferably 0.5 to 2%, of the sterols mentioned. One is very particularly preferred Mixture of non-ethoxylated phytosterol, e.g. B. Generol® 122 N and one with 5 units ten ethoxylated phytosterol, such as. B. Generol®122 N E5D. Here is preferably the Proportion of ethoxylated sterol 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 ver is particularly preferred ratio of 3: 1 wt .-%. Furthermore, the sole use of one is not preferred ethoxylated sterol, e.g. B. Generol® 122 N in the specified amounts, such as. B. 1% by weight.

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

The composition according to the invention can also contain customary auxiliaries and additives contain. These include cationic polymers as conditioning agents, such as. B. Polyquater  nium-22 (Merquat® 280), quaternized protein derivatives such as lauryldimonlum hydroxypropyl Hydrolized Soy Protein (part of Prota Flor® HSQ), silicone derivatives, e.g. B. Abil® B 8863, 8843 (Dimethicone Copolyol), protein hydrolysates or water-soluble proteins.

Furthermore, one or more stabilizers can contain small amounts (0 to 5%) his. Here belong e.g. B. complexing agents such as Trilon®BD (EDTA, Na salt), agents for pH Setting, e.g. B. citric acid, humectants such as glycerin, inorganic salts, e.g. B. Sodium chloride as a viscosity regulator.

In addition, one or more preservatives and thickeners can optionally be used (0 to 5%) must be present. Suitable preservatives are, for example, iodopro pynylbutyl carbamate, phenoxyethanol and other common preservatives, such as e.g. B. p-hydroxybenzoic acid ester, formaldehyde and releaser, sorbic acid and dehydroacetic acid re and their salts, isothiazolinones, 5-bromo-5-nitro-1,3-dioxane, methyldibromoglutanonitrile, Etc.

As a thickener z. B. Volpo® L 3 (Laureth-3) or Antil® 208 (Laureth-3, Propy lenglycol, Acrylates / Steareth-50 Copolymer), Glucamate® DOE 120 (PEG-120 Methyl Glu cose Dioleate), Comperlan® 100 (Cocamide MEA).

In particular, the cleaning preparation according to the invention can have one or more active ingredients have substances in the specified amounts. 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, euka lyptus oil, thyme oil, palmarosa oil, rosemary oil, lavender oil, menthol, ginger, linden blossom, Marigold, algae, aloe vera, echinacea, ivy leaf extract and panthenol, hydroxy ethyl salicylate, nicotinic acid ester. Depending on the intended effect, how e.g. B. the improvement of the hair or skin structure, increased blood circulation, relaxation tion, aromatherapy u. Ä. A suitable combination of active ingredients are added. If necessary, further refatting agents such as fatty acid glycerides and their ethoxylates, e.g. B. PEG-6 Caprylic / Capric Glycerides (Softigen® 767) and / or dyes such. B. Patent blue, amido blue, orange RGL, cochineal red, quinoline yellow can be used.  

In a preferred embodiment, the compositions according to the invention can conditions also an additional portion, for. B. 0.01 to 5% of one or more vesicle-forming Contain lipids. These include in particular lecithin, phospholipids, such as phosphati dylcholine, and ceramides, such as. B. ceramide-2, -3, -6 and sphingolipids, such as. B. Procera mide® L, Ceraderm® S, Ceraveg®.

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

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

The products obtained with the compositions according to the invention spontaneously form especially when used, liposomal structures. This can be done using Transmissi electron microscopy (TEM) after freeze fracture.

With the cleaning preparations according to the invention, it is possible to use existing products use their liposomes as cleaning and maintenance products. The invention Preparations are very easy to distribute. They have good cleaning and foam properties, a pleasant feeling on the skin as well as favorable olfactory properties. So they meet the requirements for cosmetics.

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

The products according to the invention also have very good stability and can without the use of special and complex equipment and manufacturing processes, such as those are usually required to provide liposomal articles. The The consistency of the products can be adjusted using small amounts of additives and Auxiliaries that do not change the skin feel are set. Because of the special Property of sterols, especially phytosterols, namely that they are plant-based  Raw materials can also positively influence the hair and skin texture, in addition to the liposomal effect, another care effect can be achieved.

It was surprisingly found that the presence of surfactants in particular has no negative impact on the presence or formation of liposomes. This could not be expected in view of the state of the technology already described nik, which found that conventional liposomal structures from z. B. Phospholi piden solubilized by such highly surface-active O / W emulsifiers or surfactants become.

By incorporating one or more of the above active ingredients, e.g. B. Indi cation shower compositions can be prepared according to the desired purpose. So can e.g. B. 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 Ing who extract, methyl nicotinate, hydroxyethyl salicylate and juniper oil are produced.

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

I. Preparation of the preparations according to the invention

The products according to the following Examples 1 to 9 were produced by the or the specified sterols in the aqueous surfactant solution, i.e. the deminerali solution water and the specified surfactants, at temperatures between 80 ° C and 90 ° C was melted. The mixture was then stirred cold and, if appropriate, the others specified additives, active ingredients and auxiliaries in the specified order at Temperatu ren between 60 ° C and 25 ° C.

example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example 8

Example 9

II. Detection of the liposomal structures in the invention Preparations

In the following Fig. 1-9, the liposomal structures (spherical structures) of the preparations according to Examples 1-9 are shown 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 8 = No. 2913
Example 9 = No. 2952

Claims (13)

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% 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, thereby 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 bubble bath composition or a shampoo. 3. Cleaning preparation according to claim 1 or 2, characterized in that as Sterol contains one or more phytosterols. 4. Cleaning preparation according to claim 1 or 2, characterized in that as Sterol contains an ethoxylated sterol with a degree of ethoxylation of 5-30 (EO) is. 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 nonioni 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 as well as alkyl benzene sulfonate, monoalkyl phosphate, monoglyceride sulfate, amide ether sulfate, alkyl sulfoacetate, α-olefin sulfonate, the amphoteric surfactant is selected from alkylaminopropionates, alkyl, alkylamido, Sulfobetaines, alkylglycinates and the nonionic surfactant selected from Alka nolamides, fatty acid ethoxylates, fatty alcohol ethoxylates, alkyl polyglucosides, Amine oxides, sorbitan esters, alkylphenol oxethylates, mixed condensates from ethylene oxide and propylene oxide. 9. Cleaning preparation according to one of claims 1 to 8, characterized in that it contains 10-25% 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 net that 0.01-5% lecithin, phosphatidylcholine, sphingolipid and / or ceramide ent are holding. 12. A method for producing a cleaning preparation according to one of claims 1 to 11, characterized in that a solution of water and surfactants manufactures, heated to the melting temperature of the sterols, this in it melts, then the mixture is stirred cold and then, if necessary, additional additives, and active ingredients at temperatures of 60 ° C to 25 ° C. 13. Use of cleaning preparations according to one of claims 1 to 11 as Wash gels, shower baths, foam baths or shampoos.