EP1539088A1 - Hair treatment agent containing an active combination of liposomes - Google Patents

Abstract

The growth of human hair can be significantly improved by treatment with an agent that contains an active ingredient complex (A). Said complex (A) contains liposomes, which can either be composed of betaines in accordance with one of the formulae (B-II) or (B-III) and/or loaded with at least one of the betaines in accordance with one of the formulae (B-I) to (B-III), in addition to at least one cosmetic raw material (P), which intensifies penetration and/or at least one polymer (G).

Description

 "Hair treatment agent containing a combination of active ingredients with liposomes"

The invention relates to hair treatment compositions comprising an active ingredient complex (A) comprising liposomes which can either be composed of betaines according to one of the formulas (B-II) and / or (B-III) and / or with at least one of the betaines according to one of the formulas (BI) to (B-III) are loaded, and at least one cosmetic raw material (P) which increases penetration and / or at least one polymer (G).

In almost all cultures, the propagated and sought-after ideal for the external appearance of people includes a full and well-groomed hair as an essential point. Therefore, a premature loss of hair, which usually occurs due to genetic predisposition, but also due to illness, medication or psychosomatic reasons, is felt by most people as a deficiency. There has been no shortage of attempts to provide agents which counteract hair loss or stimulate stronger or new hair growth. There are a number of hair restorants on the market, but their effectiveness is more than controversial.

The cause of this maladministration is a very incomplete knowledge of the biological mechanism of hair growth. There are only a few empirical statements about active principles; There are almost no approaches to a comprehensive theory of hair growth.

EP-A-102 534 describes that carboxylic acids with an odd number of carbon atoms and a number of derivatives of these carboxylic acids are distinguished by a remarkably high hair growth-stimulating effect.

K. Oba has been able to demonstrate in animal experiments (Cosmetics & Toiletries, 103 _» 69 (1 88)) that the hair follicles are supplied with energy by applying pentadecanoic acid glycerol esters to the skin. Is the usual energy supply disrupted due to the inhibition of phosphofructokinase or fails completely, as is the case with male baldness happens, there is an alternative energy source available with the lipids mentioned.

The French Offenleguήgssclirift FR 2 627 385 describes cosmetic and pharmaceutical compositions containing liposomes, the vesicles of which contain amino acids and peptides.

International publication WO 94/22468 describes that hair dyes such as melanin, tyrosinase or nucleic acids can penetrate to the hair follicles with the aid of liposomes.

The German patent application DE 101 13 446 describes hair treatment agents with betaines, which require hair growth.

However, none of the documents contains the slightest reference to the active ingredient complex (A) containing liposomes, which can either be composed of betaines according to one of the formulas (B-II) or (B-III) and / or with at least one of the Betaines (B) are loaded according to one of the formulas (BI) to (B-III), and penetration aids (P) and / or polymers (G). It has now surprisingly been found that when this complex of active ingredients is applied, hair growth and hair quality, such as, for example, the hair thickness, the shine of the hair, the combability of the wet and dry hair, the internal strength of the hair or the volume are significantly improved.

The invention thus relates to pharmaceutical and cosmetic compositions for the treatment of hair, containing conventional carriers, active ingredients and auxiliaries, characterized in that they contain the active ingredient complex (A). The active substance complex (A) contains, in addition to further constituents: a) liposomes, which can either be composed of a betaine (B) according to one of the formulas (B-II) or (B-III) and / or with at least one betaine (B) are loaded according to one of the formulas (BI) to (B-III), and b) penetration aids (P) and / or c) polymers (G). A betaine (B) in the sense of the present invention is to be understood as meaning compounds which simultaneously contain both a —NR ₃ and a —CR ₂ COO ^"group , analogous sulfobetaines and compounds which have a -JNR ₃ ⁺ and have a group -CH ₂ OH This definition is based on the definition in Römpp's Lexikon Chemie - CD-ROM version 2.0, Stuttgart New York, Georg Thieme Verlag 1999. The betaines according to the invention are to be understood in particular as those which have a formula (BI) to correspond to (B-III).

RÄV - (CR R ⁵ ) χ - (CR ⁶ R ⁷ ) _y - (CR ⁸ R ⁹ ) _Z - Y ^' (BI)

CH ₂ OR ^I3 -CHOR ¹⁴ -CH ₂ OR ¹⁵ (B-II)

CH ₂ OR ^I6 -CH ₂ OR ¹⁷ (B-III)

R ¹ , R ² , and R ³ stand here independently of one another for:

Hydrogen,

A methyl radical,

• a C2 - C8 saturated or unsaturated, branched or linear ^• or cyclic hydrocarbon residue

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ stand here independently of one another for:

• hydrogen,. -OR ¹⁰ ,

• -OCOR ¹¹ ,

A methyl radical which can carry an 1H-imidazolyl-4 substituent,

A C2 - C8 saturated or unsaturated, branched or linear or cyclic hydrocarbon radical, where R ¹⁰ stands for hydrogen, -CH ₃ or a C2 - C30 saturated or unsaturated, branched or linear or cyclic hydrocarbon test and R ⁿ stands for -CH ₃ or a C2 - C30 saturated or unsaturated, branched or linear or cyclic hydrocarbon radical, x, y and z independently of one another represent an integer from 0 to 12, with the proviso that at least one of the parameters x, y or z is different from 0, and Y ^" stands for COO ^" , COOR ¹² , SO ₃ ^" or a hydroxy group in combination with a physiologically acceptable anion, where 19

R stands for -CH ₃ , a C2 - C30 saturated or unsaturated, branched or linear or cyclic hydrocarbon radical.

R ¹³ and R ¹⁶ stand for the rest R ^! R ² R ³ N ⁺ - (CR ⁴ R ⁵ ) _X - (CR ⁶ R ⁷ ) _y - (CR ⁸ R ⁹ ) _Z - CO -, where the radicals R ¹ to R ⁹ and the parameters x, y, z as previously defined, the radicals R ¹⁴ , R ¹⁵ and R ¹⁷ each independently represent hydrogen, a radical mentioned under R ¹³ or R ¹⁶ ', or -COR ¹⁸ , where R ¹⁸ represents -CH ₃ , a C2 - C30 saturated and / or unsaturated, branched and / or linear or cyclic hydrocarbon radical. Typical and particularly preferred examples of such acyl residues are residues of fatty acids such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid, linoleic acid , Gadoleic acid, behenic acid and erucic acid as well as their technical mixtures which occur, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. The fatty acid cuts which are obtainable from coconut oil or palm oil are usually particularly preferred.

Betaines in the sense of the invention are also to be understood as meaning those substances in which the characteristic groups mentioned are only present in the dissolved substance and within certain pH ranges of the solution.

Mixed salts of betaines such as hydrochlorides, hydrobromides, hydroiodides or mixed salts with edible acids such as citric acid, lactic acid, benzoic acid, tartaric acid etc., or amino acids such as histidine, arginine, lysine, citrulline etc. can of course also be used according to the invention. Examples of the betaines (B) according to the invention are: carnitine, carnitine tartrate, carnitine magnesium citrate, acetylcarnitine, 3-O-lauroyl-L-carnitine hydrochloride, 3-O-octanoyl-L-carnitine hydrochloride, 3 -O- Palmitoyl-L-carnitine hydrochloride, carnitine triglyceride, carnitine diglyceride, carnitine monoglyceride, mixed esters of carnitine and C2 - C30 saturated and / or unsaturated, branched and / or linear fatty acids with glycerol, mixed esters of carnitine and C2 - C30 saturated and / or unsaturated, / or and / or linear fatty acids with ethylene glycol, the fatty acids being preferred are of natural origin, taurine, taurine lysylate, taurine tartrate, taurine ornithate, lysyl taurine and ornithyl taurine, betalaine ', 1,1-dimethyl-proline, hercynin (N, Nα, N - trimethyl-L-histidinium betaine), ergothioneine (thionein, 2- Mercapto-Nα, Nα, Nα-trimethyl-L-histidinium betaine), choline, choline chloride, choline bitartrate,

Choline dihydrogen citrate and the compound known as betaine N, N, N-trimethylglycine. These mixed salts can be preferred according to the invention. Furthermore, the mixed esters of betaines according to one of the formulas (B-

II) or (B-III). It is also possible according to the invention that a betaine of the formula (B-II) and / or of the formula (B-III) as the only active ingredient can be present both in liposomal form and in solution.

According to the invention, all types of isomers, such as, for example, diastereomers, enantiomers, ice-trans isomers, optical isomers, conformational isomers and racemates can be used.

Carnitine, taurine, histidine, choline, betaine and their derivatives are preferred. The agents according to the invention can contain both a compound according to one of the formulas (B-I) to (B-III) and several, in particular two, compounds according to the formulas (B-I) to (B-III). A compound according to one of the formulas (B-II) or (B-III) can be very particularly preferred.

In preparations which contain the active ingredient complex (A) according to the invention, the active ingredient betaine (B) according to the invention is at least one of the formulas (B-I) to (B-

III) in amounts of 0.001 to 20 wt .-%, based on the entire preparation. A content of 0.01 to 10% by weight is preferred.

Penetration aids (P) can be a second essential component of the active substance complex (A) according to the invention. According to the invention, this includes heteroeyclic compounds such as, for example, imidazole, pyrrolidine, piperidine, dioxolane, dioxane, morpholine and piperazine as penetration aids (PI). Derivatives of these compounds, such as, for example, the C-alkyl derivatives, Cμ-hydroxyalkyl derivatives and CM-aminoalkyl derivatives, are also suitable. Preferred substituents on both carbon atoms and nitrogen atoms of the heteroeyclic Ring systems can be positioned are methyl, ethyl, ß-hydroxyethyl and ß-amirioethyl groups.

These derivatives preferably contain 1 or 2 of these substituents.

Derivatives of heterocyclic compounds preferred according to the invention are, for example, 1-methylimidazole, 2-methylimidazole, 4 (5) -methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 2-isopropylimidazole, N-methylpyrrolidone, 1-methylpiperidine, 4-methylpiperidine, 2- Ethyl piperidine, 4-methylmorpholine, 4- (2-hydroxyethyl) morpholine, 1-ethylpiperazine, l- (2τ-hydroxyethyl) piperazine, l- (2-aminoethyl) piperazine. Imidazole derivatives preferred according to the invention are biotin, hydantoin and benzimidazole.

Among these heterocyclic penetration aids (PI), the mono- and dialkylimidazoles, biotin, hydantoin and in particular the imidazole itself are particularly preferred.

These heterocyclic compounds (P1) can be present in preparations which contain the active ingredient complex (A) according to the invention in quantities of 0.01 to 10% by weight, based on the entire preparation. Quantities of 0.01 to 5% by weight have proven to be particularly suitable.

Further penetration aids (P2) according to the invention in the active substance complex (A) can be urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, histidine and its derivatives, carbonates and hydrogen carbonates. These penetration aids (P2) can be present in the preparations which contain the active ingredient complex (A) according to the invention in amounts of 0.1 to 20% by weight, based on the entire preparation. Amounts of 01 to 10% by weight are preferred.

Furthermore, alcohols or mixtures of at least two or more alcohols are to be used as penetration aids (P3) according to the invention. According to a first embodiment, alcohols are to be understood as linear and or branched and / or cyclic, saturated and / or unsaturated alcohols having 1 to 12 carbon atoms. Examples include methanol, ethanol, propanols, butanols, pentanols, hexanols, cyclohexanols, benzyl alcohols, heptanols, octanols, nonanols, decanols, undecanols and dodecanols.

According to a further embodiment, the alcohols as penetration aids (P4) are polyols. Suitable polyols are, for example, diols and triols, in particular 1,2-diols and 1,3-diols such as, for example, 1,2-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-dodecanediol, 1,3- Propanediol, 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol, ol, glycerin and partial glycerol ether, glycol and glycol ether, propylene glycol and propylene glycol ether, for example propylene glycol monoethyl ether, 2-ethyl-l, 3-hexanediol, 1,3 -Butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, pentanediols, for example 1,2-pentanediol, hexanediols, for example 1,2-hexanediol or 1,6-hexanediol, dodecanediol, in particular 1, 2-dodecanediol, neopentyl glycol and ethylene glycol. 1,3-diols, especially 2-ethyl-l, 3-hexanediol and 1,3-butanediol, have proven to be particularly suitable.

According to the invention, alcohols which are of course only miscible with water can also be used.

“Miscible with water” means those alcohols which are not more than 10% by weight soluble in water at 20 ° C., based on the mass of water.

In many cases, triols and in particular diols have proven to be particularly suitable according to the invention. According to a further embodiment of the invention, alcohols having 4 to 20, in particular 4 to 10, carbon atoms can be used. The alcohols used can then be saturated or unsaturated and linear, branched or cyclic. Examples are butanol-1, cyclohexanol, pentanol-1, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, aryl alcohol, myristyl alcohol, myrist alcohol Caprinal alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, this list being intended to be exemplary and not limiting. The fatty alcohols, however, derive from preferably natural fatty acids, usually from a recovery from the esters of fatty acids can be assumed by reduction. Also suitable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols.

The alcohols as penetration aids (P) are contained in the preparations which contain the active ingredient complex (A) according to the invention in amounts of 0.1-70% by weight, based on the entire preparation. Amounts of 0.1-50% by weight are preferred. Amounts of 1-40% by weight are very particularly preferred.

It is of course also possible according to the invention and may even be preferred if a mixture of at least two penetration aids (P) is used. The mixture of penetration aids (P) may contain at least two compounds to be included in the same group of auxiliaries (Pl) to (P4), but very particularly preferably a mixture of at least two compounds from different groups of penetration aids (Pl) to ( P4) included.

It has also proven to be advantageous that polymers (G) can support the action of the active ingredient complex (A) according to the invention. In a preferred embodiment, polymers are therefore added to the preparations used according to the invention, with both cationic, anionic, amphoteric and nonionic polymers having proven to be effective.

Cationic polymers (G1) are understood to mean polymers which have a group in the main and / or side chain which can be “temporary” or “permanent” cationic. According to the invention, polymers which have a cationic group irrespective of the pH of the agent are referred to as “permanently cationic”. These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary In particular those polymers in which the quaternary ammonium group is linked via a Cl-4 hydrocarbon group to one of acrylic acid, methacrylic acid or the derivatives of which have a polymer main chain built up, have proven to be particularly suitable.

Homopolymers of the general formula (Gl-I), R ¹

I - [CÜ ₂ -C-] _n X ^" (Gl-I)

CO-O- (CH ₂ ) _m -N ⁺ R ² R ³ R ⁴

in which R ^{1 =} -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from Cl-4-alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X ^"is a physiologically compatible organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (Eq-I) and nonionic monomer units are particularly preferred cationic polymers. Within the scope of these polymers, those are according to the invention preferred, for which at least one of the following conditions applies: R ¹ stands for a methyl group R ² , R ³ and R ⁴ stand for methyl groups m has the value 2.

Suitable physiologically acceptable counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Halide ions, in particular chloride, are preferred.

A particularly suitable homopolymer is, if desired crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of polyolefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylene bisacrylamide, diallyl ether, polyallyl polyglyceryl ether, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylene bisacrylamide is a preferred crosslinking agent. The hordopolymer is preferably used in the form of a non-aqueous polymer dispersion which should not have a polymer content below 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (approx. 50% polymer content, further components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene ether (INCI name: PPG-1 _: Trideceth- 6)) and Salcare ^® SC 96 (approx. 50% polymer content, further components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: Propylene Glycol dicaprylate dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-l-trideceth-6)) commercially available.

Copolymers containing monomer units according to formula (Gl-I) as non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid alkyl esters and methacrylic acid-C _M-C alkyl esters. Among these nonionic monomers, acrylamide is particularly preferred. As in the case of the homopolymers described above, these copolymers can also be crosslinked. An inventively preferred copolymer is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymerized Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

According to the invention, the cationic polymers naturally also include the group of cationized protein hydrolyzates, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from plants, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms , for example from fish collagen or algae, or biotechnologically obtained protein hydrolyzates. The protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred cationic protein hydrolyzates are those whose underlying protein portion has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, are under cationic

Understand protein hydrolyzates of quaternized amino acids and their mixtures. The

Quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. Typical examples of the cationic protein hydrolyzates and derivatives according to the invention are those under the INCI names in the “International Cosmetic Ingredient Dictionary and

Handbook ", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association

1101 17 * Street, N.W., Suite 300, Washington, DC 20036-4702) and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Collagen,

Cocodimopnium hydroxypropyl hydrolyzed casein, Cocodimonium hydroxypropyl

Hydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed hair keratin,

Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl

Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed> Silk,

Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl

Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Silk Amino Acids,

Hydroxypropyl arginine lauryl / myristyl ether HC1, hydroxypropyltrimonium gelatin,

Hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimonium hydrolyzed

Collagen, hydroxypropyltrimonium hydrolyzed conchiolin protein,

Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice

Bran Protein, Hydroxyproypltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium

Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein,

Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium

Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy

Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium

Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl

Hydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen,

Lauryldimonium hydroxypropyl hydrolyzed keratin, Lauryldimonium hydroxypropyl

Hydrolyzed silk, lauryldimonium hydroxypropyl hydrolyzed soy protein,

Steardimonium hydroxypropyl hydrolyzed casein, steardimonium hydroxypropyl

Hydrolyzed collagen, steardimonium hydroxypropyl Hydrolyzed keratin, steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzedoly, Collated Hydrolyzed, 79, Quaternium Collatemium, Quatemium , Quaternium-79

I

Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Silk, Quaternium-79 Hydrolyzed Soy Protein, Quatemium-79 Hydrolyzed Wheat Protein.

The plant-based cationic protein hydrolyzates and derivatives are very particularly preferred. The agents used in the agents according to the invention are present in amounts of 0.01-10% by weight, based on the agent as a whole. Amounts of 0.1 to 5, in particular 0.1 to 3% by weight are very particularly preferred.

Other preferred cationic polymers are, for example

- Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives,

cationic alkyl polyglycosides according to DE-PS 44 13 686,

- cationized honey, for example the commercial product Honeyquat ^® 50, cationic guar derivatives, in particular the products sold under the trade names Cosme- dia ^® guar and Jaguar ^®,

Q2-7224 polysiloxanes with quaternary groups, such as the commercially available products (manufacturer: Dow Corning; a stabilized Trimethylsilylamo- dimethicone), Dow Coming ^® 929 Emulsion (containing a hydroxylamino-modi fied silicone, also referred to as amodimethicone will), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, Quaternium-80),

- Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers, - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminoethylm'ethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755,

- vinylpyrrolidone Vinylimidäzoliummethochlorid copolymers, such as those offered under the names Luviquat.RTM ^® FC 370, FC 550, FC 905 and HM 552,

- quaternized polyvinyl alcohol,

- and the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and 'Polyquaternium 27 with quaternary nitrogen atoms in the main polymer chain.

Can be used as cationic polymers (. B. commercial product, Quatrisoft ^® LM 200) under the designations Polyquaternium-24, known polymers. Likewise usable according to the invention are the copolymers of vinyl pyrrolidone, such as those available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix ^® VC 713 (manufacturer: ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 are.

Other cationic polymers of the invention are the "temporarily cationic" polymers These polymers usually contain an amino group present at certain pH values as a quaternary ammonium group and hence cationic. Preference is given, for example, chitosan and its derivatives, such as, for example, under the trade designations Hydagen ^® CMF, Hydagen ^® HCMF, Kytamer ^® PC and Chitolam ^® NB / 101 are commercially available.

Erfmdungsgemäß preferred cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ^® JR 400, Hydagen ^® HCMF and Kytamer ^® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ^® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.

The anionic polymers (G2) which can be used with the active compounds (A) in the agents according to the invention are anionic Polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers can consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups can be present in whole or in part as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer have proven to be particularly effective, the sulfonic acid group being able to be present in whole or in part as the sodium, potassium, ammonium, mono- or triethanolammonium salt ,

For example, such a homopolymer of 2-acrylamido-2-methylpropanesulfonic acid, sold under the name Rheothik ^® 11-80 commercially.

In this embodiment, it may be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, vinyl pyrrolidone, vinyl ether and vinyl ester.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with monomers containing sulfonic acid groups. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being wholly or partly as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be crosslinked, the crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxyethane, allyl sucrose, allylpentaerythritol and methylene bisacrylamide.

Also preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene can moving networking agents. Such compounds are for example available under the trademark Carbopol ^® commercially.

Copolymers ¹ of maleic anhydride and methyl vinyl ether, in particular those with crosslinks, are also very suitable polymers. A cross-linked with 1,9-decadiene painting einsäure-methyl vinyl ether copolymer is available under the name Stabileze® ^® QM.

Furthermore, amphoteric polymers (G3) can be used as> polymers in all agents according to the invention. The term amphoteric polymers includes both those polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, and also zwitterionic polymers which contain quaternary ammonium groups and -COO in the molecule Contain ^" - or - SO ₃ ^" groups, and summarize those polymers which contain -COOH or SO ₃ H groups and quaternary ammonium groups.

An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of ethyl methacrylate tert-butylamino, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group Acrylic acid, methacrylic acid and their simple esters.

Further amphoteric polymers which can be used according to the invention are the compounds mentioned in British Offenlegungsschrift 2 104 091, European Offenlegungsschrift 47 714, European Offenlegungsschrift 217 274, European Offenlegungsschrift 283 817 and German Offenlegungsschrift 28 17369.

Preferred amphoteric polymers are those polymers which essentially consist of (a) monomers with quaternary ammonium groups of the general formula (G3.-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^Θ (G3-I) in which R ¹ and R ² independently of one another represent hydrogen or a Methyl group and R ³ , R ⁴ and R ⁵ independently of one another for alkyl groups with 1 to 4 carbon atoms, Z is a NH group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and (b) monomeric carboxylic acids of the general formula (G3-II),

R ⁶ -CH = CR ⁷ -COOH (G3-II) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

These compounds can be used either directly or in salt form, which is obtained by neutralizing the polymers, for example with an alkali metal hydroxide. With regard to the details of the production of these polymers, reference is expressly made to the content of German Offenlegungsschrift 39 29 973. Those polymers in which monomers of type (a) are used, in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A ^{(_) is} a halide, methoxysulfate or ethoxysulfate, Ion is; Acrylamido-propyl-trimethyl-ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the polymers mentioned.

Furthermore, nonionic polymers (G4) can be contained in all agents according to the invention.

Suitable nonionic polymers are for example:

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are also preferred nonionic polymers.

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropylcellulose, as they are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON). shellac

- polyvinylpyrrolidones, as, for example, sold under the name Luviskol ^® (BASF).

Siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and non-volatile siloxanes are suitable, non-volatile siloxanes being understood to mean those compounds whose boiling point at normal pressure is above 200 ° C. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups. - Glycosidically substituted silicones according to EP 0612759 Bl.

It is also possible according to the invention that the agents contain several, in particular two different polymers of the same charge and / or each contain an ionic and an amphoteric and / or non-ionic polymer.

The polymers (G) are preferably present in the agents used according to the invention in amounts of 0.01 to 10% by weight, based on the total agent. Amounts from 0.1 to 5, in particular from 0.1 to 3% by weight are particularly preferred.

The active ingredient complex (A) according to the invention contains at least the betaines according to the formula (BI) as a load in the form of vesicles. These nesicles are very particularly preferably liposomes which are at least loaded with the betaines of the formula (BI) as an active ingredient. In the active ingredient complex (A) according to the invention, the betaines of the formulas (B-II) and (B-III) according to the invention can themselves form nesicles. These nesicles and very particularly preferably liposomes which are composed of the betaines of the formula (B-II) and / or of the formula (B-III) according to the invention can be present both unloaded and loaded. In the event that these liposomes from the betaines of the formula (B-II) and / or the formula (B-III) according to the invention are loaded with active substance, the active substance for loading is preferably an active substance of the formula (BI). Methods for producing liposomes are well known to those skilled in the art. From the abundance of literature on the production and use of liposomes, reference should be made to European patent specifications EP 069 307 B1, EP 158 441 B1, EP 130 577 B2 and US documents US 4,217,344 or US 5,498,420. A definition of liposomes is given in A. Domsch, "The Cosmetic Preparations", Volume III, Publishing House for the Chemical Industry, H. Ziolkowsky GmbH, Augsburg, 1994 on page 170 in Chapter 2.5. This and in particular the liposome systems disclosed there Furthermore, numerous lipophilic compounds which are able to form liposomes are known to the person skilled in the art Methods and processes for producing and loading liposomes are known to the person skilled in the art from the literature cited above. Of course, this also includes

Methods and procedures for achieving the smallest possible liposomes, so-called nanoparticles. Furthermore, it is known to the person skilled in the art from the literature listed above that liposomes naturally have a particle size distribution as a result of the production process.

Therefore, the average particle size is often given for the characterization of liposomes. Methods for determining the average particle diameter are known to the person skilled in the art, for example the dynamic light scattering used in the examples. In principle, liposomes can be monolamellar or multi-layered. The person skilled in the art can influence this by the selection of the lipids.

According to the invention, phospholipids have proven to be particularly suitable as lipophilic substances for encapsulating the active substances (B) of the active substance complex (A) in liposomes. Phospholipids are organic molecules that can be derived from glycerin or sphingosine. The most common phospholipids are substances derived from glycerin. With glycerin as a framework, two fatty acid residues and phosphoric acid are usually esterified. In addition, the phosphoric acid residue can still be esterified. The phospholipids used can be naturally occurring or synthetically produced phospholipids. Furthermore, both phosphoglycerides and phosphoglcolipids can be used according to the invention. According to the invention, phospholipids are very particularly preferably substances of the formula (I):

In formula (I), y stands for an integer from 0 to 2, x for an integer from 1 to 3, with the proviso that the sum of x and y is 3.

In the phospholipids of the formula (I) to be used according to the invention, M also represents hydrogen, an equivalent of an alkali metal or alkaline earth metal cation, an ammonium cation or an alkyl radical having 1 to 4 carbon atoms, which is optionally substituted by one or more hydroxyl groups. Compounds in which M represents a sodium cation are particularly preferred. Furthermore, B in the formula (I) of the phospholipids to be used according to the invention represents an equivalent of a physiologically tolerable anion. Examples of suitable anions are chloride, bromide, iodide, sulfate, perchlorate, tetrafluoroborate, tetraphenylborate and tetrachlorozincate. The chloride ion is preferred.

R in the formula (I) represents a radical of the formula (II),

in which z represents an integer from 1 to 4, in particular 3, and R ¹ and R ² independently of one another represent a - to C ₄ -alkyl radical which is optionally substituted by one or more hydroxyl group (s) or an acyl group is.

A stands according to the invention. for one of the units -O-CH ₂ -CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ - or -O-CH ₂ -CHOH-CH ₂ -, the unit -O-CH ₂ -CHOH- CH ₂ - is particularly preferred.

The rest R ³ stands for

(a) a branched or unbranched, saturated C ₈ - to C] ₈ -acyl radical or

(b) a branched or unbranched, mono- or polyunsaturated C ₈ to C ₁₈ acyl radical.

Particularly preferred saturated radicals R ³ are the rest of the stearic acid and the remains of the mixture of the fatty acids which are obtained from coconut oil.

A particularly preferred unsaturated residue R ³ is the residue of linoleic acid. Surprisingly, it has been found that compounds of the formula (I) in which R ^{3 is} the rest of the linoleic acid are distinguished by a higher compatibility with ionic cosmetic formulations of conventional emulsifier systems. This means that these substances are easier to incorporate into the formulations. Furthermore, formulations with compounds of the formula (I) in which R ^{3 represents} the rest of the linoleic acid have a significantly higher maintenance effect compared to compounds with saturated fatty acid residues. Examples of the C ₁ to C ₄ alkyl groups mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl groups are preferred alkyl groups. Methyl groups are very particularly preferred.

Compounds of formula (I) are already known. So. are generally described in EP-AI-13 713, the surfactant properties of these compounds. Furthermore, from DE-Al-44 08 506 the use of a connection of the. Formula (I) is known in hair colorants.

Very particularly preferred compounds of the formula (I) are the substances known under the INCI names linoleamidopropyl PG-Dimonium Chloride Phosphate, cocamidopropyl PG-Dimonium Chloride Phosphate and stearamidopropyl PG-Dimonium Chloride Phosphate. These are sold, for example, by Mona under the trade names Phospholipid EFA ^® , Phospholipid PTC ^® and Phospholipid SV ^® .

According to the invention, it is also possible to use a mixture of several phospholipids.

Other particularly preferred lipophilic substances according to the invention for forming the liposomes according to the invention are cerebrosides, sphingolipids, cephalins, phosphoaminolipids, cerebroglucosides, ganglioside, cholesterol, ceramides, sitosterols or sterols. Lecithin is particularly preferred according to the invention.

The liposomes according to the invention have an average particle diameter from 10 nm to 500 μm, preferably from 10 nm to 100 μm and very particularly preferably from 10 nm to 50 μm. At least 50% of the liposomes have this average particle diameter. However, a narrower distribution is preferred, with at least 75% of the liposomes having this average particle diameter. The use of liposomes, which is at least 90%, and thus a very narrow distribution of the particle diameters around the average particle diameter, is very particularly preferred have around. Furthermore, it can be preferred according to the invention that the liposomes are monolamellar.

The present invention also encompasses the teaching that the liposomes have a different penetration behavior depending on their size. A different penetration behavior is to be understood in relation to the kinetics of penetration and not in relation to the penetration capacity as such. All liposomes according to the invention penetrate the skin, but the kinetics of the penetration depends on the size of the skin

Liposomes. Liposomes with a small medium particle size penetrate the skin much faster than liposomes with a large medium particle size. Of course, the type of formulation, for example the addition of penetration aids, the type and structure of the substances forming the liposomes or the form of formulation, gel, O / W emulsion or W / O emulsion can have an influence on the penetration behavior. For example, liposomes with an average particle size of approximately 0.4 μm and approximately 0.09 μm were produced from nonionic phospholipids when loaded with 2.0% by weight of the active ingredient (B) in an aqueous-alcoholic solution. Both solutions differ significantly in their penetration behavior. Above a particle size of approx. 0.1 μm, the liposomes show a slow penetration behavior, below that the penetration speed increases significantly.

In addition to the particle size of the liposomes, the penetration capacity also depends on the amount of active substance loaded in them. The higher the liposomes are loaded with the same amount of phospholipid, the slower they penetrate the skin.

The vesicle-forming substances according to the invention are present in the preparations which contain the active ingredient complex (A) according to the invention in concentrations of from 0.01% by weight to 30% by weight, preferably from 0.01% by weight to 15% by weight and very particularly preferably contained in amounts of 0.01% by weight to 10% by weight.

The pharmaceutical and cosmetic compositions according to the invention can contain betaines (B) as the only pharmacologically active substances. However, it is also possible to add further pharmacologically and / or cosmetically active substances to the agents. Examples of pharmacologically active substances are corticosteroids, β-blocks, estrogens, cyproterone acetate, vasodilating substances such as diazoxide, nifedipine and minoxidil.

The agents according to the invention containing the active ingredient complex (A) can be

But I also deal with conventional hair treatment agents.

In these cases, the pharmaceutical and cosmetic compositions according to the invention can contain, in addition to the betaines mentioned, all carriers, active ingredients and auxiliaries known and customarily used in these fields.

Such hair treatment agents are, for example, shampoos, hair rinsing agents, hair gels, hair lotions, hair treatments, hair creams, hair lotions, hair sprays and hair tinctures.

These agents can be in all formulations customary for hair treatment agents, for example in the form of an aqueous solution or emulsions, for example an O / W or W / O emulsion, which can be prepared by the phase inversion temperature method, as a micro- or nanoemulsion, an aqueous -Alcoholic or alcoholic solution, a cream, a gel, a lotion or an aerosol. The agents according to the invention with the active ingredient complex (A) can be single-phase or multi-phase.

With regard to their action, the agents according to the invention can be specifically formulated for the desired properties by selecting the vesicle-forming substances and the active ingredient complex (A). If vesicle-forming substances and active substance complex (A) are chosen so that liposomes with an average particle size of less than 0.1 μm are obtained, then the liposomes loaded with the active substance complex (A) penetrate quickly into the skin. This is particularly interesting for all hair treatment products that are rinsed out of the hair after a short exposure time, such as shampoos or hair treatments. If, on the other hand, the vesicle-forming substances and the active substance complex are selected in such a way that an average particle size larger than 0.1 μm is obtained, the liposomes loaded with the active substance complex (A) penetrate into the skin more slowly. This is of particular interest for hair treatment agents that remain on the hair, such as hair lotions, leave-on care cures, etc.: With this, a depot effect or retard effect, i.e. a long-lasting effect, can be achieved through a slow penetration that lasts for several hours to days. Of course, by combining different average particle sizes of the vesicles loaded with the active ingredient complex (A), corresponding penetration profiles and thus active profiles can be created. This type of use is of particular interest for pharmaceutical applications.

Although the aforementioned hair treatment agents are preferred according to the invention, the active ingredient complex (A) according to the invention can also be used for other hair treatment agents, e.g. Hair colorants and waving agents can be added. These agents then optionally contain the known direct dyes, precursors for oxidation dyes (developer and coupler components) and oxidizing agents or reducing agents.

The preparations according to the invention preferably have a pH of 2 to 10, in particular 4 to 9.

Depending on the type of hair treatment agent and the selected formulation, the agents according to the invention can preferably contain the following further ingredients:

As additional skin and hair-caring substances, fatty substances (D) can additionally be used in the agents according to the invention. Fat substances are to be understood as meaning fatty acids, fatty alcohols, natural and synthetic waxes, which can be present both in solid form and in liquid form in aqueous dispersion, and natural and synthetic cosmetic oil components. Linear and / or branched, saturated and / or unsaturated fatty acids having 6 to 30 carbon atoms can be used as fatty acids (DI). Fatty acids with 10-22 carbon atoms are preferred. These include, for example, the isostearic acids such as the commercial products Emersol ^® 871 and Emersol ^® 875, and isopalmitic acids such as the commercial product Edenor ^® IP 95, and all other fatty acids sold under the trade names Edenor ^® (Cognis). Other typical examples of such

Fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadic acid and arenic acid, arachidic acid, arachidic acid, arachidic acid, arachidic acid, mixtures thereof, for example in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids. The fatty acid cuts which are obtainable from coconut oil or palm oil are usually particularly preferred; the use of stearic acid is generally particularly preferred.

The amount used is 0.1-15% by weight, based on the total agent. The amount is preferably 0.1-10% by weight, with amounts of 0.1-5% by weight being very particularly advantageous.

Saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ -C ₃₀ , preferably C ₁₀ -C ₂₂ and very particularly preferably C ₁₂ -C ₂₂ carbon atoms can be used as fatty alcohols (D2). For example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, capryl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol , as well as their Guerbet alcohols, this list is intended to be exemplary and not limiting. The fatty alcohols, however, derive from preferably natural fatty acids, and it can usually be assumed that they are obtained from the esters of the fatty acids by reduction. Fatty alcohol cuts that can be used according to the invention are those which, by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rape oil, cottonseed oil, soybean oil, Sunflower oil and linseed oil or from their transesterification products with the corresponding alcohols are generated fatty acid esters, and thus represent a mixture of different fatty alcohols. Such substances are, for example, under the names Stenol ^® , for example Stenol ^® 1618 or Lanette ^® , for example Lanette ^® O or Lorol ^® , for example Lorol ^® C8, Lorol ^® C14, Lorol ^® C18, Lorol ^® C8-18, HD-Ocenol ^® , Crodacol ^® , e.g. Crodacol ^® CS, Novol ^® , Eutanol ^® G, Guerbitol ^® 1.6, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or to buy Isocarb ^® 24. Of course, according to the invention, wool wax alcohols, such as those commercially available under the names Corona ^® , White Swan ^® , Coronet ^® or Fluilan ^® , can also be used. The fatty alcohols are used in amounts of 0.1-30% by weight, based on the entire preparation, preferably in amounts of 0.1-20% by weight.

Solid paraffins or isoparaffins, carnaubawacb.se, beeswaxes, candelilla waxes, ozokerites, ceresin, walrus, sunflower wax, fruit waxes such as apple wax or citrus wax, microwaxes made of PE or PP can be used according to the invention as natural or synthetic waxes (D3). Such waxes are available, for example, from Kahl & Co., Trittau. The amount used is 0.1-50% by weight, based on the total agent, preferably 0.1

- 20% by weight and, particularly preferably 0.1 - 15% by weight, based on the total agent.

The natural and synthetic cosmetic oil bodies (D4) which can be used advantageously according to the invention include, for example:

- vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach seed oil and the liquid components of coconut oil. Other triglyceride oils such as the liquid portions of beef tallow and synthetic triglyceride oils are also suitable.

liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n- nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl n-undecyl ether and di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso- Pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products l, 3-di- (2-ethyl-heχyl) -cyclohexane (Cetiol ^® S), and 'Di-n-octyl ether (Cetiol ^® OE) may be preferred.

Esteröle. Ester oils are understood to be the esters of C ₆ - C ₃₀ fatty acids with C ₂ -

C ₃₀ - fatty alcohols. The monoesters of fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are

Caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid,

Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid,

Arachic acid, gadoleic acid, behenic acid and eraic acid and their technical

Mixtures which e.g. in the pressure splitting of natural fats and oils, in the

Oxidation of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids occur. Examples of the fatty alcohol content in the

Ester oils are isopropyl alcohol, capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol,

Capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol,

Palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol,

Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, e.g. in high-pressure hydrogenation of technical

Methyl esters based on fats and oils or aldehydes from Roelen

Oxosynthesis and as a monomer fraction in the dimerization of unsaturated

Fatty alcohols occur. Isopropyl myristate is particularly preferred according to the invention

(Rilanit ^® IPM), isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), 2-ethylhexyl palmitate

(Cegesoft ^® 24), stearic acid 2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, coconut oil alcohol caprinate / caprylate (Cetiol ^® LC), n-butyl stearate, olerlerucate

(Cetiol ^® J 600), isopropyl palmitate (Rilanit ^® IPP), oleyl oleates (Cetiol ^® ), hexyl laurate (Cetiol ^® A), di-n-butyl adipate (Cetiol ^® B), myristyl myristate (Cetiol ^® MM),

Cetearyl isononanoate (Cetiol ^® SN), oleic acid decyl ester (Cetiol ^® V).

Dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate as well as diol esters such as ethylene glycol dioleate,

Ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol di-dicaprylate, symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ^® CC),

Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,

Fatty acid partial glycerides are monoglycerides, diglycerides and their technical mixtures. When using technical products, small quantities of triglycerides may still be present due to the manufacturing process. The partial glycerides preferably follow the formula (D4-I); , CH ₂ O (CH ₂ CH ₂ O) _m R ¹

I

CHO (CH ₂ CH ₂ O) _n R ² (D4-I)

CH ₂ O (CH ₂ CH ₂ O) _q R ³

in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups represents hydrogen. The sum (m + n + q) stands for 0 or numbers from 1 to 100, preferably for 0 or 5 to 25. R is preferably an acyl radical and R and R are hydrogen and the sum is (m + n + q) 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, iso stearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, eleostearic acid , Arachidic acid, gadoleic acid, behenic acid and eraic acid and their technical mixtures. Oleic acid monoglycerides are preferably used.

The amount of natural and synthetic cosmetic oils used in the agents used according to the invention is usually 0.1-30% by weight, based on the total agent, preferably 0.1-20% by weight, and in particular 0.1-15% by weight. -%. The total amount of oil and fat components in the agents according to the invention is usually 0.1-75% by weight, based on the total agent. Quantities of 0.1-3% by weight are preferred according to the invention.

Further additional components to the active ingredient (A) according to the invention can be contained in the compositions, in particular those from the surface active compounds

Group of anionic, amphoteric, zwitterionic and / or nonionic surfactants (E).

The term “surfactants” is understood to mean surface-active substances that form adsorption layers on surfaces and interfaces or that can aggregate into micelle colloids or lyotropic mesophases in volume phases. A distinction is made between anionic surfactants consisting of a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants which carry both a negative and a compensating positive charge, cationic surfactants which have a positively charged hydrophilic group in addition to a hydrophobic residue, and nonionic surfactants, which have no charges but strong dipole moments and are highly hydrated in aqueous solution. Further definitions and properties of surfactants can be found in "H.-D. Dörfler, interfacial and colloid chemistry, VCH Verlagsgesellschaft mbH. Weinheim, 1994 ". The definition given above can be found from p. 190 in this publication.

Suitable anionic surfactants (E1) in the agents according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Examples of suitable anionic surfactants are, in the form of the sodium, potassium and ammonium salts as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, - linear and branched fatty acids with 8 to 30 carbon atoms. Atoms (soaps), Ether carboxylic acids of the formula RO- (CH2 ~ CH2θ) _χ -CH2-COOH, in which R is a linear

Alkylgrappe with § to 30 carbon atoms and x = 0 or 1 to 16, acyl sarcosides having from 8 to 24 carbon atoms in the acyl group, Acyltaur ^'ide having 8 to 24 carbon atoms in the acyl group, acyl isethionates containing 8 to 24 carbon Atoms in the acyl group,

Sulphosuccinic acid mono- and dialkyl esters with 8 to 24 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates with 8 to 24 carbon atoms, linear alpha-olefin sulfonates 8 to 24 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -OSO ₃ H, in which R is a preferably linear alkyl group with 8 to 30 carbon atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354,

Sulfonates of unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3926 344,

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms, alkyl and / or alkenyl ether phosphates of the formula (El-I),

O

II

R ¹ (OCH ₂ CH ₂ ) n - O - P - OR ² (El-I)

OX in R ^{1 is} preferably for an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ² for hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹ or X, n for numbers from 1 to 10 and X for hydrogen, an alkali - or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R independently of one another represent hydrogen or a Cl to C4 hydrocarbon radical, sulfated fatty acid alkylene glycol esters of the formula (E1 -II) R ⁷ CO (AlkO) _n SO ₃ M (El-II) iri the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or, r

) unsaturated acyl radical with 6 to 22 carbon atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M for a cation, as in the DE-OS 197 36 906.5 are described,

- Monoglyceride ύlfate and Monoglyceridethersulfate of the formula (El -III)

CH ₂ O (CH ₂ CH ₂ O) _x - COR ⁸

CHO (CH ₂ CH ₂ O) _y H

I (El -III)

CH ₂ O (CH ₂ CH ₂ O) _z - SO ₃ X

in the R ⁸ CO for a linear or branched acyl radical. with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula (E 1 -III) are preferably used, in which R ⁸ CO represents a linear acyl radical having 8 to 18 carbon atoms, as described, for example, in EP-Bl 0 561 825, EP-Bl 0 561 999 DE-Al 42 04 700 or by AKBiswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and FUAhmed in J.Am.Oil.Chem.Soc. 67, 8 (1990),

Amidether carboxylic acids as described in EP 0 690 044,

- Condensation products from C ₈ - C ₃₀ fatty alcohols with protein hydrolyzates and / or amino acids and their derivatives, which are known to the person skilled in the art as protein fatty acid condensates, such as, for example, the Lamepon ^® types, Gluadin ^® types, Hostapon ^® KCG or the Amisoft ^® - guys.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl 8 to 18 C- Atoms in the alkyl group and 1 to 6 oxyethyl groups, monoglycer disulfates, alkyl and alkenyl ether phosphates and protein fatty acid condensates.

Zwitterionic surfactants (E2) are those surface-active compounds which carry at least one quaternary ammpnium group and at least one -COO ^H - or -SO ₃ ^{(_) group in the} molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylamine propyl dimethylammonium glycinate, and 2-alkyl -3-carboxymethy 1-3-hydroxy ethyl imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants (E3) are understood to mean those surface-active compounds which, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for the formation of internal ones Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkylimino-dipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid with each about 8 to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acyl sarcosine.

Nonionic surfactants (E4) contain e.g. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such connections are, for example

- Adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,

- With a methyl or C ₂ - C ₆ - alkyl end group capped end products from 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols with 8 to 30 carbon atoms, fatty acids with 8 to 30 carbon atoms and ah alkylphenols with 8 to 15 carbon atoms in the alkyl group, such as those available under the sales names Dehydol ^® LS, Dehydol ^® LT (Cognis) types

Cι ₂ -C ₃₀ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

Polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _w OR ³ (E4-I)

in the R * CO for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or methyl, R ³ for linear or branched alkyl radicals with 1 to 4 carbon atoms and w for numbers from 1 to 20 stands, amine oxides,

Hydroxy mixed ethers as described, for example, in DE-OS 19738866, sorbitan fatty acid esters and addition products of ethylene oxide onto sorbitan fatty acid esters such as, for example, the polysorbates,

Sugar fatty acid esters and adducts of ethylene oxide with sugar fatty acid esters,

Addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines, sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),

R ⁴ O- [G] _p (E4-II)

in which R ^{4 represents} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. You can use the relevant procedures of preparative organic chemistry be preserved. Representative of the extensive literature here is the review by Biermann et al. in, Starch / Starke 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) and J. Kähre et al. in SÖFW-Joumal Issue 8, 598 (1995).

The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably from glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie. the division of mono- and oligoglycosides is on and stands for a number between 1 and 10. While p must always be an integer in the individual molecule and can in particular assume the values p = 1 to 6 here, the value p is one for a certain alkyl oligoglycoside analytically determined arithmetic size, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 ^" and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can differ from primary alcohols with 4 to 11, preferably 8 to 10. Carbon atoms are typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis Preferred are alkyl oligoglucosides of chain length Cg-Cio (DP = 1 to 3), which are obtained as a preliminary step in the separation of technical C ₈ -C ₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight C ₂ -alcohol can be contaminated and alkyl oligoglucosides based on technical C _{9 /} π-oxo alcohols (DP = 1 to 3) st R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol,

Behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 1 -C 8 coco alcohol with a DP of 1 to 3 are preferred. Sugar surfactants of the fatty acid N-alkylpolyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III), R ⁶

I

R ⁵ CO-N- [Z] (E4-III)

in which R ⁵ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 Hydroxyl groups. The fatty acid N-alkylpolyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H. Kelkenberg can be found in Tens. Surf. Det. 25, '8 (1988). The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IN):

R ⁷ COΝR ⁸ - CH ₂ - (CHOH) ₄ - CH ₂ OH (E4-IV)

The preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ⁷ CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or eraic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C12 / 14 coconut fatty acid or a corresponding derivative are particularly preferred become. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The alkylene oxide adducts with saturated linear fatty alcohols and fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid, have proven to be preferred nonionic surfactants. Preparations with excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

These connections are characterized by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. Where so-called "oxo alcohols" ette as starting materials, compounds with an odd number of carbon atoms in the Alkylk ^'.

Furthermore, very particularly preferred nonionic surfactants are the sugar surfactants. These can be present in the agents used according to the invention preferably in amounts of 0.1-20% by weight, based on the total agent. Amounts of 0.5-15% by weight are preferred, and amounts of 0.5-7.5% by weight are very particularly preferred.

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues that are used in the implementation of fatty alcohols. hol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

In addition to the components mentioned, the agents can contain, as surface-active compounds, cationic surfactants (E5) of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the compounds known under the INCI names Quaternium-27 and Quaternium-83 compounds imidazolium. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats ,

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound from this group of substances which is particularly suitable according to the invention provides the the name Tegoamid ^® S 18 commercially available stearamidopropyl-dimethylamine.

The cationic surfactants (E5) are preferably present in the agents used according to the invention in amounts of 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

The surfactants (E) are used in amounts of 0.1-50% by weight, preferably 0.5-30% by weight and very particularly preferably 0.5-25% by weight, based on the total agent used according to the invention. used.

In a further preferred embodiment, emulsifiers (F) are used in the agents according to the invention. Emulsifiers cause water or oil-stable adsorption layers to form at the phase interface, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Like surfactants, emulsifiers are therefore made up of a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as a droplet-like distribution (dispersion) of a liquid in another liquid with the use of energy to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers is based on the substances to be dispersed and the particular external phase as well as the fine particle size of the emulsion. Further definitions and properties of emulsifiers can be found in "H.-D. Dörfler, interfacial and colloid chemistry, VCH Verlagsgesellschaft mbH. Weinheim, 1994 ". Emulsifiers which can be used according to the invention are, for example

- Adducts of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the Alkylgrappe,

- C ₂ -C ₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with polyols having 3 to 6 carbon atoms, in particular with glycerol,

- Ethylene oxide and polyglycerol adducts with methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides, C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, degrees of oligomerization from 1.1 to 5, in particular 1.2 to 2.0, and glucose as the sugar component being preferred,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example the commercially available product Montanov ^® 68,

- adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

- partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms, ^•

Sterols. Sterols are understood to be a group of steroids which carry a hydroxyl group on the C atom 3 of the steroid structure and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Sterols, the so-called mycosterols, are also isolated from mushrooms and yeasts.

- phospholipids. Among these are in particular the glucose phospholipids, for example, as lecithins or phosphatidylcholines for example from egg yolk or plant seeds (eg soya bean ¹⁾ are obtained understood.

Fatty acid esters of sugars and sugar alcohols, such as sorbitol,

- polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hy- droxystearat (Dehymuls ^® PGPH commercial product)

- Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The compositions according to the invention preferably contain the emulsifiers in amounts of 0.1-25% by weight, in particular 0.1-15% by weight, based on the total composition.

The compositions according to the invention can preferably contain at least one nonionic emulsifier with an HLB value of 8 to 18, according to the 10th edition, Georg Thieme Verlag Stuttgart, New in the Rompp-Lexikon Chemie (Ed. J. Falbe, M. Regitz) York, (1997), page 1764. Nonionic emulsifiers with an HLB value of 10-15 can be particularly preferred according to the invention. Protein hydrolyzates and / or amino acids and their derivatives (H) can also be contained in the agents used according to the invention. Protein hydrolyzates are product mixtures that are obtained by acidic, basic 'or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, the term protein hydrolyzates also means total hydrolyzates and individual amino acids and their derivatives, as well as mixtures of different amino acids. Furthermore, according to the invention, polymers constructed from amino acids and amino acid derivatives are understood to be protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc. Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride. Of course, ß-amino acids and their derivatives such as ß-alanine, anthranilic acid or hippuric acid can also be used according to the invention. The molecular weight of the protein hydrolyzates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

According to the invention, protein hydrolyzates of plant, animal, marine or synthetic origin can be used.

Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois ^® (Interorgana), Collapuron ^® (Cognis), Nutrilan ^® (Cognis), Gelita-Sol ^® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ^® (Inolex) and Kerasol ^® (Croda) sold.

According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, pea, potato and wheat protein hydrolyzates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), DiaMin ^® (Diamalt), Lexein ^® (Inolex), Hydrosoy ^® (Croda), Hydrolupin ^® (Croda), Hydrosesame ^® (Croda), Hydrotritium ^® (Croda) and Crotein ^® (Croda) available.

Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon® ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or crotein ^® (Croda).

The protein hydrolyzates or their derivatives are preferably present in the preparations used according to the invention in amounts of 0.1 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight are particularly preferred.

Furthermore, 2-pyrrolidinone-5-carboxylic acid and / or its derivatives (J) can be used in the preparations of the process according to the invention. Preferred are the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion carries one to three - to C ₄ - alkyl groups in addition to hydrogen. The sodium salt is very particularly preferred. The amounts used in the agents according to the invention are 0.01 to 10% by weight, based on the total agent, particularly preferably 0.1 to 5 and in particular 0.1 to 3% by weight.

The use of vitamins, provitamins and vitamin precursors and their derivatives (K) has also proven to be advantageous.

Vitamins, pro-vitamins and vitamin precursors which are usually assigned to groups A, B, C, E, F and H are preferred according to the invention.

The Grappe of the substances referred to as vitamin A include retinol (vitamin A _Ϊ ) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. According to the invention, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as palmitate and acetate come into consideration as vitamin A components. The preparations used according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the entire preparation. The vitamin B group or the vitamin B complex include

- Vitamin B _\ (thiamine)

- Vitamin B ₂ (riboflavin)

- Vitamin B ₃ . The compounds nicotinic acid and nicotinamide (niacinamide) are often listed under this name. Preferred according to the invention is nicotinic acid amide, which is contained in the agents used according to the invention preferably in amounts of 0.05 to 1% by weight, based on the total agent.

- Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Within this group, panthenol and / or pantolactone is preferably used. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, panthenol triacetate, panthenol monoethyl ether and its monoacetate and the cationic panthenol derivatives disclosed in WO 92/13829. The compounds of the vitamin B ₅ type mentioned are preferably present in the agents used according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5% by weight are particularly preferred.

- Vitamin B ₆ (pyridoxine, pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is preferably used in the agents used according to the invention in amounts of 0.1 to 3% by weight, based on the total agent. Use in the form of the palmitic acid ester, the glucosides or phosphates can be preferred. Use in combination with tocopherols may also be preferred.

Vitamin E (tocopherols, especially tocopherol). Tocopherol and its derivatives, which include in particular the esters such as acetate, nicotinate, phosphate and succinate, are preferably present in the agents used according to the invention in amounts of 0.05-1% by weight, based on the total agent ,

Vitamin F. The term “vitamin F” usually means essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid. Vitamin H. Vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexa- hydrothienol [3,4 - </ | -imidazole-4-valeric acid], for which the trivial name biotin has now become established. Biotin is contained in the agents used according to the invention preferably in amounts of 0.0001 to 1.0% by weight, in particular in amounts of 0.001 to 0.01% by weight.

The preparations used according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, E and H. Of course, several vitamins and vitamin precursors can also be present at the same time.

Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinamide and biotin are particularly preferred.

The amount of vitamins and vitamin precursors used in the agents used according to the invention is usually 0.0001-10% by weight, based on the total agent, preferably 0.0001-5% by weight, and in particular 0.0001-3% by weight. ,

Finally, plant extracts (L) can be used in the agents according to the invention.

These extracts are usually produced by extracting the entire plant. In individual cases, however, it may also be preferred to produce the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, reference is made in particular to the extracts which are listed in the table beginning on page 44 of the 3rd edition of the guide to the declaration of ingredients of cosmetic products, published by the Industry Association for Personal Care and Detergents (IKW), Frankfurt.

According to the invention, the extracts from green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, white dome, linden flowers, almond, aloe vera, spruce needles, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, Birch, mallow, cuckoo, quendel, yarrow, thyme, lemon balm, common hake, coltsfoot, marshmallow, meristem, ginseng and 'ginger root preferred.

The extracts from green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, linden flowers, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, are particularly preferred. Rosemary, birch, cuckoo flower, quendel, yarrow, harrow, meristem, ginseng and ginger root.

The extracts from green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon are particularly suitable for the use according to the invention.

Water, alcohols and mixtures thereof can be used as extractants for the production of the plant extracts mentioned. Among the alcohols, lower alcohols such as ethanol and isopropanol, but in particular polyhydric alcohols such as ethylene glycol and propylene glycol, are preferred, both as the sole extracting agent and in a mixture with water. Plant extracts based on water propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

According to the invention, the plant extracts can be used both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80% by weight of active substance and, as a solvent, the extractant or extractant mixture used in their extraction.

Furthermore, it may be preferred to use mixtures of several, in particular two, different plant extracts in the agents according to the invention.

The amount of plant extracts used in the agents used according to the invention is usually 0.01-50% by weight, based on the total agent, preferably 0.1-30% by weight, and in particular 0.1-20% by weight. Short-chain carboxylic acids (N) can also be used advantageously for the purposes of the invention. Among short-chain carboxylic acids and their derivatives in the sense of

Invention are understood to be carboxylic acids which can be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. Preferred in the sense of

I

Invention can be saturated or unsaturated straight-chain or branched carboxylic acids with a chain length of 1 to 16 carbon atoms in the chain, very particularly preferred are those with a chain length of 1 to 12 carbon atoms in the chain.

The short-chain carboxylic acids in the sense of the invention can have one, two, three or more carboxy groups. For the purposes of the invention, preference is given to carboxylic acids having a plurality of carboxy groups, in particular di- and tricarboxylic acids. The carboxy groups can be present in whole or in part as an ester, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amidoxime, nitrile, phosphonic or phosphate ester. The carboxylic acids according to the invention can of course be substituted along the carbon chain or the ring structure. The substituents of the carboxylic acids according to the invention include, for example, Cl-C8-alkyl, C2-C8-alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C2-C8-hydroxyalkyl, C2-C8-hydroxyalkenyl, Aminomethyl, C2-C8 aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are Cl-C8-alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Substituents in the α position are particularly preferred. Very particularly preferred substituents are hydroxyl, alkoxy and amino groups, where the amino function can optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore, preferred carboxylic acid derivatives are the phosphonic and phosphate esters.

Examples of carboxylic acids according to the invention are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, propolic acid, sebacic acid, azelaic acid, azelaic acid acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoyl acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid, 4,4'-dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4, 6,7-naphthalene pentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propanetricarboxylic acid, a dicarboxylic acid selected from Grappe, which is formed by compounds of the general formula (NI),

in the Z stands for a linear or branched alkyl or alkenyl group with 4 to 12 carbon atoms, n for a number from 4 to 12 and one of the two groups X and Y for a COOH Grappe and the other for hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (NI) which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids which formally form from the dicarboxylic acids of the formula (NI) by addition of a molecule of water to the double bond in the cyclohexene ring.

Dicarboxylic acids of the formula (N-I) are known in the literature.

A manufacturing process can be found, for example, in US Pat. No. 3,753,968. The dicarboxylic acids of the formula (NI) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. A polyunsaturated fatty acid is usually used as the dicarboxylic acid component. The linoleic acid accessible from natural fats and oils is preferred. Acrylic acid, but also, for example, methacrylic acid and crotonic acid are particularly preferred as the monocarboxylic acid component. Diels-Alder reactions usually produce mixtures of isomers in which one component is present in excess. According to the invention, these isomer mixtures can be used just like the pure compounds. In addition to the preferred dicarboxylic acids of the formula (NI), those dicarboxylic acids which differ from the compounds of the formula (NI) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or from these compounds, formally by addition of one molecule, can also be used according to the invention Water to form the double formation of the cyclohexene ring.

The dicarboxylic acid (mixture) which results from the reaction of linoleic acid with acrylic acid has proven to be particularly advantageous according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexen-l-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ^{® ®} 1595 (manufacturer: Westvaco).

In addition to the short-chain carboxylic acids themselves according to the invention, which have been exemplified above, their physiologically tolerable salts can also be used according to the invention. Examples of such salts are the alkali, alkaline earth, zinc and ammonium salts, which in the context of the present application are also to be understood as the mono-, di- and trimethyl, ethyl and hydroxyethyl ammonium salts. However, acids which are neutralized with alkaline reacting amino acids, such as arginine, lysine, omithin and histidine, can very particularly preferably be used in the context of the invention. For formulation reasons, it may furthermore be preferred to select the carboxylic acid from the water-soluble representatives, in particular the water-soluble salts.

Furthermore, it is preferred according to the invention to use hydroxycarboxylic acids and in this case in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxydi, tri and polycarboxylic acids. It has been shown here that, in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols with 8-22 C atoms, for example fatty alcohols or synthetic fatty alcohols. The esters of Cl2-C15 fatty alcohols are particularly preferred. Esters of this type 'are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale. Particularly preferred polyhydroxypolycarboxylic acids are polylactic acid and polytartaric acid and their esters.

Also suitable as conditioning agents are silicone oils and silicone gums, in particular dialkyl and alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Coming under the names DC 190, DC 200 and DC 1401 and the commercial product Fancorsil ^® LIM-1.

Also suitable as conditioning agents according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Coming; a stabilized trimethylsilylamodimethicone), Dow ^Coming® 939 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone) will), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80). A suitable anionic silicone oil is the product Dow Corning ^® 1784.

Other active ingredients, auxiliaries and additives are, for example

- Thickeners such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for. As methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol,

hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and silicone oils,

- perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - Fiber structure-improving agents, in particular mono-, di- and oligosaccharides, such as glucose, galactose, fructose, fructose and lactose

- conditioning agents such as paraffin oils, vegetable oils, e.g. B. sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil as well

-> Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate,

- defoamers like silicones,

Dyes for coloring the agent,

- anti-dandruff agents such as Piroctone 01 amine, zinc omadine and climbazole,

- active ingredients such as allantoin and bisabolol,

- cholesterol,

- consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,

- fats and waxes such as walrus, beeswax, montan wax and paraffins,

- fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as primary, secondary and tertiary phosphates,

- opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,

- pigments,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

- antioxidants.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. the monograph by KH Schrader, basics and recipes of cosmetics, 2nd edition, Hüthig Buch Verlag Heidelberg, 1989, referenced. The following examples are intended to explain the invention in more detail. Examples

Unless otherwise noted, all details are parts by weight

1. Synthesis of betaines of the formula (B-II) and (B-III)

In principle, the betaines of the formulas (B-II) and (B-III) can be prepared by all customary esterification methods in preparative organic chemistry. For this purpose, for example, the acidic or basic esterification, the esterification via acid halides, the esterification via anhydrides, the acidic or basic transesterification and / or the enzymatic esterification are to be expected.

1.1. Production of carnitine triglyceride:,

Implementation of L-carnitine with hydrochloric acid and glycerin

Approach: 800 mg (5 mmol) L-camitin

0.6 ml (~ 7 mmol) HC1 (conc.)

150 mg (6 mmol) glycerin

800 mg L-camitin was dissolved in 2 ml water. After 5 minutes of stirring, 0.6 ml of conc. Hydrochloric acid added dropwise with cooling (ice bath) and stirred for a further 5 minutes. A clear, colorless solution resulted.

In the second step, 150 mg of glycerol was added to this solution and the mixture was stirred for 5 minutes. The water introduced was within 5 h at 40 ° C or 6 h at 60 ° C in

Vacuum (20 mbar) distilled off. The resulting substance was clear, light yellow and viscous.

Weight: 0.82 g carnitine triglyceride 1.2. Production of mixed glycerides

Implementation of carnitine triglyceride with glycerol trioleate

Approach: 1.34 g (3 parts by weight) of L-carnitine triglyceride

3.13 g (7 pts.wt.) Edenor ^® KL {COGNIS; glycerol trioleate)

The L-Camitintriglyceridgemisch was added Edenor ^® KL 20 and a spatula tip of sodium methylate (0.1 g). The raction time is one hour. After cooling, there was a clear two-phase separation. The sediment was brownish-yellow and the liquid (oil) above it was yellow.

Weight: 4.5 g

2. Preparation of the liposomes

The liposomes can be produced by all customary methods known to the person skilled in the art. For example, reference is made to the book "Liposomes, from physicy to applications" by D. Lasic, Elsevier 1993. The following example was produced by the injection method. All weights are in% by weight.

Example 1:

Camitin tartrate 2.0

Phosphatidylcholine 5.0

Tocopherol acetate 0.2

Ethanol 30.0

Allantoin 0.1

Panthenol 0.3

Cremophor ^® RH 40 0.2

Water ad 100

Sodium hydroxide solution to adjust the pH to pH 7

Average particle size determined with dynamic light scattering: approx. 95 nm Morphology of the particles determined with the cryo-TEM technique: small, unilamellar

liposomes

The production was as follows:

Phosphatidylcholine and tocopherol acetate were dissolved in ethanol. The remaining

Substances were added gradually and at a constant stirring speed

(800 rpm) added over 15 minutes. Then the pH was adjusted

Value. The resulting mixture was 5 minutes using a homogenizer

(APV) homogenized.

Example 2:

Camitin tartrate 2.0

Phosphatidylcholine 5.0

Phosphatidylserine 0.5

Tocopherol acetate 0.2

Ethanol 5.0

Allantoin 0.1

Cremophor ^® RH40 0.2

Water ad 100

Average particle size determined with dynamic light scattering: approx. 25 nm

Morphology of the particles determined with the cryo-TEM technique: small, unilamellar

liposomes

The "thin film lipid" method was used in this example. The ethanolic solution of phosphatidylcholine, phosphatidylserine and tocopherol acetate was dried in a rotary evaporator from Resona Technics to form a lipidic film along the glass wall until the solvent had been completely removed. The resulting Film was taken up with a solution of the remaining ingredients in water. Comparative formulation without active ingredient complex (A):

Camitin tartrate 2.0

Tocopherol acetate 0.2

Ethanol 30.0

Allantoin 0.1

Panthenol 0.3

Cremophor ^® RH 40. 0.2

Water ad 100

3. Proof of effectiveness

3.1. Proof of effectiveness for betaines (B)

The in vitro model of the human hair follicles by Philpott et al., Published in Basic Cell Culture Protocols, Humana Press, Totowa, New Jersey, 1997, was used to investigate the action of the active ingredient complex (A) according to the invention. Reference is expressly made to this publication. According to this publication, the procedure was as follows:

a. Isolation of human scalp hair follicles

Occipital, full human skin was isolated.

b. Purification of the isolated human scalp follicle

The plucked hair follicles were transferred to a fresh isolation medium, collected therein and then washed several times with fresh medium under sterile conditions. Three hair follicles each were randomized into one well of a 24-well plate with 500 μl complete medium (Williams E medium was used, supplemented with 2 mM L-glutamine, 10 μg / ml hydrocortisone, 10 μg ml insulin, 10 μg / ml penicillin and 10 μg / ml Streptomyciή). Before adding the substances to be tested, the hair follicles were preincubated in the incubator for 30 minutes.

c. Testing the substances

Camitin, camitin tartrate and minoxidil were tested as reference substances with known effects. The test concentration for camitin and carnition tartrate is 50 μmol / 1 each. The hair follicles were kept in culture for 9 days. The medium including the test substances was changed daily. The length of the respective hair shafts was measured and documented on the 9th day using a measuring eyepiece on a dissection microscope.

The test of minoxidil was a positive control because minoxidil has already been described in the literature as stimulating growth for human hair follicles. According to this literature (Philpott, MP, Green, MR and Kealey, T. in Human Hair Groth in Vitro, J. Cell. Sei. 97, pp. 463-471, 1990), the minoxidil was tested. The following changes were necessary compared to testing the carnitine and the carnitine tartrate: Test concentration of the Minoxidil 10 ^"5 mol / 1 in 1% ethanol, replacement of the streptomy with 10 μg / ml ciprofloxacin.

For statistical evaluation of the results, the length of the hair shafts was calculated in% of the total average length of all hair follicles on day 0. All hair follicles of a grappe were pooled and the mean value and the standard deviation were statistically calculated using conventional methods. Significant differences were calculated using the Student T-Test. d. Results

Table 1: Results, on camitin and camitin tartrate:

Table 2: Positive control with minoxidil:

3.2 Proof of effectiveness for penetration of the active ingredient complex (A)

Penetration tests on excised udder udder skin

100 mg of the respective formulations according to Examples 1 and 2 under point 2.

Preparation of the liposomes containing 2% camitin tartrate and 75 kBq [3H] -

Ca nitin hydrochloride was applied to 5.5 cm ² excised bovine udder skin. The

Bovine udder skin was clamped in a tempered Franz chamber with two chambers. With

The receptor fluid was continuously exchanged using a peristaltic pump. The flow is about 4ml / h.

The epidermis was directed towards the donor chamber. The dermal side stood with the

Receptor solution in contact with air bubbles, which was constantly stirred with the help of a magnetic stick.

The receptor solution and diffusion chamber were kept at a constant level over a water bath

Temperature maintained at 32 ° C, which corresponds to the physiological temperature of the skin. The application was carried out for 1 hour with example 1 from point 2, or 5 hours with example 2 from point 2. At the end of the application time, the substance was absorbed by the epidermis and the surface of the skin was rinsed. The skin pieces were removed from the penetration chambers, frozen and then vertical sections with a thickness of 100 μm were made. ^'The sections were individually Solubilisierungscoctail (Solubilisierangslösung Solulyte, Baker) was dissolved, mixed with scintillation fluid and the presence in each incision amount of radioactivity was determined in a scintillation counter.

Under these conditions, after 1 h with the formulation according to Example 1 from point 2, 1.8 times the amount and after 5 h with the formulation according to Example 2 from point 2, 9.2 times the amount of carnitine compared to the comparative formulation without penetrated the active ingredient complex (A) according to the invention (see item 2, comparison formulation) into the hair follicle region (0.8-1.2 mm).

3.3 Proof of effectiveness for the penetration of the liposomes depending on their size

The tests were performed on the bovine udder skin after the BUS. Model performed. For this purpose, the formulations were applied openly and once in an amount of 1 g / 100 cm 2. With 2% by weight) of camitin tartrate in the composition, this corresponds to an amount of 200 μg / cm 2 skin of carrnitin tartrate.

4. Further formulation examples

a) Hair gel:

Cetyl / stearyl alcohol + 30 EO 19.0

Oleyl alcohol + IO EO 8.0

Cetiol ^® HE ¹ 15.0

Cetiol ^® LC ² 4.0

Camitine tartrate 4.0 Tocopheryl acetate 0.4

Panthenol 2.0

Glycerin 4.0

Lecithin 3.0

Carboxymethyl cellulose 0.2

Perfume oil 0.6

Water ad 100

¹ polyol fatty acid ester (CTFA name: PEG-7-Glyceryl Cocoate) (HENKEL)

² caprylic / capric acid esters with saturated fatty alcohols C12-C18 (CTFA name:

Coco-Caprylate / Caprate) (HENKEL)

b) hair tonic:

Sorbitan monolaurate 1.0

Carnitine Citrate 2.0

Phospholipid 1.0

Tocopheryl acetate 0.2

Menthol 0.1

Glucose 0.7

Hydagen ^® HCMF ³ 2.0

Ethanol 45.6

Perfume oil 0.4

Water ad 100

Chitosan, (INCI - name: Chitosan, COGNIS)

c) Hair foam:

Sodium lauryl (EO) sulfate 2.0

Cetiol ^® HE 3.0

Vinyl pyrrolidone / vinyl acetate copolymer 1.0

3 -O-lauroyl-L-camitin hydrochloride 3.0 mixed glyceride from oleic acid and camitin prepared according to point, 1.2 3.0

Glucose 0.5

Ascorbic acid 0.5

Ethanol 10.0

Perfume oil 0.4

Water ad 100

d) Hair tincture:

Sorbitan monolaurate 2.0

Taurine lysylate 4.0

Minoxidil 2.0

Tocopheryl nicotinate 0.2

PG-Dimonium Chloride Phosphate 3.0

Polyvinyl pyrrolidone (Luviskol K90) 0.3

Glycerin 2.0

Water ad 100

e) Regeneration lotion:

Hydrogenated castor oil + 40 EO 2.0

Acetylcamitine 3.0

Panthenol 1.0 Keratin hydrolyzate 1.0

Biotin 0.01

Safflower oil 0.5

Ethanol 10.0

2-ethyl-1,3-hexanediol 3.0

Arginine 0.5

Amodimethicone (Dow Coming 929) 0.5

Water ad 100

f) Pump spray:

C ₁₂ -C ₁₄ fatty alcohol with 2 EO 2.0

Cetiol ^® HE 2.0

Taurinomithate 4.0

Millet extract oil-soluble 0.2

Piroctone Olamine 0.1 Vinylimidazolimmethochlorid vinylpyrrolidone copolymer (Luviquat ^® FC 550) 2.5

Polyquaternium-10 (Polymer ^JR® 400) 0.3

Histidine 0.3

1,3-butanediol 5.0

Ethanol 40.0

Water ad 100

g) shampoo

Sodium lauryl (EO) sulfate 12.0

Coco betaines 5.0

Camitine tartrate 4.0

Coco Glucoside (Plantacare ^® 818 UP) 2.0

1,2-pentanediol 2.0

1,2-hexanediol 2.0 Polyquaternium-7 0.5

Cocamidopropyl PG-Dimonium Chloride Phosphate 2.5

Piroctone Olamine 0.8

Plant-based protein hydrolyzate 0.5

Perfume oil 0.8

Water ad 100

Claims

Patent claims

1. Pharmaceutical and cosmetic compositions for the treatment of hair, containing conventional carriers, active ingredients and auxiliaries, characterized in that they contain an active ingredient complex (A) which consists of liposomes, which either

Betaines can be constructed in accordance with one of the formulas (B-II) or (B-III) and / or are loaded with at least one betaine in accordance with one of the formulas (BI) to (B-III), and at least one cosmetic raw material which increases penetration (P) and / or at least one polymer (G).

2. Composition according spoke 1, characterized in that the betaine according to formula (B-I) is selected from camitin, histidine, taurine, choline, betaine and their derivatives.

3. Composition according to one of claims 1 or 2, characterized in that the liposomes are composed of one of the compounds selected from phospholipids according to the formula (I), sterol, cholesterol, sitosterol or lecithin. i

4. Agent according to one of claims 1 to 3, characterized in that the agents contain a fatty substance (D) in amounts of 0.1 to 75 wt .-%, based on the total agent.

5. Agent according to one of claims 1 to 4, characterized in that the agents contain a surfactant (E) in amounts of 0.1 to 50 wt .-%, based on the total agent.

6. Agent according to one of claims 1 to 5, characterized in that the agents contain an emulsifier (F) in amounts of 0.1 to 25 wt. ~%, Based on the total agent.

7. Agent according to one of claims 1 to 6, characterized in that the agents contain a protein hydrolyzate (H) in amounts of 0.1 to 10 wt .-%, based on the total agent.

8. Agent according to one of claims 1 to 7, characterized in that the agent is a 2-pyrrolidinone-2-carboxylic acid and / or its derivatives (J) in amounts of 0.01 to 10 wt .-%, based on the total Means included.

9. Agent according to one of claims 1 to 8, characterized in that the agents contain a vitamin or a vitamin precursor (K) in amounts of 0.0001 to 10 wt .-%, based on the total agent.

10. Agent according to one of claims 1 to 9, characterized in that the agents contain a plant extract (L) in amounts of 0.01 to 50 wt .-%, based on the total agent.

11. Agent according to one of claims 1 to 10, characterized in that the agents have a pH of 2 to 10.

12. Cosmetic method for improving hair growth, characterized in that the hair is treated with an agent according to any one of claims 1 to 11.