DE19960632A1 - Cosmetics containing natural chitosans - Google Patents

Abstract

The use of chitosans in cosmetics, which are obtained from fungi of the Mucoraceae family, is disclosed. Said chitosans comprise natural products and have properties of particular advantage for application in cosmetics.

Description

The invention relates to cosmetic preparations made from natural chitosans Contain mushrooms of the Mucoraceae family.

In contrast to most hydrocolloids, which are in the range of biological pH values are negatively charged, chitosans are cationic under these conditions Biopolymers represent. The positively charged chitosans can with opposite charged surfaces interact and are therefore preferred in cosmetic hair and body care products (see Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-232), where they are primarily used as a moisturizer and film former Act. Further overviews on this topic are also from B. Gess, for example lein et al. in HAPPI 27, 57 (1990), O. Skaugrud in Drug Cosm. Ind. 148, 24 (1991) and E. Onsoyen et al. in Seifen-Öle-Fette-Wwachs 117, 633 (1991).

From a chemical point of view, the chitosans are partially deacetylated Chitins of different molecular weights. To make the chitosans goes one from chitin, preferably the shell remains of crustaceans, which as cheap raw materials are available in large quantities. The chitin will be there Usually initially deproteinized by adding bases, by adding Mineral acids demineralized and finally by adding strong bases deacetylated, the molecular weights being distributed over a broad spectrum can. Appropriate methods are, for example, made from Makromol. Chem. 177, 3589 (1976) or French patent application FR 2701266 A1.

The use of chitosan is of microbiological origin from WO 9014071 known in cosmetic preparations. To make this chitosan  next chitin obtained from chitin-producing microorganisms, and this then deacetylated to chitosan in a chemical hydrolysis process.

There has been a strong trend towards natural ingredients in cosmetics for a long time Observe substances, which are substances that are natural raw materials are available without any chemical process steps, which to a change in the molecular composition of the natural content lead material. Non-animal organisms such as are preferred as a natural raw material for example plants or microorganisms. There is also a need after chitosans, which are of natural origin and because of their physicoche mixing properties are suitable for use in cosmetics.

The properties and possible uses of chitosans depend considerably depends on the molecular form in which these substances are present, in particular the molecular weight and the degree of deacetylation play an important role. Typical features of chitosan are its pronounced tendency to gel even at low concentrations, its poor solubility in many in the cosmos common solvents and its incompatibility with numerous their components, for example, in cosmetic formulations.

Because of these problems in handling and wording on the one hand and the practically limitless variety of chemical structure Chitosans, on the other hand, are unpredictable, even by those skilled in the art Chitosans for which purposes are suitable.

The object of the present invention was therefore to provide a for applications in the Kos Metics suitable, especially with regard to its solubility and viscosity properties to find advantageous chitosan, which in the sense of the above Definition of natural and preferably non-animal origin.

Surprisingly, it was found that chitosans, which are derived from mushrooms of the Fami Lie Mucoraceae are produced and especially those that continue to have a De Have a degree of acetylation of at least 85%, excellent as natural raw suitable for use in cosmetics.  

The invention thus relates to cosmetic preparations in a ge suitable carrier material is a natural chitosan from mushrooms of the Mucora family ceae included.

Another object of the invention are cosmetic preparations that in egg a suitable carrier material is a natural chitosan from mushrooms of the Contain Mucoraceae, the chitosan having a degree of deacetylation of at least at least 85%.

Only a few microorganisms are able to directly synthesize chitosan. These microorganisms belong to the Mucoraceae family, to the following Gat conditions include: Absidia, Rhizopus, Mucor, Phycomyces, Actinomucor, Circinella, Zy Gorhynchus, Gongronella. Of these, Absidia has the highest chitosan content, in particular Absidia coerulea ATCC 3018 and Absidia spinosa ATCC 3192. Erfin According to the invention, chitosan from fungi of the genus Absidia or Rhizopus is preferred.

Chitosan is used by fungi of the Mucoraceae family as a component of the cell wall enzyma table under the influence of the enzymes chitin deacetylase and chitin synthase produ adorns (S. Bartnicki-Garcia, L. Davis, Chitosan synthesis by the tandern action of chitin synthetase and chitin deacetylase from Mucor rouxii, Biochemistry, 1984, 23, 1065- 1075).

The chitosan is preferably obtained from the mushrooms by extraction processes as known from the prior art (S. A. White, P. R. Farina, I. Fulton, Production and isolation of chitosan from Mucor rouxii, Appl. Environ. Micro biol., 1979, 38, 323-328; K. Shimahara, Y. Takiguchi, T. Kobayashi, K. Uda, T. Sannan, Screening of mucoraceae strains suitable for chitosan production. In: Chitin and Chitosan, T. Skjak-Braek, T. Anthonsen, P. Sandford (eds.), Elsevier Appl. Sci. London - New York, 1989, 171-178; K. D. Rane, D. G. Hoover, Production of chito san by fungi, Food Biotechnol., 1993, 7 (1), 11-33: W. J. McGahren, G.A. Perkin son, J.A. Growich, R.A. Leese, G.A. Ellestad, Chitosan by fermentation, Process Biochem., 1984, 19, 88-90; S. Arcidiacono, S.J. Iombardii, D.L. Kaplan, Fermentati on processing and enzyme characterization for chitosan biosynthesis by Mucor rou xii. In: Chitin and Chitosan, T. Skjak-Braek, T. Anthonsen, P. Sandford (eds.), Else four appl. Sci. London - New York, 1989, 319-332; N. Davoust, G. Hansson, Iden tifying the conditions for development of beneficial mycelium morphology for chito san-producing Absidia spp. in submersed cultures, Appl. Microbiol. Biotechnol.,  1992, 36, 618-620; M. M. Jaworska, K. W. Stewczyk, Chitosan from Absidia sp., In: Advances in Chitin Sciences II, A. Dormard, G.F. Roberts, K.M. Varum (eds.), Jacques Andre Publisher, Lyon, France, 1997, 48-55; J. Synowiecki, N.A.A. Quawi Al-Khateeb, Mycelia of Mucor rouxii as a source of chitin and chitosan, Food Chemi stry, 1997, 60, 605-610; EP 542249 (Shin-Etsu Chemical Co., Ltd., Japan); EP 531991 (Shin-Etsu Chemical Co., Ltd., Japan). The extractable chito content san is genre-dependent and decreases in the order Absidia, Rhizopus, as well remaining genera of the Mucoraceae (K. Shimahara, Y. Takiguchi, T. Kobayashi, K. Uda, T. Sannan, Screening of mucoraceae strains suitable for chitosan production, in: Chitin and Chitosan, T. Skjak-Braek, T. Anthonsen, P. Sandford (eds.), Elsevier Appl. Sci., London-New York, 1989, 171-178; K. D. Rane, D. G. Hoover, Produc tion of chitosan by fungi, Food Biotechnol., 1993, 7 (1), 11-33).

It is still special for the use of natural chitosans in cosmetics advantageous that the microorganisms from which they are obtained under kon controlled conditions and regardless of environmental influences can. For example, the problem of heavy metal contamination from Avoided in advance, what with conventional Chi made from crustaceans tosanen depending on the location of the animals and the heavy metal pollution in the ge water not infrequently occurs. In addition, fermentative production from natural chitosan also macroscopic impurities from the outset excluded, as in Crustacea chitosan resulting from insoluble often occur.

The natural chitosan described above has properties which are particularly advantageous for use in cosmetic preparations, in particular good solubility and a comparatively low viscosity in solution, which not only facilitates the preparation of the preparations, but also the manufacture Provision of preparations with relatively high concentrations of chitosan made possible light. It is further due to the good solubility properties and low Vis particulars of the chitosans or their solutions used according to the invention ders advantageously possible, preparations with a high alcohol content and / or Manufacture use as sprays, especially those for hair care. The Formulation of such preparations with the commonly used crusta Experience has shown that ceen-chitosans often lead to considerable difficulties and Limitations in the amount of chitosans that can be used in the formulations.  

The chitosan contained in the preparations according to the invention has an average res molecular weight in the range of 100,000 to 2,000,000, preferably from 400,000 up to 1,000,000 and particularly preferably from 500,000 to 800,000 Daltons (rel ves weight against polyethylene glycol standard).

For the purposes of the invention, cosmetic preparations include cleaning agents and / or understanding of the body, especially the skin and hair. Erfin Preparations according to the invention, containing natural chitosans, are for example Hair shampoos, hair lotions, hair styling agents, hair fixers, bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, Emulsions, wax / fat masses, stick preparations, sprays, foams, powder or sal ben.

Preferred cosmetic preparations for the purposes of the invention are hair and Skin care products, including hair sprays, hair fixers and hair care products in the form foams or gels are particularly preferred.

The carriers suitable according to the invention preferably contain one or more adju vantien such as B. mild surfactants, oil bodies, emulsifiers, superfatting agents, pearlescent waxes, consistency agents, thickeners, polymers, silicone compounds, fet te, waxes, stabilizers, biogenic agents, deodorant agents, anti-dandruff agents, Film formers, swelling agents, UV light protection factors, antioxidants, hydrotropes, preservatives Curing agents, insect repellents, self-tanners, solubilizers, perfume oils, colors substances, antimicrobial agents and the like in a suitable, preferably aqueous, aqueous-alcoholic or alcoholic medium.

Typical examples of suitable mild, i.e. H. are particularly skin-friendly surfactants Fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fat acid glutamates, olefin sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acids regglucamides, alkylamido betaines and / or protein fatty acid condensates, the latter before preferably based on wheat proteins.

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids are, for example, oil bodies with linear C ₆ -C ₂₂ fatty alcohols, such as. B. myristyl myristate, myristyl palmitate, myristyl stearate lerucat, Myristylisostearat, myristyl, Myristylbehenat, Myristy, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, rat Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostea, stearyl oleate, stearyl behenate, Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isosteary loleat, tribehenate oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, Oleylbe, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Beheny lisostearat, behenyl oleate, palmitate behenyl behenate, behenyl erucate, erucyl myristate, erucyl, erucyl, Erucyl isostearate, erucyl oleate, erucyl behenate and Erucy lerucat. In addition, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids are suitable with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ - C ₁₈ fatty acids , Esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols with 1 to 22 carbon atoms or polyols with 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoin ure with linear and / or branched C ₆ -C ₂₂ alcohols (e.g. B. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid reesters with polyols, silicone oils and / or aliphatic or naphthenic carbons such as. B. as squalane, squalene or dialkylcyclohexane.

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

• 1. Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of pro pylene oxide to linear fatty alcohols with 8 to 22 carbon atoms, to fatty acids with 12 up to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group pe;
• 2. C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• 3. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids with 6 to 22 carbon atoms and their ethylene oxy dan storage products;
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;
• 5. Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or ge hardened castor oil;
• 6. Polyol and especially polyglycerol esters, such as. B. polyglycerol polyricinoleate, Polyglycerol poly-12-hydroxystearate or polyglycerol dimer isostearate. Exactly if appropriate, mixtures of compounds from several of these sub punching classes;
• 7. Adducts of 2 to 15 moles of ethylene oxide with castor oil and / or ge hardened castor oil;
• 8. Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• 9. Mono-, di- and trialkyl phosphates as well as mono-, di- and / or tri-PEG- alkyl phosphates and their salts;
• 10. wool wax alcohols;
• 11. Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• 12. Mixed ester of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 11 65 574 PS and / or mixed esters of fatty acids with 6 to 22 carbon fat, methylglucose and polyols, preferably glycerin or polyglycerin,
• 13. Polyalkylene glycols as well
• 14. Glycerol carbonate.

The adducts of ethylene oxide and / or propylene oxide with fatty alcohol hole, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and - diesters of fatty acids or castor oil are known, commercially available Products. These are mixtures of homologs, their middle alkoxy Degree of lation the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out corresponds.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. Regarding the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylam monium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acyl aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacyl aminopropyldimethylammonium glycinate, and 2 alkyl-3-carboxylm - Hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic tensi de. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 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 are capable of forming internal salts . Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylamino noethylaminopropionate and C _12/18 acyl sarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

Substances such as lanolin and lecithin can be used as superfatting agents as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides are used, wherein the latter also serve as foam stabilizers.  

Pearlescent waxes, for example, are: alkylene glycol esters, specifically Ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, counter optionally also hydroxy-substituted carboxylic acids with fatty alcohols with 6 to 22 carbons atoms of matter, especially long-chain esters of tartaric acid; Fatty substances such as Fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, all in all have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

The main consistency agents are fatty alcohols or hydroxy fatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxy fatty acids into consideration. A station wagon is preferred nation of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickeners are, for example, Aerosil types (hydrophilic pebbles acids), polysaccharides, in particular xanthan gum, guar guar, agar agar, Algi nate and tylosen, carboxymethyl cellulose and hydroxyethyl cellulose, further ho hermolecular polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (e.g. Carbopole® from Goodrich or Synthalene® from Sigma), Poly acrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as Pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with concentrated homolo gene distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammo nium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, such as B. a quaternized hydroxyethyl cellulose, which is called polymer JR 400® is available from Amerchol, cationic starch, copolymers from diallylam monium salts and acrylamides, quaternized vinyl pyrrolidone / vinyl imidazole Polymers such as B. Luviquat® (BASF), condensation products of polyglycols and Amines, quaternized collagen polypeptides, such as Lauryldimonium hy droxypropyl  hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, Polyethyleneimine, cationic silicone polymers, such as. B. Amidomethicone, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartareti ne® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Mer quat® 550 / Chemviron), polyaminopolyamides, e.g. B. described in FR 2252840 A. and their crosslinked water-soluble polymers, cationic chitinderi vate such as quaternized chitosan, optionally microcrystalline ver shares, condensation products from dihaloalkylene, such as. B. dibromobutane with bis dialkylamines such as e.g. B. bis-dimethylamino-1,3-propane, cationic guar gum, such as e.g. B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized Ammonium salt polymers, such as. B. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from the Miranol company.

As anionic, zwitterionic, amphoteric and nonionic polymers come in for example vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate Copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyls ether / maleic anhydride copolymers and their esters, un crosslinked and polyols crosslinked polyacrylic acids, acrylamidopropyl trimethylammonium chloride / acrylate copolymers, octylacrylamide / methylmethacry lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate Copolymers, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam ter polymer and optionally derivatized cellulose ethers and silicones in question.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methyl phenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds, which in Room temperature can be both liquid and resinous. Still ge suitable are simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile sili cone is also found by Todd et al. in cosm. Toil. 91, 27 (1976).

Typical examples of fats are glycerides. a. natural Waxes such as B. candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice-germ oil wax, sugar cane wax, Ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax),  Bürzelfett, Ceresin, Ozokerit (Erdwachs), Petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as. B. Montanester waxes, Sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as B. Polyalkylene waxes and polyethylene glycol waxes in question.

Metal salts of fatty acids, such as. B. magnesium, aluminum um and / or zinc stearate or ricinoleate are used.

Examples of biogenic active ingredients are tocopherol, tocopherol acetate and To copherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allan toin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudocerami de to understand essential oils, plant extracts and vitamin complexes.

As deodorants come e.g. B. antiperspirants such as aluminum chlorohydates in question. These are colorless, hygroscopic crystals that easily dissolve in the air and arise when aqueous aluminum chloride solutions are evaporated. Aluminum chlorohydrate is used for the production of antiperspirant and desodorizing preparations and is likely to act via the partial closure of the sweat glands through protein and / or polysaccharide precipitation [cf. J. Soc. Cosm. Chem. 24, 281 (1973)]. For example, an aluminum chlorohydrate that corresponds to the formula [Al ₂ (OH) ₅ Cl] * 2.5 H ₂ O and whose use is particularly preferred is commercially available under the brand Locron® from Hoechst AG, Frankfurt / FRG . J. Pharm. Pharmacol. 26, 531 (1975)]. In addition to the chlorohydrates, aluminum hydroxylactates and acidic aluminum / zirconium salts can also be used. Esterase inhibitors can be added as further deodorant active ingredients. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit enzyme activity and therefore reduce odor. The cleavage of the citro-nenoic acid ester probably releases the free acid, which lowers the pH value on the skin to such an extent that the enzymes are inhibited. Other substances which can be considered as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesteric, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester , Adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial agents that influence the bacterial flora and kill sweat-killing bacteria or inhibit their growth can also be contained in the stick preparations. Examples of these are chitosan, phenoxyethanol and chlorhexidine gluconate. 5-Chloro-2- (2,4-dichlorophen-oxy) phenol, which is sold under the Irgasan® brand by Ciba-Geigy, Basel / CH, has also proven to be particularly effective.

Climbazole, octopirox and zinc pyrethione can be used as antidandruff agents become. Common film formers are, for example, polyvinyl pyrrolidone, vinyl pyr rolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary Cel Lulose derivatives, collagen, hyaluronic acid or its salts and similar ver bonds. Montmorillonite and clay mine can be used as swelling agents for aqueous phases raw materials, Pemulen and alkyl-modified carbopol types (Goodrich) are used. Further Suitable polymers or swelling agents can be found in the review by R. Lochhead in Cosm. Toil. 108, 95 (1993).

UV light protection factors are understood to mean, for example, liquid or crystalline organic substances (light protection filters) present at room temperature, which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. B. to release heat again. UVB filters can be oil-soluble or water-soluble. As oil-soluble substances such. B. To name:

• - 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. B. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid 2- ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and 4- (Dimethylamino) amyl benzoate;
• Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4- Propyl methoxy cinnamate, isoamyl 4-methoxy cinnamate 2-cyano-3,3- phenylcinnamic acid 2-ethylhexyl ester (Octo crylene);
• Esters of salicylic acid, preferably 2-ethylhexyl salicylate, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4- methoxybenzophenone;  
• - Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2- ethylhexyl ester;
• - Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5- triazine and octyl triazone, as described in EP 0818450 A1;
• Propane-1,3-diones, such as e.g. B. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3- dion;
• - Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1.

Possible water-soluble substances are:

• - 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, Alkyl ammonium, alkanol ammonium and glucammonium salts;
• - Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4- methoxybenzophenone-5-sulfonic acid and its salts;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-3- bornylidenemethyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and its salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters Question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3- dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol 1789), or 1-phenyl-3- (4'- isopropylphenyl) propane-1,3-dione. The UV-A and UV-B filters can go without saying Lich can also be used in mixtures. In addition to the soluble substances mentioned insoluble light protection pigments are also used for this purpose, namely finely dispersed se metal oxides or salts in question. Examples of suitable metal oxides are in particular special zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon um, manganese, aluminum and cerium as well as their mixtures. Sili can be used as salts cate (talc), barium sulfate or zinc stearate can be used. The oxides and salts are in the form of pigments for skin-care and skin-protecting emulsions and used decorative cosmetics. The particles should be medium Diameter less than 100 nm, preferably between 5 and 50 nm and ins have particular between 15 and 30 nm. They can have a spherical shape have, however, it is also possible to use particles which have a ellipsoidal or otherwise deviating from the spherical shape have. The pigments can also be surface treated, i.e. H. hydrophilized or are hydrophobic. Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). As a hydrophobic coating agent  come mainly silicones and especially trialkoxyoctylsilanes or Simethicone in question. So-called sunscreens are preferred Micro or nanopigments used. Micronized zinc oxide is preferred used. Other suitable UV light protection filters are in the overview by P. Finkel in SÖFW-Journal 122, 543 (1996).

In addition to the two aforementioned groups of primary light stabilizers, secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocaninic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, Lyco pin) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g. dihydroliponic acid) , Aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl -, Oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, Penta-, Hexa-, Hep tathioninsulfoxi min) in very low tolerable doses (e.g. B. pmol to µmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phy tic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid , Biliary extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and Derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and their derivatives , α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydrogua jaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc te (e.g. ZnO, ZnSO ₄ ) selenium and its derivatives (e.g. B. selenium-methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances.

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols which come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols can also contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• - glycerin;
• Alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, Butylene glycol, hexylene glycol and polyethylene glycols with an average Chen molecular weight from 100 to 1,000 daltons;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, Trimethylolbutane, pentaerythritol and dipentaerythritol;
• Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;
• - Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or Mannitol,
• - Sugar with 5 to 12 carbon atoms, such as glucose or saccha rose;
• - aminosugars such as glucamine;
• - Dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formal dehyde solution, parabens, pentanediol or sorbic acid as well as those in Appendix 6, Part A and B of the Cosmetics Ordinance listed further substance classes. As an insect Repellents come from N, N-diethyl-m-toluamide, 1,2-pentanediol or insect Repellent 3535 in question, dihydroxyacetone is suitable as a self-tanner.

Perfume oils include mixtures of natural and synthetic smells fabrics. Natural fragrances are extracts from flowers (lily, lavender, roses, Jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain),  Fruit (anise, coriander, caraway, juniper), fruit peel (bergamot, Lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, cal mus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grass sern (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, Pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, oliba num, opoponax). Animal raw materials are also possible, such as se civet and castoreum. Typical synthetic fragrance compounds are Pro products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type fe. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethy lisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcy clohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen alde hyd, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝- Isomethylionon and Methylcedrylketon, to the alcohols Anethol, Citronellol, Euge nol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the Koh Hydrogen oils belong mainly to the terpenes and balms. Preferred who which, however, uses mixtures of different odoriferous substances, which together form a generate an appealing fragrance. Also essential oils of lower volatility, the mostly used as aroma components, are suitable as perfume oils, e.g. B. Sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, Phe nylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, Li nalool, Boisambrene Forte, Ambroxan, Indole, Hedione, Sandelice, Lemon Oil, Man darinen oil, orange oil, allylamyl glycolate, cyclover valley, lavandin oil, muscatel sal additive oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E- Super, Fixolide NP, Evernyl, Iraldein gamma, Phenylacetic acid, Geranyl acetate, Ben cyanoacetate, rose oxide, Romilllat, Irotyl and Floramat alone or in mixtures puts.

Suitable dyes are those which are suitable and approved for cosmetic purposes Substances are used, as described, for example, in the publication "Cosmetics Sche colorants "of the dye commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106 are compiled. These dyes  are usually in concentrations of 0.001 to 0.1 wt .-%, based on the whole mixture, used.

Typical examples of germ-inhibiting agents are preservatives with specific against gram-positive bacteria such as 2,4,4'-trichloro-2'- hydroxydiphenyl ether, chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) -hexane) or TCC (3,4,4'-trichlorocarbonilide). Also numerous fragrances and essential oils white have antimicrobial properties. Typical examples are the active ingredients Euge nol, menthol and thymol in clove, mint and thyme oil. An interesting natural The deodorant is terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatriene 1-ol), which is present in linden blossom oil and has a lily of the valley smell. Also Glycerol monolaurate has proven itself as a bacteriostatic.

The amount of natural chitosans used in cosmetic preparations is usually on the order of 0.1 to 5, preferably 0.5 to 3 and in particular 1 to 2% by weight, based on the total weight of the preparations.

The preparation of the preparations can be done by conventional cold or hot processes consequences; the phase inversion temperature method is preferably used.  

Examples example 1 Production of natural chitosan from Absidia coerulea ATCC 3018

After inoculating 100 µl of a lyophilized fungal culture in a preculture (10 ml Medium in a shaking flask with a volume of 100 ml with baffle; Medium, which contains 20 g glucose, 10 g peptone, 1 g yeast extract, 5 g ammo in 1 liter water nium sulfate, 1 g dipotassium hydrogen phosphate, 1 g sodium chloride, 0.5 g magnesium sulfate and 0.1 g calcium chloride and whose pH was adjusted to 4.5) was this for 48 h at 26 ° C and 150 revolutions per minute shaker speed incubated. After inoculating the pre-culture in a main culture (200 ml medium in egg shake flask with a volume of 1000 ml with chicane, medium as above) it was also poured for 48 h at 26 ° C. and 150 revolutions per minute incubated. The mushroom cell mass was then filtered off and washed twice with 200 ml of distilled water each. Then the was schene mushroom cell mass with 80 ml of 2 wt .-% sodium hydroxide solution and to comminute treated with an Ultra-Turrax for 1 min at room temperature. After autoclaving the resulting alkaline mushroom suspension (30 min, 120 ° C the insoluble fungal cell mass (alkali insoluble material) was filtered off under pressure) and washed twice with 200 ml of distilled water each. The alkali insoluble Material was then mixed with 80 ml of 2 wt .-% acetic acid and 12 h at 25 ° C. touched. After centrifugation (10 min at 5000 rpm) and separation of the supernatant the remaining alkali insoluble material was again with 80 ml 2 wt .-% Es Acetic acid was added and the mixture was stirred at 50 ° C. for 2 h. After centrifugation again (10 min at 5000 rpm) the supernatants of both centrifugations were combined (total 160 ml). Then 200 mg were freshly prepared to flocculate colloidally dissolved particles added colloidal chitin (production of colloidal chitin according to C. Jeuniaux, Chitinases, Meth. Enzymol., (1966), 8, 644-650), stirred for 5 min and on then centrifuged (10 min at 5000 rpm). The supernatant was removed and adjusted to a pH of 9.0 by adding 1% by weight sodium hydroxide solution, the chitosan failed. After centrifugation (10 min at 5000 rpm) of the chito sans it was washed with 200 ml of distilled water, by centrifugation again gation freed from the washing water and dried. 0.21 g of chitosan resulted a degree of deacetylation of 91% and an average molecular weight of  670,000 (relative weight against polyethylene glycol standard). The viscosity of a 1 wt .-% Solution in 0.5% glycolic acid was approx. 100 mPa / s.

Examples 2.1 to 2.20 Formulations with natural chitosan

Tables 1 and 2 below contain formulation examples with the na natural chitosan from Example 1.  

Table 1

Cosmetic preparations 2.1 to 2.10 (water, preservative ad 100% by weight)

Table 2

Cosmetic preparations 2.11 to 2.20 (water, preservative ad 100% by weight)

Claims (16)

1. Cosmetic preparation, characterized in that it contains a natural chitosan from fungi of the Mucoraceae family in a suitable carrier. 2. Preparation according to claim 1, characterized in that the chitosan one Has a degree of deacetylation of at least 85%. 3. Preparation according to claim 1 or 2, characterized in that the mushrooms Belong to the genus Absidia or Rhizopus. 4. Preparation according to one of claims 1 to 3, characterized in that the chitosan has an average molecular weight in the range from 100,000 to 2,000,000, preferably from 400,000 to 1,000,000 and particularly preferably from 500,000 to 800,000 daltons. 5. Preparation according to one of claims 1 to 4, characterized in that the chitosan is extracted from the mushrooms by extraction. 6. Preparation according to one of claims 1 to 5, characterized in that the chitosan in amounts of 0.1 to 5 wt .-% - based on the preparations - is included. 7. Preparation according to one of claims 1 to 6, characterized in that it the preparation is a hair care product. 8. Preparation according to one of claims 1 to 6, characterized in that it the preparation is a skin care product. 9. Preparation according to one of claims 1 to 6, characterized in that it is a spray. 10. Use of natural chitosan from mushrooms of the Mucoraceae family for Manufacture of cosmetic preparations. 11. Use according to claim 10, characterized in that the chitosan egg has a degree of deacetylation of at least 85%.   12. Use according to claim 10 or 11, characterized in that the mushrooms belong to the genus Absidia or Rhizopus. 13. Use according to one of claims 10 to 12, characterized in that the chitosan has an average molecular weight in the range from 100,000 to 2,000,000, preferably from 400,000 to 1,000,000 and particularly preferably from 500,000 to 800,000 daltons. 14. Use according to one of claims 10 to 13, characterized in that the preparation is a hair care product. 15. Use according to one of claims 10 to 13, characterized in that the preparation is a skin care product. 16. Use according to one of claims 10 to 13, characterized in that the preparation is a spray.