WO2001051011A2 - Condensation products of proteins, whereby azelaic acid is used - Google Patents

Abstract

Disclosed are condensation products of proteins and/or protein hydrolysates, whereby azelaic acid is used.

Description

Condensation products of proteins with azelaic acid

Field of the Invention

The invention is in the field of anionic surfactants and relates to new protein fatty acid condensates based on azelaic acid, a process for their preparation and their use in cosmetics and pharmacy.

State of the art

Under the term acne, the specialist subsumes a skin disease that occurs in very different forms and can have different causes. As a rule, it is characterized by non-inflammatory or even inflammatory nodules that originate from blocked hair follicles (comedones) and can ultimately lead to pustules, abscesses or scars. The most common diagnosis is acne vulgaήs, which mainly occurs during puberty. The causes here are cornification and constipation of the hair follicle mouth, the production of taig depending on the blood level of the male sex hormones, the production of free fatty acids and tissue-damaging enzymes by bacteria, such as Propioniumbacterium acnes. Therapeutic agents are known from the prior art, which are as varied as the forms of training for acne and its causes; only 13-cis-retinoic acid or halogenated glucocorticoids should be mentioned here. Azelaic acid has, however, proven to be a particularly effective anti-acne active ingredient, as is described, for example, in US Pat. No. 4,386,104 (Schering). The disadvantage here, however, is that azelaic acid, especially in higher concentrations, cannot be incorporated stably into formulations and, because of the unprotected acid group, can cause skin irritation again.

Accordingly, the object of the present invention was to provide new derivatives of azelaic acid which are at least comparable in their anti-inflammatory and anti-acne effects to the pure acid, but reliably avoid the disadvantages of the prior art. Description of the invention

The invention relates to condensation products of proteins and / or protein hydrolyzates with azelaic acid.

Surprisingly, it was found that the new condensation products have the same anti-inflammatory and anti-acne properties as the pure acid, but are additionally active as anionic emulsifiers and can thus be incorporated into preparations in higher concentrations and can also be incorporated in the process prove stable in case of temperature stress.

Proteins and protein hydrolyzates

Known protein sources, such as wheat gluten, are fundamentally possible as protein components for the new surfactants. However, instead of high molecular weight polypeptides, so-called protein hydrolyzates are preferred. Protein hydrolyzates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein, and in particular wheat, rice, pea, silk and soy protein, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then have an average molecular weight in the range of 600 to 4,000, preferably 2,000 to 3,500. Accordingly, protein hydrolyzates are oligopeptides. Overviews of the production and use of protein hydrolyzates are, for example, from G. Schuster and A. Domsch in Seifen Öle Fette Wachsen, 108, 177 (1982) and Cosm.Toil. 99, 63 (1984), by H.W.Steisslinger in Parf. Kosm. 72, 556 (1991) and F. Aurich et al. in Tens.Surf.Det. 29, 389 (1992). Wheat proteins or wheat protein hydrolyzates are preferably used as protein components.

azelaic acid

The condensation of the proteins or protein hydrolyzates can be carried out in a manner known per se, azeiaic acid chloride is preferably used. In this context, for example, the reviews by G. Schuster et al. in Parf.Kosm. 45, 337 (1964) or O. Muscio et al. in J.Am.Oil.Chem.Soc. 59, 217 (1982), in which the acylation products of proteins are described. The reaction, which is a Schotten-Baumann acylation, usually takes place at temperatures in the range from 30 to 80 and in particular 50 to 60 ° C., at a pH in the range from 8 to 12, where it is known as has proven to be particularly advantageous - based on the basic nitrogen of the protein component - from 0.1 to 2 and preferably from 0.4 to 1.6 mol equivalents of azelaic acid derivative. The condensation products are preferably passed through Addition of bases neutralizes and are then present as alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium or glucammonium salts, especially as sodium or potassium salts.

Industrial applicability

Because of their emulsifying properties and excellent skin-cosmetic compatibility, the new condensation products are particularly suitable for use in cosmetics and pharmaceuticals. Another object of the invention therefore relates to their use for the production of cosmetic and / or pharmaceutical preparations in which they can be present in amounts of 0.1 to 50, preferably 1 to 25 and in particular 5 to 10% by weight. Since the new anionic surfactants have a tyrosine-inhibiting effect, another object of the invention relates to their use as depigmenting agents. While azelaic acid is known for use in pharmacy, but it is difficult to incorporate it in stable form into preparations, especially in large quantities, these disadvantages are reliably overcome by using the new condensation products. Accordingly, further objects of the invention relate to their use as an anti-inflammatory active ingredient and for the manufacture of a medicament for acne, especially acne vulgaris.

Cosmetic and / or pharmaceutical preparations

The anionic surfactants according to the invention can be used to produce cosmetic and / or pharmaceutical preparations, such as, for example, hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations, powders or Serve ointments. These agents can also be used as further auxiliaries and additives, mild surfactants, oil bodies, co-emulsifiers, superfatting agents, pearlescent waxes, consistency agents, thickeners, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, stabilizers, biogenic agents, deodorants, antiperspirants, Antidandruff agents, film formers, swelling agents, UV light protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, tyrosine inhibitors (depigmentation agents), solubilizers, perfume oils, dyes and the like.

Typical examples of suitable mild, ie particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid taurides, fatty acid glutamates, α-Oiefinsulfonate, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides and / or alkyl amidobetaines. Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-Ci3-carboxylic acids with linear C6- C ₂₂ fatty alcohols such as myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, ristylerucat mu-, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetyle- rucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate , Stearylerucat, isostearyl, isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, isostearyl behenate, Isostearyloleat, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, 0- leyloleat, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenyli- sostearat, behenyl oleate, behenyl behenate, behenyl erucate , Erucylmyr istate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucylerucate. In addition, esters of linear C6-C22 fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols are suitable (such as propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols, triglycerides based on Cε-Cio fatty acids, liquid mono- / di- / triglyceride mixtures based on C6-Cιs fatty acids, esters of C6-C ₂ 2- Fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-Ci2-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 C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or ver branched C6-C22 alcohols (e.g. 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 esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as squalane , Squalene or dialkylcyclohexanes.

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

> Adducts of 2 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, with alkylphenols with 8 to 15 carbon atoms in the alkyl group and Alkylamines with 8 to 22 carbon atoms in the alkyl radical;

> Alkyl and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the alk (en) yl radical and their ethoxylated analogs; Addition products of 1 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;

> Adducts of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil; > Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated, branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

> Partial esters of polyglycerin (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose) / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;

> Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol.

> Mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

> Wool wax alcohols;

> Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

> Polyalkylene glycols as well

> Glycerine carbonate.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out. Ci2 / ιβ fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.

Alkyl and / or alkenyl 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 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.

Typical examples of suitable Partialgiyceride are hydroxystearic acid, stearic acid diglyceride hydroxy, isostearic acid, Isostearinsäurediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolsäuremoglycerid, Ricinolsäurediglycerid, Linolsäuremonoglycerid, Linoisäure- diglyceride, Linolensäuremonoglycerid, Linolensäurediglycerid, Erucasäuremonoglycerid, erucic acid diglyceride, tartaric acid monoglyceride, \ Λ mono acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, malic acid ediglyceride as well as their technical mixtures, which may still contain small amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the partial glycerides mentioned are also suitable.

As sorbitan sorbitan, sorbitan sesquiisostearate, Sorbitan, sorbitan triisostearate, sorbitan monooleate, sorbitan, sorbitan, sorbitan come tanmonoerucat, Sorbitansesquierucat, Sorbitandierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, sorting bitansesquiricinoleat, Sorbitandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, sorbitan sesquihydroxystearat, Sorbitandihydroxystearat, Sorbitantrihydroxystearat, Sorbitanmonotartrat , Sorbitane sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan citrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan malate, sorbitan tri- maleate and their technical gem. Addition products of 1 to 30, preferably 5 to 10, mol of ethylene oxide onto the sorbitan esters mentioned are also suitable.

Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyearylate-3 (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL) , Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Isostearate and their mixtures.

Examples of other suitable polyol esters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, taig fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.

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-dimethylammonium glycinate, for example the coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example the coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazoiine each with 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are before understood surface-active compounds which, in addition to a Cs / .β-alkyl or acyl group, contain at least one free amino group and at least one -COOH or -Sθ3H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12 / iβ-acylsarcosine.

Finally, cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.

Substances such as, for example, lanolin and lecithin and polyethoxylated or aeylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.

Pearlescent waxes, for example, are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of 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.

Suitable consistency agents are primarily fatty alcohols or hydroxyfatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.

Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates , (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, Fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.

Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as e.g. Luviquat® (BASF), condensation products of polyglycols and amines, quaternized Koliagenpolypept.de, such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, e.g. Amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, e.g. described in FR 2252840 A and its crosslinked water-soluble polymers, cationic chitin derivatives such as quaternized chitosan, optionally microcrystalline, condensation products of dihaloalkylene, such as e.g. Dibromobutane with bisdialkylamines, e.g. Bis-dimethylamino-1, 3-propane, cationic guar gum, e.g. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as e.g. Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / Vinyiacrylat copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyl / Acrylate copolymers, octylacrylamide / methyl methacrylate / tert.butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers and optionally derivatized cellulose ether.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature. Simethicones, which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable. A detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91, 27 (1976).

Typical examples of fats are glycerides, natural waxes such as candelilla wax, carpina wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice, etc. are used as waxes. germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walrus, lanolin (wool wax), pretzel fat, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes. In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives. The person skilled in the art understands the term lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Lecithins are therefore often referred to in the professional world as phosphatidylcholines (PC). Examples of natural lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. In contrast, phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats. In addition, sphingosines or sphingolipids are also suitable.

Metal salts of fatty acids, such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.

Biogenic active substances are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

Cosmetic deodorants counteract, mask or eliminate body odors. Body odors arise from the action of skin bacteria on apocrine sweat, whereby unpleasant smelling breakdown products are formed. Accordingly, deodorants contain active ingredients which act as germ-inhibiting agents, enzyme inhibitors, odor absorbers or odor maskers.

In principle, all substances effective against gram-positive bacteria are suitable as germ-inhibiting agents, such as. B. 4-hydroxybenzoic acid and its salts and esters, N- (4-chlorophenyl) -N ^' - (3,4 dichlorophenyl) urea, 2,4,4 ^' -Trichlor-2 ^' -hydroxydiphenylether (Triclosan), 4th -Chlor-3,5-dimethylphenol, 2,2 ^' - methylene-bis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1, 2-propanediol, 3-iodo-2-propynyl butyl carbamate, chlorhexidine, 3,4,4 ^' trichlorocarbanilide (TTC), antibacterial fragrances, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol , Phenoxyethanol, glycerol monolaurate (GML), diglycerol monocaprinate (DMC), salicylic acid N-alkylamides such as B. salicylic acid-n-octylamide or salicylic acid-n-decylamide. Esterase inhibitors are, for example, suitable as enzyme inhibitors. 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 thereby reduce odor. 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, monoethyl glutarate, diethyl glutarate, adipic acid, adipic acid - 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, and zinc glycinate.

Suitable odor absorbers are substances that absorb odor-forming compounds and can retain them to a large extent. They lower the partial pressure of the individual components and thus also reduce their speed of propagation. It is important that perfumes must remain unaffected. Odor absorbers are not effective against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known to the person skilled in the art as "fixators", such as, for example, the main component. B. extracts of Labdanum or Styrax or certain abietic acid derivatives. Fragrance agents or perfume oils act as odor maskers, which, in addition to their function as odor maskers, give the deodorants their respective fragrance. Perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches as well as resins and balms. Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones and methylcedryl ketone, and the alcohols are anethole, citronellellone Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Essential oils of lower volatility, which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil. Bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, citro- nenoil, mandarin oil, orange oil, allylamylglycolate, cyclovertal, lavandin oil, muscatel sage oil, ß- damascone, geranium oil bourbon, cyclohexylsalicylate, vertofix coeur, iso-e-super, fixolide np, everynyl, iraldein gamma, phenylacetic acid, benzyl acetate, geranylacetate , Romilat, Irotyl and Floramat used alone or in mixtures.

Antiperspirants (antiperspirants) reduce sweat formation by influencing the activity of the eccrine sweat glands and thus counteract armpit wetness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:

> astringent active ingredients,

> Oil components,

> nonionic emulsifiers,

> Coemuigators,

> Consistency generator,

> Auxiliaries such as B. thickeners or complexing agents and / or

> non-aqueous solvents such as As ethanol, propylene glycol and / or glycerin.

Salts of aluminum, zirconium or zinc are particularly suitable as astringent antiperspirant active ingredients. Such suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds e.g. B. with propylene glycol-1, 2nd Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds, for. B. with amino acids such as glycine. In addition, customary oil-soluble and water-soluble auxiliaries can be present in smaller amounts in antiperspirants. Such oil-soluble aids can e.g. his:

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

> synthetic skin-protecting agents and / or

> Oil-soluble perfume oils.

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

As anti-dandruff agents, Octopirox® (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1 H) -pyridone monoethanolamine salt), Baypival, Pirocton Olamin, Ketoconazol®, (4th -acetyl-1 - {- 4- [2- (2.4-dichloro- phenyl) r-2- (1 H-imidazol-1-ylmethyl) -1, 3-dioxylan-c-4-ylmethoxyphenyl} piperazine, selenium disulfide, sulfur colloidal, sulfur polyethylene glycol sorbitan monooleate, sulfuric rinole polyethoxate, sulfur tar distillates or in combination, salicylic acid Hexachlorophene), undexylenic acid monoethanolamide sulfosuccinate sodium salt, Lamepon® UD (protein undecylenic acid condensate, zinc pyrethione, aluminum pyrition and magnesium pyrithione / dipyrithione magnesium sulfate).

Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.

Montmorillonites, clay minerals, pemules and alkyl-modified carbopol types (Goodrich) can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).

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

> 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. 3- (4-methylbenzylidene) camphor as described in EP 0693471 B1;

> 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;

> Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);

> Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, 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 di-2-ethylhexyl 4-methoxybenzmalonate;

> Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1 '-hexyloxy) -1, 3,5-triazine and octyl triazone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb ® HEB);

> Propane-1,3-dione, e.g. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione;

> 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, alkylammonium, alkanolammonium 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, e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoyl-methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light protection pigments, namely finely dispersed metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs from the spherical shape in some other way. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found 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. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine) , Carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (eg dihydroliponic acid), auro- thioglucose, propylthiouracil and and are 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) as well as sulfoximine compounds (e.g. buthionocinsulphoxinoxides, homophysinoxysulfoximines, - sulfones, penta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids ( e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile 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 re 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 its derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, camosin, butylhydroxytoluene, butylhydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone and derivate, derivatives, manic acid, derivatives, manic acid and its derivatives, manic acid and its derivatives, manic acid and its derivatives, manic acid and its derivatives its derivatives (eg ZnO, ZnS0) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg 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 ingredients.

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

> Glycerin;

> Alkylene glycols, such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 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 sucrose; > Aminosugars, such as glucamm,

> Dialcohol amines, such as diethanolamm or 2-amino-1,3-propanedol

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation. NN-diethyl-m-toluamide, 1,2-pentanediol or Ethyl butylacetylaminopropionate in question, dihydroxyacetone is suitable as a self-tanning agent. Examples of tyrosine inhibitors which prevent the formation of melanin and are used in depigmenting agents are arbutin, kojic acid, cumaic acid and ascorbic acid (vitamin C)

Perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of bleeds (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchou, petitgrain), fruits (anise, coriander, cumin) , Juniper), fruit peels (bergamot, lemon, oranges), roots (macis, angelica, celery, cardamom, costus, ins calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grassers ( Tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, mountain pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials such as civet and castoreum are also suitable Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Li nalylacetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. For example, benzylethyl ether, the aldehydes such as citric acid; , to the ketones eg the ionones, α-isomethyionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams Fragrances used, which together produce an appealing fragrance. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil l, linden blutenol, juniper berry oil, vetiverol, olibanol, galbanumol, labolanumol and lavandinol. Bergamotteol, dihydromyrcenol, lilial, lyral citronellol, phenylethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldisolamide, benzene bromide, linaloole, linaloole, linaloole, linaloole, linalool, linalool, linalool, linalool, fore, linalool , Sandelice, Citronenol, Mandaπnenol, Orangenol Allylamylglycolat, Cyclovertal, Lavandinol, Muscatel Sage Oil, ß-Damascone, Geraniumol Bourbon Cyclohexylsa cylat, Vertofix Coeur, Iso-E-Super, Fixo de NP, Evernyl, Iraldein gamma, Phenyl vinegar acid, geranyl acetate, benzyl acetate, rose oxide, romilllate, irotyl and floramate used alone or in mixtures.

The dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes" by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition. The agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.

Examples

Manufacturing example H1. 1,000 kg of wheat protein hydrolyzate (M = 2,200) were adjusted to a pH of 9.5 by adding aqueous sodium hydroxide solution. The solution was heated to 50 ° C. and treated with such an amount of azelaic acid chloride that a nitrogen content was finally found in the condensation product. based on basic nitrogen in the hydrolyzate - of 1.2 mol equivalents gave the hydrochloric acid released during the condensation was collected by adding further sodium hydroxide solution. The mixture was then stirred for a further 2 h

Manufacturing example H2. Example H1 was repeated, but the nitrogen content was adjusted to a value of 1.6 molar equivalents

Manufacturing example H3. Example H1 was repeated using 1,000 kg of soy protein hydrolyzate (M = 2,500)

Manufacturing example H4. Example H1 was repeated using 1,000 kg of rice protein hydrolyzate (M = 2,800)

Manufacturing example H5. Example H1 was repeated using potassium hydroxide solution

A number of formulation examples are given in Table 1

Table 1

Cosmetic preparations (water, preservative ad 100 wt .-%)

(1-4) hair conditioner, (5-6) hair conditioner, (7-8) shower bath, (9) shower gel, (10) washing lotion Table 1

Cosmetic preparations (water, preservative ad 100 wt .-%) - continued

(11-14) “Two-in-One” shower bath, (15-20) shampoo Table 1

Cosmetic preparations (water, preservative ad 100 wt .-%) - continued 2

(21-25) bubble bath, (26) soft cream, (27, 28) moisturizing emulsion, (29, 30) night cream Table 1

Cosmetic preparations (water, preservative ad 100 wt .-%) ^■ continued 3

(31) W / O sunscreen, (32-34) W / O sunscreen, (35, 38, 40) O / W sunscreen (36, 37, 39) O / W sunscreen

Claims

claims

1. Condensation products of proteins and / or protein hydrolyzates with azelaic acid.

2. Process for the preparation of anionic surfactants, in which proteins and / or protein hydrolyzates are condensed with azelaic acid derivatives.

3. The method according to claim 2, characterized in that vegetable proteins and / or protein hydrolyzates are used.

4. Process according to claims 2 and / or 3, characterized in that wheat proteins and / or wheat protein hydrolyzates are used.

5. The method according to at least one of claims 2 to 4, characterized in that azelaic acid chloride is used.

6. The method according to at least one of claims 2 to 5, characterized in that - based on the basic nitrogen of the protein components 0.1 to 2 mol equivalents of azelaic acid derivative is used.

7. Use of condensation products according to claim 1 for the production of cosmetic and / or pharmaceutical preparations.

8. Use according to claim 7, characterized in that the preparations are depigmenting agents.

9. Use of condensation products according to claim 1 as an anti-inflammatory active ingredient

10. Use of condensation products according to claim 1 for the manufacture of a medicament for acne.