MXPA00001191A - Preservative system for personal hygiene products - Google Patents

Abstract

The invention relates to the use of a mixture of at least one quarternary ammonium compound and at least one anionic preservative and/or at least one a-hydroxycarboxylic acid as a preservative system for personal hygiene products. The invention also relates to a preservative system containing at least one quaternary ester compound (esterquat) and at least one alkaline salicylate in a weight ratio of 1:20 to 100:1.

Description

CONSERVATIVE SYSTEM FOR PERSONAL HYGIENE PRODUCTS The invention relates to the preservation of body hygiene products, especially the preservation of hair hygiene products with the aid of quaternary ammonium compounds and anionic preservatives and / or alpha-hydroxycarboxylic acids. . The invention also relates to a mixture based on special quaternary ammonium compounds, which are known as esterquats, and sodium salicylate, as well as its use as a preservative for personal care products. The human body, especially human hair, is currently treated in various ways with cosmetic preparations (hair treatment means). These treatments include the cleaning of the body and hair with shampoo and preparations for bathing, and the bleaching, dyeing and hair formation with means to make the hair have a permanent shape, dyes and preparations for styling. The hair treatment means, formulated as a hair cure or as a hair rinse, usually have water or fat-soluble ingredients of various types in aqueous emulsions. The preservation of these emulsions to maintain their capacity, especially in the case of long-term storage, is sometimes difficult. The quaternary ammonium compounds, which are used in numerous means for the care of body hygiene, especially in most of the means for the treatment of the hair, play a certain microbicidal action, which however is not sufficient for the preservation alone . It was found that a very good preservation of the product can be obtained for personal hygiene, especially a hair care product, through a preservative system having a combination of at least one quaternary ammonium compound and at least one anionic preservative. and / or at least one alpha-hydroxycarboxylic acid. Surprisingly it was observed that these substances provide a synergistic increase in action. The object of the present invention is the use of a mixture of at least one quaternary ammonium compound and at least one anionic preservative and / or at least one alpha-hydroxycarboxylic acid as a preservative system for personal care products. Preferably, it is, in the case of the personal care product, a hair care product. Among the hair care products, in accordance with the present invention, hair care products that have only an aesthetic use are also considered, such as, for example, dyes or agents to permanently maintain the shape of the hair. . As the quaternary ammonium compound, polymers and monomers can be used. Within the framework of the polymers which can be used according to the present invention, cationic polymers, which have an ammonium group, are generally present. Preferred cationic polymers are, for example: quaternary cellulose derivatives, such as those known as Celquat® and Polymer JR® which are commercially available; the compounds Celquat® H 100, Celquat® L 200 and Polymer JR® 400 are preferred quaternary cellulose derivatives; - polysiloxanes with quaternary groups - polymeric dimethyldiallylammonium salts, and their copolymers with esters and amides of acrylic acid and methacrylic acid which are known under the trademark Merquat® 100 (poly (dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) which can be found in the market and are examples of such cationic polymers; copolymers of vinylpyrrolidones with quaternary derivatives of acrylate and dialkylamino methacrylate, for example, copolymers of vinylpyrrolidone-dimethylamino quaternary methacrylate of diethyl sulfate; such compounds are commercially available under the names Gafquat® 734 and Gafquat® 755; vinylpyrrolidone-ethoimidazolinium chloride copolymers, such as those offered under the trademark Luviquat®, polyvinyl quaternary alcohol as well as the polymers known under the following trademarks - Polyquaterniu 2, Polyquaternium 7, - Polyquaternium 18 and - Polyquaternium 27 with quaternary nitrogen atoms in the main polymer chain. In general terms, it is preferable that, as quaternary ammonium compounds, a compound from the group of cationic surfactants is chosen. Among the preferred cationic surfactants are the quaternary ammonium compounds. Preferred are ammonium halides, especially chloride and bromide, such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride, such as, for example, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, dicetyl dimethyl ammonium chloride, dicetyl dimethyl ammonium bromide, stearyltrimethylammonium chloride, distearyldihanedylammonium chloride, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride. Quaternary ammonium compounds are also suitable quaternary ester compounds, which are known as "esterquats", which are preferred due to their good biological decomposition capacity. In this regard we refer for example to WO 91/01295, according to which triethanolamine is partially esterified in the presence of subphosphorous acid with fatty acids, air is passed through and finally quaternized with dimethyl sulfate or ethylene oxide. Representatives of the state of the art can be found in US 3,915,867, US 4,370,272, EP-A 0 239 910, EP-A 0 293 955 A2, EP-A 0 295 739 and EP-A 0 309 052. They can be found generalities on this topic by R. Puchta et al. in Tens.Surf.Det., 3_0, 186 (1993), M. Brock in Tens.Surf.Det., 30, 394 (1993) and R. Lager an et al. in J.Am. Oil.Chem. Soc., TI, 97 (1994). An example of esterquats are the quaternary salts of triethanolamine ester of fatty acids of the general formula I i GR, CO (-OCHÍCHJ "OCH-C? N * -C? ^^ (I), CHJCHJ0 { -CH ^ C3 ^^ OLR, wherein R 1 CO represents an acyl radical with in total from 6 to 22 carbon atoms, R 2 and R 3 independently represent hydrogen or R 1 CO, R 4 represent an alkyl radical with 1 to 4 carbon atoms or a group (CH 2 CH 20) q H -, m, n and p in sum represent 0 or numbers from 1 to 12, q represents numbers from 1 to 12 and X ~ represents haiogenide, alkyl sulfate, or alkyl phosphate.

Typical examples of triethanolamine quaternary salts of fatty acids, which may be found in accordance with the present invention, are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, acid oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid, as well as their technical mixtures, as obtained, for example, by the division of natural fats and oils under pressure. Preferably, C? 2-??? Cocoß coconut fatty acids are used, in particular partially hardened palm fatty acids or C seß-iß tallow fatty acids, as well as C? 6--_8 fatty acids rich in elaidic acid. For the preparation of the triethanolamine quaternary salts of fatty acids of the general formula I, the fatty acids and triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1. Taking into account the technical properties of use of the esterquats, the use ratios from 1.2: 1 to 2.2: 1 are preferred, and preferably from 1.5: 1 to 1.9: 1. The triethanolamine quaternary salts of preferred fatty acids of general formula I represent technical mixtures of monoesters, diesters and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from palm fatty acids or technical sesame Cißiß (iodine value). from 0 to 40). From the employment technique perspective, the triethanolamine salts of quaternary fatty acids of the general formula I are especially advantageous when R 1 CO represents an acyl radical with 16 to 18 carbon atoms, R 2 represents R 4 -CO, R 3 represents hydrogen, R 4 represents a methyl group, m, n and p represent 0 and X "represents methyl sulfate Apart from the triethanolamine quaternary salts of fatty acids of the general formula I, esterquats obtained from quaternary ester salts can also be taken into consideration. fatty acids with diethanolalkylamines of the formula II, wherein R5C0 represents an acyl radical with a total of 6 to 22 carbon atoms, R6 represents hydrogen or R5CO, as well as R7 and R8 independently represent alkyl radicals with 1 to 4 hydrogen atoms, myn overall represent 0 or numbers from 1 to 12 and X "represents haiogenide, alkyl sulfate or alkyl phosphate, etc. Suitable additional esterquats are quaternary salts of fatty acid esters with 1,2-dihydroxypropyldialkylamines of the formula III, R "0 (-CH.CH.O) _OCR» I I rRn-N * M.CH-CHOO (^: H.}. CH30.R, ^ X < m), wherein R9C0 represents an acyl radical with a total of 6 to 22 carbon atoms, R10 represents hydrogen or R9CO, R 11 R 12 and R independently between them represent alkyl residues with 1 to 4 carbon atoms, m and n globally represent 0 or numbers from 1 to 12 and X ~ represents haiogenide, alkyl sulfate or alkyl phosphate. As regards the choice of the preferred fatty acids and the optimum degrees of esterification, the examples given for I apply also for the esterquats of formulas II and III. Usually the esterquats are obtained in the form of alcoholic solutions of 50 to 90% by weight, which, depending on the need, can be diluted with water without problem.

The substances described in relation to formulas I to III are individual natural substances, so that for use in accordance with the present invention, in general terms, mixtures of these substances can also be handled. It is also possible to use mixtures of technical substances, which can be obtained from manufacturing processes in various configurations. If the quaternary ammonium compounds are not esterquats, it is preferred, in accordance with the present invention, when the quaternary ammonium compound is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride, or when it is a mixture of the two compounds. The anionic preservative is preferably an alkali metal salt of an organic acid or a mixture of alkali metal salts of one or more organic acids. Salts of organic acids which can be used, for example, for the preservation of foods and / or cosmetics as antimicrobial preservatives are preferred as to the salts used in accordance with the present invention. These include, for example, salts of formic acid, acetic acid, propionic acid, lactic acid, sorbic acid, benzoic acid, salicylic acid, or levulinic acid, or mixtures of two or more of the aforementioned acids.

As the alkali metal salts, basically all the salts of the aforementioned acids can be used with lithium, sodium, potassium, rubidium or cesium. Preferably, however, the sodium and potassium salts of the aforementioned acids, especially the sodium salts, are used. Among the preferred anionic preservatives are the alkali metal salts of salicylic acid, especially sodium salicylate. Alternatively, or in addition to at least one anionic preservative, it is possible, according to the present invention, to use at least one alpha-hydroxycarboxylic acid. Preferred alpha-hydroxycarboxylic acids are lactic acid, tartaric acid, malic acid, or citric acid; Lactic acid, malic acid and tartaric acid are preferred. Of course, alpha-hydroxycarboxylic acids can also be used in the form of their physiologically compatible salts, especially alkali metal salts, ferrous alkali metal salts and aluminum salts. The use of a combination from a quaternary ammonium compound, an anionic preservative and an alpha-hydroxycarboxylic acid as a preservative system may be preferred in accordance with the present invention. When using a binary mixture, a quaternary ammonium compound may be preferred in combination with an ammonium solvent. The weight ratio between the quaternary ammonium compound and the anionic preservative or the alpha-hydroxycarboxylic acid is, in general terms, within a range of 1:20 to 100: 1. The ammonium quaternary compounds are used, in general terms, within a concentration range of about 0.1 to about 10% by weight, relative to the overall product according to the present invention. Especially preferred are amounts of about 0.5 to 7, and more especially about 0.8 to 5% by weight. The anionic preservatives are used, in general terms, in a concentration of from about 0.1 to about 2% by weight, preferably from about 0.5 to about 1% by weight, based on the total preparation containing the anionic preservative. The alpha-hydroxycarboxylic acids are preferably used in amounts of about 0.1 to about 0.5% by weight, based on the total preparation. The aforementioned limits may, in some countries, be affected by local regulations. As regards a good biological decomposition capacity of the preservative system used, the use of a quaternary ester compound as an ammonium quaternary compound is preferred. By esterquats, within the context of the present invention, the aforementioned quaternary ammonium compounds of the general formulas I, II and III are understood. The combination of esterquats with the alkali metal salts of salicylic acids is especially preferred, the combination with sodium salicylate being especially preferred. The object of the present invention is therefore a preservative system, which contains as active substances at least one quaternary ester compound (esterquat) and at least one alkali salicylate in a weight ratio of from about 1:20 to about 100: 1 . Sodium salicylate is preferably used as the alkali salicylate. A further object of the present invention is a preservative system as described above, wherein distearoylethylhydroxyethylammonium methosulfate is used as the quaternary ester compound (INCI name: hydroxyethylammonium distearoylethyl ethosulfate, marketed, for example, as Dehyquart® F 75, manufacturer: Henkel KgaA, Dusseldorf). The object of the present invention is also the use of a preservative system, which contains as active substance at least one quaternary ester compound (esterquat) and at least one alkali salicylate in a weight ratio of 1:20 to 100: 1 in a product for body hygiene. The combination of active substances suitable as a preservative system, described above, made from quaternary ammonium compound and anionic preservative, can be used in numerous preparations for body care, especially for hair care. Among them, for example, the following agents may be mentioned for hair care such as shampoo, hair rinses, hair treatments, fluids for hair tips, dyes, hair spray or means for permanent waving of the hair. hair. In addition to the combination of active preservatives, numerous compounds can be found in the final preparation, which have, for example, a cleansing action, vitality promotion, coloring, or permanent training. If the preservative system according to the present invention is used, for example, in shampoo, then, in general terms, in addition to the combination of active preservatives there is also at least one anionic, zwitterionic, amphoteric surfactant or not ionic All surfactant, anionic substances suitable for use in the human body are, in principle, suitable for use together with the combination of active preservatives according to the present invention, the preservative system, insofar as they are not incompatible with the cationic components of the preservative system. The specialist knows whether an incompatibility of this type exists for certain compounds or can be determined by simple experiments. Such surfactant, anionic agents are characterized by an anionic group that provides solubility in water such as, for example, at least one carboxylate, sulfate, sulfonate or phosphate group and at least one hydrogencarbonate group, preferably at least one lipophilic alkyl group with from about 10 to about 20 carbon atoms. In addition, glycol ether or polyglycol ether groups, ester groups, ether groups, amide groups as well as hydroxyl can be found in the molecules. Examples of suitable anionic surfactants are: linear fatty acids with 10 to 22 carbon atoms (soaps) ether carboxylic acids of the formula R14-0 (-CH2-CH20) x- CH2-COOH, wherein R14 is a linear alkyl group with 10 to 22 carbon atoms and x = 0 or 1 to 16, amide ether carboxylate of the formula [R15-NH (-CH2-CH2-0) n-CH2-COO] mZ, wherein R15 represents a saturated acyl radical or unsaturated, linear or branched having 2 to 29 carbon atoms, n represents an integer from 1 to 10, represents the numbers 1 or 2 and z represents a cation within the group of alkali metals or ferrous alkali metals, acyl sarcoside with to 18 carbon atoms in the acyl group, acyl aramid with 10 to 18 carbon atoms in the acyl group, acyl isothionate with 10 to 18 carbon atoms in the acyl group, monoalkyl and dialkyl ester of sulfosuccinic acid with 8 to 18 atoms of carbon in the alkyl group and monoalkyl ester ilpolyoxyethyl sulphosuccinic acid with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethylic groups, linear alkane sulfonate with 12 to 18 carbon atoms, • - linear alpha-olefin sulfonate with 12 to 18 carbon atoms, alpha-sulfo fatty acid methyl ester of C 12-18 fatty acids, alkyl sulphate and alkyl propyl glycol ether sulfate of the formula R 16 (-CH 2 -CH 0) x-S 0 3 H, wherein R 16 preferably represents a linear alkyl group with 10 to 18 carbon atoms and x-0 or 1 to 12, hydroxyalkyl polyethylene glycol ether and / or hydroxyalkyl polypropylene glycol sulphated ether according to DE-A 37 23 354, sulfonate of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A 39 26 344, - ester of tartaric acid and citric acid with alcohols, which represent products of the addition of approximately 2 to 15 molecules of ethyl oxide eno and / or propylene oxide to fatty alcohols of 8 to 22 carbon atoms, all in the form of alkali metal salts, ferrous alkali metal salts and / or ammonium salts, preferably in the form of their sodium, potassium, magnesium and / or ammonium salts as well as salts of monoalkanola onium, dialkanolammonium and / or trialkanolammonium with 2 or 3 carbon atoms in the alcohol group. 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, as well as mono alkyl ether and dialkyl ether of sulfosuccinic acid with 8 to 18 carbon atoms. carbon in the alkyl group and monoalkyl polyoxyethyl ester of sulfosuccinic acid having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups. In addition to the anionic surfactants presented, nonionic surfactants may also be found in the preparations according to the present invention containing preservative system. They contain, for example, a hydrophilic group, a polyol group, a polyalkylene glycol ether group or a combination of polyol- and polyglycol ether groups. Such compounds are, for example: - addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide in linear fatty alcohol with 8 to 22 carbon atoms or in fatty acids with 12 to 22 carbon atoms or to alkylphenols with 8 to 15 carbon atoms in the alkyl group, - monoester and diester of C ?2-C22 fatty acids of addition products of 1 to 30 moles of ethylene oxide in glycerin, alkyoglycoside and C8-C22 alkyl oligoglycoside and its ethoxylated analogues as well as - addition products of 5 to 60 moles of ethylene oxide in castor oil and / or hardened castor oil. In a further embodiment, it is preferred to choose alkyl polyglycoside of the general formula R170 (-Z) x as the nonionic surfactant. In the aforementioned compounds, the alkyl radical R17 contains from 6 to 22 carbon atoms and can be both linear and branched. Preferred are primary linear or branched alkyl radicals in the methyl of the second position. Such R17 alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-arythyl, 1-cetyl and 1-stearyl radicals. Especially preferred are 1-octyl, 1-decyl, 1-lauryl or 1-myristyl radicals. By using what is known as "oxo-alcohol" as starting substances, compounds with an odd number of carbon atoms in the alkyl chain are obtained mainly. The alkyl polyglycosides that can be used in the preparations according to the present invention may contain, for example, only one alkyl radical determined R17. Alkyl polyglycosides are usually made from natural fats and oils or mineral oils. In this case the alkyl radical R17 represents mixtures corresponding to the initial compounds or corresponding to the corresponding preparation of these compounds. Alkyl polyglycosides, in which R17 represents essentially C8 and CIO alkyl groups, represents essentially C12 and C14 alkyl groups, represent essentially C8 to C16 alkyl groups or alternatively represents essentially C12 to C16 alkyl groups. As sugar Z, monosaccharides or oligosaccharides can be used. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lixose, allose, altrose, mannose, gulose, iodine, talose and sucrose. The preferred sugars are glucose, fructose, galactose, arabinose and sucrose; glucose is especially preferred. The alkyl polyglycosides that can be used according to the present invention contain, on average, from 1.1 to 5 sugar units. Preferred are alkyl polyglycosides, in which x represents from 1.1 to 1.6. Alkyl polyglycosides in which x represents from 1.1 to 1.4 are especially preferred. Also the alkoxylated homologs of the aforementioned alkyl polyglycosides can be used in accordance with the present invention. These homologs can, on average, contain up to 10 units of ethylene oxide and / or propylene oxide per alkyl glycoside unit. In the compounds used as surfactants with alkyl groups, it can be treated in each case with pure substances. However, in general terms, for the preparation of these substances, it is preferred to start from vegetable or animal raw materials in such a way that mixtures of substances are obtained with a raw material each time different according to the number of carbon atoms in the alkyl chain. In the case of surfactants, which are addition products of ethylene oxide and / or propylene oxide in fatty alcohols or derivatives of these addition products, products with a distribution of "normal" homologs such as those that present a distribution of narrow homologs. By "normal" distribution of homologs we mean mixtures of homologs which are obtained by the reaction of fatty alcohol and alkylene oxide with the use of alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrow distributions of homologs are obtained to the contrary when, for example, hydrotalcite, iron alkali metal salts of ether carboxylic acids, oxide, hydroxide or alkoxide of ferrous alkali metals are used as catalysts. The use of products with a narrow distribution of homologs may be preferred. Preferably, preparations made using a preservative system according to the present invention contain zwitterionic, anionic and / or nonionic surfactants in amounts of 0.5 to 40% by weight, especially 0.5 to 20% by weight, and greater preference of 1 to 5% by weight, in relation to the total preparation. The preparations, which contain the preservative system according to the present invention, are usually in the form of aqueous or aqueous-alcoholic solutions or dispersions. Preferably, they are water-based formulations, as well as formulations containing less than 15% by weight of alcohol, based on the weight of the total preparation, especially ethanol. In the case of special preparations, alcohol-based formulations, especially based on ethanol, may also be preferred. In addition to the combination of mandatory active preservatives mentioned above or in place of one or more of the above-mentioned additional compounds, the preparations may contain a vitamin and / or a vitamin derivative. Basically the water-soluble or oil-soluble vitamins as well as the derivatives of water-soluble or oil-soluble, natural, synthetic vitamins are suitable for this purpose. Particularly suitable vitamins and vitamin derivatives are, for example, vitamin A, vitamin E, vitamin E acetate, vitamin E nicotinate, vitamin F, vitamin B3, vitamin B, nicotinic acid amide, vitamin H, vitamin C, vitamin B5 and its derivatives, especially panthenol, pantothenic acid, calcium pantothenate, pantotenyl ethyl ether, panthenol hydroxypropyl tertiarychloride (Panthequat®, Innovachem), panthenol and panthenol triacetate. Obviously analogous derivatives, for example pantotenyl propyl ether, pantotenyl butyl ether, as well as additional saturated or unsaturated, branched or linear homologs, can also be used. The same applies in the case of pantothenic acid salts, whose counter-ions are not limited to calcium, but also include all physiologically acceptable metal cations, for example, the alkali and ferrous alkali metals, especially magnesium, sodium or potassium. The invention also encompasses the use of all possible stereoisomers of various vitamins, especially vitamin B5 and its derivatives of both D-form and L-form and all mixtures of both forms in accordance with the present invention. In general terms, vitamins or vitamin derivatives are used in the preparations according to the present invention, in amounts of 0.01 to 30% by weight, in relation to the overall preparation. Usually, ready-to-use aqueous preparations containing 0.02 to 15, especially 0.02 to 8% by weight, are preferred for processing. In many cases, amounts between 0.05 and 5% by weight are sufficient. In the case of concentrates it can be advantageous to use vitamins and / or vitamin derivatives in amounts of 0.05 to 30% by weight, especially 1 to 25% by weight, and more preferably 3 to 20% by weight. The preparations according to the present invention can also contain, in addition to the components A and B, alone or together with one or more of the aforementioned ingredients, protein hydrolysates. Under the term "protein hydrolysates" we mean a mixture of amino acids, oligopeptides and polypeptides as well as their derivatives. The amino acids that can be used according to the present invention are, for example, arginine, Usin, cysteine, glutamine, asparagine and valine. Mixtures of amino acids are also suitable, such as those obtainable by the use of essentially complete basic, acid or enzymatic hydrolysis of animal or vegetable proteins. The oligopeptides and polypeptides which can be used according to the present invention are, for example, animal or vegetable proteins or their (partial) hydrolysates obtained through the acid, basic or enzymatic route. Suitable proteins are, for example, keratin, collagen, elastin, soy protein, milk protein, casein, fibroin, sericin, wheat protein, silk protein and almond protein. Keratin as well as plant proteins may be preferred according to the present invention. By hydrolysis, mixtures of substances with average molecular masses are obtained within a range of about 400 to about 50,000 daltons. Typical average molar masses are within a range of approximately 500 to approximately 8000 daltons. In accordance with the present invention, hydrolysates obtained from keratin, silk protein and vegetable proteins are preferred. By amino acid derivatives, oligopeptides and polypeptides are understood, in accordance with the present invention, their cationic derivatives as well as their condensation products with fatty acids. A cationic derivative can be obtained by the reaction of compounds, which usually contain quaternary ammonium groups either by reaction with corresponding amines and finally by quaternization. A number of these quaternary protein hydrolysates can be obtained on the market, for example: cationic collagen hydrolyzate, for example, the product obtainable under the trade name Lamequat® L on the market (INCI Nomenclature: hydrolyzed collagen hydroxypropyl lauryldimonium; Chemische Fabri Grünau), cationic keratin hydrolyzate, for example the product that can be commercially available under the tradename Croquat® (CTFA - naming: hydrolyzed hydroxypropyl keratin from cocodimony; Croda) - cationic wheat hydrolyzate, obtainable under the trademark Hydrotriticum® QL (CTFA nomenclature: hydrolyzed wheat hydroxypropyl protein of lauryldimony; Croda) the product obtainable under the trademark Crotein® Q, in accordance with INCI a "Hydrolyzed Collagen of Hydroxypropyltrimonium" (Croda) as well as the hydrolyzate of the quaternary albumin that can be obtained as Lexein® QX 3000 (Inolex). For the production of condensation products from protein hydrolysates with fatty acids, acidic components, oleic acid, ironic acid, undecylenic acid, coconut fat acid and abietic acid are preferred. These condensation products can also be in the form of salts, especially sodium, potassium and triethanolamine salts. The condensation products based on collagen hydrolyzate also carry the following names Oleoyl Hydrolyzed Collagen, Myristoyl Hydrolyzed Collagen, Oleoyl Hydrolyzed Animal Collagen, Potassium Coco Hydrolyzed Animal Protein, TEA Abietoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collageny TEA Coconut Hydrolyzed Collagen. Commercial products are, for example, Lamepon® LPO, Lamepon® 4 SK, Lamepon® UD, Lamepon® 460, Lamepon®PA TR, Lamepon® ST 40 and Lamepon® S (Grünau) as well as Lexein® A 240, Lexein® S 620 and Lexein® A 520 (Inolex). It is also possible to use condensation products of elastin hydrolysates with fatty acids, for example lauric acid (CTFA nomenclature: Lauroyl Hydrolyzed Elastin). Crolastin®AS (Croda) is a corresponding commercial product. Under the term Promois EGCP, a hydrolysed cocoa wheat potassium protein (Seiwa) is obtained. Other commercial products that may be employed in accordance with the present invention are Lexein® 200 (Inolex), Lamepon® PO-TR, Lamepon®PA-K, Lamepon®S-MV and Lamepon®S-TR (Grünau) and Crotein® CCT (Croda). The combination of active substances according to the present invention obtained from quaternary ammonium compounds and anionic preservatives can also be used in hair regeneration preparations and also in products which have the sole purpose of changing the appearance of the hair, for example , dyes. If the combination of active substances according to the present invention is used as a dye, then in addition to at least one quaternary ammonium compound and at least one anionic preservative, said combination must also contain a dye or an initial dye product for dye the keratin fibers. To achieve the coloring effect, the oxidation dyes contain, in general terms, two groups of substances, which are known as developers and couplers. Preferred developer components, according to the present invention, are p-phenylenediamine, p-tolylene diamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) 2,5-diaminobenzole, N, N-Bis- (2-hydroxy-ethyl) -p-phenylenediamine, 2- (2,5-diaminophenoxy) -ethanol, l-phenyl-3-carboxyamido-4-amino-pyrazolone-5,4-amino-3-methylphenol, 2, 4, 5, 6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminspyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4, 5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-amino-phenol, 4,4'-diaminodiphenylamine, 4-amino-3-fluorophenol, 2-α-inomethyl-4-amino-phenol, 2-hydroxymethyl-4-aminophenol , bis- (2-hydroxy-5-aminophenyl) -methane, 1,4-bis- (4-aminophenyl) -diazacycloheptane, 1,3-bis (N (2-hydroxyethyl) -N (4-aminophenylamino)) - 2-propanol, 4-amino-2- (2-hydroxyethoxy) -phenol as well as derivatives of 4, 5-diaminopyrazole according to EP 0 740 741 or WO 94/08970, such as, for example, 4, 5-diamino-1- (2'-hydroxyethyl) -pyrazol. The preferred coupler components, according to the present invention, are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, -aminophenol , resorcinol, resorcin monomethyl ether, m-phenylenediamine, l-phenyl-3-methyl-pyrazolone-5, 2,4-dichlor-3-a-naphthol, 1,3-bis- (2,4-diaminophenoxy) -propane, 4-Chlorresorcin, 2-chlor-6-methyl-3-aminophenol, 2-methylresorcin, 5-methylresorcin, 2,5-dimethylresorcin, 2,6-dihydroxypyridine, 2,6-dia? T? Inopyridine, 2-amino- 3-hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluol, 2,6-bis- (2-hydroxyethylamino) -toluol, 2, 4-diaminophenoxyethanol, 1-methoxy-2-amino-4- (2-hydroxyethylamino) -benzole, 2-methyl-4-chlor-5-amino-phenol, 6-methyl-1, 2, 3, 4- tetrahydro-quinoxaline, 3,4-methylenedioxyphenol, 3-methylenedioxianiline, 2,6-dimethyl-3-amino-phenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2-methyl -5- (2-hydroxyethylamino (-phene) l and 2,6-dihydroxy-3,4-dimethylpyridine. These developers and couplers are usually used in free form. In the case of substances with amino groups, the salt form, especially the hydrochloride and sulphate form, may be preferred. The hair colorants contain both the developer and the coupler, preferably in an amount of 0.005 to 20% by weight, especially 0.1 to 5% by weight, relative to the overall oxidation dye. The developer and the coupler, in general, are used among them in approximately molar amounts. While it has been found that a molar use is beneficial, a certain excess of an initial product of individual oxidation dye is not a drawback, such that the developer and the coupler can be in a molar ratio of 1: 0.5 to 1. : 3, especially from 1: 1 to 1: 2. In a further embodiment the hair colorants may contain direct dyes, either as unique coloring components for further modification of the hue or in addition to initial products of oxidation dyes. The direct dyes are usually nitrophenylenediamines, nitroa inophenols, azo dyes, anthraquinone or indophenols. Direct dyes known under international trademarks are preferred, for example, brands HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC RED BN, Basic Red 76 , HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Víolet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17, as well as 4-amino-2- acid Nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1, 2, 3, 4-tetrahydrocquinoxaline, hydroxyethyl-2-nitrotoluidine, picric acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-l-hydroxy-4-nitrobenzole. The products according to the present invention, according to this embodiment, contain the direct dyes preferably in an amount of 0.01 to 20% by weight, based on the total dye. In addition, the preparations according to the present invention can also contain dyes that are found in nature such as, for example, red henna, neutral henna, black henna, chamomile flower, wood, black tea, bark, sage, blue wood, root, cato and ancusa root. Additional coloring components that may contain the dyes obtained according to the present invention are: indoles and indolines, as well as their physiologically compatible salts. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole. , 6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-rt? Ethyl-5,6-dihydroxyindoline, N-ethyl-5, 6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. As to the dyes that can be used in the hair dyes according to the present invention, we refer to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes), as well as chapter 8, pages 264-267; initial products of oxidation dye), published in volume 7 of the series "Dermatology" (Hrg.: Ch., Culnan and H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, as well as the " Europáischen Inventar der Kosmetik-Rohstoffe ", published by the European Community, which can be obtained in the form of diskette in the Bundesverband Deutscher Industrie- and Handelsunternehmen für Arzneimittel, Reformwaren und Kdrperpflegemittel eV, Mannheim. It is not necessary that the initial oxidation dye products or optional direct dyes be uniform compounds. In the hair dyes according to the present invention, according to the manufacturing processes for the individual dyes, other components can be included in smaller amounts, insofar as they do not adversely affect the result of the dye or do not have to be excluded due to other reasons such as, for example, toxicological reasons. For the preparation of the dyes, the initial products of oxidation dye are added to the preparation according to the present invention, which contains at least one component A and one component B. For hair coloring the preparations according to the present invention they are formulated with, for example, creams, aerosols, emulsions, gels or as foaming solutions containing surfactants such as, for example, shampoo, foam aerosol or otherwise suitable for application to hair. The oxidative development of the coloration can basically be done with oxygen from the air. Preferably, however, a chemical oxidant is used, especially when a brightness effect on human hair is desired apart from coloring. As the oxidant, persulfates, chlorites and especially hydrogen peroxides or their addition products in urea, melamine or sodium borate can be used. It is also possible to carry out oxidation with the help of enzymes. Enzymes can be used to transfer oxygen from the air to the developer or to enhance the effect of small amounts of oxidant present. An example of an enzymatic procedure is represented by the procedure by which the action of small quantities is reinforced (for example 1% and less, based on the total substance) of hydrogen peroxide through peroxidase. The preparation of the oxidant can be mixed directly before coloring the hair with the preparation made from initial products of oxidation dye. The ready-to-use hair colorant obtained in this way should preferably have a pH value within a range of 6 to 10. The use of hair colorant in a slightly alkaline medium is especially preferred. The temperatures of use can be within a range of 15 to 40 ° C. After a penetration time of approximately 30 minutes, the hair colorant is rinsed from the dyed hair. The subsequent washing with a shampoo is not necessary when using a strong surfactant vehicle, such as a coloring shampoo. The preservative system according to the present invention can also be used for the production of permanent products. By products for permanents we understand products that serve to give a lasting shape to the keratin fibers. A permanent form of this type is obtained, in general terms, by mechanically giving a form to the fibers and the shape is consolidated through an auxiliary. Before or after this formation, the fiber is treated with the aqueous preparation of a substance that reduces keratin (permanent product) and is rinsed with water or with an aqueous solution after a time of action *. In a second step, the fiber is treated with the aqueous preparation of an oxidizing agent (fixative). After an action time it is rinsed and the fibers are released from the mechanical training aid (rollers, etc.). Permanent products contain, as a keratin-reducing substance, mercaptan, such as, for example, thioglycolic acid, thiolactic acid, thiomalic acid, mercaptoethanesulfonic acid, as well as their salts and esters, cysteamine, cysteine, colored salts and alkaline salts of sulfuric acid. Preferably they are alkali or ammonium salts of thioglycolic and / or thiolactic acid as well as the free acids. They are used in the product for permanents, preferably in concentrations of 0.5 to 1.0 g / kg, in relation to the product for total permanents, with a pH value within a range of 5 to 10, especially from 7 to 8.5. Oxidizers, such as sodium batch, potassium bromate, or hydrogen peroxide, are used as a fixative, together with customary stabilizers of aqueous hydrogen peroxide preparations for stabilization purposes. The pH value of these aqueous H202 preparations, which usually contain about 0.5 to 3.0% by weight of H202, is preferably within a range of 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Bromate-based fixatives usually contain bromate in concentrations of 1 to 10 and the pH value of the solutions is adjusted within a range of 4 to 7. Enzyme-based fixatives (peroxidase) that do not contain oxidants or contain only small amounts of oxidants, especially H202, are also suitable. Both the permanent product and the fixative can be formulated as a cream, gel or liquid. In addition, it is possible to produce the product in the form of foam aerosol driven with a fluid gas, such as, for example, mixtures of propane-butane, nitrogen, CO2, air, N20, dimethyl ether, fluorochlorocarbon-hydrogen, or mixtures thereof. in aerosol containers with a valve for foam. The fixatives can also be formulated as solids. They contain the oxidant in the form of a solid, for example, potassium bromate or sodium bromate. Shortly before use this product is mixed with water. It may also be preferred that the oxidant be formulated as a two component system. The two components are also mixed shortly before use. The two components, of which one is preferably a solution of hydrogen peroxide or an aqueous solution of another oxidant and the other component contains the usual ingredients, they are also mixed shortly before their application. The products for hair hygiene can be products that are rinsed after a certain time of action, in general terms of approximately 1 to 45 minutes, or products that remain in the hair. The preservative system according to the present invention can be used in various pH values. Preferred are, for example, hair shampoo and hair rinses as well as conditioning lotions having a pH of 2.5 to 7.0, especially 4.0 to 6.0. The pH value of the oxidation dye is, in general terms, within a range of 6.0 to 10.0, especially 7.0 to 9.0. To adjust this pH value, virtually any acid or base that can be used for cosmetic purposes can be substituted. When an acid is used to adjust the pH value, for example, the use of acetic acid, ascorbic acid, and gluconic acid may be preferred. Eventually, alpha-hydroxycarboxylic acids such as lactic acid, tartaric acid, citric acid and malic acid, in addition to their properties as part of the preservative system, can serve to adjust the pH value. According to the use and the formulation, the preparations according to the present invention can contain all the usual cosmetic additives for these purposes. Such customary additives are: amphoteric surfactants such as, for example, N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, fatty acid - alkylaminopropionics and alkylamino acids, each having 8 to 18 carbon atoms in the alkyl group, zwitterionic surfactants such as, for example, betaines and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline, anionic polymers such such as, for example, polyacrylic and polymethacrylic acids, their salts, their copolymers with esters and amides of acrylic acid and methacrylic acid and their derivatives, which can be obtained by cross-linking with polyfunctional agents; compounds of this type are, for example, under the designations Carbopol®934, Carbopol®934", Carbopol®940, Carbopol®950, Carbopol®980 and Carbopol® of EDT type (Manufacturer: all made by BF Goodrich), as well as PNC® 400 (manufacturer: 3V Sigma); nonionic polymers such as, for example, vinylpyrrolidine / vinyl acrylate copolymers, polyvinylpyrrolidine and vinylpyrrolidone / vinyl acetate copolymers, thickening agents such as, for example, agar-agar, guar gum, alginate, cellulose ether, gelatin, pectin and / or xanthan gum, structural agents such as, for example, glucose and maleic acid, hair conditioning compounds such as, for example, phospholipids such as, for example, soy lecithin, egg lecithin and kephalin, as well as oil. silicones, essences, dimethyl siloxane and cyclodextrin, solvents such as, for example, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol, dyes, anti-dandruff agents, such as climbazole, pyroctone olamine and zinc omadine, - additional substances for adjusting the pH value, active substances such as, for example, bisabolol, allantoin, and plant extracts, light protection agents, fats and waxes such as, for example, beeswax, mountain wax, paraffin, ester, glyceride and fatty alcohols, fatty acid alkanolamide, swelling and penetration agents such as, for example, PCA, glycerin, propylene glycol monoethyl ether, carbonate, hydrogencarbonate, guanidine , ureas as well as primary, secondary and tertiary phosphates, darkening agents such as, for example, latexes or styrene / acrylamide copolymers, gloss agents such as, for example, ethylene glycol monostearate and distearate or polyethylene glycol 3-distearate , impellers such as, for example, mixtures of propane-butane, N20, dimethyl ether, CO2 and air, as well as antioxidants. The invention will be explained below through some examples. Example 1: To determine the preservation effect of the combination of active substances according to the present invention, two formulations were prepared based on the following compositions: Formulation 1: 2.5% Stenol 1618 (cetearyl alcohol) Henkel 0.5% Cutina GMS (glyceryl stearate) Henkel 0.4% Eu ulgin Bl (Cerearet-12) Henkel 0.1% Cetiol OE (dicaprilic ether) Henkel 2.4% Dehyquart A (chloride of hetrimony) Henkel 2.0% Glucose qs citric acid qs Water Formulation 2: As the formulation 1, plus 0.57% sodium salicylate pH value (both formulations): approximately 2.8 Afterwards the preservation effect of exemplary formulations 1 and 2 was studied. Test microorganisms: The bacterial cultures used for the research contained the following microorganisms: Staphylococcus aureus ATCC 6538 Enterococcus faecium ATCC 6057 Escherichia coli ATCC 11229 Enterobacter aerogenes DSM 30053 Pseudomonas aeruginosa ATCC 15442 The fungal cultures used for the investigation contained the following microorganisms: - Candida albicans ATCC 10231 - Aspergillus niger ATCC 6275 - Penicilliu rubrum CMI 113729 - Trichoderma viride BAM T 21 Suspensions of standard germs with respectively 108 KBE / ml bacteria and 107 KBE / ml fungi were prepared from the aforementioned microorganisms. Ten g each of the exemplary formulations 1 and 2 were then loaded into a sterile container with 0.1 ml of bacteria suspension and 0.1 ml of fungus suspension. The mixture of the germ suspensions was carried out in a glass homogenizer with at least 10 homogenizer blades. Of the exemplary formulations loaded in this manner, two injections were applied to standard I-THL feed agar, flavored agar, standard THL feed broth and TLH-conditioned broth. The following elimination times were found (in days): Bacteria (2.5 x 105) Fungi (6 x 10b) Formulation 1: > 21 > 35 Formulation 2: 1

Claims (5)

1. CLAIMS 1. The use of a mixture consisting of: at least one quaternary ammonium compound, chosen from cationic polymers, cationic surfactants and esterquats; and at least one anionic preservative and / or at least one alpha-hydroxycarboxylic acid as a preservative system for products for body hygiene.
2. 2. The use according to claim 1, characterized in that the product for body hygiene is a product for hair care.
3. 3. The use according to claim 1, or according to claim 2, characterized in that it is, in the case of the quaternary ammonium compound, cetyltrimethylammonium bromide and / or cetyltrimethylammonium chloride.
4. 4. The use according to any of the preceding claims characterized in that the quaternary ammonium compound is at least one quaternary ester compound.
5. 5. The use according to any of the preceding claims, characterized in that in the case of the anionic preservative it is an alkali metal salt of an organic acid. The use according to claim 5, characterized in that in the case of the alkali metal salt of organic acid it is a salt of formic acid, acetic acid, propionic acid, lactic acid, sorbic acid, benzoic acid, salicylic acid or good levulinic acid. The use according to any of the preceding claims, characterized in that at least one anionic preservative of sodium salicylate is used.