EP1657296A1 - Skin-friendly detergent mixtures - Google Patents

Skin-friendly detergent mixtures Download PDF

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Publication number
EP1657296A1
EP1657296A1 EP05023929A EP05023929A EP1657296A1 EP 1657296 A1 EP1657296 A1 EP 1657296A1 EP 05023929 A EP05023929 A EP 05023929A EP 05023929 A EP05023929 A EP 05023929A EP 1657296 A1 EP1657296 A1 EP 1657296A1
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European Patent Office
Prior art keywords
chitosan
alcohol
skin
use according
derivatives
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EP05023929A
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German (de)
French (fr)
Inventor
Claudia Panzer
Manfred Weuthen
Rolf Wachter
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present application relates to the use of cationic biopolymers or their derivatives for improving the skin-friendliness of detergent mixtures, in particular dishwashing detergents.
  • Detergent mixtures are known from WO 99/03959 A1 which contain so-called ester quats, chitosan or its derivatives and protein hydrolysis next to one another.
  • ester quats so-called ester quats
  • chitosan or its derivatives protein hydrolysis next to one another.
  • the effect of chitosan in the ternary mixture is not disclosed concretely.
  • the present application in its first embodiment is the use of chitosan and / or chitosan derivatives for improving the skin compatibility of detergent mixtures.
  • the skin compatibility in the sense of the present teaching is by means of of a patch test. In the process, 20 people plaster with the test substances (FineChambers ®) are glued to their backs and left there for 24 h. A highly dilute aqueous solution of the respective test formulation is tested (eg concentrations between 1 and 2% by weight of active substance). After removal of the patches, the skin of the subjects is visually inspected after 6, 24, 48 and 78 h, respectively. The symptoms skin redness, edema formation, exfoliation and cracking are observed.
  • Chitosans are biopolymers known per se and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins of different molecular weight containing the following - idealized - monomer unit: Unlike most hydrocolloids, which are negatively charged at biological pH levels, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used. For the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities.
  • the chitin is used in a process first described by Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum.
  • the average molecular weight is preferably in the range of 100 to 5,000,000 g / mol, and more preferably in the range of 800,000 to 1,200,000 g / mol.
  • the chitosans or their derivatives have molecular weights in the range of 50,000 to 1,200,000 g / mol.
  • Such chitosans preferably have a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation 100%, in particular up to 99% and in particular in the range of 80 to 88% and preferably an ash content of less than 0.3 wt .-%.
  • anionic or nonionically derivatized chitosans such as, for example, carboxylation, succinylation or alkoxylation products, are also suitable for the purposes of the invention, with chitosan being preferred over its derivatives.
  • chitosans or chitosan derivatives whose molecular weight is greater than 50,000 g / mol and in particular greater than 100,000 g / mol.
  • the range of 50,000 to 1,000,000 g / mol and furthermore the ranges of 50,000 to 300,000 are preferred.
  • chitosans with molecular weights of 500,000 to 5,000,000 g / mol and of 300,000 to 2,000,000 g / mol are particularly preferably used.
  • anionic or nonionically derivatized chitosans such as, for example, carboxylation, succinylation or alkoxylation products, are also suitable for the purposes of the invention.
  • Chitosan itself can be in the form of a solid powder or, preferably, in the sense of the present invention, as an aqueous solution.
  • These solutions advantageously contain 0.01 to 5 wt .-% (active substance) of chitosan or the chitosan derivative.
  • Such aqueous solutions may still contain organic and / or inorganic acids in order to adjust an acidic pH of advantageously ⁇ 7, in particular from 6.5 to 4.
  • the concomitant use of other ingredients is possible and preferred.
  • the surfactants play a special role, and both nonionic, cationic and / or amphoteric surfactants can be used.
  • Particularly preferred are anionic surfactant-free preparations, since the chitosans can react with the anionic functionalities.
  • the present technical teaching also encompasses those preparations in which chitosan derivatives and anionic surfactants are formulated together.
  • the agents are free from what are known as esterquats:
  • esterquats generally denotes quaternized fatty acid triethanolamine ester salts Understood.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 and R 3 are independently hydrogen or R 1 CO
  • R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group
  • m, n and p in total are 0 or numbers from 1 to 12
  • q is numbers from 1 to 12
  • X is halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 CO
  • R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms R 2 is hydrogen or R 1 CO
  • R 4 , R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate stands.
  • the aqueous compositions of the invention contain nonionic surfactants, preferably of the alkyl (oligo) glycoside (APG) type.
  • nonionic surfactants preferably of the alkyl (oligo) glycoside (APG) type.
  • APG alkyl glycoside
  • Such compounds follow the formula (IV), R 8 O- [G] p (IV) where R 8 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
  • the alkyl or alkenyl radical R 8 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
  • Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
  • the alkyl or alkenyl radical R 8 can also be derived from primary alcohols having 12 to 22, preferably Derive 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated C12 / 14 cocoyl alcohol with a DP of 1 to 3
  • nonionic surfactants are fatty alcohols, fatty alcohol alkoxylates, in particular the ethoxylates, hydroxylated derivatives of the fatty alcohols, alkoxylated, preferably ethoxylated carboxylic acid and polyethylene glycols and derivatives thereof. Mixtures of these surfactants are possible.
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds.
  • the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid is possible.
  • suitable betaines are the carboxyalkylation products of secondary and especially tertiary amines.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C12 / 14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine , C16 / 18-Talgalkyldimethylamin and their technical mixtures. Furthermore, carboxyalkylation of amidoamines come into consideration.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • the use of a condensation product of C8 / 18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
  • imidazolines are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • condensation products of the abovementioned fatty acids with AEEA preferably imidazolines based on lauric acid or again C12 / 14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the aqueous agents of the invention may also preferably contain anionic surfactants. Suitable examples are alkylbenzenesulfonates, alkyl sulfonates and alkyl ether sulfates. Alkylbenzenesulfonates preferably follow the formula R'-Ph-SO 3 X, in which R 'is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium , Alkylammonium, alkanolammonium or glucammonium.
  • dodecylbenzenesulfonates tetradecylbenzenesulfonates, Hexadecylbentolsulfonate and their technical mixtures are used in the form of sodium salts.
  • Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are to be understood as the sulfation products of primary alcohols which have the formula R "O-SO 3 X in the R for a linear or branched, aliphatic alkyl and / or alkenyl radical with 6 to 22, preferably 12 to 18, carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium
  • Typical examples of alkyl sulphates which can be used in accordance with the invention are the sulphation products of caproic alcohol, Caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselin
  • the sulfation products may preferably be used in the form of their alkali salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C16 / 18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
  • alkyl ether sulfates are known anionic surfactants which are industrially produced by SO 3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxoalcohol polyglycol ethers and subsequent neutralization.
  • SO 3 sulfur dioxide
  • CSA chlorosulfonic acid
  • ether sulfates are those which follow the formula R "'O- (CH 2 CH 2 O), in the R"' for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n is Numbers from 1 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products of an average of 1 to 10 and especially 2 to 5 moles of ethylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts.
  • the ether sulfates may have both a conventional and a narrow homolog distribution. Particularly preferred is the use of ether sulfates based on adducts of on average 2 to 3 moles of ethylene oxide to technical C12 / 14 or C12 / 18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • chitosans with monoglycerol ether sulfates and fatty acid condensation products in the sense of US 6,013,616 is excluded from the protection.
  • the aqueous agents preferably have a neutral, but in particular an acidic pH. Typical values are between 4.0 and 7.0. Preferably, the pH is adjusted to 5.0 to 6.5.
  • aqueous compositions according to the invention containing chitosan and other suitable ingredients according to the above description can advantageously be used as so-called "protective fluid".
  • the idea behind this is that the user first brings his skin into contact with the "protective fluid” before dishwashing, wherein the chitosan or its derivatives produces a protective film on the skin, and then the user uses the dishwashing detergent or the skin in such a way protected can bring the aqueous dishwashing liquor into contact.
  • Such “protective fluids” contain the chitosan or its derivatives preferably in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 2.5 wt .-% and in particular from 0.1 to 2.5 wt .-%, based on the total funds.
  • ethanol is used, for example, in amounts of between 1 and 45% by weight, typical values being from 5 to 35% by weight and preferably from 5 to 8% by weight.
  • the aqueous compositions may also contain other film-forming compounds, such as acrylic acid copolymers, cellulose derivatives, vinylpyrrolidone-vinyl acetate copolymers in varying proportions, polymers based on vinylpyrrolidone-vinyl acetate and vinyl propionate, polyethylene oxide resins, polyvinyl acetate, polyvinyl alcohol and protein hydrolysates.
  • Film-forming agents based on natural resins are discolored shellac, sandarak resin, benzo resins and rosin. Products based on semisynthesis (condensation products of rosin and acrylic acid) are also suitable.
  • aqueous compositions Under film formers are understood substances of different composition, each dissolved or sprayed in a solvent (water, ethanol or other) on skin or hair and form after evaporation of the solvent films that take over protective or sealing tasks and support functions can.
  • additional film formers may be present in amounts of from 1 to 35% by weight, preferably in amounts of from 1 to 25% by weight and in particular from 1 to 10% by weight.
  • Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein, and in particular silk, wheat, rice and soy protein, which are cleaved by acid, alkaline and / or enzymatic hydrolysis and thereafter average molecular weight in the range of 100 to 500,000 and preferably 100 to 50,000. Further preferred ranges are at molecular weights of 500 to 5000 and in particular in the range of 600 to 4000.
  • protein hydrolyzates in the absence of a hydrophobic group are not surfactants in the classical sense, they are often used for the formulation of surfactants because of their dispersing properties.
  • aqueous compositions may also contain other, cosmetically acceptable waxes and polymers, vitamins, herbal active ingredients such as AloeVera, but also UV filters, preservatives, perfume oils and fragrances, bodying agents, solubilizers, thickeners, hydrotropes, emulsifiers, pearlescing agents and dyes. It may also contain cosmetic or pharmaceutical agents.
  • these other ingredients can be incorporated in the form of liposomes or sponges, the so-called "sponges" in the formulations.
  • a typical recipe for such agents contains from 0.01 to max. 5% by weight of chitosan or its derivatives, 1 to 5% by weight of amphoteric surfactants and 1 to 5% by weight of nonionic and / or cationic surfactants and 0.01 to 2% by weight of preservatives.
  • the pH is preferably adjusted in the range of 4 to 8.
  • the remainder to 100% by weight is water, with demineralized water being particularly preferred in all cases. If a foaming nonionic surfactant is used, these framework formulations are suitable for the production of protective foams for the skin within the meaning of the present technical teaching.
  • compositions have a composition analogous to the "protective fluids" described above, but they still contain a foaming surfactant, with the already mentioned above Alkyloligoglykosid compounds and / or cationic surfactants are preferred.
  • protective liquid As a protective liquid or "protective fluid”, the following general formula is suitable: 0.1 to 5 wt .-% chitosan or chitosan derivatives, 0.1 to 5 wt .-% a skin-care active ingredient or active ingredient mixtures (eg protein hydrolysates) and 7 to 30 Wt .-% ethanol. The remainder to 100 wt% is again (preferably demineralized) water. The quantities are based on the active substance.
  • Another object of the present invention relates to a method for gentle manual dishwashing, wherein the skin of the hands is first brought into contact with a chitosan-containing preparation and then the dishes are cleaned manually in a conventional manner with a dishwashing detergent.
  • the present teaching also includes the idea of incorporating chitosan or its derivatives into known and customary formulations of dishwashing detergents. Typically included these 10 to 30 wt .-% of anionic surfactants, 1 to 10 wt .-% amphoteric surfactants and 0 to 10 wt .-% of nonionic and / or cationic surfactants.
  • the chitosan derivatives can preferably also be used in dishwashing detergents which contain anionic surfactants.
  • aqueous agents were prepared (Table 1) - all data in wt .-% of active substance: 1 2 3 4 5 6 Chitosan 1) 0.75 0.75 0.75 0.75 0.75 0.5 Wheat protein hydrolyzate 2) 1 1 N, N-dimethyl-N- (cocamidopropyl) ammoniumacetobetain 1.5 1.5 1.2 C 8-10 alkyl polyglucoside 1.2 0.6 C8-16-alkyl-1,4-glucoside 2.5 preservative 0.1 0.1 0.1 0.1 0.1 ethanol 20 water rest rest rest rest rest 1) Hydagen® HCMS-LA (from Cognis, 50,000 to 1,000,000 g / mol, degree of deacetylation at least 80%). 2) Gluadin® W 40 (Cognis)
  • the agents 1 to 5 can be used in foam form, as so-called "protection mousse".
  • Recipe 6 represents a liquid agent which is e.g. before manual dishwashing is applied to the skin.

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Abstract

Use of chitosan and/or its derivates (I) for the improvement of the skin compatibility of detergent mix. Independent claims are also included for: (1) an aqueous preparation (II) comprising (I) and surfactant, under the condition that (I) is free of ester group containing cationic quaternary ammonium compounds; and (2) method for skin preserving manual dishwashing comprising first applying a chitosan-containing preparation on the skin of the hands and subsequently cleaning the dishes manual in conventional method with a dishwashing agent.

Description

Die vorliegende Anmeldung betrifft die Verwendung von kationischen Biopolymeren bzw. von deren Derivaten zur Verbesserung der Hautfreundlichkeit von Detergensgemischen, insbesondere von Geschirrspülmitteln.The present application relates to the use of cationic biopolymers or their derivatives for improving the skin-friendliness of detergent mixtures, in particular dishwashing detergents.

Zur manuellen Reinigung harter Oberflächen, insbesondere von Geschirr werden üblicherweise flüssige oder gelförmige Detergensmischungen verwendet. Die Mittel sind dabei möglichst hoch konzentriert, weisen einen möglichst niedrigen Kältetrübungspunkt auf, entwickeln auch bei hoher Fettbelastung der Waschflotte noch ausreichend viel Schaum, spülen möglichst effizient und sind nicht hautreizend.
Aus dem Stand der Technik sind bereits Lösungen für dieses Anforderungsprofil bekannt: Die US 6,013,616 offenbart hautfreundliche Tensidgemische, die Monoglycerinethersulfate neben einer ternären Mischung aus Kondensationsprodukten von Fettsäure-isethionaten, -tauride und -sarcosinaten enthalten und die sich zur Herstellung bzw. zur Verwendung als Geschirrspülmittel eignen. Die Mitverwendung von Chitosan wird als optional genannt, ohne dass konkret die Wirkung dieses Additivs offenbart würde.
Aus der WO 99/03959 A1 sind Detergensgemische bekannt, die sogenannte Esterquats, Chitosan bzw. dessen Derivate und Proteinhydrolyse nebeneinander enthalten. Die Wirkung des Chitosans in der ternären Mischung wird aber nicht konkret offenbart.For manual cleaning of hard surfaces, especially dishes, usually liquid or gel detergent mixtures are used. The funds are concentrated as highly as possible, have the lowest possible cold cloud point, develop even with high levels of fat in the wash liquor still plenty of foam, rinse as efficiently as possible and are not irritating to the skin.
Solutions for this requirement profile are already known from the prior art: US Pat. No. 6,013,616 discloses skin-friendly surfactant mixtures which comprise monoglycerol ether sulfates in addition to a ternary mixture of condensation products of fatty acid isethionates, taurides and sarcosinates and which are suitable for preparation or use as dishwashing agents suitable. The concomitant use of chitosan is said to be optional without specifically disclosing the effect of this additive.
Detergent mixtures are known from WO 99/03959 A1 which contain so-called ester quats, chitosan or its derivatives and protein hydrolysis next to one another. However, the effect of chitosan in the ternary mixture is not disclosed concretely.

Es besteht aber ein konstanter Bedarf, Tensidmischungen, insbesondere solche zum manuellen Geschirrspülen, in ihrer Wirkung auf die menschliche Haut zu verbessern, insbesondere die Hautverträglichkeit. Dabei soll es insbesondere möglich sein, auch unabhängig von der Zusammensetzung des Geschirrspülmittels eine Verbesserung der dermatologischen Eigenschaften zu erzielen.However, there is a constant need to improve surfactant mixtures, in particular those for manual dishwashing, in their effect on the human skin, in particular the skin compatibility. It should be possible in particular, regardless of the composition of the dishwashing detergent to achieve an improvement in the dermatological properties.

Es wurde gefunden, dass die Verwendung bestimmter kationischer Biopolymerer, die zur Filmbildung geeignet sind diese Aufgabe lösen kann.It has been found that the use of certain cationic biopolymers suitable for film formation can accomplish this task.

Gegenstand der vorliegenden Anmeldung in ihrer ersten Ausführungsform ist dabei die Verwendung von Chitosan und/oder Chitosanderivaten zur Verbesserung der Hautverträglichkeit von Detergensgemischen. Die Hautverträglichkeit im Sinne der vorliegenden Lehre wird mittels eines Patch-Tests ermittelt. Dabei werden 20 Personen Pflaster mit den Testsubstanzen (FineChambers ®) auf den Rücken geklebt und 24 h dort belassen. Geprüft wird eine stark verdünnte wässerige Lösung der jeweiligen Testrezeptur (z.B. Konzentrationen zwischenl und 2 Gew.-% Aktivsubstanz). Nach dem Entfernen der Pflaster wird die Haut der Probanden jeweils visuell nach 6, 24, 48 und 78 h begutachtet. Dabei werden die Merkmale Hautrötung, Ödembildung, Exfoliation und Rissbildung beobachtet.
Chitosane stellen an sich bekannte Biopolymere dar und werden zur Gruppe der Hydrokolloide gezählt. Chemisch betrachtet handelt es sich um partiell deacetylierte Chitine unterschiedlichen Molekulargewichtes, die den folgenden - idealisierten - Monomerbaustein enthalten:

Figure imgb0001
Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopolymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Körperpflegemitteln sowie pharmazeutischen Zubereitungen eingesetzt. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei in einem Verfahren das erstmals von Hackmann et al. beschrieben worden ist, üblicherweise zunächst durch Zusatz von Basen deproteiniert, durch Zugabe von Mineralsäuren demineralisiert und schließlich durch Zugabe von starken Basen deacetyliert, wobei die Molekulargewichte über ein breites Spektrum verteilt sein können.
Das durchschnittliche Molekulargewicht liegt vorzugsweise im Bereich von 100 bis 5.000.0000 g/mol und insbesondere im Bereich von 800.000 bis 1.200.000 g/mol. Vorzugsweise weisen die Chitosane bzw. deren Derivate Molekulargewichte im Bereich von 50.000 bis 1.200.000 g/mol auf. Solche Chitosane weisen vorzugsweise eine Viskosität nach Brookfield (1 Gew.-%ig in Glycolsäure) unterhalb von 5000 mPas, einen Deacetylierungsgrad bis 100 %, insbesondere bis zu 99 % und insbesondere im Bereich von 80 bis 88 % auf sowie vorzugsweise einen Aschegehalt von weniger als 0,3 Gew.-%.
Neben den Chitosanen als typischen kationischen Biopolymeren kommen im Sinne der Erfindung auch anionisch bzw. nichtionisch derivatisierte Chitosane, wie z.B. Carboxylierungs-, Succinylierungs- oder Alkoxylierungsprodukte in Frage, wobei Chitosan gegenüber seinen Derivaten bevorzugt Verwendung findet.
Im Sinne der vorliegenden technischen Lehre sind insbesondere solche Chitosane bzw. Chitosanderivate bevorzugt, deren Molekulargewicht größer 50.000 g/mol und insbesondere größer 100.000 g/mol beträgt. Bevorzugt ist dabei auch der Bereich von 50.000 bis 1.000.000 g/mol und weiterhin der Bereiche von 50.000 bis 300.000. Besonders bevorzugt werden aber Chitosane mit Molgewichten von 500.000 bis 5.000.000 g/mol und von 300.000 bis 2.000.000 g/mol verwendet.
Neben den Chitosanen als typischen kationischen Biopolymeren kommen im Sinne der Erfindung auch anionisch bzw. nichtionisch derivatisierte Chitosane, wie z.B. Carboxylierungs-, Succinylierungs- oder Alkoxylierungsprodukte in Frage.The present application in its first embodiment is the use of chitosan and / or chitosan derivatives for improving the skin compatibility of detergent mixtures. The skin compatibility in the sense of the present teaching is by means of of a patch test. In the process, 20 people plaster with the test substances (FineChambers ®) are glued to their backs and left there for 24 h. A highly dilute aqueous solution of the respective test formulation is tested (eg concentrations between 1 and 2% by weight of active substance). After removal of the patches, the skin of the subjects is visually inspected after 6, 24, 48 and 78 h, respectively. The symptoms skin redness, edema formation, exfoliation and cracking are observed.
Chitosans are biopolymers known per se and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins of different molecular weight containing the following - idealized - monomer unit:
Figure imgb0001
 Unlike most hydrocolloids, which are negatively charged at biological pH levels, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used. For the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities. The chitin is used in a process first described by Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum.
The average molecular weight is preferably in the range of 100 to 5,000,000 g / mol, and more preferably in the range of 800,000 to 1,200,000 g / mol. Preferably, the chitosans or their derivatives have molecular weights in the range of 50,000 to 1,200,000 g / mol. Such chitosans preferably have a Brookfield viscosity (1% by weight in glycolic acid) below 5000 mPas, a degree of deacetylation 100%, in particular up to 99% and in particular in the range of 80 to 88% and preferably an ash content of less than 0.3 wt .-%.
In addition to the chitosans as typical cationic biopolymers, anionic or nonionically derivatized chitosans, such as, for example, carboxylation, succinylation or alkoxylation products, are also suitable for the purposes of the invention, with chitosan being preferred over its derivatives.
For the purposes of the present technical teaching, particular preference is given to those chitosans or chitosan derivatives whose molecular weight is greater than 50,000 g / mol and in particular greater than 100,000 g / mol. The range of 50,000 to 1,000,000 g / mol and furthermore the ranges of 50,000 to 300,000 are preferred. However, chitosans with molecular weights of 500,000 to 5,000,000 g / mol and of 300,000 to 2,000,000 g / mol are particularly preferably used.
In addition to the chitosans as typical cationic biopolymers, anionic or nonionically derivatized chitosans, such as, for example, carboxylation, succinylation or alkoxylation products, are also suitable for the purposes of the invention.

Chitosan selbst kann als festes Pulver vorliegen oder und im Sinne der vorliegenden Erfindung bevorzugt, als wässerige Lösung. Diese Lösungen enthalten vorteilhafterweise 0,01 bis 5 Gew.-% (Aktivsubstanz) an Chitosan bzw. dem Chitosanderivat. Bevorzugt sind wässerige Mittel, die 0,01 bis 2,5 Gew.-%, vorzugsweise 0,05 bis 1,0 Gew.-% und insbesondere 0,05 bis 0,5 Gew.-% an Chitosan bzw. den Chitosanderivaten enthalten. Solche wässerigen Lösungen können noch organische und/oder anorganische Säuren enthalten, um einen sauren pH von vorteilhafterweise < 7, insbesondere von 6,5 bis 4 einzustellen.Chitosan itself can be in the form of a solid powder or, preferably, in the sense of the present invention, as an aqueous solution. These solutions advantageously contain 0.01 to 5 wt .-% (active substance) of chitosan or the chitosan derivative. Preference is given to aqueous compositions containing from 0.01 to 2.5% by weight, preferably from 0.05 to 1.0% by weight and in particular from 0.05 to 0.5% by weight, of chitosan or the chitosan derivatives , Such aqueous solutions may still contain organic and / or inorganic acids in order to adjust an acidic pH of advantageously <7, in particular from 6.5 to 4.

Bei solchen wässerigen Zubereitungen ist die Mitverwendung von weiteren Inhaltsstoffen möglich und bevorzugt. Dabei kommt den Tensiden eine besondere Rolle zu, wobei sowohl nichtionische, kationische und/oder amphotere Tenside Mitverwendung finden können. Besonders bevorzugt sind anionentensid-freie Zubereitungen, da die Chitosane mit den anionischen Funktionalitäten reagieren können. Es sind aber von der vorliegenden technischen Lehre auch solche Zubereitungen umfasst, bei denen Chitosanderivate und anionische Tenside zusammen formuliert werden.
In einer bevorzugten Ausführungsform sind die Mittel jedoch frei von sogenannten Esterquats: Unter der Bezeichnung "Esterquats" werden im allgemeinen quaternierte Fettsäuretriethanolaminestersalze verstanden. Es handelt sich dabei um Stoffe, die den Formeln (I), (II) oder (III) folgen,

Figure imgb0002
in der R1 CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 und R3 unabhängig voneinander für Wasserstoff oder R1CO, R4 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.
Figure imgb0003
 in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff oder R1CO, R4 und R5 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.
Figure imgb0004
 in der R1CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff oder R1CO, R4, R6 und R7 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Die Mitverwendung dieser Tenside der obigen Formeln (I), (II) und (III) zusammen mit Chitosanen bzw. deren Derivaten in einer Rezeptur, wie sie in der WO 99/03959 A1 offenbart werden ist nicht Gegenstand der vorliegenden technischen Lehre.In such aqueous preparations, the concomitant use of other ingredients is possible and preferred. The surfactants play a special role, and both nonionic, cationic and / or amphoteric surfactants can be used. Particularly preferred are anionic surfactant-free preparations, since the chitosans can react with the anionic functionalities. However, the present technical teaching also encompasses those preparations in which chitosan derivatives and anionic surfactants are formulated together.
In a preferred embodiment, however, the agents are free from what are known as esterquats: The term "esterquats" generally denotes quaternized fatty acid triethanolamine ester salts Understood. These are substances which follow the formulas (I), (II) or (III),
Figure imgb0002
 in the R 1 CO for an acyl radical having 6 to 22 carbon atoms, R 2 and R 3 are independently hydrogen or R 1 CO, R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
Figure imgb0003
 in the R 1 CO for an acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen or R 1 CO, R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate.
Figure imgb0004
 in the R 1 CO for an acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen or R 1 CO, R 4 , R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate stands. The concomitant use of these surfactants of the above formulas (I), (II) and (III) together with chitosans or their derivatives in a formulation, as disclosed in WO 99/03959 A1 is not the subject of the present technical teaching.

Dagegen ist es bevorzugt, dass die erfindungsgemäßen wässerigen Mittel nichtionische Tenside, vorzugsweise vom Typ der Alkyl(oligo)glycoside (APG) enthalten. Solche Verbindungen folgen der Formel (IV),

         R8O-[G]p     (IV)

in der R8 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (IV) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muss und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R8 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R8 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.In contrast, it is preferred that the aqueous compositions of the invention contain nonionic surfactants, preferably of the alkyl (oligo) glycoside (APG) type. Such compounds follow the formula (IV),

R 8 O- [G] p (IV)

where R 8 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (IV) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here especially If p = 1 to 6 can be assumed, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R 8 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C 8 -C 10 (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C 8 -C 18 coconut fatty alcohol and in a proportion of less than 6% by weight C 12 - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 8 can also be derived from primary alcohols having 12 to 22, preferably Derive 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated C12 / 14 cocoyl alcohol with a DP of 1 to 3

Weitere bevorzugte nichtionische Tenside sind Fettalkohole, Fettalkoholalkoxylate, insbesondere die Ethoxylate, hydroxylierte Derivate der Fettalkohole, alkoxylierte, vorzugsweise ethoxylierte Carbonsäure und Polyethylenglykole und deren Derivate. Auch Mischungen dieser Tenside sind möglich.Further preferred nonionic surfactants are fatty alcohols, fatty alcohol alkoxylates, in particular the ethoxylates, hydroxylated derivatives of the fatty alcohols, alkoxylated, preferably ethoxylated carboxylic acid and polyethylene glycols and derivatives thereof. Mixtures of these surfactants are possible.

Eine andere Gruppe geeigneter und bevorzugter Tenside stellen die Betaine dar. Betaine stellen bekannte Tenside dar, die überwiegend durch Carboxyalkylierung, vorzugsweise Carboxymethylierung von aminischen Verbindungen hergestellt werden. Vorzugsweise werden die Ausgangsstoffe mit Halogencarbonsäuren oder deren Salzen, insbesondere mit Natriumchloracetat kondensiert, wobei pro Mol Betain ein Mol Salz gebildet wird. Ferner ist auch die Anlagerung von ungesättigten Carbonsäuren, wie beispielsweise Acrylsäure möglich. Beispiele für geeignete Betaine stellen die Carboxyalkylierungsprodukte von sekundären und insbesondere tertiären Aminen dar. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C16/18-Talgalkyldimethylamin sowie deren technische Gemische.Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C8/18-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat.Another group of suitable and preferred surfactants are the betaines. Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds. Preferably, the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine. Furthermore, the addition of unsaturated carboxylic acids, such as acrylic acid is possible. Examples of suitable betaines are the carboxyalkylation products of secondary and especially tertiary amines. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C12 / 14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethylmethylamine, oleyldimethylamine , C16 / 18-Talgalkyldimethylamin and their technical mixtures. Furthermore, carboxyalkylation of amidoamines come into consideration. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic, elaeostearic, arachidic, gadoleic, behenic and erucic acids and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. The use of a condensation product of C8 / 18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.

Weiterhin kommen als geeignete Ausgangsstoffe für die im Sinne der Erfindung einzusetzenden Betaine auch Imidazoline in Betracht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen, wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Also suitable as suitable starting materials for the betaines to be used in the context of the invention are imidazolines. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C12 / 14 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.

Die erfindungsgemäßen wässerigen Mittel können auch vorzugsweise anionische Tenside enthalten. Geeignet sind z.B. Alkylbezolsulfonate, Alkylsulfonaten und Alkylethersulfate.
Alkylbenzolsulfonate folgen vorzugsweise der Formel R'-Ph-SO3X, in der R' für einen verzweigten, vorzugsweise jedoch linearen Alkylrest mit 10 bis 18 Kohlenstoffatomen, Ph für einen Phenylrest und X für X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Vorzugsweise werden Dodecylbenzol-sulfonate, Tetradecylbenzolsulfonate, Hexadecylbentolsulfonate sowie deren technische Gemische in Form der Natriumsalze eingesetzt.
Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel R"O-SO3X in der R für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkali-salze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von C16/18-Talgfettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze.The aqueous agents of the invention may also preferably contain anionic surfactants. Suitable examples are alkylbenzenesulfonates, alkyl sulfonates and alkyl ether sulfates.
Alkylbenzenesulfonates preferably follow the formula R'-Ph-SO 3 X, in which R 'is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium , Alkylammonium, alkanolammonium or glucammonium. Preferably, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, Hexadecylbentolsulfonate and their technical mixtures are used in the form of sodium salts.
Alkyl and / or alkenyl sulfates, which are also frequently referred to as fatty alcohol sulfates, are to be understood as the sulfation products of primary alcohols which have the formula R "O-SO 3 X in the R for a linear or branched, aliphatic alkyl and / or alkenyl radical with 6 to 22, preferably 12 to 18, carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium Typical examples of alkyl sulphates which can be used in accordance with the invention are the sulphation products of caproic alcohol, Caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's Oxosynthes e be obtained. The sulfation products may preferably be used in the form of their alkali salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C16 / 18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.

Die Verwendung von Alkylethersulfaten in Kombination mit Chitosanen bzw. deren Derivaten ist ebenfalls möglich. Alkylethersulfate ("Ethersulfate") stellen bekannte anionische Tenside dar, die großtechnisch durch SO3- oder Chlorsulfonsäure (CSA)-Sulfatierung von Fettalkohol- oder Oxoalkoholpolyglycolethern und nachfolgende Neutralisation hergestellt werden. Im Sinne der Erfindung kommen Ethersulfate in Betracht, die der Formel R"'O-(CH2CH2O) folgen, in der R"' für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, n für Zahlen von 1 bis 10 und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele sind die Sulfate von Anlagerungsprodukten von durchschnittlich 1 bis 10 und insbesondere 2 bis 5 Mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen in Form ihrer Natrium- und/oder Magnesiumsalze. Die Ethersulfate können dabei sowohl eine konventionelle als auch eine eingeengte Homologenverteilung aufweisen. Besonders bevorzugt ist der Einsatz von Ethersulfaten auf Basis von Addukten von durchschnittlich 2 bis 3 Mol Ethylenoxid an technische C12/14- bzw. C12/18- Kokosfettalkoholfraktionen in Form ihrer Natrium- und/oder Magnesiumsalze.
Die Verwendung von Chitosanen mit Monoglycerinethersulfaten sowie Fettsäurekondensationsprodukten im Sinne der US 6,013,616 ist vom Schutz ausgenommen.The use of alkyl ether sulfates in combination with chitosans or their derivatives is also possible. Alkyl ether sulfates ("ether sulfates") are known anionic surfactants which are industrially produced by SO 3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxoalcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention ether sulfates are those which follow the formula R "'O- (CH 2 CH 2 O), in the R"' for a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n is Numbers from 1 to 10 and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of addition products of an average of 1 to 10 and especially 2 to 5 moles of ethylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts. The ether sulfates may have both a conventional and a narrow homolog distribution. Particularly preferred is the use of ether sulfates based on adducts of on average 2 to 3 moles of ethylene oxide to technical C12 / 14 or C12 / 18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
The use of chitosans with monoglycerol ether sulfates and fatty acid condensation products in the sense of US 6,013,616 is excluded from the protection.

Die wässerigen Mittel weisen vorzugsweise einen neutralen, insbesondere aber einen sauren pH-Wert auf. Typisch sind dabei Werte zwischen 4,0 und 7,0. Bevorzugt wird der pH-Wert auf 5,0 bis 6,5 eingestellt.The aqueous agents preferably have a neutral, but in particular an acidic pH. Typical values are between 4.0 and 7.0. Preferably, the pH is adjusted to 5.0 to 6.5.

Die erfindungsgemäßen wässerigen Mittel, die Chitosan und andere geeignete Inhaltsstoffe gemäß der obigen Beschreibung enthalten können vorteilhafterweise als sog. "Protective Fluid" eingesetzt werden. Dahinter steht der Gedanke, dass der Anwender seine Haut vor dem Geschirrspülen zunächst mit der "Protective Fluid" in Kontakt bringt, wobei das Chitosan bzw. dessen Derivate einen Schutzfilm auf der Haut erzeugt, und anschließend der Anwender die so geschützte Haut mit dem Geschirrspülmittel bzw. der wässerigen Geschirrspüllauge in Kontakt bringen kann. Solche "protective Fluids" enthalten das Chitosan bzw. dessen Derivate vorzugsweise in Mengen von 0,01 bis 5 Gew.-%, vorzugsweise von 0,05 bis 2,5 Gew.-% und insbesondere von 0,1 bis 2,5 Gew.-%, bezogen auf die gesamten Mittel.The aqueous compositions according to the invention containing chitosan and other suitable ingredients according to the above description can advantageously be used as so-called "protective fluid". The idea behind this is that the user first brings his skin into contact with the "protective fluid" before dishwashing, wherein the chitosan or its derivatives produces a protective film on the skin, and then the user uses the dishwashing detergent or the skin in such a way protected can bring the aqueous dishwashing liquor into contact. Such "protective fluids" contain the chitosan or its derivatives preferably in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 2.5 wt .-% and in particular from 0.1 to 2.5 wt .-%, based on the total funds.

Weiterhin ist die Mitverwendung von Ethanol bevorzugt. Dabei wird das Ethanol beispielsweise in Mengen zwischen 1 und 45 Gew.-% eingesetzt, wobei typische Werte bei 5 bis 35 und vorzugsweise 5 bis 8 Gew.-% liegen können.Furthermore, the co-use of ethanol is preferred. The ethanol is used, for example, in amounts of between 1 and 45% by weight, typical values being from 5 to 35% by weight and preferably from 5 to 8% by weight.

Die wässerigen Mittel können auch noch weitere filmbildende Verbindungen enthalten, wie beispielsweise Acrylsäure-Copolymere, Cellulose-Derivate, Vinylpyrrolidon-VinylacetatCopolymerisate in unterschiedlichem Mengenverhältnis, Polymerisate auf Basis von Vinylpyrrolidon-Vinylacetat und Vinylpropionat, Polyethylenoxid-Harze, Polyvinylacetat, Polyvinylalkohol und Eiweiß-Hydrolysate. Filmbildner auf Basis natürlicher Harze sind entfärbter Schellack, Sandarak-Harz, Benzoeharze und Kolophonium. Auch Produkte auf semisynthetischer Basis (Kondensationsprodukte aus Kolophonium und Acrylsäure) sind geeignet. Unter Filmbildner werden dabei Stoffe unterschiedlicher Zusammensetzung verstanden, die jeweils, gelöst in einem Lösemittel (Wasser, Ethanol oder andere), auf Haut oder Haar aufgetragen oder aufgesprüht werden und nach dem Verdunsten des Lösemittels Filme bilden, die neben Schutz- oder Abdichtungsaufgaben auch Stützfunktionen übernehmen können. In den erfindungsgemäßen wässerigen Mitteln können solche zusätzlichen Filmbildner in Mengen von 1 bis 35 Gew.-%, vorzugsweise in Mengen von 1 bis 25 Gew.-% und insbesondere von 1 bis 10 Gew.-% enthalten sein.The aqueous compositions may also contain other film-forming compounds, such as acrylic acid copolymers, cellulose derivatives, vinylpyrrolidone-vinyl acetate copolymers in varying proportions, polymers based on vinylpyrrolidone-vinyl acetate and vinyl propionate, polyethylene oxide resins, polyvinyl acetate, polyvinyl alcohol and protein hydrolysates. Film-forming agents based on natural resins are discolored shellac, sandarak resin, benzo resins and rosin. Products based on semisynthesis (condensation products of rosin and acrylic acid) are also suitable. Under film formers are understood substances of different composition, each dissolved or sprayed in a solvent (water, ethanol or other) on skin or hair and form after evaporation of the solvent films that take over protective or sealing tasks and support functions can. In the aqueous compositions according to the invention, such additional film formers may be present in amounts of from 1 to 35% by weight, preferably in amounts of from 1 to 25% by weight and in particular from 1 to 10% by weight.

Ein weiterer bevorzugter aber optionaler Bestandteil in wässerigen Chitosan-haltigen Mitteln im Sinne der vorliegenden Erfindung sind Proteine bzw. deren Derivate, insbesondere Proteinhydrolysate. Proteinhydrolysate stellen Abbauprodukte von tierischen oder pflanzlichen Proteinen, beispielsweise Collagen, Elastin oder Keratin und vorzugsweise Mandel- und Kartoffelprotein sowie insbesondere Seiden-, Weizen-, Reis- und Sojaprotein dar, die durch saure, alkalische und/oder enzymatische Hydrolyse gespalten werden und danach ein durchschnittliches Molekulargewicht im Bereich von 100 bis 500.000 und vorzugsweise 100 bis 50.000 aufweisen. Weitere bevorzugte Bereiche liegen bei Molgewichten von 500 bis 5000 und insbesondere im Bereich von 600 bis 4000. Obschon Proteinhydrolysate in Ermangelung eines hydrophoben Restes keine Tenside im klassischen Sinne darstellen, finden sie wegen ihrer dispergierenden Eigenschaften vielfach Verwendung zur Formulierung oberflächenaktiver Mittel.Another preferred but optional ingredient in aqueous chitosan-containing agents in the context of the present invention are proteins or their derivatives, in particular protein hydrolysates. Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein, and in particular silk, wheat, rice and soy protein, which are cleaved by acid, alkaline and / or enzymatic hydrolysis and thereafter average molecular weight in the range of 100 to 500,000 and preferably 100 to 50,000. Further preferred ranges are at molecular weights of 500 to 5000 and in particular in the range of 600 to 4000. Although protein hydrolyzates in the absence of a hydrophobic group are not surfactants in the classical sense, they are often used for the formulation of surfactants because of their dispersing properties.

Weiterhin können in den erfindungsgemäßen wässerigen Mitteln noch andere Inhaltsstoffe enthalten sein, insbesondere solche, welche die menschliche Haut schonen oder pflegen. Hier sei nur beispielhaft auf Pflanzenextrakte (wässerig, alkoholische und/oder etherische Extrakte) verwiesen. Die Mittel können aber auch andere, kosmetisch verträgliche Wachse und Polymere, Vitamine, pflanzliche Wirkstoffe, wie z.B. AloeVera, aber auch UV-Filter, Konservierungsstoffe, Parfümöle und Duftstoffe, Konsistenzgeber, Solubilisatoren, Verdickungsmittel, Hydrotope, Emulgatoren, Perlglanzmittel und Farbstoffe enthalten. Es können auch kosmetische oder pharmazeutische Wirkstoffe enthalten sein. Diese weiteren Inhaltsstoffe können in Form von Liposomen oder Schwämmchen, den sog. "sponges" in die Rezepturen eingebracht werden.Furthermore, other ingredients may be present in the aqueous compositions according to the invention, in particular those which protect or care for the human skin. Here Reference is made, by way of example only, to plant extracts (aqueous, alcoholic and / or ethereal extracts). However, the agents may also contain other, cosmetically acceptable waxes and polymers, vitamins, herbal active ingredients such as AloeVera, but also UV filters, preservatives, perfume oils and fragrances, bodying agents, solubilizers, thickeners, hydrotropes, emulsifiers, pearlescing agents and dyes. It may also contain cosmetic or pharmaceutical agents. These other ingredients can be incorporated in the form of liposomes or sponges, the so-called "sponges" in the formulations.

Eine typische Rezeptur für derartige Mittel enthält 0,01 bis max. 5 Gew.-% Chitosan bzw. dessen Derivate, 1 bis 5 Gew.-% amphoterische Tenside und 1 bis 5 Gew.-% nichtionische und/oder kationische Tenside sowie 0,01 bis 2 Gew.-% an Konservierungsmitteln. Der pH-Wert ist vorzugsweise im Bereich von 4 bis 8 eingestellt. Der Rest auf 100 Gew.-% ist Wasser, wobei in allen fällen demineralisiertes Wasser besonders bevorzugt ist. Sofern ein schäumendes nichtionisches Tensid zum Einsatz kommt, eignen sich diese Rahmenrezepturen zur Herstellung von Schutzschäumen für die Haut im Sinne der vorliegenden technischen Lehre. Dabei weisen diese Mittel eine Zusammensetzung analog zu den oben beschriebenen "protective fluids" auf, allerdings enthalten sie noch ein schäumendes Tensid, wobei die bereits oben genannten Alkyloligoglykosid-Verbindungen und/oder kationische Tenside bevorzugt sind.A typical recipe for such agents contains from 0.01 to max. 5% by weight of chitosan or its derivatives, 1 to 5% by weight of amphoteric surfactants and 1 to 5% by weight of nonionic and / or cationic surfactants and 0.01 to 2% by weight of preservatives. The pH is preferably adjusted in the range of 4 to 8. The remainder to 100% by weight is water, with demineralized water being particularly preferred in all cases. If a foaming nonionic surfactant is used, these framework formulations are suitable for the production of protective foams for the skin within the meaning of the present technical teaching. In this case, these compositions have a composition analogous to the "protective fluids" described above, but they still contain a foaming surfactant, with the already mentioned above Alkyloligoglykosid compounds and / or cationic surfactants are preferred.

Als Schutzflüssigkeit oder "protective fluid" ist die folgende Rahmenrezeptur geeignet: 0,1 bis 5 Gew.-% Chitosan bzw. Chitosanderivate, 0,1 bis 5 Gew.-% eine hautpflegenden Wirkstoffs bzw. Wirkstoffgemisches (z.B. Proteinhydrolysate) und 7 bis 30 Gew.-% Ethanol. Der Rest auf 100 Gew.-% ist wiederum (vorzugsweise demineralisiertes) Wasser. Die Mengenangaben beziehen sich auf die Aktivsubstanz.As a protective liquid or "protective fluid", the following general formula is suitable: 0.1 to 5 wt .-% chitosan or chitosan derivatives, 0.1 to 5 wt .-% a skin-care active ingredient or active ingredient mixtures (eg protein hydrolysates) and 7 to 30 Wt .-% ethanol. The remainder to 100 wt% is again (preferably demineralized) water. The quantities are based on the active substance.

Ein weiterer Gegenstand der vorliegenden Erfindung betrifft ein Verfahren zum hautschonenden manuellen Geschirrspülen, wobei zunächst die Haut der Hände mit einer Chitosan-haltige Zubereitung in Kontakt gebracht wird und anschließend das Geschirr manuell in an sich bekannter Weise mit einem Geschirrspülmittel gereinigt wird.Another object of the present invention relates to a method for gentle manual dishwashing, wherein the skin of the hands is first brought into contact with a chitosan-containing preparation and then the dishes are cleaned manually in a conventional manner with a dishwashing detergent.

Die vorliegende Lehre schließt auch den Gedanken ein, Chitosan bzw. dessen Derivate in bekannte und übliche Rezepturen von Geschirrspülmitteln einzuarbeiten. Typischerweise enthalten diese 10 bis 30 Gew.-% anionische Tenside, 1 bis 10 Gew.-% amphotere Tenside und 0 bis 10 Gew.-% nichtionische und/oder kationische Tenside.
Dabei können die Chitosanderivate vorzugsweise auch in solchen Geschirrspülmitteln Verwendung finden, die anionische Tenside enthalten.The present teaching also includes the idea of incorporating chitosan or its derivatives into known and customary formulations of dishwashing detergents. Typically included these 10 to 30 wt .-% of anionic surfactants, 1 to 10 wt .-% amphoteric surfactants and 0 to 10 wt .-% of nonionic and / or cationic surfactants.
The chitosan derivatives can preferably also be used in dishwashing detergents which contain anionic surfactants.

BeispieleExamples

Es wurden die folgenden wässerigen Mittel hergestellt (Tabelle 1) - alle Angaben in Gew.-% Aktivsubstanz: 1 2 3 4 5 6 Chitosan1) 0,75 0,75 0,75 0,75 0,75 0,5 Weizenprotein-Hydrolysat2) 1 1 N,N-Dimethyl-N-(kokosamidopropyl)ammoniumacetobetain 1,5 1,5 1,2 C8-10 Alkylpolyglucosid 1,2 0,6 C8-16-Alkyl-1.4-glucosid 2,5 Konservierungsmittel 0,1 0,1 0,1 0,1 0,1 Ethanol 20 Wasser Rest Rest Rest Rest Rest Rest 1) Hydagen® HCMS-LA (Fa. Cognis, 50.000 bis 1.000.0000 g/mol, Deacetylierungsgrad min. 80 %). 2) Gluadin® W 40 (Fa. Cognis) The following aqueous agents were prepared (Table 1) - all data in wt .-% of active substance: 1 2 3 4 5 6 Chitosan 1) 0.75 0.75 0.75 0.75 0.75 0.5 Wheat protein hydrolyzate 2) 1 1 N, N-dimethyl-N- (cocamidopropyl) ammoniumacetobetain 1.5 1.5 1.2 C 8-10 alkyl polyglucoside 1.2 0.6 C8-16-alkyl-1,4-glucoside 2.5 preservative 0.1 0.1 0.1 0.1 0.1 ethanol 20 water rest rest rest rest rest rest 1) Hydagen® HCMS-LA (from Cognis, 50,000 to 1,000,000 g / mol, degree of deacetylation at least 80%). 2) Gluadin® W 40 (Cognis)

Die Mittel 1 bis 5 können in Schaumform, als sog. "Protection Mousse" verwendet werden. Rezeptur 6 stellt ein flüssiges Mittel dar, welches z.B. vor dem manuellen Geschirrspülen auf die Haut aufgetragen wird.The agents 1 to 5 can be used in foam form, as so-called "protection mousse". Recipe 6 represents a liquid agent which is e.g. before manual dishwashing is applied to the skin.

Claims (13)

Verwendung von Chitosan und/oder Chitosanderivaten zur Verbesserung der Hautverträglichkeit von Detergensgemischen.Use of chitosan and / or chitosan derivatives to improve the skin compatibility of detergent mixtures. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass ein Chitosan und/oder Chitosanderivat mit einem Molekulargewicht von 100 bis 5.000.000 g/mol verwendet wird.Use according to claim 1, characterized in that a chitosan and / or chitosan derivative having a molecular weight of 100 to 5,000,000 g / mol is used. Verwendung nach den Ansprüchen 1 bis 2, dadurch gekennzeichnet, dass ein Chitosan und/oder Chitosanderivat mit einem Molekulargewicht von 800.000 bis 1.200.000 g/mol vorzugsweise von 50.000 bis 1.200.000 g/mol verwendet wird.Use according to claims 1 to 2, characterized in that a chitosan and / or chitosan derivative having a molecular weight of 800,000 to 1,200,000 g / mol, preferably from 50,000 to 1,200,000 g / mol is used. Verwendung nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass eine wässerige Zubereitung, enthaltend das Chitosan und/oder das Chitosanderivat verwendet wird.Use according to claims 1 to 3, characterized in that an aqueous preparation containing the chitosan and / or the chitosan derivative is used. Verwendung nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass eine wässerige Zubereitung, die 0,01 bis 2,5 Gew.-%, vorzugsweise 0,05 bis 1,0 Gew.-% und insbesondere von 0,05 bis 0,5 Gew.-% Chitosan und/oder Chitosanderivate enthält.Use according to claims 1 to 4, characterized in that an aqueous preparation containing 0.01 to 2.5 wt .-%, preferably 0.05 to 1.0 wt .-% and in particular from 0.05 to 0, Contains 5 wt .-% chitosan and / or chitosan derivatives. Verwendung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass das Chitosan in Kombination mit kationischen und/oder amphoteren Tensiden verwendet wird.Use according to claims 1 to 5, characterized in that the chitosan is used in combination with cationic and / or amphoteric surfactants. Verwendung nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, dass die Chitosanderivate in Kombination mit anionischen, kationischen und/oder amphoteren Tensiden verwendet wirdUse according to claims 1 to 5, characterized in that the chitosan derivatives are used in combination with anionic, cationic and / or amphoteric surfactants Verwendung nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, dass die Detergensgemische keine anionische Tenside enthalten.Use according to claims 1 to 7, characterized in that the detergent mixtures do not contain any anionic surfactants. Verwendung nach den Ansprüchen 1 bis 8, dadurch gekennzeichnet, dass das Chitosan und/oder die Chitosanderivate in Form eines Schaums verwendet werden.Use according to claims 1 to 8, characterized in that the chitosan and / or the chitosan derivatives are used in the form of a foam. Wässerige Zubereitung, enthaltend Chitosan und/oder Chitosanderivate, sowie Tenside, mit der Maßgabe, dass die Zubereitungen frei von estergruppenhaltigen kationischen quartären Ammoniumverbindungen sind.Aqueous preparation containing chitosan and / or chitosan derivatives, as well as surfactants, with the proviso that the preparations are free of ester group-containing cationic quaternary ammonium compounds. Wässerige Zubereitung nach Anspruch 10, dadurch gekennzeichnet, dass sie ein nichtwässeriges Lösungsmittel, vorzugsweise Ethanol enthält.Aqueous preparation according to claim 10, characterized in that it contains a non-aqueous solvent, preferably ethanol. Wässerige Zubereitung nach Anspruch 11, dadurch gekennzeichnet, dass sie ein schäumendes Tensid, vorzugsweise aus der Gruppe der Alkyl(oligo) glycoside enthält.Aqueous preparation according to claim 11, characterized in that it contains a foaming surfactant, preferably from the group of alkyl (oligo) glycosides. Verfahren zum hautschonenden manuellen Geschirrspülen, dadurch gekennzeichnet, dass zunächst die Haut der Hände mit einer Chitosan-haltige Zubereitung in Kontakt gebracht wird und anschließend das Geschirr manuelle in an sich bekannter Weise mit einem Geschirrspülmittel gereinigt wird.A method for gentle manual dishwashing, which is gentle on the skin, characterized in that first the skin of the hands is brought into contact with a preparation containing chitosan and then the dishes are cleaned manually in a manner known per se with a dishwashing detergent.
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