DE10106712A1 - Liquid aqueous detergent composition comprising one or more surfactants and enzymes includes a carbohydrate as enzyme stabilizer - Google Patents

Abstract

Liquid aqueous detergent composition comprising one or more surfactants and enzymes includes a carbohydrate.

Description

The present invention relates to liquid, aqueous cleaning agents containing active enzyme with improved cleaning effect. The present invention relates to furthermore the stabilization of enzymes in corresponding aqueous detergent additives compositions and their use for cleaning hard surfaces, in particular as a hand dishwashing liquid.

Cleaning agents based on aqueous surfactant mixtures have been in the prior art since known for a long time. Appropriate cleaning agents for cleaning hard surfaces are composed so that they have a balanced ratio of different surfactants and Contain auxiliaries which provide adequate detachment and emulsification or dispersion Ensure contamination of dirt particles.

In particular for cleaning agents for use as hand dishwashing detergents, a sufficient removal of adhering dirt on dishes and dishes to be guaranteed. Furthermore, the visual appearance, as well as the Smell through suitable additives such as dyes and perfumes to the aesthetic Conceptions of the consumer are adapted.

When washing dishes with conventional hand dishwashing detergents there Problems where leftovers and / or dirt on the dishes have dried out and ent speaking stick firmly so that these impurities only with appropriate tools such as brushes and scratching sponges, only mechanically with the appropriate effort can be cleaned.  

In particular dried sugar and starch residues as well as proteins and hardened fats are with conventional hand dishwashing detergents and the washing made from them leach with difficulty.

To solve these problems, attempts have been made to add enzymes in cleaning agents and hand dishwashing agents, dried-in crusted food and dirt residues detach in the wash liquor by enzymatic activity. The basic problem Mathematics of the use of enzymes in aqueous, liquid hand dishwashing Medium concentrates, however, are the poor stability of the sensitive enzymes. In the aqueous hand dishwashing detergent concentrates such as ionic Surfactants, acids, bases and high salt concentrations usually lead to a relative rapid loss of activity of the added enzymes. The corresponding enzyme-containing Accordingly, detergents and hand dishwashing detergents proved to be nonexistent or only limited shelf life, since most of them are in a relatively short time after their manufacture lose enzymatic activity.

For cost and safety reasons can also in the hand dishwashing liquid concentrate Enzyme quantities used are not set at any desired level. In particular due to the risk of aerosol formation during the dishwashing process, the Enzyme concentrations in appropriate dishwashing detergent compositions Avoidance of health risks should be as low as possible.

WO 00/46 333 describes liquid hand dishwashing detergent compositions which Contain amylases. The amylases are in the compositions of the WO 00/46 333 stabilized at a high pH of more than 8, with additional buffer systems are added to make the pH alkaline even in the dilute lye hold.

The disadvantage of corresponding hand dishwashing detergent compositions is above all in that the high pH values of the concentrate and the diluted washing used alkali attack human skin and corresponding intolerance reactions can cause. Furthermore, in the compositions of WO 00/46 333  Enzyme destabilizing ingredients, such as citrates, are avoided that are essential for the cleaning effect is important.

There is therefore a need for cleaning agents, especially for hand dishwashing medium compositions, with good cleaning performance even when dry Food scraps and hard-to-remove contaminants, alike are skin-friendly and long-term storage stable.

The object of the present invention is therefore to ensure long-term stability as well as ver to provide inert enzyme-containing detergent compositions, which show an improved cleaning effect.

Another object of the present invention is to stabilize or maintain the activity of enzymes in single or multi-phase detergents and hands Dishwashing detergent compositions with skin-compatible pH values.

It is also an object of the present invention to add enzymes in cleaning agents stabilize without restrictions on the choice of cleaning active Ingredients and the pH value to be subjected.

The stated tasks are solved by the features of the independent claims.

Preferred embodiments result from combination with the features of Dependent claims.

According to a first aspect, the present invention provides a liquid, aqueous Detergent composition available, containing at least one surfactant and / or surfactant mixtures and at least one active enzyme, characterized thereby records that the composition comprises at least one carbohydrate.

In a second aspect, the present invention is the use of Carbohydrates with 1,6-glycosidically linked monomers, preferably selected  from the group of dextrins, in particular maltodextrin / cyclodextrins, these optionally additional calcium chloride, for stabilizing enzymes, in particular of amylases and / or proteases, in aqueous hand dishwashing detergent composition can be added.

Surprisingly, it was found that enzymes, especially amylases and the like, in aqueous detergent compositions by the addition of Let carbohydrates stabilize permanently. It was found that the addition of carbohydrates, preferably those with 1,6-glycosidically linked monomers, in particular of dextrins and particularly preferably of maltodextrin and / or cyclo dextrins, the activity of the enzymes is permanently maintained, so that long-term storage, enzyme-containing detergent compositions can be obtained. Especially cyclodextrins are preferred because these species, in addition to the enzyme-stabilizing property secondary effects such. B. have the removal of "bad smells".

It was also surprisingly found that by adding carbohydrates Enzymes, especially amylases, can be stabilized even at acidic pH values in which, for example, amylases are usually inactivated. Especially carbohydrates with 1.6 glycosidic ver are preferred for enzyme stabilization linked monomers.

“Long-term stable” means compositions that contain an enzyme residue activity of at least 50% after 8 weeks, preferably of <65% after 8 weeks and particularly preferably have at least 70% after 8 weeks.

The terms "detergent composition" and "hand dishwashing detergent "Setting" as used here refer to concentrates that are either undiluted can be applied or in cleaning and rinsing liquors with water in the usual Way to be diluted.  

The term "dishes" as used here refers to all types of kitchenware, especially porcelain, glass and metal, pots, cutlery, wood and others usually items used in the kitchen.

In the context of the present invention - unless expressly stated otherwise - the use of a salt is just as possible as the use of the corresponding one Acid / base pair of the salt, the salt or its only in situ with neutralization Solution results, even if the respective alternative is not always in the present teaching is explicitly formulated. In this sense, potassium citrate and Combination citric acid / potassium hydroxide or potassium alkylbenzenesulfonate and the Combination alkylbenzenesulfonic acid / potassium hydroxide are equivalent alternatives.

Finally, within the scope of the present invention, a certain component can be added are used for various purposes, their use is subsequently as appropriate repeatedly deliberately described. This applies, for example, to citric acid, which is both Acid used for pH adjustment as well as a phase separation aid and builder are, as well as for the anionic sulfonic acids, which also as acids and also as anionic surfactants work.

All quantities are in the present application, unless expressly otherwise mentioned, stated in% by weight and on the undiluted composition based.

The cleaning agent according to the invention can be in the form of a single or multi-phase Wording available. A multi-phase cleaning agent according to the invention has in addition to the features of the main claim, preferably at least two not mutually miscible phases which temporarily shake into an emulsion by shaking, Have the suspension and / or dispersion transferred.

In the context of the present invention, temporary is understood to mean that 90% of the ent mixing the emulsion, suspension and / or dispersion formed by shaking in the separated phases at temperatures from about 20 ° C to about 40 ° C within  2 minutes to 10 hours and the last 2% of the separation in the phases condition before shaking within a further 15 minutes to 50 hours.

In the context of the present invention, the term "phase" includes both understood liquid as well as solid phases. Multi-phase cleaning agents in the sense of Invention are both liquid / liquid and liquid / solid mixtures as well liquid / guest-shaped mixtures.

phases

In a preferred embodiment, the compositions according to the invention single phase, with an aqueous, liquid phase. With multi-phase formulation of the Detergents according to the invention as liquid / liquid mixtures are preferably two continuous liquid phases, which are not miscible with each other and are temporarily shake into an emulsion. Preferably min at least one of the liquid phases is an aqueous phase.

In the simplest case, an agent according to the invention consists of a lower one continuous phase, which consists of the entire phase I, and an upper continuous phase, which consists of the entire phase II. One or more continuous However, phases of an agent according to the invention can also contain parts of another phase contain emulsified form, so that, for example, phase I in such an agent part is present as a continuous phase I, which is the lower continuous phase of Represents means, and to a different extent as discontinuous phase I in the upper continuous phase II is emulsified. For phase II and other continuous phases the same applies.

In a preferred embodiment of the invention, the continuous phases are I and II delimited from each other by a sharp interface.

Contained in a further preferred multiphase embodiment of the invention one or both of the continuous phases I and II parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15 vol .-%, based on the volume of the respective continuous  Phase, the other phase as dispersant. The continuous phase I is then or II reduced by the volume part, the dispersant in the other phase is distributed. Agents in which phase I in amounts of 0.1 are particularly preferred to 25 vol .-%, preferably 0.2 to 15 vol .-%, based on the volume of phase II, in Phase II is emulsified.

In a further preferred multiphase embodiment of the invention, the continuous phases I and II part of the two phases as an emulsion one of the two phases in the other phase, this emulsion being characterized by two sharp Interfaces, an upper and a lower, compared to those not involved in the emulsion Parts of phases I and II are delimited.

The multiphase agents according to the invention contain phase I and phase II in one Volume ratio of 90:10 to 10:90, preferably 75:25 to 25:75, in particular 65: 35 to 35: 65.

Cleaning agents according to the invention in the form of liquid / solid mixtures are preferred have an upper aqueous phase I and a lower solid phase II, both of which Allow phases to shake temporarily into a dispersion. Especially it is preferred if the lower, solid phase consists essentially of water-insoluble or only slightly water-soluble solid components are formed.

However, an insoluble solid component can also function as a separate, solid phase in more phase compositions with two or more liquid phases. At the Shaking such agents according to the invention temporarily forms an emulsion of the liquid phases, which disperses the solid phase.

In a further multi-phase embodiment of the invention, the cleaning agent is in a combination of a liquid and a gaseous phase. In addition to air, the gas phase preferably contains other gaseous components, such as, for. B. perfume oils, protective gas (N ₂ , argon, helium and the like), oxygen and / or ozone (preferably as an oxidizing agent / disinfectant additive). Carbon dioxide (CO ₂ ) is also suitable, especially in equilibrium with water (H ₂ O + CO ₂ = H ₂ CO ₃ ). Gaseous components which are temporarily bound in the liquid phase are preferred. They can be used for the self-emptying of the packaging material, particularly preferably PET bottles. In combination with the surfactants used, they can also be used for automatic foam build-up. In this case, the external appearance of the cleaning agent can be single-phase, homogeneous. If colored gases, such as chlorine gas, are used, slightly colored to almost colorless "gas solutions" can be produced. By adjusting the pH value appropriately, the gas equilibria in the liquid phase can be significantly stabilized. Hypochlorite solutions are particularly preferred in the neutral / alkaline pH range.

PH value

The pH of the detergent compositions according to the invention is both in concentrated form and in dilute application solution 2 to 10, preferably 4-8, particularly preferably 5-7. A pH of is particularly suitable about 6-6.5.

Corresponding pH values in the preferred range of 5-7 approximately correspond the natural pH of human skin, so that the combination according to the invention settlements are compatible with the skin and in particular skin irritation due to basic pH Values are avoided.

In a preferred embodiment of the invention, the detergent compositions are neutral to slightly acidic, with a pH of 2-7, in particular 3-7, preferably 3.5-7, in particular 4-6.5, particularly preferably 5- 6, most preferably 5-6, for example 5.5, 6 or 6.5. To adjust such a pH, acids can be added to the compositions according to the invention. Inorganic acids, for example the mineral acids, for. B. hydrochloric acid, and organic acids, for example saturated or unsaturated C ₁ -C ₆ mono-, di- and tri-carboxylic acids and hydroxycarboxylic acids with one or more hydroxy groups such as citric acid, maleic acid, formic acid and acetic acid, amino sulfuric acid, C ₆ -C ₂₂ fatty acids and anionic sulfonic acids, as well as their mixtures, e.g. B. the trichloric acid-glutaric acid-adipic acid mixture obtainable from BASF with the trade name Sokalari®DCS. Particularly preferred acids are citric acid, preferably used in the form of its monohydrate citric acid × 1 H ₂ O, and the anionic sulfonic acids, and combinations of citric acid with one or more anionic sulfonic acids, especially with alkylarinsulfonic acids. Citric acid advantageously combines acid-phase separation aid and builder properties, while the anionic sulfonic acids act simultaneously as an acid and an anionic surfactant.

If necessary, one or more alkalis can also be used, for example as alkali metal, alkaline earth metal and ammonium hydroxides and carbonates and Ammonia or amines, preferably sodium and potassium hydroxide and alkanol amines, with monoethanolamine being particularly preferred.

Because, for example, pH changes often during the dishwashing process Substances are introduced into the rinse liquor in large quantities, it is preferred for Stabilization or buffering of the pH of the compositions according to the invention Add appropriate buffer substances in the application dilution, for example wise acetates, hydrogen phosphates, hydrogen sulfates, soda or alkali metal bicarbonates. Particularly suitable buffer systems are potassium hydrogen phthalate / sodium hydroxide, Potassium dihydrogen phosphate / sodium hydroxide and the like.

enzymes

The compositions of the present invention comprise at least one active Enzyme, if necessary in combination with other enzymes, in order to obtain sufficient reini effect, for example, on dried and crusted food and dirt ensure leftovers.

Enzymes which are preferably used according to the invention are amylases, proteases, hemicellu read, peroxidases and / or lipases.  

amylases

Amylases are added to remove starch and glycogen. According to the invention Alpha, beta and gamma amylases (α, β, γ amylases) and Glucoamylases and maltogenic amylases. Suitable amylases are commercially available Lich, for example, under the names Duramyl®, Termamyl®, Fungamyl® and BAN® (Novo Nordisk), as well as Maxamyl®, or Purafect®OxAm. The amylases can come from any source, such as bacteria, fungi, pancreatic glands of animal origin, from germinated cereals, yeasts etc. Also genetically modified Amylases are, if appropriate even preferred, in the combinations according to the invention settlements can be used.

The amylase enzymes can be present in proportions in the compositions according to the invention from 0.0001% to 5% by weight, preferably from 0.0001% to about 1% by weight, particularly preferably 0.0005 to approximately 0.5% by weight and particularly preferably at about 0.01 to 0.4% by weight.

In the preferred embodiment of the present invention, the added ones are Amylase enzymes in an amount of 0.001 to 0.5% by weight, preferably 0.001 to 0.54% by weight, particularly preferably 0.01 to 0.35% by weight, particularly preferably 0.01 up to 0.2% by weight. The stated quantities refer to the original amount of enzyme used in% by weight.

proteases

In addition to amylases, proteases can also be used in the compositions according to the invention Cleavage of proteins and peptide residues are added. Proteases are suitable especially for hydrolytic cleavage and removal of protein residues, in particular dried protein residues.

Proteases suitable according to the invention are proteinases (endopeptidases) and peptidases (Exopeptidases). Proteases that can be used are plant, animal, bacterial and / or of fungal origin. Suitable proteases are in particular serine, Cysteine, aspartate and metal proteases. Genetically modified proteases are also  optionally even preferred, used in the compositions according to the invention bar.

Proteases that can be used are commercially available under the names Alcalase®, BLAP®, Durazym®, Esperase®, Everlase®, Maxapem®, Maxatase®, Optimase Purafect®OxP or Savinase® available.

Ideally, proteases in the range of 0.00001 to 1.5% by weight are particularly special preferably used in the range from 0.0001 to 0.75% by weight.

lipases

Furthermore, lipases can be solidified for removal in compositions according to the invention Use adhering grease dirt. Lipases are therefore a bio-alternative to tensi den and can in the range of 0.0001 to 1 wt .-%, the cleaning effect of the surfactants support. Suitable lipases can be obtained from plants (for example types of castor oil), Microorganisms and animal sources such as pancreatic lipases. Commercially available lipases are, for example, Lipolase®, Lipomax®, Lipozym® and Lumafast®.

The above-mentioned enzymes can be used individually or in any combination are added to one another in the compositions according to the invention. Especially amylases are preferred for use in cleaning agents according to the invention, especially alpha amylases and proteases.

The enzymes mentioned according to the invention can optionally be added any other enzymes can be combined to improve the cleaning performance of the Reini means to further improve. Other enzymes suitable according to the invention are Cellulases, hemicellulases, peroxidases, reductases, oxidases, ligninases, cutinases, Pectinases, xylanases, phenol oxidases, lipoxygenases, tannases, pentosanases, mala noses. Glucanases, arabinosidases and any mixtures of these enzymes.  

Enzyme stabilizers

The enzymes in the compositions according to the invention are used in the pH values by adding carbohydrates, preferably linked to 1.6 glycosidically Stabilized monomers and particularly preferably from the group of dextrins. It was Surprisingly, found that 1,6-glycosidically linked carbohydrates in the The added enzymes are able to stabilize, i. H. over a long period of time to obtain enzymatically active form.

Carbohydrates for the purposes of this invention are polyhydroxy aldehydes and polyhydroxy ketones, as well as higher molecular compounds, which are converted into these substances by hydrolysis Have transferred, especially mono-oligo- and polysaccharides.

Carbohydrates with 1.6 glycosidic bonds are preferred. Examples of full permanently or partially 1,6-glycosidically linked carbohydrates are isomaltose, Dextrins, especially maltodextrins, cyclodextrins, acid dextrins and the like. In addition to the enzyme stabilization effect, cyclodextrins can also have secondary properties have properties like complexing ability against "bad smells". Suitable cyclodextrins are sold, for example, by Wacker.

Dextrins are breakdown products of starch with the general formula (C ₆ H ₁₀ O ₅ ) _n .x H ₂ O, which consist of glucose chains. Dextrins in the sense of the present invention also include cyclodextrins. Dextrins are usually obtained from corn or potato starch with a molecular weight of 2000 and 30000.

In the context of the present invention, maltodextrins and / or are particularly preferred Cyclodextrins. Carbohydrates with high levels of 1,6-glycosidic bonds are preferred, since in particular the amylases do not cleave such polysaccharides capital.

Maltodextrins in the sense of this invention are enzymatic degradation of starch extractable water-soluble carbohydrates with a chain length of 5 to 10 anhydroglucose units  and a high proportion of maltose. Maltodextrins are for example available from Südzucker AG.

In a preferred embodiment of the invention, cyclodextrins are used as Enzyme stabilizers used. Suitable cyclodextrins are, for example, those under Description CAVAMAX® natural cyclodextrins sold by Wacker CAVAMAX® W6 (α-CD), CAVAMAX® W7 (β-CD), CAVAMAX® W8 γ-CD), and modified α-, β- and γ-cyclodextrins such as CAVASOL® W6 HP TL, CAVASOL® W6 M, CAVASOL® W6 TA, CAVASOL® W7 A, CAVASOL® W7 TA, CAVASOL® W7 HP, CAVASOL® W7 M, CAVASOL® W7 MCT, CAVASOL® W8 HP, CAVASOL® W8 TA and the like, also from Wacker.

It was found according to the invention that the addition of 1,6-glycosidically linked Carbohydrates, the added enzymes, especially the amylases in the Invention can stabilize compositions according to the extent that these over several months are storable without losing significant enzymatic activity.

1,6-glycosidically linked carbohydrates, preferably maltodextrin, will Compositions according to the invention in an amount of 0.1 to 5%, preferably 0.2 to 4%, particularly preferably 0.3 to 3% and particularly preferably 1 to 2% added.

It is also known from amylases that these are formed by the addition of calcium chloride Let ions stabilize. It was also found that by adding Calcium chloride, in combination with maltodextrin to the composition according to the invention can lead to further stabilization of the added enzymes. Boric acid / borates / perborates, in combination with glycerin and / or PEG, as well as niotes siden with available hydroxyl groups are other suitable stabilizing agents.

In a particularly preferred embodiment of the invention, calcium chloride, preferably in the form of the dihydrate (CaCl ₂ × 2 H ₂ O), is therefore added to the compositions according to the invention in addition to 1,6-glycosidically linked carbohydrates, preferably maltodextrin.

The amount of calcium chloride added is 0.01 to 2%, preferably 0.05 to 1%, particularly preferably 0.08 to 1% and particularly preferably approximately 0.1%, based on the hand dishwashing detergent composition.

surfactants

The agents according to the invention cannot, as surfactant component, have one or more ionic, anionic, amphoteric or cationic surfactants or surfactant mixtures from a contain several or all of these classes of surfactants.

Anionic surfactants are for economic reasons and because of their performance spectrum particularly preferred. Surfactants of the individual groups can be used as individual sub punching can be used. It is preferred to use mixtures of surfactants, with advantage Mixtures of surfactants from several of the aforementioned groups to use. As Surfactant mixtures are particularly suitable in combination with an anionic or more nonionic surfactants or betaine surfactants, wherein the betaine surfactants in this connection is to be equated with the class of amphoteric surfactants. Also the joint additional use of nonionic surfactants and betaine surfactants in Mixture can be beneficial for many applications.

Anionic surfactants

Anionic surfactants which can be used according to the invention can be aliphatic sulfates such as Fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfo nates, n-alkyl ether sulfonates, ester sulfonates, lingin sulfonates and alkyl benzene sulfonates his. Fatty acid can also be used in the context of the present invention cyanamides, sulfosuccinic acid esters, fatty acid isothionates, acylaminoalkane sulfonates (fat acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.  

As alk (en) yl sulfates, the alkali and especially the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates) of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company at available under the name DAN®, e.g. B. the products mentioned in US Pat. Nos. 5,529,724 and H 1,665, DAN® 214, a C ₁₄ -SAS with 99% 2- and 3-alkyl sulfate, DAN® 216, a C ₁₆ -SAS with 99% 2- and 3- Alkyl sulfate, and DAN® 100, a SAS with 62% 2- and 3-alkyl sulfate.

The fatty alcohol ethers are particularly preferred in the context of the present invention sulfates. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated Alcohols.

The person skilled in the art generally understands alkoxylated alcohols as the reaction products of one or more alkylene oxides, preferably of ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols, for example straight-chain or branched alcohols with chain lengths from C ₇ to C ₂₁ such as 2 - Methyl-branched C ₉ to C ₁₁ fatty alcohols with an average of 3.5 EO or the C ₁₂ to C ₁₈ fatty alcohols with 1 to 4 EO. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Another embodiment is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Low-ethoxylated fatty alcohols (0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred in the sense of the present invention.

Particularly preferred in the context of the present invention are the alkanesulfonates, in particular the secondary alkanesulfonates, which are obtained from unbranched paraffin hydrocarbons, in particular C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. A preferred secondary alkane sulfonate is the secondary Na-C _13-17 alkane sulfonate sold by Clariant as Hostapur® SAS 60.

Other suitable surfactants of the sulfonate type are alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, of the kind obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products. For the purposes of the invention, alkylbenzenesulfonates are alkylbenzenesulfonates with straight-chain or branched, saturated or unsaturated C _6-22- alkyl radicals, preferably C _8-18- alkyl radicals, in particular C _9-14- alkyl radicals, most preferably C _10-13 -alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or trialkanolammonium salts, preferably mono-, di- or triethanol and / or isopropanolammonium salts, especially mono-, di- or triethanolammonium salts, but also used as alkylbenzene sulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanolamine. Likewise, the esters of 2-sulfofatty acids (ester sulfonates), e.g. B. the 2-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

The anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular special sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts, and in the case of the sulfonates also in the form of the acid, for. B. dodecylbenzenesulfonic acid, C ₁₀ -C ₁₃ alkylbenzenesulfonic acid and / or C ₁₀ -C ₁₄ alkylbenzenesulfonic acid used. When using sulfonic acid, this is usually done in situ with one or more corresponding bases, e.g. B. alkali metal and alkaline earth metal hydroxides, especially sodium, potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or tetraalkylamine, - depending on the pH of the agent to be adjusted partially or completely - neutralized to the aforementioned salts ,

The agents contain one or more anionic surfactants in amounts, based on the Composition, from 0 to 45% by weight, preferably 1 to 40% by weight, in particular 5 up to 35% by weight, very preferably 10 to 30% by weight, very preferably 15 to 25% by weight, for example 20% by weight. In a preferred embodiment, the surfactant is based system on anionic surfactant (s), d. H. the proportion of anionic surfactant (s) is at least that Half of the total amount of surfactants, in particular even more than half of the Total amount of surfactants.

Cationic surfactants

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ⁱ ) (R ⁱⁱ ) (R ⁱⁱⁱ ) (R ^iv ) N ⁺ X ^- , in which R ⁱ to R ^iv for four identical or different types, especially two long and two short-chain, alkyl radicals and X ^{- represent} an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride, alkyldimethylhydroxyethylammonium chloride, bromide or methylsulfate, in particular with C. ₁₂ alkyl, and mixtures thereof. The compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.1 to 3% by weight.

Amphoteric surfactants

Suitable amphoteric surfactants (zwitterionic surfactants) are, for example, betaines, alkyl amidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which betaines are preferred in the context of the teaching according to the invention.

Betaine

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaine, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R ^A ) (R ^B ) (R ^C ) N ⁺ CH ₂ COO ^- , in which R ^A an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms and R ^B and R ^C , which may be interrupted by heteroatoms or heteroatom groups, mean identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetaines and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetaines, or formula A,

R ^I - [CO-X-CH ₂ ) _n ] _x -N ⁺ (R ^II ) (R ^III ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^- (A),

in the
R ^{I is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
X NH, NR ^IV with the C _1-4 alkyl radical R ^IV , O or S,
n is a number from 1 to 10, preferably 2 to 5, in particular 3,
x 0 or 1, preferably 1,
R ^II , R ^III independently of one another are a C _1-4 alkyl radical, optionally hydroxy-substituted such as, for. B. a hydroxyethyl radical, but especially a methyl radical,
m is a number from 1 to 4, in particular 1, 2 or 3,
y 0 or 1 and
Y COO, SO ₃ , OPO (OR ^V ) O or P (O) (OR ^V ) O, where R ^{V is} a hydrogen atom H or a C _1-4 alkyl radical.

The alkyl and alkyl amido betaines, betaines of formula A with a carboxylate group (Y ^- = COO ^- ), are also called carbobetaines.

Preferred amphoteric surfactants are the alkyl betaines of formula A1, the alkyl amido betaines of formula A2, the sulfobetaines of formula A3 and the amidosulfobetaines of formula A4,

R ^I -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (A1)

R ^I -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (A2)

R ^I -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (A3)

R ^I -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (A4)

in which R ^{I has} the same meaning as in formula A.

Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobe TAINE of the formula A1 and A2, most preferably the alkyl amido betaines of the formula A2. Examples of suitable betaines and sulfobetaines are the following named according to INCI Compounds: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamido propyl betaine, babassuamidopropyl betaine, behenamidopropyl betaine, behenyl Betaine, betaine, canolamidopropyl betaine, capryl / capramidopropyl betaine, carnitine, Cetyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl hydro xysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG betaines, erucamidopropyl hydroxysultaine, hydrogenated tallow betaines, isostear amidopropyl betaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaines, myristyl betaines, oleamidopropyl betaines, oleamidopropyl hydroxysultaine, Oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl Betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaines, Polytetrafluoroethylene Acetoxypropyl betaine, ricinoleamidopropyl betaine, sesamidopropyl betaine, soyami dopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl betaine and Wheat Germamidopropyl betaine. A preferred one Amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). A particularly before added amphoteric surfactant is Capryl / Capramidopropyl Betaine (CAB), for example under the trade name Tegotens® B 810 is available from Th. Goldschmidt AG.

alkylamidoalkylamines

The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula B

R ^VI -CO-NR ^VII - (CH ₂ ) _i -N (R ^VIII ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - [CH (OH)] _l -CH ₂ -Z-OM ( B)

in the
R ^{VI is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{VII is} a hydrogen atom H or a C _1-4 alkyl radical, preferably H,
i is a number from 1 to 10, preferably 2 to S. in particular 2 or 3,
R ^{VIII is} a hydrogen atom H or CH ₂ COOM (to M su),
j is a number from 1 to 4, preferably 1 or 2, in particular 1,
k is a number from 0 to 4, preferably 0 or 1,
l 0 or 1, where k = 1 if l = 1,
Z is CO, SO ₂ , OPO (OR ¹² ) or P (O) (OR ¹² ), where R ^{12 is} a C _1-4 alkyl radical or M (see below), and
M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas B1 to B4,

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ -COOM (B1)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH ₂ -COOM (B2)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -SO ₃ M (B3)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (B4)

in which R ^VI , R ^VIII and M have the same meaning as in formula B.

Exemplary alkylamidoalkylamines are the following named according to INCI Compounds: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA- Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipro pionate, disodium capryloamphodiacetate, disodium capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodi acetate, disodium cocoamphodipropionate, disodium isostearoamphodiacetate, disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipro pionate, disodium PPG-2-isodeceth-7 carboxyamphodiacetate, disodium stearoamphodi acetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Caprylo amphoacetate, sodium capryloamphohydroxypropylsulfonate, sodium capryloamphopro pionate, sodium cocoamphoacetate, sodium cocoamphohydroxypropylsulfonate, sodium Cocoamphopropionate, Sodium Comamphopropionate, Sodium Isostearoamphoacetate,  Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroampho hydroxypropylsulfonates, Sodium Lauroampho PG Acetate Phosphate, Sodium Lauro amphopropionate, sodium myristoamphoacetate, sodium oleoamphoacetate, sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleo amphoacetate, sodium stearoamphoacetate, sodium stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowampho acetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride Phosphate.

Alkyl substituted amino acids

Alkyl-substituted amino acids preferred according to the invention (INCI alkyl-substituted amino acids) are monoalkyl-substituted amino acids according to formula C,

R ^IX -NH-CH (R ^X ) - (CH ₂ ) _u COOM '(C)

in the
R ^{IX is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{X is} a hydrogen atom H or a C _1-4 alkyl radical, preferably H,
u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
M 'is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine,
alkyl-substituted imino acids according to formula D,

R ^XI -N - [(CH ₂ ) _v -COOM "] ₂ (D)

in the
R ^{XI is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
M "is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, e.g. B. can be hydrogen and sodium or twice sodium,
and mono- or dialkyl-substituted natural amino acids according to formula E,

R ^XII -N (R ^XIII ) -CH (R ^XIV ) -COOM "(E)

in the
R ^{XII is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{XIII represents} a hydrogen atom or a C _1-4 alkyl radical, optionally hydroxy or amine substituted, e.g. B. a methyl, ethyl, hydroxyethyl or aminopropyl radical,
R ^XIV the residue of one of the 20 natural a-amino acids H ₂ NCH (R ^XIV ) COOH, and
M '''is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine.

Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula C1,

R ^IX -NH-CH ₂ CH ₂ COOM '(C1)

in which R ^IX and M 'have the same meaning as in formula C.

Exemplary alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl lauryl glutamine, cocaminobutyric acid, cocaminopro pionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylene ediamine, disodium lauripropionate disodium stodionate disodium stearonate dioninodiphenion Diethylenediaminoglycine, Myristamino propionic Acid, Sodium C _12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropionate.

Acylated amino acids

Acylated amino acids are amino acids, especially the 20 natural α-amino acids, which carry the acyl radical R ^XV CO of a saturated or unsaturated fatty acid R ^XV COOH on the amino nitrogen atom, where R ^{XV is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _{8 -18} -alkyl radical, in particular a saturated C _10-16 -alkyl radical, for example a saturated C _12-14 -alkyl radical. The acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, e.g. B. mono-, di- or triethanolammonium salt can be used. Exemplary acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, e.g. B. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.

The compositions may include one or more amphoteric surfactants, in particular Alkylamido betaines, in amounts, based on the composition, of 0 to 15% by weight, preferably 0.1 to 10% by weight, in particular 1 to 8% by weight, particularly preferably 2 up to 6% by weight, most preferably 3 to 5% by weight, for example 4% by weight.

Nonionic surfactants

Suitable nonionic surfactants are, for example, C ₆ -C ₂₂ -alkyl alcohol polyglycol ethers, alkyl polyglycosides and nitrogen-containing surfactants or else di-C ₁ -C ₁₂ -sulfosuccinic acid esters or mixtures thereof, especially the first two. The compositions according to the invention can contain nonionic surfactants in amounts, based on the composition, of usually 0 to 30% by weight, preferably 0.1 to 25% by weight, in particular 1 to 20% by weight, particularly preferably 2 to 15 % By weight, most preferably 3 to 10% by weight, for example 4 or 9% by weight.

alkyl alcohol

C ₆ -C ₂₂ alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be represented by the formula I.

R ⁱ O- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH ₂ O) _e -H

are described in which R ⁱ for a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms, p for 0 or numbers from 1 to 3 and e for numbers from 1 to 20. The C ₆ -C ₂₂ alkyl alcohol polyglycol ethers of the formula I can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to oxo alcohols, the branched-chain primary alcohols obtainable by oxosynthesis, or to fatty alcohols, in particular to fatty alcohols. Typical examples are polyglycol ethers of the formula I in which R ^{i is} an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, C ₁₀ -C ₁₄ fatty alcohol + 1PO + 6EO ether (p = 1, e = 6), C ₁₂ -C ₁₆ fatty alcohol + 5.5-EO (p = 0, e = 5.5) , C ₁₂ -C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and isodecanol + 6-EO (R ¹ = isomer mixture of C ₁₀ oxo alcohol residues, p = 0, e = 6) and their mixtures , In special mixtures, at least one representative of formula I with a linear alkyl radical R ^{1 is combined} with at least one representative of formula I with a branched alkyl radical R ¹ , for example C ₁₂ -C ₁₆ fatty alcohol + 5.5-EO and isodecanol + 6-EO. It is further preferred here that the linear alkyl radical comprises more carbon atoms than the branched alkyl radical. C ₈ fatty alcohol + 1.2PO + 8.4EO, C _8-10 fatty alcohol + 5EO, C _12-14 fatty alcohol + 6EO and C _12-14 fatty alcohol + 3EO and mixtures thereof are particularly preferred.

End-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula I is etherified. The end-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C ₆ -C ₂₂ -Alkyl alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride, in the presence of bases. Typical examples are mixed ethers of the formula I in which R ^{i is} an industrial fatty alcohol radical, preferably C _12-14 cocoalkyl radical, p is 0 and e is 5 to 10, which are sealed with a butyl group.

Alkylpolyglykoside

Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula II, R ⁱⁱ O [G] _x , in which R ⁱⁱ for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar radical and x stands for a number from 1 to 10. APG are non-ionic surfactants and are known substances that can be obtained by the relevant procedures in preparative organic chemistry. The index number x in the general formula II indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligo-glycosides, and stands for a number between 1 and 10. While x must always be an integer in a given compound and here can assume the values x = 1 to 6, the value x for a certain alkyl glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6. Xylose, but especially glucose, is preferably used as the glycosidic sugar.

The alkyl or alkenyl radical R ⁱⁱ (formula II) can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms. Typical examples are capronal alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.

However, the alkyl or alkenyl radical R ⁱⁱ is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, Gado leyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.

Nitrogen-containing non-ionic surfactants

Suitable nitrogen-containing nonionic surfactants are, for example, amine oxides, Polyhydroxy fatty acid amides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 10 to 22 carbon atoms, preferably have 12 to 18 carbon atoms. The degree of ethoxylation of these compounds is usually between 1 and 20, preferably between 3 and 10. Preferred are ethanolamide derivatives of alkanoic acids with 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The particularly suitable compounds include lauric acid, Myristic acid and palmitic acid monoethanolamides.

amine oxides

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy the formula R ¹ R ² R ³ N ⁺ -O ^- in which R ^{1 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, For example, a saturated C _12-14 alkyl radical which is bonded to the nitrogen atom N in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH ₂ ) _z and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH ₂ ) _z , where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3, and R ² and R ³ independently of one another are an optionally hydroxy-substituted C _1-4 -alkyl radical such as, for. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco Morpholine oxides, decylamine oxides, decyltetradecylamine oxides, diaminopyrimidines Oxides, Dihydroxyethyl C8-10 Alkoxypropylamine Oxides, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihy droxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Mor pholine oxides, lauramidopropylamine oxides, lauramine oxides, methyl morpholines Oxides, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamido propylamine oxides, myristamine oxides, myristyl / cetyl amine oxides, oleamido propylamine oxides, oleamine oxides, olivamidopropylamine oxides, palmitamido propylamine oxides, palmitamine oxides, PEG-3 lauramine oxides, potassium dihydroxy ethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesa midopropylamine oxides, soyamidopropylamine oxides, stearamidopropylamine oxides, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Undecylene amidopropylamine Oxide and Wheat Germamidopropylamine Oxide. Preferred (s) Amine oxide (s) is / are, for example, cocamine oxides (N-cocoalkyl-N, N-dimethyl amine oxide), dihydroxyethyl tallowamine oxides (N-tallow alkyl-N, N-dihydroxyethyl amine oxide) and / or cocamidopropylamine oxides (cocoamidopropylamine oxide), in particular their cocamidopropylamine oxides.  

polyhydroxy

Other suitable surfactants are polyhydroxy fatty acid amides of the formula III,

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula IV,

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, after the teaching of international application WO-A-95/07331 by reaction with fatty acid methyl esters  in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

Compositions of the invention may also include suitable builders and chelates containing agents and solvents.

Builder

Furthermore, the composition according to the invention can be one or more builders included, especially to improve cleaning performance. Suitable builders are for example alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbo nate, especially sodium citrate, gluconate, and nitrilotriacetate, and sodium and Potassium carbonate and bicarbonate, as well as alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide, ammonia and amines, especially the Alkanolamines mono-, di- and triethanolamine, or their mixtures. Which includes also the salts of glutaric acid, succinic acid, adipic acid, tartaric acid and benzene exacarboxylic acid and aminotrimethylenephosphonic acid, hydroxyethane-1,1-diphosphone acid, 1-aminoethane-1,1-diphosphonic acid, ethylenediamine tetra (methylenephonic acid), di ethylene triamine penta (methylenephosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid and Phosphonates. In contrast, phosphates are less suitable; for example, this leads as Sodium tripolyphosphate (NaTPP) common pentasodium triphosphate often too strong Precipitations.

If the builder is also to act as a pH-stabilizing buffer, alkali metal and Alkaline earth metal carbonates and bicarbonates, preferably sodium carbonate (soda), before ugt, in particular together with citric acid or - possibly in situ from citric acid and Hydroxide generated - citrate, e.g. B. sodium or potassium citrate, particularly preferred together with the mixture of citric acid or citrate described above.

In the context of the present invention, the citrates are - if not expressly stated otherwise - the salts of triple deprotonated citric acid. However, the mono- and dihydrogen citrates can also be used according to the invention.

The builder salts mentioned can also be used in the form of their corresponding acids or bases, which are then partially or completely neutralized depending on the pH to be set. Likewise, the acids mentioned can be used in the form of their salts, preferably their alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium salts, in particular mono-, di- or triethanolmmonium salts, or mixtures thereof, in particular their sodium salts , for example citric acid in the form of its monohydrate citric acid.1H ₂ O instead of citrate. The builder salts also act as phase separation aids. The complexing builders also serve in particular to ensure a clear application solution when using the agents with hard water.

Citric acid or citrates are particularly preferred builders. Preferred is - possibly generated in situ from citric acid and hydroxide or alkanolamine - citrate from the Group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialka nolammonium citrates, preferably mono-, di- or triethanolammonium citrates, or their mixtures, especially sodium citrate and / or potassium citrate, especially before adds monoethanolammonium citrate.

In a particular embodiment, the agent according to the invention contains citric acid or citrate and magnesium chloride, especially monoethanolammonium citrate and Magnesium chloride.

solvent

The preferred solvent in cleaning agents according to the invention is water, however organic solvents can also be present.

Suitable organic solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 -hydrocarbons, preferably C _2-15 -hydrocarbons, with one or more hydroxyl groups, preferably one hydroxyl group, and optionally one or more ether functions COC, ie the oxygen atoms interrupting the carbon atom chain.

Preferred solvents are the C _1-6 alcohols, in particular ethanol, n-propanol or iso-propanol, as well as the C _2-6 alkylene glycols and poly-C _2- optionally etherified on one side with a C _1-6 alkanol. _3- alkylene glycol ethers with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, in particular the poly-C _2-3 alkylene glycol ether etherified on one side with a C _1-6 alkanol with an average of 1 to 9, preferably 2 to 3 , Ethylene or propylene glycol groups, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).

Exemplary solvents are the following compounds named according to INCI: alcohol (ethanol), buteth-3, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene glycol, dimethoxydiglycol, dimethyl ether, Dipropylene Glycol, Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, Hexanediol, 1,2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl Alcohol (iso-Propanol), 3-Methoxybutanol, Methoxydiglycol, Methoxy propanol , Methoxymethylbutanol, methoxy PEG-10, methylal, methyl alcohol, methyl hexyl ether, methyl propanediol, neopentyl glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 methyl ether, pentylene glycol , PPG-7, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3 methyl ether, PPG-2 propyl ether, propanediol, propyl alcohol (n- Propanol), propylene glycol, propylene glycol butyl ether, propylene glycol l Propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol. With aliphatic or aromatic alcohols, e.g. As methanol, ethanol, n-propanol, n-butanol, tert-butanol or phenol, or carboxylic acids, e.g. B. acetic or carbonic acid, etherified or esterified monomeric or homo- or heteropolymeric, especially monomeric and homodi- and trimeric, C ₂ -C ₄ alkylene glycols are, for example, under the trade name Dowanol® from Dow Chemical and sold under the trade names Arcosolv® and Arconate® by Arco Chemical, such as the products designated below with their INCI name in accordance with the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA), e.g. B. Butoxydiglycol (Dowanol ° DB), Methoxydiglycol (Dowanol® DM), PPG-2 Methyl Ether (Dowanol® DPM), PPG-2 Methyl Ether Acetate (Dowanol® DPMA), PPG-2 Butyl Ether (Dowanol® DPnB), PPG-2 Propyl Ether (Dowanol® DPnP), Butoxyethanol (Dowanol® EB), Phenoxyethanol (Dowano / ® EPh), Methoxyisopropanol (Dowanol® PM), PPG-1 Methyl Ether Acetate (Dowanol® PMA), Butoxyisopropanol (Dowanol® PnB ), Propylene Glycol Propyl Ether (Dowanol® PnP), Phenoxyisopropanol (Dowanol® PPh), PPG-3 Methyl Ether (Dowanol® TPM) and PPG-3 Butyl Ether (Dowanol® TPnB) as well as Ethoxyisopropanol (Arcosolv® PE), tert- Butoxyisopropanol (Arcosolv® PTB), PPG-2 tert-butyl ether (Arcosolv® DPTB) and propylene carbonate (Arconate® PC), of which butoxyisopropanol (dipropylene glycol n-butyl ether, Dowanol® PnB) and in particular PPG-2 methyl ether (dipropylene glycol methyl ether) , Dowanol® DPM) are preferred.

hydrophobic components

In a particularly advantageous embodiment of the invention, the agents contain one or more hydrophobic components. The hydrophobic components not only improve the cleaning effect against hydrophobic contaminants such as greasy dirt, but also have a positive effect on phase separation and their reversibility with multi-phase cleaning agents. Suitable hydrophobic components are, for example, dialkyl ethers with the same or different C ₄ -C ₁₄ -alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, for. B. aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, in particular limes and the pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned. Preferred mixtures of hydrophobic components are mixtures of various dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and essential oils, of hydrocarbons and essential oils, of dialkyl ethers and hydrocarbons and essential oils and of these mixtures. The agents contain hydrophobic components in amounts, based on the composition, of 0 to 20% by weight, preferably 0.1 to 14% by weight, in particular 0.5 to 10% by weight, most preferably 0.8 to 7% by weight.

Phase separation auxiliaries

If the agents according to the invention are formulated in multiple phases, they can be one or contain several phase separation aids. Suitable phase separation aids are in addition to the Citric acid or the citrates, for example the alkali metal and alkaline earth metal halides, especially chlorides, and sulfates and nitrates, especially sodium and Potassium chloride and sulfate, and ammonium chloride and sulfate or mixtures thereof.  

Such salts act as strong electrolytes which increase the ionic strength Phase separation through the salt effect. Here sodium chloride has proven to be special proven effective while sodium sulfate and especially magnesium sulfate less act phase-separating. The agents contain phase separation aids in quantities on the composition, from 0 to 30% by weight, preferably 1 to 20% by weight, in particular 3 to 15% by weight, most preferably 5 to 12% by weight.

viscosity

The viscosity of the liquid phase (s) at 20 ° C. is preferably 5 to 100,000 mPa.s, in particular 10 to 5000 mPa.s, particularly preferably 10 to 200 mPa.s, measured with a Brookfield rotary viscometer of the LVT type or LVDV 11+ with Small Sample Adapter at a speed of 30 min ^-1 , whereby the Brookfield spindle used as the measuring body should be selected so that the torque is in a favorable range and the measuring range is not exceeded. In this context, spindle 31 is preferred and - if required for viscosities above approximately 240 mPa.s - spindle 25 is preferably used.

thickener

To adjust the viscosity, the agent according to the invention can have one or more Thickeners, preferably in an amount of 0.01 to 5 wt .-%, in particular 0.05 to 2.5 wt .-%, particularly preferably 0.1 to 1 wt .-%, contain.

Suitable thickeners are organic natural thickeners (agar-agar, Carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust beans bread flour, starch, dextrins, gelatin, casein), organic modified nature substances (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, powdered meal ether), organic fully synthetic thickeners (Polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, poly ethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, Clay minerals such as montmorillonites, zeolites, silicas).  

The polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA ): Carbomer), which are also referred to as carboxy vinyl polymers. Such polyacrylic acids are available, inter alia, from BF Goodrich under the trade name Carbopol®, e.g. B. Carbopo® 940 (molecular weight approx.4,000,000), Carbopol® 941 (molecular weight approx.1,250,000) or Carbopol® 934 (molecular weight approx.3,000,000). The following also include the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C _1-4 alkanols, to which, for example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name in accordance with Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® are available, e.g. B. the anionic non-associative polymers Aculyn 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, including the copolymers of C _10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 -Alkanols formed, esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and which are available for example from BF Goodrich under the trade name Carbopol®, for. B. the hydrophobized Carbopol® ETD 2623 and Carbopol® 1382 (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473). In addition to the thickening effect, these agents in detergents can have other effects, such as. B. graying protection.

Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, Carrageene and its salts, guar, guaran, tragacant, gellan, ramsan, or dextran Xanthan and its derivatives, e.g. B. propoxylated guar, and their mixtures. Other  Alternatively, polysaccharide thickeners, such as starches or cellulose derivatives, may be preferred but be used in addition to a polysaccharide rubber, for example Starches of various origins and starch derivatives, e.g. B. hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, Methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl or hydroxy ethyl methyl cellulose or cellulose acetate.

A particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 × 10 ⁶ and is available, for example, from Kelco under the trade name Keltrol®, z. B. as cream-colored powder Keltrol® T (Transparent) or as white granulate Keltrol® RD (Readily Dispersable).

Auxiliaries and additives

In addition to the components mentioned, the agents according to the invention can contain further auxiliaries. and contain additives as are customary in such agents. Which includes especially polymers, soil release agents, solubilizers, hydrotropes (e.g. Sodium cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), emulsifiers (e.g. Gallus soap), thickeners, gloss drying additives, cleaning enhancers, anti microbial agents or disinfectants, antistatic agents, preservatives (e.g. Glutaraldehyde), bleaching systems, perfumes, fragrances and dyes and opacifiers or also skin protection agents as described in EP-A-522 556. The amount of Such additives are usually not more than 12% by weight in the cleaning agent. The The lower limit of use depends on the type of auxiliary and additive and can for example with dyes up to 0.001 wt .-% and below. Preferably the amount of auxiliaries and additives is between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

Examples Storage stability tests of detergents containing enzymes

To determine the storage stability of the detergent compositions according to the invention These were settled in closed glass vessels at a storage temperature of 40 ° C kept. After one, two, six and eight weeks a sample of the each detergent and the enzymatic activity determined and compared with the initial activity (= 100%) of the composition [status of Technology, enzyme analysis].

There were three surfactant mixtures according to the combination given in Table 1 settlement by mixing the components.

Table 1

Examples 1-3

0.3% by weight of amylase was added to each of the compositions listed in Table 1 (Duramyl® 300 L, Novo Northern Ireland) added (Examples 1-3). The Reini thus obtained Agents of Examples 1-3 were after the storage stability test given above checked. The results are shown in Table 2.  

Examples 4-6

0.3% by weight of amylase was added to each of the compositions listed in Table 1 (Duramyl® 300 L, Novo Northern Ireland) and 2% by weight of maltodextrin were added (Examples 4-6). The cleaning agents of Examples 4-6 thus obtained were prepared according to the above Storage stability test checked. The results are shown in Table 2.

Examples 7-9

0.3% by weight of amylase (Duramyl® 300 L, Novo Nordirsk), 2% by weight of maltodextrin and 0.2% by weight of CaCl ₂ × 2H ₂ O were added to each of the compositions mentioned in Table 1 (examples 7-9). The cleaning agents of Examples 7-9 thus obtained were tested according to the storage stability test given above. The results are shown in Table 2.

Table 2

The results in Table 2 show that the stabilization of the amylase used Enzyme is mainly done by maltodextrin. The not stabilized together Settlements (Examples 1, 4 and 7) show an enzyme activity that decreases sharply with time, which has partially disappeared after 6 weeks. It also becomes clear  that the overall stability depends very little on the surfactant mixture used Stabilizer effects clearly outweigh.

Examples 10-12

A two-phase (liquid / liquid) surfactant mixture according to that in Table 3 specified compositions prepared by mixing the components.

Table 3

Example 10

0.3% by weight of amylase (Duramyl® 300 L, Novo Northern Ireland) added (Example 10).

Example 11

0.3% by weight of amylase (Duramyl® 300 L, Novo Nordirsk) and 2 wt .-% maltodextrin added (Example 11).  

Example 12

0.3% by weight of amylase (Duramyl® 300 L, Novo Nordirsk), 2% by weight of maltodextrin and 0.2% by weight of CaCl ₂ × 2H ₂ O were added to composition 4 mentioned in Table 3 (example 12).

The results are shown in Table 4.

Table 4

The storage stability of Examples 10, 11 and 12 was determined using the above Storage stability tests determined. Already after 2 weeks the maltodextrin-free No more enzyme activity can be measured. In comparison was able to achieve good enzyme activity in the compositions of Examples 11 and 12 be measured.

Claims (15)

1. Liquid, aqueous cleaning composition comprising at least one surfactant and / or surfactant mixtures and at least one active enzyme, characterized in that the composition comprises at least one carbohydrate. 2. Composition according to claim 1, characterized in that the carbohydrate 1,6-glycosidically linked monomers having. 3. Composition according to claim 1 or 2, characterized in that the carbohydrate content based on the Total composition from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight, particularly preferably from 0.3 to 3% by weight and in particular from 1 to 2% by weight accounts. 4. Composition according to one of claims 1 to 3, characterized in that the carbohydrate from the group of dextrins is selected and is particularly preferably maltodextrin and / or a cyclodextrin. 5. Composition according to one of the preceding claims, characterized in that the pH in the range from 2 to 10, preferably 4- 8, and is particularly preferably 5-7. 6. Composition according to one of the preceding claims, characterized in that the enzymes from the group of amylases, proteases, Peroxidases and lipases is selected.   7. Composition according to one of the preceding claims, characterized in that the active enzyme content is 0.00001-5% by weight, based on the total composition. 8. Composition according to one of the preceding claims, characterized in that the composition further contains calcium chloride. 9. Composition according to one of the preceding claims, characterized in that the composition is at least one anionic Contains surfactant, preferably a secondary alkyl sulfonate. 10. Composition according to one of the preceding claims, characterized in that the composition is a nonionic surfactant from the Contains group of alkyl sulfates and / or alkyl ether sulfates. 11. Composition according to one of the preceding claims, characterized in that the composition is single phase. 12. Composition according to one of the preceding claims, characterized in that the composition is multi-phase and preferred has at least two immiscible phases, which are characterized by Transfer shaking temporarily to an emulsion, suspension and / or dispersion to let. 13. Use of a composition according to one of the preceding claims as Cleaning supplies. 14. Use of a composition according to any one of the preceding claims as Detergent for cleaning hard surfaces, as a hand dishwashing liquid and / or all-purpose cleaner.   15. Use of carbohydrates with 1,6-glycosidically linked monomers, preferably from the group of dextrins, in particular maltodextrin, and optionally calcium chloride, for stabilizing enzymes, especially of Amylases, in aqueous hand dishwashing detergent compositions.