WO2003054125A1 - Cleaning agent comprising microcapsules - Google Patents

Abstract

The invention relates to a sprayable, thickened (thixotropic), liquid, aqueous cleaning agent having a defined viscosity and containing a surfactant combination of alkyl ether sulfate, secondary alkane sulfonate and an amphoteric surfactant, in addition to microcapsules comprising at least one active ingredient. Said cleaning agent is produced by stirring together the individual constituents, incorporating the microcapsules last. The inventive cleaning agent can optionally be used as a product combined with a spray dispenser, for cleaning hard surfaces or for washing up.

Description

 "Detergent with microcapsules"

The invention relates to a sprayable aqueous cleaning agent for hard surfaces, in particular a hand dishwashing liquid, with microcapsules.

Hand dishwashing detergents are usually used either by dosing the detergent into a container with warm water, adding the items to be washed and, if necessary, cleaning them with a sponge, a brush, a cloth or other aids after a short soaking time, or by diluting the detergent undiluted a sponge, cloth or other auxiliary material and the dishes, if necessary after a brief immersion in warm water, cleaned under running water. In both cases, the consumer faces several dosage problems. Especially thin liquids are often overdosed, since it is difficult to control the delivery from the storage bottle. Furthermore, dishwashing detergents can often not be removed cleanly from the storage bottle, so that drops then run down the bottle. As a result, the consumer comes into undesirable contact with the undiluted agent the next time it is removed. Although this disadvantage can be eliminated by setting a higher viscosity, it can sometimes be difficult, particularly with more viscous agents, to completely empty the storage bottle.

After cleaning the dishes, the items to be washed are either simply left to dry or are dried in a further operation, usually with the aid of an absorbent article. Simply letting it dry is less labor-intensive, but takes longer and often leads to the formation of undesirable visible residues such as stains (water stains) or stripes, as well as to a loss of gloss or dull appearance, particularly in the case of glasses and other glass dishes. When a cleaned glass or plate is removed from the wash liquor, the wash liquor is first poured or poured off and the glass or plate is placed to dry. The rinsing liquor layer remaining on the surface of the glass or plate now runs off slowly until the rinsing liquor layer on the surface has become so thin that it no longer runs off, but only decreases through (self-) drying. Drying also takes place during the process. US Pat. No. 5,883,062 describes a hand dishwashing detergent comprising 1 to 80% by weight of anionic surfactant and 0.05 to 10% by weight of divalent ions (calcium, magnesium or mixtures), which is formulated in such a way that a 1% strength aqueous solution is added 20 ° C has a pH between 3.5 and 4.5. The agent should preferably be used in such a way that it is sprayed onto the dishes to be cleaned, so that the more heavily soiled parts are treated with larger amounts than the more easily soiled parts, and rinsed off again after a short exposure time. There is no indication of improved drainage and drying behavior.

US 3,708,429 teaches a detergent composition that is used primarily as a hand dishwashing detergent. The composition comprises a substantially anhydrous mixture of a surfactant, an alkaline catalyst, an acid releasing agent and a lower aliphatic alcohol, preferably ethanol or methanol. For use, the agent is preferably sprayed onto the items to be cleaned in order to avoid skin contact with the initially strongly alkaline agent. The alkalinity should remove grease dirt in particular. The subsequent addition of water releases the acid and at least partially neutralizes the agent so that it is less harmful to the skin. This agent is also not characterized by a particularly good drainage and drying behavior.

The published patent application DE 100 03 567 presents a surfactant combination which contains one or more alkyl ether sulfates, one or more alkyl sulfonates in an amount, based on the surfactant combination, of less than 50% by weight and one or more amphoteric surfactants, and one such surfactant combination containing aqueous, liquid agent and its use for cleaning hard surfaces and especially for washing dishes. Here, the amphoteric surfactants and especially the alkyl ether sulfates primarily contribute to the cleaning effect, while the alkyl sulfonates above all have a positive influence on the drying or drainage behavior, i.e. in particular, increase the drying speed and reduce residue formation. The examples show that the composition usually contains 15-40% by weight of surfactants.

The stable incorporation of especially sensitive ingredients often represents a further problem. Attempts are made to use conventional agents to try out certain active ingredients (including skin-feel-improving or nourishing additives such as liposomes, proteins, vitamins, plants). zen extracts, etc .; performance enhancing additives such as acetic acid, etc .; antibacterial additives such as lactic acid, benzoic acid, etc .; Incorporating esthetics (aesthetics, in particular smell and appearance as well as haptics) improving additives, such as perfume oils, dyes, etc.) into a hand dishwashing liquid, this can quickly result in a loss of effectiveness (e.g. with liposomes) due to the direct action of the surfactant components on the active ingredient , Another problem are difficulties with the stable incorporation of active ingredients into the detergent formulation (e.g. with perfumes or antibacterial active ingredients), discoloration (e.g. with plant extracts or proteins), odor problems (e.g. with the addition of vinegar, antibacterial active ingredients or plant extracts) or incompatibilities between the active ingredient component and the detergent (eg disinfectants, antibacterial substances or bleaches such as hydrogen peroxide, persulfates, peracids, perborates or percarbonates).

An elegant method for incorporating sensitive, chemically or physically incompatible and volatile ingredients is the use of microcapsules, in which these ingredients are enclosed during storage and transport and from which they are released mechanically, chemically, thermally or enzymatically for or during use.

Microcapsules are finely dispersed liquid or solid phases coated with film-forming polymers, in the production of which the polymers are deposited on the material (active ingredient) to be encased after emulsification and coacervation or interfacial polymerization. The active ingredient is enclosed in a shell-like membrane (microcapsule in the narrower sense) or enclosed in a matrix (microsphere or sphere). In the following, the term microcapsule is used in a summarizing sense for both variants. The microcapsules can be dried like powder. In this way e.g. Petrol, water, alcohol, pharmaceuticals, solvents, vitamins, enzymes, liquid crystals, food flavors and perfumes are converted into a dry mass that cannot dry out. Microencapsulation is used e.g. for perfume powders that are more comfortable and longer-lasting to use as microcapsules.

German Offenlegungsschrift DE 2 215 441 describes aqueous liquid dishwashing detergents containing 20 to 45% by weight of anionic and / or nonionic surfactants, 3 to 10 % By weight of electrolyte and capsules of 1 to 4000 μm in diameter made from the polymers carrageenan, polyvinyl alcohol or cellulose ether, the polymer and the electrolyte concentration being selected such that the stability of the capsules in the composition and the dissolution of the capsules when diluted with Water are guaranteed. Such a dishwashing detergent contains, for example, 10% by weight capsules with a diameter of 4000 μm, 25% by weight sodium dodecylbenzenesulfonate, 5% by weight coconut monoethanolamide, 7% by weight sodium sulfate, 1.5% by weight synthetic clay or 5% by weight capsules with a diameter of 4000 μm, 20% by weight sodium alkylbenzenesulfonate, 5% by weight sodium C ₁ . _16- α-olefin sulfonate, 5% by weight lauric acid diethanolamide, 7% by weight sodium xylene sulfonate, 3% by weight ethanol, 1% by weight potassium chloride, 1% by weight synthetic clay and 0.2% by weight % EDTA.

DE 36 15514 A1 discloses an aqueous hand dishwashing detergent with 22% by weight sodium α-olefin sulfonate, 6% by weight magnesium alkylbenzenesulfonate, 2% by weight sodium sulfate, 0.725% by weight sodium chloride, 3% by weight ethanol , 0.5% by weight of fragrance and 1.5% by weight of fragrance-containing microcapsules with a size of 200 to 500 μm, which dissolve when diluted with water.

British Patent GB 1 471 406 relates to liquid aqueous detergents containing at least 2% by weight of triethanolamine lauryl sulfate and a total of 8 to 50% by weight of surfactant and 0.5 to 2% by weight of water-soluble crosslinked polyacrylic acid with a molecular weight of more than 1,000 .000 and 0.1 to 5 wt .-% suspended phase, for example contain spheroidal capsules with a diameter of 0.1 to 5 mm and have a pH of 5.5 to 11.

U.S. Patent 5,141,664 teaches a clear, gel-form surfactant-containing detergent composition with suspended active ingredient capsules. The gel contains 5 to 80% by weight of water, 0.05 to 25% by weight of at least one surfactant, 0.1 to 10% by weight of a crosslinked polycarboxy polymer as a thickener and 0.01 to 2% by weight. % Alumina. In addition, particles of a bleach or a bleach precursor with a protective shell are contained in a gel: particle ratio between 500: 1 and 5: 1. In addition to many other substances, the coating substance can also include Waxes and homopolymers and copolymers such as polyacrylates, polyvinyl acetate or styrene-alkyl acrylate copolymers are used.

Finally, WO 00/65020 describes a thickened aqueous hand dishwashing detergent with anionic surfactant, amphoteric surfactant, polymer and microcapsules, in which one or more ingredients of the hand dishwashing detergent are wholly or partly incorporated. It deals is a precisely meterable, easy-to-clean, skin-compatible, temperature and storage stable, pourable hand dishwashing liquid, in which the possibly physically or chemically incompatible or sensitive ingredients are incorporated in temperature, storage and transport stable, easy to handle and visually appealing form. These ingredients are only released immediately before or during use.

The object of the invention was to provide an improved sprayable cleaning agent for hard surfaces, in particular hand dishwashing liquid.

The invention relates to an agent of defined viscosity, containing a surfactant combination of alkyl ether sulfate, sec. Alkane sulfonate and amphoteric surfactant, as well as microcapsules that encase one or more other ingredients.

This agent is particularly suitable for spray application on soiled surfaces, in particular dishes, and particularly for use on soils which are difficult to access, for example on the inside of thermos flasks or flower vases.

In a second embodiment, the invention therefore relates to a product consisting of the agent according to the invention and a spray dispenser.

The third subject of the invention is the use of an agent according to the invention for cleaning hard surfaces, in particular dishes. The agent according to the invention is preferably used for the manual cleaning of hard surfaces, in particular for the manual cleaning of dishes. In addition to crockery, all other hard surfaces, in particular made of glass, ceramic, plastic or metal, in household and commercial use can be considered as hard surfaces.

When the agent according to the invention is used as a detergent for hard surfaces and in particular as a hand dishwashing detergent (abbreviated as detergent), the amphoteric surfactants and especially the alkyl ether sulfates primarily contribute to the cleaning action, while the alkyl sulfonates have a positive effect, above all, on the drying and drainage behavior, i.e. in particular the drying rate increase and residue formation reduce. At the same time, the microcapsules allow stable incorporation of active ingredients that are otherwise not or only partially usable in such agents.

The advantage of the agent according to the invention or the use according to the invention is the improved drying or draining behavior, in particular the high drying rate or short drying time, the high draining rate or short draining time as well as the low residue formation and the retained gloss. Drying is understood here to mean both the drying as a whole, in particular until moisture is not perceptible on the surface visually or haptically, and in particular the drying after the expiration.

Another advantage of the agent according to the invention or the use according to the invention lies in the possible use of microcapsules. These capsules or "pearls" allow the active ingredients, which would otherwise be incompatible with the agent, to be incorporated in a temperature, storage and transport stable manner in an easily manageable and visually appealing form. As such, for example, essential oils, care substances for the surfaces to be cleaned, bleaching systems To name enzymes or skin care substances.

Yet another advantage of the agent according to the invention or the use according to the invention is the high cleaning action (synonyms: cleaning performance or ability or rinsing effect, performance or ability), especially on greasy soiling. Incorporated additives can, for example, significantly improve the bleaching effect, e.g. Hydrogen peroxide, citric acid, partial citric acid esters, perborates or peracids.

A particular advantage of the product from the agent according to the invention and a spray dispenser is the easy handling, the exact and clean dosing and the possibility of applying the agent precisely and specifically to soiled areas, even if these are cleaned with a cloth, a brush or using an agent in a standard bottle with pouring spout are difficult or impossible to access. Another advantage of the agent according to the invention is the high storage stability.

An increased viscosity is required for the stable suspension of the microcapsules. At the same time, however, the agent should be sprayable. In order to ensure the sprayability in spite of the viscosity of the agent necessary for the stable suspension of the microcapsules, these are generally thixotropic agents. In the case of non-thixotropic agents, this is usually Resetting force of the trigger pump is not sufficient, so that a second pump stroke is only possible with a delay.

Compositions according to the invention

Substances that also serve as ingredients of cosmetic products are referred to below in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are only listed according to Linne in Latin. So-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the "International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997)" published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 ^th Street NW, Suite 300, Washington, DC 20036, USA, and has more than 9000 INCI names and references to more than 37000 trade names and technical names including the associated distributors from over 31 Countries. The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes, for example "polymeric ethers", and one or more functions (functions), for example "surfactants - cleaning agents", which it in turn explained in more detail. This will also be referred to below if necessary.

The statement CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.

Unless explicitly stated otherwise, the stated amounts in percent by weight (% by weight) relate to the entire composition.

In contrast to the ingredients related to the entire hand dishwashing detergent, the active ingredients only mean the part contained in the microcapsules.

microcapsules

Microcapsules are finely dispersed liquid or solid phases coated with film-forming polymers. The active ingredient (core) is encased in a shell-like membrane (shell) (microcapsule in the narrower sense) or enclosed in a matrix (microsphere or sphere). In the following, the term microcapsule is used in a summarizing sense for both variants. The microcapsules contain at least one solid or liquid core which is enclosed by at least one continuous shell. Accordingly, two or more cores are distributed in the continuous shell material in multi-core microcapsules, also called microspheres, and single or multi-core microcapsules can be enclosed by an additional second, third, etc. shell. Mononuclear microcapsules with a continuous shell are preferred.

The shell can consist of natural, semi-synthetic or synthetic materials. Of course, wrapping materials are, for example, gum arabic, agar, agarose, maltodextrins, alginic acid or their salts, e.g. Sodium or calcium alginate, fats and fatty acids, cetyl alcohol, gelatin, albumin, shellac, polysaccharides such as starch or dextran, sucrose and waxes. Semi-synthetic wrapping materials include chemical modified celluloses, especially cellulose esters and ethers, e.g. Cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and carboxymethyl cellulose, as well as starch derivatives, in particular starch ethers and esters. Synthetic covering materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinyl pyrrolidone.

In a preferred embodiment, pearlescent agents (INCI opacifying agents) are additionally incorporated into the shell material, so that the microcapsules have the appearance of pearls. Because of their aesthetic appearance, these “active substance beads” lead to increased acceptance of the agent according to the invention by the consumer.

All surfactant-stable microcapsules on the market can be used as microcapsules, for example the commercial products Hallcrest Microcapsules (shell material: gelatin, gum arabic) from Hallcrest, Inc. (US), Coletica Thaiaspheres (shell material: maritime collagen) from Coletica (FR) , Lipotec Millicapseln (shell material: alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres (wrapping material: lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) and Unicerin C30 (wrapping material: lactose, microcrystalline cellulose, hydroxypropylmethylcellulose) from Induchem AG (CH), Kobo Glycospheres (wrapping material: modified starch, fatty acid esters and phospholipids) Softspheres (shell material: modified agar agar) from Kobo (US) and Kuhs Probiol Nanospheres (shell material: phospholipids) from Kuhs (DE).

The cores of the microcapsules can be liquids in the form of solutions or emulsions or suspensions and preferably contain one or more active ingredients. If the capsules are not to be transparent, solids or dispersions, which can also be colored, can also be used. Preferred active substances in the context of the invention are essential oils, for example perfumes, limonene, geraniol or nerol, bleaching system components, for example bleach activator, enzymes and care and protective components for the hard surface such as, for example, cationic polymers, silicone oils or stearyl mercaptan as silver protection, and additives for Improvement of the wash load gloss, eg vinegar. In addition, active substances within the meaning of the invention are also other ingredients that are customary in detergents and cleaning agents and cosmetics, including dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen Partial hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil etc., plant extracts such as aloe vera, alene, witch hazel extracts, algae extracts etc., Aliantoin, AHA complexes. Active substances in the sense of the invention are also antibacterial active substances, such as, for example, benzoic acid, lactic acid, salicylic acid, sorbic acid, or their mixtures or their salts, and quaternary ammonium compounds. Active substances according to the invention for improving the appearance are dyes, color pigments or pearlescent components.

The microcapsules can have any shape in the production-related frame, but they are preferably egg-shaped or ellipsoidal or approximately spherical. Depending on the active ingredient and application, their diameter along their greatest spatial extent is usually between 10 nm (not visually recognizable as a capsule) and 10 mm, possibly even more. Visible microcapsules with a diameter in the range from 0.01 to 6 mm, in particular from 0.05 to 4 mm, most preferably from 0.1 to 2 mm, are preferred. Microcapsules that are no longer perceptible to the naked eye preferably have a diameter in the range from 20 to 500 nm, preferably 50 to 200 nm.

The active ingredient can be released from the microcapsules primarily by mechanical action, both by grinding the microcapsules during the cleaning process and by breaking them open using a suitable metering device, for example in a dispenser or spray valve, for example in the form of shear forces crushing the microcapsules or with a capsule diameter from about 1 mm cutting blades. Another option is to dissolve the capsules when diluted by introducing the cleaning agent into the rinse liquor. It is also conceivable to release the active ingredient by changing the temperature (introducing it into warm soapy water), by shifting the pH value, changing the electrolyte content, etc. The content of microcapsules is usually from 0.005 to 5.0% by weight, preferably from 0.01 to 2.0% by weight, in particular from 0.1 to 1.0% by weight, the agent according to the invention exclusively may contain similar microcapsules or else mixtures of different types of microcapsules.

The microcapsules are preferably incorporated into thixotropic agents with a high zero shear viscosity, so that the individual “beads” are suspended in a stable manner and can therefore be metered without shaking beforehand.

To improve the visual appearance, gas bubbles, e.g. Air, argon, oxygen, nitrogen, carbon dioxide, but also propane, butane, propellant gases and gas mixtures can be incorporated into the agent according to the invention.

viscosity

The viscosity which is favorable for the agent according to the invention is 20 ° C. and a shear rate of 30 rpm - measured with a Brookfield LV DV II viscometer and spindle 31 - in the range from 100 to 10000 mPa-s, preferably 500 to 9000 mPa -s, particularly preferably 650 to 8000 mPa-s. In contrast, at a shear rate of 0.3 rpm, the viscosity is preferably 8000 to 130,000 mPas, particularly preferably 10,000 to 120,000 mPas, in particular 12,000 to 110,000 mPas. Accordingly, they are preferably thixotropic agents.

For this purpose, the viscosity of the agent according to the invention can be increased by thickening agents, in particular if the agent has a low surfactant content.

thickener

For thickening, the agent according to the invention can additionally contain one or more electrolyte salts and / or one or more polymeric or (optionally nanoparticulate) inorganic thickeners.

electrolyte salts

For the purposes of the present invention, electrolyte salts are salts which break down into their ionic constituents in the aqueous composition according to the invention.

The salts, in particular alkali metal and / or alkaline earth metal salts, are preferred, an inorganic acid, preferably an inorganic acid from the group comprising the hydrohalic acids, nitric acid and sulfuric acid, in particular the chlorides and sulfates. A particularly preferred electrolyte salt is magnesium sulfate, in particular MgSO ₄ -7H ₂ O, also known as Epsom salt and minerally known as epsomite.

Within the framework of the teaching according to the invention, an electrolyte salt can also be used in the form of its corresponding acid / base pair, for example hydrochloric acid and sodium hydroxide instead of sodium chloride.

The electrolyte salt content is usually not more than 8% by weight, preferably between 0.1 and 6% by weight, particularly preferably between 0.2 and 4% by weight, in particular between 0.3 and 2% by weight. % and most preferably between 0.5 and 1% by weight, for example 0.7% by weight.

Polymeric thickeners

For the purposes of the present invention, polymeric thickeners are the polycarboxylates which act as thickeners as polyelectrolytes, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers, such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular Heteropolysacchar.de, and other customary ones thickening polymers.

Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenan and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar and their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide rubber, for example starches of various origins and starch derivatives, e.g. Hydroxyethyl starch, starch phosphate ester or starch acetate, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.

A preferred polymeric thickener 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 2-15 * 10 ⁶ and for example from Kelco under the trade name Keltrof or from is available from Rhodia under the trade name RhodopoP, for example as a cream-colored powder Keltrof T or Rhodopoi ^® T (transparent) or as white granulate Keltroi ^® RD (readily dispersible). Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available from BFGoodrich, among others, under the trade name CarbopoP, for example Carbopoi ^® 940 (molecular weight approx. 4,000,000), Carbopoi ^® 941 (molecular weight approx. 1,250,000) or CarbopoP 934 (molecular weight approx. 3,000,000) ,

However, particularly suitable polymeric thickeners are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C 1-4 -alkanols, to which example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and for example from Messrs. Rohm & Haas under the trade names Aculyn ^® and AcusoP are available, for example the anionic non-associative polymers Aculyn ^® 33 (crosslinked), Acusoi ^® 810 and Acusoi ^® 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers crosslinked with an allyl ether of sucrose or pentaerythritol of Cιo- ₃ o-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C ^ -alkanols formed, include esters (INCI acrylates / C _{10. 30} alkyl acrylate Crosspolymer) and which are obtainable for example from the company. BFGoodrich under the tradename Carbopoi ^®, for example, the hy- drophobierte Carbopoi ^® ETD 2623 and CarbopoP 1382 (INCI acrylates / C 10 -30 alkyl acrylate cross polymer) and Carbopoi ^® AQUA 30 (formerly Carbopoi ^® EX 473).

The polymeric thickener content is usually between 0.01 and 8% by weight, but preferably not more than 5% by weight, particularly preferably between 0.1 and 3% by weight, in particular between 0.3 and 3% by weight .-%.

The viscosity of the agents according to the invention is adjusted or controlled essentially via the polymer content, the amounts required being able to vary from polymer to polymer. The surfactant composition used also plays a role in the choice of quantity.

Inorganic thickeners

Inorganic thickeners from the group of metal oxides, oxide hydrates, hydroxides, carbonates and phosphates and silicates can also be used. In In a particular embodiment, nanoparticulate compounds are used. Particles with an average particle size of 1 to 200 nm, preferably 5 to 100 nm, in particular 10 to 50 nm, are usually referred to as such, the value relating to the particle diameter in the longitudinal direction, ie in the direction of the greatest expansion of the particles.

Suitable oxides are, for example, magnesium oxide, aluminum oxide (Al ₂ O ₃ ), titanium dioxide, zirconium oxide and zinc oxide and silicon dioxide. A suitable oxide hydrate is, for example, aluminum oxide hydrate (boehmite) and suitable hydroxides are, for example, calcium hydroxide and aluminum hydroxide. Suitable silicates are, for example, magnesium silicate and aluminum silicates such as zeolites.

Nanoparticulate oxides, oxide hydrates or hydroxides can be produced by known processes, e.g. according to EP-A-0 711 217 (Nanophase Technologies Corp.). Oxide hydrates and hydroxides can also be obtained in very fine distribution by hydrolysis of organometallic compounds.

The company Nanophase Technologies Corp. sells under the trade name NanoTek ^® . the nanoparticulate oxides NanoTek ^® Aluminum Oxide (average particle size 37 nm), NanoTek ^® Antimony Tin Oxide, NanoTek ^® Barium Titanate, NanoTek ^® Barium Strontium Titanate, NanoTek ^® Cerium Oxide (average particle size 11 nm), NanoTek ^® Copper Oxide, NanoTek ^® Indium Oxide, NanoTek ^® Indium Tin Oxide (average particle size 14 nm), NanoTek ^® Iron Oxide (average particle size 26 nm), NanoTek ^® Iron Oxide, Black, NanoTek ^® Silicon Dioxide, NanoTek ^® Tin Oxide, NanoTek ^® Titanium Dioxide (average particle size 34 nm), NanoTek ^® Yttrium Oxide and NanoTek ^® Zinc Oxide (average particle size 36 nm) as well as NanoTek ^® Barium Oxide, NanoTek ^® Calcium Oxide, NanoTek ^® Chromium Oxide, NanoTek ^® Magnesium Oxide, NanoTek ^® Manganese Oxide, NanoTek ^® Molybdenum Oxide, NanoTek ^® Neodymium Oxide, NanoTek ^® Strontium Oxide and NanoTek ^® Strontium Titanate as well as the nanoparticulate silicate NanoTek ^® Zirconium Silicate. Suitable silicates are available under the trade names OptigeP from Süd-Chemie AG or Laponite ^® from Laporte Ltd. available.

Preferred silicates are layered silicates (phyllosilicates), in particular bentonites (as the main minerals of smectites, especially montmorillonite), montmorillonites (AI ₂ [(OH) ₂ / Si ₄ O _10] ^■ n H ₂ O or Al ₂ O ₃ ^■ 4 SiO ₂ ^• H ₂ O ^• n H ₂ O, clay mineral belonging to the dioctahedral (mica) smectites), kaolinite (Al ₂ [(OH) ₄ / Si ₂ O ₅ ] or Al ₂ O ₃ ^• 2 SiO ₂ ^■ 2 H ₂ O, triclinic two-layer clay mineral (1: 1 phyllo-silicate)), talc (hydrated magnesium silicate with the composition Mg ₃ [(OH) ₂ / Si O ₁₀ ] or 3 MgO ^• 4 SiO ₂ ^• H ₂ O) and particularly preferably hectorite (M ⁺ o, 3 (Mg _2ι7 Lio _{, 3} ) [Si ₄ O ₁₀ (OH) ₂ ], M ⁺ mostly = Na ⁺ , monoclinic clay mineral belonging to the smectites, similar to montmorillonite).

A preferred carbonate is hydrotalcite (international free name for dialuminium hexa- magnesium carbonate hexadecahydroxide tetrahydrate, Al ₂ Mg ₆ (OH) ₁₆ CO 3 ^• 4 H ₂ O).

Another preferred inorganic thickener is nanoparticulate boehmite (AIO (OH), aluminum oxide hydrate), which is available, for example, from Condea under the trade names DisperaP Sol P3 and DisperaP Sol P2.

In a particular embodiment of the invention, nanoparticulate inorganic compounds with a specific surface area of more than 200 m ² / g are used. A preferred nanoparticulate compound of this type is magnesium silicate of the layered silicate type with a specific surface area of 200 to 500 m ² / g, in particular 300 to 400 m ² / g. This material is inexpensively available in large quantities. The product is available under the trade names OptigeP SH (Süd-Chemie AG) and Laponite ^® XLG (Laporte Ltd.).

The content of optionally nanoparticulate inorganic thickeners is 0 to 5.0% by weight, preferably 0.1 to 3.5% by weight, particularly preferably 0.5 to 2.0% by weight.

In a particularly preferred embodiment, however, only polymeric thickeners are used.

surfactants

The agent according to the invention contains surfactants in a total amount of usually 0.5 to 40% by weight, preferably 1 to 20% by weight, in particular 3 to 18% by weight.

In the context of the present invention, unless otherwise stated, fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably having 6 to 22 carbon atoms. The former are preferred for ecological reasons, in particular because of their vegetable basis than based on renewable raw materials, but without restricting the teaching according to the invention to them. In particular, the oxo alcohols or their derivatives obtainable, for example, according to ROELEN's oxo synthesis can also be used accordingly. Whenever alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of the substance - sufficient to balance the charge - like the anion.

alkyl ether

Alkyl ether sulfates (fatty alcohol ether sulfates, INCI alkyl ether sulfates) are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, for the purposes of the present invention preferably with longer-chain alcohols, ie with aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms. As a rule, a complex mixture of addition products of different degrees of ethoxylation (n = 1 to 30, preferably 1 to 20, in particular 1 to 10, particularly preferably 1 to 5) is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Very particularly preferred according to the present invention are NIE derethoxylierte fatty alcohols with 1 to 4 ethylene oxide (EO), especially 1 to 2 EO, for example 1, 3 EO, such as Na-C ₁₂ fatty alcohol + 1.3EO -ι _4-sulfate. These are available, for example, under the trade name Texapon ^® SPN 70 (Cognis). Due to the production process, the alkyl ether sulfates always contain residual contents of non-alkoxylated fatty alcohol sulfates (n = 0), at least at the lower degrees of ethoxylation preferred here.

The agent according to the invention contains one or more alkyl ether sulfates in an amount of usually 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, in particular 2 to 8% by weight. -%.

alkylsulfonates

The alkyl sulfonates (INCI sulfonic acids) usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or poly-unsaturated, preferably branched, acyclic, saturated, alkyl radical with 6 to 22, preferably 9 to 20, in particular 11 to 18 and particularly preferably 13 to 17 carbon atoms. Suitable alkyl sulfonates are accordingly the saturated alkane sulfonates, the unsaturated olefin sulfonates and the ether sulfonates, which are formally derived from the alkoxylated alcohols on which the alkyl ether sulfates are also based, in which terminal ether sulfonates (/ 7-ether sulfonates) are bonded to the polyether chain with sulfonate Function and internal ether sulfonates (/ ether sulfonates) with sulfonate function linked to the alkyl radical differentiates.

According to the invention, preference is given to the alkanesulfonates, in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-C ₁₃ . ₁₇ alkane sulfonate (INCI Sodium C14-17 alkyl sulfonates lake), as is for example provided by the company Clariant under the name Hostapur ^® SAS 60th

The agent according to the invention contains one or more alkyl sulfonates in an amount of usually 0.05 to 10% by weight, preferably 0.25 to 7.5% by weight, in particular 0.5 to 5% by weight.

The alkyl ether sulfates and alkyl sulfonates and the further anionic surfactants are usually used as alkali metal, alkaline earth metal and / or mono-, di- or trialkanol ammonium salt and / or in the form of their with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and / or mono -, Di- or trialkanolamine used in situ to neutralize corresponding acid. Preferred as alkali metals are potassium and especially sodium, alkaline earth metals calcium and especially magnesium, and alkanolamines are mono-, di- or triethanolamine. The sodium salts are particularly preferred.

amphoteric

The amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include betaines, alkylamidoalkylamines, alkyl-substituted amino acids, aeylated amino acids or biosurfactants, of which betaines are preferred in the context of the teaching according to the invention.

The agent according to the invention contains one or more amphoteric surfactants in an amount of usually 0.05 to 10% by weight, preferably 0.25 to 5% by weight, in particular 0.5 to 3% by weight. Betaine

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazoliniumbetaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula I,

R ¹ - [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ² ) (R ³ ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y- (I) in R ^{1 is} a saturated or unsaturated C ₆ . ₂₂ -Alkylrest, preferably C ₈ -ι ₈ alkyl residue, in particular a saturated C ₁₀ - ₁ 6 alkyl residue, for example a saturated C _{12th 14} -alkyl radical,

X NH, NR ⁴ with the C 1-4 alkyl radical R ⁴ , 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 ² , R ³ independently of one another are a C 1 -C 4 -alkyl radical, optionally hydroxy-substituted, such as, for example, 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 ⁵ ) O or P (O) (OR ⁵ ) O, where R ^{5 is} a hydrogen atom

Is H or a C 1-4 alkyl radical.

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

Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamido betaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (I),

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (la)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (Ib)

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ S0 ₃ - (Ic)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ - (ld) in which R ^{1 has} the same meaning as in formula I.

Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula (Ia) and (Ib), most preferably the alkylamidobetaines of the formula (Ib).

Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamido propyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenylbe taine, betaine, canolamidopropyl betaine, capryl / capramidopropyl betaine, carnitine, cetyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, coco betaine, coco-hydroxysultaine, coco / oleamidopropyl betaine, coco-sultaine, decyl betaine Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaineyl, Betaine Milau , Minkamidopropyl Betaines, Myristamidopropyl Betaines, Myristyl Betaines, Oleamidopropyl Betaines, Oleamidopropyl Hydroxysultaine, Oleyl Betaines, Olivamidopropyl Betaines, Palmamidopropyl Betaines, Palmitamidopropyl Betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaines, Polytetrafluoroidene Betayl, Propylamidopinyl Betaine, Acetoxyin Propyl Betaine ropyl betaine, soyamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallow amidopropyl hydroxysultaine, tallow betaine, tallow dihydroxyethyl betaine, undecylene amidopropyl betaine and wheat germamidopropyl betaine. A preferred betaine is, for example, Cocamidopropyl Betaine (cocoamidopropyl betaine) (Dehyton ^® PK 45, Cognis).

alkylamidoalkylamines

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

(II)

R ⁶ -CO-NR ⁷ - (CH ₂ ) iN (R ⁸ ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - [CH (OH)] _l -CH ₂ -Z-OM (II) in R ^{6 is} a saturated or unsaturated C ₆ . ₂₂ -alkyl radical, preferably C ₈ . ₁₈ -alkyl radical, in particular a saturated C ₁₀ .i ₆ -alkyl radical, for example a saturated C ₁₂ . ₁₄ -alkyl radical,

R ⁷ 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 5, in particular 2 or 3,

R ^{8 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,

I 0 or 1, where k = 1 if I = 1,

Z CO, SO ₂ , OPO (OR ⁹ ) or P (O) (OR ⁹ ), where R ^{9 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, for example protonated mono-, di- or triethanolamine, is.

Preferred representatives satisfy the formulas lla to lld,

R ⁶ -CO-NH- (CH ₂ ) ₂ -N (R ⁸ ) -CH ₂ CH ₂ O-CH ₂ -COOM (lla)

R ⁶ -CO-NH- (CH ₂ ) ₂ -N (R ⁸ ) -CH ₂ CH ₂ O-CH ₂ CH ₂ -COOM (Mb)

R ⁶ -CO-NH- (CH ₂ ) ₂ -N (R ⁸ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -SO ₃ M (llc)

R ⁶ -CO-NH- (CH ₂ ) ₂ -N (R ⁸ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (lld) in which R ⁸ and M have the same meaning as in formula (II).

Exemplary alkylamido alkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropio- nate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearo - amphodipropionate, Disodium Laureth-5 diacetate Carboxyamphodiacetate, Disodium Lauroampho-, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipro- pionic Acid, Quaternium-85, Sodium Caproamphoacetate , Sodium caproamphohydroxy propyl sulfonate, sodium caproamphopropionate, sodium capryloamphoacetate, sodium capryloamphohydroxypropyl sulfonate, So dium Capryloamphopropionate, sodium coco amphoacetates, nate Cocoamphohydroxypropylsulfonate Sodium, Sodium Cocoamphopropio-, Sodium Comamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearo- amphopropionates, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropylsulfo- nate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate , Sodium Oleoamphohydroxypro- pylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, phopropionate Stearoam- Sodium, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, decylenoamphoacetate Sodium Unalloyed, Sodium Undecylenoamphopropionate, Sodium Wheat Germam- phoacetate and Trisodium Lauroampho PG-Acetate phosphate Chloride ,

Alkyl substituted amino acids

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

R ¹⁰ -NH-CH (R ¹¹ ) - (CH ₂ ) _U -COOM '(III) in R ^{10 is} a saturated or unsaturated C ₆ . ₂₂ -alkyl radical, preferably C ₈ . ₁₈ alkyl radical, in particular a saturated C-io- _. e-alkyl radical, for example a saturated C ₁₂ . ₁₄ -alkyl radical, R ^{11 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. protonated mono-, di- or triethanolamine, is alkyl-substituted imino acids according to formula (IV),

R ¹² -N - [(CH ₂ ) _v -COOM "] ₂ (IV) in which R ^{12 is} a saturated or unsaturated C _{6. 22} alkyl radical, preferably C _{8. 18} alkyl radical, in particular a saturated C ₁₀ - . ₆ alkyl group, for example a saturated _{C12. 14} -alkyl radical, v is a number from 1 to 5, preferably 2 or 3, especially 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, for example hydrogen and sodium or twice sodium , and mono- or dialkyl-substituted natural amino acids according to formula (V), R ¹³ -N (R ¹⁴ ) -CH (R ¹⁵ ) -COOM "'(V) in which R ^{13 is} a saturated or unsaturated C _{6. 22} - Alkyl radical, preferably C ₈ -C ₈ alkyl radical, in particular a saturated C _{10 6} alkyl radical, for example a saturated C ₁₂ alkyl radical, R ^{14 is} a hydrogen atom or a C _{1 4} alkyl radical, optionally hydroxy - or amine-substituted, for example a methyl, ethyl, hydroxyethyl or amine propyl radical, R ¹⁵ the residue of one of the 20 natural α-amino acids H ₂ NCH (R ¹⁵ ) COOH, and M "'a hydrogen, an alkali metal Alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolam in, is.

Particularly preferred alkyl-substituted amino acids are the aminopropionates according to the formula (purple), R ¹⁰ -NH-CH ₂ CH ₂ COOM '(purple) in which R ¹⁰ and M' have the same meaning as in formula (III).

Exemplary alkyl-substituted amino acids are the following compounds named according to INCI: aminopropyl lauryl glutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium laurododipropionate, aminodropropionate, disodium steariminodimine, disodium steariminodimine, disodium steariminodimine, disodium steariminodimine, disodium steariminodimine, disodium steariminodimine, disodium steariminodinodiphenate, disodium stearin imidodipinate, disodium stearin iminodiphenate, , Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropate.

Acylated amino acids

Acylated amino acids are amino acids, especially the 20 natural α-amino acids, which carry the acyl radical R ¹⁶ CO of a saturated or unsaturated fatty acid R ¹⁶ COOH on the amino nitrogen atom, where R ^{16 is} a saturated or unsaturated C ₆ . ₂₂ -alkyl radical, preferably C ₈ . ₁₈ -alkyl radical, in particular a saturated C ₁₀ . ₁₆ -A! Kylrest, for example a saturated C ₁₂ .ι ₄ alkyl. The acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt. Exemplary acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.

Amphotensidkombinationen

In a particular embodiment of the invention, a combination of two or more different amphoteric surfactants, in particular a binary amphoteric surfactant combination, is used.

The amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, particularly preferably cocoamidopropylbetaine.

Further, the amphoteric surfactants preferably contains at least one amphoteric surfactant is selected from group comprising Natriumcarboxyethylkokosphosphoethylimidazolin (phosphate photeric ^® TC-6), C _{8 10} -Amidopropylbetain (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ^® 810), N-2-hydroxyethyl-N- carboxymethyl-fettsäureamido-ethyl-Na

(Rewoteric ^® AMV) and N-Capryl / Caprin-amidoethyl-N-ethylether-propionate-Na (Rewoteric ^® AMVSF) and the betaine 3- (3-cocoamido-propyl) -dimethylarnmonium-2-hydroxypropanesulfonate (INCI Sultaine; Rewoteric ^® AM CAS) and the alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl- N "-carboxyethylaminoethyl) -essigsäureamido] -N, N-dimethyl-N-co- cos ammonium betaine (Rewoteric QAM ^® 50), in particular together with Cocoamido- propylbetain.

In a further particular embodiment, the agent according to the invention contains one or more amphoteric surfactants in an amount of less than 10% by weight.

In addition to alkyl ether sulfates, alkyl sulfonates and amphoteric surfactants, the agent according to the invention, in particular for improving the cleaning action, run-off behavior and / or drying behavior, can additionally contain one or more further anionic surfactants, nonionic surfactants and / or cationic surfactants.

Other anionic surfactants

The agent according to the invention can additionally contain one or more further anionic surfactants, usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 3% by weight, most preferably 0.5 to 2.5% by weight, for example 2% by weight.

Suitable further anionic surfactants are, in particular, aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates, as well as ester (sulfo fatty acid esters), Ligninsulfo- nate, alkylbenzenesulfonates, fatty acid cyanamides, anionic Sulfobemsteinsäuretenside, fatty acylaminoalkanesulfonates (taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

Suitable further anionic surfactants are also anionic gemini surfactants with a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula O ₃ S (C ₆ H ₃ R) O (C ₆ H ₃ R ') SO ₃ ^", in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R ¹ is R or H (Dowfax ^® Dry hydrotropes Powder with C ₁₆ alkyl radical (s); INCI Sodium Hexyldiphenyl ether sulfonates, Disodium Decyl phenyl ether disulfonate, disodium lauryl phenyl ether disulfonate, disodium cetyl phenyl ether disulfonate) and fluorinated anionic surfactants, in particular perfluorinated alkyl sulfonates such as ammonium C _9/10 perfluoroalkyl sulfonate (Fluorad ^® FC 120) and perfluorooctane sulfonic acid potassium salt (fluorad ^® FC 95). Anionic sulfosuccinic acid surfactants

Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, in particular sulfosuccinates and sulfosuccinamates, extremely preferably sulfosuccinates. The sulfosuccinates are the salts of the mono- and diesters of sulfosuccinic acid HOOCCH (SO ₃ H) CH ₂ COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of Understands sulfosuccinic acid. A. Domsch and B. Irrgang in Anionic surfactants: organic chemistry (edited by HW Stäch; Surfactant science series; volume 56; ISBN 0-8247-9394-3; Marcel Dekker, Inc., New York provide a detailed description of these known anionic surfactants 1996, pp. 501-549).

The salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts, most preferably sodium salts.

In the sulfosuccinates, one or both carboxyl groups of sulfosuccinic acid are preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acylclic or cyclic, optionally alkoxylated alcohols with 4 to 22, preferably 6 to 20, in particular 8 to 18 , particularly preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified. Particularly preferred are the esters of unbranched and / or saturated and / or acyclic and / - or alkoxylated alcohols, in particular unbranched, saturated fatty alcohols and / - or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols with a degree of alkoxylation from 1 to 20, preferably 1 to 15, in particular 1 to 10, particularly preferably 1 to 6, extremely preferably 1 to 4. In the context of the present invention, the monoesters are preferred over the diesters. A particularly preferred sulfosuccinate is sulfosuccinic acid, lauryl polyglycol ester di-sodium salt (lauryl-EO sulfosuccinate, di-Na salt; INCI Disodium Laureth sulfosuccinate), which, for example, as Tego ^® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate content of 30 wt .-% is commercially available.

In the sulfosuccinamates or sulfosuccinamides, one or both of the carboxyl groups of sulfosuccinic acid preferably form with a primary or secondary amine, the one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals with 4 to 22, preferably 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, most preferably 12 to 14 carbon atoms, a carboxamide. Unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals, are particularly preferred.

Also suitable are, for example, the following sulfosuccinates and sulfosuccinamates designated according to INCI, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: ammonium dinonyl sulfosuccinate, ammonium lauryl sulfosuccinate, diammonium dimethicone copolyol sulfosuccinate, diammonium lauramido-MEA sulfosuccinate, sulfonuccinate, diammonium Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Cisuccinate Sulfosuccinate, Dioctyl Sodium Disosamino -Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate, Disodium Coco- Glucoside Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium C ₁₂ . ₁₅ Pareth Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium Deceth-6 Sulfosuccinate, Disodium Dihydroxyethyl Sulfosuccinylundecylenate, Disodium Dimethicone Copolyol Sulfosuccinate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Isodecyl Sulfosuccinate, Disodium Isostinosulfinate, Disodium Isostinosulfinate , Disodium Laneth-5 Sulfosuccinate, Disodium Lauramido MEA-Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate, Disodium Lauramido PEG-5 Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Laur Disyl Myristamido MEA sulfosuccinate, disodium nonoxynol-10 sulfosuccinate, disodium oleamido MEA sulfosuccinate, disodium oleamido MIPA sulfosuccinate, disodium oleamido PEG-2 sulfosuccinate, disodium oleth-3 sulfosuccinate, disodium oleyl sulfosuccinate, disodium palmit e, disodium palmitoleamido PEG-2 sulfosuccinate, disodium PEG-4 cocamido MIPA sulfosuccinate, disodium PEG-5 lauryl citrate sulfosuccinate, disodium PEG-8 palm glycerides sulfosuccinate, disodium ricinoleamido MEA sulfosuccinate, disodium sitosterethine, 14 disodium sitosterethane, 14 disodium Stearamido MEA-Sulfosuccinate, Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA-Sulfosuccinate, Disodium Tallow Sulfosuccinamate, Disodium Tridecylsulfosuccinate, Disodium UndecylenamecidamidoA Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Di-TEA-Oleamido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / MEA Laureth-2 Sulfosuccinate and Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate. Another suitable sulfosuccinamate is disodium C ₁₆ -. _8- alkoxypropylene sulfosuccinamate.

Preferred anionic sulfosuccinic are imidosuccinate, mono-Na-sulfosuccinic acid diisobutyl ester (Monawet MB ^® 45), mono-Na-sulfosuccinic acid di-octyl ester (Monawet MO-84 ^® R2W, Rewopol SB ^® DO 75), Mono-Na sulfosuccinic acid di-tridecyl ester (Monawet ^® MT 70), fatty alcohol polyglycol sulfosuccinate-Na-NH ₄ salt (sulfosuccinate S-2), di-Na sulfosuccinic acid mono-C _12/1 -3EO-ester (Texapon ^® SB-3), diisooctyl sodium sulfosuccinate (Texin ^® DOS 75) and di-Na sulfosuccinic acid mono-C _12/18 ester (Texin ^® 128-P), in particular those with the inventive tenside combination with regard to the runoff and / or drying behavior synergistically interacting mono-Na-sulfosuccinic acid di-octyl esters.

In a particular embodiment, the agent according to the invention contains, as anionic sulfosuccinic acid surfactants, one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 2% by weight, extremely preferably 0.5 to 1.5% by weight, for example 1% by weight.

Nonionic surfactants

The agent according to the invention can additionally contain one or more nonionic surfactants, usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0 , 2 to 2.5% by weight, most preferably 0.5 to 2% by weight.

Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers are also suitable. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides. Fettalkoholpolyglykolether

According to the invention, fatty alcohol polyglycol ethers are C ₁₀ alkoxylated with ethylene (EO) and / or propylene oxide (PO), unbranched or branched, saturated or unsaturated. To understand ₂₂ alcohols with a degree of alkoxylation of up to 30, preferably ethoxylated C _{10 8} fatty alcohols with a degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular 1 to 12, particularly preferably 1 to 8, most preferably from 2 to 5, for example C ₁₂ . ₁₄ fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of C ₁₂ . -Fatty alcohol ethoxylates with 3 and 4 EO in a weight ratio of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO.

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 formula VI,

_R 17 _R 18 _R 19 _{N +} _ ₀ _ _{(V |)}

R ¹⁷ - [CO-NH- (CH ₂ ) _w ] _z -N ⁺ (R ¹⁸ ) (R ¹⁹ ) -O- (VI) in R ^{17 is} a saturated or unsaturated C ₆ . ₂₂ -alkyl radical, preferably C ₈ . ₁₈ alkyl radical, preferably a saturated C _10-16 alkyl group, for example a saturated C _{12th 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 ) ₂ , where z in each case represents a number from 1 to 10, preferably 2 to 5, in particular 3, and

R ⁸ , R ¹⁹ independently of one another are a C 1 -C 4 -alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following named according to INCI compounds: Almondamidopropylamine oxides, Babassuamidopropylamine oxides, Behenamine oxides, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-mor- pholine oxides, Decylamine Oxide, Decyltetradecylamine oxides, Diaminopyrimidine Oxide, Dihydroxyethyl C. _{8 10} Alkoxypropylamine oxides, dihydroxyethyl Cg-n Alkoxypropylamine oxides, dihydroxyethyl C _12-15 Alkoxypropylamine oxides, dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine oxides, dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxides, hydroxyethyl hydroxypropyl C ₁₂ -ι ₅ alkoxypropylamine oxides, isostearamidopropylamine oxides, isostearamidopropyl morpholine oxides, lauramidopropylamine oxides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amine oxides, minkamidopropylamine oxides, myristamidopropylamine oxides, myristamidopropylamine oxides, myrististopropylamine oxides, myrististopropylamine oxides, Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Oxamide, Oxide, Stamide Taliowamine Oxide, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide. A preferred amine oxide is, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide).

sugar surfactants

Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerol amides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides, such as those described in WO 97/00609 (Henkel Corporation) publications cited therein are described (pages 4 to 12), to which reference is made in this regard and the content of which is hereby incorporated into this application. Preferred sugar surfactants in the context of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters. The ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C.sub.14 alcohols or glycols such as ethylene and / or propylene glycol, the sugar hydroxy group also comprising polyethylene glycol - Can carry col and / or polypropylene glycol residues. The esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, in particular a C ₆ . ₂₂ fatty acid.

sugar amides

Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, with 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "for a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, with 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, a Cvs-alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, te / f-butyl or n-pentyl radical, or hydrogen and Z for one Sugar residue, ie a monosaccharide residue. Particularly preferred sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.

Alkylpolyglykoside

In the context of the teaching according to the invention, the alkyl polyglycosides (APG) are particularly preferred sugar surfactants and preferably satisfy the general formula R ²⁰ O (AO) _a [G] _x , in which R ^{20 is} a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a represent the average degree of alkoxylation from 0 to 20. The group (AO) _{a may} also contain various alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, where a is the average total degree of alkoxylation, ie the sum of the degree of ethoxylation and propoxylation. Unless otherwise specified below, the APG alkyl radicals R ²⁰ are linear unsaturated radicals with the number of carbon atoms indicated.

APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry. The index number x indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be an integer in a given compound and here can take on the values x = 1 to 6, the value x is for a certain alkyl glycoside an analytically calculated quantity, 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 is 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 ²⁰ can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol as well as their technical mixtures as they are for example 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 ²⁰ 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, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures are also to be mentioned.

Particularly preferred APGs are not alkoxylated (a = 0) and satisfy the formula RO [G] _x , in which R, as before, for a linear or branched, saturated or unsaturated alkyl radical having 4 to 22 carbon atoms, [G] for a glycosidically linked sugar radical, preferably glucose residue, and x is a number from 1 to 10, preferably 1.1 to 3, in particular 1, 2 to 1, 6. Accordingly, preferred alkyl polyglycosides are C ₈ . ₁₀ - and a C ₁₂ . _14- alkyl polyglucoside with a DP degree of 1.4 or 1.5, in particular C ₈ . ₁₀ - alkyl-1, 5-glucoside and C ₁₂ -ι ₄ -alkyl-1, 4-glucoside.

Cationic surfactants

The agent according to the invention can additionally contain one or more cationic surfactants (cationic surfactants; INCI Quaternary Ammonium Compounds), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 up to 3% by weight, particularly preferably 0.2 to 3% by weight, extremely preferably 0.5 to 2.5% by weight, for example 2% by weight.

Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, as described, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5. - Stuttgart, New York: Thieme, 1995) as antimicrobial agents By using quaternary surface-active compounds with antimicrobial activity, the agent can be endowed with an antimicrobial activity or its antimicrobial activity, which may already be present due to other ingredients, can be improved.

Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV; INCI Quaternary Ammonium Compounds) according to the general formula (R ^I ) (R ") (R ^I ") (R ^IV ) N ⁺ X ^" , in which R ¹ to R ^{ιv are the} same or various C, - ₂₂ -alkyl radicals, C _{7, 28} - aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, as in pyridine, even three radicals together with the nitrogen atom being the hetero- form a cycle, for example a pyridinium or imidazolinium compound, and X ^{~ are} halide ions, sulfate ions, hydroxide ions or similar anions. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are by reacting tertiary amines with alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyldimethyl-C ₁₂ -alkylammonium chloride, CAS No 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0) , Benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1, 1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0 ), Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride ( CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Preferred QAV are the benzalkonium chloride with C ₈ -C ₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -Aklyl-benzyl-dimethylammonium chloride. A particularly preferred QAC is Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ^®).

To avoid possible incompatibilities of the cationic surfactants with the anionic surfactants contained according to the invention, anionic surfactant-compatible and / or as little cationic surfactant as possible is used or, in a particular embodiment of the invention, cationic surfactants are completely dispensed with.

solvent

The water content of the aqueous composition according to the invention is usually 60 to 99% by weight, preferably 75 to 95% by weight. The agent according to the invention can advantageously additionally contain one or more water-soluble organic solvents, usually in an amount of 0.1 to 8% by weight, preferably 1 to 6% by weight.

Within the framework of the teaching according to the invention, the solvent is used, in particular, as a hydrotrope, viscosity regulator and / or cold stabilizer. It has a solubilizing effect, especially for surfactants and electrolytes, as well as perfume and dye, and thus contributes to their incorporation, prevents the formation of liquid-crystalline phases and plays a part in the formation of clear products. The viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can cause an excessive drop in viscosity. Finally, the cold cloud and clear point of the agent according to the invention decrease with increasing amount of solvent.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1 -C 8 -hydrocarbons, preferably C ₂ . ₁₅ -hydrocarbons, with at least one hydroxyl group and optionally one or more ether functions COC, ie oxygen atoms interrupting the carbon atom chain.

Preferred solvents are the C ₂ —etherly etherified on one side with a C 1-4 alkanol. ₆ -alkylene glycols and poly-C ₂ . _3- alkylene glycol ethers with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule as well as the C ^ e-alcohols, preferably ethanol, n-propanol or / so-propanol, especially ethanol.

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 (/ so-Propanol), 3-Methoxybutanol, Methoxydiganol, Methoxy , Methoxyisopropanol, 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), pro- pylene glycol, propylene glycol butyl ether, propylene glycol propyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

Particularly preferred solvents are the poly-C ₂ etherified on one side with a C _L e-alkanol. _3- alkylene glycol ethers 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).

Extremely preferred solvents are the C ₂ . _3- Alcohols ethanol, n-propanol and / or / so-propanol, in particular ethanol.

In addition to the solvents described above, alkanolamines and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical can also be used as solubilizers, in particular for perfume and dyes.

additives

To further improve the runoff and / or drying behavior, the agent according to the invention can contain one or more additives from the group of the surfactants, the polymers and the builders (builders), usually in an amount of 0.001 to 5% by weight, preferably 0, 01 to 4% by weight, in particular 0.1 to 3% by weight, particularly preferably 0.2 to 3% by weight, extremely preferably 0.5 to 2.5% by weight, for example 2% by weight %.

Suitable surfactants as additives are certain of the amphoteric surfactants, further anionic surfactants, nonionic surfactants and cationic surfactants already described above, which are repeated here. The content of surfactant additives should preferably be chosen so that the total surfactant content is in the quantitative ranges outlined above.

For the additives mentioned below, one or more trade names are sometimes given in parentheses, under which the respective one is commercially available.

As additives suitable amphoteric surfactants are, in particular Natriumcarboxyethylkokos- phosphoethylimidazolin (Phosphoteric ^® TC-6), C _{8 10} -Amidopropylbetain (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ^® 810), N-2-hydroxyethyl-N-carboxymethyl-fatty acid amido- ethylamine-Na (Rewoteric ^® AMV) and N-capryl / caprin-amidoethyl-N-ethylether-propionate-Na (Rewoteric ^® AMVSF) and betaine 3- (3-cocoamido-propyl) -dimethylammonium-2- hydroxypropanesulfonate (INCI Sultaine; Rewoteric ^® AM CAS) and the alkylami- doalkylamin N- [N '(N "-2-hydroxyethyl-N" -carboxyethyIaminoethyl) -essigsäureamido] -N, N-dimethyl-N-coco-ammonium betaine (Rewoteric QAM ^® 50).

Other anionic surfactants suitable as additives are, in particular, anionic gemini surfactants with a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula O ₃ S (C ₆ H ₃ R) O (C ₆ H ₃ R ^, ) Sθ ₃ ^", in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax ^® Dry hydrotropes Powder with C ₁₆ alkyl radical (s); INCI Sodium Hexyldiphenyl ether sulfonates, Disodium Decyl phenyl ether disulfonate, disodium lauryl phenyl ether disulfonate, disodium cetyl phenyl ether disulfonate) and the fluorinated anionic surfactants ammonium-C _9/10 perfluoroalkyl sulfonate (Fluorad ^® FC 120), perfluoro-octane sulfonic acid potassium salt (Fluorad ^® FC 95) as well as the sulfosuccinic acid surfactants imidosuccinate, mono-Na sulfosuccinic acid di-isobutyl ester (Monawet ^® MB 45), mono-Na sulfosuccinic acid di-octyl ester (Monawet ^® MO 84 R2W, Rewopol ^® SB DO 75), mono Na sulfobernsteinsäur e-di-tridecyl ester (Monawet ^® MT 70), fatty alcohol polyglycolsulfosuccinate-Na-NH ₄ salt (sulfosuccinate S-2), di-Na-sulfosuccinic acid mono-C _{12 14} -3EO-ester (Texapon ^® SB-3 ), Diisooctyl sodium sulfosuccinate (Texin ^® DOS 75) and di-Na sulfosuccinic acid mono-C _{12 18} ester (Texin ^® 128 P).

Nonionic surfactants suitable as additives are, in particular, C ₁₀ dimethylamine oxide (Ammonyx ^® DO), C _10/14 fatty alcohol + 1.2PO + 6.4EO (Dehydol ^® 980), C _12/14 fatty alcohol + - 6EO (Dehydol ^® LS6) , C ₈ fatty alcohol + 1, 2PO + 9EO (Dehydol ^® O10), C _16/20 -Guerbet alcohol + 8EO, n-butyl-sealed (Dehypon ^® G2084), mixture of several n-butyl-sealed nonionic surfactants and C _{8 10} APG (Dehypon ^® Ke 2555), C _8/10 fatty alcohol + 1PO + - 22EO- (2-hydroxydecyl) ether (Dehypon ^® Ke 3447), C _12/14 fatty alcohol + 5EO + 4PO (Dehypon ^® LS 54 G), Cι _2/14 -fatty alcohol + 5EO + 3PO, methyl-locked (Dehypon ^® LS 531), C _12/14 -fatty alcohol + 10EO, n-butyl-locked (Dehypon ^® LS 104 L), C _{ι r} Oxo alcohol + 8EO (Genapol ^® UD 088), C ₁₃ oxo alcohol + 8EO (Genapol ^® X 089), C _{13 /} ι ₅ fatty alcohol EO adduct, n-butyl sealed (Plurafac ^® LF 221) and alkoxylated Fatty alcohol (Tegotens ^® EC-11).

As additives suitable cationic surfactants are particularly compatible with anionic surfactants, cationic surfactants such as quaternary ammonium compounds, for example Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ^®).

Polymers that are suitable as additives are primarily nonionic substances from the group of solubilizers. The polyalkylene glycols should be mentioned here in particular. sur- It has been found that, when using up to 5% by weight of additives from this group of substances, it is possible to achieve a particularly good foaming behavior of the composition. Polyalkylene glycols with a branched chain and, among these, the polypropylene glycol are particularly preferred. Good foaming behavior means that the undiluted agent produces little foam when sprayed and half of this foam is broken down after only five minutes. If, on the other hand, the agent is used in dilute solution, sufficient amounts of a stable foam which is stable for at least 15 minutes, preferably at least 30 minutes, are formed. This foaming behavior is desired by the consumer because it is synonymous with high effectiveness and cleaning performance.

The agent according to the invention can contain 0 to 5% by weight, preferably 1 to 4% by weight, particularly preferably 2% by weight, of polyalkylene glycols. Polyalkylene glycols with a branched chain are preferably used, particularly preferably polypropylene glycol (PPG) with molar masses from 200 to 10,000, preferably 400 to 2000, in particular the polypropylene glycols PPG 400 and PPG 2000. The use of PPG 2000 is preferred if the agent is particularly suitable for spraying should be low foaming. If a stronger foam development is desired, the PPG 400 is preferably used, on the other hand, a polypropylene glycol is not added to an agent that is supposed to be particularly foaming when sprayed. The foaming behavior was determined according to Wagner.

Other suitable polymers are maleic acid-acrylic acid copolymer Na salt (Sokalan ^® CP 5), modified polyacrylic acid Na salt (Sokalan ^® CP 10), modified polycarboxylate Na salt (Sokalan ^® HP 25) , polyalkylene oxide modified heptamethyl trisiloxane (Silwet ^® L-77), polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ^® L-7608) and polyether (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether), preferably water-soluble linear polyether having terminal polyether as Tegopren ^® 5840, Tegopren ^® 5843, Tegopren ^® 5847, Tegopren ^® 5851, Tegopren ^® 5863, Tegopren ^® 5878).

Particularly suitable builder substances are polyaspartic acid sodium salt, ethylenediamine triacetate cocoalkylacetamide (Rewopol ^® CHT 12), methylglycinediacetic acid tri-sodium salt (Trilon ^® ES 9964) and acetophosphonic acid (Turpinal ^® SL).

Mixtures with surfactant or polymeric additives show synergisms in the case of Monawet ^® MO-84 R2W, Tegopren ^® 5843 and Tegopren ^® 5863. The use of the Tegoprene types 5843 and 5863 is, however, for the application on hard surfaces made of glass, especially glass dishes, less preferred because they can pull silicone surfactants onto glass.

In a particular embodiment of the invention, the additives mentioned are dispensed with.

Dicarboxylic acids (salts)

To stabilize the composition of the invention, particularly at high surfactant content, one or more dicarboxylic acids and / or their salts are added, particularly to a composition of Na salts of adipic, glutaric and succinic acid, for example, under the trade name Sokalan ^® DSC is available. The use here is advantageously in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1, 3 to 6% by weight and particularly preferably 2 to 4% by weight.

A change in the dicarboxylic acid (salt) content - especially in amounts above 2% by weight - can contribute to a clear solution of the ingredients. It is also possible to influence the viscosity of the mixture by this agent within certain limits. This component also influences the solubility of the mixture. "This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30% by weight.

However, if they can be dispensed with, the agent according to the invention is preferably free of dicarboxylic acid (salts).

enzymes

The agent according to the invention can furthermore contain one or more optionally stabilized enzymes.

In particular on chemically diverse soiling, it can be advantageous to use several different washing and / or cleaning-active enzymes. These include, for example, proteases, but also lipases, cutinases, esterases, pullulanases, celluloses, hemicellulases and / or xylanases, and mixtures thereof. Other enzymes extend the cleaning performance of the corresponding agents by their specific enzymatic performance. These include, for example, oxidoreductases or peroxidases as components of enzymatic bleaching systems, for example laccases, β-glucanases or pectin-dissolving enzymes. The agent according to the invention can furthermore contain one or more different amylolytic enzymes, in particular α-amylases. examples Games for commercially available amylases are BAN ^® , Termamyl ^® , Purastar ^® , Amylase-LT ^® , Maxamyl ^® , Duramyl ^® and / or Purafect ^® OxAm.

As described, for example, in European patent EP 0 564 476 or in international patent applications WO 94/23005, the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. The enzymes are particularly preferably stabilized against oxidative degradation, as is known from international patent application WO 94/18314.

The cleaning agent can contain enzymes in amounts of 0 to 1% by weight. Enzymes used with particular preference are proteases, amylases, peroxidases, lipases and glucanases.

Auxiliaries and additives

In addition, one or more other additives and additives - especially in hand dishwashing detergents and cleaning agents for hard surfaces - can be used, especially UV stabilizers, perfume, pearlescent agents (INCI opacifying agents; e.g. glycol distearate, e.g. Cutina ^® AGS from Henkel KGaA, or mixtures containing this, for example the Euperlane ^® from Henkel KGaA), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7) also known as bronopol) which is commercially available for example as Myacide ^® BT or as Boots Bronopol ST from Boots, or under the trade name Parmetol® A28 by the company. Schülke & Mayr commercially available isothiazolinone Bromnitro- propanediol preparation) and skin feel-improving or caring additives (e.g. dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydr olysate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., Allantoin, AHA complexes), in amounts of usually not more than 5% by weight. Some of these adjuvants can also serve to aid cleaning performance or enhance other desirable properties. For example, terpene hydrocarbons (eg limonene), which have a fat-dissolving effect, can be contained in the perfume; Mint extracts have antibacterial properties, for example. The pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, a range from 4 to 13, preferably 5.5 to 12, being preferred. The pH is measured in bulk.

To adjust and / or stabilize the pH, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0 , 01 to 2% by weight, particularly preferably 0.05 to 1% by weight, extremely preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid and citrates, in particular sodium and potassium lead rates, for example trisodium citrate-2 H ₂ O and tripotassium citrate-H ₂ O.

manufacturing

The agent according to the invention can be prepared by stirring the individual components together in any order. Only the microcapsules are last worked into the agent to avoid shearing during the manufacturing process. Gas bubbles, e.g. Air, argon, oxygen, nitrogen, carbon dioxide or also propane, butane, propellant gases and gas mixtures are also incorporated last by opening and / or by direct introduction of the corresponding gas (s). Water, surfactants and, if appropriate, further ingredients mentioned above are preferably stirred together. If unencapsulated perfume and / or dye are used, they are then added to the solution obtained. The pH is then adjusted as previously described. If a thickener is used, longer stirring may be necessary for reasons of solubility.

spray dispenser

The cleaning agent according to the invention is sprayable and can therefore be used in a spray dispenser. The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers, self-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate. Spray dispensers are Licher in WO 96/04940 (Procter & Gamble) and the US patents cited therein for spray dispensers, to which all references are made in this regard and the content of which is hereby incorporated into this application. WO 97/02896 (Procter & Gamble) also describes a suitable spray dispenser which is used to spray viscous and / or solids-containing liquids. Spray dispensers which can preferably be used for the cleaning agents according to the invention can also be found in applications WO 00/76876, WO 00/33969 and WO 00/33970 (all Afa Polytek). To spray higher viscosity agents and in particular to spray the microcapsules, the spray dispenser, especially the spray nozzle used, must be adapted accordingly, in particular the diameter of the spray opening must be modified accordingly. In addition, the selection of the appropriate capsule material can counteract premature shearing or clogging of the spray nozzle.

By selecting suitable nozzle parameters, the noise generated when the agent is sprayed can also be modified. By using a tube as a resonance body in front of the nozzle, a low tone is generated when using the cleaner, while the spray jet causes a higher hissing sound in conventional spray dispensers. The sound pressure increases in the range from 0 to 8000 Hz by at least 10 dB (A), preferably by at least 20 dB (A). In the high frequency range (> 10000 Hz), however, the increase is preferably less than 10 dB (A); It is particularly preferred if the increase is negative, that is to say the sound pressure decreases in this area, since these sounds are often perceived as unpleasant. In the range between 4000 and 10000 Hz, the increase in sound pressure is preferably linear.

The tube upstream of the nozzle thus serves to amplify the tones of lower frequencies, which are generally perceived as more pleasant, while high-frequency tones, which are often perceived as unpleasant, are perceived to a lesser extent, for example as shrill whistling, hissing or squeaking preferably weakened, i.e. perceived more quietly. A further modification of the spray noise is possible by varying the recipe. Examples

The following compositions of the invention were made. The pH values were adjusted in the usual way by adding 30% sodium hydroxide solution. The proportions of the ingredients in the composition are shown in the table in% by weight.

a: Texapon SPN 70 (Cognis) b: e.g. Dehyton PK 45 (Henkel) or Tego Betain F 50 DW c: Hostapur SAS 60 (Clariant) d: Dehydol 980 (Cognis) e: Rhodopol T (Rhodia) f: Keltrol RD ( CP Kelco) g: Kelzan ASXT (CP Kelco) h: Carbopoi ETD 2623 (BF Goodrich) i: Carbopoi Aqua 30 (BF Goodrich) j: Acusoi 830 (Rohm & Haas) k: Myacide BT (Bronopol = 2-bromo-2 -nitropropan-1, 3-diol, boots)

I: Lipotec A2 Type 3 (pearls filled with aloe vera, Lipotec)

Viscosity 1 means the viscosity at a shear force of 0.3 rpm, viscosity 2 means that at 30 rpm. Measurements were made at 20 ° C using a Brookfield viscometer, spindle 31.

Claims

claims

1. Sprayable liquid aqueous cleaning agent, characterized in that it is a surfactant combination of alkyl ether sulfate, sec. Contains alkane sulfonate and amphoteric surfactant and microcapsules with one or more active ingredients.

2. Cleaning agent according to claim 1, characterized in that it is thixotropic.

3. Cleaning agent according to one of claims 1 and 2, characterized in that it is 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-%, in particular 2 to Contains 8 wt .-% alkyl ether sulfate.

4. Cleaning agent according to one of the preceding claims, characterized in that it 0.05 to 10 wt .-%, preferably 0.25 to 7.5 wt .-%, in particular 0.5 to 5 wt .-% sec. Contains alkanesulfonate.

5. Cleaning agent according to one of the preceding claims, characterized in that it contains 0.05 to 10 wt .-%, preferably 0.25 to 7.5 wt .-%, in particular 0.5 to 5 wt .-% amphoteric surfactant.

6. Cleaning agent according to one of the preceding claims, characterized in that at least one betaine is used as the amphoteric surfactant.

7. Cleaning agent according to one of the preceding claims, characterized in that it contains further anionic, nonionic, amphoteric and / or cationic surfactants.

8. Cleaning agent according to one of the preceding claims, characterized in that it contains at least one thickener in amounts of 0.1 to 3 wt .-%.

9. Cleaning agent according to one of the preceding claims, characterized in that it contains electrolyte salts and / or one or more polymers or (possibly nanoparticulate) inorganic thickeners as thickeners.

10. Cleaning agent according to one of the preceding claims, characterized in that it contains a polysaccharide, preferably a xanthan gum, as a thickener.

11. Cleaning agent according to one of the preceding claims, characterized in that it contains water-soluble organic solvents in amounts of 0.1 to 8 wt .-%, preferably 1 to 5 wt .-%.

12. Cleaning agent according to one of the preceding claims, characterized in that it contains at least one mono- or polyhydric alcohol as water-soluble organic solvent, preferably at least one monohydric alcohol, particularly preferably ethanol.

13. Cleaning agent according to one of the preceding claims, characterized in that the microcapsules are visible to the naked eye and a diameter of 0.01 to 6 mm, in particular from 0.05 to 4 mm, most preferably from 0.1 to 2 mm to have.

14. Cleaning agent according to one of the preceding claims, characterized in that the microcapsules contain active substances, the active substances being preferably essential oils, perfumes, bleaching system components, enzymes, care and protective components for the hard surface, additives for improving the wash load gloss, dermatologically active substances, antibacterial agents as well as dyes or pearlescent agents are used.

15. Cleaning agent according to one of the preceding claims, characterized in that it contains further additives, auxiliaries and additives such as builders, UV stabilizers, corrosion inhibitors and / or preservatives.

16. Cleaning agent according to one of the preceding claims, characterized in that its viscosity at a shear rate of 30 rpm 100 to 10000 mPa-s, preferably 500 to 9000 mPa-s, particularly preferably 650 to 8000 mPa-s and at a shear rate from 0.3 min is 8000 to 130,000 mPas, preferably 10,000 to 120,000 mPas, particularly preferably 12,000 to 110,000 mPas (20 ° C., Brookfield viscometer, spindle 31).

17. Cleaning agent according to one of the preceding claims, characterized in that it has a pH of 4 to 13, preferably 5.5 to 12.

18. Product containing an agent according to any one of claims 1 to 17 and a spray dispenser.

19. Sprayable cleaning agent according to one of the preceding claims 1 to 17 as part of a product according to claim 18, characterized in that when spraying i) the sound pressure in the range from 0 to 8000 Hz increases by at least 10 dB (A), preferably by at least 20 dB (A); ii) the increase in sound pressure in the range between 4000 and 10000 Hz is almost linear and iii) the sound pressure in the frequency range above 10000 Hz increases by less than 10 dB (A), preferably decreases.

20. Use of an agent according to one of claims 1 to 17 and 19 or a product according to claim 18 for dishwashing.

21. Use of an agent according to one of claims 1 to 17 and 19 or a product according to claim 18 for cleaning hard surfaces.

22. A process for the preparation of an agent according to any one of claims 1 to 17 and 19, characterized in that the individual components are stirred together in any order and the microcapsules are last incorporated.