DE10162649A1 - Detergent with 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

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

Hand dishwashing detergents are usually used by either Dosage in a container with warm water, the dishes and if necessary after a short soak time with a sponge, brush, cloth or other Aid cleans, or the agent is undiluted on a sponge, a cloth or another aid and the dishes, if necessary after a brief immersion in warm water, cleaned under running water. In both cases, the consumer faced several problems of dosage. Especially thin liquids are often overdosed, since it is difficult to control the delivery from the storage bottle. Furthermore, dishwashing detergents often cannot be cleaned properly from the storage bottle remove so that drops run down the bottle. Hereby comes the consumer undesirably comes into contact with the next time it is removed undiluted means. This disadvantage can be avoided by setting a higher viscosity can be eliminated, however, sometimes it can be especially with more viscous agents it may be difficult to completely empty the storage bottle.

After cleaning the dishes, the dishes will either simply dry left or dried in a further operation, usually with the help of a absorbent article. Simply letting it dry is less labor-intensive and takes time but longer and often leads especially to glasses and other glass dishes Formation of undesirable visible residues such as stains (water stains) or streaks as well as a loss of gloss or dull appearance. When removing a cleaned glass or plates from the washing liquor, the washing liquor is first removed or poured off and placed glass or plate to dry. The on the surface of the Glases or Teller's remaining rinsing liquor layer now runs slowly until finally the rinsing liquor layer on the surface has become so thin that it no longer expires, but only decreases through (self-) drying. The drying takes place too already take place during the process.

US Pat. No. 5,883,062 describes a hand dishwashing detergent comprising 1 to 80% by weight Anionic surfactant and 0.05 to 10% by weight of divalent ions (calcium, magnesium or mixtures), which is formulated so that a 1% aqueous solution at 20 ° C one pH is between 3.5 and 4.5. The agent should preferably be used in this way come that it is sprayed onto the dishes to be cleaned, so that the stronger contaminated parts are treated with larger amounts than the lighter ones dirty, and after a short exposure time rinsed off again. There will be no reference to an improved drainage and drying behavior.

US 3,708,429 teaches a detergent composition which is primarily as Hand dishwashing liquid is used. The composition essentially comprises one anhydrous mixture of a surfactant, an alkaline catalyst, an acid releasing substance and a lower aliphatic alcohol, preferably ethanol or Methanol. The agent is preferably applied to the items to be cleaned sprayed on to make skin contact with the initially strongly alkaline agent avoid. The alkalinity should remove grease dirt in particular. Through the Subsequent addition of water releases the acid and at least the agent partially neutralized so that it is less harmful to the skin. This means too is not characterized by a particularly good drainage and drying behavior.

In the published patent application DE 100 03 567, a surfactant combination is presented, the one or more alkyl ether sulfates, one or more alkyl sulfonates in an amount on the surfactant combination, of less than 50% by weight and one or more Contains amphoteric surfactants and an aqueous liquid composition containing this surfactant combination and its use for cleaning hard surfaces and in particular for Wash the dishes. Here, the amphoteric surfactants and especially the alkyl ether sulfates primarily carry contribute to the cleaning effect, while the alkyl sulfonates primarily the drying or Positively influence runoff behavior, d. H. especially the drying rate increase and reduce residue formation. The examples show that the agent usually contains 15-40 wt .-% surfactants.

The stable incorporation of especially sensitive ingredients is often another Problem. If you try to use conventional agents certain active ingredients (including Skin feel-improving or nourishing additives, such as. B. liposomes, proteins, vitamins, Plant extracts, etc .; performance-enhancing additives, such as B. acetic acid, etc .; antibacterial Additives such as B. lactic acid, benzoic acid, etc .; Esthetics (aesthetics, in particular Odor and appearance as well as haptics) improving additives, such as. B. perfume oils, Dyes, etc.) in a hand dishwashing detergent, so it can - by immediate effect of the surfactant components on the active ingredient - quickly Loss of effectiveness (e.g. with liposomes). Another problem is the difficulty with stable incorporation of active ingredients into the detergent formulation (e.g. for perfumes or antibacterial agents), discoloration (e.g. with plant extracts or proteins), Odor problems (e.g. with the addition of vinegar, antibacterial agents or Plant extracts) or incompatibilities between the active ingredient and the Detergent (e.g. disinfectant, antibacterial substances or bleach such as Hydrogen peroxide, persulfates, peracids, perborates or percarbonates).

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

Microcapsules are finely dispersed liquid or solid coated with film-forming polymers Phases in which the polymers are produced after emulsification and coacervation or interfacial polymerization on the material to be wrapped (active ingredient) knock down. The active ingredient is enveloped in a shell-like manner by a solid membrane (Microcapsule in the narrower sense) or enclosed by a matrix (microsphere or Sphere). In the following the term microcapsule is used for both variants summary sense used. The microcapsules can be dried like powder. To this Ways can e.g. B. gasoline, water, alcohol, pharmaceuticals, solvents, vitamins, Enzymes, liquid crystals, food flavors and perfumes in a dry mass be converted that can not dry out. Microencapsulation is used z. B. for perfume powder, the microcapsules in the handling more convenient and longer are effective.

German published patent application DE 22 15 441 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 Known, the polymer and the electrolyte concentration are selected so that the stability of the capsules in the agent and the dissolution of the capsules are guaranteed when diluted with water. 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 _14-16 -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 15 514 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 fragrance and 1.5 wt .-% fragrance-containing microcapsules of a size of 200 to 500 microns, which in the Dilute with water.

British Patent GB 1 471 406 relates to liquid aqueous detergents which 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 cross-linked polyacrylic acid with a Molecular weight of more than 1,000,000 and 0.1 to 5 wt .-% suspended phase, e.g. B. spheroidal capsules with a diameter of 0.1 to 5 mm, contain and a pH Have a value from 5.5 to 11.

U.S. Patent 5,141,664 teaches a clear gel-like surfactant Detergent composition with suspended active ingredient capsules. The gel contains 5 to 80% by weight Water, 0.05 to 25% by weight of at least one surfactant, 0.1 to 10% by weight of one cross-linked polycarboxy polymer as a thickener and 0.01 to 2% by weight Alumina. In addition, particles are a bleach or a bleach precursor with a protective shell in a gel: particle ratio between 500: 1 and 5: 1 contain. As a coating substance, u. a. waxes as well as homo- and copolymers such as polyacrylates, polyvinyl acetate or styrene-alkyl acrylate Copolymers serve.

Finally, WO 00/65020 describes a thickened aqueous hand dishwashing detergent with anionic surfactant, amphoteric surfactant, polymer and microcapsules in which one or more All or part of the ingredients in the hand dishwashing detergent are incorporated. It is a precisely dosed, good cleaning, skin compatible, temperature and storable, pourable hand dishwashing liquid, in which the physical or chemically incompatible or sensitive ingredients in temperature, storage and transport stable, easy to handle and visually appealing form are incorporated. 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 To provide surfaces, especially 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, which encase one or more other ingredients.

This agent is particularly suitable for spray application on soiled surfaces, especially dishes, and especially for use in hard-to-reach areas Soiling, for example on the inside of thermos 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, especially dishes. Preferably that is means according to the invention used for manual cleaning of hard surfaces, especially for the manual cleaning of dishes. As hard surfaces come alongside Dishes also all other hard surfaces, especially made of glass, ceramics, Plastic or metal, in household and commercial use.

When using the agent according to the invention as a cleaning agent for hard Surfaces and especially as hand dishwashing detergent (abbreviated to: dishwashing detergent) carry the Amphoteric surfactants and especially the alkyl ether sulfates primarily contribute to the cleaning effect, while the alkyl sulfonates, above all, have a positive effect on the drying and drainage behavior, d. H. in particular increase the drying speed and the formation of residues reduce. The microcapsules also allow stable incorporation otherwise Active substances which cannot be used in such agents, or only to a limited extent.

The advantage of the agent according to the invention or the use according to the invention is that improved drying and drainage behavior, especially the high one Drying speed or short drying time, the high drain speed or short Expiration time as well as the low residue formation and the retained shine. Under drying both drying as a whole is understood here, in particular up to neither optically still tactile moisture is perceptible on the surface, as well as in particular drying after draining.

Another advantage of the agent according to the invention or of the invention Use lies in the possible use of microcapsules. These capsules or "pearls" allow the temperature, storage and transport-stable incorporation of active ingredients that would otherwise be incompatible with the agent, in an easily manageable and optically appealing shape. As such, essential oils are, for example, care substances for the cleaning surfaces, bleaching systems, enzymes or skin-care substances call.

Yet another advantage of the agent or agents according to the invention Use is the high cleaning effect (synonyms: cleaning performance or -power or flushing effect, -power or -power), especially on fatty ones Soils. Incorporated additives can, for example, significantly improve the bleaching effect improve, e.g. B. hydrogen peroxide, citric acid, citric acid partial esters, perborates or Peracids.

A particular advantage of the product from the agent according to the invention and one Spray dispenser is easy to use, precise and clean dosing as well the ability to apply the product precisely and specifically to soiled areas, too if this is done with a cloth, a brush or using an agent in a commercially available 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. To ensure sprayability despite the to ensure stable suspension of the microcapsules necessary viscosity of the agent, it is usually a thixotropic agent. 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 only is possible with a delay.

Compositions according to the invention

Substances that also serve as ingredients in 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 Linné 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)" by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 ^th Street NW, Suite 300, Washington, DC 20036 , USA, is published and contains more than 9000 INCI names as well as 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-Cleansing Agents", which it in turn explains in more detail , This will also be referred to below where appropriate.

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

Unless explicitly stated otherwise, the quantities given refer to Percentage by weight (% by weight) of the total composition.

In contrast to the ingredients related to the entire hand dishwashing detergent is meant by the active ingredients only the part contained in the microcapsules.

microcapsules

Microcapsules are finely dispersed liquid or solid coated with film-forming polymers Phases. The active substance (core) is enveloped in a shell-like manner by a solid membrane (shell) (Microcapsule in the narrower sense) or enclosed by a matrix (microsphere or Sphere). In the following the term microcapsule is used for both variants summary sense used.

The microcapsules contain at least one solid or liquid core is enclosed in at least one continuous shell. Accordingly, in multinuclear microcapsules, also called microspheres, two or more nuclei in the continuous shell material and can be single or multi-core microcapsules of one additional second, third, etc. envelope. Mononuclear are preferred Microcapsules with a continuous shell.

The shell can be made from natural, semi-synthetic or synthetic materials consist. Of course, wrapping materials are, for example, gum arabic, agar, agarose, Maltodextrins, alginic acid or their salts, e.g. As sodium or calcium alginate, fats and Fatty acids, cetyl alcohol, gelatin, albumin, shellac, polysaccharides such as starch or Dextran, sucrose and waxes. Semi-synthetic shell materials are among others chemically modified celluloses, especially cellulose esters and ethers, e.g. B. Cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and Carboxymethyl cellulose, and starch derivatives, especially 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 are additionally in the shell material (INCI Opacifying Agents) incorporated so that the microcapsule's appearance of pearls. These "active ingredient pearls" lead due to their aesthetic Appearance to an increased acceptance of the agent according to the invention by the Consumer.

All surfactant-stable products available on the market can be used as microcapsules Use microcapsules, for example the commercial products Hallcrest Microcapsules (Shell material: gelatin, gum arabic) from Hallcrest, Inc. (US), Coletica Thalaspheres (shell material: maritime collagen) from Coletica (FR), Lipotec Millicapsules (shell material: alginic acid, agar-agar) from Lipotec S.A. (It), Induchem Unispheres (shell material: lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose) and Unicerin C30 (shell material: lactose, microcrystalline cellulose, Hydroxypropylmethylcellulose) from Induchem AG (CH), Kobo Glycospheres (shell material: modified Starch, fatty acid esters, phospholipids) and soft spheres (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 in the form of solutions or liquids 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. Preferred active substances in the sense of Invention are essential oils, e.g. B. perfumes, limes, geraniol or nerol, Bleaching system components, e.g. B. bleach activator, enzymes and care and protective components for the hard surface such as cationic polymers, silicone oils or Stearyl mercaptan as silver protection, further additives to improve the wash load gloss, e.g. B. Vinegar. Furthermore, active ingredients in the sense of the invention are also others in washing and Detergents and cosmetics usual ingredients, among others dermatological effective substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial Hydrolysates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as B. lecithin, soybean oil, etc., plant extracts such. B. Aloe Vera, Azulene, witch hazel extracts, algae extracts etc., allantoin, A.H.A. complexes. Active substances in According to the invention, antibacterial agents, such as. B. benzoic acid, Lactic acid, salicylic acid, sorbic acid, or their mixtures or their salts as well 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 framework have, but they are preferably egg-shaped or ellipsoidal shape or approximately spherical. Their diameter along their greatest spatial extent depends on Active ingredient and application usually between 10 nm (visually not as a capsule recognizable) and 10 mm, possibly also above. Visible microcapsules with a are preferred Diameters in the range from 0.01 to 6 mm, in particular from 0.05 to 4 mm, extremely preferably from 0.1 to 2 mm. Microcapsules no longer perceptible to the naked eye preferably have a diameter in the range from 20 to 500 nm, preferably 50 up to 200 nm.

The release of the active ingredient from the microcapsules can be achieved primarily by mechanical means Exposure, both by grinding the microcapsules during the cleaning process as well as by breaking open using a suitable metering device, for. B. in a dispenser or spray valve, for example in the form of the microcapsules crushing shear forces or, with a capsule diameter of about 1 mm or more, cutting them Sound. Another option is to dissolve the capsules when diluted Introduce the cleaning agent into the washing solution. A release of the is also conceivable Active ingredient by changing the temperature (introduction into warm soapy water) by Shift in pH, change in electrolyte content, etc.

The microcapsule content 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 Agents according to the invention exclusively have similar microcapsules or else mixtures can contain various types of microcapsules.

The microcapsules are preferably in high thixotropic agents Zero shear viscosity incorporated, so that the individual beads are "stably suspended and therefore without previous shaking can be dosed.

To improve the visual appearance, gas bubbles, for. B. Air, argon, oxygen, nitrogen, carbon dioxide, but also propane, butane, propellants as well as gas mixtures, are incorporated into the agent according to the invention.

viscosity

The viscosity favorable for the agent according to the invention is 20 ° C. and one Shear rate of 30 rpm - measured with a Brookfield LV DV II and Spindle 31 - in the range from 100 to 10,000 mPa.s, preferably 500 to 9000 mPa.s, particularly preferably 650 to 8000 mPa.s. At a shear rate of 0.3 rpm, this is In contrast, viscosity is preferably 8000 to 130,000 mPa.s, particularly preferably 10,000 up to 120,000 mPa.s, in particular 12,000 to 110,000 mPa.s. Hence it is preferably by thixotropic agents.

For this purpose, the viscosity of the agent according to the invention can be particularly good at low surfactant content of the agent - can be increased by thickeners.

thickener

For thickening, the agent according to the invention can additionally have one or more Electrolyte salts and / or one or more polymeric or (possibly nanoparticulate) inorganic Contain thickeners.

electrolyte salts

Electrolyte salts in the sense of the present invention are salts which in the aqueous agents according to the invention disintegrate into their ionic constituents.

The salts, in particular alkali metal and / or alkaline earth metal salts, are preferred inorganic acid, preferably an inorganic acid from the group, comprising the hydrohalic acids, nitric acid and sulfuric acid, especially the Chlorides and sulfates.

A particularly preferred electrolyte salt is magnesium sulfate, in particular MgSO ₄ .7H ₂ O, which is also known as Epsom salt and occurs minerally as Epsomit.

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

The content of the electrolyte salt 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 very preferably between 0.5 and 1% by weight, for example 0.7% by weight.

Polymeric thickeners

Polymeric thickeners in the sense of the present invention are as Polyelectrolytes thickening polycarboxylates, preferably homopolymers and copolymers acrylic acid, especially acrylic acid copolymers such as Acrylic acid-methacrylic acid copolymers, and the polysaccharides, especially heteropolysaccharides, and others usual 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. B. propoxylated guar and their mixtures. Other polysaccharide thickeners, such as starches or Cellulose derivatives can be used alternatively, but preferably in addition to one Polysaccharide rubber can be used, for example starches of various origins and Starch derivatives, e.g. B. hydroxyethyl starch, starch phosphate ester or starch acetates, 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 Keltrol® or from Rhodia is available under the trade name Rhodopol®, e.g. B. as cream-colored powder Keltrol® T or Rhodopof® T (transparent) or as white granulate Keltrol® RD (Readily Dispersible).

Acrylic acid polymers suitable as polymeric thickeners are, for example high molecular weight with a polyalkenyl polyether, in particular an allyl ether of Sucrose, pentaerythritol or propylene, cross-linked homopolymers of acrylic acid (INCI Carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are u. a. available from BFGoodrich under the trade name Carbopol®, e.g. B. Carbopol® 940 (molecular weight approx.4,000,000), Carbopol® 941 (molecular weight approx. 1,250,000) or Carbopol® 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 of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C _1-4 -alkanols, to which such as 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 which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol® are, e.g. B. the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers of C _10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 -Alkanols formed, esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopol®, e.g. B. the hydrophobized Carbopol® ETD 2623 and Carbopol® 1382 (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® 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 significantly above the polymer content adjusted or controlled, the required amounts of polymer to polymer can be different. The surfactant composition used also plays a role in Quantity selection matters.

Inorganic thickeners

Inorganic thickeners from the group of metal oxides, oxide hydrates, hydroxides, carbonates and phosphates and silicates are used. In A particular embodiment involves nanoparticulate compounds used. As such, particles with an average particle size of 1 to 200 nm, preferably 5 to 100 nm, in particular 10 to 50 nm, the Value on the particle diameter in the longitudinal direction, d. H. in the direction of largest particle size.

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

Nanoparticulate oxides, oxide hydrates or hydroxides can be made according to known ones Manufacture process, e.g. B. according to EP-A-0 711 217 (Nanophase Technologies Corp.). Also by hydrolysis of organometallic compounds, oxide hydrates and hydroxides are very much fine distribution accessible.

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, NanoTetk® 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) and NanoTek® Barium Oxide, NanoTek® Calcium Oxide, NanoTek® Chromium Oxide, NanoTek® Magnesium Oxide, NanoTek® Manganese Oxide, NanoTeh® Molybdenum Oxide, NanoTek® Neodymium Oxide, NanoTek® Strontium Oxide and NanoTek® Strontium Titanate and the nanoparticulate silicate NanoTek® Zirconium Silicates. Suitable silicates are available under the trade names Optigel® from Süd-Chemie AG or Laponite® from Laporte Ltd. available.

Preferred silicates are the layer silicates (phyllosilicates), in particular bentonites (containing smectites as main minerals, especially montmorillonite), montmorillonites (Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .n H ₂ O or Al ₂ O ₃ .4 SiO ₂ .H ₂ On 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 ₄ O ₁₀ ] or 3 MgO.4 SiO ₂ .H ₂ O) and particularly preferred Hectorite (M ⁺ _0.3 (Mg _2.7 Li _0.3 ) [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 name for dialuminium hexamagnesium carbonate hexadecahydroxide tetrahydrate, Al ₂ Mg ₆ (OH) ₁₆ CO ₃ .4 H ₂ O).

Another preferred inorganic thickener is nanoparticulate boehmite (AlO (OH), Alumina hydrate), which, for example, under the trade names Disperal® Sol P3 and Disperal® Sol P2 is available from Condea.

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 Optigel® SH (Süd-Chemie AG) and Laponite® XLG (Laporte Ltd.).

The content of possibly 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 polymers are used Thickener 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.

The present invention relates to fatty acids or fatty alcohols or their Unless otherwise stated, derivatives represent branched or unbranched Carboxylic acids or alcohols or their derivatives with preferably 6 to 22 Carbon atoms. The former are particularly due to their plant-based renewable raw materials preferred for ecological reasons, but without the to limit teaching according to the invention to them. In particular, the for example, oxo alcohols obtainable from ROELEN's oxo synthesis or their Derivatives can be used accordingly.

Whenever in the following alkaline earth metals as counterions for monovalent anions are mentioned, it means that the alkaline earth metal naturally only in half - to Sufficient charge balance - amount of substance as the anion is present.

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, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form 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). A further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO, such as Na-C _12-14 fatty alcohol + 1.3 EO sulfate, are very particularly preferred for the purposes of the present invention. These are e.g. B. available 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 from 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 one straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 11 to 18 and especially preferably 13 to 17 carbon atoms.

Suitable alkyl sulfonates are accordingly the saturated alkane sulfonates, the unsaturated olefin sulfonates and which - formally differ from those of alkyl ether sulfates underlying alkoxylated alcohol-derived - ether sulfonates, in which one terminal ether sulfonates (n-ether sulfonates) with those attached to the polyether chain Sulfonate function and internal ether sulfonates (i-ether sulfonates) with the alkyl radical linked sulfonate function differs.

Preferred according to the invention are the alkanesulfonates, in particular alkanesulfonates with a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-C _13-17 alkanesulfonate (INCI Sodium C14-17 alkyl sec sulfonate), as is provided, for example, by Clariant under the name Hostapur® SAS 60.

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 up to 5% by weight.

The alkyl ether sulfates and alkyl sulfonates and the other anionic surfactants are usually as alkali metal, alkaline earth metal and / or mono-, di- or Trialkanolammoniumsalz and / or in the form of their with the corresponding Alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine in situ neutralizing corresponding acid used. Alkali metals are preferred Potassium and especially sodium, as alkaline earth metals calcium and in particular Magnesium, as well as alkanolamines mono-, di- or triethanolamine. Particularly preferred are the sodium salts.

amphoteric

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

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 imidazolinium betaines, 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 which R ^{1 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
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 _1-4 alkyl radical, optionally hydroxy-substituted such as, for. B. a hydroxyethyl radical, but especially a methyl radical,
m is a number from 1 to 4, in particular 1, 2 or 3,
y 0 or 1 and
Y COO, SO ₃ , OPO (OR ⁵ ) O or P (O) (OR ⁵ ) O, where R ^{5 is} a hydrogen atom H or a C _1-4 alkyl radical,
is.

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 (Id),

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (Ia)

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 SO ₃ ^- (Ic)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (Id)

in which R ^{1 has} the same meaning as in formula I.

Particularly preferred amphoteric surfactants are the carbobetaines, especially those Carbobetaines of formula (Ia) and (Ib), most preferably the alkylamidobetaines of formula (Ib).

Examples of suitable betaines and sulfobetaines are the following named according to INCI Compounds: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamidopropyl Betaine, Babassuamidopropyl Betaine, Behenamidopropyl Betaine, Behenyl Betaine, betaine, canolamidopropyl betaine, capryl / capramidopropyl betaine, carnitine, Cetyl betaines, cocamidoethyl betaines, cocamidopropyl betaines, cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco- Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG betaines, erucamidopropyl hydroxysultaine, hydrogenated tallow betaines, Isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaines, myristyl betaines, oleamidopropyl betaines, oleamidopropyl hydroxysultaine, Oleyl betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl Betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaines, Polytetrafluoroethylene Acetoxypropyl betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, Soyamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl 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 ) _i -N (R ⁸ ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - [CH (OH)] _l -CH ₂ -Z-OM ( II)

in which R ^{6 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{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,
l 0 or 1, where k = 1 if I = 1,
Z is 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, e.g. B. protonated mono-, di- or triethanolamine,
is.

Preferred representatives satisfy the formulas IIa to IId,

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

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

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

R ⁶ -CO-NH- (CH ₂ ) ₂ -N (R ⁸ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (IId)

in which R ⁸ and M have the same meaning as in formula (II).

Exemplary alkylamidoalkylamines are the following named according to INCI Compounds: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-isodeceth-7 carboxyamphodiacetate, disodium stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG Acetate Phosphate, Sodium Lauroamphopropionate, Sodium myristoamphoacetate, sodium oleoamphoacetate, sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG Acetate Chloride Phosphate.

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 which R ^{10 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{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. B. 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 _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
M "is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups may have the same or two different meanings, e.g. B. can be hydrogen and sodium or twice sodium,
is
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 _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{14 is} a hydrogen atom or a C _1-4 alkyl radical, optionally hydroxy or amine substituted, e.g. B. a methyl, ethyl, hydroxyethyl or aminopropyl radical,
R ^{15 is} the residue of one of the 20 natural α-amino acids H ₂ NCH (R ¹⁵ ) COOH, and
M '''is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine,
is.

Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula (IIIa)

R ¹⁰ -NH-CH ₂ CH ₂ COOM '(IIIa)

in which R ¹⁰ and M 'have the same meaning as in formula (III).

Exemplary alkyl substituted amino acids are the following named according to INCI Compounds: aminopropyl laurylglutamine, cocaminobutyric acid, cocaminopropionic Acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, lauryl diethylenediaminoglycine, myristaminopropionic acid, sodium C12-15 alkoxypropyl iminodipropionate, sodium cocaminopropionate, sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA lauraminopropionate and TEA myristaminopropionate.

Acylated amino acids

Acylated amino acids are amino acids, in particular 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 _10-18 alkyl radical, for example a saturated C _12-14 alkyl radical. The acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, e.g. B. mono-, di- or triethanolammonium salt can be used. Exemplary acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, e.g. B. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.

Amphotensidkombinationen

In a special embodiment of the invention, a combination of two or more different amphoteric surfactants, especially a binary amphoteric surfactant combination used.

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

Furthermore, the amphoteric surfactant combination preferably contains at least one amphoteric surfactant from the group comprising sodium carboxyethyl cocosphosphoethylimidazoline (Phosphoteric® TC-6), C _8/10 amidopropyl betaine (INCI Capryl / Capramidopropyl betaine; Tego® Betaine 810), N-2-hydroxyethyl-N-carboxymethyl -fatty acid amido-ethylamine-Na (Rewoteric® AMV) and N-capryl / caprin-amidoethyl-N-ethylether-propionate-Na (Rewoteric® AMVSF) as well as the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfonate (INCI Sultaine; Rewoteric® AM CAS) and the alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl-N" -carboxyethylaminoethyl) -acetic acid amido] -N, N-dimethyl-N-cocos-ammonium betaine (Rewoteric® QAM 50 ), especially together with cocoamidopropyl betaine.

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

In addition to alkyl ether sulfates, alkyl sulfonates and amphoteric surfactants, this can Agents according to the invention, in particular for improving the cleaning effect, drainage behavior and / or drying behavior, additionally one or more further anionic surfactants, contain nonionic surfactants and / or cationic surfactants.

Other anionic surfactants

The agent according to the invention can additionally one or more further anionic Surfactants contain, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 up 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 and ester sulfonates (sulfofatty acid esters), Lignin sulfonates, alkyl benzene sulfonates, fatty acid cyanamides, anionic Sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid 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 represents an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R 'represents R or H (Dowfax® Dry Hydrotrope 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 perfluorooctanesulfonic 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 sulfosuccinic acid. A. Domsch and B. Irrgang in Anionic surfactants: organic chemistry (edited by HW Stache; 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 around lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts, extremely preferably sodium salts.

In the sulfosuccinates there is one or both carboxyl groups of sulfosuccinic acid preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acylclic or cyclic, optional 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. Especially the esters are preferably unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols, especially 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 of 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 compared preferred to 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), for example as Tego® Sulfosuccinat F 30 (Goldschmidt) with a sulfosuccinate content of 30% by weight is commercially available.

One or both form in the sulfosuccinamates or sulfosuccinamides Carboxyl groups of sulfosuccinic acid preferably with a primary or secondary Amine, one or two of the same 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 bears 12 to 14 carbon atoms, a carboxamide. Especially unbranched and / or saturated and / or acyclic alkyl radicals are preferred, in particular unbranched, saturated fatty alkyl residues.

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, diammonium ammonium PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, DisIPamosidomino-Cocos, Disodium Amino-Coconut Cocamido PEG-3 sulfosuccinate, disodium coco-glucoside sulfosuccinate, disodium cocoyl butyl gluceth-10 sulfosuccinate, disodium C12-15 pareth sulfosuccinate, disodium deceth-5 sulfosuccinate, disodium deceth-6 sulfos uccinate, disodium dihydroxyethyl sulfosuccinylundecylenate, disodium dimethicone copolyol sulfosuccinate, disodium hydrogenated cottonseed glyceride sulfosuccinate, disodium isodecyl sulfosuccinate, disodium isostearamido MIPA-sulfosuccinate disulfide disodium, Lauramido PEG-2 Sulfosuccinate, Disodium Lauramido PEG-5 Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauryl Sulfosuccinate, Disodium Myristamido MEA-Sulfosuccinate, Disodium OloxynolA-10 -Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG-2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate-Disodium PEG-IP uccinate, Disodium PEG-5 Laurylcitrate Sulfosuccinate, Disodium PEG-8 Palm Glycerides Sulfosuccinate, Disodium Ricinoleamido MEA-Sulfosuccinate, Disodium Sitostereth-14 Sulfosuccinate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Stearyl Sulfosuccinylate, Disodium Stinamate, Disodium Stinamate, Disodium Tallowamido MEA-Sulfosuccinate, Disodium Tallow Sulfosuccinamate, Disodium Tridecylsulfosuccinate, Disodium Undecylenamido MEA-Sulfosuccinate, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Wheat Germamido MEA-Sulfosuccinate, Disodium Wheat Germucco-PEG-Sulfate-PEG-2 Sulfate Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / MEA Laureth-2 Sulfosuccinate and Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate. Another suitable sulfosuccinamate is disodium C _16-18 alkoxypropylene sulfosuccinamate.

Preferred anionic sulfosuccinic acid surfactants are 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- 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 _12/14 -3EO-ester (Texapon® SB-3) , Sodium sulfosuccinic acid _diisooctyl ester (Texin® DOS 75) and di-Na-sulfosuccinic acid _mono -C _12/18 ester (Texin® 128-P), especially the mono-Na- synergistically interacting with the ternary surfactant _combination according to the invention with regard to the expiration and / or drying behavior sulfosuccinic acid di-octyl ester.

In a particular embodiment, the agent according to the invention contains anionic Sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or Sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, especially 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, most preferably 0.5 to 1.5% by weight, for example 1% by weight.

Nonionic surfactants

The agent according to the invention can additionally one or more nonionic surfactants contain, usually in an amount of 0.001 to 5 wt .-%, 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 ether, alkylphenol polyglycol ether, end group capped Polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Likewise Block polymers of ethylene oxide and propylene oxide and fatty acid alkanolamides are suitable and fatty acid polyglycol ether. Important classes of nonionic according to the invention Surfactants are also the amine oxides and the sugar surfactants, especially those Alkylpolyglucosides.

Fettalkoholpolyglykolether

According to the invention, fatty alcohol polyglycol ethers are to be understood according to the invention to be alkoxylated, unbranched or branched, saturated or unsaturated C _10-22 alcohols with an ethylene (EO) and / or propylene oxide (PO) alcohol having a degree of alkoxylation of up to 30, preferably ethoxylated C _10-18 fatty alcohols a degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, particularly preferably from 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 the C _12-14 fatty alcohol ethoxylates with 3 and 4 EO in the 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 ⁺ -O ^- (VI)

R ¹⁷ - [CO-NH- (CH ₂ ) _w ] _z -N ⁺ (R ¹⁸ ) (R ¹⁹ ) -O ^- (VI)

in which R ^{17 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical, which in the alkylamidoamine oxides has a carbonylamidoalkylene group -CO-NH- (CH ₂ ) _z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH ₂ ) _z - is bound to the nitrogen atom N, where z is in each case a number from 1 to 10, preferably 2 to 5, especially 3, stands, and
R ¹⁸ , R ¹⁵ independently of one another are a C _1-4 alkyl radical, optionally hydroxy-substituted such as, for. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C8-10 alkoxypropylamine oxides, dihydroxyethyl C9-11 alkoxypropylamine Oxides, dihydroxyethyl C12-15 alkoxypropylamine oxides, dihydroxyethyl cocamine oxides, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxides, hydroxyethyl hydroxypropyl C12-15 alkoxypropylamine oxides, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amine oxides, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl / Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxides, palmitamidopropylamine oxides, palmitamine oxides, PEG-3 lauramine oxides, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide. On 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, as described, for example, in WO 97/00609 (Henkel Corporation) Publications 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 _1-22 alcohols or glycols such as ethylene and / or propylene glycol, the sugar hydroxy group also comprising polyethylene glycol - And / or polypropylene glycol residues can wear. 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 C _1-5 alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-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 lauroylmethyl glucamide.

Alkylpolyglykoside

The alkyl polyglycosides (APG) are particularly preferred sugar surfactants in the context of the teaching according to the invention 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. B. an ethyleneoxy or propyleneoxy group, and a stand for the average degree of alkoxylation from 0 to 20. The group (AO) _{a may} also contain various alkyleneoxy units, e.g. B. ethyleneoxy or propyleneoxy units, in which case a is the average total degree of alkoxylation, ie the sum of the degree of ethoxylation and propoxylation. Unless stated otherwise or in more detail below, the alkyl radicals R ^{20 of} the APG are linear unsaturated radicals with the stated number of carbon atoms.

APG are non-ionic surfactants and are known substances that according to the relevant methods of preparative organic chemistry can be obtained. The Index number x indicates the degree of oligomerization (DP degree), i. H. the distribution of mono and Oligoglycosides, and stands for a number between 1 and 10. While x in one given connection must always be an integer, and above all the values x = 1 to 6 can assume, the value x for a certain alkyl glycoside is an analytically determined arithmetical size, which usually represents a fractional number. Preferably be Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are 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. As Glycosidic sugar is preferably used xylose, but especially glucose.

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 and their technical mixtures, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.

However, the alkyl or alkenyl radical R 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, for example, 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 _12-14 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) contain, usually in one Quantity from 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.

Preferred cationic surfactants are the quaternary surface-active compounds, especially with an ammonium, sulfonium, phosphonium, iodonium or Arsonium group, as described, for example, by K. H. Wallhäußer in "Praxis der Sterilisierung, Disinfection - Preservation: Germ Identification - Industrial Hygiene "(5th ed. - Stuttgart; New York: Thieme, 1995) as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial activity can do that Agents are provided with an antimicrobial effect or, if appropriate, its due to other ingredients already existing antimicrobial effect improved become.

Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV; INCI Quaternary Ammonium Compounds) according to the general formula (R ^I ) (R ^II ) (R ^III ) (R ^IV ) N ⁺ X ^- , in which R ^I to R ^{IV are the} same or various C _1-22 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, the heterocycle, for. B. a pyridinium or imidazolinium compound, form, represent and X ^- 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. B. 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 succeeds particularly easily, even the quaternization of tertiary amines with two long ones Residues and a methyl group can be mild with the help of methyl chloride Conditions. Amines that have three long alkyl residues or Hydroxy-substituted alkyl radicals are not very reactive and are preferred with dimethyl sulfate quaternized.

Suitable QAV are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyl-dimethyl-C ₁₂ -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl dodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium 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-decyl- dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethyl-ammonium chloride, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No 1576448-1) and their mixtures. Preferred QAV are the benzalkonium chlorides with C ₈ -C ₁₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethylammonium chloride. A particularly preferred QAV is cocospentaethoxymethylammonium methosulfate (INCI PEG-5 Cocomonium methosulfate; Rewoquat® CPEM).

To avoid possible incompatibilities of the cationic surfactants with the Anionic surfactants contained according to the invention become compatible with anionic surfactants as far as possible and / or as little cationic surfactant as possible or in a special one Embodiment of the invention completely dispenses with cationic surfactants.

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 have one or more contain water-soluble organic solvents, usually in an amount of 0.1 to 8% by weight, preferably 1 to 6% by weight.

The solvent is used as part of the teaching of the invention used in particular as a hydrotrope, viscosity regulator and / or cold stabilizer. It acts as a solvent, 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 contributes to the formation of clear products. The viscosity of the agent according to the invention decreases with increasing amount of solvent. Too much However, solvent can cause an excessive drop in viscosity. Finally sinks with increasing amount of solvent the cloudiness and clear point of the agent according to the invention.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 -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 _2-6 alkylene glycols and poly-C _2-3 alkylene glycol ethers, optionally etherified on one side with a C ₁₄ alkanol, with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, and also C _{1 -6-} Alcohols, preferably ethanol, n-propanol or iso-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, isopentyl diol, isopropyl alcohol (iso-propanol), 3-methoxybutanol, Methoxydiglycol, methoxyethanol, 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), Propylene glycol, propylene glycol butyl ether, propylene glycol propyl ether, Tetrahydrofurfuryl alcohol, trimethylhexanol.

Particularly preferred solvents are the poly-C _2-3 alkylene glycol ether etherified on one side with a C _1-6 alkanol glycol ether 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 iso-propanol, in particular ethanol.

As solubilizers in particular for perfume and dyes can besides those previously described solvents, for example also alkanolamines and Alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical are used.

additives

This can be used to further improve the drainage and / or drying behavior Agents according to the invention one or more additives from the group of surfactants, the polymers and the builder, usually in an amount of 0.001 up 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.

Surfactants suitable as additives are certain of those already described above amphoteric surfactants, other anionic surfactants, nonionic surfactants and cationic surfactants, which are repeated here. The content of surfactant Additives should preferably be chosen so that the total surfactant content in the above exported quantity ranges.

Some of the additives mentioned below include one or more trade names in brackets, under which the respective is commercially available.

Suitable amphoteric surfactants as additives are in particular sodium carboxyethyl cocosphosphoethylimidazoline (Phosphoteric® TC-6), C _8/10 amidopropyl betaine (INCI Capryl / Capramidopropyl betaine; Tego® betaine 810), N-2-hydroxyethyl-N-carboxymethyl fatty acid amidoethylamine (Rewoteric® AMV) and N-Capryl / Caprin-amidoethyl-N-ethylether-propionate-Na (Rewoteric® AMVSF) as well as the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfonate (INCI Sultaine; Rewoteric® AM CAS) and the alkylamidoalkylamine N- [N '(N "-2-hydroxyethyl-N" -carboxyethylaminoethyl) acetic acid amido] -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 ' ) SO ₃ ^- , in which R represents an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R 'represents R or H (Dowfax® Dry Hydrotrope Powder with C _1-6 alkyl radical (s); INCI sodium hexyldiphenyl ether Sulfonates, disodium decyl phenyl ether disulfonates, disodium lauryl phenyl ether disulfonates, disodium cetyl phenyl ether disulfonates) and the fluorinated anionic surfactants ammonium C _9/10 perfluoroalkyl sulfonate (Fluorad® FC 120), perfluorooctane sulfonic acid potassium salt (Fluorad® FC 95 ) and 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 sulfosuccinic acid -ditridecy 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), sodium sulfosuccinic acid diisooctyl ester (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), C _12/14 fatty alcohol + 5EO + 3PO, methyl-capped (Dehypon® LS 531), C _12/14 fatty alcohol + 10EO, n-butyl capped (Dehypon® LS 104 L), C ₁₁ -oxoalcohol + 8EO (Genapol® UD 088), C ₁₃ oxo alcohol + 8EO (Genapol® X 089), C _13/15 - fatty alcohol EO adduct, n-butyl sealed (Plurafac® LF 221) and alkoxylated fatty alcohol (Tegotens® EC- 11).

Cationic surfactants suitable as additives are, in particular, with anionic surfactants compatible cationic surfactants such as quaternary ammonium compounds, for example Cocospentaethoxymethylammonium methosulfate (INCI PEG-5 Cocomonium methosulfate; Rewoquat® CPEM).

Polymers that are suitable as additives are primarily non-ionic substances from the group the mediator. The polyalkylene glycols should be mentioned here in particular. Surprisingly, it was found that when using up to 5% by weight Additives from this group of substances achieve a particularly good foaming behavior of the agent can be. Here are polyalkylene glycols with a branched chain and among them again the polypropylene glycol is particularly preferred. Good foaming behavior means here that the undiluted agent produces little foam when sprayed and this Half of the foam is broken down after just five minutes. One turns on the other hand, the agent in dilute solution, sufficient amounts of one form stable and at least 15 minutes, preferably at least 30 minutes Foam. This foaming behavior is desired by the consumer because it is with him high effectiveness and cleaning performance can be equated.

The agent according to the invention can contain 0 to 5% by weight, preferably 1 to 4% by weight, particularly preferably contain 2% by weight of polyalkylene glycols. To be favoured Polyalkylene glycols with a branched chain are used, particularly preferably polypropylene glycol (PPG) with molecular weights from 200 to 10,000, preferably 400 to 2000, especially the Polypropylene glycols PPG 400 and PPG 2000. Thereby the use of PPG 2000 preferred if the agent should be particularly low foaming when sprayed. Is a If more foam is desired, the PPG 400 is preferred used, an agent that is particularly foaming when sprayed polypropylene glycol is not added. The foaming behavior was thereby Wagner determines.

Other polymers suitable as additives are in particular 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 heptamethyltrisiloxane (Silwet® L-77), polyalkylene oxide, modified Heptamethyltrisiloxane (Silwet® L-7608) and polyether siloxanes (copolymers of polymethylsiloxanes with Ethylene oxide / propylene oxide segments (polyether blocks), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863, Tegopren® 5878).

Builder substances suitable as additives are, in particular, polyaspartic acid Na Salt, ethylenediamine triacetate cocoalkylacetamide (Rewopol® CHT 12), Methylglycinediacetic acid tri-Na salt (Trilon® ES 9964) and acetophosphonic acid (Turpinal® SL).

Mixtures with surfactant or polymeric additives show in the case of Monawet® MO-84 R2W, Tegopren® 5843 and Tegopren® 5863 synergisms. The use of the Tegoprene types 5843 and 5863 are however used on hard surfaces made of glass, especially glassware, less preferred because this silicone surfactant on glass can raise.

In a special embodiment of the invention, the additives mentioned waived.

Dicarboxylic acids (salts)

To stabilize the agent according to the invention, especially with a high surfactant content, one or more dicarboxylic acids and / or their salts can be added, in particular a composition of Na salts of adipine, amber and Glutaric acid, such as z. B. is available under the trade name Sokalan® DSC. The stake is advantageously carried out 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 can - especially in amounts above 2% by weight - contribute to a clear solution of the ingredients. Is also an influence on the viscosity of the mixture by this within certain limits Means possible. This component also influences the solubility of the mixture. This component is particularly preferably used with high surfactant contents, especially with 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 one or more optionally stabilized enzymes contain.

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

The enzymes can, as for example in the European patent EP 0 564476 or described in international patent applications WO 94/23005 Carriers can be adsorbed and / or embedded in coating substances to protect them against premature Protect inactivation. The enzymes are particularly preferred against oxidative Degradation stabilized, as known from international patent application WO 94/18314 is.

The cleaning agent can contain enzymes in amounts of 0 to 1% by weight. Especially preferred enzymes are proteases, amylases, peroxidases, lipases and Glucanases.

Auxiliaries and additives

In addition, one or more others - especially in Hand dishwashing detergents and detergents for hard surfaces - common auxiliaries and additives, especially UV stabilizers, perfume, pearlescent agents (INCI opacifying agents; for example glycol distearate, e.g. B. Cutina® AGS from Henkel KGaA, or containing it Mixtures, e.g. B. Euperlane® from Henkel KGaA), dyes, Corrosion inhibitors, preservatives (e.g. the technical 2-bromo 2-nitropropane-1,3-diol (CAS 52-51-7), for example as Myacide® BT or as Boots Bronopol BT is commercially available from the company Boots, or which under the Commercial names Parmetol A28 available from Schülke & Mayr Isothiazolinone-bromnitropropanediol preparation) and skin feel-improving or nourishing additives (e.g. 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 B. lecithin, soybean oil, etc., plant extracts such as z. B. aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, A.H.A. complexes), in amounts of usually not more than 5% by weight. Some these auxiliaries can also serve to support the cleaning performance or reinforce other desirable properties. For example, in perfume Terpene hydrocarbons may be included (e.g. limonene) which have a fat-dissolving effect have; Mint extracts have e.g. B. antibacterial properties.

PH value

The pH of the agent according to the invention can be adjusted using conventional pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, with a range of 4 to 13, preferably 5.5 to 12 is 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 citrates, for example trisodium citrate. ₂ H ₂ O and tripotassium citrate. H ₂ O.

manufacturing

The agent according to the invention can be achieved by stirring the individual together Manufacture components in any order. Only the microcapsules are last in the Means incorporated to prevent shearing during the manufacturing process avoid. Gas bubbles, e.g. B. air, argon, oxygen, nitrogen, carbon dioxide or propane, Butane, propellant gases as well as gas mixtures are also last by whipping and / or incorporated by direct introduction of the corresponding gas (s).

Water, surfactants and, if appropriate, further ones of the aforementioned are preferred Ingredients stirred together. In this respect, unencapsulated perfume and / or dye are used, they are then added to the solution obtained. Subsequently the pH is adjusted as previously described. Becomes a thickener 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 one Spray dispensers are used. The spray dispenser is preferably a manually activated one Spray dispenser, in particular selected from the group comprising Aerosol spray dispensers, self-building spray dispensers, pump spray dispensers and Trigger spray dispenser, in particular pump spray dispenser and trigger spray dispenser with a container made of transparent polyethylene or polyethylene terephthalate. Become a spray dispenser in more detail in WO 96/04940 (Procter & Gamble) and the spray dispensers therein cited U.S. patents, all of which are referenced in this regard and their contents is hereby incorporated into this application. Also WO 97/02896 (Procter 8 Gamble) describes a suitable spray dispenser for spraying serves viscous and / or solid-containing liquids. For the invention Spray dispensers that can preferably be used for cleaning agents can also be found in the Applications WO 00/76876, WO 00/33969 and WO 00/33970 (all Afa Polytek).

For spraying agents of higher viscosity and in particular also for spraying the microcapsules, the spray dispenser, especially the spray nozzle used, be adjusted accordingly, in particular the diameter of the spray opening be modified accordingly. In addition, by choosing the appropriate one Capsule material from premature shearing or clogging of the spray nozzle be counteracted.

By selecting suitable nozzle parameters, this can also be the case when spraying the Modified using generated noise. By using a tube as Sound box in front of the nozzle produces a low tone when using the cleaner, while the spray jet causes a higher hissing sound in conventional spray dispensers. 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.

Under viscosity 1 is the viscosity at a shear force of 0.3 rpm, under viscosity 2 to understand that at 30 rpm. Measurements were taken at 20 ° C using a Brookfield Viscometer, spindle 31.

Claims (21)

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 0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, particularly preferably 1 to Contains 10 wt .-%, in particular 2 to 8 wt .-% alkyl ether sulfate. 4. Cleaning agent according to one of the preceding claims, characterized characterized in that it is 0.05 to 10% by weight, preferably 0.25 to 7.5% by weight, in particular 0.5 up to 5 wt% sec. Contains alkanesulfonate. 5. Cleaning agent according to one of the preceding claims, characterized characterized in that it is 0.05 to 10% by weight, preferably 0.25 to 7.5% by weight, contains in particular 0.5 to 5% by weight of amphoteric surfactant. 6. Cleaning agent according to one of the preceding claims, characterized characterized in that at least one betaine is used as the amphoteric surfactant. 7. Cleaning agent according to one of the preceding claims, characterized characterized in that there are further anionic, nonionic, amphoteric and / or cationic Contains surfactants. 8. Cleaning agent according to one of the preceding claims, characterized characterized in that it contains at least one thickener in amounts of 0.1 to 3% by weight contains. 9. Cleaning agent according to one of the preceding claims, characterized characterized in that it contains electrolyte salts and / or one or more as thickeners Contains polymers or (possibly nanoparticulate) inorganic thickeners. 10. Cleaning agent according to one of the preceding claims, characterized characterized in that it is a polysaccharide, preferably a xanthan gum, as Contains thickeners. 11. Cleaning agent according to one of the preceding claims, characterized characterized in that it contains water-soluble organic solvents in amounts of 0.1 to 8 wt .-%, preferably 1 to 5 wt .-%, contains. 12. Cleaning agent according to one of the preceding claims, characterized characterized in that it as a water-soluble organic solvent at least one or contains polyhydric alcohol, preferably at least one monohydric alcohol, particularly preferably ethanol. 13. Cleaning agent according to one of the preceding claims, characterized characterized in that the microcapsules are visible to the naked eye and one Diameters from 0.01 to 6 mm, in particular from 0.05 to 4 mm, most preferably from 0.1 to 2 mm. 14. Cleaning agent according to one of the preceding claims, characterized characterized in that the microcapsules contain active ingredients, preferred as active ingredients essential oils, perfumes, bleaching system components, enzymes, care and Protective components for the hard surface, additives to improve the wash load gloss, dermatologically active substances, antibacterial agents and dyes or Pearlescent agents are used. 15. Cleaning agent according to one of the preceding claims, characterized characterized in that there are other additives, auxiliaries and additives such as builders, UV stabilizers, Contains corrosion inhibitors and / or preservatives. 16. Cleaning agent according to one of the preceding claims, characterized characterized in that its viscosity is 100 to 10,000 mPa.s at a shear rate of 30 rpm, preferably 500 to 9000 mPa.s, particularly preferably 650 to 8000 mPa.s and at a shear rate of 0.3 rpm 8000 to 130,000 mPa.s, preferably 10,000 to 120,000 mPa.s, particularly preferably 12,000 to 110,000 mPa.s (20 ° C, Brookfield viscometer, spindle 31). 17. Cleaning agent according to one of the preceding claims, characterized 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 one Spray dispenser. 19. Use of a medium according to one of claims 1 to 17 or one Product according to claim 18 for dishwashing. 20. Use of an agent according to any one of claims 1 to 17 or one Product according to claim 18 for cleaning hard surfaces. 21. A method for producing an agent according to any one of claims 1 to 17, characterized in that the individual components in any order are stirred together and the microcapsules are worked in last.