DE102004062338A1 - Packed washing or cleaning agent - Google Patents

Abstract

A rigid container having a maximum container height h¶max¶ and a particulate, bleach-containing detergent or cleaning agent present in the rigid container, the container having a footprint A with a minimum diameter d¶min¶ and an upper-side container opening having an area A 'and having a maximum diameter dmax, characterized in that d¶min¶ is greater than h¶max¶ and d¶min¶ greater than d¶max¶, is suitable for the safe packaging and handling of the bleaching agent containing funds.

Description

The present invention is in the field of detergents or cleaners, in particular the packaged detergent or cleaner.

washing or detergents are for the consumer in diverse Offer forms available. In addition to powders and granules, this offer includes, for example also detergent concentrates in the form of extruded or tableted Compositions. These solid, concentrated or compacted Forms of supply are characterized by a reduced volume per Dosing and thus reduce the cost of packaging and transport. In particular, the washing or cleaning agent tablets meet here additionally the desire of the consumer for simple dosage. The corresponding Agents are comprehensively described in the art. In addition to the cited However, compacted detergents also have advantages Series of disadvantages. In particular, tableted forms of offer are often characterized by a delayed decay due to their high compression and thus a delayed Release of their ingredients. To resolve this "conflict" between sufficient tablet hardness and short disintegration times have been numerous in the patent literature technical solutions disclosed at this point by way of example to the use so-called tablet disintegrant should be referenced. This Decay accelerators add to the tablets in addition to the washing or cleaning active Substances are added, although they themselves generally do not wash or cleaning-active properties, and increase this way the complexity and the cost of these funds. Another disadvantage of tableting of active substance mixtures, in particular washing or cleaning-active substance-containing Mixtures, is the inactivation of the active substances contained by the compaction pressure occurring during tableting. Inactivation of the active substances may also be due to in Consequence of tableting enlarged contact surfaces of the Ingredients are made by chemical reaction. Powder or granules are therefore preferable to compact data in cases where through the early Release of certain washing or cleaning substances the cleaning performance can be improved and / or by a Compacting an inactivation of the washing or cleaning active Substance is caused. A washing or cleaning substance, for the reasons mentioned above with preference in particulate or liquid Preparations is used, the bleaching agents, in particular the oxygen bleaching agents such as the sodium percarbonate, but also enzymes.

The Packaging particulate Detergents or cleaners are usually made by simple fill of the contents in the appropriate packaging. The dosage of the bulk material can for example, by weighing the filled pack or by means a dosing be realized. Such devices can Dosierkammern have, which formed in so-called dosing or metering rollers are. While a dosing tube when filling regularly in one Füllgutbett are inserted, are the on the outer circumference of a metering roller one by one or several distributed dosing chambers one after the other under the bottom opening a product container during her positioned in the respective filling process, and it becomes the powdery contents in the respective metering chamber from the powder bed or from the reservoir sucked. For emptying that is in the respective metering chamber located filling material then by overpressure in a respectively prepared container again from the metering chamber blown out.

Either in the dosage as well as in the bulk of the filling act squeezing and Shear forces on the particulate Components contributing to a mechanical destruction of the individual powder particles and an increase in the weight fraction finest Particles lead can. A turbulence during the preparation of washing or cleaning agents accumulating dust should, if it can not be avoided, in the largest possible Scope be avoided. Of course, the same applies for the Turbulence of these dusts in the application of the resulting packaged detergents or cleaners.

Of the The present application was therefore based on the object of packaging for washing or to provide detergents with a high bleach content, which enables the safe packaging and handling of these agents. In particular, the bottling should be of detergents or cleaners with potentially irritating or allergenic Components and their storage and use by the consumer be made simpler and safer.

It has now been found that the abovementioned objects can be achieved by the choice of the packaging material used. A first subject of the present application is therefore a combination of a rigid container with a maximum container height h _max and a present in the rigid container particulate, bleach-containing washing or cleaning agent, wherein the container has a footprint A with a minimum diameter d _max and an upper-side container opening having a surface A 'and a maximum diameter d _max , characterized in that d _{min is} greater than h _max and d _{min is} greater than d _max .

One The first component of the agents according to the invention is a rigid one Container. Be as "rigid" container while self-supporting, that is without external influence in their spatial form persisting, called container. Examples for such rigid container For example, cardboard boxes, tin cans or plastic bottles.

The inventive container preferably made of plastics. Plastics, in particular polymeric plastics to the most versatile materials for industrial production Goods. Important Properties of plastics are, for example, their high mechanical properties Strength, the favorable ratio of Strength and density and high resistance to chemicals. In the context of the present invention, containers are therefore preferred. the at least partially from water-insoluble polymers and / or water Polymergemsichen exist.

Under The term "plastics" and "polymers" are used in the context the present application in particular polymers, polyadducts and polycondensates combined.

When Polymers in this application are such high molecular weight compounds referred to, whose construction is based on a chain-growth mechanism. preferred Polymers are in the context of the present application polyethylene, Polypropylene, poly-1-butene, poly-4-methyl-1-pentene, polyvinyl chloride, polyvinylidene chloride, Polyacrylonitrile and / or polystyrene.

polyadducts arise by polyaddition, so polyreactions, where by repetitive and independent linking reactions of bis- or polyfunctional starting materials (monomers) via reactive Finally, oligomers Polymers are formed. Preferred polyadducts are polyurethanes.

polycondensates arise as the polyadducts by repeatedly repeating and independent linking reactions discrete oligomers and monomers, but in contrast to polyaddition simultaneously a cleavage of low molecular weight compounds. Preferred polycondensates in the context of the present invention are Polyamides, polycarbonates and polyesters.

plastics are characterized by a special versatility also with regard to on their processability. Plastics can be processed by extrusion or injection molding are processed as shaping, as by drawing process. At the Drawing (thermoforming) is a preheated plastic plate or - foil between the two parts of the tool, the positive and the negative, introduced and then squeezed whereby the plastic part gets its shape. Similarly, the so-called cold deformation runs; Here, however, the plate or film to be deformed is not preheated. If no negative tool is available, it is called deep drawing. Within the scope of the present invention it is now particularly preferred that as a container a deep-drawn or injection-molded or bottle-blown container is used. With particular preference, injection molded containers are used.

Independent of the type of molding process has a preferred container in dependence from the water insoluble used Plastic preferably has a wall thickness between 5 microns and 2000 microns, preferably between 10 μm and 1000 μm and in particular between 50 microns and 504 μm on.

The containers used according to the invention have a maximum container height h _max , a base A with a minimum diameter d _min and a container opening surface A 'with a maximum diameter d _max .

In a first preferred embodiment, the outer container bottom, that is the outer surface of the container bottom, is flat and smooth. If such a container is standing upright on a flat and smooth surface, then the footprint A denotes the surface enclosing all those points where sub ground and containers are in direct contact.

In a further preferred embodiment is the container bottom, So the outer surface of the container bottom, not plan and smooth but has, for example, convex and / or concave bulges and / or coins on. Is such a container upright on a flat and smooth surface, so the container has a or several substandard areas on that only part of the outer surface of the container bottom taking. The stand area A results as specified the present application in such a not as a simple sum the substandard areas but rather corresponds to the area enclosed by a line becomes, which both the substandards and the between the substandard areas located areas of the tank bottom encloses.

The base is preferably round. However, however, square footprints, for example, footprints with three, four, five, six, seven, eight or more corners are feasible. The shortest possible straight line, which leads through the center of the standing surface A and connects two points at the edge of the standing surface, is referred to as the minimum diameter of the base A. If the base A is a circular base, the minimum diameter d _{min of} this base corresponds to the diameter of the circle. For a square footprint, the minimum diameter d _{min of} this footprint corresponds to the side length of the square.

For the safety in packaging and handling of the bleach-containing agents, it has proven to be advantageous that the ratio between minimum diameter d _{min of} the footprint A and maximum container height h _max between 1: 0.95 and 1: 0.2, preferably between 1: 0.95 and 1: 0.4, preferably between 1: 0.95 and 1: 0.6 and in particular between 1: 0.95 and 1: 0.7.

The Room shape of the container is subject in principle no other than the limitations disclosed in the claim. The basic or standing area of the container may be round or oval, three, four, five, six, be seven-, eight- or polygonal. Stand, side or top surfaces can be flat or domed be configured, with both concave and convex curvatures are feasible.

One inventive container can For example, have a cuboid shape, wherein one of the surfaces of Cuboid the stand area forms while a part of the opposite area the container opening corresponds. Furthermore, a container is preferred in the form of a straight circular cylinder, in which one of the circular area the Floor space, So the floor space forms while the second circular area, So the top surface, the container opening comprises. In a further preferred embodiment, the container has the Shape of a hemisphere, wherein the sectional surface of the ball of the base of the container matches while the container opening up the sphere surface located. Naturally, containers according to the invention can also be used have a conical shape with the cone base as a standing surface and a tapered opening in the container opening side wall.

In a preferred embodiment are standing area and container opening opposite Sides of the container.

It is further preferred that the container has rounded corners and Has edges.

As well like the spatial form of the container Basically, the shape of the container opening is not subject to any Restriction. Due to the better closeability, in particular with screw caps are used in the present however, circular container openings prefers. The container opening area A 'is preferably in a certain ratio to the stand area A of the container, such combinations of the invention are preferred in which the relationship between floor space A and Container opening area A 'between 1: 0.9 and 1: 0.2, preferably between 1: 0.9 and 1: 0.4, preferably between 1: 0.9 and 1: 0.5 and in particular between 1: 0.9 and 1: 0.6.

The Internal or filling volume the container is preferably between 100 and 5000 ml, preferably between 100 and 2000 ml, preferably between 200 and 1800 ml.

Of the inventive container has preferably a resealable closure. This Closure can for example, by a screw, latch, plug, adhesive or snap closure connected to the container be. With particular preference, the container has a screw cap, wherein this screw cap in a particularly preferred embodiment has a so-called child safety device.

Combinations according to the invention, characterized in that the container opening is an adhesive, latching, Snap or screw cap, preferably has a screw cap, according to the invention are particularly prefers.

Of the Closure of the container is with particular preference from the above-mentioned plastics or polymers manufactured. Compositions according to the invention, where the container and the shutter off the same plastic (s) is made according to the invention are particularly prefers.

As already for the container also described the shutter all technically feasible Shapes have. Are conceivable in addition to closures with a in the supervision round profile, for example, also four- or polygonal closures. Especially prefers closures are rotationally symmetric in the view. If a screw cap is used as closure, so this screw is for easier handling preferably have a round profile. As "supervision" is the view in a viewing direction orthogonal to the top of the closure referred to.

The inventive container preferably to facilitate their packaging and their transport stackable. In a preferred embodiment, therefore, the container bottom as well as the container top, which optionally at least partially formed by a closure will, plan. The corresponding containers can be stacked in a simple manner be without tilting. Nevertheless, the resulting container stacks are only to a limited extent against slipping of the container with lateral force on the container stack secured. The slip resistance of the container according to the invention, for example, by the processing of non-slip materials on the top and / or Bottom of the container be improved. In a particularly preferred embodiment

A further preferred embodiment the combination according to the invention is therefore characterized in that the container opening has a convex closure, which corresponds in shape with a concave embossing in the container bottom.

Around the stability (e.g., tear strength) and / or the optical attractiveness of containers according to the invention increase or the permeability the container can reduce these containers in a preferred embodiment have a metal coating. Such a coating can in this case, for example, by a vapor deposition or bonding with a metal foil can be realized. The metal vaporization or the Metal foil can be found both on the inside of the container wall (inside the container in contact with the bleach-containing washing or cleaning agent) or on the outside of the container (without contact with the bleach-containing detergent) are located.

to optical enhancement, it is further preferred to use the container To provide product information. With this product information For example, it may be the product name, the product composition or application or safety instructions. The product information can directly on the container and / or the closure printed be. Alternatively or in addition can the container be provided for example with a printed band.

In a further preferred embodiment comprises the combination according to the invention furthermore a dosing auxiliary. With particular preference this includes combination product according to the invention next to the washing power amplifier, the main cleaner and the instructions for use Dosing aids. Combination products, characterized that the combination product further comprises a dosing aid for the detergency booster and / or for the Main cleaning agent, are preferred in the invention. As dosing aids, for example, all devices are suitable and objects, which are suitable washing or cleaning agent in the dishwasher or to meter their dosing chamber; and / or to the dimension of a certain volume or weight. For dosing aids it may be an integral part of the rigid container, for example a pouring device, or a separate means, such as a (measuring) cup, a (measuring) scoop or a (measuring) spoon act. These dosing aids can be made, for example, of polymers, Metal, glass, paper or cardboard to be made.

Next the containers described above comprises the combination according to the invention furthermore a particulate Bleach-containing detergent or cleaner.

For the purposes of the present application, "particulate" compositions are defined as solid detergents or cleaners having a particle size of up to 10,000 μm Combination for the safe filling and application of particulate detergents or cleaning agents with particle sizes well below 10000 μm. According to the invention, therefore, particular preference is given to those combinations according to the invention in which at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight of the particles have a size below 6000 m, preferably below 3000, more preferably below 2000 and especially between 200 and 2000. Examples of preferred forms of preparation of these particulate detergents or cleaners are powders or granules or extrudates or compactates.

powder is a general term for a form of fragmentation solid substances and / or mixtures of substances obtained by crushing, this means Grinding or crushing in the mortar (pulverizing), grinding in mills or as a result of sputtering or lyophilized. A particularly fine division is often called atomization or micronization; The corresponding powders are called micro-powder designated.

To the grain size is one coarse classification of the powders in coarse, fine and. Very fine powder usual; a closer one Classification powdered Bulk goods take over their bulk density and through sieve analysis. Preferred in the context of the present application Powders, however, have lower particle sizes below 5000 microns, preferably less than 3000 μm, preferably less than 1000 μm, most preferably between 50 and 1000 microns and in particular between 100 and 800 μm on.

powder can be extruded, pressed, rolled, briquetted, pelletized and compact and agglomerate related processes. Each of the im Prior art for the agglomeration of particulate mixtures known method is in principle suitable, those in the inventive compositions produce solids. In the context of the present Invention are preferably used as a solid (e) agglomerates in addition to the granules, the compacts and extrudates.

When Granules become accumulations of granules designated. A granule (granule) is an asymmetric aggregate from powder particles. Granulation processes are in the state of the art broadly described. Granules can by wet granulation, by dry granulation or compaction and produced by melt solidification granulation.

The common Granulation technology is the wet granulation, since this technique the least restrictions Underpinned and safest to granules with cheap Properties leads. The wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably used in mixers, fluidized beds or spray towers, wherein said mixer, for example, equipped with stirring and kneading tools could be. For the Granulation, however, are also combinations of fluidized bed (s) and Mixer (s), or combinations of different mixers used. The granulation is dependent from the starting material as well as the desired product properties under the influence of low to high shear forces.

He follows the granulation in a spray tower so can as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (Spray drying) solid sub stances are used, which at the top of a Turmes be sprayed in a defined droplet size, in free fall solidify or dry and at the bottom of the tower as Granules accumulate. The melt solidification is generally suitable especially for the shaping of low-melting substances in the range the melting temperature are stable (eg, urea, ammonium nitrate u. various formulations such as enzyme concentrates, pharmaceuticals, etc.), The corresponding granules are also called prills. The spray drying is especially for the production of detergents or detergent ingredients used.

Further The agglomeration techniques described in the prior art are the Extruder or perforated roll granulation, which optionally with granulating staggered powder mixtures when pressed through perforated disks (extrusion) or plastically deformed on perforated rolls. The products of Extruder granulation are also referred to as extrudates.

The in the combination according to the invention Detergents or cleaners contain bleach.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. width Examples of useful bleaching agents are peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Farther can Also bleach from the group of organic bleach used become. Typical organic bleaches are the diacyl peroxides, such as. Dibenzoyl. Other typical organic bleaches are the peroxyacids, Examples being the alkyl peroxyacids and the aryl peroxyacids become. Preferred representatives are (a) the peroxybenzoic acid and their ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, like peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic and N-nonylamido-succinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N, N-Terephthaloyl-di (6-aminopercapronate) can be used.

Combinations according to the invention, characterized in that the washing or cleaning agent a Oxygen bleaching agent, preferably sodium percarbonate contains particularly preferred.

The agents according to the invention Contained as a bleaching agent with particular preference percarbonate, this being Percarbonate in a particularly preferred embodiment, a coating having. As coating materials are in addition to inorganic Salts, in particular sulphates, carbonates and / or bicarbonates, preferably water-soluble used organic polymers.

When Bleach can alternatively or in addition to the aforementioned oxygen bleaches also chlorine or bromine releasing substances are used. Among the suitable For example, chlorine or bromine releasing materials are used heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Combinations according to the invention, characterized in that the washing or cleaning agent a Contains chlorine bleach, are also preferred.

The in the combination according to the invention covered containers enable the safe filling and Handling bleach-containing detergent or cleaning agent and are therefore particularly suitable for washing or high bleach detergent. In a special preferred embodiment the bleach-containing detergents or cleaners therefore a Bleach content significantly above the bleach content more usual Detergents or cleaners. Combinations, characterized that the bleach content of the detergent or cleaner more as 10 wt .-%, preferably more than 15 wt .-%, preferably between 20 and 90% by weight and in particular between 25 and 80 wt .-%, each based on the weight of the detergent or cleaning agent is therefore preferred according to the invention. in the Particularly preferred within the scope of the present application are washing or detergent with a bleach content above 30% by weight, Bleach levels between 30 and 90 wt .-%, preferably between 35 and 90% by weight, more preferably between 40 and 90 Wt .-% and in particular between 50 and 90 wt .-% are preferred.

Next The bleaching agents described above may be those in the combination according to the invention included detergents or cleaners other washing or cleaning active Contain substances. As the combination according to the invention in particular for the safe filling, Storage and use of potentially irritating or allergenic washing or detergent ingredients is suitable by means of this Combination preferably also enzyme-containing detergents or cleaning agents packaging. In a further preferred embodiment, the washing or detergent, therefore, in addition to the bleaching agent, continue to enzyme (s).

Enzymes are added to the washing or cleaning agent to increase the washing or cleaning performance. The enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples include the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and the proteases, but not the subtilases but subtilisins in the strict sense TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes ALS, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase of B. amyloliquefaciens is Vertrie from Novozymes under the name BAN ^® ben, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, also from Novozymes.

Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is, for example, the amylase ^LT® .

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacills sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The β-glucanase obtained from B. subtilis is named Ce Available REFLO ^® from Novozymes.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The For example, enzymes are either originally derived from microorganisms, about the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are used according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

The Purification of the enzymes concerned is preferably carried out by itself established methods, for example about precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

The Enzymes can used in any form established in the prior art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are as in enclosed in a solidified gel or in those of the core-shell type, in which a enzyme-containing core coated with a water, air and / or chemical impermeable protective layer is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

One Protein and / or enzyme may be particularly harmful during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters, including derivatives in particular with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic, or their salts or esters. As peptidic protease inhibitors include ovomucoid and leupeptin; a additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols, such as glycerol, ethylene glycol, Pro pylene glycol or sorbitol are other frequently used enzyme stabilizers. Also used are calcium salts, such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

reducing agent and increase antioxidants the stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulfite.

Prefers For example, combinations of stabilizers are used made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing Salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers is through the combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further amplified.

A combination according to the invention, characterized in that the washing or cleaning agent enzyme (s) contains wherein the enzyme content is preferably between 0.1 and 15 wt .-%, preferably between 0.2 and 10 wt .-%, more preferably between 0.4 and 8 wt .-% and in particular between 0.6 and 6 wt .-%, each based on the total weight of the washing or cleaning agent, is therefore preferred according to the invention.

The previously described inventive agent or after the produced previously described inventive method Means can in addition to the bleaching agents and enzymes described, further washing and cleaning-active substances, preferably washing and cleaning-active Substances from the group of builders, surfactants, polymers, Bleach activators, glass corrosion inhibitors, corrosion inhibitors, Disintegration aids, fragrances and perfume carriers included. These and more preferred ingredients are described in more detail below.

builders

To the builders counting in particular the zeolites, silicates, carbonates, organic cobuilders and where no ecological Prejudices against their use exist - also the phosphates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O • (1 - n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

With particular preference, in particular as a constituent of automatic dishwashing compositions, crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O are used, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1 , 9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

If the silicates are used as a constituent of automatic dishwasher detergents, these compositions preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 20% by weight of from 0.2 to 15% by weight .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred in particular if such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% is silicate of the general formula NaMSi _x O _{2x + 1} · y H ₂ O.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have se kundärwascheigenschaften. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

in the Within the scope of the present invention, it is preferred that this (s) Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent are included.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. This applies in particular to the use according to the invention or by inventive method prepared agent as a machine dishwashing detergent, which in the context the present application is particularly preferred. Among the multitude the commercially available Phosphates have the alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the di hydrate (density 1.91 gcm ^-3 , melting point 60 °) or in the form of the monohydrate (density 2.04 gcm ^-3 ), the disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , anhydrous or with 2 moles (density 2.066 gcm ^-3 , water loss at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), but in particular the trisodium phosphate (tertiary sodium phosphate) Na ₃ PO ₄ , which is used as dodecahydrate, as decahydrate (corresponding to 19-20% P ₂ O ₅ ) and in anhydrous form (corresponding to 39-40%). P ₂ O ₅ ) can be used.

Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which is in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water), and the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ .

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, colorless, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. The corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is marketed, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate used according to the invention.

Become in the context of the present application phosphates as washing or cleaning active Substances used in detergents or cleaners, so included preferred agents are said phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75% by weight, in particular, from 20 to 70% by weight, respectively based on the weight of the washing or cleaning agent.

Prefers it is in particular potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1 use. Particularly preferred is exclusively potassium tripolyphosphate to use without admixtures of other phosphates.

Further builders are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and Sodium. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their compared with other builders low chemical compatibility with the rest Ingredients of detergents or cleaning agents, the alkali metal hydroxides preferably only in small amounts, preferably in amounts below 10 Wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Especially preferred are agents which are less based on their total weight contain as 0.5 wt .-% and in particular no alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular from 7.5 to 30 wt .-%, each based on the weight of the washing or cleaning agent. Particularly preferred are agents which, based on the weight of the washing or Detergent less than 20 wt .-%, preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9 wt.% Of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (e ), more preferably sodium carbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they can be used in the form of their sodium salts polycarboxylic where among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids in itself can be used. The acids In addition to their builder effect, they also typically have the property an acidifying component and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

When builders are further polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaning agents on (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Further useful organic cobuilders are, for example, acetylated hydroxy or their salts, which may also be present in lactone form can and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

surfactants

to Group of surfactants are the nonionic, the anionic, the cationic and the amphoteric surfactants counted.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, comprise nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as other nonionic surfactants and alkyl glycosides of the general formula RO (G) _x are used in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol representing a glycose moiety having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

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

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

With Particular preference is furthermore given to using surfactants which have a or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer contain.

nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

Especially preferred are nonionic surfactants which have a melting point above Have room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which are solid at room temperature or highly viscous. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Prefers surfactants to be used which are solid at room temperature from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Particular preference is therefore given to ethoxylated nonionic surfactants which consist of C _6-20 monohydroxyalkanols or C _6-20 -alkylphenols or C _6-20 -fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and more preferably more than 70% by weight of the total molecular weight of such Nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular to to 15% by weight of the total molecular weight of the nonionic surfactant.

Further particularly preferred nonionic surfactants with melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15 are further particularly preferred nonionic surfactants.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, end-capped poly (oxyalkylated) nonionic surfactants are of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, preference being given to surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² , in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} one even number of carbon atoms and is usually unbranched, the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x R ² , in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical and x stands for values between 1 and 40.

In a particularly preferred embodiment of the present application, R ³ in the abovementioned general formula is H. From the group of the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x R ² In particular those nonionic surfactants are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxy groups and x stands for values between 1 and 40.

In particular, those end-capped poly (oxyalkylated) nonionic surfactants are preferred which are in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) -. x in this formula stands for values between 1 and 90.

Particular preference is given to nonionic surfactants of the general formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , which in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) - and in which x is between 40 and 80, preferably between 40 and 60.

The corresponding end-capped poly (oxyalkylated) nonionic surfactants of the above formula can be prepared, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ Obtained CH ₂ OH.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (CH ₃ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently of one another values between 1 and 32, nonionic surfactants having values for x of 15 to 32 and y of 0, 5 and 1.5 are very particularly preferred.

in der R¹ und R² unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R³ unabhängig voneinander ausgewählt ist aus -CH₃ -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂, vorzugsweise jedoch für -CH₃ steht, und x und y unabhängig voneinander für Werte zwischen 1 und 32 stehen, sind erfindungsgemäß bevorzugt, wobei Niotenside mit Werten für x von 15 bis 32 und y von 0,5 und 1,5 ganz besonders bevorzugt sind.Surfactants of the general formula

in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein nonionic surfactants with values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

Of course, the aforementioned nonionic surfactants not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants be used. As surfactant mixtures are not mixtures nonionic surfactants referred to in their entirety under one of the above general formulas, but rather such mixtures, the two, three, four or more nonionic Containing surfactants by different of the aforementioned general Formulas can be described.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are also suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as used in the preparation by Veres obtained from a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

When other anionic surfactants are especially soaps into consideration. Suitable are saturated fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

The including anionic surfactants the soaps can in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

are the anionic surfactants component of automatic dishwashing detergents, so is their content, based on the total weight of the funds preferably less than 4% by weight, preferably less than 2% by weight and most especially preferably less than 1% by weight. Automatic dishwashing detergents, which do not contain anionic surfactants are particularly preferred.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergents, is the content of cationic and / or amphoteric surfactants preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents, which contain no cationic or amphoteric surfactants particularly preferred.

polymers

to Group of polymers count in particular the washing or cleaning Poylmere, for example the rinse aid polymers and / or as a softener effective polymers. In general, detergents and cleaners are non-ionic Polymers also cationic, anionic and amphoteric polymers can be used.

"Cationic Polymers "in the sense The present invention relates to polymers which are a positive charge in the polymer molecule wear. This can be present, for example, in the polymer chain (Alkyl) ammonium moieties or other positively charged groups will be realized. Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary Groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

"Amphorere Poylmere "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units. These groups may be, for example to carboxylic acids, sulfonic acids or phosphonic acids act.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen , at least one quaternized nitrogen atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one Aminogr uppe with a positive charge is.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

werden im Falle von X^–= Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet.Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

werden im Falle von X^–= Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention preferred Polymers are used which are diallyldimethylammonium salts as monomer units and / or acrylamidopropyltrimethylammonium salts.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

preferred usable amphoteric polymers are from the group of alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers as well as the copolymer of unsaturated Carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Prefers usable zwitterionic polymers are from the group of Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their Alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Prefers are further amphoteric polymers, which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Especially preferred amphoteric polymers are from the group of the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Especially preference is given to amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

washing or detergents contain the aforementioned cationic and / or amphoteric polymers, preferably in amounts between 0.01 and 10 % By weight, based in each case on the total weight of the washing or cleaning agent. In the context of the present application, however, such washing or detergents in which the weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8 wt .-%, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent, is.

When softeners effective polymers are, for example, the sulfonic acid-containing Polymers which are used with particular preference.

Especially preferably as sulfonic acid-containing Polymers can be used are copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally further ionic or nonionic Monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Especially preferred sulfonic acid group-containing Monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene 1-sulfonic acid, styrene, vinylsulfonic 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, Sulfomethylmethacrylamid and water-soluble salts of said Acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

• i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in the R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above, or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in the R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms and X is an optionally present spacer group which is selected from - (CH ₂ ) _n - where n = 0 to 4, -COO- (CH ₂ ) _k - where k = 1 to 6, -C (O) - NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionic or nonionic monomers are particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H, in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausge wählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas: H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ )
• iii) optionally further ionogenic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

For example, copolymers which are structural units of the formula are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CH ₂ C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CH ₂ C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula - [CH ₂ -CHCOOH] _m - [CH ₂ -CH (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, as well preferably as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CH (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CH ₂ C (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CH (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ )- stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas - [CH ₂ -CHCOOH] _m - [CH ₂ -CH ₂ C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CH ₂ C (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -CH (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CH (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CH ₂ C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CH (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic acid atom of the sulfonic acid group in some or all of them Sulfonic acid groups against Metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partial or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

The Monomer distribution of the copolymers preferably used according to the invention is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

Bleach activators

Bleach activators are used in detergents or cleaning agents, for example, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds, the under perhydrolysis aliphatic Peroxocar bonsäuren with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O and / or N-acyl groups of said carbon atom number and / or optionally substituted Wear benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_2-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH _2, -CN, an alkyl or alkenylaryl radical with a C _2-24 alkyl group, or a substituted alkyl- or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates , in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium Acetonitrile methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams , for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

Provided in addition to the Nitrilquats further bleach activators are used are preferred bleach activators from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing Medium, used.

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts are used. For these substances These are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of bleach activator-containing agent; used. But in special cases can also more bleach activator can be used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of cloudiness, Streaks and scratches but also iridescence of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors come from the group of Magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds used to prevent glass corrosion can be used are insoluble Zinc salts.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ) and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The mentioned zinc compounds are preferably used in amounts which has a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0 wt .-%, each based on the total glass corrosion inhibitor-containing Means, effect. The exact content of the agent on the zinc salt or The zinc salts are naturally dependent on the type of zinc salts - ever less soluble the zinc salt used is, the higher its concentration should be to be in the media.

There the insoluble Zinc salts during the Geschirreinigungsvorgangs mostly unchanged remain, is the particle size of the salts a criterion to be observed so that the salts do not affect glassware or attach machine parts. Here, agents are preferred in which the insoluble Zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble Zinc salts below 1.7 mm are insoluble residues in the dishwasher not to be afraid. Preferably, this has insoluble Zinc salt has a mean particle size that is well below This value is in order to further minimize the risk of insoluble residues, for example a mean particle size smaller 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing Particle size. at very poorly soluble Zinc salts, the average particle size is preferably below 100 μm. For still poorly soluble Salts can be even lower; for example, that's for the very most poorly soluble Zinc oxide mean particle sizes below of 60 μm prefers.

A Another preferred class of compounds are magnesium and / or Zinc salt (s) of at least one monomeric and / or polymeric organic Acid. These do not cause the surfaces of glassware even with repeated use changed corrosively, in particular no clouding, Streaks or scratches but also no iridescence of the glass surfaces caused become.

Even though all magnesium and / or zinc salt (s) monomeric and / or polymeric used organic acids can be After all, the magnesium and / or zinc salts are monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated Monocarboxylic acids, the branched saturated or unsaturated Monocarboxylic acids, the saturated one and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, of the amino acids and / or the polymeric carboxylic acids prefers.

The Spectrum of the invention preferred Zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts that are heavy or insoluble in water, So a solubility below 100 mg / l, preferably below 10 mg / l, especially below 0.01 mg / l, to such salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C Water temperature). For example, the first group of zinc salts include the zinc citrate, the zinc oleate and the zinc stearate, to the group the soluble Zinc salts belong for example, zinc formate, zinc acetate, zinc lactate and the zinc gluconate.

With Particular preference is given as a glass corrosion inhibitor at least one Zinc salt of an organic carboxylic acid, more preferably in order a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, Zinc acetate, zinc lactate and / or zinc citrate used. Also zinc ricinoleate, Zinc abietate and zinc oxalate are preferred.

In the context of the present invention, the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

corrosion inhibitors

corrosion inhibitors serve the protection of the dishes or the machine, being particularly in the field of machine dishwashing Silver protectants have a special meaning. Can be used the known substances of the prior art. Generally, you can all silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. As examples of preferred according to the invention 3-amino-5-alkyl-1,2,4-triazoles to be used can be mentioned: propyl, Butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl, isononyl, versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, (5-oxo-2-pyrrolidinyl) -, 3-amino-1,2,4-triazole. In dishwashing detergents are the alkyl-amino-1,2,4-triazoles or their physiologically acceptable Salts in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for the Salt formation are hydrochloric, sulfuric, phosphoric, carbonic, sulphurous Acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Very effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles as well as mixtures of these substances.

In addition, cleaner formulations frequently contain active chlorine-containing agents, which are the corrosives significantly reduce the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of from or in addition to the silver protectants described above, for example the Benzotriazoles, can redox-active substances are used. These substances are preferably inorganic redox-active substances from the group Manganese, Titanium, Zirconium, Hafnium, Vanadium, Cobalt and Cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III, IV, V or VI.

The used metal salts or metal complexes should at least partially soluble in water be. The counterions suitable for salt formation include all common ones mono-, di- or tri-negatively charged inorganic anions, e.g. Oxide, sulphate, nitrate, fluoride, but also organic anions such as. Stearate.

metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally in addition one or more of the o.g. Anions exist. The central atom is one the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions which are monodentate or polydentate; the term "ligands" within the meaning of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 " in a metal complex the charge of the central atom and the charge of the ligand (s) is not zero, so, depending on whether a cationic or an anionic charge excess is present, either one or more of the above. Anions or one or more Cations, e.g. Sodium, potassium, ammonium ions, for charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition for "oxidation state" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

These metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners. Thus, for example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from the SO ₃ preparation (contact method) is suitable, as is the case by diluting a Ti (SO ₄ ) ₂ - Solution resulting titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely with a waterproof, but easily soluble at the cleaning temperatures Material coated, to their premature decomposition or oxidation during storage too prevent. Preferred coating materials which, according to known methods, such as Sandwik's melt coating process from the food industry, are applied, paraffins, microwaxes, waxes are natural Origin like carnauba wax, candellila wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids. there is the solid at room temperature coating material in molten Condition applied to the material to be coated, e.g. by finely divided material to be coated in continuous stream through a likewise continuously generated spray zone of the molten coating material is spun. The melting point must be chosen be that the coating material during the silver treatment easily dissolves or melted quickly. The melting point should ideally be in Range between 45 ° C and 65 ° C and preferably in the range 50 ° C up to 60 ° C lie.

The mentioned metal salts and / or metal complexes are in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing Contain funds.

disintegration aid

Around the disintegration of prefabricated moldings to facilitate, it is possible Disintegration aids, so-called tablet disintegrants, in to incorporate these agents to reduce disintegration times. Under Tablet disintegrants or disintegrants are used according to Römpp (9. Auflage, Bd. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, Pp. 182-184) are excipients which are responsible for the rapid disintegration of tablets in water or gastric juice and for ensure the release of the pharmaceuticals in a resorbable form.

These Substances that are also referred to as "explosives" due to their effect increase when water enters their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are for example synthetic Polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Prefers are disintegration aids in amounts of 0.5 to 10 wt .-%, preferably 3 to 7% by weight and in particular 4 to 6% by weight, respectively based on the total weight of the desintegrationshilfsmittelhaltigen By means of, used.

Preferred disintegrating agents used are cellulose-based disintegrating agents, so that preferred washing and cleaning agents contain such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrant-containing agent.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually However, the gas-releasing effervescent system in turn from at least two components that are together under gas formation react. While here a variety of systems is thinkable and executable, for example Nitrogen, oxygen or hydrogen will release the both in the detergents and cleaners used effervescent system on the basis of economic as well as ecological Select points of view to let. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

at The alkali metal carbonates or bicarbonates are the sodium and potassium salts for cost reasons across from the other salts clearly preferred. Of course you do not have to the respective pure alkali metal carbonates or bicarbonates be used; rather, you can Mixtures of different carbonates and bicarbonates preferred be.

Prefers be used as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 wt .-% and in particular from 3 to 10% by weight of an acidifying agent, respectively based on the total weight of the agent used.

Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

Prefers are Acidifizierungsmittel in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

fragrances

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count to the Ethern for example, benzyl ethyl ether, to the aldehydes e.g. the linear ones Alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the Ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures of various are preferred Fragrances are used, which together create an appealing fragrance produce. Such perfume oils can also natural Fragrance mixtures as available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also Muscat, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum oils are also suitable Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The general description of the applicable perfumes (see above) provides in general the different substance classes of fragrances In order to be perceptible, a fragrance must be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during vaporizing, whereby the odor impressions in "top note", "middle note" body) and "base note" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

Tenacious Fragrances that can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, Gurjunbalsamöl, Helichrysumöl, Ho oil, Ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copaia balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme Oil, Verbena Oil, Vetiver Oil, Juniper Berry Oil, Vermouth Oil, Wintergreen oil, Ylang-Ylan g oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling ones or solid odoriferous natural or of synthetic origin in the context of the present invention as adherent fragrances or Fragrance mixtures, so fragrances are used. To this Counting connections the following compounds as well as mixtures of these: Ambrettolide, α-amylcinnamaldehyde, Anethole, anisaldehyde, aniseediol, aniseed oil, methyl anthranilate, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, Benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, Borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, Fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, Heptincarbonsäuremethylester, Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, Indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, Camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, Methyl n-amyl ketone, methyl anthranilate, p-methyl acetophenone, Methylchavikol, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, Methyl n-nonyl ketone, Muskon, β-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, Pentadecanolide, β-phenylethyl alcohol, Phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vaniline, veratrum aldehyde, Cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamate, Zimtsäurebenzylester. To the more volatile Scents count especially the lower-boiling fragrances natural or synthetic origin used alone or in mixtures can be. examples for more volatile Fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, Linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, Phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

The Fragrances can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

dyes

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated substrates such as for example textiles, glass, ceramics or plastic dishes, so as not to stain them.

When choosing the colorant, it must be taken into account that in the case of textile detergents, the colorants do not have too high an affinity for textile surfaces and, in particular, for synthetic fibers, whereas in the case of detergents an excessive affinity for glass, ceramic or plasticware must be avoided. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^-3 to 10 ^-4 wt .-% ,

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Further suitable colorants Pigmosol come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ^® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

In addition to so far in detail described components can the detergents and cleaners contain other ingredients, which the application and / or aesthetic properties of this Improve funds further. Preferred agents include one or several substances from the group of electrolytes, pH adjusters, fluorescers, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Antistatic agents, ironing aids, Phobic and impregnating agents, Swelling and anti-slip agents as well as UV absorbers.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the washing or cleaning agents is preferred.

Around the pH of detergents or cleaners in the desired The use of pH-adjusting agents may be indicated be. Can be used here all known acids or alkalis, provided that their use is not from application technology or ecological establish or for reasons consumer protection. Usually exceeds the amount of these adjusting agents 1 wt .-% of the total formulation not.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils usually are clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa.s.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

optical Brighteners (so-called "whiteners") can Detergents or cleaners are added to graying and to eliminate yellowing of the treated textiles. These Substances attract to the fiber and cause a whitening and feigned Bleaching action by turning invisible ultraviolet radiation into visible length wavy Convert light, with the ultraviolet absorbed from sunlight Light as slightly bluish Fluorescence is emitted and with the yellow of the bated or yellowed laundry pure white results. Suitable compounds are derived, for example, from the substance classes 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, benzisoxazole and benzimidazole systems and the by Heterocycles substituted phenyl derivatives.

graying have the task of removing the dirt from the fiber in the fleet to keep it suspended, thus allowing the dirt to be recovered prevent. These are water-soluble Colloids mostly organic nature suitable, for example, the water-soluble Salts of polymeric carboxylic acids, glue, Gelatin, salts of ether sulfonic acids the strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Farther can be soluble Starch preparations and other than the aforesaid starch products use, e.g. degraded starch, aldehyde etc. Also, polyvinylpyrrolidone is useful. As grayness inhibitors Cellulose ethers such as carboxymethylcellulose (Na salt) can also be used, Methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and their Mixtures.

There textile fabrics, in particular of rayon, rayon, cotton and mixtures thereof, for Can tend to wrinkles, because the individual fibers against bending, bending, pressing and squeezing are sensitive to the grain direction, synthetic crease inhibitors be used. These include, for example synthetic products based on fatty acids, fatty acid esters, fatty acid amides, Alkylolestern, -alkylolamiden or fatty alcohols, usually with Ethylene oxide reacted or products based on lecithin or modified phosphoric acid ester.

phobicizing and impregnation method serve the equipment of textiles containing substances which are the deposit of dirt prevent or make it easier to wash out. Preferred phobic and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, Silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical-coupled, polymerizable compounds. Also Antistatics can be included. The dirt-repellent finish with phobic and impregnating agents Often classified as an easy-care item. The intrusion the impregnating agent in the form of solutions or emulsions of the active substances in question can be made by adding Wetting agents that minimize the surface tension. One Another field of application of repellents and impregnating agents is the water-repellent equipment of textiles, tents, tarpaulins, leather, etc., in contrast for waterproofing the tissue pores are not closed, the fabric thus remains breathable (hydrophobing). The water repellent coat the water repellents used Textiles, leather, paper, wood, etc. with a very thin layer hydrophobic groups, such as longer Alkyl chains or siloxane groups. Suitable water repellents are e.g. Paraffins, waxes, metal soaps etc. with additives Aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, Urea derivatives, fatty acid-modified Melamine resins, chromium complex salts, silicones, tin organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobicized Feel materials not greasy; nevertheless, similar to greasy substances, water drops drip at them without moistening. Thus, e.g. silicone Impregnated Textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

to fight of microorganisms can antimicrobial agents are used. This is different depending on the antimicrobial spectrum and mechanism of action between Bacteriostats and bactericides, fungistats and fungicides etc .. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlylsulfonates, halophenols and Phenolmercuriacetat, wherein also completely on these compounds can be dispensed with.

Unwanted changes caused by oxygen and other oxidative processes In order to prevent deterioration of detergents and / or treated textiles, the products may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

One increased Comfort can come from the extra Use of antistatics will result. Antistatic agents increase the surface conductivity and allow thus an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecule ligand and give on the surfaces a more or less hygroscopic film. These mostly surface-active Antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid ester) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatics for Textiles or as an additive to detergents, with an additional Avivageeffekt is achieved.

to Care of the textiles and to improve the textile properties like a softer "grip" (avivage) and reduced electrostatic charge (elevated Wearing comfort) softener be used. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic groups, such as the Disteraryldimethylammoniumchlorid, which, however, because of its insufficient biodegradability increasingly through quaternary Ammonium compounds is replaced in their hydrophobic residues Ester groups as breaking points for biodegradation included.

Such "ester quats" with improved biodegradability are available, for example, that mixtures of methyldiethanolamine and / or triethanolamine with fatty acids esterified and the reaction products then in a conventional manner quaternized with alkylating agents. Suitable as a finish is dimethylolethyleneurea.

to Improvement of water absorbency, rewettability treated textiles and to facilitate ironing treated textiles can Silicone derivatives are used. These additionally improve that rinse behavior of detergents or cleaners by their foam-inhibiting Properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes which may optionally be derivatized can and are then amino-functional or quaternized or Si-OH-, Si-H- and / or Si-Cl bonds. Other preferred silicones are the polyalkylene oxide-modified Polysiloxanes, ie polysiloxanes, which are, for example, polyethylene glycols and also the polyalkylene oxide-modified Dimetylpolysiloxane.

Finally, according to the invention, UV absorbers which are applied to the treated textiles and the light resistance improve the fibers. Compounds that have these desired properties are, for example, by radiationless deactivation effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well Natural substances such as umbelliferone and the body's own urocanic acid are suitable.

protein are due to their fiber care effect more in the context of present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures, by acid, base or enzymatically catalyzed degradation of Proteins (proteins) to be obtained. According to the invention, protein hydrolysates be used both of plant and animal origin. Animal protein hydrolysates are, for example, elastin, collagen, Keratin, silk and milk protein protein hydrolysates, too may be in the form of salts. According to the invention preferred is the use of protein hydrolysates of plant origin, e.g. Soy, almonds, rice, pea, potato and wheat protein hydrolysates. Although the use of protein hydrolysates is preferred as such is, can in their place, if appropriate, otherwise obtained amino acid mixtures or individual amino acids such as arginine, lysine, histidine or pyrroglutamic acid used become. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

Non-aqueous solvents which can be used according to the invention include, in particular, the organic solvents, of which only the most important can be mentioned here: Al alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones ( Acetone, butanone, cyclohexanone), esters (acetic esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), Halogenated hydrocarbons (dichloromethane, chloroform, tetrachloromethane, tri-, tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons (benzines, petroleum ethers, cyclohexane, methylcyclohexane, decalin, terpene solvents, benzene, toluene, xylenes). Alternatively, instead of the pure solvents, their mixtures, which advantageously combine, for example, the dissolution properties of various solvents, can also be used. Such a solvent mixture which is particularly preferred in the context of the present application is, for example, benzine, a mixture of various hydrocarbons suitable for dry cleaning, preferably containing C12 to C14 hydrocarbons above 60% by weight, more preferably above 80% by weight and in particular above 90 wt .-%, each based on the total weight of the mixture, preferably having a boiling range of 81 to 110 ° C.

Claims (9)

Combination of a rigid container with a maximum container height h _max and a present in the rigid container particulate, bleach-containing detergent or detergent, wherein the container has a footprint A with a minimum diameter d _min and a top-side container opening with a surface A 'and a maximum diameter d _max , characterized in that d _{min is} greater than h _max and d _{min is} greater than d _max . Combination according to claim 1, characterized in that that the bleach content of the detergent or cleaner more as 10 wt .-%, preferably more than 15 wt .-%, preferably between 20 and 90 wt .-% and in particular between 25 and 80 wt .-%, respectively based on the weight of the detergent or cleaning agent. Combination according to one of Claims 1 or 2, characterized in that that the washing or Detergent an oxygen bleach, preferably sodium percarbonate contains. Combination according to one of claims 1 to 3, characterized that the washing or Detergent contains a chlorine bleach. Combination according to one of Claims 1 to 4, characterized that the washing or Detergent contains enzyme (s), wherein the enzyme content is preferably between 0.1 and 15 wt .-%, preferably between 0.2 and 10 wt .-%, more preferably between 0.4 and 8 wt .-% and in particular between 0.6 and 6 wt .-%, each based on the total weight of the washing or cleaning agent. Combination according to one of claims 1 to 5, characterized in that the ratio between minimum diameter d _{min of} the footprint A and maximum container height h _max between 1: 0.95 and 1: 0.2, preferably between 1: 0.95 and 1 : 0.4, preferably between 1: 0.95 and 1: 0.6 and in particular between 1: 0.95 and 1: 0.7. Combination according to one of Claims 1 to 6, characterized that the ratio between stand space A and container opening area A 'between 1: 0.9 and 1: 0.2, preferably between 1: 0.9 and 1: 0.4, preferably between 1: 0.9 and 1: 0.5 and in particular between 1: 0.9 and 1: 0.6. Combination according to one of Claims 1 to 7, characterized that the container opening a Adhesive, latching, snap or screw closure, preferably having a screw cap. Combination according to claim 8, characterized in that that the container opening a has convex closure, which corresponds in shape with a concave embossing in the container bottom.