DE102005045440A1 - Portioned detergent or cleaner composition - Google Patents

Abstract

Portioned detergent or cleaning agent compositions comprising a) a water-soluble or water-dispersible container, b) at least one first solidified melt adhering to the container material, which contains sugar, and c) at least one further phase, are characterized by improved cleaning performance and an appealing one Optics.

Description

The The present invention relates to portioned detergent compositions, methods for preparing portioned detergent or cleaner compositions as well as the use of these portioned medium portions.

washing or detergents are available to the consumer in a variety of forms today available. In addition to washing 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 Detergent tablets fulfill this requirement additionally the desire of the consumer for simple dosage.

When Alternative to the previously described particulate or compacted washing or detergents are becoming increasingly solid in recent years or liquid Detergents or cleaning agents containing a water-soluble or water-dispersible coating like foils. These remedies stand out like the tablets by a simplified dosage, since they work together with the water-soluble wrapping in the washing machine or the dishwasher can be dosed, on the other hand allow but at the same time also the packaging liquid or powdery Detergents or cleaners, which are compared to the Kompaktaten by a better resolution and distinguish faster effectiveness. The individual in this way Dosing units packaged cleaning products can easily through Insert one or more bags directly into the washing machine or dishwasher or in their Einspülkammer, or by injection into a predetermined amount of water, for example in a bucket or in hand washing or sink, be dosed.

These Portions have the disadvantage, not the high degree of compactness to possess, as it tablets have. The filling of Tubular bags leads on the one hand to a low degree of compaction, on the other hand to a technically caused void volume, so that measured for a washing or cleaning cycle Amount of a detergent or cleaner a larger space occupies as a corresponding amount in tableted form. moreover does that Void volume to be filled Bag against mechanical influences are unstable and can burst.

Furthermore have filled Tubular bag only low aesthetic Stimuli on. The consumer accepts this form of offer only slightly and does not trust the corresponding remedy a high level of performance. Becomes Packed in a bag only one uniform composition, In addition, it is not possible to visualize the multifunctional advantages of means.

In addition exists the problem is that the lower density compared to tablets the portioned packaged compositions to space problems in Dosing devices in dishwashers to lead can. If necessary, it must be dosed lower, so that the Portion can be applied, resulting in poorer cleaning results leads.

in the The prior art are therefore packaging made of water-soluble Materials disclosed which are not in the form of tubular bags but produced by methods such as injection molding or deep drawing are. These more rigid containers are filled and after filling locked. When filled with a uniform composition containers succeed But here too, not the visualization of multi-functional advantages the means.

A possibility for the visualization of multi-functional advantages offers the use of multi-chamber containers, the with compositions of different consistency and / or color filled become. The production of containers, which in the filled Condition partitions between the individual compositions is, however, with Additional costs due to an increase the number of steps for container production and filling as well as enlarged apparatus Effort connected. Generally, with every increase in the Chamber number in a container also the total cost of Production and filling of the container climb.

Are compositions of different consistency such as a powder or granules and one or more large-sized solids (tablets, lozenges, balls, solidified melts, etc.), a liquid and one or more large-sized solids or a gel and one or more large-sized solids are filled into a container and the individual compositions are not separated by partitions, the composition with the higher flowability will be distributed around the less flowable body, ie Powders, liquids and gels undermine large-scale solids. As a result, the attractiveness of the portioned agent decreases. In the case in which the large-scale solid is still visible to the eye, it is still possible to visualize the multi-functional properties of the agent, but the agent is not very attractive, since no clear contours are more recognizable inside the container and the powder or Liquid components between the large solids and a transparent packaging are perceived by the consumer as contaminants. If the flowable composition has been distributed evenly and the large-scale solid can no longer be recognized by the packaging with the eye, the multifunctional advantages of the portioned agent are no longer perceived by the consumer.

regardless this aesthetic Problems occurs in medium portions, which are two different Contain compositions within a compartment, as Another problem is a loss of washing or cleaning activity over the Time. When used by the consumer, that is after Packaging, storage and transport, the funds have a clear lower washing or cleaning activity than the sum of the Agents contained active ingredients before filling in the container. When Consequence must be to guarantee an acceptable cleaning power a higher amount of funds in the Washing or cleaning procedures are used, which in turn to space problems in dosing of dishwashers or the like Cause problems can.

One especially big Performance degradation is observed with agents containing bleach compositions and enzyme compositions within a compartment.

One comparable but less pronounced waste in the washing or Cleaning performance is also observed with such portioned agents the per receiving chamber of a container only one composition included.

Of the The present invention was based on the object, a portioned To provide washing or cleaning agent, which in comparison to known means an improved washing or cleaning performance having. The process should be inexpensive and a visual one attractive product, which does not solve the problems described above has to deliver.

It it has now been found that portioned detergent or cleaning compositions, in which a solidified melt comprising sugar adheres with a water-soluble or water-dispersible packaging, has a high attractiveness and washing or cleaning compositions of the prior art Technology in the washing or cleaning performance exceeds.

object the present invention is a portioned detergent or cleaning composition, comprising a) a water-soluble or water-dispersible containers, b) at least one first, adhesively bonded to the container material, solid phase and c) at least one further phase, the first Phase is a solidified melt containing sugar.

Preferably contains the solidified melt at least one washing or cleaning active Component.

In a preferred embodiment the portioned according to the invention Detergent or detergent composition are the first phase (s) and the second phase (s) in the same compartment of the water-soluble or water-dispersible container contain. In this case, it may be preferred that the container only has a compartment. Also the filling of a compartment a multi-compartment container with at least a first and at least a second phase and the filling one or more compartments with air, gas, a liquid, a gel, a molding and / or a powder or granules is conceivable. Is possible it also contains several to all compartments of a multi-compartment container respectively to fill with one or more first and second phases and the remaining compartments with air, gas, a liquid, a gel, a molding or to fill a powder or granules.

In a preferred embodiment the first and second phases are in a closed state container and have no contact with the outside atmosphere. Surprisingly, it was found that the ingredients of washing or cleaning agent portions according to the invention, which one completely closed container include, completely and controllable solve or disperse and not to form lumps or so-called Gel phases tend.

In a special embodiment can the container one or more up to 0.5 mm, preferably up to 0.3 mm and in particular up to 0.1 mm openings and not completely closed to the outside atmosphere.

According to the invention first, with the container material adherent connected phase. Under fixed phases are in the frame the application understood all those phases which have a dimensional stability and therefore their shape when placed on a surface within one week, preferably within a month and in particular not noticeably change within a year.

shrinking or swelling and decomposition effects are intended here in the determination the "strength" of a phase is not considered become. According to the application, compositions are therefore also their elasticity / strength can be compared with those of glass or chewing gum. Thus, can a solidified inventive Melt solid or hard as a salt crystal, or elastic Have properties. With preference, however, the melt has a low elasticity on and deforms under pressure only in one with imperceptible to the eye.

In special embodiments It may be preferred that the melt by the action of Pressure can be deformed, However, after removal of this pressure, not back to the original Form or an intermediate state returns, but the deformed Maintains shape.

Surprised it was found that portioned detergent or cleaning compositions in the context of measuring accuracy over the time a more constant washing or cleaning performance, if the melt contains sugar as the basic ingredient. Preferably contains the solidified melt 10 to 99 wt .-%, preferably 20 to 90 wt .-%, particularly preferably from 30 to 80% by weight, more preferably from 35 to 70% by weight and in particular from 40 to 65% by weight of sugar.

Under The term sugar also covers sugar derivatives in the context of the notification such as sugar alcohols and / or sugar acids understood.

Sugar alcohols are crystalline, readily water-soluble polyhydroxy compounds, which are formed by reduction of the carbonyl group from sugars. The monosaccharide sugar alcohols (C _n H _{2n + 2} O _n ) include the food compounds important xylitol (a pentitol), d-sorbitol (also d-glucitol, a hexitol) and d-mannitol (a hexitol), to the disaccharide sugar alcohols (C _n H _2n O _n-1) maltitol, palatinit ^® and lactitol. Sugar alcohols are less reactive than sugar because of the missing carbonyl group. A distinction is made in these generally crystalline, water-soluble polyols according to the number of hydroxyl groups contained in the molecule Tetrite, Pentite, Hexite, etc. When heated no caramelization takes place, with protein components no browning (Maillard reaction) instead. Most monosaccharide sugar alcohols, such as adonite (ribitol), arabitol, (dulcitalactite), erythritol, glycerol, d-mannitol (hexitol), d-sorbitol (glucitol), threitol, xylitol (pentitol), come in small quantities in nature before, disaccharide sugar alcohols are purely synthetic products.

Sugar acids are polyhydroxycarboxylic acids prone to lactone formation which are formed by oxidation of the aldehyde and / or the primary Alcohol groups from simple sugars (monosaccharides) to carboxy groups arise. Many of the sugars occur as metabolites and / or components are more polymeric Natural substances, such as pectins, glycosaminoglycans or of chondroitin sulfate. Mild oxidation of sugars leads to Formation of aldonic acids, when the aldehyde to Carboxy group is oxidized. If, on the other hand, the primary alcohol oxidized to the carboxy group, we obtain uronic acids. Ketoaldonic arise formally by oxidation of a primary OH group of ketoses, technically by Oxidation of a secondary OH group of aldonic acids. More energetic oxidation of sugars leads to aldaric acids. The by nitric acid oxidation Oxalic acid formed by sugar was earlier sugar acid called. Today, in the technician jargon by the oxidation of d-glucose or sucrose or, better, starch resulting in nitric acid glucaric referred to as "sugar acid" par excellence, from which the saccharates are derived.

The compounds mentioned are generally not only sufficiently soluble but are also characterized by low costs and good processability. So can be sugar and sugar derivatives, in particular the mono- and disaccharides and their derivatives, process in the form of their melts, these melts have a good dissolving power both for dyes and for many washing or cleaning-active substances. The solid bodies resulting from the solidification of the sugar melts are also distinguished by a smooth surface and advantageous appearance, such as a high surface brilliance or a transparent appearance.

Among the group of preferred as material for the melt in the present application sugar from the group of mono- and disaccharides and derivatives of mono- and disaccharides include in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin and Isomalt ^® and mixtures of two, three, four or more mono- and / or disaccharides and / or the derivatives of mono- and / or disaccharides. Thus, mixtures of isomalt ^® and glucose, isomalt ^® and lactose, isomalt ^® and fructose, isomalt ^® and ribose, isomalt ^® and maltose, glucose and sucrose, isomalf ^® and maltodextrin or isomalt ^® and sucrose as materials for the melt is particularly preferred.

Farther as material for the melt most preferred are mixtures of maltodextrin and glucose, maltodextrin and lactose, maltodextrin and fructose, Maltodextrin and ribose, maltodextrin and maltose or maltodextrin and sucrose.

When Maltodextrin are in the context of the present application by enzymatic Removal of starch recovered water-soluble Carbohydrates (Dextrose equivalents, DE 3-20) with one chain length of 5-10 anhydroglucose units and a high level of maltose designated. Maltodextrin will help improve the food rheological u. added caloric properties, taste only a little sweet u. tend not for retrogradation. Commercial products, such as the company Cerestar, are usually called spray-dried free-flowing powder offered and have a water content of 3 to 5 wt .-%.

^® as isomalt is within the scope of the present application, a mixture of 6-O-α-D-glucopyranosyl-D-sorbitol (1,6-GPS) and 1-O-α-D-glucopyranosyl-D-mannitol (1,1 GPM). In a preferred embodiment, the weight fraction of 1,6-GPS in the total weight of the mixture is less than 57% by weight. Such mixtures can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the resulting isomaltose to form an odorless, colorless and crystalline solid.

In a preferred embodiment the portioned detergent composition however, the melt is less than 50% by weight, preferably less than 30% by weight, more preferably less than 10% by weight, more preferably less than 5% by weight and in particular no sugar alcohols and / or Sugar acids. With preference, the sugar (s) contained in the melt selected from the group of mono- and disaccharides, preferably from Group glucose, fructose, ribose, maltose, lactose and sucrose as well as mixtures of these. Very particularly preferred is the use of glucose and / or maltose. Are mixtures of glucose and one or more other sugars used is glucose in preferably at least 30% by weight of these mixtures at least 45% by weight, more preferably at least 60% by weight, to preferably at least 75 wt .-%, most preferably at least 90% by weight and in particular at least 99% by weight contain.

Surprisingly it has been found that portioned detergent or cleaning compositions, on the one hand melting, comprising 10 to 99 wt .-% glucose, Fructose, ribose, maltose, lactose and / or sucrose and at least another active and, on the other hand, one or more others also include active-agent-containing phases, a higher washing or cleaning activity, as already known agents. The washing or cleaning power of these sugar-containing agents is changing even during storage and transport not and does not decrease as at always to observe known means, over time. So For example, in agents according to the invention, which bleach, Bleach catalysts and / or bleach activators in the first phase, ie the melt, and enzymes in the second phase (in a powder, Granules, liquid or gel), less inactivation of the enzymes as well the other ingredients than in the prior art agents. Particularly good results are obtained when glucose and / or Maltose is used as sugar.

A marked improvement in the stability of individual components over time could also be achieved with separation of bleach / perfume, bleach / dye, nonionic / anionic surfactant, nonionic surfactant / polymer, antioxidants / nonionic surfactant, antioxidants / dye, antioxidants / perfume, antioxidants / enzyme, Bleach activator / perfume, bleach activator / dye, nonionic surfactant / bleach activator, Bleach activator / polymer, antioxidants / bleach activator, bleach activator / dye, phosphates / phosphonates, pH adjustor / perfume, pH adjuster / enzyme, bleach catalyst / perfume, bleach catalyst / dye, nonionic / bleach catalyst, bleach catalyst / polymer, antioxidants / bleach catalyst, bleach catalyst / Dye and nonionic surfactant / builder.

Out processing reasons and due to the different stability profiles in the melt usable active ingredients, it may be preferred that the melt has a low melting point and so at low temperatures can be processed. In special cases it may be preferable that the melt is below 100 ° C, preferably below 85 ° C, preferably below 70 ° C and in particular below 55 ° C is flowable and can be processed. A lowering of the melting point can be achieved by adding suitable substances such as salts. in the Framework of work has been surprising that agents according to the invention comprising at the Melt processed temperatures, over the time particularly stable Show washing or cleaning services.

With Preference is given in the inventive compositions Melting at temperatures between 50 and 150 ° C, preferably flowable at temperatures between 60 and 120 ° C, but solid at 20 ° C is / are. In particular, those agents are preferred in which the Melting between 65 and 90 ° C and especially between 75 and 85 ° C from the solid to the flowable state.

preferred Sugars have a melting point between 50 and 150 ° C and in particular between 65 and 115 ° C on.

Next contains the sugar or sugars the melt preferably one or more further active ingredients. In general, the use of any active ingredient of detergents or cleaning agents in melts according to the invention conceivable. A range of suitable active ingredients / washing or cleaning ingredients for the packaging within the melt according to the invention will be listed in the course of the following text. With special preference contains the first phase one or more active substance (s) from the field the detergent or cleaner ingredients, preferably from the Group of soil repellent polymers, optical brighteners, perfumes, Bentonites, bleaches, bleach catalysts, bleach activators, preferably bleaches, bleach catalysts and / or bleach activators, preferably in amounts of 1 to 90 wt .-%, particularly preferably in Amounts of 5 to 80 wt .-%, most preferably in amounts of From 10 to 70% by weight and in particular from 15 to 60% by weight, related to the first phase.

Next the active substances optional solvent / solubilizer in the first phase like water, but also non-aqueous solvent be included. To the non-aqueous solvents which used according to the invention can be counting in particular the organic solvents, of which only the most important can be listed here: 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 acid esters, Glycol esters), amides and other nitrogen compounds (dimethylformamide, Pyridine, N-methylpyrrolidone, acetonitrile), sulfur linkages (Carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (Nitrobenzene), halogenated hydrocarbons (dichloromethane, chloroform, Tetrachloromethane, tri-, tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), Hydrocarbons (gasolines, petroleum ethers, cyclohexane, methylcyclohexane, Decalin, terpene solvent, Benzene, toluene, xylenes). Alternatively, instead of pure solvents also their mixtures, which, for example, the solution properties of various solvent merge advantageous, are used .. Preferably, the first contains Phase water, polyhydric alcohols and / or polyethylene glycols independently in each case in amounts of from 0 to 50% by weight, preferably from 5 to 20% by weight, related to the first phase.

Next the first phase, which is in the form of a solidified melt, contains the container according to the invention at least another, second phase. This second phase is preferably in the form of a powder, in the form of granules, in the form of a or several extrudates, in the form of compacts such as tablets or in Shape of one or more casting before. With particular preference, however, the second phase takes the form of a Powder or the form of granules. Are next to the first one Phase several more phases in the composition of the invention can contain these other phases the same consistency and color, but also have divergent Kon sistenzen or colors. As well can the other phases the same composition, or compositions containing one or more active substances.

In a preferred embodiment of the invention, the second phase is liquid or gel shaped.

The volume ratio of the first / first phase (s) and second / second phase (s) is preferably between 1: 100 and 2: 1, preferably between 1:50 and 1: 1, more preferably between 1:20 and 1: 2 and especially between 1:10 and 1: 3.

The first phase preferably takes between 5 and 90% by volume, preferably between 8 and 75% by volume, more preferably between 11 and 50% by volume and in particular between 14 and 25% by volume of the compartment, in which first and second phase (s) are located. With preference the container according to the invention is a One-compartment containers and the first phase fills between 5 and 90% by volume, preferably between 8 and 75% by volume, more preferably between 11 and 50% by volume and in particular between 14 and 25% by volume of the container.

Basically it is possible that an active substance or an active substance group both in the first Phase as well as in the second phase. In a special embodiment the agents according to the invention can Compositions of the first and second phase almost to fully match. Prefers However, it is the first phase and second phase at least in an active or an active group. For example contain first and second phase incompatible active ingredients, thus in the agent according to the invention "from each other separated "present. Thus it is preferred if the first phase bleach, bleach catalyst and / or bleach activator, while the second phase contains one or more enzymes. It is also possible that the enzymes are contained in the first phase while bleaching-active compounds exclusively Part of the second phase.

With contains particular advantage the first phase amylase.

There it is advantageous to use certain detergent or cleaning agent components at different times in the washing or clear rinse release, it is preferred that the first phase (s) and the second phase (s) in water at 20 ° C solve different fast or dispersing, wherein the first (n) phase (s) preferably Slower releases / slower disperses / disperse as at least one of the second, preferably all second phases.

pronounced good washing results are also after 4 to 18 weeks of storage including transport obtained when the portioned detergent composition what a serlöslichen container of polyvinyl alcohol, a melt, which, based on the melt 35 to 70 wt .-%, preferably 40 to 65 wt .-% glucose, maltose and / or fructose and 15 to 60 wt.%, preferably 20 to 50 wt.% and in particular contains 25 to 40 wt .-% bleach-active substances and a other solid or liquid, preferably particulate Phase, preferably comprising enzyme and optional builder, wherein the melt with the container wall is connected, the melt is preferably self-adhesive and the relationship between the two phases is between 1:20 and 1: 2.

Surprisingly these detergent or cleaner portions have a higher "whitening effect", i.e. an improved capital for cleaning white Laundry on, as known means.

Prefers are in the slower-solving Phase, preferably in the first phase, bleach, bleach catalysts and / or bleach activators. Other components of washing or cleaning agents such as soil repellent polymers, optical brighteners, Perfume, Bentonites, fluorescers, grayness inhibitors, shrinkage inhibitors, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Antistatic agents, ironing aids, Phobic and impregnating agents, Swelling and anti-slip agents, UV absorbers or rinse aid substances are also preferably used ingredients of the later dissolving phase, which is preferably the first phase.

In special embodiments can one or can several of these ingredients also in the second phase, which are preferred is faster than the melt dissolving powder / granules, be included.

The agents according to the invention are particularly suitable as detergents for household or industrial washing machines or as a dishwashing liquid for machine dishwashers in the household or in the gastronomy.

If the inventive agents described above are used as detergents, they contain preferably in addition to the substances already mentioned further active ingredients, preferably from the group of builders, surfactants, polymers, Disintegrationshilfsmittel, fragrances and perfume carriers. These preferred ingredients will be described in more detail below. Suitable enzymes, bleaches, bleach catalysts and bleach activators, fluorescers, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatics, ironing aids, repellents and impregnants, swelling and anti-slip agents and UV absorbers are also listed.

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) ), 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.

Preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, with particular preference preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. 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. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and also, above all, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (Nansi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H 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 ).

Detergents or cleaning agents 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, preferably 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 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 preferably delayed release and have secondary washing properties. 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 understood to mean 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 having a width of several degrees of diffraction angle , cause.

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray-amorphous silicates are used whose silicate particles give washed-out 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 X-ray amorphous silicates also have a dissolution delay compared to 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 Alkalidisilikate, in detergents or in cleaning agents in amounts of from 3 to 60% by weight, preferably from 8 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. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium 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.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably 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, Thus preferred agents contain this phosphate (s), preferably Alkali metal phosphate (s), more preferably pentasodium or Pentakalium triphosphate (sodium or potassium tripolyphosphate), in Amounts of from 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the washing or cleaning agent.

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 For example, a builder system containing a mixture of tripolyphosphate and sodium carbonate. Because of her in comparison with others Builders low chemical compatibility with the other ingredients from washing or Detergents, the alkali metal hydroxides are preferred only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, more preferably below 4% by weight and in particular below 2 wt .-%, each based on the total weight of the washing or cleaning agent used. Especially preferred are means which, in relation to their total weight, are less than Contain 0.5 wt .-% and in particular no alkali metal hydroxides.

Especially preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30 wt .-%, each based on the Weight of washing or cleaning agent.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, To name polyacetals, dextrins and phosphonates. These substance classes are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, 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 use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, here are citric acid, Bern to call stearic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

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.

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 either as a powder or as an aqueous one solution be used. The content of detergents or cleaners of (co) polymeric polycarboxylates is preferably from 0.5 to 20 Wt .-% and 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 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 in particular in zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

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.

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 contain nonionic surfactants from the group of 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). Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit 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 nachfolgender 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 are usually prepared by reductive amination of a reducing Zu ckers with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.

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 Connections 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 continues to be combinations of one or several tallow fatty alcohols with 20 to 30 EO and silicone defoamers used.

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 nonionic surfactants, or the PO / AO / PO nonionic surfactants, especially the PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.

Examples of anionic surfactants used in detergents are those of the sulfonate and sulfates type. 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 suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the 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.

Also, the Schwefelsäuremonoester the oxide with 1 to 6 moles of ethylene oxide ethoxylated straight-chain or branched C _7-21 alcohols, such as C 2-methyl-branched _9-11 alcohols containing on average 3.5 moles of ethylene (EO), or C _12-18 Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are used in detergents or cleaners only 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.

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; R¹ = R² 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 ¹ = R ² 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.

to Care of the textiles and to improve the textile properties like a softer "grip" (avivage) and reduced electrostatic charge (elevated Wearing comfort) fabric softening compounds are used. The active ingredients these formulations are quaternary Ammonium compounds having two hydrophobic radicals, such as the Disteraryldimethylammoniumchlorid, which, however, because of his inadequate biodegradability increasingly replaced by quaternary ammonium compounds is in their hydrophobic residues ester groups as predetermined breaking points for the contain biodegradation.

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 Group of polymers count in particular the washing or cleaning-active polymers and / or as softeners effective polymers. Generally in detergents or cleaners in addition to nonionic 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.

"Amphoteric Polymers "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.

washing or cleaning agents 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 detergent. Are preferred in the context of the present Registration, however, such detergents or cleaning agents in which the proportion by weight of the cationic and / or amphoteric polymers between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4 wt .-%, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, respectively based on the total weight of the washing or cleaning agent.

The bleaching agents are a particularly preferred washing or cleaning substance. 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. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming 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.

When Bleach can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, 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.

According to the invention Washing or cleaning agents which are 1 to 35 wt .-%, preferably 2.5 to 30 wt .-%, particularly preferably 3.5 to 20 wt .-% and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate, based to the entire portioned detergent or cleaning composition, contain.

Bleach activators are used, for example, in detergents or cleaners to achieve an improved bleaching action when cleaned at temperatures of 60 ° C and below. As bleach activators, it is 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 Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetylxylose and octaacetyl lactose and 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.

These Bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight, and especially preferably 2 to 6 wt .-%, each based on the total weight the bleach activator containing agent, that is, the total weight of the agents according to the invention used.

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_1-24-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(CN₃)-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, vorzugsweise aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat. 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 having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having 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 (CN 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, preferably from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate. is.

Particularly preferred are 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 ^- , 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 chloride, bromide, iodide, Hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is particularly preferred.

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 inventive agent used. In special cases can However, more bleach activator can be used.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ )] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ ( TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (MeOH) TACN) _2] (ClO _{4) 2} [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me TACN) _2] (ClO _{4) 3,} [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These 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 or cleaning agents, 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.

Under Proteases are preferred to those of the subtilisin type. Examples therefor are the subtilisins BPN 'and Carlsberg and its advanced forms, the protease PB92, subtilisins 147 and 309, the Bacillus alkaline protease lentus, subtilisin DY and the subtilases, but not anymore the enzymes subtilisins in the strict sense, thermitase, Proteinase K and the proteases TW3 and TW7.

Examples for inventively usable Amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as those for use in washing and Detergents improved developments of the aforementioned Amylases. 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).

Usable according to the invention are still lipases or cutinases, especially because of their Triglyceride-splitting activities, but also to in situ peracids from suitable precursors produce. These include for example, the original one from Humicola lanuginosa (Thermomyces lanuginosus) available, respectively further developed lipases, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, the original from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose starting enzymes originally from Pseudomonas mendocina and Fusarium solanii have been isolated.

Farther can Enzymes are used, which are summarized by the term hemicellulases. These include for example mannanases, xanthan lyases, pectin lyases (= pectinases), Pectinesterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

to increase the bleaching effect oxidoreductases according to the invention, for example, oxidases, oxygenases, catalases, peroxidases, such as Halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) be used. Advantageously, organic, particularly preferably aromatic, interacting with the enzymes Compounds added to the activity of the respective oxidoreductases to reinforce (Enhancer) or at very different redox potentials between the oxidizing enzymes and the soiling the electron flow to ensure (Mediators).

Especially Preference is given to using perhydrolases in the compositions according to the invention.

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.

Furthermore, it is possible to assemble two or more enzymes together, so that a Zelnes 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.

Prefers are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in Amounts of 0.1 to 5 wt .-%, preferably, from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agents, that is to the entire portioned detergent or cleaning composition, used.

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 disintegrators are adjuvants understood that for the rapid disintegration of tablets in water or other media and for the swift one Release of the active ingredients.

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 are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise 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 cellulosic derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the disintegration agent based on cellulose. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The Cellulose used as disintegration aid is preferably not used in finely divided form, but before mixing transferred to the premixes to be compressed in a coarser form, for example, granulated or compacted. The particle sizes of such Disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.

As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, but the crystalline regions (about 70%) and un leave damaged. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

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 in the washing or cleaning agent used effervescent system both 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.

When Acidifying agents consisting of the alkali salts in aqueous solution Carbon dioxide release, for example, boric acid as well Alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given used organic Acidifizierungsmittel, wherein the citric acid a particularly preferred acidifying agent. Preferred are Acidifier in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

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. Prefers However, mixtures of different fragrances are used, the together create an appealing scent. Such perfume oils can also natural Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

Around to be perceptible, a fragrance must be volatile, being next to the Nature of the functional groups and the structure of the chemical Compound also plays a role in the molecular weight. So own most fragrances have molecular weights up to about 200 daltons, while molar masses from 300 daltons and above constitute an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during Evaporation, whereby the odor impressions in "top note", "middle note" (middle note or body) and "base note" (end note or dry divided out). Because the smell perception to a large extent too 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.

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.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time, when choosing suitable colorants, it must be taken into account 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 Dyes in the detergents or cleaners. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight are typically selected. By contrast, in the case of the particularly preferred, but less readily water-soluble, pigment dyes due to their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 to 10 ^-4 % by weight.

It become colorants preferably, which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be beneficial proved, colorants to be used in water or at room temperature in liquid organic Substances are soluble. Suitable are, for example, anionic colorants, e.g. anionic Nitroso.

In addition to so far in detail described components can the detergent as well as the later treated detergents contain other ingredients which the performance and / or aesthetic properties of this Improve funds further. Preferred agents contain one or more 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 before linear-polymer silicones, which are constructed according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 and 150,000 and viscosities between 10 and 1,000,000 mPa · s.

suitable Anti redeposition agent, also referred to as soil repellents are, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of 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 pyrene derivatives.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. For this purpose, water-soluble col loide mostly organic nature, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

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 Quet rule 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 u. Zirconium salts, organic silicates, silicones, polyacrylate 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 are facilitated by the surface tension decrease. 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.

Around unwanted, caused by oxygen and other oxidative processes changes on the washing or on the cleaning agents and the treated To prevent or limit textiles, the agents can antioxidants contain. For example, this class of compounds includes substituted ones Phenols, hydroquinones, catechols and aromatic amines as well 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.

Silicone derivatives can be used to improve water absorbency, rewettability of the treated fabrics and to facilitate ironing of the treated fabrics. These additionally improve the rinsing behavior of detergents or cleaning agents 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 and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.

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 the washing or cleaning agent. 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.

Become the inventive agents described above as cleaning agents for the automatic dishwashing used, they preferably contain in addition to those already mentioned Substances other washing or cleaning substances, preferably from the group of builders, Surfactants, polymers, bleaches, bleach catalysts, bleach activators, Enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, Perfumes and perfume carriers. These preferred ingredients will be described in more detail below. suitable Enzymes, bleaches, bleach catalysts and bleach activators and rinse aids are also listed.

Some which can be used with preference in detergents for automatic dishwashing Detergent or cleaner ingredients (Builders, nonionic surfactants, enzymes, disintegrants, fragrances and Dyes, etc.) has already been used in preferred ingredients for detergents according to the invention listed. To avoid repetition is explicit here the relevant text passages and the preferred ingredients not listed again in these places.

In Cleaning agents for automatic dishwashing It is preferred to use nonionic surfactants which have a Have melting point above room temperature. Nonionic (s) Surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, especially preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become Used nonionic surfactants which are highly viscous at room temperature, so it is preferred that this has a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Also nonionic surfactants, which are waxy at room temperature, are ever preferred according to their intended use.

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.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. In front Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular 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 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

Prefers Surfactants to be used come from the groups of the alkoxylated Nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control out.

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.

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} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C 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.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² in which R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 -alkyl or -alkenyl radical; A, A ', A''andA''' are independently of one another a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ - CH _{2 is} -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0, are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which are of 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 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60.

Particularly preferred are 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.

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 (R 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 represents -CH ₃ , and x and y independently of one another represent values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

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.

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 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.

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. These Substance classes have already been used in the preferred ingredients of detergents according to the invention described.

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.

to Group of polymers count in particular the washing or cleaning-active polymers, 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. Some cationic and amphoteric polymers have already been used in the preferred ingredients of detergents according to the invention.

Preferred automatic dishwashing detergents 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 ³ and R ^{4 is} independently selected is 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 N 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 amino group with a positive charge.

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 polyme As a monomer unit contained 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 chloride, bromide, iodide, sulfate, hydrogen sulfate, 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.

wird 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 is 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 the acrylic acid, the (meth) acrylic acid, the (dimethyl) acrylic acid, the (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 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 Acrylamidoalkyltrialky-Iammoniumchlorid / acrylic acid copolymers and their alkali metal 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. Among other things, it is suitable for the preparation of the polymers

• 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.

Machinery Dishwashing liquid contain the aforementioned cationic and / or amphoteric polymers preferably in amounts between 0.01 and 10 wt .-%, respectively on the total weight of the dishwashing detergent. To be favoured in the context of the present application, however, such automatic dishwasher detergents, where 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, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 % By weight, based in each case 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 CN 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, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts the acids mentioned.

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 g each other for -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, with -NH ₂ , -OH or -COOH substituted Alkyl or alkenyl radicals as defined above or is -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 ) -
• 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 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.

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 optionally present spacer group 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 -CHC (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 -CHC (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 -C (CH ₃ ) 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 which is selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, where spacer groups in which Y is -O- (CH _{2) n} - with n = 0 to 4, is -O- (C ₆ H ₄₎ -, (-NH-C CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, particularly preferably, are just as preferred as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (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 -CHC (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 -C (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 ) - are, are preferred.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (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 in Co polymers which contain only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably from 50 to 90% by weight of monomer from the group i) and from 10 to 50 % By weight of 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 .

For use in automatic dishwashing detergents suitable bleaching agents, bleach activators and bleach catalysts have already been described in the preferred ingredients of detergents according to the invention. Machine dishwashing detergent included next or in addition to the already mentioned bleaching agents, bleach activators and bleach catalysts preferably (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-nonylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic, such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic, the diperoxyphthalic acids, 2-Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).

According to the invention automatic dishwashing detergents, preferably 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15 Wt .-% bleach, preferably sodium percarbonate.

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 bleach activator 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.

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 zinc salts as well as the magnesium and zinc complexes.

The Spectrum of the invention preferred Zinc salts, preferably organic acids, more 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, in particular below 0.01 mg / L, to such salts dissolved in water a solubility above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubility at 20 ° C water temperature). The first group of zinc salts includes, for example, zinc citrate, the zinc oleate and the zinc stearate, to the group of 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 one Zinc salt from the group of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, Zinc lactate and zinc citrate used. Also zinc ricinoleate, zinc abs and zinc oxalate are preferred.

In the context of the present invention, the content of zinc salt in dishwasher detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt 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, that is, the total weight of the automatic dishwashing detergent.

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. According to the invention preferred are 3-amino-5-alkyl-1,2,4-triazoles or their physiologically acceptable Salts used, these substances with particular preference in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 used to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% become. Preferred acids for the Salt formation are hydrochloric, sulfuric, phosphoric, carbonic, sulphurous Acid, organic carboxylic acids such as acetic, glycolic, citric and 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.

you In addition, cleaning agent formulations often contain active chlorine Means that can significantly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trivalent phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds used. Also salt- and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are 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 and manganese sulfate. Also can Zinc compounds used to prevent corrosion of items to be washed become.

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.

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-l, 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 ₆ , 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 ,

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 are paraffins, microwaxes, waxes of natural origin like carnauba wax, candellila wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids.

The mentioned metal salts and / or metal complexes are in detergents and especially in automatic dishwashing detergents, preferably in one Amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, respectively based on the total mean.

Portioned according to the invention Detergent compositions include a water-soluble one or water-dispersible container.

Preferably is this container transparent or translucent and allows the consumer the individual Phases through the container wall to recognize through. This embodiment allows it, the consumer the multifunctional properties of the agent to visualize. Corresponding products are characterized by a attractive appearance, which the consumer in the purchase decision is taken into account. For the purposes of this invention, transparency is understood to mean that the permeability within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, very preferred greater than 40% and in particular greater than 50% is. Thus, once a wavelength of the visible spectrum the light a permeability greater than 20%, it is to be regarded as transparent within the meaning of the invention.

Especially it is preferred if at least one side / surface of the container is transparent or translucent is and the first phase through at least one container wall is visible. In a particularly preferred embodiment according to the invention or detergent, the container is transparent or translucent and the first phase is through at least one, preferably only a container wall visible, noticeable.

According to the invention first phase with the container wall adhesively connected. In the case of a container, which transparent or translucent and non-translucent or translucent Having container walls, Is it possible, that the first phase with a non-transparent or non-translucent container wall is adhesively connected and through another container wall, the transparent or translucent, is visible. However, the first phase is preferred through the container wall, with which it is adhesively attached, visible. This combination leads to that best optical result.

In a special embodiment the portioned according to the invention Detergent compositions are the first phase through two opposite ones Container walls visible. A Such a design is with a very high attractiveness of the average portion connected.

It is possible, a container wall Completely to cover the first phase and the second phase (s) above the fill in the first phase, so that the second phase (s) does not interfere with the container wall completely covered with the first phase in touch is / are. Preferably, however, the first phase covers the vessel wall not completely, but only 10 to 90 area%, preferably only to 15 to 75 area% and more preferably only from 20 to 50 area%.

With more preferably, the first phase covers the vessel wall not in the area of corners and edges, but exclusively in the Area of the areas (middle).

In In a particularly advantageous embodiment, the melt is translucent until clear and is preferably between two opposite Container walls, so that the consumer can look through the melt.

Even though in this application always the composition, shape and positioning "of the first Phase "described will, can inventive agent also contain two, three, four or more "first phases" in Form solidified melts are present. These can have the same composition, Color, elasticity, size and / or Or in one, several or all of these properties differ from each other. In a preferred embodiment, the agent according to the invention contains at least two, at least three, at least four, at least five, preferably 2 to 50 solid, with the container material adhesively bonded phases, preferably of different shape and / or Colour. For production reasons, it is preferred if these optionally visually differing "first phases" - possibly up to the dye have the same compositions.

As already explained above may be preferred in order to minimize production costs the container has only one compartment. This embodiment is within the scope of Present invention due to the saving of time and Costs particularly preferred. The present invention makes it possible incompatible with each other Active substances within a compartment in an attractive appearance to assemble in such a way that the active substances mutually do not decompose.

In agents according to the invention, incompatible active substances can be present even within one and the same phase, in the sugar melt, without decomposing. Surprisingly, ge found that in melting according to the invention, which contain two incompatible active ingredients such as enzyme and bleach / bleach activator / bleach catalyst, even over a period of several weeks or months, takes place almost no decomposition of the active ingredients. So far, only the strict separation of incompatible active ingredients within different container or container compartments has been known as a way to stabilize mutually incompatible ingredients of detergents or cleaners.

The present invention enables access to highly active resources, which is cost effective in a single compartment container can be made up. The use of multi-compartment containers is possible, although here compared to multi-compartment containers, which only one composition per compartment, an advantage exists as the number of required Compartments in the containers of the invention due to the filling of a Compartment with two or more phases, is given.

ever according to purpose container with two, three, four or more, but preferably with two compartments with at least a first phase and at least a second phase and other phases filled become.

According to the invention first phase adhering to the container material connected. This adhesive connection between container material and first phase can be achieved by the use of an adhesive bond become.

The Adhesive bond can be achieved, for example, that the location of the water-soluble packaging, at which the core is used is moistened. This will the water-soluble Serving in places partially dissolved, whereby a highly concentrated polymer solution is generated quasi "in situ", which as adhesion promoter can serve. Of course can but other adhesion agents are used.

preferred Materials for the adhesive bond are adhesives or so-called adhesion promoters. In the context of the present invention, these are adhesion promoters Solutions, Dispersions, emulsions or melts, which have a viscosity below of 3000 mPas.

in the Within the scope of the present invention, the viscosity values relate on viscosity measurements a sample temperature which is the processing temperature of the / Adhesive (s) is (see below), with a Carrimed plate-plate rheometer, at a shear force of 50 N per square meter, a plate diameter of 5 cm and a measuring system gap of 250 μm, the value was read after 10 seconds measuring time.

preferred Adhesive agents have a viscosity below during processing of 2500 mPas, preferably below 2000 mPas and in particular below 1000 mPas.

The Processing temperature of the adhesion promoter (s) depends on the material nature of the adhesion promoter used and the desired Time within which the adhesion agent unfolds its adhesive property should. Here are temperatures from room temperature (the in winter months partly 10 to 15 ° C can be) up to high temperatures above the boiling point feasible of water. In the context of the present invention preferred embodiments of adhesive bonds are the adhesion promoters at a temperature between 10 and 130 ° C, preferably between 20 and 110 ° C and in particular between 20 and 90 ° C to the container material and / or dosed to the first phase.

Of the or the adhesion promoter can be metered as a melt, which is usually temperatures above of 30 ° C, preferably above 40 ° C and especially above 50 ° C may require.

in the Particularly preferred fusible under the present invention Adhesion promoters are substances from the group of polyethylene and polypropylene glycols. Also substance mixtures containing these substances are preferred. Adhesion promoters from the groups of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are used are therefore preferred embodiments of the present invention.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol, those of the general formula H- (O-CH ₂ -CH ₂ ) _n -OH satisfy, where n can assume values between 1 (ethylene glycol) and over 100,000. Decisive in the assessment of whether a polyethylene glycol is used according to the invention, is the viscosity of the PEG at the processing temperature. Since working in preferred processes above 20 ° C and below 90 ° C, the polyethylene glycols of the above formula are particularly suitable in which n values between about 15 to about 150 takes. The polyethylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferably used in the context of the present invention.

For cosmetic Ingredients is another nomenclature used in the Shorthand PEG is provided with a hyphen and directly to the hyphen follows a number corresponding to the number n in the above Formula corresponds. According to this nomenclature, for example, according to the invention PEG-32, PEG-40, PEG-55, PEG-60, PEG-75 and PEG-100 are preferred in the invention used.

Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 540 (Union Carbide), Emkapol ^® 2000 (ICI Americas), Lipoxol ^® 2000 QMED (Huls America), polyglycol ^® E-1550 (Dow Chemical), Lutrol ^® E2000 (BASF) and the corresponding trade name with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und ca. 1000 annehmen kann. Ähnlich wie bei den vorstehend beschriebenen PEG kommt es bei der Bewertung, ob ein Polypropylenglycol erfindungsgemäß einsetzbar ist, auf die Viskosität des PPG bei der Verarbeitungstemperatur an. Im Rahmen der vorliegenden Erfindung sind die technisch gebräuchlichen Polypropylenglycole PPG 1550, PPG 3000, PPG 4000 und PPG 6000 bevorzugt einsetzbar.Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which are of the general formula

satisfy, where n can assume values between 1 (propylene glycol) and about 1000. Similar to the PEGs described above, in assessing whether a polypropylene glycol is employable in the present invention, it depends on the viscosity of the PPG at the processing temperature. In the context of the present invention, the industrially customary polypropylene glycols PPG 1550, PPG 3000, PPG 4000 and PPG 6000 are preferably used.

Farther it may be preferable to solutions or dispersions of room temperature solid adhesion promoters or use emulsions of liquid at room temperature adhesion promoters. Here, the emulsions have problems that may arise later in the adhesion of the melt to the container material only a minor Importance. The dispersions are also because of settling problem less processing compared to the more preferred solutions suitable.

Especially preferred adhesion promoters are solutions certain non-ionic substances. Here are as primer solutions from solid polyhydric alcohols and / or sugars at room temperature preferred, with solutions preference is given to which, based on the solution, at least 30% by weight, preferably at least 40% by weight and in particular at least 50% Wt .-% solid (s) included.

polyvalent Alcohols in the context of the present invention are compounds, which have at least two hydroxyl groups. The aggregate state of these compounds at room temperature (20 ° C) is solid. Particularly suitable Polyhydric alcohols are, for example, trimethylolpropane, Pentaerythritol and the "sugar alcohols", i. those from monosaccharides by reduction of the carbonyl group resulting polyhydroxy compounds. These are differentiated according to the number of hydroxyl groups contained in the molecule Tetrite, Pentite, Hexite, etc. In the context of the present invention Particularly suitable sugar alcohols are, for. B. Threit u. erythritol, Adonite (Ribit), Arabit (formerly: Lyxite) and xylitol, dulcitol (galactitol), mannitol and sorbitol (glucitol), the latter is also referred to as sorbitol.

A preferred adhesion promoter which can be used in the form of a solution is the sorbitol. Preferred embodiments are those in which solutions of sorbitol are used as adhesion promoters which, based on the solution, contain at least 50% by weight, preferably at least 60% by weight and in particular min contain at least 70 wt .-% sorbitol.

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlstenstoffatomen und n jeweils für Zahlen von 5 bis 2000 stehen.Another preferred class of substances which can be used in the form of their solution as adhesion promoters are water-soluble polyurethanes. Among these, certain representatives are particularly preferred. In this case, preference is given to processes according to the invention in which solutions or suspensions of polyurethanes of diisocyanates (A) and diols (B) are used as adhesion promoters. O = C = NR ¹ -N = C = O (A), HOR ² -OH (B), be used, wherein the diols are at least partially selected from polyethylene glycols (a) and / or polypropylene glycols (b)

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n are each from 5 to 2,000.

With Preference is the first phase by means of an adhesive such as one Melt or aqueous Solution, preferably a melt and in particular a sugar-containing melt with adhering to the container material connected.

alternative can be the adhesive connection between container material and first phase be achieved by a self-adhesive on the container material first phase is used. In a particularly preferred embodiment the agent according to the invention the first phase is self-adhesive.

self-adhesive is the first phase in terms of filing when the container material and stick the first phase together without adhesive. In the term Adhesive is also included here water, as water uses can be a water-soluble container material such as polyvinyl alcohol and dissolve the thus prepared highly concentrated PVAL solution to be used as the actual adhesive.

Surprised It was found that the first phase has good properties in the field the "self-adhesion" has and the portioned detergent or cleaner composition an improved washing or Cleaning performance when the first phase is 20 to 90% by weight, preferably 30 to 80% by weight and in particular 35 to 70% by weight Glucose, fructose and / or maltose, in particular glucose or maltose and 10 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 60 wt .-% of active ingredients, preferably bleach, bleach catalyst and / or bleach activator.

• – mindestens eine feste, mit dem Behältermaterial haftend verbundene, vorzugsweise selbsthaftende erste Phase, umfassend, jeweils bezogen auf das Gesamtgewicht der jeweiligen ersten Phase,
• – 20 bis 90 Gew.-% vorzugsweise 30 bis 80 Gew.-% eines Mono- oder Disaccharids, bevorzugt Glucose, Fructose oder Maltose,
• – 10 bis 70 Gew.-%, vorzugsweise 15 bis 60 Gew.-% Bleichmittel, Bleichaktivator, Bleichkatalysator, Enzyme, Soil-Repellet-Polymere, optische Aufheller, Parfüm, Bentonite, Fluoreszenzmittel, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobielle Wirkstoffe, Germizide, Fungizide, Antioxidantien, Antistatika, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel, UV-Absorber und/oder Klarspülsubstanzen
• – insgesamt 0 bis 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-% Wasser, mehrwertige Alkohole und/oder Polyethylenglykole
• – und mindestens eine weitere, flüssige, gelförmige oder feste, vorzugsweise partikelförmige Phase, umfassend reinigungs- oder waschaktive Substanzen, und
• – einen Behälter aus einem wasserlöslichen oder wasserdispergierbaren Material, bevorzugt aus PVA und insbesondere aus PVA-Folie.

An object of the present invention is a ported detergent or cleaning composition comprising

• At least one solid, preferably self-adhering first phase adhesively bonded to the container material, comprising, in each case based on the total weight of the respective first phase,
• From 20 to 90% by weight, preferably from 30 to 80% by weight, of a mono- or disaccharide, preferably glucose, fructose or maltose,
• From 10 to 70% by weight, preferably from 15 to 60% by weight, of bleach, bleach activator, bleach catalyst, enzymes, soil repellents, optical brightener, perfume, bentonites, fluorescers, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents , Germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, UV absorbers and / or rinse aids
• - A total of 0 to 30 wt .-%, preferably 5 to 20 wt .-% water, polyhydric alcohols and / or polyethylene glycols
• - And at least one further liquid, gel or solid, preferably particulate phase comprising cleaning or washing-active substances, and
• A container of a water-soluble or water-dispersible material, preferably of PVA and in particular of PVA film.

• – mindestens eine feste, mit dem Behältermaterial haftend verbundene, vorzugsweise selbsthaftende erste Phase, umfassend, jeweils bezogen auf die jeweilige erste Phase,
• – 20 bis 90 Gew.-% vorzugsweise 30 bis 80 Gew.-% bevorzugt Glucose, Fructose oder Maltose, insbesondere Glucose oder Maltose,
• – 10 bis 70 Gew.-%, vorzugsweise 15 bis 60 Gew.-% Bleichmittel, Bleichaktivator, Bleichkatalysator oder Enzym sowie
• – insgesamt 0 bis 30 Gew.-%, vorzugsweise 5 bis 20 Gew.-% Wasser, mehrwertige Alkohole und/oder Polyethylenglykole
• – und mindestens eine weitere, vorzugsweise partikelförmige Phase, umfassend reinigungs- oder waschaktive Substanzen, und
• – einen Behälter aus einem wasserlöslichen oder wasserdispergierbaren Material, bevorzugt aus PVA und insbesondere aus PVA-Folie.

Another object of the present invention is a portioned detergent or cleaning composition comprising

• At least one solid, preferably self-adhering first phase adhering to the container material, comprising, in each case based on the respective first phase,
• From 20 to 90% by weight, preferably from 30 to 80% by weight, preferably glucose, fructose or maltose, in particular glucose or maltose,
• - 10 to 70 wt .-%, preferably 15 to 60 wt .-% bleach, bleach activator, bleach catalyst or enzyme and
• - A total of 0 to 30 wt .-%, preferably 5 to 20 wt .-% water, polyhydric alcohols and / or polyethylene glycols
• - And at least one further, preferably particulate phase comprising cleaning or washing-active substances, and
• A container of a water-soluble or water-dispersible material, preferably of PVA and in particular of PVA film.

The according to the invention or detergents are highly active even after storage and transportation and are characterized by a very appealing look. An infiltration the first phase through the second phase does not take place. Additionally lends the solidified melt the medium strength, while the second phase so is flowable, that a mechanical stress of the means not, as with tablets to break or crumble from corners and edges or as with liquid and gel agents too an unsightly deformation of the entire container leads. Compositions according to the invention thus stand apart from the improved look and favorable Production method by an increased mechanical and chemical (stability of the active ingredients) stability out.

The portioned according to the invention Detergent compositions are in water-dispersible or water-soluble container packed up. A preferred container For the purposes of the present invention, the washing or cleaning agent portion envelops Completely. Suitable packaging materials are known in the art known and originate, for example, the group (acetalized) Polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin and mixtures thereof.

Especially preferred portioned according to the invention Detergent or detergent compositions are characterized that the water-soluble or water-dispersible containers one or more water-soluble (s) Polymer (s), preferably a material from the group (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, Gelatin, cellulose, and derivatives thereof and mixtures thereof.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, the as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have hydrolysis degrees of 98-99 and 87-89 mol%, respectively So still a residual content of acetyl groups. To be characterized the polyvinyl alcohols from the manufacturers by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are toxicologically un classified critically and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

in the Within the scope of the present invention, it is preferred that the water-soluble or water-soluble water-dispersible containers a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 Mol%, preferably 80 to 90 mol%, particularly preferably 81 to Is 89 mole% and especially 82 to 88 mole%.

Polyvinyl alcohols having a specific molecular weight range are preferably used as materials for the containers, it being preferred in accordance with the invention for the water-soluble or water-dispersible container to comprise a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

Of the Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as material for the container are shown in the following table:

Other suitable as a material for the container polyvinyl alcohols are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).

The Water of PVAL can be obtained by post-treatment with aldehydes (acetalization) or ketones (ketalization) changed become. Being particularly preferred and pronounced because of it good cold water solubility Polyvinyl alcohols have proven particularly advantageous in this case, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof are acetalated or ketalized. As extremely beneficial to use are the reaction products of PVAL and starch.

Examples of suitable water PVAL films under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be adjusted to the exact degree and films of this product series are available which are soluble in aqueous phase at all temperature ranges relevant for the application.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. commercial PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and be as white, hygroscopic powder or as aqueous solutions offered.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), mainly by Hydrolysis of the collagen contained in the skin and bones of animals is obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only small Use.

Prefers in the context of the present invention are also agents according to the invention, their packaging of at least partially water-soluble film of at least a polymer from the group starch and Starch derivatives, Cellulose and cellulose derivatives, especially methylcellulose and Mixtures consists of this.

Strength is a homoglycan, wherein the glucose units are linked α-glycosidically. Strength is composed of two components of different molecular weight: from about 20 to 30% straight-chain amylose (molecular weight about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (molecular weight about 300,000 to 2,000,000). In addition, there are still small amounts of lipids, phosphoric acid and cations. While the amylose due to binding in the 1,4-position long, helical, entangled Branches with about 300 to 1,200 glucose molecules forms, branches the chain in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like Forms with about 1,500 to 12,000 molecules of glucose. Besides pure strength are for producing water-soluble wrappings the detergent, dishwashing detergent and detergent portions within the scope of the present invention also starch derivatives which are obtainable by polymer-analogous reactions of starch. Such chemically modified starches include, for example, products of esterification or etherification, in which hydroxy hydrogen atoms have been substituted. But also Strengthen, in which the hydroxy groups against functional groups that do not have a Oxygen atom bound, replaced, can be used as starch derivatives deploy. Into the group of starch derivatives fall, for example, alkali, carboxymethyl (CMS), starch ester and ethers, and amino acids.

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 5,000 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, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocellulo sen.

Prefers includes the water-soluble or water-integrated container material at least partially polyvinyl alcohol.

The water-soluble or water-dispersible containers, which means of the invention can contain prepared by any of the methods described in the prior art become.

So Is it possible, Use foil bags (so-called pouches) as a container. Prefers are, however, by injection molding, casting or thermoforming, preferably produced by thermoforming process container used.

Become the invention as packaging selected container made of film, it is preferred that the water-soluble film, the container forms, a thickness of 1 to 150 microns, preferably from 2 to 100 μm, more preferably from 5 to 75 microns and in particular from 10 to 50 μm, having. The film is preferably cast or blown by extrusion produced and then deep-drawn to a container.

As "thermoforming" are in the context the present application in this case called such method, in those a first film-like wrapping material after spending over a receiving trough located in a die forming the thermoforming tray and molding the wrapping material in this receiving trough by the action of pressure and / or vacuum is deformed. The wrapping material can do this before or during forming by the action of heat and / or solvent and / or conditioning modified by environmental conditions relative humidities and / or temperatures are pretreated. The pressure can be applied through two parts of a tool, which behave as positive and negative to each other and one deforming film when deformed between these tools. As pressure forces However, the action of compressed air and / or the are also suitable Dead weight of the film and / or the weight of one on the top the film spent active substance.

The deep-drawn shell materials after deep drawing, preferably by use of a vacuum within the receiving troughs and in their by the deep drawing process Fixed spatial form fixed. The vacuum is preferably continuous from deep drawing to filling preferably until sealed and in particular until dicing created the receiving chambers. With comparable success, however also the use of a discontinuous vacuum, for example for drawing the receiving chambers and (after a break) before and during of filling the admission chambers, possible. Also, the continuous or discontinuous vacuum in his strength vary and for example at the beginning of the process (deep drawing the film) higher Accept values as their end (when filling or sealing or separating).

As already mentioned, can the shell material before or during the shaping into the receiving troughs of the matrices by the action of heat pretreated. The wrapping material, preferably a water-soluble or water-dispersible polymer film will be up to 5 seconds, preferably for 0.1 to 4 seconds, more preferably for 0.2 to 3 seconds and in particular for 0.4 up to 2 seconds at temperatures above 60 ° C, preferably above 8 ° C, especially preferably between 100 and 120 ° C and heated in particular to temperatures between 105 and 115 ° C. to removal this heat, but especially for removal the through the filled in the deep-drawn receiving chambers means introduced heat (especially melts), it is preferred that the matrices used and to cool the receiving troughs located in these matrices. The cooling takes place preferably at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C. Preferably, the cooling continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. For cooling are particularly suitable Coolants, preferably water, which in special cooling lines within the die be circulated.

These cooling has as well as the previously described continuous or discontinuous Applying a vacuum the advantage of shrinking the deep-drawn containers to prevent after deep drawing, which not only the appearance of the Process product is improved, but at the same time the leakage the filled in the receiving chambers Means over the edge of the receiving chamber, for example, in the seal areas the chamber is avoided. Problems with the sealing of the filled chambers are avoided.

at leaves the thermoforming process between methods in which the wrapping material is moved horizontally into a forming station and from there in a horizontal manner for filling and / or sealing and / or Separation is led and methods in which the shell material over a Continuously rotating die forming roller (optionally optional with a counter-current out Patrizenformwalze, which the forming upper punches to the cavities of Lead die roll) guided will differ. The first mentioned variant of the method Flatbed process is both continuous and discontinuous to operate, the process variant using a molding roll usually takes place continuously. All the mentioned thermoforming processes are suitable for the preparation of the inventively preferred means. The receiving troughs located in the matrices can be arranged "in series" or offset be.

The inventive container preferably produced by deep drawing. The in the deep drawing process used film is preferably by means of blowing, calendering and casting process produced. In a preferred method, the films are included starting from a melt with air over a glass mandrel to a Hose blown. In the calendering, which also zu belongs to the preferred manufacturing method, which are by suitable additions plasticized raw materials for shaping the films. Here it may be necessary in particular to the atomizations a Drying connect. In the casting process, which is also one of the preferred manufacturing processes is an aqueous one Polymer preparation placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film as a film deducted. If necessary, this film is before or during the Pulling off additionally powdered.

One further, for the production of water-soluble according to the invention or water-dispersible container The method used is injection molding. Injection molding is called while forming a molding material such that in a mass cylinder for more as an injection molding process contained mass under heat plastically softened and pressurized through a nozzle into the cavity of a previously enclosed tool flows. The process is mainly at non-curable Applied molding compounds that solidify in the tool by cooling. Injection molding is a very economical modern method of manufacture non-cutting shaped objects and is especially suitable for the automated mass production. In practical operation, one heats the thermoplastic molding compounds (powders, granules, cubes, pastes and others) up to the liquefaction (up to 180 ° C) and injects them under high pressure (up to 140 MPa) into closed, two-piece, this means from Gesenk (formerly Matrix) and core (formerly Patrize) existing, preferably water-cooled molds, where they cool and solidify. Piston and screw injection molding machines can be used. Suitable molding compounds (injection molding compounds) are water-soluble polymers wie beispielsewei the above cellulose ethers, pectins, polyethylene glycols, Polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or Strength.

The shell materials can also be poured into molds.

According to the invention preferred is an embodiment according to the container as a whole water-soluble or water-dispersible, d. H. when used as intended when washing or machine cleaning, completely dissolves when intended for release Conditions are reached. Essential advantage of this embodiment is that the container within a practically relevant short time - as a non-limiting example can be a few seconds to 5 min - under exactly defined conditions at least partially dissolve in the cleaning liquor and thus accordingly the requirements of the wrapped content, d. H. the cleaning-active material or several materials, in bring in the fleet.

In another embodiment of the invention, which is also preferred because of its advantageous properties, the water-soluble container comprises regions which are less soluble in water or only soluble in water at elevated temperature and regions which are readily soluble in water or soluble in water at low temperature. In other words, the container does not consist of a uniform, in all areas the same water solubility having material, but of materials of different water solubility. On the one hand, areas of good water solubility are to be distinguished from areas with less good water solubility, with poor or even absent water solubility or areas in which the water solubility reaches the desired value only at a higher temperature or only at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This may result in certain areas of the container being released under normal use under adjustable conditions while other areas remain intact. Thus, a container provided with pores or holes is formed, into which water and / or liquor can penetrate, which can dissolve washing-active, rinse-active or cleaning-active ingredients and remove them from the container. In the same way, systems in the form of multi-chamber containers or in the form of nested containers ("onion system") can be provided. Let it be to produce controlled release systems of the detergent-active, rinse-active or detergent-active ingredients.

to Training of such systems, the invention is not limited. So can container be provided in which a uniform polymer material is small Areas of incorporated compounds (for example, salts) includes, the faster water soluble are considered the polymer material. On the other hand also several polymer materials with different water solubility be mixed (polymer blend), making the faster soluble polymer material under defined conditions by water or the fleet faster is disintegrated as the slower soluble.

It corresponds to a particularly preferred embodiment of the invention that the less water-soluble Areas or not water-soluble Areas or only at higher Temperature water-soluble Areas of containers Are areas of a material that is chemically substantially the same the well water soluble Ranges or at lower temperature water-soluble areas, but a higher one Has layer thickness and / or a modified degree of polymerization of the same polymer and / or a higher degree of crosslinking thereof Having polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or a content of water-insoluble Has salt components and / or a content of a water-insoluble Having polymers. Even taking into account the fact that the containers not completely to solve, can such portioned detergent or cleaning compositions according to the invention be provided, the beneficial properties in the release the detergent composition in the respective Fleet exhibit.

• a) Herstellung eines Behälters aus wasserlöslichem oder wasserdispergierbarem Material;
• b) teilweises Befüllen des Behälters mit einer Schmelze, welche nach dem Erstarren an dem Behältermaterial anhaftet und Zucker enthält;
• c) nach Erstarren der Schmelze weiteres Befüllen des Behälters mit mindestens einer weiteren festen oder flüssigen Phase;
• d) optional Verschließen des Behälters.

Another object of the present invention is a process for preparing a portioned detergent or cleaning composition in a water-soluble or water-dispersible container comprising the steps

• a) preparation of a container of water-soluble or water-dispersible material;
• b) partially filling the container with a melt which, after solidification, adheres to the container material and contains sugar;
• c) after solidification of the melt further filling of the container with at least one further solid or liquid phase;
• d) optionally closing the container.

Preferably the solidified melt adheres after solidification due to their adhesive Properties on the container material.

alternative to use a self-adhesive melt, a solidified Melting also with the aid of an adhesive or by partial Softening the solidified melt are glued to the container material.

• a) Herstellung eines Behälters aus wasserlöslichem oder wasserdispergierbarem Material;
• b) Herstellen einer oder mehrerer erstarrter Schmelzen, welche Zucker enthalten,
• c) Ankleben der erstarrten Schmelze(n) an das Behältermaterial durch
• i) teilweises Erweichen der erstarrten Schmelze und Aufsetzen der teilweise erweichten Phase auf das Behältermaterial oder
• ii) Einsatz eines Klebemittels, vorzugsweise einer Schmelze und insbesondere einer Zucker-haltigen Schmelze,
• d) weiteres Befüllen des Behälters mit mindestens einer weiteren festen oder flüssigen Phase;
• e) optional Verschließen des Behälters.

Accordingly, another aspect of the invention is a process for preparing a portioned detergent or cleaning composition in a water-soluble or water-dispersible container comprising the steps

• a) preparation of a container of water-soluble or water-dispersible material;
• b) producing one or more solidified melts containing sugar,
• c) adhering the solidified melt (s) to the container material
• i) partial softening of the solidified melt and placing the partially softened phase on the container material or
• ii) use of an adhesive, preferably a melt and in particular a sugar-containing melt,
• d) further filling the container with at least one further solid or liquid phase;
• e) optionally closing the container.

In the case of using a melt or a gel which is dimensionally stable between 5 and 45 ° C as the second phase, it is possible not to close the container. Preferably, however, the filled compartment is closed, for which purpose preferably another film is placed on the fully or partially filled compartment and sealed by means of heat or solvent. Compositions according to the invention, which comprise sealed containers, are characterized by an improved release behavior, which results in an increased cleaning performance. It is particularly preferred that a flowable powder or granules used as a second phase and the container is closed after filling. It is with Vor zug to the container to at least 75 vol .-%, preferably at least 80 vol .-%, more preferably at least 85 vol .-%, more preferably at least 90 vol .-% and in particular at least 95 vol .-% filled and thus the void volume of the container as small as possible. To further avoid excess container material, the container can be shrunk after the filling and Veschlussvorgang by the action of heat and / or vacuum.

The container are preferably by injection molding, thermoforming, preferably Deep drawing, made. It is particularly preferred when the container is manufactured is replaced by a or Blasextrusionsverfahren produced water-soluble or water-dispersible film is deep-drawn.

The first phase may be in any form in the methods of the invention to be poured. So it is possible Pyramids, truncated pyramids, Cones, truncated cones, (Semi-) bullets, cylinders, prisms, or even animals, clouds, leaves, or flowers Stars in the run-up to the filling of the container to pour and then on the container material stick or appropriate objects with the help of suitable Mold directly onto the container material to pour. These objects preferably have a volume between 2 and 50 ml, preferably between 5 and 40 ml, preferably between 10 and 30 ml.

Also the casting smaller portions from 0.5 to 2 ml, preferably from 0.5 to 1 ml, which preferably as (distorted) spherical sections on the container material or solidify a suitable substrate is possible. Prefers be 2 to 50, preferably 5 to 20 of these smaller portions, which may have different colors, directly on the container material cast. After the solidification of these melts, the second phase becomes filled and the container subsequently optionally closed.

The agents according to the invention are especially preferred in a textile cleaning process used. Another use of the agents according to the invention is in use in a purification process, preferably in a machine dishwasher.

Claims (19)

Portioned detergent composition comprising a) a water-soluble or water-dispersible container, b) at least a first adhesive to the container material associated solid phase, and c) at least one further phase, characterized in that the first phase is a solidified melt, which Contains sugar. Portioned detergent or cleaner composition according to claim 1, characterized in that the first phase a solidified melt which is 10 to 99 wt .-%, preferably 20 to 90 wt .-%, particularly preferably 30 to 80 wt .-%, to this preferred 35 to 70 wt .-% and in particular 40 to 65 wt .-% sugar, based on the melt, contains. Portioned detergent or cleaner composition according to claim 2, characterized in that the sugar is selected from the group of mono- and disaccharides, preferably from Group glucose, fructose, ribose, maltose, lactose and sucrose and mixtures of these and in particular glucose and / or maltose. Portioned detergent or cleaner composition according to one of the claims 2 or 3, characterized in that the melt (s) at temperatures between 50 and 150 ° C, preferably at temperatures between 60 and 120 ° C flowable, at 20 ° C, however is / are fixed. Portioned detergent or cleaner composition according to one of the claims 1 to 4, characterized in that the first phase one or several active substances (e) from the field of washing or cleaning agent components, preferably from the group of soil repellent polymers, optical brighteners, Perfumes, Bentonites, bleaches, bleach catalysts, bleach activators, preferably bleaches, bleach catalysts and / or bleach activators, preferably in amounts of 1 to 90 wt .-%, particularly preferably in Amounts of 5 to 80 wt .-%, most preferably in amounts of From 10 to 70% by weight and in particular from 15 to 60% by weight, in relation to the first phase. Portioned detergent or cleaner composition according to one of the claims 1 to 5, characterized in that the first phase is water, polyvalent Alcohols and / or polyethylene glycols independently of one another in each case Quantities of 0 to 50 wt .-%, preferably from 5 to 20 wt .-%, based on the first phase, contains. Portioned detergent or cleaner composition according to one of the claims 1 to 6, characterized in that the first (n) phase (s) and the second phase (s) dissolve at different speeds in water at 20 ° C dispersing, wherein the first (n) phase (s) preferably slower dissolves / slower disperses / disperse as at least one of the second, preferably all second phases. Portioned detergent or cleaner composition according to one of the claims 1 to 7, characterized in that the second phase in the form a powder, in the form of granules, in the form of one or more Extrudates, compacts such as tablets or castings, but preferably in Form of a powder or granules is present. Portioned detergent or cleaner composition according to one of the claims 1 to 7, characterized in that the second phase is liquid or gel is. Portioned detergent or cleaner composition according to one of the claims 1 to 9, characterized in that the volume ratio of first / first phase (s) and second / second phase (s) between 1: 100 and 2: 1, preferably between 1:50 and 1: 1, more preferably between 1:20 and 1: 2, and especially between 1:10 and 1: 3. Portioned detergent or cleaner composition according to one of the claims 1 to 10, characterized in that the water-soluble or water-dispersible containers is transparent or translucent and the first phase through at least one, preferably only visible through a container wall. Portioned detergent or cleaner composition according to one of the claims 1 to 11, characterized in that the first phase by means of a An adhesive such as a melt or aqueous solution, preferably a melt and in particular a sugar-containing melt with the container material is attached. Portioned detergent or cleaner composition according to one of the claims 1 to 11, characterized in that the first phase self-adhesive is. Process for producing a portioned washing or detergent composition in a water-soluble or water-dispersible container comprising the steps a) Preparation of a container water-soluble or water-dispersible material; b) partial filling of the container with a melt which adheres to the container material after solidification and sugar; c) after solidification of the melt further filling of the container with at least one further solid or liquid phase; d) optional close of the container. Process for producing a portioned washing or detergent composition in a water-soluble or water-dispersible container comprising the steps a) Preparation of a container water-soluble or water-dispersible material; b) producing one or several solidified melts containing sugar, c) Stick the solidified melt (s) to the container material i) partial softening of the solidified melt and placing the partially softened phase on the container material or ii) the use of an adhesive, preferably a melt and in particular a sugar-containing melt, d) further filling of the container with at least one other solid or liquid phase; e) optional close of the container. Method according to one of claims 14 or 15, characterized that the container by injection molding, Thermoforming process, preferably deep drawing, is produced. Method according to one of claims 14 to 16, characterized that the container is prepared by a casting or bubble extrusion process produced water-soluble or water-dispersible film is deep-drawn. Use of a portioned detergent or cleaner composition according to one the claims 1 to 13 in a textile cleaning process. Use of a portioned detergent or cleaner composition according to one the claims 1 to 13 in a cleaning process, preferably in a machine Dishwasher.