DE102020203400A1 - Washing machine or dishwasher with generator of cold plasma - Google Patents

Abstract

A washing machine with a washing chamber for receiving washing liquid and textiles to be cleaned or a dishwasher with a cleaning chamber for receiving cleaning liquid and dishes to be cleaned is provided with an activation device that generates cold plasma and is supplied via an inlet for introducing washing. or cleaning liquid from the washing or cleaning chamber into the activating device and an outlet for guiding washing or cleaning liquid out of the activating device into the washing or cleaning chamber.

Description

The present invention relates to a washing machine or a dishwasher which comprises a device which is suitable for emitting a cold plasma into the washing or cleaning liquid in the washing or dishwasher or for generating a cold plasma in this liquid.

As before, inter alia, the problem of the bleaching effect, in particular in the case of bleach-free liquid detergents and bleach-free dishwashing detergents, has not been satisfactorily solved. The present invention uses cold plasma to remove, in particular, colored soiling from textiles and from hard surfaces.

Cold plasma is a state of matter in which electrons, positively charged atoms or molecules and neutral atoms or molecules are present next to each other and the temperature of the electrons is higher, usually more than 10,000 K higher, than the temperature of the other components, which are below usual atmospheric pressure conditions are present and usually have room temperature. Because of the low density of electrons, the total temperature of the plasma is essentially determined by the other plasma components, so that one speaks of cold plasma.

Devices for generating cold plasma are known. So the international patent application discloses WO 2007/031250 A1 a plasma source for wound disinfection, which consists of an ionization chamber with a gas inlet and a gas outlet as well as several electrodes located in the ionization chamber for gas ionization, the distance between the electrodes and the distance between the electrodes from the ionization chamber wall having a certain ratio. From the European patent specification EP 2 147 582 B1 a low-temperature plasma source through which gas flows, which is suitable for wound disinfection and has a Laval nozzle arranged upstream of the ionization chamber, is known.

The present invention relates to a washing machine ( 1 ) with a washing chamber ( 2 ) for taking up a washing liquid and textiles to be cleaned and with an activation device ( 3 ) that have an inlet ( 4th ) for introducing washing liquid from the washing chamber ( 2 ) into the activation device ( 3 ) and via an outlet ( 5 ) to lead washing liquid out of the activation device ( 3 ) into the washing chamber ( 2 ), whereby the activation device ( 3 ) generates cold plasma.

The washing machine according to the invention can basically be an otherwise normal household, rectangular washing machine with a capacity of about 4 to 12 kg of laundry, but other types of washing machine, for example industrial washing machines with a different design and significantly larger capacity, are also possible. The washing chamber is the space through which washing liquid flows during a washing cycle. In the case of a normal household washing machine, this is generally a washing drum and the space immediately surrounding it.

Another object of the invention is a dishwasher with a cleaning chamber for receiving a cleaning liquid and dishes to be cleaned and with an activation device, which via an inlet for introducing cleaning liquid from the cleaning chamber into the activation device and via an outlet for directing cleaning liquid out of the Activation device has in the cleaning chamber, wherein the activation device generates cold plasma.

The dishwasher according to the invention can basically be an otherwise normal household, cuboid dishwasher, in which rotating nozzles first spray water, then a cleaning liquid and finally a rinse aid liquid against the dishes. The cleaning chamber is the interior of the machine that includes the dishes to be cleaned.

The machine according to the invention has an activation device into which the washing or cleaning liquid can be introduced from the washing or cleaning chamber. A generator for cold plasma, which is suitable for releasing cold plasma into the washing or cleaning liquid within the activation device, is arranged in the activation device. The washing or cleaning liquid treated in this way is then passed back out of the activation device and into the washing or cleaning chamber and fed to the further washing or cleaning process in the washing machine or dishwasher.

In the washing machine according to the invention, both the inlet for introducing the washing liquid from the washing chamber into the activating device and the outlet for directing the washing liquid out into the washing chamber are preferably designed in such a way that textiles cannot get into the activating device. For this purpose, the inlet and / or the outlet of the Activation device, for example, be equipped with suitable filters or grids, which are not passable for textiles, but for the washing liquid. The dimensions, in particular the cross-sectional area of the inlet and / or the outlet, can also be dimensioned in such a way that textiles cannot enter the activation device.

The activation device is characterized in that the surface of the plasma-generating device is selected to be as large as possible in order to enable intensive contact of the plasma with the washing or cleaning liquid.

The generator of cold plasma located in the activation device through which the washing or cleaning liquid flows can also be flowed through by the washing or cleaning liquid, so that the cold plasma is created directly in the washing or cleaning liquid, or the washing or cleaning liquid flows to the plasma generator and absorbs the plasma generated by it from air or other gases in the washing machine or dishwasher. The plasma is preferably generated using one of the following methods: magnetically organized plasma layer technology, surface micro-discharge technology, microwave plasma technology and venturi plasma technology. The plasma can be generated from vaporous water, air or other gases, which may also be present in combinations. Plasma generation not from air can have an advantageous effect for reasons of increased performance or through specific interaction with the washing liquor or contamination, the service life of the plasma or in terms of avoiding undesirable by-products such as nitrous gases or ozone. For this purpose, nitrogen, helium or another noble gas or mixtures of these gases are preferably introduced into the plasma generator by means of a gas inlet system via a compressed gas cartridge or via a gas pump and aerator, whereby the introduction of vaporous water or air is also possible. The plasma can be generated as required by means of an electronic control device for the plasma generator and can be individually adapted to the items of laundry or crockery in the machine. Another advantage is that the plasma generation by means of an electronic control device for the plasma generator can only be switched on during certain periods of the washing or cleaning process, so that damage to other active substances such as enzymes by the plasma during the period can be excluded which they should develop their effect.

The onset, the intensity and the duration of the process for the formation of the cold plasma in the activation device can preferably be regulated. The start of the process can be linked to the achievement of certain operating parameters, for example to a certain temperature of the washing or cleaning liquid or to a certain phase of the washing or cleaning cycle. For a temperature-dependent regulation, for example, a temperature sensor can be provided through which the temperature of the washing or cleaning liquid can be detected. Purely time-based regulation can also be provided, in which the plasma generation process starts at a point in time that can be preset. The duration of the plasma generation process can also be set so that it stops as soon as a certain bleaching result is achieved. In the case of washing or cleaning cycles with textiles or dishes, in each case without bleachable soiling, the onset of the plasma generation process can also be completely prevented. When washing or cleaning particularly heavily soiled textiles or dishes, however, the intensity and duration of the plasma generation process can be increased accordingly.

According to one embodiment of the invention, the activation device can be permanently installed in a housing of the washing machine or dishwasher. Here, the voltage supply for the plasma generator can be coupled to the voltage supply of the washing machine or dishwasher. The activation device can be attached, for example, below the drum or on the inside of the door of the washing machine. To feed the washing or cleaning liquid into and out of the activation device, appropriate lines can be provided in the washing machine or dishwasher, which can be connected to the inlet and the outlet of the activation device. For example, the washing or cleaning chamber can have a washing or cleaning liquid outlet which can be connected to the inlet of the activation device. Correspondingly, the outlet of the activation device can be connected to a washing or cleaning liquid inlet of the washing or cleaning chamber, so that the treated washing or cleaning liquid can be fed back from the activation device into the washing or cleaning chamber.

Another object of the invention is a method for washing laundry with the aid of a washing machine described above, in which soiled laundry is brought into contact with a surfactant-containing, preferably aqueous, washing liquid, with a cold plasma acting on the laundry for at least part of the washing process.

Another object of the invention is a method for cleaning dishes with the aid of a dishwasher described above, in which dishes to be cleaned are brought into contact with a surfactant-containing, preferably aqueous cleaning liquid, with a cold plasma acting on the dishes for at least part of the washing process .

A method according to the invention for washing laundry is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 60 ° C., and / or over a period of 1 minute to 2 hours, in particular from 15 minutes to 1 hour. It is preferred to allow a period of up to 30 minutes, in particular from 15 minutes to 30 minutes, to elapse before cold plasma generated with the aid of the activation device is used. If the cold plasma is not to be used until the end of the washing process, it is preferred to use it over a period of 1 minute to 1 hour, in particular from 15 minutes to 30 minutes.

A method according to the invention for cleaning dishes is preferably carried out at temperatures in the range from 20 ° C. to 75 ° C., in particular from 30 ° C. to 55 ° C., and / or over a period of 1 minute to 2 hours, in particular from 1 minute to 1 hour. It is preferred to allow a period of up to 20 minutes, in particular from 15 minutes to 20 minutes, to elapse before cold plasma generated with the aid of the device according to the invention is used. If the cold plasma is not to be used until the end of the cleaning process, it is preferred to use it over a period of 30 minutes to 2 hours, in particular from 15 minutes to 20 minutes.

The invention is explained in more detail below with reference to the accompanying drawings. the 1 and 2 each show a schematic view of a washing machine with an activation device.

In the 1 washing machine shown in simplified form 1 has a drum 13th on what part of a wash chamber 2 and below which the activation device containing a generator for cold plasma 3 is arranged. The washing chamber 2 consists of the washing drum 13th and the space immediately surrounding it, through which the washing liquid flows during the wash cycle. The flow of liquid through the activation device 3 is indicated by arrows.

Alternatively, the activation device 3 also, as in 2 shown in the area of a door 12th of the washing machine 1 be arranged. In 2 is the activation device 3 on the inside of the door 12th of the washing machine 1 assembled.

In the method according to the invention and during the operation of the washing machine or dishwasher according to the invention, it is possible to use conventional washing or cleaning agents which contain ingredients, in particular surfactants, which are usually present in such agents.

The agents can in particular builder substances, surface-active surfactants, bleaching agents based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, graying inhibitors, foam regulators and dyes and fragrances contain. In preferred embodiments, the agents are liquid and free from bleaching agents and bleach activators.

Detergents preferably contain one or more surfactants, anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants being suitable.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned in terms of the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical, can also be used.

in der R¹CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² 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. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im Allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten „Spacer“ voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im Allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig „dimere“, sondern auch entsprechend „trimere“ Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate. Endgruppenverschlossene dimere und trimere Mischether zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Extremely low-foam compounds are usually used, particularly in agents for use in mechanical processes. These include preferably C ₁₂ -C ₁₈ -alkyl polyethylene glycol polypropylene glycol ethers with in each case up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, other known low-foam nonionic surfactants can also be used, such as, for example, C ₁₂ -C ₁₈ -alkyl polyethylene glycol polybutylene glycol ethers with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, as well as end-capped alkyl polyalkylene glycol mixed ethers. The hydroxyl-containing alkoxylated alcohols, so-called hydroxy mixed ethers, are also particularly preferred. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number - which as a variable to be determined analytically can also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Polyhydroxy fatty acid amides of the formula are also suitable

in which R ¹ CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula

in which R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, C ₁ -C ₄ -alkyl or phenyl radicals being preferred, and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. Here too, [Z] is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also 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 that. So-called gemini surfactants are suitable as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are usually separated from one another by a so-called “spacer”. This spacer is usually a carbon chain that should be long enough that the hydrophilic groups are sufficiently spaced so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood to mean not only such “dimeric” surfactants, but also correspondingly “trimeric” surfactants. Suitable Gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are distinguished in particular by their bi- and multifunctionality. The end-group-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides can also be used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Surfactants of the sulfonate type are preferably C ₉ -C ₁₃ -alkylbenzenesulfonates, olefin sulfonates, that is, mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bonds by sulfonation gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. _{Alkane sulfonates obtained from C 12} -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. The esters of α-sulfo fatty acids (ester sulfonates) are also suitable, for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are obtained by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin at 8 to 20 ° C Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are possible. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, may be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts, are used with particular advantage. Further suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as they are in the production by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid _{half esters of the C 12} -C ₁₈ fatty alcohols, for example from 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the appropriate compounds based on oleochemical raw materials. From the point of view of washing technology, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are particularly preferred. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol radicals or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyltaurine (tauride) and / or of N-methylglycine (sarcoside), come into consideration as further anionic surfactants. Particularly preferred are the sarcosides or the sarcosinates, and here above all sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate. Soaps, in particular, are suitable as further anionic surfactants. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Surfactants are contained in detergents in proportions of normally 1% by weight to 50% by weight, in particular 5% by weight to 30% by weight.

A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycine diacetic acid, methylglycine diacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamin-N, N'-disuccinic acid, ethylenediamine-N, n'-disuccinic acid, and especially methyl-phosphonosuccinic acid, and especially poly-phospho-phosuccinic acid, and, in particular, poly-phospho-phosphonosuccinic acid, and also aminotra-phosphonosuccinic acid, and, in particular, poly-phosphonosuccinic acid. Ethylenediamine tetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids and mixed polymers from these which can also contain small amounts of polymerizable substances without carboxylic acid functionality in polymerized form. The relative average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight. Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. The third monomeric unit is formed in this case by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate. Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred , 5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight %, preferably 15% by weight to 25% by weight methallyl sulfonic acid or methallyl sulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably builds predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can, in particular for the production of liquid agents, be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. The water-insoluble inorganic builder materials used are in particular crystalline or amorphous, water-dispersible alkali metal alumosilicates, in amounts not exceeding 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of 5% by weight. % to 15% by weight are used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular do not have any particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Their calcium binding capacity is usually in the range of 100 mg to 200 mg CaO per gram.

In addition or as an alternative to the water-insoluble aluminosilicate and alkali metal carbonate mentioned, further water-soluble inorganic builder materials can be contained. In addition to the polyphosphates such as sodium triphosphate, these include, in particular, the water-soluble crystalline and / or amorphous alkali silicate builders. Such water-soluble inorganic builder materials are contained in the agents preferably in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight. The alkali metal silicates which can be used as builder materials preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na ₂ Si _x Oz _{x + 1} y H ₂ O, in which x, the so-called module, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned has the values 2 or 3 accepts. In particular, both ß- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred. Practically anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, which are produced from amorphous alkali silicates, can also be used in the agents. In a further preferred embodiment, a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda, is used. Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Detergents can, if desired, contain a customary color transfer inhibitor, this then preferably in amounts of up to 2% by weight, in particular 0.1% by weight to 1% by weight, which in preferred embodiments is selected from the polymers of vinylpyrrolidone and vinylimidazole , Vinyl pyridine-N-oxide or the copolymers of these. Both polyvinylpyrrolidones with molecular weights of 15,000 g / mol to 50,000 g / mol and polyvinylpyrrolidones with higher molecular weights of, for example, up to over 1,000,000 g / mol, in particular from 1,500,000 g / mol to 4,000,000 g / mol, can be used. mol, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxamides, polyesters and polyamides containing pyrrolidone groups, grafted polyamidoamines and polyethyleneimines, polyamine-N-oxide polymers and polyvinyl alcohols. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide, or a substance that provides hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, and the aforementioned polymeric dye transfer inhibitor active ingredients can also be used. Polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 g / mol to 60,000 g / mol, in particular in the range from 25,000 g / mol to 50,000 g / mol. Among the copolymers are those of vinylpyrrolidone and vinylimidazole in a molar ratio 5 : 1 to 1: 1 with an average molar mass in the range from 5,000 g / mol to 50,000 g / mol, in particular 10,000 g / mol to 20,000 g / mol, preferred. In preferred embodiments of the invention, however, detergents are used which are free from dye transfer inhibitors because the cold plasma also very effectively bleaches dyes that have been detached from the textile.

Detergents can contain, for example, derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof as optical brighteners. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which, instead of morpholino -Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyryl type can be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned optical brighteners can also be used.

Suitable foam inhibitors in detergents are, for example, soaps of natural or synthetic origin which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silicic acid or bisfatty acid alkylenediamides. Mixtures of various foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular carrier substance which is soluble or dispersible in water. Mixtures of paraffins and bistearyl ethylene diamide are particularly preferred.

Dishwashing detergents contain one or more builders. The builders include, in particular, carbonates, organic cobuilders and silicates. Cleaning agent supply forms used according to the invention are preferably characterized in that the builder is selected from the group of carbonates, hydrogen carbonates, citrates, silicates, polymeric carboxylates, polymers containing sulfonic acid groups and mixtures thereof.

A copolymeric polysulfonate, in particular a hydrophobically modified copolymeric polysulfonate, is preferably used as the polymer containing sulfone groups. The copolymers can have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to at least one monomer containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids. The unsaturated carboxylic acids used are particularly preferably those of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ^3, independently of one another, represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical 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 with -NH2, -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. Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. The unsaturated dicarboxylic acids can also be used. In the case of monomers containing sulfonic acid ^{groups, preference is given to 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, represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, _{alkyl or alkenyl radicals substituted with -NH 2} , -OH or -COOH or for -COOH or -COOR ⁴ R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO - (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and - C (O) -NH-CH (CH ₃ ) -CH ₂ -. 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 or 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 and -CH (CH ₃ ) ₂ and X stands for an optionally present 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 -, -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -. Particularly preferred monomers containing sulfonic acid groups 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-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-styrenesulphonic acid, vinylsulphonic acid, vinylsulphonic acid, 3-sulfylacrylate, 3-sulphonylsulphonic acid -Sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, the sulfonic acid groups can be wholly or partially in neutralized form, which means that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred. In copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, the proportion of the monomer containing sulfonic acid groups is preferably 50% by weight to 90% by weight and the proportion of the monomer containing carboxylic acid groups is preferably 10% by weight 50% by weight. The molar mass of the preferably used sulfo copolymers can be varied in order to adapt the properties of the polymers to the desired use. Preferred cleaning agents are characterized in that the copolymers have molar masses from 2000 g / mol to 200,000 g / mol, preferably from 4000 g / mol to 25000 g / mol and in particular from 5000 g / mol to 15000 g / mol. In a further preferred embodiment, the copolymers furthermore comprise, in addition to carboxyl group-containing monomer and sulfonic acid group-containing monomer, at least one nonionic, preferably hydrophobic, monomer. By The use of these hydrophobically modified polymers can also improve the rinsing performance of dishwashing detergents. The nonionic monomers used are preferably monomers of the general formula R ¹ - (R ² ) C =C (R ³ ) -XR ⁴ , in which R ¹ to R ³ independently of one another represent -H, -CH ₃ or -C ₂ H ₅ X stands for an optionally present spacer group which is selected from -CH ₂ -, -C (O) O- and -C (O) -NH-, and R ^{4 stands} for a straight-chain or branched, saturated alkyl radical having 2 to 22 Carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, 1-hexene, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4 -Trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4,4 -Dimethylhexane-1, ethylcyclohexyn, 1-octene, α-olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C ₂₂ - α-olefin, 2-styrene, α- Methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl acrylate, butyl acrylate, pentyl acrylate (Methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, methacrylate Octyl ester, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, stearyl methacrylate, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate, and behenyl methacrylate, and mixtures thereof, in particular behenyl acrylate, or 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof. Preferred agents contain 2% by weight to 50% by weight, preferably 6% by weight to 45% by weight and in particular 10% by weight to 40% by weight builder, the information in% by weight here and in the following is based in each case on the weight of the agent, unless otherwise stated. It is particularly preferred to use builders from the group of carbonates and / or hydrogen carbonates, preferably alkali metal carbonates, particularly preferably sodium carbonate, in amounts from 2% by weight to 30% by weight, preferably from 4% by weight to 25% by weight. -% and in particular from 6% by weight to 20% by weight.

Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. Polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, provided that such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for the agent. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular. Particularly preferred agents contain citrate, preferably in amounts from 2% by weight to 40% by weight, in particular from 3% by weight to 25% by weight and particularly preferably from 4% by weight to 20% by weight . Citrate and citric acid, alone or both together, have proven themselves particularly in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and / or the polymers containing sulfonic acid groups, in terms of cleaning performance and rinsing performance and, in particular, deposit inhibition proven effective builders. Preference is given to agents which contain citrate in amounts of 3% by weight to 25% by weight, in particular 4% by weight to 20% by weight, and carbonate in amounts of 4% by weight to 25% by weight, in particular from 6% to 20% by weight.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 g / mol to 70,000 g / mol, in particular from 2000 g / mol to 10,000 g / mol, and especially preferably from 3000 g / mol to 5000 g / mol. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which, based on the weight of the polymer, contain 50% by weight to 90% by weight acrylic acid and 50% by weight to 10% by weight maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is generally 2000 g / mol to 70,000 g / mol, preferably 20,000 g / mol to 50,000 g / mol and in particular 30,000 g / mol to 40,000 g / mol. The content of (co) polymeric polycarboxylates in the automatic dishwashing detergents is preferably 0.5% by weight to 20% by weight and in particular 3% by weight to 10% by weight.

Dishwashing detergents can use crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred ones Values for x are 2, 3, or 4, and y is a number of 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties. In preferred dishwashing detergents, the content of silicates, based on the total weight of the automatic dishwashing detergent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight. Particularly preferred dishwashing detergents are silicate-free.

Particularly preferred liquid dishwashing detergents are characterized in that they each contain at least one builder from the group of carbonates and citrates and from the group of polymers containing sulfonic acid groups, the proportion by weight of these builders in the agent preferably being 2% by weight to 50% by weight. -%, in particular 5% by weight to 45% by weight and particularly preferably 10% by weight to 40% by weight. The combination of two or more builders from the group mentioned above has proven to be advantageous.

The agents can contain a complexing agent which is different from the abovementioned builders and builders, preferably in amounts from 2% by weight to 60% by weight, in particular from 4% by weight to 55% by weight and particularly preferred from 8% to 50% by weight. The preferred complexing agents include the phosphonates, provided they can be used for regulatory reasons. This also includes hydroxyalkane and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. The dishwashing detergents can contain two or more different phosphonates (if permitted by the regulations). The proportion by weight of the phosphonates in the agents is preferably 1% by weight to 9% by weight, in particular 1.2% by weight to 8% by weight and particularly preferably 1.5% by weight to 6% by weight %. Particularly preferred agents are characterized in that they additionally contain further complexing agents selected from the group of hydroxyethylethylenediamine triacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, iminodisuccinic acid, hydroxyimino-disuccinic acid, aspartic acid diacetic acid, hydroxyethane-1,1-diphosphonic acid or their mixtures.

An agent can contain L-glutamic acid-N, N-diacetic acid and / or the corresponding alkali salt (GLDA), preferably the tetrasodium salt, and / or methylglycinediacetic acid and / or the corresponding alkali salt (MGDA), preferably the trisodium salt, as a complexing agent. The trisodium salt of methylglycinediacetic acid is very particularly preferably contained. The terms methylglycinediacetic acid and L-glutamic acid-N, N-diacetic acid include not only the free acids but also their salts, for example their sodium or potassium salts. Preferred agents are characterized in that they contain 3% by weight to 30% by weight, preferably 10% by weight to 20% by weight, in particular 11% by weight to 18% by weight and particularly preferably 12% by weight % to 15.5% by weight and very particularly preferably 13% by weight to 15% by weight of glutamic acid-N, N-diacetic acid and / or methylglycinediacetic acid and / or salts thereof.

A dishwashing detergent preferably contains at least one surfactant, in particular selected from anionic, nonionic, zwitterionic and amphoteric surfactants. Surfactants are preferably contained in the agents in an amount of up to 40% by weight, in particular from 2% by weight to 38% by weight and particularly preferably in an amount from 5% by weight to 30% by weight .

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohol 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 7 EO. The stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants can also Fatty alcohols with more than 12 EO are used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Block copolymers with EO-PO block units or PO-EO block units can be used here, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but rather statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols. Preferably, nonionic 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 stands} for a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical, R ^{2 stands} for a linear or branched hydrocarbon radical with 2 to 26 carbon atoms, A, A ', A '' and A '''independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , _{-CH 2} -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ) stand, w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0, are used. The nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² , in which R ^{1 stands} for a straight-chain or branched, saturated or mono- or polyunsaturated C, have proven to be particularly effective _6-24 -alkyl or -alkenyl radical, R ^{2 stands} for a linear or branched hydrocarbon radical with 2 to 26 carbon atoms, A stands for a radical from the group CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ --CH (CH3), and w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40. The group of these nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers. Nonionic surfactant is preferably used in amounts from 1% by weight to 20% by weight, in particular from 2% by weight to 18, particularly preferably from 4.0 to 15% by weight and from 6.0 to 12% by weight. -%. In addition to nonionic surfactants, the agent can also contain anionic surfactants. The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Surfactants of the sulfonate type are preferably C _9-13 alkylbenzenesulfonates, olefin sulfonates, that is, mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products are considered. _{Alkane sulfonates obtained from C 12-18} alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. The esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a preferred embodiment, the content of anionic surfactants in the agent is 0.1% by weight to 30% by weight, preferably 2% by weight to 20% by weight.

A preferred pH value of liquid water-containing dishwashing detergents is in the range from 6 to 9 or between 9 and 14, in particular between 9 and 12. The adjustment of the pH value can, if necessary, by means of appropriate pH adjusters, in particular sodium or potassium hydroxide, take place. In particular, acidifying agents can be added to dishwashing detergents in order to lower the pH of the liquor in the rinse cycle when they are used. Both inorganic acids and organic acids can be used as acidifying agents, provided they are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, formic acid, citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred. Organic sulfonic acids such as sulfamic acid can also be used. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS, a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid (max. 33 wt. -%). Agents containing one or more acidifying agents, preferably mono-, oligo- and polycarboxylic acids, particularly preferably formic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid and especially formic acid, acetic acid and / or citric acid in amounts of 0, 1% by weight to 12% by weight, in particular 0.2% by weight to 10% by weight and particularly preferably 0.3% by weight to 8.0% by weight, are preferred.

The agents used in the context of the invention preferably contain at least one washing or cleaning enzyme. Enzymes, in particular proteases and amylases, are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These ready-made preparations include, for example, those by granulation, extrusion or Solid preparations obtained by lyophilization or, in particular for use in liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or mixed with stabilizers or other auxiliaries. Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, 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 enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage. Preferred particularly liquid agents contain 7% by weight to 40% by weight, in particular 10% by weight to 30% by weight protease preparations and 2% by weight to 20% by weight, in particular 4% by weight % to 16% by weight of amylase preparations each containing, based on the preparation, 0.4% by weight to 20% by weight, in particular 0.8% by weight to 10% by weight, of active protein . The enzymes used with particular preference include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available, which are accordingly preferred. The agents preferably contain enzymes in total amounts of 1 × 10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the biuret method. Examples of amylases are the α-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus and, in particular, their improved further developments for use in detergents or cleaning agents. The enzyme from Bacillus licheniformis is available from the Novozymes company under the name Termamyl® and from the Danisco / Genencor company under the name Purastar® ST. Further development products of this α-amylase are available from Novozymes under the trade names Duramyl® and Termamyl® ultra, from Danisco / Genencor under the name Purastar® OxAm and from Daiwa Seiko Inc. as Keistase®. The α-amylase from Bacillus amyloliquefaciens is marketed by the Novozymes company under the name BAN®, and variants derived from the α-amylase from Bacillus stearothermophilus under the names BSG® and Novamyl®, also by the Novozymes company. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948) should be emphasized. The amylolytic enzymes described in the international patent applications can also be used WO 2003/002711 , WO 2003/054177 and WO 2007/079938 are disclosed. Fusion products of the molecules mentioned can also be used. In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available from the Novozymes company under the trade names Fungamyl® are suitable. Further commercial products that can be used advantageously are, for example, Amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus®, likewise from the Novozymes company. Variants of these enzymes obtainable by point mutations can also be used. In various preferred embodiments, detergents or cleaning agents can contain at least one second amylase and / or at least one second protease, wherein the second amylase is different from the first amylase and is selected from the group mentioned above and wherein the second protease is different from the first protease. If two amylases are present, these can preferably be used in a mass ratio of 50: 1 to 1:50, preferably 30: 1 to 1:10 (in each case based on the amount of active protein amylase 1 to amylase 2). It is particularly preferred to use a first amylase in a ratio of 20: 1 to 2: 1, preferably 15: 1 to 3: 1, particularly preferably 12: 1 to 5: 1, for example 10: 1, to a second amylase. Further preferred especially liquid agents contain 0.1% by weight to 30% by weight, preferably 1% by weight to 25% by weight and in particular 2% by weight to 20% by weight cellulase preparations. Further preferred, particularly liquid agents contain 0.1% by weight to 30% by weight, preferably 1% by weight to 25% by weight and in particular 2% by weight to 20% by weight of mannanase preparations. It is also possible to use lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid substitution D96L. Furthermore, for example, the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used. It is also possible to use lipases or cutinases whose starting enzymes are originally from Pseudomonas mendocina and Fusarium solanii have been isolated. Further preferred, particularly liquid agents contain 0.1% by weight to 30% by weight, preferably 1% by weight to 25% by weight and in particular 2% by weight to 20% by weight lipase preparations. It is also possible to use enzymes which are summarized under the term hemicellulases. In addition to the mannanase already mentioned, these include, for example, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. A plurality of enzymes and / or enzyme preparations, preferably liquid protease preparations and / or amylase preparations, and optionally cellulase preparations and / or mannanase preparations are preferably used.

Another optional component of the agent is a boric acid or a boric acid derivative. In addition to boric acid, boronic acids or their salts or esters are preferably used, including in particular derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA), or the salts or Esters of the compounds mentioned. The weight fraction of the boric acid and / or the boric acid derivatives is preferably 0.001% by weight to 10% by weight, in particular 0.002% by weight to 6% by weight and particularly preferably 0.05% by weight to 3% by weight %.

Another optional component of the means is a Ca or Mg ion source. Ca or Mg ion sources are preferably used in amounts from 0.01% by weight to 10% by weight, in particular from 0.2% by weight to 8% by weight and particularly preferably from 0.5% by weight up to 5% by weight. The organic calcium salts have proven to be particularly effective sources of calcium ions.

For enzyme stabilization, the agents can also contain polyols, in particular sorbitol.

Liquid agents preferably contain 30% by weight and less, preferably 25% by weight and less, in particular 15% by weight and less, water. In further preferred embodiments, the agents contain 0.5% by weight to 30% by weight, in particular 1% by weight to 25% by weight and particularly preferably 1.5% by weight to 30% by weight of water .

The especially liquid agents can contain at least one hydrotrope. Preferred hydrotropes are xylene sulfonate, cumene sulfonate, urea, N-methylacetamide and mixtures thereof, in particular cumene sulfonate and / or xylene sulfonate, and particularly preferably cumene sulfonate. Hydrotrope is preferably in an amount from 2% by weight to 25% by weight, in particular from 4% by weight to 20% by weight and particularly preferably from 6% by weight to 15% by weight, in the agent contain.

Organic solvents are an optional component of dishwashing detergents. Preferred organic solvents come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, monoethanolamine, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-glycol ether, ethylene glycol mono-glycol ether , Dietethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Preferred solvents are preferably selected from glycerol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol and polyethylene glycols, in particular those polyethylene glycols which have an average molecular weight in the range from 100 g / mol to 800 g / mol, in particular 200 g / mol to 600 g / mol. Organic solvents are preferably in the range from 5% by weight to 80% by weight, in particular from 10% by weight to 60% by weight and preferably from 20% by weight to 50% by weight. A particularly preferred organic solvent is 1,2-propylene glycol. Agents which contain 5% by weight to 80% by weight, preferably 10% by weight to 60% by weight and in particular 20% by weight to 50% by weight 1,2-propylene glycol have proven to be useful proved to be particularly stable, so that corresponding contents are preferred.

Dishwashing detergents preferably contain at least one glass corrosion inhibitor. Glass corrosion inhibitors are preferably selected from water-soluble zinc salts, preferably zinc chloride, zinc sulfate and / or zinc acetate, particularly preferably zinc acetate, polyalkyleneimines, in particular polyethyleneimines, and mixtures thereof. Zinc salt is preferably used in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular 0.1% by weight up to 2% by weight. Polyethyleneimines, such as are available, for example, under the name Lupasol®, are preferably used in amounts of up to 5% by weight, in particular from 0.01% by weight to 2% by weight.

Individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, may be used as perfume oils or fragrances which can be contained in the agents used in the context of the invention. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance. Such perfume oils can also contain natural odorant mixtures, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. In order to be perceptible, an odoriferous substance must be volatile, with the molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound. Most fragrances have molar masses of up to about 200 g / mol, while molar masses of 300 g / mol and above are more of an exception. Due to the different volatility of odoriferous substances, the odor of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the olfactory impressions are divided into "top note", "heart note" (middle note or body) and " Base note "(end note or dry out). Since odor perception is largely based on the odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie firmly adhering odorous substances. When composing perfumes, more volatile odoriferous substances can, for example, be bound to certain fixatives, which prevents them from evaporating too quickly. When the odorous substances are classified into “more volatile” or “firmly adhering” odorous substances, nothing is said about the odor impression and about whether the corresponding odorous substance is perceived as a top note or a heart note. The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers that ensure a long-lasting fragrance through a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, it being possible for the cyclodextrin-perfume complexes to be coated with further auxiliaries. Particularly preferred fragrances are linalyl acetate, dihydromyrcenol, citronellonitrile, menthyl acetate, methylphenylbutanol and / or eucalyptol and mixtures thereof. The known ricinolates, in particular zinc ricinoleates, for example, can be used as scent catchers (or, as will also be used synonymously below, odor neutralizers or fragrance neutralizers, agents against malodour or bad smells). Also preferred as scent catchers are 2-menthyl-5-cyclohexylpentanol and 1-cyclohexylethanol. Activated carbon and / or cyclodextrins and / or zeolites, preferably acid-modified zeolites, can also be used with particular preference. Zinc ricinoleate alone or in combination with one or more of the aforementioned fragrances and / or fragrance traps is particularly preferred, since it also has a positive effect on inhibiting glass corrosion during the rinsing process.

To combat microorganisms, antimicrobial agents can be used in the agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistats and fungicides and so on. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, and these compounds can also be dispensed with entirely.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• WO 2007/031250 A1 [0004]
• EP 2147582 B1 [0004]
• WO 2003/002711 [0048]
• WO 2003/054177 [0048]
• WO 2007/079938 [0048]

Claims (10)

Washing machine with a washing chamber for receiving a washing liquid and textiles to be cleaned and with an activating device which has an inlet for introducing washing liquid from the washing chamber into the activating device and an outlet for directing washing liquid out of the activating device into the washing chamber, wherein the activation device generates cold plasma. Washing machine after Claim 1 , characterized in that both the inlet for introducing the washing liquid from the washing chamber into the activation device and the outlet for discharging the washing liquid into the washing chamber are designed in such a way that textiles cannot get into the activation device. Dishwasher with a cleaning chamber for receiving cleaning fluid and dishes to be cleaned and with an activation device which has an inlet for introducing cleaning fluid from the cleaning chamber into the activation device and an outlet for directing cleaning fluid out of the activation device into the cleaning chamber, wherein the activation device generates cold plasma. Washing machine after Claim 1 or 2 or dishwasher Claim 3 , characterized in that the surface of the plasma-generating device is selected to be as large as possible in order to enable intensive contact of the plasma with the washing or cleaning liquid. Machine according to one of the preceding claims, characterized in that the plasma is generated by magnetically organized plasma layer technology, surface micro-discharge technology, microwave plasma technology or venturi plasma technology. Method of washing laundry with the help of a washing machine according to one of the Claims 1 , 2 , 4th or 5 , in which soiled laundry is brought into contact with a surfactant-containing, in particular aqueous, washing liquid, with a cold plasma acting on the laundry for at least part of the washing process. Procedure according to Claim 6 , characterized in that it is carried out at temperatures in the range from 10 ° C to 95 ° C, in particular from 20 ° C to 60 ° C, and / or over a period of 1 minute to 2 hours, in particular from 15 minutes to 1 hour , and / or that a period of up to 30 minutes, in particular from 15 minutes to 30 minutes, is allowed to elapse before cold plasma generated with the aid of the activation device is used, and if the cold plasma does not finish of the washing process is to be used, it begins over a period of 1 minute to 1 hour, in particular from 15 minutes to 30 minutes. Method for cleaning dishes using a dishwasher according to one of the Claims 3 until 5 , in which dishes to be cleaned are brought into contact with a surfactant-containing, preferably aqueous, cleaning liquid, with a cold plasma acting on the dishes for at least part of the cleaning process. Procedure according to Claim 8 , characterized in that it is carried out at temperatures in the range from 20 ° C to 75 ° C, in particular from 30 ° C to 55 ° C, and / or over a period of 1 minute to 2 hours, in particular from 1 minute to 1 hour , performs, and / or a period of up to 20 minutes, in particular from 15 minutes to 20 minutes, is allowed to elapse before cold plasma generated with the aid of the activation device is used, and if the cold plasma is not used until the end of the Cleaning process is to be used, it begins over a period of 30 minutes to 2 hours, in particular from 15 minutes to 20 minutes. Method according to one of the Claims 6 until 9 , characterized in that conventional washing or cleaning agents are used which contain ingredients usually present in such agents, in particular surfactant.

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