EP3875566A1 - Nitroxide compounds in detergents or cleaning compositions - Google Patents

Abstract

The cleaning performance of detergents and cleaning agents, in particular with regard to bleachable soiling, should be increased without damage to the textile treated with them during use. This was essentially achieved through the use of 4-imidazolidinone-nitroxide radical compounds, which can optionally be produced electrochemically in situ from the corresponding N-oxides or hydroxylamines.

Description

The present invention relates to the use of certain nitroxide compounds for enhancing the cleaning performance of detergents and cleaning agents against soiling, washing and cleaning processes using such compounds, and washing and cleaning agents which contain these compounds.

Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidizing effect of these substances depends strongly on the temperature in dilute solutions; For example, with H ₂ O ₂ or perborate in alkaline bleaching liquors, sufficiently rapid bleaching of soiled textiles is only achieved at temperatures above about 80 ° C. At lower temperatures, the oxidizing effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, which are capable of delivering peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous proposals, especially from the classes of N- or O-acyl compounds, for example reactive ones Esters, polyacylated alkylenediamines, in particular N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl anhydrides, and carboxylic anhydrides, and in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy-benzenesulfonate, O-acylated sugar derivatives, such as pentaacetylglucose, and N-acylated lactams, such as N-benzoylcaprolactam, have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that essentially the same effects occur at temperatures around 60 ° C as with the peroxide liquor alone at 95 ° C.

In the endeavor to achieve energy-saving washing and bleaching processes, application temperatures well below 60 ° C, in particular below 45 ° C down to cold water temperature, have also become more important in recent years.

At these low temperatures, the activity of the previously known activator compounds generally diminishes noticeably. There has therefore been no lack of efforts to develop more effective activators for this temperature range. The use of transition metal compounds, in particular transition metal complexes, to increase the oxidizing power of peroxygen compounds or even atmospheric oxygen in detergents and cleaning agents has also been proposed on various occasions. The transition metal compounds proposed for this purpose include, for example, manganese, iron, cobalt, ruthenium or molybdenum-salen complexes, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, cobalt, Ruthenium, Molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, and manganese complexes with polyazacycloalkane ligands, such as TACN. A disadvantage of such metal complexes, however, is that they either do not have sufficient bleaching capacity, especially at low temperatures, or, if the bleaching capacity is sufficient, undesirable damage to the colors of the material to be washed or cleaned and possibly even to the material itself, for example the textile fibers.

From the international patent application WO 2013/017476 A1 it is known that from sterically hindered N-hydroxy compounds such as, for example, 1-hydroxy-2,2,6,6-tetramethylpiperidine, by means of electrolysis, bleach-active species can be generated which have a bleach-intensifying effect. From the international patent application WO 2015/162008 A1 it is known that the effects of 1-hydroxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpiperidine-N-oxide and (2,2,6,6-tetramethylpiperidin-1-yl) oxyl can be increased if an anionic substituent is present.

It has surprisingly been found that nitroxides of certain 5-membered N-heterocyls are superior to the known piperidine derivatives.

in denen R¹, R², R³ und R⁴ unabhängig voneinander für einen Methyl- oder Ethylrest, R⁵ für H, SO₂CH₃ oder einen SO₃ ^--monosubstituierten C_2-5-Alkylrest mit ladungsausgleicher Anzahl von Kationen, insbesondere Ammonium-, Natrium- und/oder Kaliumionen, R⁶ für einen trialkylammonium-,

oder pyridinium-monosubstiuierten C_3-5-Alkylrest mit ladungsausgleichender Anzahl von Anionen, insbesondere Halogeniden wie Chlorid, Bromid und lodid, Halogenaten wie Chlorat und lodat, Sulfat und/oder Methylsulfat sowie deren Mischungen, steht, zur Verstärkung der Reinigungsleistung von Wasch- und Reinigungsmitteln, insbesondere gegenüber bleichbaren und/oder proteinhaltigen Anschmutzungen, in wässriger, insbesondere tensidhaltiger Flotte.The invention accordingly relates to the use of compounds of the 4-imidazolidinone nitroxide radical type of the general formula I, II or III,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent a methyl or ethyl radical, R ^{5 represents} H, SO ₂ CH ₃ or an SO ₃ ^- -monosubstituted C _2-5 -alkyl radical with a charge-balanced number of cations, in particular ammonium, sodium and / or potassium ions, R ⁶ for a trialkylammonium,

or pyridinium-monosubstituted C _3-5 -alkyl radical with a charge-balancing number of anions, in particular halides such as chloride, bromide and iodide, halogenates such as chlorate and iodate, sulfate and / or methyl sulfate and mixtures thereof, to enhance the cleaning performance of washing and cleaning Cleaning agents, especially for bleachable and / or protein-containing soiling, in an aqueous, especially surfactant-containing liquor.

Further objects of the invention are a method for washing textiles and a method for cleaning hard surfaces, in particular for machine cleaning of dishes, using a compound of the general formula I, II or III in an aqueous, in particular surfactant-containing liquor.

In the compounds of the general formula I or III, R ¹ and R ² are preferably not simultaneously ethyl radicals and not simultaneously R ³ and R ^{4 are} ethyl radicals. In the compounds of the general formula I, II or III, R ⁵ and R ^{6 are} preferably linear and the substituents are located on the C atom of the radicals furthest away from the N atom of the 4-imidazolidinone ring.

The nitroxide radical compounds of the general formulas I, II and III can also be prepared electrochemically by anodic oxidation from the corresponding hydroxylamines or amines. The latter serve as starting materials for the synthesis of nitroxides by chemical oxidation. The preparation of the amines is generally known and is described in Example 1 of the nitroxides I, II and III.

Anodic oxidation of sterically hindered amines to nitroxides is also known and has been described, for example von Kagan, E. Sh .; Zhukova, I. Yu .; Yanilkin, VV; Morozov, VI; Nastapova, NV; Kashparova, VP; Kashparov, II: "Mechanism of electrochemical oxidation of spatially hindered amines of 2,2,6,6-tetramethylpiperidine series", Russian Journal of Electrochemistry (2011), 47 (11), 1199-1204 .

The hydroxylamines can be made from the amines by chemical oxidation. For example, there is an overview of various methods for such oxidation Geffken, D .; Koellner, MA "Hydroxylamines", Science of Synthesis (2008), 40b, 937-1082 .

The anodic oxidation of hydroxylamines to nitroxides is described by Fish, Judith R .; Swarts, Steven G .; Seville, Michael D .; Malinski, Tadeusz: "Electrochemistry and spectroelectrochemistry of nitroxyl free radicals", Journal of Physical Chemistry, (1988), 92 (13), 3745-51 .

For this reason, it is also possible in the context of the present invention not to use the compound of the general formulas I, II or III directly, but to use the corresponding amines or hydroxylamines and, from these precursor compounds, to use the compounds of the general formulas I, II or III electrochemically to be generated in situ, as will be explained in more detail below. In connection with the use according to the invention and the method according to the invention, the presence of a corresponding electrolysis device has the advantage that the compounds formed from the nitroxide radical compounds during the oxidation of the substrate desired according to the invention can be converted electrochemically back into the nitroxide radical compounds. Thus, the compound of the general formula I, II or III or its precursor compound be used in a sub-stoichiometric amount based on the substrate.

The compounds of the general formula I, II or III show an effective bleaching effect on colored stains, for example those with anthocyanin-containing dyes, for example from berries, or dyes of the carrotinoid group, for example from tomatoes or carrots. Their use does not lead to unwanted discoloration, for example of textile dyes.

The bleach-active compound of the general formula I, II or III can be produced in a simple manner by adding an aqueous system which contains the precursor compound, an electrical potential difference between at least two electrodes, which is preferably 0.2 V to 5 V, in particular 1 V to 3 V, so that the precursor compound releases an electron and a reaction sequence is started by which the radical compound of the general formula I, II or III is formed. Without wishing to be bound by this theory, it is conceivable that the free radical species generated in this way reaches the dirt with the aqueous liquor, removes an electron from the dirt and thus a less colored and / or more water-soluble and / or water-dispersible material emerges from the dirt . The precursor compound is formed from the bleach-active species through reaction with the soil, its substrate, so that a reversible redox system is present.

The nitroxides of the general formula I, II or III can, however, also be oxidized electrochemically by means of a one-electron oxidation into the corresponding oxoammonium salts. These are even stronger oxidizing agents and can remove an electron from the dirt even more efficiently than the nitroxides themselves. These would be regressed from the oxoammonium salts during the reaction with the dirt. This would result in a second redox system consisting of nitroxide-oxoaamonium salt. The laws of electrochemical oxidation of nitroxides in oxoammonium salts have been investigated, for example by Fish, Judith R .; Swarts, Steven G .; Seville, Michael D .; Malinski, Tadeusz: "Electrochemistry and spectroelectrochemistry of nitroxyl free radicals", Journal of Physical Chemistry, (1988), 92 (13), 3745-51 .

Electron transfer reactions of nitroxides or oxoammonium salts have been extensively studied, for example by Zhang, FaLiu, You Cheng: "Electron transfer reactions of piperidine aminoxyl radicals", Chin. Sci. Bull. (2010), 55 (25), 2760-2783 .

It is possible to electrolyze the liquor containing the precursor compound continuously or once or several times for certain periods of time, for example 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes, the electrolysis time being adapted to the degree of soiling of the laundry can be; It is irrelevant whether the precursor compound itself was used at the beginning or whether it was formed after the first reaction cycle from the compound of the general formula I, II or III used initially. The production of the bleach-active compound of the general formula I, II or III is also possible in that the precursor compound, Particularly when using a conventional flushing device, an electrolysis device passes before the inlet into the chamber of a washing machine or dishwasher, in particular an electrolysis cell flows through an aqueous solution or slurry, which can be installed in the feed line inside or outside the machine. Alternatively, it is possible at the beginning of the process to let other active ingredients, for example enzymes, perform their performance unaffected, and only later to start the bleaching effect of the compound of the general formula I, II or III by switching on the electrolysis device.

In a preferred embodiment of the invention, the electrolysis device is installed inside a washing machine or dishwasher in the flooded area of the washing or cleaning room, in the case of a drum washing machine preferably outside the washing drum. The device can be a permanently installed component of the washing machine or dishwasher or a separate component. The electrolysis device, in particular designed as an electrolysis cell, is designed in a further embodiment of the invention as a separate device which is separate from a washing machine or dishwasher and which is operated with its own power source, for example a battery (e-bleach ball). Another embodiment according to the invention consists in integrating the electrolysis device into an additional water circuit within the machine. In all embodiments, it is important that the electrodes of the electrolysis device can come into contact with the electrolyte (the washing or cleaning liquor, or the industrial water supplied) that contains the precursor compound, for example if the e-bleach ball is during the washing process located in the drum of a washing machine. The electrolysis device is advantageously designed as two half-cells connected by means of an ion-permeable membrane, each half-cell being equipped with an electrode.

It is particularly advantageous that the activity of the bleach can be easily modified by regulating the current strength, if desired depending on the degree of soiling or the fabric. In the case of textile washing processes, there is no damage to the textile treated in this way that goes beyond the extent that occurs when using commercially available agents.

In the context of the use according to the invention and the method according to the invention, it is preferred if the concentration of the compound of the general formula I, II or III including the precursor compounds which can be electrochemically converted into them in the aqueous washing or cleaning liquor is 0.05 mmol / l to 5 mmol / l , in particular 0.1 mmol / l to 2 mmol / l. The use according to the invention and the process according to the invention are each preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C. The use according to the invention and the method according to the invention are each preferably carried out at pH values in the range from pH 2 to pH 12, in particular from pH 4 to pH 11.

The use according to the invention and the method according to the invention can be particularly simple by using a washing or cleaning agent which contains the compound of the general formula I, II or III or the precursor compound with an amine or hydroxylamine function. Detergents for cleaning textiles and agents for cleaning hard surfaces, in particular dishwashing detergents and, among these, preferably those for machine use which contain a compound of the general formula I, II or III or the precursor compound in addition to the usual ingredients that are compatible therewith, in particular a surfactant, are therefore further objects of the invention. Although the success according to the invention is already achieved through the presence of the compound of the general formula I or II, an agent according to the invention can additionally also contain, in particular, peroxygen-containing bleaching agent. It is particularly advantageous, however, that both bleach and conventional bleach activators can be dispensed with, so that, as a result, a smaller amount of detergent or cleaning agent has to be used per washing or cleaning cycle. In a preferred embodiment, an agent according to the invention is therefore free from bleach and conventional bleach activator. In a preferred embodiment, an agent according to the invention contains water and is liquid.

In agents according to the invention, 0.05% by weight to 10% by weight, in particular 0.1% by weight to 5% by weight, of the compound of the general formula I, II or III or of the precursor compound with amine or Contain hydroxylamine function. When using an agent according to the invention, the cleaning-enhancing effect of the compound of the general formula I, II or III obtained from the precursor compound can, if desired, be switched off by completely omitting the electrolysis, if it is to be dispensed with, for example, with only lightly soiled laundry or extremely bleach-sensitive textiles. The consumer therefore only needs a single detergent to wash insensitive, usually white, and sensitive, usually colored textiles.

The agents according to the invention, which can be in particular pulverulent solids, in compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known ingredients that are customary in such agents, in addition to the compound to be used according to the invention. The agents according to the invention can in particular builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, graying inhibitors, crease-reducing polymeric active ingredients and shape-retaining polymeric active ingredients, bleaching agents, bleach activators, and other auxiliaries such as optical brighteners, foam regulators, dyes and fragrances.

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but cationic and / or amphoteric surfactants can also be included. Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 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 with 5 to 12 carbon atoms in the alkyl radical, can also be used.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Soaps that can be used are preferably the alkali salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The sulfate-type surfactants which can be used include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation. The sulfonate-type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed when corresponding monoolefins are reacted with sulfur trioxide, and alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are contained in the cleaning agents or detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the disinfectants according to the invention as well as cleaning agents according to the invention preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist. Die kationischen Tenside weisen übliche Anionen in zum Ladungsausgleich notwendiger Art und Anzahl auf, wobei diese neben beispielsweise Halogeniden auch aus den anionischen Tensiden ausgewählt werden können. In bevorzugten Ausführungsformen der vorliegenden Erfindung kommen als kationische Tenside Hydroxyalkyl-trialkyl-ammonium-verbindungen, insbesondere C_12-18-Alkyl(hydroxyethyl)dimethylammoniumverbindungen, und vorzugsweise deren Halogenide, insbesondere Chloride, zum Einsatz. Ein erfindungsgemäßes Mittel enthält vorzugsweise 0,5 Gew.-% bis 25 Gew.-%, insbesondere 1 Gew.-% bis 15 Gew.-% kationisches Tensid.The agents according to the invention, especially if they are intended for the treatment of textiles, can contain, as cationic active substances with a textile softening effect, in particular one or more of the cationic textile softening substances of the general formulas X, XI or XII:

wherein each group R ^{1 is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each group R ^{2 is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5. The cationic surfactants have customary anions in the type and number necessary for charge balancing, it being possible for these to be selected from the anionic surfactants in addition to, for example, halides. In preferred embodiments of the present invention, the cationic surfactants used are hydroxyalkyl trialkylammonium compounds, in particular C _12-18 alkyl (hydroxyethyl) dimethylammonium compounds, and preferably their halides, in particular chlorides. An agent according to the invention preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of a cationic surfactant.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builders include polycarboxylic acids, particularly citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, especially amino-tris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxyl compounds such as dextrin and polymeric (poly) carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides such as dextrins, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality as polymerized units. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based in each case on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative 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 an esterified vinyl alcohol 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 away. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a relative molecular weight between 1,000 g / mol and 200,000 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 pasty or liquid, in particular water-containing, agents according to the invention.

Particularly suitable water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. The water-insoluble, water-dispersible inorganic builder materials used are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and, in liquid agents, in particular from 1% by weight to 5% by weight, used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally 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 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali 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 O _{2x + 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 assumes the values 2 or 3. In particular, both β- and δ-sodium disitics (Na ₂ Si ₂ O ₅ · y H ₂ O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a module of 2 to 3 is used, as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention. In a preferred embodiment of the agents according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

The detergents or cleaning agents according to the invention preferably contain builder substances in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat, und
4. d) bis zu 10 Gew.-% polymerem Polycarboxylat,

wobei die Mengenangaben sich auf das gesamte Wasch- oder Reinigungsmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben.In a preferred embodiment of the invention, an agent according to the invention has a water-soluble builder block. The use of the term “builder block” is intended to express that the agents do not contain any other builder substances than those that are water-soluble, that is, all of the builder substances contained in the agent are summarized in the “block” characterized in this way, with the amounts of Substances are excluded that may be contained in small amounts in the other ingredients of the agents as impurities or stabilizing additives. The term “water-soluble” should be understood to mean that the builder block dissolves without residue at the concentration that results from the amount of agent containing it under the usual conditions. The agents according to the invention preferably contain at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block. This is preferably composed of the components

1. a) 5% by weight to 35% by weight citric acid, alkali citrate and / or alkali carbonate, which can also be at least partially replaced by alkali hydrogen carbonate,
2. b) up to 10% by weight alkali silicate with a modulus in the range from 1.8 to 2.5,
3. c) up to 2 wt .-% phosphonic acid and / or alkali metal phosphonate, and
4. d) up to 10% by weight of polymeric polycarboxylate,

the quantities given relate to the total detergent or cleaning agent. This also applies to all of the following quantities, unless expressly stated otherwise.

In a preferred embodiment of agents according to the invention, the water-soluble builder block contains at least 2 of components b), c) and d) in amounts greater than 0% by weight.

With regard to component a), in a preferred embodiment of agents according to the invention, 15% by weight to 25% by weight of alkali metal carbonate, which can be at least partially replaced by alkali metal hydrogen carbonate, and up to 5% by weight, in particular 0.5% by weight, are % to 2.5% by weight of citric acid and / or alkali citrate. In an alternative embodiment of agents according to the invention, 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight of citric acid and / or alkali citrate and up to 5% by weight, in particular, are used as component a) 1% by weight to 5% by weight alkali metal carbonate, which can be at least partially replaced by alkali metal hydrogen carbonate. If both alkali carbonate and alkali hydrogen carbonate are present, component a) preferably has alkali carbonate and alkali hydrogen carbonate in a weight ratio of 10: 1 to 1: 1.

With regard to component b), a preferred embodiment of agents according to the invention contains 1% by weight to 5% by weight alkali metal silicate with a modulus in the range from 1.8 to 2.5.

With regard to component c), agents according to the invention contain 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate in a preferred embodiment. Phosphonic acids are also understood to mean optionally substituted alkylphosphonic acids which can also have several phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, such as, for example, dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenyl-methanediphosphonic acid, 1-hydroxyethane -1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine-tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.

With regard to component d), a preferred embodiment of agents according to the invention contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Of these, the homopolymers of acrylic acid and, among these, those with an average molar mass in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.

Enzymes that can be used in the agents are those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases, oxidases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean® , Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and / or Carezyme®. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable. The optionally used enzymes can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing, cleaning and disinfecting agents according to the invention preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, enzymes stabilized against oxidative degradation being particularly preferred will.

In a preferred embodiment of the invention, the agent contains 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5 % By weight to 40% by weight builder substance and 0.2% by weight to 2% by weight enzyme, selected from proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof .

Peroxygen compounds that may be present in the agents, but which can preferably be omitted in agents intended for use in the process according to the invention, include, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and, under the washing conditions, inorganic hydrogen peroxide that give off hydrogen peroxide Salts such as perborate, percarbonate and / or persilicate can be considered. Hydrogen peroxide can also be generated with the help of an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions containing 3% by weight to 10% by weight hydrogen peroxide are particularly preferably used. If desired, peroxygen compounds, if present, are present in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight, in washing or cleaning agents according to the invention.

In addition, customary bleach activators, which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and / or customary transition metal complexes which activate bleach can be used. The optional, in particular in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators can be coated or granulated in a known manner with coating substances to avoid interaction with the per compounds during storage, with the aid of carboxymethyl cellulose granulated tetraacetylethylenediamine with average particle sizes of 0.01 mm to 0.8 mm, granulated 1.5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile made up in particulate form is particularly preferred. In washing or cleaning agents, such bleach activators, if present, are preferably contained in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

The organic solvents that can be used in the agents according to the invention, especially when they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the cited classes of compounds. Such water-miscible solvents are present in the detergents according to the invention preferably not more than 30% by weight, in particular from 6% by weight to 20% by weight.

To set a desired pH value, which does not result from the mixture of the other components, the agents according to the invention can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably contained in the agents according to the invention not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Polymers with the ability to release soil, which are often referred to as "soil release" active ingredients or, because of their ability to make the treated surface, for example the fiber, soil-repellent, as "soil repellents", are, for example, nonionic or cationic cellulose derivatives. The particularly polyester-active soil-releasing polymers include copolyesters made from dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The preferably used dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ¹¹ -) _a OH, which is also known as a polymer Diol H- (O- (CHR ¹¹ -) _a ) _b OH may be present. Ph here denotes an o-, m- or p-phenylene radical which has 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof R ^{11 is} hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. The polyesters obtainable from these preferably contain both monomer diol units -O- (CHR ¹¹ -) _a O and polymer diol units - (O- (CHR ¹¹ -) _a ) _b O- before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 The acid on which the remainder Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be contained in the soil-releasing polyester instead of the HOOC-Ph-COOH monomer. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000. If desired, these polyesters can also be end-capped, with possible end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids. Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 are preferred, used alone or in combination with cellulose derivatives.

The dye transfer inhibitors suitable for use in the inventive agents for washing textiles include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.

The agents according to the invention for use in laundry can contain anti-crease agents, since textile fabrics, in particular made of rayon, wool, cotton and their mixtures, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing and squeezing across the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

The task of graying inhibitors is to keep the dirt detached from the hard surface and in particular from the textile fiber suspended in the liquor. Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use starch derivatives other than those mentioned above, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used.

The agents can contain optical brighteners, among these in particular derivatives of diaminostilbene disulfonic acid or their alkali metal salts. 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.

In particular when used in machine washing or cleaning processes, it can be advantageous to add customary foam inhibitors to the agents. Soaps of natural or synthetic origin which have a high proportion of C ₁₈ -C ₂₄ fatty acids are suitable as foam inhibitors. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica 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.

In the agents according to the invention, it is also possible to use active ingredients to avoid tarnishing of objects made of silver, so-called silver corrosion inhibitors. Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, if appropriate alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the metals mentioned are in one of the oxidation states II, III, IV, V or VI are present.

The production of solid compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation. For the production of agents according to the invention with an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a method comprising an extrusion step is preferred. Detergents, cleaning agents or disinfectants in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. In a preferred embodiment of means for the particularly machine cleaning of dishes, these are in the form of tablets.

Examples Example 1: Production of compounds essential to the invention

Table 1: Overview of compounds essential to the invention T1

T10

T2

T11

T3

T12

T4

T13

T5

T14

T6

T15

T7

T16

T8

T17

T9

A. Making T1

1. a) intermediate stage
   
   29.9 g (0.190 mol) of T12 in 300 ml of dichloromethane were placed under Ar in a 750 ml sulphonation flask. 0.7 g of 4-dimethylaminopyridine and 23.07 g (0.228 mol) of triethylamine were added to the suspension. The suspension was cooled to 5 ° C. and then 50.18 g (0.228 mol) of 6-bromohexanoyl chloride were added dropwise over the course of 30 minutes. The mixture was then stirred at room temperature for 2 hours. Then 80 ml of water were added, the organic phase was separated off, _{washed with 80 ml of saturated NaHCO 3} solution and with 80 ml of water and dried over 45 g of MgSO 4. The red solution was filtered through a layer of silica gel (2.5 cm high, 7 cm diameter) and this was then washed with dichloromethane. The filtrate was evaporated on a rotary evaporator at 50 ° C. and finally 0.1 mbar. 64.2 g of the above intermediate stage were obtained as a red oil.
2. b) In a 100 ml round bottom flask, 11.7 g (0.035 mol) of the above intermediate were dissolved in 20.89 g of pyridine under argon, and the solution was stirred at 50 ° C. for 16 hours. The excess pyridine was then distilled off at 60 ° C. and 20 mbar. The residue was taken up in 100 ml of tert-butyl methyl ether (TBME) and stirred vigorously for 18 h. The orange suspension was then filtered, the solid was washed with TBME and dried at 50 ° C./200 mbar. 13.85 g of the nitroxide T1 were obtained as a red powder.

B: Making T2

1. a) intermediate stage
   
   The above intermediate was prepared in analogy to the intermediate from T1 but with 4-bromobutyryl chloride instead of 6-bromohexanoyl chloride as a red oil.
2. b) The nitroxide T2 was produced from the above intermediate stage in analogy to T4 as a red powder.

C: Manufacture of T3

A solution of 3.1179 g (0.010 mol) of silver sulfate in 600 ml of warm (80 ° C.) water was added to a solution of 7.3058 g (0.020 mol) T2 in 400 ml of water. The deposited precipitate was filtered off through 1 cm thick Hyflo Supercell, and the filtrate was evaporated on a rotary evaporator at 50 ° C./210 mbar. 5.5 g of the nitroxide T3 were obtained as a red solid.

D: Manufacture of T4

In a 100 ml round bottom flask, 14.73 g (0.044 mol) of the intermediate described under T1 were treated with 66 ml of a 1M solution of trimethylamine in tetrahydrofuran under argon, and the solution was stirred at 35 ° C. for 15 hours. 100 ml of tert-butyl methyl ether (TBME) were then added, the orange suspension was filtered, the solid was washed with TBME and dried at 40 ° C./200 mbar. 11.02 g of the nitroxide T4 were obtained as a red powder.

E: making T5

The nitroxide T5 was obtained from T4 in analogy to T3 as a red solid.

Q: Making T6

In a 50 ml round bottom flask, 1.87 g of 1-methylimidazole (0.023 mol) and 5.01 g (0.015 mol) of the intermediate described under T1 were dissolved in 25 ml of acetonitrile under argon and the solution was stirred at 70 ° C. for 16 h. The acetonitrile was then distilled off and the solid residue was suspended three times in 25 ml of diethyl ether each time and each time filtered off. After drying at 40 ° C./200 mbar, 5.58 g of the nitroxide T6 were obtained as a red solid.

G: making T7

3.0 g (0.026 mol) of DABCO and 5.9 g (0.018 mol) of the intermediate described under T1 in 25 ml of acetonitrile were placed in a 50 ml round bottom flask under argon, and the solution was left to stand at room temperature for 72 h. The acetonitrile was then distilled off, the solid residue was suspended in 50 ml of diethyl ether and then filtered off. After drying at 40 ° C./200 mbar, 7.60 g of the nitroxide T7 were obtained as a yellow-orange solid.

H: Manufacture of T8

In a 100 ml round bottom flask 5.0 g (0.011 mol) of the nitroxide T7 in 50 ml acetonitrile were placed under argon. 4 ml of methyl iodide were added to this solution and the mixture was stirred at room temperature for 16 hours. The resulting suspension was admixed with 30 ml of diethyl ether and the solid was filtered off. After drying at 50 ° C./200 mbar, 6.40 g of the nitroxide T8 were obtained as a red solid.

I: making T9

7.80 g (0.050 mol) of T12 and 4.91 g (0.050 mol) of sodium tert-butoxide in 50 ml of dry dimethylformamide were placed in a 100 ml three-necked flask under argon. 6.83 g (0.050 mol) of 1,4-butane sultone were then added to the stirred solution. The mixture was then stirred for 4 hours at 82 ° C., then cooled to room temperature and washed with 330 ml of tert-butylmethyl Ether added. The precipitated solid was filtered off and dried at 60 ° C./200 mbar. 15.6 g of the nitroxide T9 were obtained as a red solid.

J: Making T10

6.29 g (0.04 mol) of T12, 0.5 g of potassium tert-butoxide, 0.5 g of tetrabutylammonium bromide and 10 ml of propylene oxide in 50 ml of tetrahydrofuran were placed in a 100 ml round bottom flask under argon and the mixture was then stirred at 60 ° C. for 17 hours. The solvent was then distilled off and the residue was chromatographed over silica gel with ethyl acetate. 6.6 g of the nitroxide T10 were obtained as a red oil.

K: making T11

1.4 g (0.034 mol) of sodium hydride (55% in paraffin) in 30 ml of dry dimethylformamide were placed in a 100 ml round bottom flask under argon. The suspension was cooled to 5 ° C. and then 4.80 g (0.031 mol) of T12 were added in portions. The mixture was stirred for 90 minutes and then 4.0 g (0.035 mol) methanesulfonyl chloride were added dropwise. The mixture was stirred for 3 hours and then poured into 200 ml of water. The precipitated solid was filtered off with suction, washed with water and dried. 5.4 g of the nitroxide T11 were obtained as a red solid, melting point 141-144 ° C.

L: making T12

The production of the nitroxide T12 was carried out according to the instructions from Toda, Toshimasa; Morimura, Syoji; Mori, Eiko; Horiuchi, Hideo; Murayama, Keisuke; Bulletin of the Chemical Society of Japan (1971), 44 (12), 3445-50

M: Manufacture of T13

The production of the nitroxide T13 was carried out according to the instructions in WO 98/30601 A2 .

N: Manufacture of T14

1. a) intermediate stage
   
   The above intermediate was produced from T13 in analogy to the intermediate from T1 as a red oil.
2. b) The nitroxide T14 was prepared as an orange solid from the above intermediate stage in analogy to T4.

○: Manufacture of T15

The nitroxide T15 was produced from T13 in analogy to T9 as a red solid.

P: making T16

The production of the nitroxide T16 was carried out according to the instructions from Nesvadba, Peter; Bugnon, Lucienne; Maire, Pascal; Novak, Petr: Chemistry of Materials (2010), 22 (3), 783-788

Q: Manufacture of T17

The nitroxide T17 was produced from T16 in analogy to T9 as a red solid.

Example 2: bleaching performance

An electrolysis device consisting of two half-cells connected by means of an ion-permeable membrane was used. Each half-cell was equipped with a stainless steel electrode. The electrolysis device was each with a 2 millimolar aqueous solution of T1 or T2 prepared in Example 1 or, for comparison, of 1-hydroxy-2,2,6,6-tetramethylpiperidine (V1), which also contained 0.1 mol / l Na ₂ SO ₄ contained, filled. To quantify the bleaching effect, two-dimensional pieces of cotton textile, which had previously been provided with the standardized soiling A1 (blueberry juice) or A2 (blackberry juice) specified in the table below, were placed in the anode half-cell. At 20 ° C. and pH 6, electrolysis was carried out with a potential difference of 3 V over a period of 2 hours, the convection in the solution being supported by the use of a magnetic stirrer. The cotton textile pieces were then removed, rinsed with water, dried with exclusion of light and measured with a color spectrometer in the L · a · b color space. Table 2 below shows the values thus obtained and those of the soiled unwashed pieces of textile. Table 2: L, a, b - values A1; L / a / b A2; L / a / b unwashed 61.71 / 22.66 / -0.87 72.02 / 16.26 / 4.52 T1 77.0 / 3.3 / 12.6 91.8 / -1.5 / 4.78 T2 77.7 / 3.2 / 12.8 92.6 / -0.76 / 4.1 V1 79.5 / 4.5 / 17.3 83.5 / 3.7 / 15.3

It can be seen that T1 and T2 had a significantly lower tendency towards undesired discoloration of the soiling (lower b-value) compared to V1.

Claims (10)

Washing or cleaning agent, characterized in that it is a compound of the general formula I, II or III,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent a methyl or ethyl radical, R ^{5 represents} H, SO ₂ CH ₃ or an SO ₃ ^- -monosubstituted C _2-5 -alkyl radical with a charge-balanced number of cations, R ⁶ for a trialkylammonium,

or pyridinium-monosubstituted C _3-5 -alkyl radical with a charge-balancing number of anions, or contains an N-oxide or hydroxylamine corresponding to the formula I, II or III. Agent according to Claim 1, characterized in that it contains 0.05% by weight to 10% by weight, in particular 0.1% by weight to 5% by weight, of the compound and / or free of bleaching agent and conventional bleach activator is. Agent according to Claim 1 or 2, characterized in that it contains water and is liquid. Use of compounds of the general formula I, II or III,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent a methyl or ethyl radical, R ^{5 represents} H, SO ₂ CH ₃ or an SO ₃ ^- -monosubstituted C _2-5 -alkyl radical with a charge-balanced number of cations, R ⁶ for a trialkylammonium,

or pyridinium monosubstituted C _3-5 -alkyl radical with a charge-balancing number of anions, or an amine or hydroxylamine corresponding to the formula I, II or III in an aqueous, in particular surfactant-containing liquor to enhance the cleaning performance of detergents and cleaning agents. Process for washing textiles or for cleaning hard surfaces, in particular for machine cleaning of dishes, using a compound of general formula I, II or III,

in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent a methyl or ethyl radical, R ^{5 represents} H, SO ₂ CH ₃ or an SO ₃ ^- -monosubstituted C _2-5 -alkyl radical with a charge-balanced number of cations, R ⁶ for a trialkylammonium,

or pyridinium-monosubstituted C _3-5 -alkyl radical with a charge-balancing number of anions, or one of the formula I, II or III corresponding N-oxide or hydroxylamine to enhance the cleaning performance of detergents and cleaning agents in aqueous, especially surfactant-containing liquor. Process according to Claim 5, characterized in that the liquor containing the compound is electrolyzed continuously or once or several times for specific periods of time, in particular 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes, with the aid of an electrolysis device. Method according to Claim 5 or 6, characterized in that the electrolysis device, in particular designed as an electrolysis cell, is designed as a separate device which is separate from a washing machine or dishwasher and which is operated with its own power source. Process according to Claim 5, characterized in that the amine or hydroxylamine corresponding to formula I, II or III, in particular when using a conventional flushing device, has an electrolysis device upstream of the inlet into the chamber of a washing machine happens, especially in aqueous solution or slurry flowing through an electrolytic cell. Use according to claim 4 or method according to one of claims 5 to 8, characterized in that the concentration of the compound in the aqueous washing or cleaning liquor is 0.05 mmol / l to 5 mmol / l, in particular 0.1 mmol / l to 2 mmol / l. Use or method according to one of Claims 4 to 9, characterized in that it is carried out at pH values in the range from pH 2 to pH 12, in particular from pH 4 to pH 11.