EP3875567B1 - Nitroxide compounds in detergents or cleaning compositions - Google Patents

Description

The present invention relates to the use of certain nitroxide compounds for enhancing the cleaning performance of washing 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 disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature; 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 oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, which are able to provide peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous proposals have been made, especially from the substance classes of N- or O-acyl compounds, for example reactive esters, multiply acylated alkylenediamines, in particular N,N,N',N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate (NOBS), sodium isononanoyloxybenzenesulfonate, 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 even at temperatures of around 60 °C, essentially the same effects occur as with the peroxide liquor alone at 95 °C.

In the effort 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 become increasingly important in recent years.

At these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There has therefore been no lack of efforts to develop more effective activators for this temperature range. The use of transition metal compounds, particularly transition metal complexes, to increase the oxidizing power of peroxygen compounds or atmospheric oxygen in detergents and cleaning agents has also been proposed on various occasions. The transition metal compounds proposed for this purpose include 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 power, particularly at low temperatures, or, even if they do have sufficient bleaching power, they can cause 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.

The patent application DE 44 45 088 A1 relates to bleaching systems comprising oxidizing agents, oxidoreductases, mediators which may contain N-oxy function, and free amines of the mediators. The patent application US 2007/0079446 A1 discloses hindered nitroxyl and hydroxylamine compounds as stabilizers in household products, among others. The patent US 6 274 186 B1 relates to a purification process using a combination of cyclic nitroxyl compound and hypohalite. From the international patent application WO 2013/017476 A1 It is known that bleach-active species which have a bleach-enhancing effect can be produced from sterically hindered N-hydroxy compounds such as 1-hydroxy-2,2,6,6-tetramethylpiperidine by means of electrolysis. From the international patent application WO 2015/162008 A1 It is known that the effect 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 further enhanced when an anionic substituent is present.

Surprisingly, it was found that nitroxides of certain 5-membered N-heterocyl compounds are superior to the known piperidine derivatives.

in denen X für ONa, NH₂ oder NHRY, R für eine C_2-3-Alkylengruppe, Y für OH, NR¹R² oder N⁺R¹R²R³ Z^-, R¹, R², und R³ unabhängig voneinander für H oder einen C_1-2-Alkylrest und Z für ein Anion, insbesondere ein Halogenid wie Chlorid, Bromid und lodid, Halogenat wie Chlorat und Iodat, ½ Sulfat und/oder ½ 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 general formula I or II,

in which X is ONa, NH ₂ or NHRY, R is a C _2-3 alkylene group, Y is OH, NR ¹ R ² or N ⁺ R ¹ R ² R ³ Z ^- , R ¹ , R ² , and R ³ independently of one another are H or a C _1-2 alkyl radical and Z is an anion, in particular a halide such as chloride, bromide and iodide, halogenate such as chlorate and iodate, ½ sulfate and/or ½ methyl sulfate and mixtures thereof, for enhancing the cleaning performance of washing and cleaning agents, in particular against bleachable and/or protein-containing soiling, in aqueous, in particular 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 or II in an aqueous, particularly surfactant-containing, liquor.

When Y in the compounds of general formula I or II is OH, R is preferably a 1,2-ethylene group. When Y in the compounds of general formula I or II is NR ¹ R ² or N ⁺ R ¹ R ² R ³ Z, R is preferably a 1,3-propylene group.

The 3-pyrroline and pyrolidine nitroxide radical compounds of the general formulas I and II can be prepared electrochemically by anodic oxidation from the corresponding hydroxylamines or amines. The latter serve as starting materials for the synthesis of the nitroxides by chemical oxidation. The preparation of the amines is generally known and 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, by 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 produced from the amines by chemical oxidation. An overview of various methods for such oxidation is given, for example, Geffken, D.; Koellner, MA "Hydroxylamines", Science of Synthesis (2008), 40b, 937-1082 .

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 within the scope 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 to generate the compounds of the general formulas I, II or III electrochemically in situ from these precursor compounds, as explained in more detail below. The presence of a corresponding electrolysis device has the advantage in connection with the use according to the invention and the method according to the invention that the compounds formed from the nitroxide radical compounds during the oxidation of the substrate desired according to the invention can be electrochemically converted back into the nitroxide radical compounds. The compound of the general formula I, or II or its precursor compound can thus be used in a substoichiometric amount based on the substrate.

The bleach-active compound of the general formula I, II or III can be produced in a simple manner by subjecting an aqueous system containing the precursor compound to 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 thereby started by which the radical compound of the general formula I, II or III is formed. Without wishing to be bound to this theory, it is conceivable that the radical species thus produced reaches the dirt with the aqueous liquor, withdraws an electron from the soil and thereby a less colored and/or more water-soluble and/or water-dispersible material is formed from the soil. The precursor compound is regenerated from the bleach-active species by reaction with the soil, its substrate, so that a reversible redox system is present.

The nitroxides of the general formula !, II or III can also be oxidized electrochemically by a one-electron oxidation into the corresponding oxoammonium salts. These are even stronger oxidizing agents and can remove an electron from the soiling more efficiently than the nitroxides themselves. These would be regenerated from the oxoammonium salts during the reaction with the soiling. This would create a second redox system consisting of nitroxide-oxoamonium salt. The laws of the electrochemical oxidation of nitroxides into 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 specific periods of time, for example 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes, the duration of the electrolysis being able to be adapted to the degree of soiling of the laundry; it is irrelevant whether the precursor compound itself was initially used or whether it was formed after the first reaction cycle from the compound of general formula I or II initially used. The bleach-active compound of general formula I or II can also be produced by passing the precursor compound, particularly when using a conventional rinsing device, through an electrolysis device before being admitted to the chamber of a washing machine or dishwasher, in particular by flowing in an aqueous solution or slurry through an electrolysis cell which can be installed in the feed line inside or outside the machine. Alternatively, it is possible to allow other active substances, such as enzymes, to perform their function uninfluenced at the beginning of the process and only later to start the bleaching effect of the compound of general formula I or II 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 chamber, preferably outside the washing drum in a drum washing machine. The device can be a permanently installed component of the washing machine or dishwasher or a separate component. In a further embodiment of the invention, the electrolysis device, which is designed in particular as an electrolysis cell, is designed as a separate device that is separate from a washing machine or dishwasher and is operated with its own power source, for example a battery (e-bleach ball). A further 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 supplied service water) that contains the precursor compound, for example when the e-bleach ball is in the washing drum of a washing machine during the washing process. The electrolysis device is advantageously designed as two half-cells connected by an ion-permeable membrane, each half-cell being equipped with an electrode.

A particular advantage is that the activity of the bleach can be easily modified by regulating the current intensity, depending on the degree of soiling or the fabric, if required. Textile washing processes do not cause any damage to the textile treated in this way that goes beyond the extent that occurs when using commercially available products.

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 or II, including the precursor compounds that 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 method according to the invention are each preferably carried out at temperatures in the range from 10 °C to 95 °C, in particular 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 implemented particularly easily by using a washing or cleaning agent which contains the compound of the general formula I or II or the precursor compound with 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 or II or the precursor compound in addition to The invention therefore further relates to detergents which contain the usual compatible ingredients, in particular a surfactant. 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 contain, in particular, peroxygen-containing bleach. However, it is particularly advantageous that both bleach and conventional bleach activator can be dispensed with, so that as a result a smaller amount of washing or cleaning agent needs to be used per washing or cleaning cycle. In a preferred embodiment, an agent according to the invention is therefore free of bleach and conventional bleach activator. In a preferred embodiment, an agent according to the invention is water-containing and liquid.

Agents according to the invention preferably contain 0.05% by weight to 10% by weight, in particular 0.1% by weight to 5% by weight, of the compound of general formula I or II or of the precursor compound with N-oxide or hydroxylamine function. When using an agent according to the invention, the cleaning-enhancing effect of the compound of general formula I or II obtained from the precursor compound can, if desired, be eliminated by completely omitting electrolysis if, for example, it is to be dispensed with in the case of only slightly 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 present in particular as powdered solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known ingredients that are usual in such agents, in addition to the compound to be used according to the invention. The agents according to the invention can in particular contain builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, color transfer inhibitors, graying inhibitors, crease-reducing polymeric active ingredients and shape-retaining polymeric active ingredients, bleaching agents, bleach activators, and other auxiliary substances, such as optical brighteners, foam regulators, dyes and fragrances.

The agents according to the invention can contain one or more surfactants, whereby anionic surfactants, non-ionic surfactants and mixtures thereof are particularly suitable, but cationic and/or amphoteric surfactants can also be included. Suitable non-ionic 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 C atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, 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 with regard to the alkyl part, as well as alkylphenols with 5 to 12 C atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those that 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 with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. Useful sulfate-type surfactants include the salts of the sulfuric acid semiesters 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 C atoms in the alkyl part, alkanesulfonates with 12 to 18 C atoms, as well as olefinsulfonates with 12 to 18 C atoms, which are formed during the reaction of corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the disinfectants according to the invention as well as cleaning agents according to the invention preferably contain 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight of 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 Hydroxyalkyltrialkyl-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, in particular when they are intended for the treatment of textiles, can contain as cationic active substances with 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 conventional anions in the type and number necessary for charge balancing, and these can be selected from the anionic surfactants as well as halides, for example. In preferred embodiments of the present invention, hydroxyalkyltrialkylammonium compounds, in particular C _12-18 alkyl(hydroxyethyl)dimethylammonium compounds, and preferably their halides, in particular chlorides, are used as cationic surfactants. An agent according to the invention preferably contains 0.5% to 25% by weight, in particular 1% to 15% by weight, of 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 builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(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 such as dextrins, and/or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality polymerized in. The relative molecular mass 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, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular mass of 50,000 to 100,000. Suitable, although 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 proportion of acid is 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 the 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 is particularly preferred, and/or a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a relative molecular mass of between 1,000 g/mol and 200,000 g/mol. Other preferred copolymers are those which have acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, in particular for the production of liquid agents. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal 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% to 8% by weight. Amounts close to the stated upper limit are preferably used in paste-like or liquid, in particular water-containing, agents according to the invention.

Particularly suitable water-soluble inorganic builder materials are polymeric alkali phosphates, which can be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Particularly suitable water-insoluble, water-dispersible inorganic builder materials are crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents in particular from 1% to 5% by weight. Among these, preference is given to crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X. Amounts close to the upper limit mentioned are preferably used in solid, particulate agents. Suitable aluminosilicates in particular do not contain any particles with a grain 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 generally in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali 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 SiO2 of less than 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 Na2O:SiO2 of 1:2 to 1:2.8. As crystalline silicates, which can be present alone or in a mixture with amorphous silicates, preferably crystalline layered silicates of the general formula Na ₂ Si _x O _2x+1 y H ₂ O are used, in which x, the so-called module, is a number from 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 layered silicates are those in which x in the general formula mentioned takes on the values 2 or 3. In particular, both ß- and δ-sodium disilicates (NazSizOs 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, produced 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 sodium layer silicate with a modulus of 2 to 3 is used, such 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 agents according to the invention, a granular compound of alkali silicate and alkali carbonate is used, such as is commercially available 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.

Builder substances are preferably contained in the washing or cleaning agents according to the invention 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 builder substances other than those that are water-soluble, i.e. all builder substances contained in the agent are combined in the "block" characterized in this way, with the exception of the amounts of substances that may be commercially available in small quantities as impurities or stabilizing additives in the other ingredients of the agents. The term "water-soluble" is to be understood to mean that the builder block dissolves without residue at the concentration that results from the amount of the agent containing it used under normal conditions. Preferably, 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 are contained in the agents according to the invention. This is preferably composed of the components

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

The quantities refer to the entire washing or cleaning product. This also applies to all subsequent 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), a preferred embodiment of agents according to the invention contains 15% to 25% by weight of alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate, and up to 5%, in particular 0.5% to 2.5% by weight of citric acid and/or alkali citrate. In an alternative embodiment of agents according to the invention, component a) contains 5% to 25% by weight, in particular 5% to 15% by weight of citric acid and/or alkali citrate and up to 5%, in particular 1% to 5% by weight of alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate. If both alkali carbonate and alkali hydrogen carbonate are present, component a) preferably contains 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 the compositions according to the invention contains 1% to 5% by weight of alkali silicate with a modulus in the range from 1.8 to 2.5.

With regard to component c), a preferred embodiment of agents according to the invention contains 0.05% by weight to 1% by weight of phosphonic acid and/or alkali phosphonate. 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 dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, aminotris(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. Among these, the homopolymers of acrylic acid and, among these, those with an average molecular weight in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.

Enzymes that can be used in the products are those from the class of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases, oxidases and peroxidases as well as 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 ^® . Enzymatic active substances 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 enzymes used, if any, can be adsorbed on carriers 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, with particular preference being given to using enzymes stabilized against oxidative degradation.

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

Peroxygen compounds which may be present in the agents, but which can preferably be omitted in agents intended for use in the process according to the invention, are particularly suitable organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and/or persilicate. Hydrogen peroxide can also be produced with the aid 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. Particular preference is given to using alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain 3% to 10% by weight of hydrogen peroxide. 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, conventional bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and/or conventional transition metal complexes which activate the bleach can be used. The optional component of the bleach activators, which is present in particular in amounts of 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds usually used, 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 anhydrides, especially phthalic anhydride, carboxylic esters, especially sodium isononanoylphenolsulfonate, and acylated sugar derivatives, especially pentaacetylglucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators can be coated with coating substances or granulated in a known manner to avoid interaction with the per compounds during storage, with tetraacetylethylenediamine granulated with the aid of carboxymethylcellulose with average grain sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/or trialkylammonium acetonitrile prepared in particle form being 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 entire agent.

The organic solvents that can be used in the detergents according to the invention, especially when they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and mixtures thereof and the ethers that can be derived from the above-mentioned classes of compounds. Such water-miscible solvents are preferably present in the detergents according to the invention in amounts of no more than 30% by weight, especially from 6% by weight to 20% by weight.

To set a desired pH value that does not arise automatically from the mixture of the other components, the agents according to the invention can contain system- and environmentally-compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are preferably contained in the agents according to the invention in amounts of no more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Examples of soil-removing polymers, which are often referred to as "soil release" agents or as "soil repellents" because of their ability to make the treated surface, for example the fiber, dirt-repellent, are non-ionic or cationic cellulose derivatives. The soil-removing polymers, which are particularly polyester-active, include copolyesters of 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 soil-removing polyesters that are preferably used include those compounds that are formally accessible by esterification of two monomer parts, where the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR ¹¹ -) _a OH, which can also be present as a polymeric diol H-(O-(CHR ¹¹ -) _a ) _b OH. Ph here means an o-, m- or p-phenylene radical which has 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, the polyesters obtainable from these contain both monomer diol units -O-(CHR ¹¹ -) _a O- and polymer diol units -(O-(CHR ¹¹ -) _a ) _b O-. 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 underlying the residue Ph 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, instead of the monomer HOOC-Ph-COOH, small amounts, in particular not more than 10 mol% based on the amount 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. 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 alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids being possible as end groups. 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 color 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 textile washing 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 protected against bending, kinking, pressing and squeezing. are sensitive across the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylol amides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

The purpose 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, usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferred, for example in amounts of 0.1 to 5% by weight, based on the agent.

The agents can contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable examples are 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 carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the above-mentioned optical brighteners can also be used.

Particularly when used in machine washing or cleaning processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different 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, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bis-stearylethylenediamide are particularly preferred.

In the agents according to the invention, active ingredients for preventing tarnishing of silver objects, so-called silver corrosion inhibitors, can also be used. Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally 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 present in one of the oxidation states II, III, IV, V or VI.

The production of solid agents 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. To produce agents according to the invention with increased bulk density, in particular in the range from 650 g/l to 950 g/l, a process comprising an extrusion step is preferred. Washing, cleaning or disinfecting agents in the form of aqueous solutions or solutions containing other conventional 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 agents for the machine cleaning of dishes in particular, these are in tablet form.

Examples Example 1: Preparation of compounds essential to the invention

A: Production of T1

Nitroxide T1 was manufactured according to the instructions of: Krishna, Murali C.; DeGraff, William; Hankovszky, Olga H.; Sar, Cecilia P.; Kalai, Tamas; Jeko, Jozsef; Russo, Angelo; Mitchell, James B.; Hideg, Kalman, Journal of Medicinal Chemistry (1998), 41(18), 3477-3492 .

B: Production of T2

Nitroxide T2 was manufactured according to the instructions of: Wright, Karen; Dutot, Laurence; Wakselman, Michel; Mazaleyrat, Jean-Paul; Crisma, Marco; Formaggio, Fernando; Toniolo, Claudio, Tetrahedron (2008), 64(19), 4416-4426 .

C: Production of T3

Nitroxide T3 was manufactured according to the instructions of: Krishna, Murali C.; DeGraff, William; Hankovszky, Olga H.; Sar, Cecilia P.; Kalai, Tamas; Jeko, Jozsef; Russo, Angelo; Mitchell, James B.; Hideg, Kalman, Journal of Medicinal Chemistry (1998), 41(18), 3477-3492 .

D: Production of T4

To a solution of 5.37 g (0.020 mol) of nitroxide T3 in 25 ml of dry acetonitrile were added 3.03 g (0.024 mol) of dimethyl sulfate and the solution was left to stand at room temperature for 22 hours. The acetonitrile was then distilled off at 50 °C / 20 mbar. The oily residue was stirred with 100 ml of tert-butyl methyl ether for 1 hour. The ether phase was then decanted off and the residue was dried at 50 °C / 0.5 mbar. 7.8 g of nitroxide T4 were obtained as a red resin.

E: Production of T5

4.0126 g (21.547 mmol) of 3-carboxy-2,2,5,5-tetramethylpyrrolidin-1-oxyl (purchased from ABCR GmbH, Germany) and 1.8102 g (21.547 mmol) of sodium hydrogen carbonate were placed in 50 ml of water. The mixture was stirred at 50 °C for 30 minutes. The resulting clear solution was evaporated on a rotary evaporator at 50 °C/20 mbar. 4.46 g of the nitroxide T5 were obtained as a red powder.

Q: Manufacturing of T6

Nitroxide T6 was manufactured according to the instructions of: Sosnovsky, George; Cai, Zhen-wie, Journal of Organic Chemistry (1995), 60(11), 3414-18 .

G: Production of T7

Under an argon atmosphere, 10.01 g (0.050 mol) of 3-methoxycarbonyl-2,2,5,5-tetramethyl-3-pyrrolidin-1-oxyl (prepared according to Hatano, Bunpei et al.: Heterocycles, 81(2), 349-356; 2010 ), 2.088 g (0.015 mol) 1,5,7-triazabicyclo[4.4.0]dec-5-ene and 6.131 g (0.060 mol) 3-dimethylamino-1-propylamine and stirred for 18 hours at 75 °C. Subsequent chromatography on silica gel with methanol + 5% triethylamine and crystallization from dichloromethane yielded 10.0 g of the nitroxide T7 as orange crystals, mp 86.9 - 90.5°C

H: Production of T8

The nitroxide T8 was produced in analogy to T4 from T7 as a red powder.

Example 2: Bleaching performance

An electrolysis device consisting of two half-cells connected by an ion-permeable membrane was used. Each half-cell was equipped with a stainless steel electrode. The electrolysis device was filled with a 2 millimolar aqueous solution of T1 or T2 prepared in Example 1 or, for comparison, 1-hydroxy-2,2,6,6-tetramethylpiperidine (V1), each of which also contained 0.1 mol/l Na ₂ SO _4. To quantify the bleaching effect, flat pieces of cotton textile that had previously been stained with the standardized stains A1 (baby food carrot/potato), A2 (bell pepper), A3 (blueberry juice) or A4 (tea) shown in the table below were placed in the anode half-cell. Electrolysis was carried out at 20 °C and pH 6 with a potential difference of 2 V over a period of 2 hours, with convection in the solution being supported by the use of a magnetic stirrer. The cotton textile pieces were then removed, rinsed with water, dried in the absence of light and measured with a color spectrometer in the L·a·b color space. The values obtained in this way and those of the soiled, unwashed textile pieces are listed in Table 2 below. Table 2: L,a,b - values A1; L/a/b A2; L/a/b A3; L/a/b A4; L/a/b unwashed 88.96 / 2.65 / 22.68 72.9 / 26.56 / 37.46 31.71 / 22.66 / -0.87 74.08 / 7.11 / 24.51 T1 31.5 / 3.1 / 6.4 92.6 / 1.2 / 5.3 84.9/3.7/11.1 82.4 / 3.9 / 14.4 T2 32.4 / 3.1 / 4.9 92.6 / 1.7 / 4.5 88.2 / 2.4 / 12.7 85.7 / 3.0 / 15.4 V1 32.2 / 3.1 / 6.0 92.5 / 0.18 / 8.3 85.4 / 4.4 / 13.7 82.8 / 4.1 / 16.5

It can be seen that T1 showed a significantly lower tendency towards unwanted discoloration of the stains (lower b-value) compared to V1. T2 also showed a lower tendency towards unwanted discoloration (lower b-value) coupled with a significantly better cleaning effect (higher L-value).

Claims (10)

1. A washing or cleaning agent, characterized in that it contains a compound of general formula I or II,

   

   in which X represents ONa, NH₂ or NHRY, R represents a C_2-3 alkylene group, Y represents OH, NR¹R² or N⁺R¹R²R³ Z^-, R¹, R² and R³ represent, independently of one another, H or a C_1-2 alkyl functional group, and Z- represents an anion, or contains an amine or hydroxylamine corresponding to formula I or II.
2. The agent according to claim 1, characterized in that it contains 0.05 wt.% to 10 wt.%, in particular 0.1 wt.% to 5 wt.%, of the compound and/or is free of bleach and conventional bleach activator.
3. The agent according to claim 1 or 2, characterized in that it is water-containing and liquid.
4. A use of compounds of general formula I or II,

   

   in which X represents ONa, NH₂ or NHRY, R represents a C_2-3 alkylene group, Y represents OH, NR¹R² or N⁺R¹R²R³ Z^-, R¹, R² and R³ represent, independently of one another, H or a C_1-2 alkyl functional group, and Z^- represents an anion, or of an N-oxide or hydroxylamine corresponding to formula I or II in an aqueous, in particular surfactant-containing, liquor for improving the cleaning performance of washing and cleaning agents.
5. A method for washing textiles or for cleaning hard surfaces, in particular for the automatic cleaning of dishes, using a compound of general formula I or II,

   

   in which X represents ONa, NH₂ or NHRY, R represents a C_2-3 alkylene group, Y represents OH, NR¹R² or N⁺R¹R²R³ Z^-, R¹, R² and R³ represent, independently of one another, H or a C_1-2 alkyl functional group, and Z^- represents an anion, or an amine or hydroxylamine corresponding to formula I or II, in order to improve the cleaning performance of washing and cleaning agents in an aqueous, in particular surfactant-containing, liquor.
6. The method according to claim 5, characterized in that the liquor containing the compound is electrolyzed continuously or one or more times for certain periods, in particular 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes, by means of an electrolysis device.
7. The method according to claim 5 or 6, characterized in that the electrolysis device, in particular designed as an electrolytic cell, is designed as a separate device separated from a washing machine or dishwasher, which separate device is operated with its own power source.
8. The method according to claim 5, characterized in that the amine or hydroxylamine corresponding to formula I or II, in particular when using a conventional dispensing apparatus, passes through an electrolysis device before entering the chamber of a washing machine, in particular flows through an electrolysis cell in aqueous solution or slurry.
9. The use according to claim 4 or the 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.
10. The use or method according to one of claims 4 to 9, characterized in that said use or method is carried out at pH values in the range from pH 2 to pH 12, in particular from pH 4 to pH 11.