EP3875567B1 - Composés de nitroxyde dans des détergents ou des nettoyants - Google Patents

Composés de nitroxyde dans des détergents ou des nettoyants Download PDF

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Publication number
EP3875567B1
EP3875567B1 EP20161455.9A EP20161455A EP3875567B1 EP 3875567 B1 EP3875567 B1 EP 3875567B1 EP 20161455 A EP20161455 A EP 20161455A EP 3875567 B1 EP3875567 B1 EP 3875567B1
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Prior art keywords
acid
washing
cleaning
weight
compound
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German (de)
English (en)
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EP3875567A1 (fr
Inventor
Boray TORUN
Peter Schmiedel
Bent Rogge
Roland Ettl
Peter Nesvadba
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP20161455.9A priority Critical patent/EP3875567B1/fr
Priority to PCT/EP2021/055021 priority patent/WO2021175770A1/fr
Publication of EP3875567A1 publication Critical patent/EP3875567A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

Definitions

  • 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.
  • 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 isononanoy
  • 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 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.
  • 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, 1 ⁇ 2 sulfate and/or 1 ⁇ 2 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.
  • a halide such as chloride, bromide and iodide
  • halogenate such as chlorate and iodate
  • 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.
  • R is preferably a 1,2-ethylene group.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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.
  • active substances such as enzymes, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an agent according to the invention can additionally contain, in particular, peroxygen-containing bleach.
  • an agent according to the invention is therefore free of bleach and conventional bleach activator.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m. 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.
  • crystalline silicates which can be present alone or in a mixture with amorphous silicates
  • 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.
  • both ß- and ⁇ -sodium disilicates NazSizOs y H 2 O
  • 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.
  • 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.
  • a granular compound of alkali silicate and alkali carbonate is used, such as is commercially available under the name Nabion ® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10:1.
  • 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.
  • the water-soluble builder block contains at least 2 of components b), c) and d) in amounts greater than 0% by weight.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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-tetraki
  • 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.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and/or maleic acid.
  • 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
  • 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.
  • 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.
  • 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.
  • 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 cati
  • 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.
  • 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 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.
  • 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.
  • 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
  • b is a number from 1 to 300.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • anti-crease agents 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.
  • graying inhibitors 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.
  • 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.
  • silver corrosion inhibitors active ingredients for preventing tarnishing of silver objects
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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 .
  • 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 .
  • Nitroxide T6 was manufactured according to the instructions of: Sosnovsky, George; Cai, Zhen-wie, Journal of Organic Chemistry (1995), 60(11), 3414-18 .
  • the nitroxide T8 was produced in analogy to T4 from T7 as a red powder.
  • 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.
  • V1 1-hydroxy-2,2,6,6-tetramethylpiperidine
  • 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.
  • 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).

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Claims (10)

  1. Agent de lavage ou de nettoyage, caractérisé en ce qu'il contient un composé de formule générale I ou II,
    Figure imgb0012
     dans lesquelles X représente ONa, NH2 ou NHRY, R représente un groupe alkylène en C2-3, Y représente OH, NR1R2 ou N+R1R2R3 Z-, R1, R2 et R3 représentent, indépendamment les uns des autres, H ou un radical alkyle en C1-2 et Z- représente un anion, ou une amine ou hydroxylamine correspondant à la formule I ou II.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient 0,05 % en poids à 10 % en poids, en particulier 0,1 % en poids à 5 % en poids, du composé et/ou est exempt d'agent de blanchiment et d'activateur de blanchiment conventionnel.
  3. Agent selon la revendication 1 ou 2, caractérisé en ce qu'il contient de l'eau et est liquide.
  4. Utilisation de composés de formule générale I ou II,
    Figure imgb0013
     dans lesquelles X représente ONa, NH2 ou NHRY, R représente un groupe alkylène en C2-3, Y représente OH, NR1R2 ou N+R1R2R3 Z-, R1, R2 et R3 représentent, indépendamment les uns des autres, H ou un radical alkyle en C1-2 et Z- représente un anion, ou une N-oxyde ou hydroxylamine correspondant à la formule I ou II, dans un bain aqueux, en particulier contenant des tensioactifs, pour l'amélioration de la performance de nettoyage d'agents de lavage et de nettoyage.
  5. Procédé permettant le lavage de textiles ou le nettoyage de surfaces dures, en particulier permettant le nettoyage en machine de vaisselle, en utilisant un composé de formule générale I ou II,
    Figure imgb0014
     dans lesquelles X représente ONa, NH2 ou NHRY, R représente un groupe alkylène en C2-3, Y représente OH, NR1R2 ou N+R1R2R3 Z-, R1, R2 et R3 représentent, indépendamment les uns des autres, H ou un radical alkyle en C1-2 et Z- représente un anion, ou une amine ou hydroxylamine correspondant à la formule I ou II, pour l'amélioration de la performance de nettoyage d'agents de lavage et de nettoyage dans un bain aqueux, en particulier contenant des tensioactifs.
  6. Procédé selon la revendication 5, caractérisé en ce que le bain contenant le composé est électrolysé à l'aide d'un dispositif d'électrolyse en continu ou une ou plusieurs fois pendant des périodes déterminées, en particulier 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes ou 60 minutes.
  7. Procédé selon la revendication 5 ou 6, caractérisé en ce que le dispositif d'électrolyse réalisé en particulier en tant que cellule d'électrolyse est réalisé en tant que dispositif séparé d'un lave-linge ou d'un lave-vaisselle qui fonctionne avec sa propre source de courant.
  8. Procédé selon la revendication 5, caractérisé en ce que, en particulier lors de l'utilisation d'un dispositif de rinçage courant, l'amine ou hydroxylamine correspondant à la formule I ou II passe dans un dispositif d'électrolyse avant l'entrée dans la chambre d'un lave-linge, en particulier traverse une cellule d'électrolyse dans une solution ou suspension aqueuse.
  9. Utilisation selon la revendication 4 ou procédé selon l'une des revendications 5 à 8, caractérisé en ce que la concentration du composé dans le bain de lavage ou de nettoyage aqueux est de 0,05 mmol/l à 5 mmol/l, en particulier de 0,1 mmol/l à 2 mmol/l.
  10. Utilisation ou procédé selon l'une des revendications 4 à 9, caractérisé en ce qu'il est mis en oeuvre à des valeurs de pH dans la plage allant de pH 2 à pH 12, en particulier de pH 4 à pH 11.
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