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EP3875566B1 - 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
EP3875566B1
EP3875566B1 EP20161451.8A EP20161451A EP3875566B1 EP 3875566 B1 EP3875566 B1 EP 3875566B1 EP 20161451 A EP20161451 A EP 20161451A EP 3875566 B1 EP3875566 B1 EP 3875566B1
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EP
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Prior art keywords
weight
acid
monosubstituted
iii
functional group
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German (de)
English (en)
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EP3875566A1 (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 EP20161451.8A priority Critical patent/EP3875566B1/fr
Priority to PCT/EP2021/055019 priority patent/WO2021175769A1/fr
Publication of EP3875566A1 publication Critical patent/EP3875566A1/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

Definitions

  • the present invention relates to the use of certain nitroxide compounds to enhance the cleaning performance of detergents and cleaning agents against soiling, washing and cleaning methods using such compounds, and detergents and cleaning agents which contain these compounds.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to liberate 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.degree.
  • the oxidizing effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, which are able to produce peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which there are numerous proposals, especially from the N- or O-acyl compound classes, for example reactive ones Esters, polyacylated alkylenediamines, in particular N,N,N',N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate (NOBS), sodium isononanoyloxybenzen
  • transition metal compounds in particular 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, 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, especially at low temperature, sometimes do not have sufficient bleaching power or, with sufficient bleaching power, there is undesirable damage to the colors of the material to be washed or cleaned and possibly even the material itself, for example of the textile fibers.
  • An object of the invention is accordingly the use of compounds of the type of 4-imidazolidinone nitroxide radical compounds of the general formula I, II or III, in which R 1 , R 2 , R 3 and R 4 independently represent a methyl or ethyl radical, R 5 represents H, SO 2 CH 3 or a SO 3 - -monosubstituted C 2-5 -alkyl radical with a charge-balanced number of cations, in particular ammonium, sodium and/or potassium ions, R 6 is a trialkylammonium, or pyridinium-monosubstituted C 3-5 -alkyl radical with a charge-balancing number of anions, in particular halides such as chloride, bromide and iodide, halogenates such as chlorate and iodate, sulfate and/or methyl sulfate and mixtures thereof, to enhance the cleaning performance of detergents and Cleaning agents, in particular for bleachable and/or proteinaceous soil
  • the invention further provides a method for washing textiles and a method for cleaning hard surfaces, in particular for machine cleaning of dishes, using a compound of the general formula I, II or III in an aqueous liquor, in particular one containing surfactants.
  • R 1 and R 2 are preferably not both ethyl radicals and R 3 and R 4 are not both ethyl radicals.
  • R 5 and R 6 are preferably linear and the substituents are located on the C atom of the radicals which is furthest away from the N atom of the 4-imidazolidinone ring.
  • nitroxide radical compounds of the general formulas I, II and III can also be prepared electrochemically by anodic oxidation from the corresponding hydroxylamines or amines. The latter serve as starting materials for the synthesis of nitroxides by chemical oxidation.
  • the preparation of the amines is generally known and is described in example 1 of 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 prepared 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 compounds of the general formula I, II or III exhibit an efficient bleaching effect on colored stains, for example those containing dyes containing anthocyanin, for example from berries, or dyes from the carrotenoid group, for example from tomatoes or carrots. Their use does not lead to unwanted discolouration, for example of textile dyes.
  • the preparation of the active bleaching compound of the general formula I, II or III can be carried out in a simple manner by subjecting an aqueous system, which contains the precursor compound, to an electrical potential difference between at least two electrodes, which is preferably 0.2 V to 5 V, is in particular 1 V to 3 V, so that the precursor compound emits an electron and thereby a reaction sequence is started by which the radical compound of the general formula I, II or III is formed.
  • the radical species generated in this way gets to the dirt with the aqueous liquor, withdraws an electron from the soiling and thereby results in a less colored and/or more water-soluble and/or water-dispersible material from the soiling .
  • the precursor compound regenerates from the bleach-active species by reacting with the soil, its substrate, so that a reversible redox system is present.
  • the nitroxides of the general formula I, II or III can also be oxidized electrochemically by a one-electron oxidation to give the corresponding oxoammonium salts. These are even stronger oxidizing agents and can remove an electron from the soiling even more efficiently than the nitroxides themselves. These would be reformed from the oxoammonium salts when they reacted with the soiling. Thus, a second redox system consisting of nitroxide oxoaammonium salt would be present.
  • Electron transfer reactions of nitroxides or oxoammonium salts have been extensively studied, e.g Zhang, FaLiu, You Cheng: “Electron transfer reactions of piperidine aminoxyl radicals", Chin. science Bull. (2010), 55 (25), 2760-2783 .
  • the liquor containing the precursor compound continuously or one or more times for specific periods of time, for example 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or 60 minutes, with the electrolysis time being adapted to the degree of soiling of the laundry can be; it is irrelevant whether the precursor compound itself was used initially or whether it was formed after the first reaction cycle from the compound of the general formula I, II or III initially used.
  • the production of the active bleaching compound of the general formula I, II or III is also possible in that the precursor compound, in particular when using a conventional flushing device, before the inlet into the chamber of a washing machine or dishwasher passes an electrolysis device, in particular in aqueous solution or slurry flows through an electrolysis cell which can be fitted in the supply line inside or outside the machine.
  • active ingredients for example enzymes, perform their work unaffected at the beginning of the process and only later to start the bleaching effect of the compound of the general formula I, II or III by switching on the electrolysis device.
  • the electrolysis device is installed inside a washing machine or dishwasher in the flooded area of the washing or cleaning room, 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 service water supplied), which contains the precursor compound, for example if the e-bleach ball during the washing process located in the drum of a washing machine.
  • the electrolysis device is advantageously designed as two half-cells connected by means of an ion-permeable membrane, each half-cell being equipped with an electrode.
  • the activity of the bleach can be easily modified by controlling the current strength, if desired as a function of the degree of soiling or the fabric.
  • the current strength if desired as a function of the degree of soiling or the fabric.
  • the concentration of the compound of the general formula I, II or III, including the precursor compounds which can be electrochemically converted into them, in the aqueous washing or cleaning liquor is 0.05 mmol/l to 5 mmol/l , in particular 0.1 mmol/l to 2 mmol/l.
  • the use according to the invention and the method according to the invention are each preferably carried out at temperatures in the range from 10.degree. C. to 95.degree. C., in particular 20.degree. C. to 40.degree.
  • the use according to the invention and the method according to the invention are each preferably carried out at pH values in the range from pH 2 to pH 12, in particular from pH 4 to pH 11.
  • the use according to the invention and the method according to the invention can be particularly simple by using a washing or cleaning agent which contains the compound of the general formula I, II or III or the precursor compound with an amine or hydroxylamine function.
  • a washing or cleaning agent which contains the compound of the general formula I, II or III or the precursor compound with an amine or hydroxylamine function.
  • Detergents for cleaning textiles and detergents for cleaning hard surfaces, in particular dishwashing detergents and, among these, preferably those for machine use, which contain a compound of the general formula I, II or III or the precursor compound in addition to conventional ingredients compatible therewith, in particular a surfactant, are therefore further objects of the invention.
  • a composition according to the invention can additionally also contain, in particular, a peroxygen-containing bleaching agent.
  • a particular advantage is that both bleaching agents and conventional bleaching activators can be dispensed with, with the result that a smaller amount of detergent or cleaning agent has to be used per washing or cleaning cycle.
  • a composition according to the invention is therefore free of bleach and conventional bleach activator.
  • an agent according to the invention contains water and is liquid.
  • the cleaning-enhancing effect of the compound of the general formula I, II or III obtained from the precursor compound can be eliminated if desired by completely omitting the electrolysis if, for example, it is to be dispensed with in the case of only lightly soiled laundry or extremely bleach-sensitive textiles. The consumer therefore only needs a single detergent to wash non-sensitive, generally white, and sensitive, generally colored textiles.
  • the agents according to the invention which can be in the form of, in particular, powdered solids, in post-compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known ingredients customary in such agents in addition to the compound to be used according to the invention.
  • the agents according to the invention can in particular contain builders, 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, bleaching activators, and other auxiliaries such as optical brighteners, foam regulators, dyes and fragrances.
  • the agents according to the invention can contain one or more surfactants, with anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable, but cationic and/or amphoteric surfactants can also be present.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and/or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
  • Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali metal ions as cations.
  • Soaps that can be used are preferably the alkali metal salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the usable surfactants of the sulfate type include the salts of the sulfuric acid half esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants with a low degree of ethoxylation.
  • the surfactants of the sulfonate type that can be used include linear alkyl benzene sulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from 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 from 8% by weight to 30% by weight, while the disinfectants according to the invention and cleaning agents according to the invention preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight, of surfactants.
  • the cationic surfactants have the usual anions in the type and number necessary for charge equalization, and these can also be selected from the anionic surfactants in addition to, for example, halides.
  • hydroxyalkyl-trialkyl-ammonium compounds in particular C 12-18 -alkyl(hydroxyethyl)dimethylammonium compounds, and preferably their halides, in particular chlorides, are used as cationic surfactants.
  • a composition according to the invention preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of cationic surfactant.
  • a composition 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, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and polyaspartic acid, polyphosphonic acids, especially 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 mixed polymers of these, which can also contain small amounts of polymerizable substances without carb
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, and 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 molecular weight 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 the 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, especially from (meth)acrylic acid away.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred, and/or a derivative of an allyl sulfonic acid substituted in the 2-position with an alkyl or aryl radical.
  • Such polymers generally have a relative molecular weight of between 1000 g/mol and 200,000 g/mol.
  • Further preferred copolymers are those which contain 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, particularly 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% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular aqueous, compositions according to the invention.
  • water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples 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.
  • crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials.
  • the crystalline detergent grade sodium aluminosilicates particularly zeolite A, P and optionally X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • suitable aluminosilicates do not have any particles with a particle 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 usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates which can be used as builders in the detergents according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8.
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x+1 y H 2 O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x has the value 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 y H 2 O
  • a granular compound of alkali metal silicate and alkali metal carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • alkali metal 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.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.
  • the detergents or cleaning agents according to the invention preferably contain builder substances in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • the water-soluble builder block contains at least 2 of components b), c) and d) in amounts greater than 0% by weight.
  • component a) in a preferred embodiment of agents according to the invention, 15% by weight to 25% by weight is alkali metal carbonate, which can be replaced at least in part by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and/or alkali citrate.
  • component a) contains 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight, of citric acid and/or alkali metal citrate and up to 5% by weight, in particular 1% by weight to 5% by weight of alkali metal carbonate, at least some of which can be replaced by alkali metal bicarbonate. If both alkali metal carbonate and alkali metal bicarbonate are present, component a) preferably has alkali metal carbonate and alkali metal bicarbonate in a weight ratio of from 10:1 to 1:1.
  • a preferred embodiment of agents according to the invention contains 1% by weight to 5% by weight of alkali metal 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 metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkyl phosphonic acids which can also have several phosphonic acid groups (so-called polyphosphonic acids).
  • hydroxy and/or aminoalkylphosphonic acids and/or their alkali metal salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane -1,1-diphosphonic acid, amino-tris(methylenephosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • alkali metal salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane -1,1-diphosphonic acid, amino-tris(methylenephosphonic acid), N,N,N',N'-ethylenediaminet
  • 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, in turn, those with an average molar mass in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.
  • Enzymes that can be used in the agents are those from the class of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases, oxidases and peroxidases and mixtures thereof, for example proteases such as BLAP® , Optimase® , Opticlean® , Maxacal® , Maxapem® , Alcalase® , Esperase® , Savinase® , Durazym® and/or Purafect ® OxP, amylases such as Termamyl ® , Amylase-LT ® , Maxamyl ® , Duramyl ® and/or Purafect ® OxAm, lipases such as Lipolase ® , Lipomax ® , Lumafast ® and/or Lipozym ® , cellulases such as Celluzyme ® and /or
  • 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.
  • Any enzymes used can be adsorbed on carriers and/or embedded in encapsulating substances in order to protect them against premature inactivation. They are preferably present in the detergents, cleaning agents and disinfectants according to the invention in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, enzymes stabilized against oxidative degradation being particularly preferably used will.
  • the agent contains 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, of anionic and/or nonionic surfactant, up to 60% by weight, in particular 5 40% by weight builder substance and 0.2% to 2% by weight enzyme selected from the group consisting of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof .
  • Peroxygen compounds which may be present in the detergents, but which can preferably be omitted in detergents intended for use in the process according to the invention, include in particular organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic substances which release hydrogen peroxide under the washing conditions Salts such as perborate, percarbonate and/or persilicate. Hydrogen peroxide can also be generated with the help of an enzymatic system, ie an oxidase and its substrate.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • Alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions containing 3% by weight to 10% by weight of hydrogen peroxide is particularly preferably used.
  • 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 detergents or cleaning agents according to the invention.
  • customary bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and/or customary bleach-activating transition metal complexes can be used.
  • the component of the bleach activators which is optionally present, in particular in amounts of from 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds which are customarily used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pen
  • the bleach activators may have been coated with encapsulating substances or granulated in a known manner, granulated tetraacetylethylenediamine having an average grain size of 0.01 mm to 0.8 mm, granulated 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/or trialkylammoniumacetonitrile formulated in particulate form is particularly preferred.
  • Such bleach activators if present, are present in detergents or cleaning agents, preferably in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the detergent as a whole.
  • the organic solvents that can be used in the agents 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 , in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned.
  • Such water-miscible solvents are preferably present in the detergents according to the invention in not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali metal hydroxides.
  • the detergents according to the invention preferably contain no more than 20% by weight of such pH regulators, in particular from 1.2% by weight to 17% by weight.
  • Polymers capable of releasing dirt which are often referred to as "soil release” active substances or as “soil repellents” because of their ability to make the treated surface, for example the fiber, dirt-repellent, are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release polymers 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 preferably used dirt-removing polyesters include those compounds that are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO-(CHR 11 -) a OH, which can also be used as a polymeric diol H-(O-(CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which carries 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof can
  • R 11 is hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the polyesters obtainable from these preferably contain both monomer diol units -O-(CHR 11 -) a O ⁇ - and polymer diol units -(O-(CHR 11 -) a ) b O-.
  • 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 in the polymer diol units 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-removing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000
  • the acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred.
  • HOOC-Ph-COOH monomer small proportions, in particular not more than 10 mol % based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the soil-removing polyester.
  • these include, for example, alkylene and alkenylenedicarboxylic 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 molar mass in the range from 1000 to 6000.
  • these polyesters can also be end-capped, suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids.
  • Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have a molecular weight of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, are preferably used alone or in combination with cellulose derivatives.
  • the color transfer inhibitors suitable for use in detergents according to the invention 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 detergents 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 mixtures thereof, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction.
  • anti-crease agents include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular from the textile fibers 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 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 preferably used, for example in amounts of 0.1 to 5% by weight, based on the detergent.
  • the agents can contain optical brighteners, including, in particular, derivatives of diaminostilbene disulfonic acid or their alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds that instead of morpholino - carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, or4- (4-chlorostyryl)-4'-(2-sulfostyryl)diphenyls. Mixtures of the aforementioned optical brighteners can also be used.
  • foam inhibitors are soaps of natural or synthetic origin which have a high proportion of C 18 -C 24 fatty acids.
  • suitable non-surfactant foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanated silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also used with advantage, for example those made of 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 bistearylethylenediamide are particularly preferred.
  • Agents according to the invention can also contain active ingredients to prevent objects made of silver from tarnishing, so-called silver corrosion inhibitors.
  • 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 in one of the oxidation states II, III, IV, V or VI available.
  • 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 having an extrusion step is preferred.
  • Detergents, cleaning agents or disinfectants in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added to an automatic mixer as such or as a solution.
  • agents for cleaning dishes in particular in a machine, these are in the form of tablets.
  • Table 1 Overview of compounds essential to the invention T1 T10 T2 T11 T3 T12 T4 T13 T5 T14 T6 T15 T7 T16 T8 T17 T9
  • 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 each filled with a 2 millimolar aqueous solution of T1 or T2 prepared in Example 1 or, for comparison, of 1-hydroxy-2,2,6,6-tetramethylpiperidine (V1), which also each contained 0.1 mol/l Na 2 SO 4 contained filled.
  • V1 1-hydroxy-2,2,6,6-tetramethylpiperidine
  • flat pieces of cotton textile were placed in the anode half-cell, which had previously been provided with the standardized soiling A1 (blueberry juice) or A2 (blackberry juice) given in the table below. Electrolysis was carried out at 20° C.
  • T1 and T2 showed a significantly lower tendency to unwanted discoloration of the soiling (lower b value) compared to C1.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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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, Il ou III,
    Figure imgb0038
     dans lesquelles R1, R2, R3 et R4 représentent indépendamment les uns des autres un radical méthyle ou éthyle, R5 représente H, SO2CH3 ou un radical alkyle en C2-5 monosubstitué par SO3 - et comportant un certain nombre de cations d'équilibrage de charge, R6 représente un radical alkyle en C3-5 monosubstitué par le trialkylammonium,
    Figure imgb0039
     ou le pyridinium et comportant un certain nombre d'anions d'équilibrage de charge, ou un N-oxyde ou une hydroxylamine correspondant à la formule I, Il ou III.
  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, Il ou III,
    Figure imgb0040
     dans lesquelles R1, R2, R3 et R4 représentent indépendamment les uns des autres un radical méthyle ou éthyle, R5 représente H, SO2CH3 ou un radical alkyle en C2-5 monosubstitué par SO3 - et comportant un certain nombre de cations d'équilibrage de charge, R6 représente un radical alkyle en C3-5 monosubstitué par le trialkylammonium,
    Figure imgb0041
     ou le pyridinium et comportant un certain nombre d'anions d'équilibrage de charge, ou d'une amine ou d'une hydroxylamine correspondant à la formule I, Il ou III dans un bain aqueux, en particulier contenant des tensioactifs, pour l'augmentation 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, à l'aide d'un composé de formule générale I, Il ou III,
    Figure imgb0042
     dans lesquelles R1, R2, R3 et R4 représentent indépendamment les uns des autres un radical méthyle ou éthyle, R5 représente H, SO2CH3 ou un radical alkyle en C2-5 monosubstitué par SO3 - et comportant un certain nombre de cations d'équilibrage de charge, R6 représente un radical alkyle en C3-5 monosubstitué par le trialkylammonium,
    Figure imgb0043
     ou le pyridinium et comportant un certain nombre d'anions d'équilibrage de charge, ou d'un N-oxyde ou d'une hydroxylamine correspondant à la formule I, Il ou III pour l'augmentation 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 l'amine ou l'hydroxylamine correspondant à la formule I, Il ou III, en particulier lors de l'utilisation d'un dispositif de rinçage courant, 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 une 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 œuvre à des valeurs de pH dans la plage de pH 2 à pH 12, en particulier de pH 4 à pH 11.
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DE4445088A1 (de) * 1994-12-16 1996-06-20 Ibv Ind Bioverfahren Mehrkomponentenbleichsystem aus Oxidoreductasen, Oxidationsmitteln, Mediatoren und Mediator-verstärkenden oder recyclierenden Verbindungen zur Verwendung mit waschaktiven Substanzen
NL1003225C2 (nl) * 1996-05-29 1997-12-03 Heineken Tech Services Werkwijze voor het reinigen van apparatuur die toegepast is bij het brouwen van bier.
WO1998030601A2 (fr) 1997-01-10 1998-07-16 E.I. Du Pont De Nemours And Company Procede de controle de la structure et du poids moleculaires d'un polymere
WO2005042828A2 (fr) * 2003-11-03 2005-05-12 Ciba Specialty Chemicals Holding Inc. Produits de soins corporels, produits menagers, textiles et tissus stabilises
DE102011080099A1 (de) 2011-07-29 2013-01-31 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit elektrochemisch aktivierbarer Mediatorverbindung
DE102014207673A1 (de) 2014-04-24 2015-10-29 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit elektrochemisch aktivierbarer anionischer Mediatorverbindung

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