WO2021175770A1 - Composés nitroxyde dans des agents de lavage ou de nettoyage - Google Patents

Composés nitroxyde dans des agents de lavage ou de nettoyage Download PDF

Info

Publication number
WO2021175770A1
WO2021175770A1 PCT/EP2021/055021 EP2021055021W WO2021175770A1 WO 2021175770 A1 WO2021175770 A1 WO 2021175770A1 EP 2021055021 W EP2021055021 W EP 2021055021W WO 2021175770 A1 WO2021175770 A1 WO 2021175770A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
acid
cleaning
washing
compound
Prior art date
Application number
PCT/EP2021/055021
Other languages
German (de)
English (en)
Inventor
Boray TORUN
Peter Schmiedel
Bent Rogge
Roland Ettl
Peter Nesvadba
Original Assignee
Henkel Ag & Co. Kgaa
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Ag & Co. Kgaa, Basf Se filed Critical Henkel Ag & Co. Kgaa
Publication of WO2021175770A1 publication Critical patent/WO2021175770A1/fr

Links

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

  • Nitroxide compounds in detergents or cleaning agents are Nitroxide compounds in detergents or cleaning agents
  • the present invention relates to the use of certain nitroxide compounds for enhancing the cleaning performance of detergents and cleaning agents against soiling, washing and cleaning processes using such compounds, and washing and cleaning agents which contain these compounds.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidizing effect of these substances depends strongly on the temperature in dilute solutions; For example, with H2O2 or perborate in alkaline bleaching liquors, a sufficiently fast bleaching of soiled textiles is only achieved at temperatures above about 80 ° C.
  • bleach activators which are able to deliver peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous proposals, especially from the classes of N- or O-acyl compounds, for example reactive ones esters, polyacylated alkylenediamines, in particular N, N, N ', N' -Tetraacetylethylendiamin (TAED), acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazine, urazoles diketo piperazine, sulfuryl amides and cyanurates, also Carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate (NOBS), sodium isononanoyl
  • transition metal compounds in particular transition metal complexes, to increase the oxidizing power of peroxygen compounds or even atmospheric oxygen in detergents and cleaning agents has also been proposed on various occasions.
  • 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.
  • 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 capacity, especially at low temperatures, or, if the bleaching capacity is sufficient, undesirable damage to the colors of the material to be washed or cleaned and possibly even to the material itself, for example the textile fibers.
  • the invention accordingly relates to the use of compounds of the general formula I or II, in which X is ONa, NH2 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 for H or a Ci-2-alkyl radical and Z for an anion, in particular a halide such as chloride, bromide and iodide, halogenate such as chlorate and iodate, 1 sulfate and / or 1 methyl sulfate and mixtures thereof, to enhance the cleaning performance of washing and cleaning agents, especially for bleachable and / or protein-containing soiling, in an aqueous, especially 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, especially surfactant-containing liquor.
  • R is preferably a 1,2-ethylene group. If Y in the compounds of the general formula I or II is NR 1 R 2 or N + R 1 R 2 R 3 Z, R is preferably a 1,3-propylene group.
  • the 3-pyrroline and pyrolidine nitroxide radical compounds of the general formulas I and II can be prepared electrochemically by anodic oxidation from the corresponding hydroxylamines or amines. The latter serve as starting materials for the synthesis of nitroxides by chemical oxidation.
  • the preparation of the amines is generally known and is described in Example 1 of the nitroxides I, II and III.
  • Anodic oxidation of sterically hindered amines to nitroxides is also known and has been described, for example, by Kagan, E. Sh .; Zhukova, I. Yu .; Yanilkin, V. V .; Morozov, V.I .; Nastapova, N. V .; Kashparova, V. P .; Kashparov, I.I .: "Mechanism of electrochemical oxidation of spatially hindered amines of 2,2,6,6-tetramethylpiperidine series" Russian Journal of Electrochemistry (2011), 47 (11), 1199-1204.
  • the hydroxylamines can be made from the amines by chemical oxidation.
  • An overview of various methods for such oxidation is given, for example, by Geffken, D .; Koellner, M. A. "Hydroxylamines", Science of Synthesis (2008), 40b, 937-1082.
  • the presence of a corresponding electrolysis device has the advantage that the compounds formed from the nitroxide radical compounds during the oxidation of the substrate desired according to the invention can be converted electrochemically back into the nitroxide radical compounds.
  • the compound of the general formula I or II or or its precursor compound can be used in a sub-stoichiometric amount based on the substrate.
  • the bleach-active compound of the general formula I, II or III can be produced in a simple manner by adding an aqueous system which contains the precursor compound, an electrical potential difference between at least two electrodes, which is preferably 0.2 V to 5 V, in particular 1 V to 3 V, so that the precursor compound releases an electron and a reaction sequence is started by which the radical compound of the general formula I, II or III is formed.
  • the free radical species generated in this way gets to the dirt with the aqueous liquor, removes an electron from the dirt and thus a less colored and / or more water-soluble and / or water-dispersible material emerges from the dirt .
  • the precursor compound is formed from the bleach-active species through reaction with the soil, its substrate, so that a reversible redox system is present.
  • nitroxides of the general formula I, II or III can, however, also be oxidized electrochemically by means of a one-electron oxidation into the corresponding oxoammonium salts. These are even stronger oxidizing agents and can remove an electron from the dirt even more efficiently than the nitroxides themselves. These would regress from the oxoammonium salts during the reaction with the dirt. This would result in a second redox system consisting of nitroxide-oxoaamonium salt.
  • Electron transfer reactions of nitroxides or oxoammonium salts have been studied in detail, for example by Zhang, FaLiu, You Cheng: “Electron transfer reactions of piperidine aminoxyl radicals", Chin. May be. Bull. (2010), 55 (25), 2760-2783.
  • the electrolysis time being adapted to the degree of soiling of the laundry can be; It is irrelevant here whether the precursor compound itself was used at the beginning or whether it was formed after the first reaction cycle from the compound of the general formula I or II used initially.
  • the production of the bleach-active compound of the general formula I or II is also possible in that the precursor compound, in particular when using a conventional flushing device, passes through an electrolysis device before the inlet into the chamber of a washing machine or dishwasher, in particular an electrolysis cell in aqueous solution or slurry flows through, which can be attached in the feed line inside or outside the machine.
  • the electrolysis device is installed inside a washing machine or dishwasher in the flooded area of the washing or cleaning room, in the case of a drum washing machine preferably outside the washing drum.
  • the device can be a permanently installed component of the washing machine or dishwasher or a separate component.
  • the electrolysis device in particular designed as an electrolysis cell, is designed in a further embodiment of the invention as a separate device which is separate from a washing machine or dishwasher and which is operated with its own power source, for example a battery (e-bleach ball).
  • Another embodiment according to the invention consists in integrating the electrolysis device into an additional water circuit within the machine.
  • the electrodes of the electrolysis device can come into contact with the electrolyte (the washing or cleaning liquor, or the industrial water supplied) that contains the precursor compound, for example if the e-bleach ball is during the washing process located in the drum of a washing machine.
  • the electrolysis device is advantageously designed as two half-cells connected by means of an ion-permeable membrane, each half-cell being equipped with an electrode.
  • the activity of the bleach can be easily modified by regulating the current strength, if desired depending on the degree of soiling or the fabric.
  • the current strength in the case of textile washing processes, there is no damage to the textile treated in this way that goes beyond the extent that occurs when using commercially available agents.
  • the concentration of the compound of the general formula I or II 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 Is 0.1 mmol / L to 2 mmol / L.
  • the use according to the invention and the process according to the invention are each preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C.
  • the use according to the invention and the method according to the invention are each preferably carried out at pH values in the range from pH 2 to pH 12, in particular from pH 4 to pH 11.
  • the use according to the invention and the process 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 an 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 an amine or hydroxylamine function.
  • Detergents for cleaning textiles and agents for cleaning hard surfaces, in particular dishwashing detergents and, among these, preferably those for machine use which contain a compound of the general formula I or II or the precursor compound The invention therefore furthermore relates to the usual ingredients that are compatible therewith, in particular a surfactant.
  • an agent according to the invention can additionally also contain, in particular, peroxygen-containing bleaching agent.
  • an agent according to the invention is therefore free from 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 or II obtained from the precursor compound can, if desired, be switched off by completely omitting the electrolysis if it is to be dispensed with, for example, with only lightly soiled laundry or extremely bleach-sensitive textiles. The consumer therefore only needs a single detergent to wash insensitive, usually white, and sensitive, usually colored textiles.
  • the agents according to the invention which can be in particular pulverulent solids, in compacted particle form, as homogeneous solutions or suspensions, can in principle contain all known ingredients that are customary in such agents, in addition to the compound to be used according to the invention.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, graying inhibitors, crease-reducing polymeric active ingredients and shape-retaining polymeric active ingredients, bleaches, Contain bleach activators, and other auxiliaries such as optical brighteners, foam regulators, dyes and fragrances.
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but cationic and / or amphoteric surfactants can also be included.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • N-alkylamines vicinal diols, fatty acid esters and fatty Acid amides
  • alkylphenols with 5 to 12 carbon atoms in the alkyl radical
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Soaps that can be used are preferably the alkali salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the sulfate-type surfactants which can be used include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the sulfonate-type surfactants that can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed when corresponding monoolefins are reacted with sulfur trioxide, and alpha-sulfo fatty acid esters, which are formed during the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are contained in the cleaning agents or detergents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the disinfectants according to the invention as well as cleaning agents according to the invention preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight surfactants.
  • the cationic surfactants have customary anions in the type and number necessary for charge balancing, it being possible for these to be selected from the anionic surfactants in addition to, for example, halides.
  • the cationic surfactants used are hydroxyalkyl trialkylammonium compounds, in particular C 2 -C 8 -alkyl (hydroxyethyl) dimethylammonium compounds, and preferably their halides, in particular chlorides.
  • An agent according to the invention preferably contains 0.5% by weight to 25% by weight, in particular 1% by weight to 15% by weight, of a cationic surfactant.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular aminotrisine-1-methylene-phosphonic acid, in particular aminotrisine-1-methylenephosphonic acid, in particular aminotrisine-1-methylenephosphonic acid, in particular aminotrisine-1-methylenephosphonic acid, in particular aminotrisine-1-methylenephosphonic acid, in particular aminotrisine-1-methylenephosphonic acid, in particular aminotrisine-1-methylenephosphonic acid, in particular aminotrisine-1-methylene-phosphonic acid, in particular aminotrisine-1-methylene-phosphonic acid,
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based in each case on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-C8 carboxylic acid and preferably from a C 3 C 4 monocarboxylic acid, in particular (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C4- Ce dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulphonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a relative molecular weight between 1,000 g / mol and 200,000 g / mol.
  • Further preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can, in particular for the production of liquid agents, be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali salts.
  • Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the upper limit mentioned are preferably used in pasty or liquid, in particular water-containing, agents according to the invention.
  • Particularly suitable water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • the water-insoluble, water-dispersible inorganic builder materials used are in particular crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and, in liquid agents, in particular from 1% by weight to 5% by weight. %, used.
  • the crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no 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 said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to S1O2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: Si0 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x 0 2x + i y H2O, in the x, the so-called module, 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 sheet silicates are those in which x is in the general formula mentioned takes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 05 y H2O) are preferred.
  • Virtually anhydrous crystalline alkali silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, which are produced from amorphous alkali silicates, can also be used in agents according to the invention.
  • a crystalline layered sodium silicate with a module of 2 to 3 is used, as can be produced from sand and soda.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • alkali aluminosilicate, in particular zeolite is also present as an additional builder substance
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the detergents or cleaning agents according to the invention preferably contain builder substances in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • an agent according to the invention has a water-soluble builder block.
  • builder block is intended to express that the agents do not contain any other builder substances than those that are water-soluble, that is, all of the builder substances contained in the agent are summarized in the “block” characterized in this way, with the amounts of Substances are excluded that may be contained in small amounts in the other ingredients of the agents as impurities or stabilizing additives.
  • water-soluble should be understood to mean that the builder block dissolves without residue at the concentration that results from the amount of agent containing it under the usual conditions.
  • the agents according to the invention preferably contain at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block.
  • This is preferably composed of the components a) 5 wt .-% to 35 wt .-% citric acid, alkali citrate and / or alkali carbonate, which can also be at least partially replaced by alkali hydrogen carbonate, b) up to 10 wt .-% alkali silicate with a module in the range from 1.8 to 2.5, c) up to 2 wt.% phosphonic acid and / or alkali metal phosphonate, and d) up to 10 wt. or purchase detergents.
  • the water-soluble building 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 of alkali metal carbonate, which can be at least partially replaced by alkali metal hydrogen carbonate, and up to 5% by weight, in particular 0.5% by weight, are Contain% to 2.5% by weight citric acid and / or alkali citrate.
  • 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight of citric acid and / or alkali citrate and up to 5% by weight, in particular are used as component a) 1% by weight to 5% by weight alkali metal carbonate, which can be at least partially replaced by alkali metal hydrogen carbonate. If both alkali carbonate and alkali hydrogen carbonate are present, component a) preferably has alkali carbonate and alkali hydrogen carbonate in a weight ratio of 10: 1 to 1: 1.
  • a preferred embodiment of agents according to the invention contains 1% by weight to 5% by weight alkali metal silicate with a modulus in the range from 1.8 to 2.5.
  • phosphonic acid and / or alkali metal phosphonate are contained.
  • Phosphonic acids are also understood to mean optionally substituted alkylphosphonic acids which can also have several phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali metal salts, such as, for example, dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenyl-methanediphosphonic acid, 1 -Hydroxy-ethane-1, 1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine-tetrakis- (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures .
  • alkali metal salts such as, for example, dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenyl-methanediphosphonic acid, 1 -Hydroxy-ethane-1
  • 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 molar mass in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.
  • Enzymes that can be used in the agents are those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases, oxidases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean® , Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and / or Carezyme®.
  • proteases such as BLAP®, Optimas
  • Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable.
  • the optionally used enzymes can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the washing, cleaning and disinfecting agents according to the invention preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, enzymes stabilized against oxidative degradation being particularly preferred will.
  • the agent contains 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5 % By weight to 40% by weight builder substance and 0.2% by weight to 2% by weight enzyme, selected from proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof .
  • enzyme selected from 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 in particular organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and, under the washing conditions, hydrogen peroxide donating inorganic salts, such as perborate, percarbonate and / or persilicate, into consideration. Hydrogen peroxide can also be generated with the help 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.
  • Alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions containing 3% by weight to 10% by weight hydrogen peroxide are particularly preferably used.
  • 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.
  • present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example poly-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well Carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenol sulfonate, and acylated sugar derivatives
  • N- or O-acyl compounds for example poly-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydr
  • the bleach activators can have been coated or granulated in a known manner with coating substances to avoid interaction with the per compounds during storage, with the aid of carboxymethyl cellulose granulated tetraacetylethylenediamine with average particle sizes of 0.01 mm to 0.8 mm, granulated 1.5 Diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or trialkylammonium acetonitrile packaged in particulate form is 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 total agent.
  • the organic solvents that can be used in the agents according to the invention include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the cited classes of compounds.
  • Such water-miscible solvents are present in the detergents according to the invention preferably not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the agents according to the invention can contain systemic 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 contain mineral acids, especially sulfuric acid, or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are contained in the agents according to the invention preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Polymers with the ability to release soil which are often referred to as "soil release” active ingredients or, because of their ability to make the treated surface, for example the fiber, soil-repellent, as “soil repellents", are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil-releasing polymers include copolyesters made from dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • the preferably used dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR 11 -) a OH, which is also known as a polymer Diol H- (0- (CHR 11 -) a ) b0H may be present.
  • the polyesters obtainable from these preferably contain both monomer diol units -0- (CHR 11 -) a 0- and polymer diol units - (0- (CHR 11 -) a ) b0-.
  • the acid on which the remainder Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred.
  • small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be contained in the soil-releasing polyester instead of the HOOC-Ph-COOH monomer.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2- dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000. If desired, these polyesters can also be end-capped, with possible end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids.
  • Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 are preferred, used alone or in combination with cellulose derivatives.
  • the dye transfer inhibitors suitable for use in the inventive agents for washing textiles include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the agents according to the invention for use in laundry can contain anti-crease agents, since textile fabrics, in particular made of rayon, wool, cotton and mixtures thereof, can tend to crease because the individual fibers prevent bending, kinking, pressing and squeezing are sensitive across the grain.
  • anti-crease agents include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid esters or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the task of graying inhibitors is to keep the dirt detached from the hard surface and in particular from the textile fiber suspended in the liquor.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use starch derivatives other than those mentioned above, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, for example in amounts of 0.1 to 5% by weight, based on the agent, are preferably used.
  • the agents can contain optical brighteners, among these in particular derivatives of diaminostilbene disulphonic acid or their alkali metal salts.
  • optical brighteners among these in particular derivatives of diaminostilbene disulphonic acid or their alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds which, instead of morpholino -Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type can be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
  • Mixtures of the aforementioned optical brighteners can also be used.
  • foam inhibitors In particular when used in machine washing or cleaning processes, it can be advantageous to add customary foam inhibitors to the agents.
  • Soaps of natural or synthetic origin which have a high proportion of C18-C24 fatty acids, are suitable as foam inhibitors.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylenediamides.
  • Mixtures of various foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular carrier substance which is soluble or dispersible in water. Mixtures of paraffins and bistearyl ethylene diamide are particularly preferred.
  • active ingredients it is also possible to use active ingredients to avoid tarnishing of objects made of silver, so-called silver corrosion inhibitors.
  • Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, 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 named Metals are present in one of the oxidation states II, III, IV, V or VI.
  • compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation.
  • a method comprising an extrusion step is preferred.
  • Detergents, cleaning agents or disinfectants in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. In a preferred embodiment of means for the particularly machine cleaning of dishes, these are in the form of tablets.
  • the Nitroxid 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.
  • the Nitroxid 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.
  • the Nitroxid T6 was manufactured according to the instructions of: Sosnovsky, George; Cai, Zhen-wie, Journal of Organic Chemistry (1995), 60 (11), 3414-18.
  • T8 Manufacture of T8
  • 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 means of an ion-permeable membrane was used. Each half-cell was equipped with a stainless steel electrode. The electrolysis device was each with a 2 millimolar aqueous solution of T1 or T2 prepared in Example 1 or, for comparison, of 1-hydroxy-2,2,6,6-tetramethylpiperidine (V1), which also contained 0.1 mol / l Na 2 SC > 4 contained, filled.
  • V1 1-hydroxy-2,2,6,6-tetramethylpiperidine
  • two-dimensional pieces of cotton textile were placed in the anode half-cell, which had previously been provided with the standardized soiling A1 (baby food carrots / potatoes), A2 (paprika), A3 (blueberry juice) or A4 (tea) specified in the table below.
  • T1 compared to V1 had a significantly lower tendency to unwanted discoloration of the spots (lower b value).
  • T2 also showed a lower tendency towards undesired discoloration (lower b-value) paired with a significantly better cleaning effect (higher L-value).

Landscapes

  • 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)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'objectif de l'invention est d'améliorer la puissance de nettoyage d'agents de lavage et de nettoyage, notamment vis-à-vis de taches blanchissables, tout en évitant tout endommagement du textile traité avec lesdits agents de lavage et de nettoyage. A cet effet, on utilise des composés radicalaires de type 3-pyrroline-et pyrolidine-nitroxyde qui peuvent éventuellement être produits in situ par voie électrochimique à partir des N-oxydes ou hydroxylamines correspondants.
PCT/EP2021/055021 2020-03-06 2021-03-01 Composés nitroxyde dans des agents de lavage ou de nettoyage WO2021175770A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20161455.9A EP3875567B1 (fr) 2020-03-06 2020-03-06 Composés de nitroxyde dans des détergents ou des nettoyants
EP20161455.9 2020-03-06

Publications (1)

Publication Number Publication Date
WO2021175770A1 true WO2021175770A1 (fr) 2021-09-10

Family

ID=69960217

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/055021 WO2021175770A1 (fr) 2020-03-06 2021-03-01 Composés nitroxyde dans des agents de lavage ou de nettoyage

Country Status (2)

Country Link
EP (1) EP3875567B1 (fr)
WO (1) WO2021175770A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6274186B1 (en) * 1996-05-29 2001-08-14 Heineken Technical Services B.V. Method for cleaning items in particular filters, used during foodstuff production
US20070079446A1 (en) * 2003-11-03 2007-04-12 Lupia Joseph A Stabilized body care products, household products, textiles and fabrics
WO2013017476A1 (fr) 2011-07-29 2013-02-07 Henkel Ag & Co. Kgaa Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement
WO2015162008A1 (fr) 2014-04-24 2015-10-29 Henkel Ag & Co. Kgaa Lessive ou détergent comprenant un composé médiateur anionique activable par voie électrochimique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US6274186B1 (en) * 1996-05-29 2001-08-14 Heineken Technical Services B.V. Method for cleaning items in particular filters, used during foodstuff production
US20070079446A1 (en) * 2003-11-03 2007-04-12 Lupia Joseph A Stabilized body care products, household products, textiles and fabrics
WO2013017476A1 (fr) 2011-07-29 2013-02-07 Henkel Ag & Co. Kgaa Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement
WO2015162008A1 (fr) 2014-04-24 2015-10-29 Henkel Ag & Co. Kgaa Lessive ou détergent comprenant un composé médiateur anionique activable par voie électrochimique

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
FISH, JUDITH R.SWARTS, STEVEN G.SEVILLA, MICHAEL D.MALINSKI, TADEUSZ: "Electrochemistry and spectroelectrochemistry of nitroxyl free radicals", JOURNAL OF PHYSICAL CHEMISTRY, vol. 92, no. 13, 1988, pages 3745 - 51
GEFFKEN, D.KOELLNER, M. A.: "Hydroxylamines", SCIENCE OF SYNTHESIS, vol. 40b, 2008, pages 937 - 1082
HATANO, BUNPEI ET AL., HETEROCYCLES, vol. 81, no. 2, 2010, pages 349 - 356
KAGAN, E. SH.ZHUKOVA, I. YU.YANILKIN, V. V.MOROZOV, V. I.NASTAPOVA, N. V.KASHPAROVA, V. P.KASHPAROV, I. I.: "Mechanism of electrochemical oxidation of spatially hindered amines of 2,2,6,6-tetramethylpiperidine series", RUSSIAN JOURNAL OF ELECTROCHEMISTRY, vol. 47, no. 11, 2011, pages 1199 - 1204
KRISHNA, MURALI C.DEGRAFF, WILLIAMHANKOVSZKY, OLGA H.SAR, CECILIA P.KALAI, TAMASJEKO, JOZSEFRUSSO, ANGELOMITCHELL, JAMES B.HIDEG, , JOURNAL OF MEDICINAL CHEMISTRY, vol. 41, no. 18, 1998, pages 3477 - 3492
SOSNOVSKY, GEORGECAI, ZHEN-WIE, JOURNAL OF ORGANIC CHEMISTRY, vol. 60, no. 11, 1995, pages 3414 - 18
WRIGHT, KARENDUTOT, LAURENCEWAKSELMAN, MICHELMAZALEYRAT, JEAN-PAULCRISMA, MARCOFORMAGGIO, FERNANDOTONIOLO, CLAUDIO, TETRAHEDRON, vol. 64, no. 19, 2008, pages 4416 - 4426
ZHANG, FALIUYOU CHENG: "Electron transfer reactions of piperidine aminoxyl radicals", CHIN. SCI. BULL., vol. 55, no. 25, 2010, pages 2760 - 2783

Also Published As

Publication number Publication date
EP3875567B1 (fr) 2024-05-01
EP3875567A1 (fr) 2021-09-08

Similar Documents

Publication Publication Date Title
EP2440641B1 (fr) Dioxyde de manganèse nanoparticulaire
EP2802644B1 (fr) Acylhydrazones utilisées comme renforçateurs de blanchiment
EP2737042B2 (fr) Procédé de lavage ou de nettoyage avec un composé médiateur activable électrochimiquement
DE102009001692A1 (de) Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
DE102009001691A1 (de) Wasch- oder Reinigungsmittel mit gegebenenfalls in situ erzeugtem bleichverstärkendem Übergangsmetallkomplex
EP0902832A1 (fr) Esters d'enol s'utilisant comme activateurs de blanchiment pour detergents et nettoyants
EP3134500B1 (fr) Lessive ou détergent comprenant un composé médiateur anionique activable par voie électrochimique
EP1747259A1 (fr) Agent de lavage comprenant un complexe de metal de transition qui renforce le blanchiment et est produit eventuellement in situ
EP1749084B1 (fr) Combinaison de renforcement d'agents de blanchiment a utiliser dans des produits de lavage et de nettoyage
EP2504419B1 (fr) Agent de lavage ou de nettoyage comprenant un complexe de métaux de transition activateur de blanchiment, produit in situ
EP2504418B1 (fr) Agent de lavage ou de nettoyage comprenant un complexe de métaux de transition activateur de blanchiment, éventuellement produit in situ
EP3875567B1 (fr) Composés de nitroxyde dans des détergents ou des nettoyants
EP3875566B1 (fr) Composés de nitroxyde dans des détergents ou des nettoyants
EP3167038A1 (fr) Procédé de lavage d'un nouveau type utilisant un composé médiateur électrochimiquement activable
WO2021099243A1 (fr) Activateur de blanchiment ayant un groupe cationique et produit détergent ou nettoyant le contenant
EP4061918A1 (fr) Activateur de blanchiment ayant un groupe cationique et produit détergent ou nettoyant le contenant
EP3095845A1 (fr) Acylhydrazones en tant qu'agents actifs renforçant le blanchiment
EP0866116A2 (fr) Bisacylacetal dérivés comme activateurs de blanchiment pour les compositions détergentes à lessive
EP0879875A2 (fr) Oxa-esters d'acides carboxyliques comme activateurs de blanchiment pour compositions détergentes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21707728

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21707728

Country of ref document: EP

Kind code of ref document: A1