EP0944707B2 - Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents - Google Patents

Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents Download PDF

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Publication number
EP0944707B2
EP0944707B2 EP97951944A EP97951944A EP0944707B2 EP 0944707 B2 EP0944707 B2 EP 0944707B2 EP 97951944 A EP97951944 A EP 97951944A EP 97951944 A EP97951944 A EP 97951944A EP 0944707 B2 EP0944707 B2 EP 0944707B2
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weight
detergent
formula
compound corresponding
alkyl
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EP97951944A
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EP0944707B1 (fr
EP0944707A2 (fr
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Christian Nitsch
Rainer Jeschke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/39—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
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • 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
    • 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

Definitions

  • the present invention relates to dishwashing detergents the certain acetonitrile derivatives as activators for in particular inorganic peroxygen compounds for bleaching colored stains Dishes included.
  • Inorganic peroxygen compounds especially hydrogen peroxide and solid peroxygen compounds. which dissolve in water releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate. have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides.
  • bleach activators for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides.
  • Triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates in addition to carboxylic acid anhydrides, especially phthalic anhydride, carboxylic esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl-glucose. have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.
  • Japanese Patent Application JP 1-198 700 discloses dishwashing compositions which contain ammonium acetonitrile derivatives whose quaternary nitrogen atom carries two C 1-3 alkyl groups and one C 1-22 alkyl group.
  • European patent application EP 0 464 880 discloses the use of similar substances having two C 1-4 alkyl or hydroxyalkyl groups and a C 1-24 alkyl, alkelnyl or alkyl ether group.
  • European Patent Application EP 0 303 520 discloses bleaching textile detergents containing ammonium acetonitrile derivatives whose quaternary nitrogen atom is part of an optionally substituted pyridine ring.
  • EP-A 0 790 244 relates to ammonium nitriles and their use as bleach activators.
  • the ammonium nitriles used have the general structure shown there on page 2, lines 40 to 50, wherein R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 carbon atoms, this ring in addition to Nitrogen atom may contain 1 or 2 oxygen or nitrogen atoms instead of carbon atoms.
  • ammonium nitriles are used as bleach activators in bleaching washes Detergents used. You can et al be used as a dishwasher cleaner,
  • Another problem particularly with automatic dishwashing detergents is the need. in such agents to incorporate corrosion inhibitors for silverware, in particular when the means in More recently, conventional oxygen-based bleaching or oxidizing agents are included.
  • Silver can when cleaning with sulfur-containing substances that are dissolved or dispersed in the rinse water, react, because When cleaning dishes in household dishwashers are leftovers and thus, among other things Mustard, peas, egg and other sulfur-containing compounds such as mercapto amino acids introduced into the rinsing liquor.
  • the much higher temperatures during the mechanical rinsing and the longer contact times with the sulphurous food residues favor the tarnishing of silver compared to manual rinsing.
  • the intensive cleaning process in the dishwasher the silver surface is also completely degreased and thus more sensitive to chemical influences.
  • Such active oxygen bleaching agents become. usually together with bleach activators. especially in modern low alkaline machine dishwashing detergents of the new generation of cleaners are used.
  • builder component complexing agent / dispersant
  • alkali carrier alkali carrier
  • Bleach system bleach and bleach activator combination
  • enzyme and surfactant are usually not only formed in the presence of silver sulfidic, but by the oxidizing attack of intermediately formed peroxides or the active oxygen also oxidic deposits on the silver surfaces.
  • the present invention has the improvement of the oxidation and bleaching action, in particular inorganic Peroxygen compounds at low temperatures below 80 ° C. especially in the temperature range from about 15 ° C to 55 ° C, to the destination.
  • the invention relates to a means for cleaning dishes, which is characterized in that it is 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of a compound of general formula I.
  • Another object of the invention is a means for cleaning dishes, which is characterized in that it is 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of a compound of general formula I.
  • Another object of the invention is a means for cleaning dishes, which is characterized in that it is 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of a compound of general formula I.
  • R 1 is preferably an alkyl group having 1 to 3 C atoms, in particular a methyl group.
  • the anions X - include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, metho and ethosulfate, chlorate, perchlorate, and the anions of carboxylic acids such as formate, acetate, benzoate or citrate.
  • Methosulfate is - preferred is the use of compounds of the formula in which X is.
  • a dishwashing detergent according to the invention contains the bleach-activating acetonitrile derivative and optionally a peroxygen-containing oxidizing agent, preferably selected from the group comprising organic Peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
  • the conditions can be widely varied. So come in addition to purely aqueous solutions, mixtures of water and suitable organic solvents as the reaction medium in question.
  • the amounts of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen available.
  • the amount of bleach activating acetonitrile derivative used depends on the application from. Depending on the desired degree of activation, 0.00001 mol to 0.25 mol, preferably 0.001 mol to 0.02 moles of activator per mole of peroxygen compound used, but in special cases these limits also be exceeded or fallen below.
  • the cleaning agents of the invention as powdered or tablet-like solids, homogeneous solutions or suspensions may, in principle except the bleach activator used in the invention contain all known and customary in such agents ingredients.
  • the agents according to the invention can in particular builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic Solvents, enzymes. Sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, Foam regulators, additional bleach-enhancing agents, as well as dyes and fragrances.
  • a cleaning agent according to the invention can have abrasive components, in particular from the group comprising quartz flours, wood flours. Plastic flours, chalks and glass microspheres and mixtures thereof. contain. Abrasives are preferably not more than 20% by weight in the detergents according to the invention, in particular from 5% to 15% by weight.
  • a further subject of the invention is a means for mechanically cleaning dishes containing 15 Wt .-% to 70 wt .-%, in particular 20 wt .-% to 60 wt .-% of water-soluble builder component, 5 wt .-% bis 25 wt .-%, in particular 8 wt .-% to 17 wt .-% bleaching agent based on oxygen, in each case based on the total
  • Such an agent is preferably lower alkyl, that is, its 1 weight percent solution a pH of 8 to 11.5, especially from 9 to 11.
  • Alkaliphosphate in the form of their alkaline neutral or acidic sodium or potassium salts may be present.
  • examples of these are trisodium phosphate, tetrasodium diphosphate. disodium, Pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization from 5 to 1000, especially 5 to 50, and mixtures of sodium and potassium salts.
  • Your Amounts can range up to about 55% by weight based on the total agent; are preferred Low alkaline agents according to the invention free of such phosphates.
  • Other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, especially in hard water regions.
  • polyacrylic acids are suitable and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids.
  • commercial Products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • polymers of native origin include oxidized starches, such as those from international sources Patent Application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, Dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred builder components include the salts of citric acid, especially sodium citrate.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the pH adjusted to the compositions according to the invention can also at least proportionally be added to the said co-builder salts corresponding acids are present.
  • alkali perborate mono-abstraction-tetrahydrate is primarily used and / or alkali metal percarbonate and alkali persulfates, persilicates and percarbonates, with sodium being the preferred Alkali metal is.
  • the use of sodium percarbonate has particular advantages in dishwashing detergents, because it has a particularly favorable effect on the corrosion behavior of glasses.
  • the bleaching agent based on oxygen is therefore preferably an alkali metal percarbonate, in particular sodium percarbonate.
  • peroxycarboxylic acids for example dodecanedioic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic be included.
  • the addition can also small amounts of known bleach stabilizers such as phosphonates, borates or Metaborates and metasilicates and magnesium salts such as magnesium sulfate be useful.
  • bleach-activating acetonitrile derivatives according to formula I known conventional Bleach activators, that is, compounds which under perhydrolysis conditions are aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted Perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and the from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated Sorbitol and mannitol or their mixtures described in European patent application EP 0 5
  • German Patent Application DE 196 16 769 known hydrophilic substituted acylacetals and in the German Patent Application DE 196 16 770 and the international patent application WO 95/14075 Acyllactame described are also preferably used. Also known from German Patent Application DB 44 43 177 Combinations of conventional bleach activators can be used. Such conventional bleach activators are in the usual amount range, preferably in amounts of 0.1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 7 wt .-%, based on the total agent included.
  • the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleach catalysts.
  • Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salene complexes known from German patent application DE 195 29 905 and their N-analogues known from German patent application DE 196 20 267, which are known from US Pat German Patent Application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl, the described in the German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium , Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium-ammine complexes known from German patent application DE 196 20 411, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese complex known from European patent application EP 0
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal salts and / or complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in conventional amounts, preferably up to 1 wt .-%, in particular of 0.0025 wt % to 0.5 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • Particularly preferred bleach catalyst complexes include cobalt, iron, copper and ruthenium ammine complexes, for example [Co (NH 3 ) 5 Cl] Cl 2 and / or [Co (NH 3 ) 5 NO 2 ] Cl 2 .
  • the machine dishwashing detergents according to the invention preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali metal bicarbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight. based on the total agent, be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight is. Depending on which pH is ultimately desired, the ratio of carbonate used and hydrogen carbonate used varies.
  • compositions according to the invention 20% by weight to 60% by weight are more water-soluble organic builder, in particular alkali citrate, 3% by weight to 20% by weight alkali carbonate and 5% by weight to 40% by weight Alkalidisilicate included.
  • anionic, nonionic and / or amphoteric surfactants in particular low-foaming nonionic surfactants, which serve to better remove greasy soilings, as wetting agents and optionally as granulation aids in the preparation of the cleaning agents.
  • Their amount can be up to 20 wt .-%, in particular up to 10 wt .-% and is preferably in the range of 0.5 wt .-% to 5 wt .-%.
  • extremely low-foam compounds are used in particular in detergents for use in automatic dishwashing processes.
  • C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
  • surfactants from the family of glucarnides for example alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides.
  • silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl-, aminoalkyl- or aryl-substituted triazoles such as Benzotriazole, isocyanuric acid, manganese, cobalt, titanium, zirconium, hafnium, vanadium or cerium salts and / or Complexes in which the metals mentioned are present in one of the oxidation states II, III, IV, V or VI, depending on the metal.
  • the content of silver corrosion inhibitors in compositions according to the invention is preferably in the range of 0.01% by weight.
  • the agents of the invention can enzymes such as proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect® OxP and / or Durazym®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect® OxP and / or Durazym®
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®,
  • the optionally used enzymes as for example in the international patent applications WO 92/11347 or WO 94/23005, adsorbed on carriers and / or be embedded in encasing substances, against them Protect premature inactivation. They are preferably present in the detergents according to the invention in quantities up to 2 wt .-%, in particular from 0.1 wt .-% to 1.5 wt .-%, containing, with particular preference against oxidative Degradation stabilized enzymes, such as from International Patent Applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.
  • the cleaning agents foam too much during use, they can still preferably up to 6 wt .-%, in particular about 0.5 wt .-% to 4 wt .-% of a foam-pressing compound, preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other further known commercially available Defoamer be added.
  • a foam-pressing compound preferably from the Group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the bis-fatty acid amides, and other further known commercially available Defoamer be added.
  • Further optional ingredients in the agents according to the invention are, for example Perfume oils.
  • usable organic solvents include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, Isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their Mixtures and the derivable from the said classes of compounds ethers.
  • Such water-miscible solvents are preferably not more than 20% by weight, in particular of 1, in the cleaning agents according to the invention Wt .-% to 15 wt .-%, present.
  • the agents of the invention system- and environmentally friendly acids in particular Citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular Ammonium or alkali hydroxides.
  • Such pH regulators are in the inventive compositions preferably not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • Detergents according to the invention in the form of aqueous or other conventional solvent-containing solutions be particularly advantageous by simply mixing the ingredients in substance or as a solution in an automatic mixer can be made.
  • the agents according to the invention are preferably in the form of powdered, granular or tablet-shaped preparations before, in a conventional manner, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and the bleach activator are to be expected can be produced.
  • a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can be carried out by a first process step, the builder components with at least a proportion of liquid mixture components mixed with increasing the bulk density of this premix and subsequently - if desired after a Intermediate drying - the other ingredients of the agent, including the bleach catalyst, with the thus obtained Pre-mix united.
  • Detergent cleaning compositions according to the invention can be used both in household dishwashers used in commercial dishwashers. The addition is carried out by hand or by means of suitable metering devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program will generally be followed by some intermediate rinse cycles following the cleaning cycle supplemented with clear water and a rinse with a common rinse aid and completed. After drying, the use of compositions according to the invention gives completely clean and hygienic products Respectable dishes.
  • a detergent (V1) for the machine cleaning of dishes containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium carbonate, 30 parts by weight of sodium bicarbonate, each 1 part by weight of protease and amylase granules, 2 wt.
  • the grades of the agents according to the invention given in Table 2 are significantly better than the value for the comparative products V1 and V2 , which contained the standard bleach activator TAED.
  • composition of automatic dishwashing detergent medium additive M1 3 parts by weight of N-methyl-morpholinium-acetonitrile-methosulfate M2 3 parts by weight of N-methyl-morpholinium acetonitrile methosulfate and 0.03 parts by weight of nitropentammine cobalt (III) chloride M3 4 parts by weight of N-methyl-morpholinium-acetonitrile methosulfate M4 4 parts by weight of N-methyl-morpholinium acetonitrile methosulfate and 0.03 parts by weight of nitropentammine cobalt (III) chloride M5 6 parts by weight of N-methyl-morpholinium-acetonitrile methosulfate V2 4 parts by weight TAED Grades for the pad removal medium plaque removal M1 5 M2 7 M3 7 M4 9 M5 9 V1 2 V2 4

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  • Life Sciences & Earth Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (10)

  1. Détergent pour laver la vaisselle, caractérisé en ce qu'il renferme 1 à 10 % en poids, en particulier 3 à 6 % en poids d'un composé de la formule générale I R1R2R3N+CH2CN X- dans laquelle R1, R2 et R3 représentent indépendamment les uns des autres un groupe alkyle, alcényle ou aryle comportant 1 à 18 atomes de C, les groupes R1 et R2 faisant partie d'un hétérocycle comprenant l'atome d'azote et éventuellement d'autres hétéroatomes, et X étant un anion équilibrant la charge, ainsi qu'un inhibiteur de la corrosion de l'argent de même que des ingrédients usuels compatibles avec le composé conforme à la formule I.
  2. Détergent pour laver la vaisselle, caractérisé en ce qu'il renferme 1 à 10 % en poids, en particulier 3 à 6 % en poids d'un composé de la formule générale I R1R2R3N+CH2CN X- dans laquelle R1, R2 et R3 représentent indépendamment les uns des autres un groupe alkyle, alcényle ou aryle comportant 1 à 18 atomes de C, les groupes R1 et R2 faisant partie d'un hétérocycle comprenant l'atome d'azote et éventuellement d'autres hétéroatomes, et X étant un anion équilibrant la charge, de même que des ingrédients usuels compatibles avec le composé conforme à la formule I, et se présente sous la forme d'une matière solide en comprimé.
  3. Détergent pour laver la vaisselle, caractérisé en ce qu'il renferme 1 à 10 % en poids, en particulier 3 à 6 % en poids d'un composé de la formule générale I R1R2R3N+CH2CN X- dans laquelle R1, R2 et R3 représentent indépendamment les uns des autres un groupe alkyle, alcényle ou aryle comportant 1 à 18 atomes de C, les groupes R1 et R2 faisant partie d'un hétérocycle comprenant l'atome d'azote et éventuellement d'autres hétéroatomes, et X étant un anion équilibrant la charge, ainsi que des sels de métaux de transition ou des complexes de métaux de transition renforçant le blanchiment, de même que des ingrédients usuels compatibles avec le composé conforme à la formule I.
  4. Détergent pour laver la vaisselle en machine, contenant 15 à 70 % en poids, en particulier 20 à 60 % en poids de composant adjuvant soluble dans l'eau, 5 à 25 % en poids, en particulier 8 à 17 % en poids d'agent de blanchiment à base d'oxygène, dans chaque cas par rapport à la totalité du détergent, caractérisé en ce qu'il contient un dérivé d'acétonitrile activateur de blanchiment conforme à la formule I, en proportions de 3 à 6 % en poids.
  5. Détergent selon une des revendications 1 à 4, caractérisé en ce qu'il contient un composé peroxydique appartenant au groupe comprenant les peracides organiques, l'eau oxygénée, le perborate et le percarbonate ainsi que les mélanges de ceux-ci.
  6. Détergent selon une des revendications 1 à 5, caractérisé en ce qu'il contient en plus des composés conformes à la formule I, 0,5 à 7 % en poids de composés clivant les acides peroxocarboxyliques dans les conditions de perhydrolyse.
  7. Détergent selon une des revendications 1 à 6, caractérisé en ce que dans le composé conforme à la formule I, R2 et R3 forment un cycle morpholine en incluant l'atome d'azote quaternaire.
  8. Détergent selon une des revendications 1 à 7, caractérisé en ce que dans le composé conforme à la formule I, R1 est un groupe alkyle comportant 1 à 3 atomes de C, en particulier un groupe méthyle.
  9. Détergent selon une des revendications 1 à 8, caractérisé en ce que l'anion X- équilibrant la charge est sélectionné parmi les halogénures tels que le chlorure, le fluorure, l'iodure et le bromure, le nitrate, l'hydroxyde, l'hexafluorophosphate, le métho- et l'éthosulfate, le chlorate, le perchlorate et les anions d'acides carboxyliques tels que le formiate, l'acétate, le benzoate ou le citrate.
  10. Détergent selon une des revendications 1 à 9, caractérisé en ce que l'anion X- équilibrant la charge est le méthosulfate.
EP97951944A 1996-11-29 1997-11-21 Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents Expired - Lifetime EP0944707B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01115441A EP1138754A1 (fr) 1996-11-29 1997-11-21 Dérivés d'acétonitrile utilisés comme activateurs de blanchiment dans des détergents

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19649375 1996-11-29
DE19649375A DE19649375A1 (de) 1996-11-29 1996-11-29 Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
PCT/EP1997/006527 WO1998023719A2 (fr) 1996-11-29 1997-11-21 Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents

Related Child Applications (1)

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EP01115441A Division EP1138754A1 (fr) 1996-11-29 1997-11-21 Dérivés d'acétonitrile utilisés comme activateurs de blanchiment dans des détergents

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EP0944707A2 EP0944707A2 (fr) 1999-09-29
EP0944707B1 EP0944707B1 (fr) 2002-02-06
EP0944707B2 true EP0944707B2 (fr) 2005-06-01

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EP (2) EP1138754A1 (fr)
JP (1) JP4097295B2 (fr)
AT (1) ATE213013T1 (fr)
DE (2) DE19649375A1 (fr)
ES (1) ES2172825T5 (fr)
WO (1) WO1998023719A2 (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6010994A (en) * 1995-06-07 2000-01-04 The Clorox Company Liquid compositions containing N-alkyl ammonium acetonitrile salts
US7390432B2 (en) 1998-06-30 2008-06-24 Sandia Corporation Enhanced formulations for neutralization of chemical, biological and industrial toxants
US7282470B2 (en) * 2002-07-19 2007-10-16 Sandia Corporation Decontamination formulation with sorbent additive
JP2002532615A (ja) * 1998-12-15 2002-10-02 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 漂白活性剤としてのアセトニトリル誘導体
DE19908069A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Compoundierte Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE19908051A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
DE19943254A1 (de) 1999-09-10 2001-03-15 Clariant Gmbh Bleichaktive Metallkomplexe
US6214782B1 (en) * 2000-03-24 2001-04-10 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Cationic nitriles for providing a silver tarnish benefit in machine dishwashing detergent applications
DE10019877A1 (de) 2000-04-20 2001-10-25 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend bleichaktive Dendrimer-Liganden und deren Metall-Komplexe
DE10038845A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Waschmitteln
DE10038832A1 (de) * 2000-08-04 2002-03-28 Henkel Kgaa Umhüllte Bleichaktivatoren
DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
DE10038844A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Kationischen Bleichaktivator enthaltende Wasch- und Reinigungsmittel
DE10057045A1 (de) 2000-11-17 2002-05-23 Clariant Gmbh Teilchenförmige Bleichaktivatoren auf der Basis von Acetonitrilen
DE10064636A1 (de) * 2000-12-22 2002-07-04 Henkel Kgaa Flüssiges Wasch-und/oder Reinigungsmittel
DE10142124A1 (de) 2001-08-30 2003-03-27 Henkel Kgaa Umhüllte Wirkstoffzubereitung für den Einsatz in teilchenförmigen Wasch- und Reinigungsmitteln
DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
DE10159386A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von Bleichaktivatorgranulaten
DE10211389A1 (de) * 2002-03-15 2003-09-25 Clariant Gmbh Ammoniumnitrile und deren Verwendung als hydrophobe Bleichaktivatoren
JP2006504809A (ja) * 2002-05-02 2006-02-09 ザ プロクター アンド ギャンブル カンパニー 洗剤組成物及びその成分
DE10233832A1 (de) * 2002-07-25 2003-07-17 Henkel Kgaa MGSM mit speziell konfektionierten Bleichaktivatoren
DE60327248D1 (de) * 2002-12-18 2009-05-28 Procter & Gamble Organischer aktivator

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01198700A (ja) † 1988-02-03 1989-08-10 Kao Corp 自動食器洗浄機用洗剤
EP0790244A1 (fr) † 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium

Family Cites Families (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
US4915863A (en) * 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
ES2100925T3 (es) 1990-05-21 1997-07-01 Unilever Nv Activacion de blanqueador.
GB9011618D0 (en) * 1990-05-24 1990-07-11 Unilever Plc Bleaching composition
GB9012001D0 (en) 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
DE4041752A1 (de) 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
ATE155165T1 (de) 1991-07-31 1997-07-15 Ausimont Spa Verfahren zur erhöhung der bleichwirksamkeit eines inorganischen persalzes
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
AU682314B2 (en) 1992-07-17 1997-10-02 Genencor International, Inc. High alkaline serine proteases
EP0651794B1 (fr) 1992-07-23 2009-09-30 Novozymes A/S Alpha-amylase mutante, detergent et agent de lavage de vaisselle
DE4228786A1 (de) 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4232170C2 (de) 1992-09-25 1999-09-16 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
CZ293163B6 (cs) 1993-02-11 2004-02-18 Genencor International, Inc. Mutanta alfa-amylázy, její použití, kódová DNA pro tuto mutantu, vektor pro expresi, hostitelské buňky, čisticí prostředek a prostředek pro zkapalnění škrobu
AU6000594A (en) 1993-02-22 1994-09-14 Unilever Plc Machine dishwashing composition
DE4310506A1 (de) 1993-03-31 1994-10-06 Cognis Bio Umwelt Enzymzubereitung für Wasch- und Reinigungsmittel
DK39093D0 (da) 1993-04-01 1993-04-01 Novo Nordisk As Enzym
DE4325922A1 (de) 1993-08-02 1995-02-09 Henkel Kgaa Silberkorrosionsschutzmittel I
DE4315397A1 (de) 1993-05-08 1994-11-10 Henkel Kgaa Reinigungsmittel mit Verhinderung des Anlaufens von Tafelsilber in Geschirrspülmaschinen
ATE169003T1 (de) 1993-05-20 1998-08-15 Procter & Gamble Bleichmittel, welche einen substituierten benzoyl caprolactam bleichaktivator enthalten
BR9406306A (pt) 1993-05-20 1995-12-26 Procter & Gamble Composições de branqueamento compreendendo ativadores n-acil caprolactama
CN1065563C (zh) 1993-05-20 2001-05-09 普罗格特-甘布尔公司 用于手洗或其它低水洗涤体系的包括n－酰基己内酰胺的漂白组合物
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
DK100893D0 (da) 1993-09-09 1993-09-09 Novo Nordisk As Enzym
DE4338922A1 (de) 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
EP0730631B1 (fr) 1993-11-25 1999-07-07 WARWICK INTERNATIONAL GROUP LIMITED (Company No. 2982784) Compositions de blanchiment
US5534196A (en) 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
MX9604643A (es) 1994-04-07 1997-11-29 Procter & Gamble Composiciones blanqueadoras que consisten de catalizadores de blanqueo que contienen metal.
DE4416438A1 (de) 1994-05-10 1995-11-16 Basf Ag Ein- oder mehrkernige Metall-Komplexe und ihre Verwendung als Bleich- und Oxidationskatalysatoren
DE69533149T2 (de) 1994-07-21 2005-08-25 Ciba Specialty Chemicals Holding Inc. Bleichmittelzusammensetzung für Gewebe
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
US5599781A (en) * 1995-07-27 1997-02-04 Haeggberg; Donna J. Automatic dishwashing detergent having bleach system comprising monopersulfate, cationic bleach activator and perborate or percarbonate
ATE209245T1 (de) * 1995-02-02 2001-12-15 Procter & Gamble Verfahren zur entfernung von teeflecken in geschirrspülern mit zusammensetzungen enthaltend kobalt (iii)- katalysator
DE19518693A1 (de) 1995-05-22 1996-11-28 Henkel Kgaa Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel
US5739327A (en) * 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5814242A (en) * 1995-06-07 1998-09-29 The Clorox Company Mixed peroxygen activator compositions
US5888419A (en) * 1995-06-07 1999-03-30 The Clorox Company Granular N-alkyl ammonium acetontrile compositions
US5792218A (en) * 1995-06-07 1998-08-11 The Clorox Company N-alkyl ammonium acetonitrile activators in dense gas cleaning and method
DE19529905A1 (de) 1995-08-15 1997-02-20 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19536082A1 (de) 1995-09-28 1997-04-03 Henkel Kgaa Aktivatorkomplexe für Persauerstoffverbindungen
DE19605688A1 (de) 1996-02-16 1997-08-21 Henkel Kgaa Übergangsmetallkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19613103A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19620411A1 (de) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe als Aktivatoren für Persauerstoffverbindungen
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01198700A (ja) † 1988-02-03 1989-08-10 Kao Corp 自動食器洗浄機用洗剤
EP0790244A1 (fr) † 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium

Also Published As

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US6225274B1 (en) 2001-05-01
EP0944707B1 (fr) 2002-02-06
ES2172825T5 (es) 2005-12-01
WO1998023719A2 (fr) 1998-06-04
ES2172825T3 (es) 2002-10-01
WO1998023719A3 (fr) 1998-07-30
EP0944707A2 (fr) 1999-09-29
JP4097295B2 (ja) 2008-06-11
DE59706340D1 (de) 2002-03-21
DE19649375A1 (de) 1998-06-04
ATE213013T1 (de) 2002-02-15
EP1138754A1 (fr) 2001-10-04
JP2001504883A (ja) 2001-04-10

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