EP0944707B1 - 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
EP0944707B1
EP0944707B1 EP97951944A EP97951944A EP0944707B1 EP 0944707 B1 EP0944707 B1 EP 0944707B1 EP 97951944 A EP97951944 A EP 97951944A EP 97951944 A EP97951944 A EP 97951944A EP 0944707 B1 EP0944707 B1 EP 0944707B1
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weight
detergent
formula
compounds
alkyl
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EP97951944A
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German (de)
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EP0944707B2 (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 containing certain acetonitrile derivatives as activators for in particular inorganic peroxygen compounds for bleaching colored ones Soiling on dishes contain.
  • Inorganic peroxygen compounds especially hydrogen peroxide and solid peroxygen compounds, which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, Hydrotriazine, urazoles, diketopiperazines, sulfuryl amides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, Carbonklareester, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, are known in the literature , By adding these substances, the bleaching effect of
  • dishwashing detergents which contain ammonium acetonitrile derivatives, the quaternary nitrogen atom of which 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 one C 1-24 alkyl alkelnyl or alkyl ether group.
  • European patent application EP 0 303 520 discloses bleaching textile detergents which contain ammonium acetonitrile derivatives, the quaternary nitrogen atom of which is part of an optionally substituted pyridine ring.
  • Another one especially for cleaning agents for automatic dishwashing Problem is the need to use corrosion inhibitors for silverware in such agents to incorporate, especially if the agents are the bleaching or Oxygen-based oxidizers included.
  • Silver can when cleaning with sulfur-containing substances that are dissolved or dispersed in the rinse water are reacting, because when cleaning dishes in household dishwashers are leftovers and thus among other things mustard, peas, egg and others sulfur-containing compounds such as mercaptoamino acids introduced into the washing liquor.
  • the much higher temperatures during machine washing and the longer ones Contact times with the sulfur-containing food residues favor compared to manual purging the tarnishing of silver. Due to the intensive cleaning process in the silver surface is also completely degreased in the dishwasher and thereby more sensitive to chemical influences.
  • tarnishing silver becomes particularly acute if it is an alternative to the sulfur-containing substances oxidatively "defusing" active chlorine compounds active oxygen compounds, such as sodium perborate or sodium percarbonate are used to remove bleachable soiling, such as for example tea stains / tea deposits, coffee residues, dyes from vegetables, lipstick residues and the like serve.
  • active chlorine compounds such as sodium perborate or sodium percarbonate are used to remove bleachable soiling, such as for example tea stains / tea deposits, coffee residues, dyes from vegetables, lipstick residues and the like serve.
  • Such active oxygen bleaching agents usually together with bleach activators, especially in modern low-alkaline machine dishwashing detergents of the new generation of cleaners used.
  • These means generally consist of the following Functional components: builder component (complexing agent / dispersant), alkali carrier, Bleaching system (combination of bleach and bleach activator), enzyme and Surfactant.
  • builder component complexing agent / dispersant
  • alkali carrier alkali carrier
  • Bleaching system combination of bleach and bleach activator
  • enzyme and Surfactant Surfactant.
  • the present invention has in particular the improvement of the oxidation and bleaching effect inorganic peroxygen compounds at low temperatures below 80 ° C, especially in the temperature range of approx. 15 ° C to 55 ° C, for Aim.
  • the invention relates to an agent for cleaning dishes, which is characterized in that it contains 1% by weight to 10% by weight, in particular 3% by weight to 6% by weight, of a compound of the general formula I.
  • R 1 R 2 R 3 N + CH 2 CN X - in which R 1 , R 2 and R 3 independently of one another are an alkyl, alkenyl or aryl group having 1 to 18 C atoms, the groups R 1 and R 2 being part of a heterocycle which includes the N atom and optionally further hetero atoms, and X is a charge-balancing anion, in addition to the usual ingredients which are compatible with the compound of the formula I.
  • R 1 is preferably an alkyl group with 1 to 3 carbon 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.
  • 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.
  • Is methosulfate - preferred is the use of compounds according to formula I in which X is.
  • a cleaning agent for dishes according to the invention contains the bleach-activating agent Acetonitrile derivative and optionally an oxidizing agent containing peroxygen, preferably selected from the group comprising organic peracids, hydrogen peroxide, Perborate and percarbonate and their mixtures.
  • the conditions can vary widely become.
  • 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 are present.
  • the amount used bleach activating acetonitrile derivative depends on the application. Depending on what you want The degree of activation will be 0.00001 mol to 0.25 mol, preferably 0.001 mol up to 0.02 mole of activator per mole of peroxygen compound used, but can in In special cases, these limits are also exceeded or undershot.
  • the cleaning agents according to the invention which are in powder or tablet form Solids, homogeneous solutions or suspensions can also be present Bleach activator used according to the invention in principle all known and in such Contain common 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, contain additional bleach-boosting active ingredients as well as colors and fragrances.
  • a cleaning agent according to the invention can also have an abrasive effect Components, in particular from the group comprising quartz flours, wood flours, Plastic flours, chalks and micro glass balls and their mixtures.
  • Abrasives are preferably not present in the cleaning agents according to the invention 20 wt .-%, in particular from 5 wt .-% to 15 wt .-%, contain.
  • Another object of the invention is a means for machine cleaning Tableware containing 15% by weight to 70% by weight, in particular 20% by weight to 60% by weight water-soluble builder component, 5% by weight to 25% by weight, in particular 8% by weight up to 17% by weight of bleaching agent based on oxygen, in each case based on the total agent, which a bleach activating acetonitrile derivative according to formula I in amounts of 3% to 6% by weight.
  • Such an agent is preferably lower alkaline, that is, its 1% by weight solution has a pH of 8 to 11.5, in particular from 9 to 11 on.
  • alkali phosphates which in Form of their alkaline neutral or acidic sodium or potassium salts can.
  • alkali phosphates which in Form of their alkaline neutral or acidic sodium or potassium salts can.
  • alkali phosphates which in Form of their alkaline neutral or acidic sodium or potassium salts can.
  • examples include trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization from 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.
  • lower alkaline agents according to the invention are preferably free of such agents 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. In consideration come for example polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids. Commercial products are for example Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • co-builder usable polymers of native origin include, for example, oxidized starches, as known for example from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • More possible Builder components are naturally occurring hydroxycarboxylic acids such as Example mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • To the preferred builder components include the salts of citric acid, in particular Sodium citrate.
  • Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used.
  • the pH value set can also be at least partially those of the co-builder salts mentioned corresponding acids are present.
  • the main bleaches used are oxygen-based or alkali perborate mono tetrahydrate and / or alkali percarbonate and alkali persulfates, persilicates and percitrates, with sodium being the preferred alkali metal.
  • the use of sodium percarbonate has been found particularly in detergents for dishes Advantages, since it has a particularly favorable effect on the corrosion behavior on glasses.
  • the oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate.
  • peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic, are included.
  • bleach stabilizers such as for example of phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activating acetonitrile derivatives according to formula I above known conventional bleach activators, that is, compounds that under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used.
  • aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used.
  • Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in mixtures described in European patent application EP 0 525 239 (SORMAN), acy
  • the sulfonimines 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 bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine 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 complexes known from European patent application EP
  • 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 customary amounts, preferably up to 1% by weight, in particular 0.0025% by weight .-% to 0.5 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • the particularly preferred bleach catalyst complexes include cobalt, iron, copper and ruthenium-amine 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 such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 40% by weight, based on the total agent. However, the use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which are present in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight is. Depending on which pH value is ultimately desired, the ratio of carbonate and bicarbonate used varies.
  • agents according to the invention are 20% by weight to 60% by weight of water-soluble organic builder, in particular alkali citrate, 3% by weight to Contain 20 wt .-% alkali carbonate and 5 wt .-% to 40 wt .-% alkali disilicate.
  • Anionic, nonionic and / or amphoteric surfactants in particular weakly foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to improve the detachment of greasy soils, as wetting agents and optionally as granulating aids in the preparation of the cleaning agents.
  • Their amount can be up to 20% by weight, in particular up to 10% by weight, and is preferably in the range from 0.5% by weight to 5% by weight.
  • Extremely low-foaming compounds are usually used in particular in cleaning agents for use in automatic dishwashing processes.
  • C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • you can also use other known low-foaming nonionic surfactants such as C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14- alkyl polyglucosides with a degree of polymerization of about 1 to 4 (e.g.
  • surfactants from the family of glucarnides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably comes 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.
  • cleaning agents according to the invention can be used for cleaning silver corrosion inhibitors are used in dishes.
  • Preferred silver corrosion inhibitor are organic sulfides such as cystine and cysteine, divalent or trivalent 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 depend on the metal are in one of the oxidation states II, III, IV, V or VI.
  • the content of silver corrosion inhibitors in agents according to the invention is preferably in the range of 0.01% by weight to 1.5% by weight, in particular from 0.1% by weight to 0.5% by weight.
  • the manganese (III) - or known from international patent application WO 94/19445 Manganese (IV) complexes which in international patent application WO 94/07981 as Silver protection agent disclosed cysteine, which in the German patent application DE 195 18 693 as having a silver corrosion inhibiting effect alone or in particular in Combination with isocyanuric acid described cystine, and / or that in the German patent applications Titanium, described in DE 43 25 922 and DE 43 15 397, Zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes in which the metals are in one of the oxidation states II, III, IV, V or VI, and mentioned there Manganese (II) salts or complexes for preventing silver corrosion in the invention Funds are used.
  • the agents according to the invention can contain enzymes such as proteases, amylases, Contain 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®, Max
  • the optionally used enzymes can, as for example in the international patent applications WO 92/11347 or WO 94/23005
  • Carriers can be adsorbed and / or embedded in coating substances to protect them against premature Protect inactivation. They are in the cleaning agents according to the invention preferably in amounts up to 2% by weight, in particular from 0.1% by weight to 1.5% by weight, contain, particularly preferably enzymes stabilized against oxidative degradation, as for example from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, are used become.
  • the cleaning agents foam too much during use, they can still preferably up to 6% by weight, in particular about 0.5% by weight to 4% by weight of one foam-suppressing compound, preferably from the group of silicone oils, mixtures made of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amides, and others other known commercially available defoamers can be added.
  • one foam-suppressing compound preferably from the group of silicone oils, mixtures made of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amides, and others other known commercially available defoamers can be added.
  • foam-suppressing compound preferably from the group of silicone oils, mixtures made of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amides, and
  • usable organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, Diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and their mixtures and the ethers derived from the compound classes mentioned.
  • Such water-miscible solvents are in the cleaning agents according to the invention preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight, available.
  • the agents according to the invention cannot be systemic and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, however also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or Contain bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are preferably not more than 10% by weight in the agents according to the invention, in particular from 0.5% by weight to 6% by weight.
  • the preparation of the solid 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, take place, the peroxygen compound and bleaching catalyst optionally being separated later be added.
  • Cleaning agents according to the invention in the form of aqueous or other conventional Solutions containing solvents are particularly advantageous by simple Mixing the ingredients in bulk or as a solution in an automatic Mixers can be made.
  • the agents according to the invention are preferably powdered, granular or tablet-shaped preparations in a known manner, for example by Mixing, granulating, roller compacting and / or by spray drying the thermally resilient components and admixing the more sensitive components, which include in particular enzymes, bleaching agents and the bleach activator, can be produced.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 5 Pa to 1,500 ⁇ 10 5 Pa pressed.
  • conventional tablet presses for example eccentric presses or rotary presses
  • pressures in the range from 200 ⁇ 10 5 Pa to 1,500 ⁇ 10 5 Pa pressed.
  • unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N.
  • a tablet manufactured in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • agents 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 up to 1000 g / l can be achieved in that the Builder components with at least a portion of liquid mixture components mixed by increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other components of the agent, including the bleach catalyst, combined with the premix obtained in this way.
  • Agents for cleaning dishes according to the invention can be used both in household dishwashers as used in commercial dishwashers. The addition is done by hand or by means of suitable dosing devices.
  • the application concentrations in the cleaning liquor are usually about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program is generally followed by some on the Cleaning cycle following intermediate rinse cycles with clear water and one Rinse aid supplemented with a customary rinse aid and ended. After this Drying is completely clean and in when using agents according to the invention hygienically perfect dishes.
  • a cleaning agent (V1) for the automatic cleaning of dishes containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium carbonate, 30 parts by weight of sodium hydrogen carbonate, 1 part by weight of protease and amylase granules, 2 parts by weight.
  • 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 bleach activator TAED which has become standard.
  • composition of automatic dishwashing detergents 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 part 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 part by weight of nitropentammine cobalt (III) chloride M5 6 parts by weight of N-methyl-morpholinium-acetonitrile-methosulfate V2 4 parts by weight of TAED Sheet removal marks medium plaque removal M1 5 M2 7 M3 7 M4 9 M5 9 V1 2 V2 4

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Claims (8)

  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 font partie d'un atome de N et d'un hétérocycle comprenant éventuellement d'autres hétéroatomes, et X est un anion équilibrant la charge, de même que d'autres ingrédients usuels compatibles avec le composé conforme à la formule I.
  2. 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 selon la formule I en proportion de 3 à 6 % en poids.
  3. Détergent selon la revendication 1 ou 2, 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.
  4. Détergent selon une des revendications 1 à 3, caractérisé en ce qu'il contient en plus des composés selon la formule I, 0,5 à 7 % en poids de composés clivant les acides peroxocarboxyliques dans les conditions de perhydrolyse.
  5. Détergent selon une des revendications 1 à 4, caractérisé en ce que dans le composé selon la formule I, R2 et R3 forment un cycle morpholine en incluant l'atome de N quaternaire.
  6. Détergent selon une des revendications 1 à 5, caractérisé en ce que dans le composé selon la formule I, R1 est un groupe alkyle comportant 1 à 3 atomes de C, en particulier un groupe méthyle.
  7. Détergent selon une des revendications 1 à 6, 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.
  8. Détergent selon une des revendications 1 à 7, 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

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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 true EP0944707B1 (fr) 2002-02-06
EP0944707B2 EP0944707B2 (fr) 2005-06-01

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EP97951944A Expired - Lifetime EP0944707B2 (fr) 1996-11-29 1997-11-21 Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents
EP01115441A Ceased EP1138754A1 (fr) 1996-11-29 1997-11-21 Dérivés d'acétonitrile utilisés comme activateurs de blanchiment dans des détergents

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US (1) US6225274B1 (fr)
EP (2) EP0944707B2 (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
DE19908051A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
DE19908069A1 (de) * 1999-02-25 2000-08-31 Henkel Kgaa Compoundierte Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
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
DE10038844A1 (de) * 2000-08-04 2002-02-21 Henkel Kgaa Kationischen Bleichaktivator enthaltende Wasch- und Reinigungsmittel
DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
DE10038832A1 (de) * 2000-08-04 2002-03-28 Henkel Kgaa Umhüllte Bleichaktivatoren
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
ATE350450T1 (de) * 2002-05-02 2007-01-15 Procter & Gamble Waschmittelzusammensetzungen und komponenten davon
DE10233832A1 (de) * 2002-07-25 2003-07-17 Henkel Kgaa MGSM mit speziell konfektionierten Bleichaktivatoren
CN1741989A (zh) * 2002-12-18 2006-03-01 宝洁公司 有机活化剂

Family Cites Families (56)

* 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
JP2551962B2 (ja) * 1988-02-03 1996-11-06 花王株式会社 自動食器洗浄機用洗剤
GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
DE69125309T2 (de) 1990-05-21 1997-07-03 Unilever Nv Bleichmittelaktivierung
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
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
GB9127060D0 (en) 1991-12-20 1992-02-19 Unilever Plc Bleach activation
CA2085642A1 (fr) 1991-12-20 1993-06-21 Ronald Hage Activation de blanchiment
KR950702633A (ko) 1992-07-17 1995-07-29 한스 발터 라벤 고알칼리성 세린 프로테아제(high alkaline serine proteases)
WO1994002597A1 (fr) 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction
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
PT867504E (pt) 1993-02-11 2003-08-29 Genencor Int Alfa-amilase estavel a oxidacao
WO1994019445A1 (fr) 1993-02-22 1994-09-01 Unilever N.V. Composition de lavage pour lave-vaisselle
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
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
CN1057117C (zh) 1993-05-20 2000-10-04 普罗格特-甘布尔公司 包括n－酰基己内酰胺活化剂的漂白组合物
CA2161214C (fr) 1993-05-20 2000-06-27 Alan David Willey Composes de blanchiment renfermant des activateurs de blanchiment a base de derive de substitution benzoylique de caprolactame
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
JP2941430B2 (ja) 1994-04-07 1999-08-25 ザ、プロクター、エンド、ギャンブル、カンパニー 金属含有漂白触媒を含む漂白組成物
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
JPH10513215A (ja) * 1995-02-02 1998-12-15 ザ、プロクター、エンド、ギャンブル、カンパニー コバルト▲ｉｉｉ▼触媒を含む自動皿洗い組成物
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
DE19518693A1 (de) 1995-05-22 1996-11-28 Henkel Kgaa Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel
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
US5739327A (en) 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
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
DE19605526A1 (de) * 1996-02-15 1997-08-21 Hoechst Ag Ammoniumnitrile und deren Verwendung als Bleichaktivatoren
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
DE19616769A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetale als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616770A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Acyllactame als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616693A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Enolester als Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19616767A1 (de) 1996-04-26 1997-11-06 Henkel Kgaa Bleichaktivatoren für Wasch- und Reinigungsmittel
DE19620267A1 (de) 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen

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ES2172825T5 (es) 2005-12-01
DE59706340D1 (de) 2002-03-21
JP2001504883A (ja) 2001-04-10
JP4097295B2 (ja) 2008-06-11
US6225274B1 (en) 2001-05-01
ES2172825T3 (es) 2002-10-01
DE19649375A1 (de) 1998-06-04
WO1998023719A2 (fr) 1998-06-04
ATE213013T1 (de) 2002-02-15
EP0944707B2 (fr) 2005-06-01
EP1138754A1 (fr) 2001-10-04
EP0944707A2 (fr) 1999-09-29
WO1998023719A3 (fr) 1998-07-30

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