EP0944707A2 - Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents - Google Patents

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

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Publication number
EP0944707A2
EP0944707A2 EP97951944A EP97951944A EP0944707A2 EP 0944707 A2 EP0944707 A2 EP 0944707A2 EP 97951944 A EP97951944 A EP 97951944A EP 97951944 A EP97951944 A EP 97951944A EP 0944707 A2 EP0944707 A2 EP 0944707A2
Authority
EP
European Patent Office
Prior art keywords
weight
formula
compound
compounds
bleach
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP97951944A
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German (de)
English (en)
Other versions
EP0944707B1 (fr
EP0944707B2 (fr
Inventor
Christian Nitsch
Rainer Jeschke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP01115441A priority Critical patent/EP1138754A1/fr
Publication of EP0944707A2 publication Critical patent/EP0944707A2/fr
Publication of EP0944707B1 publication Critical patent/EP0944707B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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

  • Acetonitrile derivatives as bleach activators in cleaning agents are Acetonitrile derivatives as bleach activators in cleaning agents
  • the present invention relates to the use of certain acetonitrile derivatives as activators for, in particular, inorganic peroxygen compounds for bleaching colored stains on dishes and cleaning agents for dishes which contain such activators.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of 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 classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides.
  • bleach activators for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides.
  • the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.
  • Silver can react with sulfur-containing substances that are dissolved or dispersed in the rinsing water when cleaning, because when cleaning dishes in household dishwashers, food residues and, among other things, mustard, peas, egg and other sulfur-containing compounds such as mercaptoamino acids are introduced into the washing liquor.
  • the much higher temperatures during machine rinsing and the longer contact times with the sulfur-containing food residues also favor the tarnishing of silver compared to manual rinsing. Due to the intensive cleaning process in the dishwasher, the silver surface is also completely degreased and therefore more sensitive to chemical influences.
  • tarnishing silver becomes particularly acute when, as an alternative to the sulfur-containing substances, oxidatively "defusing" active chlorine compounds, active oxygen compounds, such as sodium perborate or sodium percarbonate, are used, which are used to remove bleachable stains, such as tea stains / tea deposits, coffee residues, vegetable dyes, lipstick residues and the like serve.
  • active chlorine compounds such as sodium perborate or sodium percarbonate
  • bleachable stains such as tea stains / tea deposits, coffee residues, vegetable dyes, lipstick residues and the like serve.
  • Such active oxygen bleaching agents are used, usually together with bleach activators, especially in modern, low-alkaline machine dishwashing detergents of the new generation of detergents.
  • These agents generally consist of the following functional components: builder component (complexing agent / dispersant), alkali carrier, bleaching system (combination of bleaching agent and bleach activator), enzyme and surfactant.
  • the aim of the present invention is to improve the oxidation and bleaching effect, in particular of inorganic peroxygen compounds, at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 55 ° C.
  • the invention relates to the use of compounds of the general formula IR ⁇ R CF NX " (I) in which R 1 , R 2 and R 3 are independently an alkyl, alkenyl or aryl group having 1 to 18 carbon atoms, the Groups R and R can also be part of a heterocycle including the N atom and optionally further hetero atoms, and X is a charge-balancing anion, as activators for in particular inorganic peroxygen compounds in aqueous cleaning solutions for dishes.
  • R 2 and R 3 form a morpholinium ring, including the quaternary N atom.
  • 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. Preference is given to the use of compounds of the formula I in which X "is methosulfate.
  • An acetonitrile derivative according to formula I is preferably used in cleaning solutions for dishes for bleaching colored stains.
  • bleaching is understood here to mean both the bleaching of dirt located on the surface of the dishes, in particular tea, and the bleaching of dirt located in the dishwashing liquor and detached from the surface.
  • the invention relates to cleaning agents for dishes, and among them preferably those for use in machine cleaning processes which contain a compound according to formula I described above, and a method for cleaning dishes using such a compound.
  • the use according to the invention as a bleach activator essentially consists in creating, in the presence of a dish surface contaminated with colored soiling, conditions under which a peroxidic oxidizing agent and the bleach activating acetonitrile derivative can react with one another with the aim of obtaining secondary products with a stronger oxidizing action.
  • a peroxidic oxidizing agent and the bleach activating acetonitrile derivative can react with one another with the aim of obtaining secondary products with a stronger oxidizing action.
  • Such conditions exist in particular when both reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the acetonitrile derivative to an optionally detergent-containing solution.
  • the method according to the invention is particularly advantageously carried out using a dishwashing detergent according to the invention which 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.
  • a peroxygen-containing oxidizing agent preferably selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
  • the peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free cleaning agent is used.
  • the conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium.
  • the amounts of peroxygen compounds used are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen.
  • the amount of bleach activating acetonitrile derivative used also depends on the intended use. Depending on the desired degree of activation, 0.00001 mol to 0.25 mol, preferably 0.001 mol to 0.02 mol, of activator per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen short of.
  • Another object of the invention is a cleaning agent for dishes, which 1 wt .-% to 10 wt .-%, in particular 3 wt .-% to 6 wt .-% of an acetonitrile derivative according to formula I in addition to conventional, compatible with the compound Contains ingredients.
  • the bleach activator can be adsorbed onto carriers in a manner known in principle and / or be embedded in coating substances.
  • the cleaning agents according to the invention which can be present in powder or tablet form as solids, homogeneous solutions or suspensions, can in principle contain all the known ingredients which are customary in such agents.
  • the agents according to the invention can in particular contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as silver corrosion inhibitors, foam regulators, additional bleach-boosting active ingredients and colorants and fragrances.
  • a cleaning agent according to the invention can also contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls, and mixtures thereof.
  • Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
  • Another subject matter of the invention is an agent for machine cleaning of dishes, containing 15% by weight to 70% by weight, in particular 20% by weight to 60% by weight of water-soluble builder component, 5% by weight to 25% by weight.
  • oxygen-based bleaching agent in each case based on the total agent, which is a bleach-activating acetonitrile derivative according to formula I, in particular in amounts of 3% by weight to 6% by weight , contains.
  • Such an agent is preferably lower alkaline, that is to say its 1% strength by weight solution has a pH of 8 to 11.5, in particular 9 to 11.
  • Suitable water-soluble builder components are in principle all builder substances usually used in agents for the automatic cleaning of dishes, for example alkali metal phosphates, which may be present in the form of their alkaline neutral or acidic sodium or potassium salts.
  • alkali metal phosphates which may be present in the form of their alkaline neutral or acidic sodium or potassium salts.
  • alkali metal phosphates which may be present in the form of their alkaline neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization in the range from 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.
  • the low-alkaline agents according to the invention are preferably 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, particularly in hard water regions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Polymers of native origin that can be used as co-builders 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.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as, for example, mono-, di-hydroxysuccinic acid, hydroxypropionic acid and gluconic acid.
  • the preferred builder components include the salts of citric acid, especially sodium citrate.
  • Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the co-builder salts mentioned can also be present, at least in part.
  • Suitable oxygen-based bleaches are primarily alkali perborate or tetrahydrate and / or alkali percarbonate and alkali persulfates, persilicates and percitrates, with sodium being the preferred alkali metal.
  • the use of sodium percarbonate has advantages in particular in cleaning agents for dishes, 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.
  • known peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can also be useful.
  • bleach activators that is to say compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid be used.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric 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 the mixtures described in European patent application EP 0 525 239 (S
  • hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used.
  • Conventional bleach activators of this type are present in the customary quantitative range, preferably in amounts of 0.1% by weight to 10% by weight, in particular 0.5% by weight to 7% by weight, based on the total agent.
  • 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 salen 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 comp.
  • 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 from 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.
  • 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 is contained in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight .
  • the ratio of the carbonate used and the hydrogen carbonate used varies.
  • agents according to the invention are 20% by weight to 60% by weight of water-soluble organic builders, in particular alkali citrate, 3% by weight to 20% by weight of alkali carbonate and 5% by weight to 40% by weight of alkali disilicate contain.
  • the agents according to the invention can optionally also contain anionic, nonionic and / or amphoteric surfactants, in particular weakly foaming nonionic surfactants are added, which serve the better detachment of greasy soiling, as a wetting agent and, if necessary, as a granulating aid in the production 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 machine dishwashing processes.
  • C 2 -C 8 -alkylpolyethylene glycol polypropylene glycol ether each with 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, for example, -C 8 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 4 alkyl polyglucosides with a degree of polymerization of about 1 to 4 (z. B.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably originates from a fatty alcohol with the C chain length C 6 -C 1. It is sometimes 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 can be used in the cleaning agents according to the invention for cleaning dishes.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- 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 are in one of the oxidation states II, III, IV, V or VI, depending on the metal.
  • the content of silver corrosion inhibitors in agents according to the invention is preferably in the range from 0.01% by weight to 1.5% by weight, in particular from 0.1% by weight to 0.5% by weight.
  • 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 manganese (II) salts or complexes mentioned there to prevent the Silver corrosion can be used in agents according to the invention.
  • the agents according to the invention can contain 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 enzymes which may be used, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are contained in the cleaning agents according to the invention preferably in amounts of up to 2% by weight, in particular from 0.1% by weight to 1.5% by weight, particular preference being given to enzymes stabilized against oxidative degradation, for example from the international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known.
  • the cleaning agents foam too much during use, they can preferably contain up to 6% by weight, in particular approximately 0.5% by weight to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils Silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amide, and other other known commercially available defoamers can be added.
  • a foam-suppressing compound preferably from the group of silicone oils
  • silicone oils silicone oils
  • hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bis fatty acid amide, and other other known commercially available defoamers can be added.
  • Other optional ingredients in the agents according to the invention are, for example, perfume oils.
  • the organic solvents which 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 derivable from the compound classes mentioned.
  • Such water-miscible solvents are preferably not present in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 15% by weight.
  • the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also contain mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • the preparation of the solid compositions according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleaching catalyst optionally being added separately later.
  • Cleaning agents according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, to which enzymes, bleaching agents and the bleach activator in particular can be counted.
  • the procedure is preferably such that all the components mixed together in a mixer and the mixture using conventional tablet presses, for example eccentric presses or rotary presses with press pressures in the range of 200 10 5 Pa to 1 500 '10 5 Pa pressed.
  • a tablet produced 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 can be produced in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / 1 by carrying out the builder components with at least a portion of liquid mixture components in a first process stage Increasing the bulk density of this premix is mixed and subsequently - if desired after an intermediate drying - the further components of the agent, including the bleaching catalyst, are combined with the premix obtained in this way.
  • Agents according to the invention for cleaning dishes can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / 1, preferably 2 to 5 g / 1.
  • a machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water and a rinse cycle with a customary rinse aid after the cleaning cycle. After drying, when using the agents according to the invention, completely clean and hygienically correct dishes are obtained. Examples
  • a cleaning agent (VI) for the automatic cleaning of dishes containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium arbonate, 30 parts by weight of sodium hydrogen carbonate, 1 part by weight of protease and amylase granules, 2 Parts by weight of nonionic surfactant and 10 parts by weight of sodium perborate monohydrate, and agents according to the invention (Ml to M5), which were otherwise composed as VI, but additionally contained the additives (parts by weight) given in Table 1, where the acetonitrile derivative was added separately as an aqueous solution at the beginning of the main wash cycle, were tested as follows:
  • the grades of the agents according to the invention given in Table 2 are significantly better than the value for the comparative products VI and V2, which contained the bleach activator TAED which has become standard.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)

Abstract

L'invention vise à améliorer l'effet d'oxydation et de blanchiment des composés peroxygénés inorganiques lors du nettoyage, notamment en machine, de la vaisselle. On utilise à cet effet des composés de la formule R?1R2R3N+CH¿2CN X-, dans laquelle R?1, R2 et R3¿ sont indépendamment les uns des autres un groupe alkyle, alcényle ou aryle avec 1 à 18 atomes de C, les groupes R2 et R3 pouvant être également une partie d'un hétérocycle renfermant l'atome de N et éventuellement d'autres hétéroatomes, et X étant un anion égalisateur de charge. Des agents pour le nettoyage, notamment en machine, de la vaisselle contiennent environ 1 % en poids à 10 % en poids d'une telle substance active renforçant le blanchiment.
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)

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

Publications (3)

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

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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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DE (2) DE19649375A1 (fr)
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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
JP4097295B2 (ja) 2008-06-11
DE59706340D1 (de) 2002-03-21
DE19649375A1 (de) 1998-06-04
EP0944707B2 (fr) 2005-06-01
ATE213013T1 (de) 2002-02-15
EP1138754A1 (fr) 2001-10-04
JP2001504883A (ja) 2001-04-10

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