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WO2000050553A1 - Preparation a base de derives d'acetonitrile utilisee comme activateur de blanchiment dans des produits de nettoyage - Google Patents

Preparation a base de derives d'acetonitrile utilisee comme activateur de blanchiment dans des produits de nettoyage Download PDF

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Publication number
WO2000050553A1
WO2000050553A1 PCT/EP2000/001248 EP0001248W WO0050553A1 WO 2000050553 A1 WO2000050553 A1 WO 2000050553A1 EP 0001248 W EP0001248 W EP 0001248W WO 0050553 A1 WO0050553 A1 WO 0050553A1
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weight
compound
formula
compounds
charge
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PCT/EP2000/001248
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German (de)
English (en)
Inventor
Andreas Lietzmann
Christian Nitsch
Gerhard Blasey
Horst-Dieter Speckmann
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU26724/00A priority Critical patent/AU2672400A/en
Publication of WO2000050553A1 publication Critical patent/WO2000050553A1/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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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

Definitions

  • the present invention relates to the use of compounded ncetonitrile derivatives as activators for, in particular, inorganic peroxygen compounds for bleaching colored stains on dishes and cleaning agents for dishes which contain such activator compounds.
  • 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 oxidation 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 the addition of so-called bleach activators, for which numerous suggestions, especially from the classes of the ⁇ - or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, ⁇ - acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy benzene sulfonate, sodium isononanonate sulfonate, glucosulfonate, acyl benzyl sulfonate, acyl benzyl sulfulf
  • 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.
  • active oxygen compounds such as sodium perborate or sodium percarbonate
  • bleachable stains such as tea stains / tea deposits, coffee residues, dyes from vegetables, Lipstick remnants and the like
  • 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.
  • 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.
  • a problem with such acetonitrile derivatives is their storage stability in alkaline cleaning agents, which is often perceived as inadequate.
  • storage-stable preparations are obtained by compounding the acetonitrile derivatives with alkali metal phosphates, although such phosphates have an alkaline reaction in water.
  • a possible explanation for this could be that the hydration of the phosphate binds the water so strongly that it is not detrimental to the stability of the acetonitrile derivatives.
  • the storage stability of the acetonitrile derivative can be further improved in the presence of phosphonic acids or phosphonates in the compounds.
  • a first object of the invention is therefore a particulate preparation (compound) containing 0.1% to 60% by weight of a compound of the general formula (I),
  • Another object of the invention is the use of compounds of general 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, sulfate, hydrogen sulfate, methosulfate and ethosulfate, chlorate, perchlorate, and the anions of carboxylic acids such as formate, acetate, benzoate or citrate .
  • X is sulfate, hydrogen sulfate or methosulfate.
  • Compounds according to formula I can be prepared by known processes or in accordance with them, as described, for example, by Abraham in Progr. Phys. Org. Chem. 11 (1974), S. Iff, or by Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff.
  • Some compounds according to general formula I are described in international patent application WO 96/40661.
  • the content of a compound of the formula I is 0.5% by weight to 30% by weight, in particular 5% by weight to 20% by weight, based in each case on the compound.
  • Suitable alkali metal phosphates are, in particular, the salts of phosphoric acid present in the form of alkaline, neutral or acidic sodium or potassium compounds. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexamaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and mixtures of the sodium salts mentioned with the corresponding potassium salts.
  • the alkali phosphate content is 35% by weight to 99.5% by weight, in particular 40% by weight to 70% by weight, based in each case on the compound.
  • a compound according to the invention can additionally contain phosphonic acids or optionally functionally modified phosphonic acids, for example hydroxy- or aminoalkanephosphonic acids, and / or their alkali metal salts, in particular their sodium salts.
  • the phosphonic acids include, for example, 1-hydroxyethane-l, l-diphosphonic acid (HEDP) or the dialkali salt or the tetraalkali salt of this acid, ethylenediamine-tetramethylenephosphonic acid (EDTMP), diethylenetriamine-pentamethylenephosphonic acid (DTPMP) and their higher homologs, and also these can be used in the form of their alkali salts, in particular their sodium salts.
  • Such phosphonic acids or their alkali metal salts are preferably present in compounds according to the invention in amounts of 0.1% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight.
  • Compounding aids in particular are polymeric polycarboxylates, such as, for example, polyacrylic acids 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 that can also be used as compounding aids 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.
  • Compounding agents of this type are preferably present in compounds of the invention in amounts of 0.1% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight.
  • An acetonitrile derivative according to formula I in compounded form 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 described above, and a method for cleaning dishes using such a compound.
  • Compounds according to the invention are preferably produced by mixing and granulating alkali phosphate with an aqueous solution of a compound of the formula (I).
  • phosphonic acid and or alkali phosphonate if desired as an aqueous solution or in solid form, can also be added in the mixing stage. It is also possible to add a compounding aid in aqueous solution or in solid form. If the amount of liquid is high enough, granules already form during the mixing process. If the amount of liquid is small, the fine-particle mixture is preferably converted into granules by mechanical compression. This The compression step is preferably pelleting or compacting. After the granulate formation, the compound can optionally be dried.
  • the use of the compound according to the invention essentially consists in creating conditions in the presence of a dish surface contaminated with colored soiling, 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.
  • Such conditions exist in particular when both reactants meet in aqueous solution. This can be done by adding the peroxygen compound and the compound separately 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 compound 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 are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions.
  • 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 with the aid of alkali phosphate as a carrier material contains compounded form.
  • 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. %, in particular 8% by weight to 17% by weight, of an oxygen-based bleaching agent, in each case based on the total agent, which contains a bleach-activating acetonitrile derivative of the formula I in a form compounded with the aid of alkali metal phosphate as carrier material, in particular in amounts of 3% by weight .-% to 6 wt .-%, 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.
  • builder commonly used, for example the alkali metal phosphates mentioned above as part of the compounds according to the invention.
  • Their amounts - including the amount of alkali metal phosphate originating from the compound according to the invention and any compounding aid which may have been present - can, if desired, be in the range up to about 65% by weight, based on the total agent.
  • Other possible water-soluble builder components are, for example, organic polymers of native or synthetic origin, in particular the polymeric polycarboxylic acids or their salts listed above under the compounding aids, which act as co-builders in particular in hard water regions.
  • Other possible builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic 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.
  • known conventional 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 as well as acetylated sorbitol and mannitol or their 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.
  • bleaching catalysts In addition to the conventional bleach activators listed above or in their place, those from European patent specifications EP 0 446 982 and Known EP 0 453 003 sulfonimines and or bleach-enhancing transition metal salts or transition metal complexes may be included 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 compl.
  • 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 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 metal drug 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.
  • 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 machine 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 - (such as APG® 225 and APG® 600 from Henkel.) alkyl polyglucosides with a degree of polymerization of about 1 to 4 and / or C I2 -C -Alkylpolyethylenglykole having 3 to 8 Ethylene oxide units in the molecule.
  • 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 4 . 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.
  • the manganese (III) or manganese (IV) complexes known from international patent application WO 94/19445, the cysteine disclosed in international patent application WO 94/07981 as silver protection agent, and the one disclosed in German patent application DE 195 18 693 as silver corrosion inhibiting effect alone or in particular in combination with isocyanuric acid, and / or the titanium, zirconium, hafnium, vanadium, cobalt or cerium salts described in German patent applications DE 43 25 922 or DE 43 15 397 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 are used to prevent silver corrosion 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®, Dur
  • 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 agents according to the invention can include acids which are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and or adipic acid, but also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
  • acids which are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and or adipic acid, but also mineral acids, especially sulfuric acid or 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.
  • 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. gene, the peroxygen compound and the compound according to the invention optionally being added separately later.
  • 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, in particular enzymes, bleaching agents and the bleach activator can be expected to be manufactured.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is pressed 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 .
  • 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 constituents of the composition, including the compound according to the invention, 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 con 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 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 agents according to the invention, completely clean and hygienically correct dishes are obtained.
  • a cleaning formulation obtainable by mixing the individual particulate components given in Table 1 below, spraying on the nonionic surfactant and spraying on the perfume was used.
  • one of the components Na tripolyphosphate (Ml), sodium carbonate (VI), sodium perborate (V2), sodium disilicate (V3) or nonionic surfactant (V4) was obtained separately with 4 parts by weight (each on total average) of an approx. 50% aqueous N-methyl-morpholinium-acetonitrile-methosulfate solution (Sokalan® BM from BASF; MMA solution) mixed (for example 11 g sodium phosphate with 0.8 g of the solution or 4, 6 g sodium carbonate with 0.8 g of the solution, etc.).
  • the entire cleaner formulation was also treated with the solution (V5).
  • the agents prepared in this way were stored for 30 minutes and then used in the dishwasher.
  • a compound CI according to the invention was produced by mixing 63% by weight of sodium tripolyphosphate (Thermphos® S) and 37% by weight of the above-mentioned 50% MMA solution with subsequent roller compaction in an Alexander roller. The slug was broken in a sieve granulator and the granulate fraction between 0.6 mm and 1.6 mm was sieved. These granules were stored for 3 weeks at room temperature and mixed with the other ingredients listed in Table 1 (including additional sodium tripolyphosphate) to form a cleaning agent M2 with the same gross composition as Ml.

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Abstract

L'invention a pour objet d'améliorer l'action d'oxydation et de blanchiment de composés de péroxoacide lors notamment du nettoyage de vaisselle en machine. Pour ce faire, on utilise essentiellement comme matériau support, à l'aide d'alcaliphosphate, des composés mélangés de la formule R?1R2R3N+CH¿2CN X?-, où R1, R2 et R3¿ indépendamment l'un de l'autre, représentent un groupe alkyle, alcényle ou aryle ayant 1 à 18 atomes de carbone. Les groupes R2 et R3 peuvent également constituer une partie d'un hétérocycle incluant l'atome d'azote et éventuellement d'autres hétéroratomes, et X est un anion compensant la charge. Des produits destinés au nettoyage de vaisselle en machine contiennent environ 1 à 10 % en poids d'un principe actif renforçant le blanchiment selon la formule R?1R2R3N+CH¿2CN X- sous forme mélangée correspondante.
PCT/EP2000/001248 1999-02-25 2000-02-16 Preparation a base de derives d'acetonitrile utilisee comme activateur de blanchiment dans des produits de nettoyage WO2000050553A1 (fr)

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AU26724/00A AU2672400A (en) 1999-02-25 2000-02-16 Compounded acetonitrile derivatives used as bleach activators in cleaning agents

Applications Claiming Priority (2)

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DE19908069.0 1999-02-25
DE1999108069 DE19908069A1 (de) 1999-02-25 1999-02-25 Compoundierte Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln

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WO2000050553A1 true WO2000050553A1 (fr) 2000-08-31

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7316995B2 (en) 2003-02-10 2008-01-08 Henkel Kommanditgesellschaft Auf Aktien Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
US7375072B2 (en) 2003-02-10 2008-05-20 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative
US7431739B2 (en) 2005-06-08 2008-10-07 Henkel Kommanditgesellschaft Auf Aktien Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol
US7456143B2 (en) 2002-12-20 2008-11-25 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Bleach-containing washing or cleaning agents containing a sulfate/silicate coated percarbonate

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DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
DE10057045A1 (de) * 2000-11-17 2002-05-23 Clariant Gmbh Teilchenförmige Bleichaktivatoren auf der Basis von Acetonitrilen
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
BR0317351A (pt) 2002-12-18 2005-11-16 Procter & Gamble Ativador orgânico, processo para a produção, composição de limpeza e método de limpeza do mesmo
DE102005026544A1 (de) 2005-06-08 2006-12-14 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
GB0917951D0 (en) * 2009-10-14 2009-11-25 Chemlink Specialities Ltd Composition including one or more hydrolytically unstable components

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EP0458396A1 (fr) * 1990-05-24 1991-11-27 Unilever N.V. Composition de blanchiment
EP0464880A1 (fr) * 1990-05-30 1992-01-08 Unilever N.V. Composition blanchissante
EP0742280A2 (fr) * 1995-05-08 1996-11-13 The Procter & Gamble Company Compositions pour lave-vaisselle automatique comprenant des activateurs de blanchiment multiquaternaires
EP0790244A1 (fr) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
WO1998023602A1 (fr) * 1996-11-29 1998-06-04 The Clorox Company Sels d'acetonitrile d'ammonium n-alkyle, procedes associes et compositions contenant ces sels
WO1998023534A1 (fr) * 1996-11-29 1998-06-04 The Clorox Company Compositions activatrices peroxygenees mixtes
WO1998023531A1 (fr) * 1996-11-29 1998-06-04 The Clorox Company Compositions granulaires d'acetonitrile d'ammonium n-alkyle
WO1998023719A2 (fr) * 1996-11-29 1998-06-04 Henkel Kommanditgesellschaft Auf Aktien Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents
DE19713852A1 (de) * 1997-04-04 1998-10-08 Henkel Kgaa Aktivatoren für Persauerstoffverbindungen in Wasch- und Reinigungsmitteln

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458396A1 (fr) * 1990-05-24 1991-11-27 Unilever N.V. Composition de blanchiment
EP0464880A1 (fr) * 1990-05-30 1992-01-08 Unilever N.V. Composition blanchissante
EP0742280A2 (fr) * 1995-05-08 1996-11-13 The Procter & Gamble Company Compositions pour lave-vaisselle automatique comprenant des activateurs de blanchiment multiquaternaires
EP0790244A1 (fr) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
WO1998023602A1 (fr) * 1996-11-29 1998-06-04 The Clorox Company Sels d'acetonitrile d'ammonium n-alkyle, procedes associes et compositions contenant ces sels
WO1998023534A1 (fr) * 1996-11-29 1998-06-04 The Clorox Company Compositions activatrices peroxygenees mixtes
WO1998023531A1 (fr) * 1996-11-29 1998-06-04 The Clorox Company Compositions granulaires d'acetonitrile d'ammonium n-alkyle
WO1998023719A2 (fr) * 1996-11-29 1998-06-04 Henkel Kommanditgesellschaft Auf Aktien Derives d'acetonitrile utilises comme activateurs de blanchiment dans des detergents
DE19713852A1 (de) * 1997-04-04 1998-10-08 Henkel Kgaa Aktivatoren für Persauerstoffverbindungen in Wasch- und Reinigungsmitteln

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7456143B2 (en) 2002-12-20 2008-11-25 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Bleach-containing washing or cleaning agents containing a sulfate/silicate coated percarbonate
US7316995B2 (en) 2003-02-10 2008-01-08 Henkel Kommanditgesellschaft Auf Aktien Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
US7375072B2 (en) 2003-02-10 2008-05-20 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative
US7431739B2 (en) 2005-06-08 2008-10-07 Henkel Kommanditgesellschaft Auf Aktien Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol

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CA2299437A1 (fr) 2000-08-25
AU2672400A (en) 2000-09-14

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