EP0944707B1 - Acetonitrile derivatives as bleaching activators in detergents - Google Patents

Acetonitrile derivatives as bleaching activators in 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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Prior art keywords
weight
detergent
formula
compounds
alkyl
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EP97951944A
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German (de)
French (fr)
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EP0944707A2 (en
EP0944707B2 (en
Inventor
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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Priority to EP01115441A priority Critical patent/EP1138754A1/en
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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

Abstract

Use of compounds of formula (I) as activators for (preferably inorganic) peroxy compounds in aqueous cleaning solutions for crockery is claimed : R1R2R3N<+>CH2CN X<-> (I) R1-R3 = alkyl, alkenyl or aryl of 1-18C (sic), or NR2R3+optional further heteroatoms can also form a heterocyclic ring; and X = anion. Also claimed are: (i) the use of (I) in crockery cleaning solutions for bleaching coloured stains, (ii) crockery cleaning agents containing 1-10 (3-6) wt.% (I) and other conventional components; and (iii) dishwasher detergents containing 3-6 wt.% (I), 15-70 (20-60) wt.% water soluble builder components and 5-25 (8-17) wt.% oxygen-based bleaching agents.

Description

Die vorliegende Erfindung betrifft Reinigungsmittel für Geschirr die bestimmte Acetonitril-Derivate als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen zum Bleichen von gefärbten Anschmutzungen an Geschirr enthalten.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.

Anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Persauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lösen, wie Natriumperborat und Natriumcarbonat-Perhydrat, werden seit langem als Oxidationsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung dieser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80°C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoffverbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy-benzolsulfonat und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. Durch Zusatz dieser Substanzen kann die Bleichwirkung wäßriger Peroxidflotten so weit gesteigert werden, daß bereits bei Temperaturen um 60 °C im wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 °C eintreten. Aus der japanischen Patentanmeldung JP 1-198 700 sind Geschirrspülmittel bekannt, welche Ammoniumacetonitrilderivate enthalten, deren quaternäres Stickstoffatom zwei C1-3-Alkylgruppen und eine C1-22-Alkylgruppe trägt. Aus der europäischen Patentanmeldung EP 0 464 880 ist der Einsatz ähnlicher, zwei C1-4-Alkyl- oder Hydroxyalkylgruppen und eine C1-24-Alkyl- Alkelnyl- oder Alkylethergruppe aufweisender Substanzen bekannt. Die europäische Patentanmeldung EP 0 303 520 offenbart bleichende Textilwaschmittel, die Ammoniumacetonitrilderivate enthalten, deren quaternäres Stickstoffatom Teil eines gegebenenfalls substituierten Pyridinrings ist.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. At lower temperatures, 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, Carbonsäureester, 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 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. From Japanese patent application JP 1-198 700 dishwashing detergents are known 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.

Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den letzten Jahren Anwendungstemperaturen deutlich unterhalb 60 °C, insbesondere unterhalb 45 °C bis herunter zur Kaltwassertemperatur an Bedeutung. In the effort for energy-saving washing and bleaching processes have won in recent years Application temperatures well below 60 ° C, especially below 45 ° C down to Chilled water temperature is of importance.

Bei diesen niedrigen Temperaturen läßt die Wirkung der bisher bekannten Aktivatorverbindungen in der Regel erkennbar nach. Es hat deshalb nicht an Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Aktivatoren zu entwickeln, ohne daß bis heute ein überzeugender Erfolg zu verzeichnen gewesen wäre.At these low temperatures, the effect of the activator compounds known hitherto usually recognizable after. There has been no shortage of efforts for to develop more effective activators in this temperature range without having to date convincing success would have been recorded.

Ein insbesondere bei Reinigungsmitteln für das maschinelle Geschirrspülen weiteres Problem ist die Notwendigkeit, in derartige Mittel Korrosionsinhibitoren für Tafelsilber einzuarbeiten, insbesondere wenn die Mittel die in neuerer Zeit üblichen Bleich- beziehungsweise Oxidationsmittel auf Sauerstoffbasis enthalten. Silber kann beim Reinigen mit schwefelhaltigen Substanzen, die im Spülwasser gelöst beziehungsweise dispergiert sind, reagieren, denn bei der Reinigung von Geschirr in Haushaltsgeschirrspülmaschinen werden Speisereste und damit unter anderem auch Senf, Erbsen, Ei und sonstige schwefelhaltige Verbindungen wie Mercaptoaminosäuren in die Spülflotte eingebracht. Auch die während des maschinellen Spülens viel höheren Temperaturen und die längeren Kontaktzeiten mit den schwefelhaltigen Speiseresten begünstigen im Vergleich zum manuellen Spülen das Anlaufen von Silber. Durch den intensiven Reinigungsprozeß in der Spülmaschine wird die Silberoberfläche außerdem vollständig entfettet und dadurch empfindlicher gegenüber chemischen Einflüssen.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. Also 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.

Das Problem des Silberanlaufens wird insbesondere dann akut, wenn alternativ zu den schwefelhaltige Substanzen oxidativ "entschärfenden" Aktivchlorverbindungen Aktivsauerstoffverbindungen, wie beispielsweise Natriumperborat oder Natriumpercarbonat eingesetzt werden, welche zur Beseitigung bleichbarer Anschmutzungen, wie beispielsweise Teeflecken/Teebeläge, Kaffeerückstände, Farbstoffe aus Gemüse, Lippenstiftreste und dergleichen dienen.The problem of 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.

Derartige Aktivsauerstoff-Bleichmittel werden, in der Regel zusammen mit Bleichaktivatoren, vor allem in modernen niederalkalischen maschinellen Spülmitteln der neuen Reinigergeneration eingesetzt. Diese Mittel bestehen im allgemeinen aus den folgenden Funktionsbausteinen: Builderkomponente (Komplexbildner/Dispergiermittel), Alkaliträger, Bleichsystem (Kombination aus Bleichmittel und Bleichaktivator), Enzym und Tensid. Unter den bei Einsatz derartig aufgebauter Mittel auftretenden Spülbedingungen bilden sich in Gegenwart von Silber in der Regel nicht nur sulfidische, sondern durch den oxidierenden Angriff der intermediär gebildeten Peroxide beziehungsweise des Aktivsauerstoffs auch oxidische Beläge auf den Silberoberflächen.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. Under the rinsing conditions that occur when using such compositions In the presence of silver, they usually form not only from the sulfidic but also from the oxidizing attack of the intermediately formed peroxides or the active oxygen also oxidic deposits on the silver surfaces.

Die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung insbesondere anorganischer Persauerstoffverbindungen bei niedrigen Temperaturen unterhalb von 80 °C, insbesondere im Temperaturbereich von ca. 15 °C bis 55 °C, zum Ziel.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.

Es wurde nun gefunden, daß bestimmte Acetonitril-Derivate, die einen quaternären Stickstoffsubstituenten tragen, eine deutliche bleichverstärkende Wirkung bei Einsatz zusammen mit peroxidischen Bleichmitteln gegenüber gefärbten Anschmutzungen haben, die sich an Geschirr, wie Tassen, Tellern oder Besteckteilen, befinden.It has now been found that certain acetonitrile derivatives that have a quaternary nitrogen substituent wear, a clear bleach-enhancing effect when used together with peroxidic bleaches against colored stains, on dishes such as cups, plates or cutlery.

Gegenstand der Erfindung ist ein Mittel zur Reinigung von Geschirr, welches dadurch gekennzeichnet ist, daß es 1 Gew.-% bis 10 Gew.-%, insbesondere 3 Gew.-% bis 6 Gew.-% einer Verbindung der allgemeinen Formel I R1R2R3N+CH2CN X- in der R1, R2 und R3 unabhängig voneinander eine Alkyl-, Alkenyl oder Arylgruppe mit 1 bis 18 C-Atomen ist, wobei die Gruppen R1 und R2 Teil eines das N-Atom und gegebenenfalls weitere Heteroratome einschließenden Heterocyclusses sind und X ein ladungsausgleichendes Anion ist, neben üblichen, mit der Verbindung gemäß Formel I verträglichen Inhaltsstoffen enthält.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.

Die Herstellung von Verbindungen gemäß Formel I kann nach bekannten Verfahren oder in Anlehnung an diese erfolgen, wie sie zum Beispiel von Abraham in Progr. Phys. Org. Chem. 11 (1974), S. 1ff, oder von Amett in J. Am. Chem. Soc. 102 (1980), S. 5892ff veröffentlicht worden sind. Einige Verbindungen gemäß allgemeiner Formel I sind in der nicht vorveröffentlichten internationalen Patentanmeldung PCT/US 96/08497 beschrieben.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), pp. 1ff, or by Amett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. Some compounds according to general formula I are described in the unpublished international patent application PCT / US 96/08497.

Besonders bevorzugt sind Mittel, welche Verbindungen gemäß Formel I, in denen R2 und R3 unter Einbeziehung des quaternären N-Atoms einen Morpholinium-Ring bilden, enthalten. In diesen ist R1 vorzugsweise eine Alkylgruppe mit 1 bis 3 C-Atomen, insbesondere eine Methylgruppe. Agents which contain compounds of the formula I in which R 2 and R 3 form a morpholinium ring, including the quaternary N atom, are particularly preferred. In these, R 1 is preferably an alkyl group with 1 to 3 carbon atoms, in particular a methyl group.

Zu den Anionen X- gehören insbesondere die Halogenide wie Chlorid, Fluorid, Iodid und Bromid, Nitrat, Hydroxid, Hexafluorophosphat, Metho- und Ethosulfat, Chlorat, Perchlorat, und die Anionen von Carbonsäuren wie Formiat, Acetat, Benzoat oder Citrat. Bevorzugt ist der Einsatz von Verbindungen gemäß Formel I, in denen X- Methosulfat ist.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. Is methosulfate - preferred is the use of compounds according to formula I in which X is.

Ein erfindungsgemäßes Reinigungsmittel für Geschirr enthält das bleichaktivierende Acetonitril-Derivat und gegebenenfalls ein persauerstoffhaltiges Oxidationsmittel, vorzugsweise ausgewählt aus der Gruppe umfassend organische Persäuren, Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische. 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.

Bei der Anwendung erfindungsgemäßer Mittel können die Bedingungen weit variiert werden. So kommen neben rein wäßrigen Lösungen auch Mischungen aus Wasser und geeigneten organischen Lösungsmitteln als Reaktionsmedium in Frage. Die Einsatzmengen an Persauerstoffverbindungen werden im allgemeinen so gewählt, daß in den Lösungen zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 ppm und 5 000 ppm Aktivsauerstoff vorhanden sind. Auch die verwendete Menge an bleichaktivierendem Acetonitril-Derivat hängt vom Anwendungszweck ab. Je nach gewünschtem Aktivierungsgrad werden 0,00001 Mol bis 0,25 Mol, vorzugsweise 0,001 Mol bis 0,02 Mol Aktivator pro Mol Persauerstoffverbindung verwendet, doch können in besonderen Fällen diese Grenzen auch über- oder unterschritten werden.When using agents according to the invention, the conditions can vary widely become. In addition to purely aqueous solutions, there are also mixtures of water and suitable organic solvents as a reaction medium in question. The quantities used of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5,000 ppm active oxygen are present. Also 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.

Die erfindungsgemäßen Reinigungsmittel, die als pulver- oder tablettenförmige Feststoffe, homogene Lösungen oder Suspensionen vorliegen können, können außer dem erfindungsgemäß verwendeten Bleichaktivator im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie Silberkorrosionsinhibitoren, Schaumregulatoren, zusätzliche bleichverstärkende Wirkstoffe sowie Farb- und Duftstoffe enthalten.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.

Ein erfindungsgemäßes Reinigungsmittel kann darüber hinaus abrasiv wirkende Bestandteile, insbesondere aus der Gruppe umfassend Quarzmehle, Holzmehle, Kunststoffmehle, Kreiden und Mikroglaskugeln sowie deren Gemische, enthalten. Abrasivstoffe sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-%, enthalten. 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.

Ein weiterer Erfindungsgegenstand ist ein Mittel zum maschinellen Reinigen von Geschirr, enthaltend 15 Gew.-% bis 70 Gew.-%, insbesondere 20 Gew.-% bis 60 Gew.-% wasserlösliche Builderkomponente, 5 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, welches ein bleichaktivierendes Acetonitril-Derivat gemäß Formel I in Mengen von 3 Gew.-% bis 6 Gew.-%, enthält. Ein derartiges Mittel ist vorzugsweise niederalkalisch, das heißt seine 1-gewichtsprozentige Lösung weist einen pH-Wert von 8 bis 11,5, insbesondere von 9 bis 11 auf.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.

Als wasserlösliche Builderkomponenten insbesondere in derartigen niederalkalischen Reinigungsmitteln kommen prinzipiell alle in Mitteln für die maschinelle Reinigung von Geschirr üblicherweise eingesetzten Builder in Frage, zum Beispiel Alkaliphosphate, die in Form ihrer alkalischen neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie Gemische aus Natrium- und Kaliumsalzen. Ihre Mengen können im Bereich von bis zu etwa 55 Gew.-%, bezogen auf das gesamte Mittel liegen; vorzugsweise sind niederalkalische erfindungsgemäße Mittel frei von solchen Phosphaten. Weitere mögliche wasserlösliche Builderkomponenten sind zum Beispiel organische Polymere nativen oder synthetischen Ursprungs, vor allem Polycarboxylate, die insbesondere in Hartwasserregionen als Co-Builder wirken. In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5, CP 10 und PA 30 der Firma BASF. Zu den als Co-Builder brauchbaren Polymeren nativen Ursprungs gehören beispielsweise oxidierte Stärken, wie zum Beispiel aus der internationalen Patentanmeldung WO 94/05762 bekannt, und Polyaminosäuren wie Polyglutaminsäure oder Polyasparaginsäure. Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie zum Beispiel Mono-, Dihydroxybernsteinsäure, α-Hydroxypropionsäure und Gluconsäure. Zu den bevorzugten Builderkomponenten gehören die Salze der Citronensäure, insbesondere Natriumcitrat. As water-soluble builder components, especially in such low-alkaline cleaning agents In principle, all come in agents for the automatic cleaning of dishes commonly used builders in question, for example 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. Their amounts can range up to about 55% by weight based on the total Means lie; 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. To the 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, α-hydroxypropionic acid and gluconic acid. To the preferred builder components include the salts of citric acid, in particular Sodium citrate.

Als Natriumcitrat kommen wasserfreies Trinatriumcitrat und vorzugsweise Trinatriumcitratdihydrat in Betracht. Trinatriumcitratdihydrat kann als fein- oder grobkristallines Pulver eingesetzt werden. In Abhängigkeit vom letztlich in den erfindungsgemäßen Mitteln eingestellten pH-Wert können zumindest anteilig auch die zu den genannten Co-Builder-Salzen korrespondierenden Säuren vorliegen.Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are used as sodium citrate into consideration. Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used. Depending on ultimately in the agents according to the invention The pH value set can also be at least partially those of the co-builder salts mentioned corresponding acids are present.

Als Bleichmittel auf Sauerstoffbasis kommen in erster Linie Alkaliperboratmonobeziehungsweise -tetrahydrat und/oder Alkalipercarbonat sowie Alkalipersulfate,-persilikate und -percitrate in Betracht, wobei Natrium das bevorzugte Alkalimetall ist. Der Einsatz von Natriumpercarbonat hat insbesondere in Reinigungsmitteln für Geschirr Vorteile, da es sich besonders günstig auf das Korrosionsverhalten an Gläsern auswirkt. Das Bleichmittel auf Sauerstoffbasis ist deshalb vorzugsweise ein Alkalipercarbonat, insbesondere Natriumpercarbonat. Zusätzlich oder insbesondere alternativ können auch bekannte Peroxycarbonsäuren, zum Beispiel Dodecandipersäure oder Phthalimidopercarbonsäuren, die gegebenenfalls am Aromaten substituiert sein können, enthalten sein. Überdies kann auch der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat zweckdienlich sein.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. In addition or in particular alternatively also known peroxycarboxylic acids, for example dodecanediperic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic, are included. In addition, the addition of small amounts of known bleach stabilizers such as for example of phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

Zusätzlich zu den oben bleichaktivierenden Acetonitril-Derivaten gemäß Formel I können bekannte konventionelle Bleichaktivatoren, das heißt Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den deutschen Patentanmeldungen DE 196 16 693 und DE 196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP 0 525 239 beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 und WO 95/17498 bekannt sind. Die aus der deutschen Patentanmeldung DE 196 16 769 bekannten hydrophil substituierten Acylacetale und die in der deutschen Patentanmeldung DE 196 16 770 sowie der internationalen Patentanmeldung WO 95/14075 beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DB 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige konventionelle Bleichaktivatoren sind im üblichen Mengenbereich, vorzugsweise in Mengen von 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,5 Gew.-% bis 7 Gew.-%, bezogen auf gesamtes Mittel, enthalten.In addition to the 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. Substances that are O- and / or are suitable N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. 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), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known are. The hydrophilically substituted known from German patent application DE 196 16 769 Acylacetale and those in German patent application DE 196 16 770 and the international patent application WO 95/14075 described acyllactams also preferably used. Even those from the German patent application DB 44 43 177 known combinations of conventional bleach activators can be used. Such conventional bleach activators are in the usual quantity range, preferably in amounts of 0.1% by weight to 10% by weight, in particular 0.5 wt .-% to 7 wt .-%, based on the total, included.

Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP 0 446 982 und EP 0 453 003 bekannten Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein. Zu den in Frage kommenden Übergangsmetallverbindungen gehören insbesondere die aus der deutschen Patentanmeldung DE 195 29 905 bekannten Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Salenkomplexe und deren aus der deutschen Patentanmeldung DE 196 20 267 bekannte N-Analogverbindungen, die aus der deutschen Patentanmeldung DE 195 36 082 bekannten Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Carbonylkomplexe, die in der deutschen Patentanmeldung DE 196 05 688 beschriebenen Mangan-, Eisen-, Cobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden, die aus der deutschen Patentanmeldung DE 196 20 411 bekannten Cobalt-, Eisen-, Kupfer- und Ruthenium-Amminkomplexe, die in der deutschen Patentanmeldung DE 44 16 438 beschriebenen Mangan-, Kupfer- und Cobalt-Komplexe, die in der europäischen Patentanmeldung EP 0 272 030 beschriebenen Cobalt-Komplexe, die aus der europäischen Patentanmeldung EP 0 693 550 bekannten Mangan-Komplexe, die aus der europäischen Patentschrift EP 0 392 592 bekannten Mangan-, Eisen-, Cobalt- und Kupfer-Komplexe und/oder die in der europäischen Patentschrift BP 0443 651 oder den europäischen Patentanmeldungen EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 und EP 0 544 519 beschriebenen Mangan-Komplexe. Kombinationen aus Bleichaktivatoren und Übergangsmetall-Bleichkatalysatoren sind beispielsweise aus der deutschen Patentanmeldung DE 196 13 103 und der internationalen Patentanmeldung WO 95/27775 bekannt. Bleichverstärkende Übergangsmetallsalze und/oder -komplexe, insbesondere mit den Zentralatomen Mn, Fe, Co, Cu, Mo, V, Ti und/oder Ru, werden in üblichen Mengen, vorzugsweise bis zu 1 Gew.-%, insbesondere von 0,0025 Gew.-% bis 0,5 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,1 Gew.-%, jeweils bezogen auf gesamtes Mittel, eingesetzt. Zu den besonders bevorzugten Bleichkatalysatorkomplexen gehören Cobalt-, Eisen-, Kupfer- und Ruthenium-Amminkomplexe, beispielsweise [Co(NH3)5Cl]Cl2 und/oder [Co(NH3)5NO2]Cl2.In addition to the conventional bleach activators listed above or in their place, 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 0 693 550 xe, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592 and / or those described in European patent BP 0443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519 described manganese complexes. Combinations of 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 .

Vorzugsweise enthalten die erfindungsgemäßen maschinellen Geschirreinigungsmittel die üblichen Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2/M2O (M = Alkaliatom) von 1 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 40 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Auf den Einsatz der hoch alkalischen Metasilikate als Alkaliträger wird jedoch vorzugsweise ganz verzichtet. Das in den erfindungsgemäßen Mitteln-bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und -hydrogencarbonat, das in einer Menge von bis zu 50 Gew.-%, vorzugsweise 5 Gew.-% bis 40 Gew.-%, enthalten ist. Je nachdem, welcher pH-Wert letztendlich gewünscht wird, variiert das Verhältnis von eingesetztem Carbonat und eingesetztem Hydrogencarbonat.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. The alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO 2 / M 2 O (M = alkali atom) of 1: 1 to 2.5: 1. 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.

In einer weiteren Ausführungsform erfindungsgemäßer Mittel sind 20 Gew.-% bis 60 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 3 Gew.-% bis 20 Gew.-% Alkalicarbonat und 5 Gew.-% bis 40 Gew.-% Alkalidisilikat enthalten.In a further embodiment, 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.

Den erfindungsgemäßen Mitteln können gegebenenfalls auch anionische, nichtionische und/oder amphotere Tenside, insbesondere schwach schäumende nichtionische Tenside zugesetzt werden, die der besseren Ablösung fetthaltiger Anschmutzungen, als Netzmittel und gegebenenfalls im Rahmen der Herstellung der Reinigungsmittel als Granulierhilfsmittel dienen. Ihre Menge kann bis zu 20 Gew.-%, insbesondere bis zu 10 Gew.-% betragen und liegt vorzugsweise im Bereich von 0,5 Gew.-% bis 5 Gew.-%. Üblicherweise werden insbesondere in Reinigungsmitteln für den Einsatz in maschinellen Geschirrspülverfahren extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel C12-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül, endgruppenverschlossene Alkylpolyalkylenglykolmischether sowie die zwar schäumenden, aber ökologisch attraktiven C8-C14-Alkylpolyglucoside mit einem Polymerisierungsgrad von etwa 1 bis 4 (z. B. APG® 225 und APG® 600 der Firma Henkel) und/oder C12-C14-Alkylpolyethylenglykole mit 3 bis 8 Ethylenoxideinheiten im Molekül. Ebenfalls geeignet sind Tenside aus der Familie der Glucarnide wie zum Beispiel Alkyl-N-Methyl-Glucamide, in denen der Alkylteil bevorzugt aus einem Fettalkohol mit der C-Kettenlänge C6-C14 stammt. Es ist teilweise vorteilhaft, wenn die beschriebenen Tenside als Gemische eingesetzt werden, zum Beispiel die Kombination Alkylpolyglykosid mit Fettalkoholethoxylaten oder Glucamid mit Alkylpolyglykosiden.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. These preferably include 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. But 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. APG® 225 and APG® 600 from Henkel) and / or C 12 -C 14 -alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule. Also suitable are 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.

Gewünschtenfalls können in erfindungsgemäßen Reinigungsmitteln für die Reinigung von Geschirr Silberkorrosionsinhibitoren eingesetzt werden. Bevorzugte Silberkorrosionsschutzmittel sind organische Sulfide wie Cystin und Cystein, zwei- oder dreiwertige Phenole, gegebenenfalls alkyl-, aminoalkyl- oder arylsubstituierte Triazole wie Benzotriazol, Isocyanursäure, Mangan-, Cobalt-, Titan-, Zirkonium-, Hafnium-, Vanadium- oder Cersalze und/oder -komplexe, in denen die genannten Metalle je nach Metall in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen. Der Gehalt_an Silberkorrosionsinhibitoren in erfindungsgemäßen Mitteln liegt vorzugsweise im Bereich von 0,01 Gew.-% bis 1,5 Gew.-%, insbesondere von 0,1 Gew.-% bis 0,5 Gew.-%. So können die aus der internationalen Patentanmeldung WO 94/19445 bekannten Mangan(III)- oder Mangan(IV)-Komplexe, das in der internationalen Patentanmeldung WO 94/07981 als Silberschutzmittel offenbarte Cystein, das in der deutschen Patentanmeldung DE 195 18 693 als mit silberkorrosionsinhibierender Wirkung allein oder insbesondere in Kombination mit Isocyanursäure beschriebene Cystin, und/oder die in den deutschen Patentanmeldungen DE 43 25 922 beziehungsweise DE 43 15 397 beschriebenen Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- oder Cersalze und/oder -komplexe, in denen die Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen, und dort genannte Mangan(II)salze oder -komplexe zur Verhinderung der Silberkorrosion in erfindungsgemäßen Mitteln eingesetzt werden.If desired, 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. So can 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.

Zusätzlich können die erfindungsgemäßen Mittel Enzyme wie Proteasen, Amylasen, Pullulanasen, Cutinasen und Lipasen enthalten, beispielsweise Proteasen wie BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect® OxP und/oder Durazym®, Amylasen wie Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® und/oder Purafect® OxAm, Lipasen wie Lipolase®, Lipomax®, Lumafast® und/oder Lipozym®. Die gegebenenfalls verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise in Mengen bis zu 2 Gew.-%, insbesondere von 0,1 Gew.-% bis 1,5 Gew.-%, enthalten, wobei besonders bevorzugt gegen oxidativen Abbau stabilisierte Enzyme, wie zum Beispiel aus den internationalen Patentanmeldungen WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 oder WO 95/07350, bekannt, eingesetzt werden.In addition, 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®. 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.

Sofern die Reinigungsmittel bei der Anwendung zu stark schäumen, können ihnen noch vorzugsweise bis zu 6 Gew.-%, insbesondere etwa 0,5 Gew.-% bis 4 Gew.-% einer schaumdrückenden Verbindung, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffine, Parafin-Alkohol-Kombinationen, hydrophobierter Kieselsäure, der Bisfettsäureamide, und sonstiger weiterer bekannter im Handel erhältliche Entschäumer zugesetzt werden. Weitere fakultative Inhaltsstoffe in den erfindungsgemäßen Mitteln sind zum Beispiel Parfümöle. If 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. Further Optional ingredients in the agents according to the invention are, for example, perfume oils.

Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Reinigungsmitteln vorzugsweise nicht über 20 Gew -%, insbesondere von 1 Gew.-% bis 15 Gew.-%, vorhanden.To those in the agents according to the invention, especially when they are in liquid or pasty form, 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.

Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 6 Gew.-%, enthalten.To set a desired, by mixing the other components 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.

Die Herstellung der erfindungsgemäßen festen Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbindung und Bleichkatalysator gegebenenfalls später getrennt zugesetzt werden.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.

Erfindungsgemäße Reinigungsmittel in Form wäßriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.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.

Die erfindungsgemäßen Mittel liegen vorzugsweise als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich bekannter Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung der thermisch belastbaren Komponenten und Zumischen der empfindlicheren Komponenten, zu denen insbesondere Enzyme, Bleichmittel und der Bleichaktivator zu rechnen sind, hergestellt werden können.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.

Zur Herstellung von erfindungsgemäßen Reinigungsmitteln in Tablettenform geht man vorzugsweise derart vor, daß man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 · 105 Pa bis 1 500 · 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeiten von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durchmesser von 35 mm bis 40 mm.For the preparation of cleaning agents according to the invention in tablet form, 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. In this way, unbreakable tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally over 150 N. Preferably, 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.

Die Herstellung erfindungsgemäßer Mittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 800 bis 1000 g/l kann dadurch erfolgen, daß man in einer ersten Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Mittels, darunter den Bleichkatalysator, mit dem so gewonnenen Vorgemisch vereinigt.The preparation of 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.

Erfindungsgemäße Mittel zur Reinigung von Geschirr können sowohl in Haushaltsgeschirrspülmaschinen wie in gewerblichen Spülmaschinen eingesetzt werden. Die Zugabe erfolgt von Hand oder mittels geeigneter Dosiervorrichtungen. Die Anwendungskonzentrationen in der Reinigungsflotte betragen in der Regel etwa 1 bis 8 g/l, vorzugsweise 2 bis 5 g/l.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.

Ein maschinelles Spülprogramm wird im allgemeinen durch einige auf den Reinigungsgang folgende Zwischenspülgänge mit klarem Wasser und einem Klarspülgang mit einem gebräuchlichem Klarspülmittel ergänzt und beendet. Nach dem Trocknen erhält man beim Einsatz erfindungsgemäßer Mittel völlig sauberes und in hygienischer Hinsicht einwandfreies Geschirr. 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.

BeispieleExamples

Ein Reinigungsmittel (V1) für die maschinelle Reinigung von Geschirr, enthaltend 45 Gew.-Teile Natriumcitrat, 5 Gew.-Teile Natriumcarbonat, 30 Gew.-Teile Natriumhydrogencarbonat, jeweils 1 Gew.-Teil Protease- und Amylase-Granulat, 2 Gew.-Teile nichtionisches Tensid sowie 10 Gew.-Teile Natriumperborat-Monohydrat, und Mittel gemäß der Erfindung (M1 bis M5), die ansonsten wie V1 zusammengesetzt waren, aber zusätzlich die in Tabelle 1 angegebenen Zusätze (Gew.-Teile) enthielten, wobei das Acetonitril-Derivat als wäßrige Lösung separat zu Beginn des Hauptspülgangs zugegeben wurde, wurden wie nachfolgend angegeben getestet: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. Parts of nonionic surfactant and 10 parts by weight of sodium perborate monohydrate, and agents according to the invention (M1 to M5 ), which were otherwise composed as V1 , but additionally contained the additives (parts by weight) given in Table 1, the Acetonitrile derivative was added separately as an aqueous solution at the beginning of the main wash cycle, and was tested as follows:

Zur Herstellung standardisierter Teebeläge wurden Teetassen in eine 70°C warme Teelösung 25 mal eingetaucht. Anschließend wurde jeweils etwas der Teelösung in jede Teetasse gegeben und die Tasse im Trockenschrank getrocknet. In einer Geschirrspülmaschine Miele® G 590 (Dosierungen von jeweils 20 g Mittel, Wasserhärte ca. 17 °dH, Betriebstemperatur 55 °C) wurden jeweils 8 der mit Teebelägen versehenen Tassen gespült und die Belagsentfernung anschließend visuell auf einer Skala von 0 (= unverändert sehr starker Belag) bis 10 (= kein Belag) benotet. Die in Tabelle 2 angegebenen Noten der erfindungsgemäßen Mittel liegen signifikant besser als der Wert für die Vergleichsprodukte V1 und V2, welches den zum Standard gewordenen Bleichaktivator TAED enthielt. Zusammensetzung maschineller Geschirrspülmittel Mittel Zusatz M1 3 Gew.-Teile N-Methyl-Morpholinium-Acetonitril-Methosulfat M2 3 Gew.-Teile N-Methyl-Morpholinium-Acetonitril-Methosulfat und 0,03 Gew.-Teile Nitropentammin-cobalt(III)-chlorid M3 4 Gew.-Teile N-Methyl-Morpholinium-Acetonitril-Methosulfat M4 4 Gew.-Teile N-Methyl-Morpholinium-Acetonitril-Methosulfat und 0,03 Gew.-Teile Nitropentammin-cobalt(III)-chlorid M5 6 Gew.-Teile N-Methyl-Morpholinium-Acetonitril-Methosulfat V2 4 Gew.-Teile TAED Noten für die Belagsentfernung Mittel Belagsentfernung M1 5 M2 7 M3 7 M4 9 M5 9 V1 2 V2 4 To produce standardized tea coverings, tea cups were immersed 25 times in a 70 ° C tea solution. Then some of the tea solution was added to each tea cup and the cup dried in the drying cabinet. In a Miele® G 590 dishwasher (doses of 20 g each, water hardness approx. 17 ° dH, operating temperature 55 ° C), 8 of the cups with tea toppings were washed and the topping removed visually on a scale of 0 (= unchanged very much thick topping) to 10 (= no topping). 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

Man erkennt, daß durch die erfindungsgemäße Verwendung eine signifikant bessere Bleichwirkung erreicht werden kann als durch den konventionellen Bleichaktivator TAED.It can be seen that the use according to the invention is significantly better Bleaching effect can be achieved than with the conventional bleach activator TAED.

Claims (8)

  1. A dishwashing detergent, characterized in that it contains 1% by weight to 10% by weight and, more particularly, 3% by weight to 6% by weight of a compound corresponding to general formula I: R1R2R3N+CH2CN X) in which R1, R2 and R3 independently of one another represent an alkyl, alkenyl or aryl group containing 1 to 18 carbon atoms, the groups R1 and R2 being part of a heterocycle including the N atom and optionally other hetero atoms, and X is a charge-equalizing anion,
    in addition to typical ingredients compatible with the compound corresponding to formula I.
  2. A machine dishwashing detergent containing 15% by weight to 70% by weight and, more particularly, 20% by weight to 60% by weight of a water-soluble builder component and 5% by weight to 25% by weight and, more particularly, 8% by weight to 17% by weight of an oxygen-based bleaching agent, based on the detergent as a whole, characterized in that it contains a bleach-activating acetonitrile derivative corresponding to formula I in quantities of 3% by weight to 6% by weight.
  3. A detergent as claimed in claim 1 or 2, characterized in that it contains a peroxygen compound from the group consisting of organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.
  4. A detergent as claimed in any of claims 1 to 3, characterized in that quantities of 0.5% by weight to 7% by weight of compounds which form peroxocarboxylic acids under perhydrolysis conditions are present in addition to the compounds corresponding to formula I.
  5. A detergent as claimed in any of claims 1 to 4, characterized in that, in the compound corresponding to formula I, R2 and R3 together with the quaternary N atom form a morpholinium ring.
  6. A detergent as claimed in any of claims 1 to 5, characterized in that, in the compound corresponding to formula I, R1 is an alkyl group containing 1 to 3 carbon atoms, more particularly a methyl group.
  7. A detergent as claimed in any of claims 1 to 6, characterized in that the charge-equalizing anion X) is selected from 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.
  8. A detergent as claimed in any of claims 1 to 7, characterized in that the charge-equalizing anion X) is methosulfate.
EP97951944A 1996-11-29 1997-11-21 Acetonitrile derivatives as bleaching activators in detergents Expired - Lifetime EP0944707B2 (en)

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DE19649375A DE19649375A1 (en) 1996-11-29 1996-11-29 Acetonitrile derivatives as bleach activators in detergents
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EP0944707A2 (en) 1999-09-29
DE59706340D1 (en) 2002-03-21
US6225274B1 (en) 2001-05-01
EP1138754A1 (en) 2001-10-04
WO1998023719A2 (en) 1998-06-04
ES2172825T5 (en) 2005-12-01
ATE213013T1 (en) 2002-02-15
WO1998023719A3 (en) 1998-07-30
JP4097295B2 (en) 2008-06-11
ES2172825T3 (en) 2002-10-01
DE19649375A1 (en) 1998-06-04
EP0944707B2 (en) 2005-06-01
JP2001504883A (en) 2001-04-10

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