WO2000050553A1

WO2000050553A1 - Compounded acetonitrile derivatives used as bleach activators in cleaning agents

Info

Publication number: WO2000050553A1
Application number: PCT/EP2000/001248
Authority: WO
Inventors: Andreas Lietzmann; Christian Nitsch; Gerhard Blasey; Horst-Dieter Speckmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-02-25
Filing date: 2000-02-16
Publication date: 2000-08-31
Also published as: DE19908069A1; AU2672400A; CA2299437A1

Abstract

The aim of the invention is to improve the oxidizing action and bleaching action of inorganic peroxygen compounds used, in particular, for the machine cleaning of dishes. This is achieved, in particular, by using compounds which are compounded with the aid of alkali phosphate provided as a supporting material and which are of formula R?1R2R3N+CH¿2CN X- in which R?1, R2 and R3¿, independent of one another, represent an alkyl group, alkenyl group or aryl group with 1 to 18 C atoms, whereby groups R?2 and R3¿ can also be part of a heterocycle which includes the N atom and optionally includes additional heteroatoms, and X represents a charge-compensating anion. Agents used, in particular, for the machine cleaning of dishes contain, in a correspondingly compounded form, approximately 1 wt. % to 10 wt. % of an active ingredient which intensifies bleaching and which is of formula R?1R2R3N+CH¿2CN X-.

Description

Compounded acetonitrile derivatives as bleach activators in detergents

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. At lower temperatures, 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 Ν- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, Ν- 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 sulfonate, acyl benzyl sulfonate, benzyl sulfate Literature has become known. 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 as with the peroxide liquor only at 95 ° C.

In the effort to save energy in washing and bleaching, application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years.

At these low temperatures, the effect of the activator compounds known to date generally diminishes appreciably. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date.

A further problem, particularly in the case of cleaning agents for machine dishwashing, is the need to incorporate corrosion inhibitors for silverware into such agents, particularly if the agents contain the oxygen-based bleaching or oxidizing agents which have been customary in recent times. 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.

The problem of tarnishing silver becomes particularly acute when, as an alternative to the sulfur-containing substances, oxidatively "defusing" active chlorine compounds, active oxygen compounds, such as sodium perborate or sodium percarbonate, are used, which are used to remove bleachable stains, such as tea stains / tea deposits, coffee residues, dyes from vegetables, Lipstick remnants and the like are used. Such active oxygen bleaching agents are used, usually together with bleach activators, especially in modern, low-alkaline machine dishwashing detergents of the new generation of detergents. These agents generally consist of the following functional components: builder component (complexing agent / dispersant), alkali carrier, bleaching system (combination of bleaching agent and bleach activator), enzyme and surfactant. Under the purging conditions that occur when such compositions are used, not only sulfidic deposits are formed in the presence of silver, but also oxidic deposits on the silver surfaces due to the oxidizing attack of the intermediately formed peroxides or the active oxygen.

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.

For example, from international patent application WO 98/23719 it is known that certain acetonitrile derivatives which carry a quaternary nitrogen substituent have a marked bleach-boosting effect when used together with peroxidic bleaching agents against colored stains which are found on dishes such as cups, plates or cutlery items , are located.

A problem with such acetonitrile derivatives, however, is their storage stability in alkaline cleaning agents, which is often perceived as inadequate. Surprisingly, it has now been found that 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. It has also been shown that 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),

R'R ² R ³ N ⁺ CH ₂ CN X ^" (I) in which R ¹ , R ² and R ^{3 are} independently an alkyl, alkenyl or aryl group having 1 to 18 C atoms, the groups R ² and R ^{3 can} also be part of a heterocycle including the N atom and optionally further hetero atoms, and X is a charge-balancing anion, and 30% by weight to 99.9% by weight of alkali metal phosphate and optionally up to 10% by weight of phosphonic acid and / or alkali phosphonate and optionally up to 10% by weight of compounding aid.

Another object of the invention is the use of compounds of general formula I,

R'R ² R ³ N ⁺ CH ₂ CN X ^" (I) 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 ² and R ^{3 can} also be part of a heterocycle including the N atom and optionally further hetero atoms, and X is a charge-balancing anion which has been compounded in solid form with the aid of alkali metal phosphate as carrier material, as activators for in particular inorganic peroxygen compounds in aqueous Cleaning solutions for dishes.

Among the compounds of the formula I, those in which R ² and R ³ form a morpholinium ring, including the quaternary N atom, are particularly preferred. In the compounds according to 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 . Preference is given to the use of compounds of the formula I in which 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.

In preferred embodiments of the invention, 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. In preferred embodiments of the invention, 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. The term 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.

Furthermore, 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). Optionally, 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. However, 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. 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.

In addition to the bleach activator used according to the invention, 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.

In principle, all water-soluble builder components, in particular in such low-alkaline cleaning agents, come in agents for the mechanical cleaning of equipment. WO 00/50553 ^{"y '} PCT / EP00 / 01248

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, α-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. Depending on the pH ultimately set in the agents according to the invention, 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. In addition or in particular as an alternative, known peroxycarboxylic acids, for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present. In addition, the addition of small amounts of known 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. In addition to the bleach-activating acetonitrile derivative compounds, 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. Preferred are 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 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated and glucamine, and or N-acylated lactams, for example N-benzoyl-caprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498. The 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.

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. Known from European patent application EP 0 693 550 exe, the manganese, iron, cobalt and copper complexes known from European patent EP 0 392 592 and / or those described in European patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, Manganese complexes described in EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519. 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 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. The alkali carriers usually 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 is contained in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight . Depending on which pH value is ultimately desired, the ratio of the carbonate used and the hydrogen carbonate used varies.

In a further embodiment, 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. 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 - (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. Also suitable are 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.

If desired, 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. For example, 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.

In addition, 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®. 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.

If 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. Other optional ingredients in the agents according to the invention are, for example, perfume oils.

In order to set a desired pH value which does not result automatically from the mixture of the other components under the conditions of use, 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. Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5% by weight to 6% by weight.

The preparation of 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. 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.

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 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 . In this way, break-resistant tablets are obtained which, under application conditions, dissolve sufficiently quickly, with bending strengths of normally more than 150 N. Preferably, 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.

Examples

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. To determine the most suitable carrier material, 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.). For comparison, 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. In addition, 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.

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 21.6 g each of the agent to be tested, water hardness approx. 17 ° dH, operating temperature 55 ° C), 8 of the cups provided with tea toppings were rinsed and the deposit removal then visually on a scale of 0 (= unchanged very thick base) to 10 (= no base) graded. The grades given in Table 2 using the active compound compounded according to the invention are significantly better than the values for the comparative products. Table 1: Gross composition of funds [ ^" parts by weight]

Table 2: Cleaning performance

It can be seen that the compounding of the acetonitrile derivative with phosphate results in an improved cleaning performance of the agent.

Claims

claims

1. Particulate preparation (compound) containing 0.1% by weight to 60% by weight of a compound of the general formula (I),

2. Preparation according to claim 1, characterized in that it contains 0.5 wt .-% to 30 wt .-%, in particular 5 wt .-% to 20 wt .-% of the compound of formula I.

3. Preparation according to claim 1 or 2, characterized in that it contains 35 wt .-% to 99.5 wt .-%, in particular 40 wt .-% to 70 wt .-% alkali phosphate.

4. Preparation according to one of claims 1 to 3, characterized in that the alkali phosphate is a salt in the form of an alkaline, neutral or acidic sodium or potassium compound of the optionally oligomeric or polymeric phosphoric acid.

5. Preparation according to one of claims 1 to 4, characterized in that the alkali metal phosphate from the group comprising 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 the sodium mentioned with the corresponding potassium salts is selected.

6. Preparation according to one of claims 1 to 5, characterized in that form a morpholinium ring in the compound of the formula IR ² and R ³ , including the quaternary N atom.

7. Preparation according to one of claims 1 to 6, characterized in that in the compound of formula IR ^{1 is} an alkyl group having 1 to 3 carbon atoms, in particular a methyl group.

8. Preparation according to one of claims 1 to 7, characterized in that in the compound according to formula I the charge-balancing anion X ^" from the halides, such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, sulfate, hydrogen sulfate, metho - And ethosulfate, chlorate, perchlorate and the anions of carboxylic acids, such as formate, acetate, benzoate or citrate, is selected.

9. Preparation according to one of claims 1 to 8, characterized in that in the compound of formula I, the charge-balancing anion X ^"is sulfate, hydrogen sulfate or methosulfate.

10. Use of compounds of the general formula I,

1 1. Use according to claim 10, characterized in that form a morpholinium ring in the compound of the formula IR ² and R ³ , including the quaternary N atom.

12. Use according to claim 10 or 11, characterized in that in the compound of formula IR ^{1 is} an alkyl group having 1 to 3 carbon atoms, in particular a methyl group.

13. Use according to one of claims 10 to 12, characterized in that in the compound of formula I the charge-balancing anion X ^' from the halides, such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, sulfate, hydrogen sulfate, metho - And ethosulfate, chlorate, perchlorate and the anions of carboxylic acids, such as formate, acetate, benzoate or citrate, is selected.

14. Use according to any one of claims 10 to 13, characterized in that the charge-balancing anion X ^"is sulfate, hydrogen sulfate or methosulfate.

15. Use according to one of claims 10 to 14, characterized in that the peroxygen compound to be activated is selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.

16. Means for cleaning dishes, 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'R ² R ³ N ⁺ CH ₂ CN X ^" (I) in which R ¹ , R ² and R ³ independently of one another is an alkyl, alkenyl or aryl group having 1 to 18 C atoms, the groups R ¹ and R ^{2 can} also be part of a heterocycle which includes the N atom and optionally further hetero atoms, and X is a charge-balancing anion which has been made up in solid form with the aid of alkali metal phosphate as carrier material, in addition to conventional ingredients which are compatible with the compound of the formula I. contains.

17. Agent for the automatic 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 wt .-% to 25 wt .-%, in particular 8 wt .-% to 17 wt .-% oxygen-based bleach, in each case based on the total agent, characterized in that it is a bleach-activating acetonitrile derivative according to formula I, the has been made up in solid form with the aid of alkali metal phosphate, in particular in amounts of 3% by weight to 6% by weight.

18. Composition according to claim 16 or 17, characterized in that it contains a peroxygen compound from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.

19. Composition according to one of claims 16 to 18, characterized in that in addition to the compounds of the formula I 0.5% by weight to 7% by weight under perhydrolysis conditions, compounds which split off peroxocarboxylic acids are present.

20. Composition according to one of claims 16 to 19, characterized in that in addition to the compound of formula I bleach-catalyzing transition metal salts or - complexes, in particular in amounts of 0.0025 wt .-% to 0.5 wt .-%, are present .

21. A composition according to claim 20, characterized in that in addition to the compound of formula I bleach-catalysing cobalt, iron, copper or ruthenium-amine complexes, in particular [Co (NH ₃ ) ₅ Cl] Cl ₂ and / or [Co ( NH ₃ ) ₅ NO ₂ ] Cl ₂ , are present.