EP1141211B1 - Acetonitrile derivatives formulated in particulate form as bleach activators in solid detergents - Google Patents

Description

The present invention relates to the use of ready-made particles Acetonitrile derivatives as activators for in particular inorganic peroxygen compounds for bleaching tea stains on dishes and cleaning agents for dishes containing such activators.

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 the addition of 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, in particular tetraacetylethylenediamine, acylated glycolurils, in particular 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.

In the effort to save energy in washing and bleaching have won in recent years Years of application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.

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, convincing success would have been recorded.

Another one especially for cleaning agents for automatic dishwashing The problem is the need to use corrosion inhibitors for silverware in such agents to incorporate, especially if the agents are the bleaching or Contain oxidizing agents based on oxygen. 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, 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 flushing tarnishing silver. Due to the intensive cleaning process in the dishwasher also completely degreases the silver surface and thereby more sensitive to chemical influences.

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, which for the removal, bleachable stains, such as for example tea stains / tea deposits, coffee residues, dyes from vegetables, lipstick residues and the like serve.

Such active oxygen bleaching agents are usually used together with bleach activators used in automatic dishwashing detergents. These funds generally consist of the following function blocks: builder component (complexing agent / dispersant), Alkali carrier, bleaching system (combination of bleach and bleach activator), Enzyme and surfactant. Among those that occur when using such structured means Flushing conditions generally not only form sulfidic, but also but through the oxidizing attack of the intermediate peroxides or the active oxygen also oxidic deposits on the silver surfaces.

It is known from international patent application WO 98/23719 that compounds 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 are,} independently of one another, an alkyl, alkenyl or aryl group having 1 to 18 C atoms, the groups R ² and R ³ also being part of a heterocycle which includes the N atom and optionally further hetero atoms and X is a charge-balancing anion, can be used as activators for in particular inorganic peroxygen compounds in aqueous cleaning solutions for dishes. This results in an improvement in the oxidation and bleaching effect, in particular of inorganic peroxygen compounds, at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 55 ° C. The compounds according to general formula (I), particularly in combination with further ingredients of detergents and cleaning agents, are usually not very stable in storage and in particular extremely sensitive to moisture. Some of the representatives of the compounds according to general formula (I) which have a particularly good bleach-boosting effect are liquid at room temperature; others occur in the course of their production in liquid form, for example as an aqueous solution, and can only be converted from this into the pure solid with considerable losses. In both cases, their use in solid, for example particulate, media presents difficulties.

A subclass of the particulate agents are cleaning agents in tablet form. Tableted detergents have compared to powdered or liquid products A number of advantages: They are easier to dose and to handle due to its compact structure, advantages in storage and transport. It there is therefore an extremely broad state of the art in washing and Detergent tablets, which can also be found in an extensive patent literature reflected. The developers of tablet-shaped products came up with the idea early on come determined over differently composed areas of the molded body Ingredients only under defined conditions in the washing or cleaning cycle release, in order to improve the cleaning success. In addition to the Core / shell tablets and ring / core tablets well known from pharmacy in particular multilayered molded articles, which are used today for many Areas of washing and cleaning or hygiene are offered.

Multi-phase cleaning tablets for the toilet are used, for example, in Europe Patent application EP 0 055 100 described. This document discloses blocks of toilet detergent, which is a molded body made from a slowly soluble detergent composition include in which a bleach tablet is embedded. This font at the same time reveals the most diverse forms of design in a multi-phase manner Formköiper. The molded articles are produced according to the teaching of this document either by inserting a compressed bleach tablet into a mold and Pour this tablet around with the detergent composition, or by Pour some of the detergent composition into the mold, followed by the Insert the compressed bleach tablet and possibly pour it over with another detergent composition.

European patent application EP 0 481 547 also describes multi-phase detergent tablets, those according to this document for machine dishwashing should be used. These tablets have the shape of core / shell tablets and are produced by gradually compressing the components: Compression of a bleaching agent composition into a shaped body which is incorporated in a a polymer composition half-filled die is inserted, which then with filled up another polymer composition and one with a polymer jacket provided bleach molding is pressed. The procedure is then followed by an alkaline detergent composition repeated so that a three-phase molded body results.

From international patent application WO 98/23531 are N-alkyl ammonium nitriles of the type described above by formula (I) known in granular form have been assembled, with the support materials for the N-alkyl-ammonium nitriles for example called silica, silicates and aluminum oxide become.

U.S. Patent Application US 5,814,242 describes Bleaching compositions containing N-alkyl ammonium nitriles.

International patent application WO 98/231002 also discloses N-alkyl ammonium nitriles that have been made up in granular form are, for example, as carrier materials for the N-alkyl ammonium nitriles Silicic acid, silicates and aluminum oxide can be called.

It has now been found that acetonitrile derivatives prepared in this way in particulate form eliminating the above disadvantages, stable in storage, in particular tablet-shaped detergents can be incorporated, as another The advantage of an increased bleaching performance compared to agents that do Acetonitrile derivative included as a simple admixture or individual component.

The invention relates to the use of compounds of the general formula I which are made up in particulate form with the aid of inorganic carrier materials which contain silicon R ¹ R ² R ³ N ⁺ CH ₂ CN X ^- in which R ¹ , R ² and R ^{3 are,} independently of one another, an alkyl, alkenyl or aryl group having 1 to 18 C atoms, the groups R ² and R ³ also being part of a heterocycle which includes the N atom and optionally further hetero atoms and X is a charge-balancing anion, as activators for in particular inorganic peroxygen compounds in solid cleaning agents, in particular for dishes, which are used in essentially aqueous cleaning solutions.

Compounds of the 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 Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. Some compounds according to general formula I and their preparation are described in international patent application WO 96/40661.

It is particularly preferred to use compounds of the formula I in which R ² and R ³ form a morpholinium ring, including the quaternary N atom. In these, 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.

The compound according to general formula I is in the cleaning agents in Particulate form, that is applied to an inorganic Carrier material used. The application to the carrier material can be done in this way happen that one in an aqueous solution, the compound according to formula I, as in In the context of their manufacture, the carrier material is stirred in and the aqueous Solvent is removed in vacuo, if appropriate at elevated temperature. One can but also spray the solution of the compound according to formula I onto the carrier material and subject it to a drying process, if necessary or subsequently. there it is preferred if the particles resulting from the packaging process have a diameter in the range of 0.4 mm to 1.2 mm.

As the silicon-containing inorganic carrier materials, such are preferably used whose inner surface area ranging from 10 m ² / g to 500 m ² / g, more preferably 100m ² / g to 450 m ² / g is. Silicates, silicas, silica gels and clays and mixtures thereof are suitable, for example. However, the carrier material is preferably free of zeolites.

Silicas that have been produced using a thermal process (flame hydrolysis of SiCl ₄ (so-called pyrogenic silicas) can be used as well as silicas produced by wet processes. Silica gels are colloidal silicas with elastic to solid consistency and a largely loose pore structure, which results in a high fluid absorption capacity They can be produced by the action of mineral acids on water glass Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite The use of aluminum silicate as a carrier material or as a component of a carrier material mixture is possible, and the carrier material preferably has particle sizes in the range from 100 μm to 1.5 mm.

The particulate compounds of formula I are preferably 10 to 50 parts by weight of the silicon-containing carrier material and 50 to 90 parts by weight the compound of formula I.

The particulate made with the support material containing silicon Acetonitrile derivative can additionally be an organic material with a melting point above 40 ° C, especially non-ionic surfactant and / or with such to be enveloped. This can reduce the decay properties of the corresponding particle in affect aqueous systems and / or its storage stability positively.

An acetonitrile derivative according to formula I which is made up in this way in particulate form preferably incorporated into cleaning agents for use in cleaning solutions are provided for dishes for bleaching colored stains. The term bleaching means both bleaching on its own Dish dirt, especially tea, as well as the bleaching of dirt detached from the surface of the dishwashing liquid Roger that.

Furthermore, the invention relates to solid cleaning agents for dishes and among them preferably those for use in machine cleaning processes, the one above Compound according to formula I described in a corresponding particulate Knfektionierung included, and a process for cleaning dishes using such a compound.

The use according to the invention as a bleach activator essentially consists in Presence of a dish surface contaminated with colored stains to create, among which a peroxidic oxidizing agent and the bleach activating Acetonitrile derivative can react with each other, with the aim of stronger to obtain oxidizing secondary products. Such conditions lie in particular then when both reactants meet in aqueous solution. This can by separately adding the peroxygen compound and the acetonitrile derivative to one if necessary, detergent-containing solution. Is particularly advantageous the inventive method, however, using an inventive Dishwashing detergent containing the bleach activating acetonitrile derivative and optionally an oxidizing agent containing peroxygen, preferably selected from the group includes organic peracids, hydrogen peroxide, perborate and percarbonate as well as their mixtures. The peroxygen compound can also separately, in bulk or as a preferably aqueous solution or suspension for Solution can be added if a peroxide-free cleaning agent is used.

The conditions can be varied widely depending on the intended use. So come in addition to purely aqueous solutions, also mixtures of water and suitable organic solutions Solvents as a reaction medium in question. The quantities of peroxygen compounds used 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 is present. Also the amount of bleach activating used Acetonitrile derivative depends on the application. Depending on the desired degree of activation become 0.00001 mol to 0.25 mol, preferably 0.001 mol to 0.02 mol activator per mole of peroxygen compound used, but in special cases these limits are also exceeded or fallen below.

Another object of the invention is a solid detergent for dishes, which 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 6 wt .-% of a Acetonitrile derivative according to formula I in particulate as described above Assembled form in addition to usual ingredients compatible with the compound contains.

The solid 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 is a bleach activating acetonitrile derivative according to formula I, especially in Amounts from 2% to 6% by weight in particulate as described above contains form. Such an agent is in a preferred embodiment lower alkaline, i.e. its 1% by weight solution has a pH value from 8 to 11.5, in particular from 9 to 11.

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 dihydrogeridiphosphate, Pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization from 5 to 1000, especially 5 to 50, as well as mixtures of sodium and potassium salts. Your quantities can range up to about 55% by weight based on the total agent. Other possible water-soluble builder components are organic, for example Polymers of native or synthetic origin, especially polycarboxylates act as a co-builder especially in hard water regions. Be considered for example polyacrylic acids and copolymers of maleic anhydride and acrylic acid as well as the sodium salts of these polymer acids. Commercial products are for Example Sökalan® CP 5, CP 10 and PA 30 from BASF. To the co-builder Useful polymers of native origin include, for example, oxidized starches, such as known for example from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible builder components are naturally occurring hydroxycarboxylic acids such as Mono-, dihydroxysuccinic acid, α-hydroxypropionic acid and gluconic acid. To the preferred Builder components include the salts of citric acid, in particular Sodium citrate. Anhydrous trisodium citrate and preferably come as sodium citrate Trisodium citrate dihydrate. Trisodium citrate dihydrate can be fine or coarse-crystalline powder can be used. Depending on the ultimately in the invention The pH value set can also be at least partially proportional to the corresponding co-builder salts mentioned acids are present.

Alkaline perborate mono- or tetrahydrate and / or alkali percarbonate and alkali persulfates, -persilicates and -percitrate into consideration, with sodium being the preferred alkali metal. The The use of sodium percarbonate has particular advantages 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. Additionally or in particular alternatively, too 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.

In addition to the bleach activating acetonitrile derivatives essential to the invention according to formula I, known conventional bleach activators, that is Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Are suitable Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or if appropriate carry substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German Patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well acetylated sorbitol and mannitol or their in the European Patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated, glucamine and Gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which 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. The from the German patent application DE 196 16 769 known hydrophilically substituted acylacetals and in German patent application DE 196 16 770 and international Patent application WO 95/14075 described acyllactams are also preferred used. Also known from German patent application DE 44 43 177 Combinations of conventional bleach activators can be used. such conventional bleach activators are in the usual range, preferably in Quantities from 0.1% by weight to 10% by weight, in particular 0.5% by weight to 7% by weight, based on total mean.

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 catalyst. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of 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 19605688 Vanadium and copper complexes with nitrogenous tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, the manganese, copper described in German patent application DE 44 16 438 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 , 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, 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 Rü, are used in customary amounts, preferably up to 1% by weight, in particular from 0.0025% by weight. % to 0.5% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent. 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 . In a further preferred embodiment, the agents contain, in addition to the bleach activator according to formula I, which is made up in particulate form, a bleach-intensifying active ingredient combination which, according to European patent application EP 0 832 969, consists of intimately mixing a water-soluble salt of a divalent transition metal, selected from cobalt, iron, copper and ruthenium, and also their mixtures, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen and inert carrier material are available in amounts of preferably 0.25% by weight to 25% by weight, in particular 1% by weight to 10% by weight; A preferred use of the bleach activator of the formula I, which is made up in particulate form, takes place in the presence of such a combination of active substances.

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 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 is ultimately desired, the ratio of carbonate and bicarbonate used can be varied.

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.

If appropriate, 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 better detach fatty soils, as wetting agents and, if appropriate, 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 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 ₁₄ . It is partially beneficial. 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, 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 Becizotriazole, 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.

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, such as from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, are used become.

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.

To set a desired, by mixing the other components the agents according to the invention cannot system and result from a self-determined pH value 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 bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular, in the agents according to the invention from 0.5% by weight to 6% by weight.

In order to facilitate the disintegration of agents according to the invention, in particular if they are in the form of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for the rapid disintegration of Tablets in water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form. These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling), and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. In preferred process variants, the premixes to be compressed into tablets contain 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 to 4% by weight, of a disintegration aid, in each case based on the premix. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 to 4% by weight .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 Glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrants, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

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 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 particulate made up bleaching catalyst according to formula I with which premix thus obtained combined.

In a preferred embodiment of agents according to the invention, these are in the form compressed body, in particular tablets, before, for the manufacture of which Premix containing all the ingredients suitable above for agents according to the invention can, pressed. As described above, the premix can be obtained from the be composed of different substances. Independent of Composition of the premixes to be compressed can have physical parameters the premixes are chosen so that advantageous molded body properties result. In preferred variants, the particulate to be pressed has Premixed bulk weights above 600 g / l, preferably above 700 g / l and especially above 800 g / l.

The particle size in the premixes to be pressed can also be obtained advantageous molded body properties can be set. In preferred procedures the compressed particulate premix has a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight, and in particular less than 5% by weight of the particles are larger than 1600 μm or smaller than 200 μm. Here are narrower particle size substitutions more preferred. Particularly advantageous variants are characterized in that the particulate premix to be compressed has a particle size distribution in which more than 30% by weight, preferably more a particle size than 40% by weight and in particular more than 50% by weight of the particles show between 600 and 1000 µm.

To produce tablet-shaped moldings, the premix is made in a so-called The die is compacted between two punches to form a solid compact. This process, which is briefly referred to below as tableting, is divided into four Sections dosing, compression (elastic deformation), plastic deformation and Ejection.

The premix is first introduced into the die, the filling quantity and so that the weight and shape of the resulting molded body by the position of the lower stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of The upper plunger touches the premix when tabletting and descends further of the lower stamp. With this compression, the particles of the premix pressed closer together, with the void volume within the filling between the stamps decreases continuously. From a certain position of the upper stamp (and thus from a certain pressure on the premix) the plastic begins Deformation in which the particles flow together and it to form the Shaped body comes. Depending on the physical properties of the premix also some of the premixed particles are crushed and it comes at even higher pressures to sinter the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities.

In the last step of tableting, the finished molded body is made using the lower stamp pressed out of the die and by subsequent transport devices carried away. At this point, only the weight of the molded body is final determined because the compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, not only the Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the way a conventional four-stroke engine works. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses vary from a few hundred to a maximum of 3000 tablets per hour depending on the type.

For larger throughputs, rotary tablet presses are usually selected, on which a so-called matrix table a larger number of matrices circular is arranged. The number of matrices varies between 6 and 55, depending on the model Larger matrices are also commercially available. Every die is on the die table an upper and lower stamp assigned, again the pressure is active only by the upper or lower stamp, but can also be built up by both stamps. The Matrix table and the stamp move around a common vertical Axis, the stamp with the help of rail-like cam tracks during circulation in the positions for filling, compression, plastic deformation and discharge to be brought. Wherever a particularly serious increase or Lowering the stamp is required (filling, compacting, ejecting), these will be Curved tracks by additional low pressure pieces, low tension rails and Lifting lanes supported. The matrix is filled using a rigidly arranged one Feeding device, the so-called filling shoe, which with a storage container for the Premix is connected. The pressure on the premix is over the press paths for Upper and lower stamp individually adjustable, whereby the pressure build-up by The stamp shaft heads roll past adjustable pressure rollers. Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must be gone through. For the production of two- and multi-layer moldings several filling shoes arranged one behind the other without the slightly pressed first Layer is ejected before further filling. Through suitable process control In this way, coated and dot tablets can also be produced have onion-shell-like structure, the top of the Core or core layers is not covered and thus remains visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs are more modern Rotary tablet presses are over a million tablets per hour.

Suitable tableting machines are available, for example, from the Apparatebau company Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU). Particularly suitable is for example the hydraulic double pressure press HPF 630 from LAEIS, D.

The moldings can be in a predetermined spatial shape and a predetermined size are manufactured. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with circular or oval Cross-section. This last embodiment covers the form of presentation from the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The spatial shape of another embodiment of the shaped body is in its dimensions adapted the dosing chamber of commercial dishwashers, so that the Shaped bodies can be metered directly into the induction chamber without a metering aid where they are released from during the cleaning process. It goes without saying but also an easy use of the detergent tablets via dosing aids possible.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to σ = 2 P π dt

Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the molded body causes, D is the molded body diameter in meters and t is the height of the moldings.

In the production of molded articles, one is not limited to that a particulate premix is pressed into a shaped body. Rather, extend the process to the extent that one in a conventional manner produces multilayered molded articles by making two or more premixes prepares that are pressed together. This is the premix that is filled in first slightly pre-pressed to create a smooth and parallel to the bottom of the molding To get top, and after filling the second premix to the finished Molded body finally pressed. In the case of three-layer or multi-layer moldings, each is carried out Pre-mix addition another pre-compression before adding the last Premixed the molded body is finally pressed.

Due to the increasing technical effort, in practice are maximum two-layer moldings preferred. It can be determined from the distribution of certain Ingredients on the individual layers benefits can be achieved. So it is possible to get one to produce two-layer molded articles by two different particulate Premixes are pressed together, one of which contains one or more bleaches and the other the particulate bleach activator according to formula I. contains, so that the resulting agent in one layer the bleach in the form of especially inorganic peroxygen compound and in the second layer has bleach activator according to formula I made up in particulate form. By the Use of the bleach activator is in particulate form according to the invention however, it is also possible to use the bleach and the bleach activator in the same way Incorporate layer and other sensitive components, especially enzymes, in incorporate a separate second layer of the molded body.

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 common rinse aid and ended. After this Drying is completely clean and in when using agents according to the invention hygienically perfect dishes.

Examples

Two-phase tablets M1 (weight 25 g each) were produced by pressing the ingredients listed in the table below Composition of the 2-phase tablet (% by weight, based on the entire tablet) first phase second phase sodium tripolyphosphate 30 25 Na perborate monohydrate 10 - MMA Granulatat 3 - Polycarboxylate (Sokalan® CP5) 1 - nonionic surfactant 2 - sodium 15 - Sheet-silicate (SKS-6) 6 - Complexing agent (Turpinal® 2NZ) Protease Granules (Blap 200) - 2 Amylase granules (Duramyl® 60 T) - 2 dye - 0.9 Perfume - 0.1

For comparison, tablets of the same composition were otherwise produced, which instead of the MMA granules were a mixture of 2% by weight of TAED ( V1 ) or 2% by weight of N-methylmorpholinium acetonitrile methosulfate ( V2 ) or 2% by weight of N-methylmorpholinium acetonitrile -Hydrogen sulfate (V3) each containing 1 wt .-% silica. The detergent tablets were rinsed using a Miele® G 590 dishwasher, water hardness 14-16 ° dH, operating temperature 45 or 55 ° C, with the addition of an increased dirt load (frozen cube), 8 cups each provided with a standardized tea deposit and the deposit removed afterwards was visually graded on a scale from 0 (= unchanged very thick base) to 10 (= no base). Table 2 below shows the cleaning grades for the freshly prepared agents (initial value) and agents stored for 2 weeks (room temperature or 30 ° C, 80% relative humidity). cleaning notes output value Storage at room temperature Storage at 30 ° C, 80% rel. LF M1 at 45 ° C 9 9 9 M1 at 55 ° C 10 not determined not determined V1 at 45 ° C 5 5 5 V1 at 55 ° C 6 not determined not determined V2 at 45 ° C 6 4 4 V3 at 45 ° C 8th 6 6

It can be seen that the improvement in performance which can be achieved by MMA compared to the TAED standard can be stably formulated in tablets by means of the particulate formulations. Results as good as for the agent M1 were obtained if, instead of N-methylmorpholinium acetonitrile methosulfate, N-methylmorpholinium acetonitrile hydrogen sulfate was used.

Claims (21)

1. Use of compounds of the general formula I, formulated in particulate form with the help of inorganic carrier materials which comprise silicon, R¹R²R³N⁺CH₂CNX^- in which R¹, R² and R³, independently of the others, is an alkyl, alkenyl or aryl group having 1 to 18 carbon atoms, where the groups R² and R³ may also be part of a heterocycle including the N atom and optionally further heteroatoms, and X is a charge-balancing anion, as activators for in particular inorganic peroxygen compounds in solid dishwashing compositions, which are used in essentially aqueous cleaning solutions, for the bleaching of tea stains.
2. Use according to Claim 1, characterized in that the silicon-containing inorganic carrier material has an internal surface area in the range from 10 m²/g to 500 m²/g, in particular 100 m²/g to 450 m²/g.
3. Use according to Claim 1 or 2, characterized in that the silicon-containing inorganic carrier material is chosen from the group consisting of silicates, silicas, silica gels and clays, and mixtures thereof.
4. Use according to one of Claims 1 to 3, characterized in that, in the particulate formulation form, 10 to 50 parts by weight of the silicon-containing carrier material and 50 to 90 parts by weight of the compound according to formula I are present.
5. Use according to one of Claims 1 to 4, characterized in that in the compound according to formula I R² and R³ form a morpholinium ring by incorporating the quaternary N atom.
6. Use according to Claim 5, characterized in that in the compound according to formula I R¹ is an alkyl group having 1 to 3 carbon atoms, in particular a methyl group.
7. Use according to one of Claims 1 to 6, characterized in that the charge-balancing anion X^- is chosen from the halides, such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, hexafluorophosphate, sulphate, hydrogensulphate, methosulphate and ethosulphate, chlorate, perchlorate and the anions of carboxylic acids, such as formate, acetate, benzoate or citrate.
8. Use according to one of Claims 1 to 7, characterized in that the charge-balancing anion X^- is sulphate, hydrogensulphate or methosulphate.
9. Use according to one of Claims 1 to 8, characterized in that the peroxygen compound to be activated is chosen from the group consisting of organic peracids, hydrogen peroxide, perborate and percarbonate, and mixtures thereof.
10. Use according to one of Claims 1 to 9, characterized in that at the same time a bleach-boosting active ingredient combination which is obtainable by intimately mixing a water-soluble salt of a divalent transition metal chosen from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen, and inert carrier material is present.
11. Dishwashing composition, characterized in that it comprises 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight, of a compound of the general formula I, formulated in particulate form with the help of inorganic carrier materials which comprise silicon, R¹R²R³N+CH₂CNX^- in which R¹, R² and R³, independently of the others, is an alkyl, alkenyl or aryl group having 1 to 18 carbon atoms, where the groups R¹ and R² may also be part of a heterocycle including the N atom and optionally further heteroatoms, and X is a charge-balancing anion, as well as customary ingredients which are compatible with the compound according to formula I.
12. Machine dishwashing composition comprising 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 bleach based on oxygen, in each case based on the total composition, characterized in that it comprises, in particular in amounts of from 2% by weight to 6% by weight, a compound of the general formula I formulated in particulate form with the help of inorganic carrier materials which comprise silicon.
13. Composition according to Claim 11 or 12, characterized in that it comprises a peroxygen compound from the group consisting of organic peracids, hydrogen peroxide, perborate and percarbonate, and mixtures thereof.
14. Composition according to one of Claims 11 to 13, characterized in that, in addition to the compounds according to formula I, 0.5% by weight to 7% by weight of compounds which release peroxocarboxylic acids under perhydrolysis conditions are present.
15. Composition according to one of Claims 11 to 14, characterized in that, in addition to the compounds according to formula I, it comprises a bleach-boosting active ingredient combination which is obtainable by intimately mixing a water-soluble salt of a divalent transition metal chosen from cobalt, iron, copper and ruthenium, and mixtures thereof, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen, and inert carrier material.
16. Composition according to one of Claims 11 to 14, characterized in that, in addition to the compound according to formula I, bleach-catalyzing transition metal salts or complexes are present, in particular in amounts of from 0.0025% by weight to 0.5% by weight.
17. Composition according to Claim 16, characterized in that, in addition to the compound according to formula I, bleach-catalyzing cobalt-, iron-, copper- or ruthenium-ammine complexes, in particular [Co(NH₃)₅Cl]Cl₂ and/or [Co (NH₃)₅NO₂]Cl₂, are present.
18. Composition according to one of Claims 11 to 17, characterized in that it is in the form of tablet-shaped bodies.
19. Composition according to Claim 18, characterized in that the tablet-shaped body has two layers.
20. Composition according to Claim 19, characterized in that, in one layer, it has the bleach in the form of the in particular inorganic peroxygen compound and, in the second layer, the bleach activator according to formula I formulated in particulate form.
21. Composition according to Claim 19, characterized in that it has the bleach in the form of the in particular inorganic peroxygen compound and the bleach activator according to formula I formulated in particulate form in the same layer, and further sensitive constituents, in particular enzymes, in a second layer.