DE10038845A1 - Particle-formulated acetonitrile derivatives as bleach activators in solid detergents - Google Patents

Abstract

The invention aims to improve the oxidating and bleaching properties of inorganic peroxygen compounds during textile washing in a storage-resistant manner. In order to achieve this, particle-shaped compounds of formula (I) are essentially used, wherein R<1> represents H, CH3, a C2-24 alkyl or alkenyl radical, a substituted C2-24 alkyl or alkenyl radical comprising at least one substituent from the group Cl, Br, OH, NH2, CN, an alkyl or alkenylaryl radical comprising a C1-24 alkyl group, or a substituted alkyl or alkenylaryl radical comprising a C1-24 alkyl group and at least one further substituent on the aromatic ring; R<2> and R<3> are independently chosen from CH2-CN, CH3, CH2-CH3, CH2-CH2-CH3, CH(CH3)-CH3, CH2-OH, CH2-CH2-OH, -CH(OH)-CH3, CH2-CH2-CH2-OH, CH2-CH(OH)-CH3, CH(OH)-CH2-CH3, (CH2CH2-O)nH, n being equal to 1, 2, 3, 4, 5 or 6; R<4> and R<5> independently have one of the designations cited above for R<1>, R<2> or R<3>; and X represents a charge equalising anion. Textile detergent contains approximately 0.1 wt. % to 10 wt. % of one such bleaching agent.

Description

The present invention relates to the use of ready-made particles Acetonitrile derivatives as activators for, in particular, inorganic peroxygen compounds bleaching of colored textile soils and detergents contain such activators.

Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidants for disinfection and bleaching purposes. The oxidizing effect of these substances strongly depends on the temperature in dilute solutions; 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 the numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril , N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium-isononanoyloxy pentene sulfonate, and ac 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 occur as with the peroxide liquor alone at 95 ° C.

In the effort for energy-saving washing and bleaching processes have won in the last 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 previously known activator compound leaves usually recognizable. There has been no shortage of efforts for which sen temperature range to develop more effective activators, without that to date convincing success would have been recorded.

From international patent application WO 98/23719 it is known that compounds of the general formula A

R ¹ R ² R ³ N ⁺ CH ₂ CN X ^- (A)

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 also being part of a heterocycle which includes the N atom and optionally further hetero atoms can, and X is a charge-balancing anion, can be used as activators for in particular inorganic per oxygen compounds in aqueous cleaning solutions for dishes. This gives an improvement in the oxidation and bleaching effect, in particular in particular inorganic peroxygen compounds at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 55 ° C. However, the compounds of the general formula (A) are usually not very stable in storage, in particular in combination with other ingredients of detergents and cleaning agents, and in particular are extremely sensitive to moisture. Some of the representatives of the compounds of the general formula (A) which have a particularly good bleach-enhancing 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 is difficult.

A subclass of such particulate agents are tablet detergents. Tableted agents have a number of powder or liquid products Advantages: They are easier to dose and to use and because of their  compact structure Advantages in storage and transport. There is therefore one extremely broad state of the art for detergent tablets, which itself is also reflected in an extensive patent literature. That is early on Developers of tablet-shaped products got the idea about different Composed areas of the shaped body certain ingredients only under defined To release conditions in the washing or cleaning cycle in order to ensure cleaning success to improve. In addition to those well known from pharmacy Core / shell tablets and ring / core tablets, in particular multi-layer molded articles prevailed today for many areas of washing and cleaning or hygiene Tobe offered.

Multi-phase cleaning tablets for the toilet are used, for example, in Europe Patent application EP 0 055 100 described. This document discloses toilet cleaning middle blocks that form a molded body from a slowly soluble detergent comprise composition 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 Moldings. The moldings are produced according to the teaching of this document either by inserting a compressed bleach tablet into a mold and Pour this tablet over the detergent composition, or by Pour a portion 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 cleaning medium shaped body used according to this document for machine dishwashing should be. These tablets have the shape of core / shell tablets and are produced by gradually pressing the components: First, the pressing takes place a bleach composition to a shaped body, which in one with a Polymer composition half-filled matrix is inserted, which then with another Filled polymer composition and provided with a polymer jacket Bleach molding is pressed. The procedure is then followed by a  alkaline detergent composition repeated so that there is a three-phase Shaped body results.

International patent application WO 98/23531 describes heterocyclic N-alkyl Ammonium nitriles of the type otherwise described above by formula (A) 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.

It has now been found that certain particulate formulated acetonitrile Derivatives, while eliminating the disadvantages mentioned above, stable in storage, in particular tablet-shaped textile detergents can be incorporated, being another 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 have been made up in particulate form with the aid of inorganic carrier materials which contain, in particular, silicate,

in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another for R ¹ , R ² or R ³ have the meaning given and X is a charge-balancing anion, as activators for, in particular, inorganic peroxygen compounds in solid textile detergents which are used in essentially aqueous water ash solutions are used.

The preparation of compounds according to formula I can by known methods or following these, 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 have been published.

Preference is given to the use of compounds of the formula I in which R ¹ , R ² and R ^{3 are} identical. Among these, preference is given to those compounds in which the radicals mentioned mean methyl groups. On the other hand, preference is also given to those compounds in which at least 1 or 2 of the radicals mentioned are methyl groups and the others have more than one carbon atom.

The anions X ^- include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C _1-20 alkyl sulfate, C. _1-20 alkyl sulfonate, optionally C _1-18 alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C _1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.

Preference is given to using compounds of the formula I in which X is chloride, sulfate, Hydrogen sulfate, ethosulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate, Cumene sulfonate, xylene sulfonate or methosulfate or mixtures thereof. Under Toluene sulfonate or cumene sulfonate are the anion of the ortho-, meta- or para isomers of methylbenzenesulfonic acid or isopropylbenzenesulfone acid and any mixtures of these understood. Para-isopropylbenzenesulfonic is particularly preferred.  

The compound according to general formula I becomes particulate in the detergents assembled form, i.e. applied to an inorganic carrier material, used. It can be applied to the carrier material in such a way that in a solution of the compound of formula I as used in the preparation thereof is obtained, the support material is stirred in and the optionally aqueous solvent in the Vacuum, if necessary at an elevated temperature. One can find the solution to the Spray compound of formula I but also on the carrier material and or if necessary then subject to a drying process. It is preferred if the particles resulting from the packaging process have a diameter have in the range of 0.4 mm to 1.2 mm.

Suitable carrier materials are all inorganic substances which do not interact in an unacceptably negative way with the compound according to the formula, for example alkali metal carbonates, alkali metal sulfates, alkali metal hydrogen sulfates, alkali metal hydrogen carbonates, alkali metal phosphates, alkali metal hydrogen phosphates, dialkali metal hydrogen phosphates and alkali metal silicates and mixtures thereof. Support materials are preferably used whose inner surface is in the range from 10 m ² / g to 500 m ² / g, in particular 100 m ² / g to 450 m ² / g. The silicate carrier materials which are particularly suitable in the context of the present invention include, for example, both alkali silicates and also silicas, silica gels and clays and mixtures thereof. However, the carrier material is preferably free of zeolites. In addition to the silicate component, silicate-containing carrier material optionally contains further particulate inert constituents which do not unreasonably impair the stability of the compounds of the formula I.

Silicas which have been produced by 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 firm 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 also possible. The carrier material preferably has particle sizes in the range from 100 μm to 1.5 mm.

There are preferably 10 in the particulate compounds of formula I up to 50 parts by weight of the carrier material and 50 to 90 parts by weight of the compound according to Formula I before. The particles can also be mixed with inorganic and / or organic Materials, completely or at least partially, are encased.

Particulate with the help of the silicate-containing carrier material Assembled acetonitrile derivative can additionally contain an organic material Melting point above 40 ° C, especially nonionic surfactant, contain and / or with be encased in one. This can reduce the decay properties of the corresponding Particle in aqueous systems and / or affect its storage stability positively.

An acetonitrile derivative according to formula I which is made up in particulate form is preferably incorporated in detergent for use in washing solutions for Textiles for bleaching colored stains are provided. It is under the term bleaching means both the bleaching of itself on the textile surface End dirt, especially tea, as well as the bleaching of in the wash liquor Chem understood, dirt detached from the textile.

Furthermore, the invention relates to solid detergents and, preferably, those among them for use in machine washing processes, the compound described above according to formula I contained in appropriate particulate packaging, and a Method for washing laundry using such a made-up Connection.

The use according to the invention as a bleach activator essentially consists in Presence of a textile contaminated with colored stains create, among which a peroxidic oxidizing agent and the bleach activating Acetonitrile derivative can react with each other, with the aim of being more oxidizing  to obtain subsequent products. Such conditions exist in particular if the two reactants meet in aqueous solution. This can be done through separate Add the peroxygen compound and the acetonitrile derivative to an optionally detergent solution happen. The invention is particularly advantageous However, the method using a detergent according to the invention, which the bleach-activating acetonitrile derivative and optionally a peroxygen-containing oxide agents, preferably selected from the group comprising organic peracids, Contains hydrogen peroxide, perborate and percarbonate and their mixtures leads. The peroxygen compound can also be separate, in bulk or as preferred aqueous solution or suspension, added to the solution if a peroxide-free Detergent 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 Solvents as a reaction medium in question. The quantities of peroxygen compound used are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen are available. Also the amount of bleach activating acetonitrile derivative used depends on the application. Depending on the desired level of activation 0.00001 mol to 0.25 mol, preferably 0.001 mol to 0.02 mol activator per mol Peroxygen compound used, but in special cases these limits can also be exceeded or fallen below.

Another object of the invention is a solid detergent containing 0.1 wt .-% to 10 wt .-%, in particular 0.22 wt .-% to 6 wt .-% of an acetonitrile derivative according to Formula I in particulate form as described above in addition to conventional contains ingredients compatible with the compound.

The solid agents according to the invention, for example as powder or tablet Solids can be present in addition to the one used according to the invention Bleach activator, in principle, all known ingredients that are common in such agents contain. The agents according to the invention can in particular builder substances, upper  surfactants, peroxygen compounds, water-miscible organic solutions agents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries substances such as color transfer inhibitors, foam regulators, additional bleach intensifiers de contain active ingredients as well as colors and fragrances.

As peroxygen compounds suitable for use in agents according to the invention arrive in particular under the washing conditions that give off hydrogen peroxide organic salts, to which the alkali perborates, percarhonates, persilicates and / or per sulfates such as caroate belong, but also organic peracids or peracid Salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of Diperdodecanedioic acid. Such solid peroxygen compounds can for example in the form of powders or granules, which are also used in Principle can be encased in a known manner. Peroxygen compounds are in quantities of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight and particularly preferably from 8% by weight to 25% by weight. The addition less Amounts of known bleach stabilizers such as phosphonates, Borates or metaborates and metasilicates as well as magnesium salts such as Magnesium sulfate can be useful.

The agents according to the invention can contain one or more surfactants, wherein in particular anionic surfactants, nonionic surfactants and their mixtures, but also cationic, zwitterionic and amphoteric surfactants come into question.

Suitable nonionic surfactants are especially alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched Alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups. Corresponding ethoxylation and / or propoxylie are also Rung products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid ami those that ent the long-chain alcohol derivatives mentioned with respect to the alkyl part speak, as well as alkylphenols with 5 to 12 carbon atoms in the alkyl group.  

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Extremely low-foam connections can be used in particular in compositions for use in mechanical 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 -Alkylpo lyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and end-capped alkyl polyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European patent application EP 0 300 305, so-called hydroxy mixed ethers. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (II) in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R ³ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁴ for a linear, branched or cyclic alkylene radical or an arylene radical with 2 to 8 carbon atoms and R ⁵ for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C ₁ -C ₄ alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them. So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups per molecule. These groups are usually separated from one another by a so-called "spacer". This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is understood not only to mean "dimeric" but also "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061. End group-blocked dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are particularly characterized by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides as described in the international patent applications WO 95/19953, WO 95/19954 and WO 95/19955 can also be used.

Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkane sulfonates, and also disulfonates such as are obtained, for example, from C ₁₂ -C ₁₈ monoolefins having a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by α-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 ° C. - Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight. -%, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol be preserved. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are particularly preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are also suitable as further anionic surfactants. The sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred. Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. The known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.

The anionic surfactants, including the soaps, can be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine and / or isopropanolamine. Preferably, the anionic surfactants in the form of their sodium or potassium salts, in particular in the form of Sodium salts.

In detergents according to the invention, surfactants are preferred in quantitative proportions 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, contain.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and also polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphinophosphonic acid), ethylenediamine (ethylenediamine), ethylenediamine (ethylenediamine), ethylenediamine (ethylenediamine), ethylenediamine (ethylenediamine), ethylenediamine (ethylenediamine), ethylenediamine (1) -di phosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of the European patent EP 0 625 992 or the international patent application WO 92/18542 or the European patent EP 0 232 202 accessible by oxidation of polysaccharides or dextrins , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which also polymerize small amounts of polymerizable substances without carboxylic acid functionality can hold. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 30,000 to 120,000, each based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 30,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an alkyl sulfonic acid which is substituted in the 2-position by an alkyl or aryl radical , Such polymers can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, in amounts up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight be included.

Alkali silicates, in particular, come as water-soluble inorganic builder materials, Alkali carbonates and alkali phosphates, in the form of their alkaline, neutral or acidic Sodium or potassium salts can be considered. examples for this are Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentana trium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the ent speaking potassium salts or mixtures of sodium and potassium salts. As Water-insoluble, water-dispersible inorganic builder materials are used special crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular of 1% by weight up to 5% by weight. Among these are the crystalline sodium aluminosilicates in  Detergent quality, especially zeolite A, P and optionally X, alone or in Mixtures, for example in the form of a co-crystallizate from the zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta S.p.A.). amounts near the upper limit are preferably in solid, particulate media used. Suitable aluminosilicates in particular have no particles with a grain Size over 30 microns and preferably consist of at least 80 wt .-% of particles with a size below 10 µm. Your calcium binding capacity, which according to the information of German patent specification DE 24 12 837 can be determined, is usually in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. As crystalline silicates, which may be present alone or in a mixture with amorphous silicates, preference is given to using crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x + 1} .y H ₂ O, in which x, the so-called modulus, is a number of 1 , 9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and are preferred values for x 2, 3 or 4. Crystalline layer silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ .y H ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428 described, can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of agents according to the invention. Crystalline layered silicates of the above formula are sold by Clariant GmbH under the trade name Na-SKS, e.g. B. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, makatite). Of these, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ) are particularly suitable .3H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ .3H ₂ O, Kanemit), Na-SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline layered silicates is given, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33-38 and in "Soap-oil-fat waxes, 116th year, No. 20/1990" on pages 805 -808 published articles. In a preferred embodiment of agents according to the invention, a granular compound composed of crystalline layered silicate and citrate, of crystalline layered silicate and the (co) polymeric polycarboxylic acid mentioned above, as described for example in German patent application DE 198 19 187, or of alkali silicate and alkali carbonate a, as described for example in the international patent application WO 95/22592 or as it is commercially available for example under the name Nablon® 15.

Builder substances can optionally be present in amounts in the agents according to the invention up to 90 wt .-% can be included. They are preferably in amounts up to 75% by weight, in particular from 5% by weight to 50% by weight.

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 result in optionally substituted perbenzoic acid can be used. Are suitable Substances containing O and / or N-acyl groups with the number of carbon atoms mentioned and / or against also 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, especially phthal acid anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol di acetate, 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 and acetylated sorbitol and Mannitol or their in European patent application EP 0 525 239 written mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acety gelled, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam, from the 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 those in the German patent application DE 196 16 770 and international patent application WO 95/14075 Acyl lactams are also preferred. Even those from the German patent Application DE 44 43 177 known combinations of conventional bleach activators can be used. Such conventional bleach activators are if desired in the usual range of amounts, preferably in amounts of 0.1% by weight up to 10% by weight, in particular 0.5% by weight to 7% by weight, based on the total average, contain.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes, the cobalt complexes described in European patent application EP 0 272 030, the manganese comp. Known from European patent application EP 0 693 550 lexes, 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, if desired, 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 particulate bleach activator according to formula I, a bleach-enhancing combination of active ingredients 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 as well as their mixtures, a water-soluble ammonium salt and optionally an oxidizing agent based on peroxygen and inert carrier material, 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 according to formula I, which is made up in particulate form, takes place in the presence of such a combination of active substances.

In addition, the agents according to the invention can contain enzymes such as proteases, amylases, pullu lanases, mannanases, xylanases, cutinases, lipases, hemicellulases and cellulases contain, 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®, cellulases such as Celluzyme®, Ecostone® and / or Carezyme®. The enzymes that may be used, such as for example in international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or embedded in coating substances to protect them against premature inactivation. They are in the 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 for example from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350, known, can be used.

Regarding those suitable for use in textile detergents according to the invention Color transfer inhibitors include, in particular, polyvinyl pyrrolidones, polyvinyl imidazoles, polymeric N-oxides such as poly- (vinylpyridine-N-oxide) and copolymers of vinyl pyrrolidone with vinylimidazole.

Graying inhibitors have the task of removing the dirt detached from the textile fiber to keep the fleet suspended. For this purpose, water-soluble colloids are usually more organic Suitable in nature, for example starch, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above Use starch derivatives, for example aldehyde starches. To be favoured  Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxy propyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in Amounts of 0.1 to 5 wt .-%, based on the agent used.

To increase the cleaning performance, the detergents according to the invention can in particular contain soil release polymers, so-called soil-release polymers, which are generally composed of carboxylic acid units and optionally polymeric diol units and contain, for example, ethylene terephthalate and polyoxyethylene terephthalate groups. Other monomer units, for example propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfo-substituted phthalic acid isomers can be contained in the dirt-releasing polymer. End-capped derivatives, that is to say polymers which have neither free hydroxyl groups nor free carboxyl groups, but instead carry, for example, C _1-4 -alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can also be used. Also suitable are the polyesters known from European patent application EP 0 241 985 which, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units contain and are closed with C ₁ - to C ₄ -alkyl groups, the soil release polymers used in the agents of the European patent application EP 0 253 567 made of ethylene terephthalate and polyethylene oxide-terephthalate with a molecular weight of 900 to 9000, the polyethylene glycol Units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, which are end groups which are known from European patent application EP 0 272 033 and are at least partially capped by C _1-4 alkyl or acyl radicals Polyester with poly-propylene terephthalate and poly oxyethylene terephthalate units, the sulfoethyl mentioned in the European patent application EP 0 274 907 End-capped terephthalate-containing soil-release polyester, the soil-release polyester produced by sulfonation of unsaturated end groups with terephthalate, alkylene glycol and poly-C _2-4 glycol units of the European patent application EP 0 357 280, which is derived from the European patent application EP 0 398 133 known cationic soil release polyesters with amine, ammonium and / or amine oxide groups and the cationic soil release polyesters with ethoxylated, quaternized morpholine units of European patent application EP 0 398 137. Polymers are also suitable from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 and their use in detergents in German patent DE 28 57 292 is described, and polymers with a molecular weight of 15,000 to 50,000 from Eth yl terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, which according to German patent application DE 33 24 258 can be used in detergents ,

Textile detergents according to the invention can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. Suitable Examples are salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) style ben-2,2'-disulfonic acid or similar compounds that replace the morpho lino group, a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Brighteners of the type of substituted diphenylstyryl, for example the alkali salts of 4,4'-bis (2- sulfostyryl) diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyls, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl). Mixtures of the aforementioned optical brighteners can also be used.

If the agents foam too much during use, they can still be preferred up to 5 wt .-%, in particular about 0.1 wt .-% to 3 wt .-% of a foam regulating Compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, more hydrophobic Silicic acid, the bis fatty acid amides, and other other known commercially available Defoamers can be added. Other optional ingredients in the invention Agents are, for example, perfume oils.  

To set a desired, by mixing the other components the agents according to the invention cannot be systemic and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, apples 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 in the agents according to the invention preferably not more than 10% by weight, in particular of 0.5% to 6% by weight.

In order to facilitate the disintegration of agents according to the invention, in particular if they are present as 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 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 approximately 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 gives 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 to which  in particular enzymes, bleaching agents and the bleach activator are to be expected can be.

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 from 800 to 1000 g / l can be achieved by adding the builder Components with at least a proportion of liquid mixture components under Er Increase the bulk density of this premix and subsequently - desired if after an intermediate drying - the other components of the agent, including the Particulate bleaching catalyst according to formula I, with which won combined premix.

In a preferred embodiment of agents according to the invention, these are in the form compressed body, in particular tablets, for the manufacture of which one 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 The composition of the premixes to be compressed can include physical parameters of the Premixes are selected so that advantageous molded body properties result. So have, in preferred variants, the particulate premixes to be compressed Bulk weights above 600 g / l, preferably above 700 g / l and in particular 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 distributions 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  than 40% by weight and in particular more than 50% by weight of the particles a particle size have 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 Dosing, compression (elastic deformation), plastic deformation and Ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one 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 tableting the upper stamp touches the premix and continues to lower in the direction of the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper stamp (and from a certain pressure on the premix) the plastic begins Deformation in which the particles flow together and it to form the molded body comes. Depending on the physical properties of the premix, a part also becomes the premixed particles are crushed and there is a pressure at even higher pressures Sintering 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 article 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 or double stamps can be equipped. In the latter case, not only 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 operation of a conventional four-stroke engine. 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 placed in the positions for filling, compression, plastic deformation and discharge become. At those points where there is a particularly serious increase or decrease 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 stamps 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 become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion skin-like structure have, in the case of the point tablets the top of the core or the Core layers are not covered and thus remain visible. Also Rotary tablet presses can 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 one 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). Is particularly suitable 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 presentation form of 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 the metering chamber of commercial dishwashers adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid; of where they are released from during the cleaning process. It goes without saying the detergent tablets can also be used without problems using dosing aids.  

After pressing, the shaped bodies have a high level of 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

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 shaped body causes, D is the shaped body diameter in meters and t is the Height of the molded body.

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 preparing two or more premixes, which are pressed together. This makes the premix, which is filled in first, light pre-pressed to a smooth and parallel to the top of the molded body top get, and after filling the second premix to the finished molded body final compression. In the case of three-layer or multi-layer moldings, Add another pre-compression before adding the last premix Shaped body is finally pressed.

Due to the increasing technical effort, the maximum is in practice 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 easily possible to add the bleach and the bleach activator to the incorporate the same layer and other sensitive components, in particular Enzymes to work into a separate second layer of the molded body.

Claims (19)

1. Use of compounds of the general formula I which have been made up in particulate form with the aid of inorganic support materials which contain silicate,
in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another for R ¹ , R ² or R ³ have the meaning given and X is a charge-balancing anion, as activators for, in particular, inorganic peroxygen compounds in solid textile detergents which are used in essentially aqueous water ash solutions are used. 2. Use according to claim 1, characterized in that the carrier material has an inner surface in the range from 10 m ² / g to 500 m ² / g, in particular 100 m ² / g to 450 m ² / g. 3. Use according to claim 1 or 2, characterized in that the carrier material Silicate from the group comprising alkali silicates, silicas, silica gels and clays and their mixtures.   4. Use according to one of claims 1 to 3, characterized in that in the Particulate form 10 to 50 parts by weight of the carrier material and 50 to 90 parts by weight of the compound of the formula I are present. 5. Use according to one of claims 1 to 4, characterized in that in the compound of formula IR ¹ , R ² and R ^{3 are the} same. 6. Use according to claim 5, characterized in that in the compound of formula IR ¹ , R ² and R ^{3 are} methyl groups. 7. Use according to one of claims 1 to 6, characterized in that the charge-compensating anion X ^- from the halides, such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, Carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C _1-20 alkyl sulfate, C _1-20 alkyl sulfonate, optionally C _1-18 alkyl substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C _1-24 carboxylic acids such as formate, acetate , Laurate, benzoate or citrate, alone or in any mixtures. 8. Use according to one of claims 1 to 7, characterized in that the charge-compensating anion X ^- chloride, sulfate, hydrogen sulfate, ethosulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or methosulfate or mixtures of these. 9. Use according to one of claims 1 to 8, characterized in that the activating peroxygen compound from the group comprising organic peracids, Hydrogen peroxide, perborate and percarbonate and their mixtures is selected. 10. Use according to one of claims 1 to 9, characterized in that the same timely a bleach-enhancing combination of active ingredients that through intimate mixing a water-soluble salt of a divalent transition metal selected from Cobalt, iron, copper and ruthenium and their mixtures, a water-soluble  Ammonium salt and optionally an oxidizing agent based on peroxygen as well as inert carrier material is available. 11. Solid detergent, characterized in that it contains 0.1% by weight to 10% by weight, in particular 0.2% by weight to 6% by weight, of an inorganic carrier material which in particular contains silicate, Particulate compound of the general formula I
in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another one given above for R ¹ , R ² or R ³ Have meaning and X is a charge-balancing anion, in addition to the usual ingredients which are compatible with the compound of the formula I. 12. Composition according to claim 11, characterized in that it is a peroxygen compound from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof. 13. Composition according to claim 11 or 12, characterized in that in addition to the Ver Bonds according to formula I 0.5 wt .-% to 7 wt .-% under perhydrolysis conditions Compounds releasing peroxocarboxylic acids are present.   14. Composition according to one of claims 11 to 13, characterized in that it is additionally to the compounds according to formula I a bleach-enhancing combination of active ingredients, by intimately mixing a water-soluble salt of a divalent Transition metal, selected from cobalt, iron, copper and ruthenium and their Mixtures, a water-soluble ammonium salt and optionally an oxide Per-oxygen-based agents and inert carrier material is available. 15. Agent according to one of claims 11 to 13, characterized in that in addition to the compound of formula I bleach-catalyzing transition metal salts or complexes, in particular in quantities of 0.0025% by weight to 0.5% by weight, are present are. 16. Composition according to one of claims 11 to 15, characterized in that it as tablet-shaped molded body is present. 17. Composition according to claim 16, characterized in that the tablet-shaped Shaped body is two layers. 18. Composition according to claim 17, characterized in that it in one layer Bleaching agent in the form of the particularly inorganic peroxygen compound and in the second layer with the aid of inorganic carrier materials, which contain in particular silicate, according to particulate assembled bleach activator Formula I has. 19. Composition according to claim 17, characterized in that it is the bleach in the form of especially inorganic peroxygen compound and with the help of inorganic Carrier materials, which contain in particular silicate, particulate confection ned bleach activator according to formula I in the same layer and more sensitive Liche components, in particular enzymes, in a second layer.