EP1749084B1 - Bleach reinforcer combination for use in washing and cleaning agents - Google Patents

Abstract

The performance of peroxide compounds, in particular when associated with bleaches for washing ink stains out of textiles, can be improved by a composition comprising: (i) a peroxygen-containing bleaching agent, (ii) a bleach activator selected from the group consisting of amide bleach activators, sulfonyl phenyl ester bleach activators, quaternary nitrogen substituted acetonitrile bleach activators, and mixtures thereof, and (iii) a compound selected from the group consisting of ligands corresponding to the general formula (I), bleach catalysts corresponding to the general formula (II), and mixtures thereof: wherein Y<SUP>m- </SUP>represents an anion, M represent a manganese or iron atom, each X independently represents an inorganic ligand and the mathematical product of m and n equals 2.

Description

The present invention relates to the use of a combination of a bleach activator with a terpyridine compound which is capable of complexing with iron and manganese ions, or a suitably preformed iron or manganese complex for activating peroxygen compounds and / or atmospheric oxygen, in particular for bleaching Paint stains when washing textiles, as well as detergents, cleaners and disinfectants containing such Bleach amplifier combinations.

Inorganic peroxygen compounds, particularly 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 disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by addition of so-called bleach activators which are able to provide peroxycarboxylic under the abovementioned perhydrolysis and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example from the British patent GB 836 988 known reactive esters, polyacylated alkylenediamines, in particular N, N, N ', N'-tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, in addition Carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy-benzenesulfonate, O-acylated sugar derivatives, such as pentaacetyl glucose, and N-acylated lactams, such as N-benzoyl-caprolactam, have become known in the literature. By adding these substances, the bleaching effect aqueous peroxide liquors are increased so much that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

In a differentiating approach, however, it is observed that under fabric washing conditions, such bleach activators that release relatively short chain peroxocarboxylic acids (most important example is TAED) have a particularly pronounced effectiveness against hydrophilic stained soils, while bleach activators release relatively longer chain peroxocarboxylic acids (an example being NOBS ), have a higher efficacy over hydrophobic stains. In order to achieve averaged over all soiling a high bleaching performance is variously, for example in the international patent application WO 96/17920 A2 or the European patent application EP 0 257 700 A2 proposed the use of mixtures of bleach activators which release peroxocarboxylic acids of various chain lengths.

In the effort to achieve energy-saving washing and bleaching processes, in addition, application temperatures still gain significantly less than 60 ° C., especially below 45 ° C., down to the cold water temperature in recent years.

At these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There has therefore been no lack of efforts to develop more effective activators for this temperature range. However, it must be noted in individual cases that a highly effective at low temperatures bleach activator its effectiveness in the medium or high temperature range, in the case of high demands on the cleaning performance of the detergent or cleaning also quite an increase in bleaching performance over that of the pure oxidant may be desired, loses.

The use of transition metal compounds, in particular transition metal complexes, to increase the oxidation power of peroxygen compounds or atmospheric oxygen in detergents and cleaners has also been proposed on several occasions Service. The transition metal compounds proposed for this purpose include, for example, those of the German patent application DE 195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 196 20 267 known N-analogues known from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes described in the German patent application DE 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which are known from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes described in the German patent application DE 44 16 438 described manganese, copper and cobalt complexes described in the European patent application EP 0 272 030 cobalt complexes described in the European patent application EP 0 693 550 known manganese complexes, from the European patent EP 0 392 592 known manganese, iron, cobalt and copper complexes resulting from international patent applications WO 96/23859 . WO 96/23860 and WO 96/23861 known cobalt complexes and in the European patent specification EP 0 443 651 or the 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. Also according to the European patent application EP 0 832 969 Available bleach-enhancing active ingredient combination is to be mentioned here. Combinations of bleach activators and transition metal bleach catalysts are, for example, from that of the international patent application WO 95/27775 and the German patent application DE 196 13 103 , which relates to electrochemically in certain potential ranges with the highest possible current density oxidizable transition metal complexes known.

The international patent application WO 2004/039934 concerns pyrimidine ligands.

The international patent application WO 2004/007657 refers to certain manganese, titanium, iron, cobalt, nickel or copper complexes having a terpyridine ligand substituted with at least one quaternary nitrogen-carrying radical and their use as catalysts for oxidation reactions. This use of the complexes can also be effected by a washing, cleaning, disinfecting or bleaching agent containing them, conventional bleach activators being mentioned among the other customary ingredients of such agents.

Surprisingly, it has now been found that the combination of certain bleach activators, namely those of the amide type, of the sulfonylphenyl ester type and of the quaternary nitrogen-substituted acetonitrile type, with certain manganese or iron complexes, namely those having a ligand of the terpyridine type as described below. Type, has an excellent bleach-activating effect and also this bleach-activating effect over the entire temperature requirement profile of a detergent or cleaning agent is maintained, without it when using the agent or the joint use of its aforementioned components to damage the treated textile, which is about the go beyond the usual market means.

in der M für Mangan oder Eisen, X für einen anorganischen Liganden und Y^m- für ein Anion steht und das Produkt der ganzen Zahlen m und n gleich 2 ist, zum Bleichen von Farbanschmutzungen beim Waschen von Textilien, insbesondere in wäßriger, tensidhaltiger Flotte. Ein weiterer Gegenstand der Erfindung ist die entsprechende Verwendung zum gleichzeitigen oder alternativen Desinfizieren des Waschgutes.Accordingly, an object of the invention is the use of a combination of peroxygen-containing bleach, amide-type bleach activator, sulfonylphenyl ester-type and / or quaternary nitrogen-substituted acetonitrile-type bleach catalyst according to formula (II),

in which M is manganese or iron, X is an inorganic ligand and Y ^{m- is} an anion and the product of integers m and n is 2, for bleaching paint stains when washing textiles, especially in aqueous, surfactant-containing liquor. Another object of the invention is the corresponding use for simultaneous or alternative disinfecting the laundry.

in der Y^m- für ein Anion steht und das Produkt (m· n) gleich 2 ist, zum Bleichen von Farbanschmutzungen und/oder Desinfizieren des Waschgutes beim Waschen von Textilien, in wäßriger, insbesondere tensidhaltiger Flotte, die Mangan- und/oder Eisen-Ionen enthält.The inventively intended success also occurs when one does not use the complex of formula II, but only the corresponding terpyridine ligand and the coming fleet used iron and / or manganese ions, wherein the oxidation state of said metals because of in the wash liquor usually rapidly adjusting redox equilibrium among the different oxidation states usually not essential. A further subject of the invention is therefore the use of a combination of peroxygen-containing bleach, amide-type bleach activator, sulfonylphenyl ester-type and / or quaternary nitrogen-substituted acetonitrile-type and compound of formula (I),

in which Y ^{m- is} an anion and the product (m · n) is 2, for bleaching color stains and / or disinfecting the laundry when washing textiles, in aqueous, especially surfactant-containing liquor, the manganese and / or iron Contains ions.

In a compound of formula (I) or of formula (II), the anion (Y ^m- ) is preferably an organic anion, for example citrate, oxalate, tartrate, formate, a C _2-18 -carboxylate, a C _1-18 - Alkyl sulfate, in particular methosulfate, or a corresponding alkanesulfonate. In a compound of formula (II), the inorganic ligand (X) is preferably a halide, in particular chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide.

The uses according to the invention can be particularly easily by the use of a detergent, cleaning or disinfecting agent, the pers oxygen bleach, bleach activator of the type mentioned and a compound of formula (I) or a bleach catalyst according to formula (II) in addition to conventional with the bleach activator and said Compound or the bleach catalyst compatible ingredients contains realized. These means are therefore further objects of the invention.

Preferably 0.01 to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% of the compound according to formula (I) in inventive compositions. If a compound according to formula (I) is included, it is preferred that the agent additionally Manganese and / or iron salt and / or a manganese and / or iron complex without a ligand which corresponds to the compound according to formula (I) contains. Then, the molar ratio of manganese or iron or the sum of manganese and iron to the compound of the formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1. In a further preferred embodiment of compositions according to the invention, these contain from 0.01% by weight to 1.5% by weight, in particular from 0.05% by weight to 1% by weight, of a bleach catalyst according to formula (II).

Suitable peroxygen compounds are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing or cleaning conditions, such as perborate, percarbonate and / or persilicate. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. In particular, in detergents or cleaners according to the invention, peroxygen compounds are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, while in the disinfectants according to the invention preferably of 0.5% by weight. % to 40 wt .-%, in particular from 5 wt .-% to 20 wt .-%, of peroxygen compounds are included.

The bleach activator of the amide type as a preferred further component of the combination or agents to be used according to the invention is preferably a derivative of ammonia or of a mono- or bis-alkylamine. It is preferably made of the compounds of formula (III),

(R ¹ -CO-) _n X (III)

in the R ^{1 is} an aryl, alkyl, alkenyl or cycloalkyl radical having 1 to 10 C atoms, n is a number from 1 to 4 and X is a nitrogen-containing leaving group with direct bond between nitrogen on the one hand and the acyl group R ¹ - CO on the other hand, and their mixtures selected. Preference is given to the compounds of the formula (III) where R ¹ = phenyl, C ₁ - to C ₅ -alkyl, 9-decenyl and mixtures thereof, where the alkyl radicals can be linear or branched-chain. Among the compounds of the formula (III) with linear radicals R ¹ , those having 1 to 9 C atoms are particularly preferred. These compounds according to formula (III) can be prepared by N-acylation with reactive R ¹ -CO-derivatives, for example acid chlorides, of the corresponding unsubstituted compounds H _n X according to known methods. Preferred nitrogen-containing leaving groups X are those in which the nitrogen carries at least one further acyl group in addition to the acyl group R ¹ -CO- to be split off. Examples of such compounds according to formula (III) are the triacylation products of ammonia and the diacylation products of primary alkylamino groups, such as those of ethylenediamine. If the abovementioned at least one further acyl group is likewise not an acyl radical R ¹ -CO-, it is preferred, if it has such a graded perhydrolysis activity, that under the conditions of use substantially only from the group R ¹ -CO- corresponding peroxycarboxylic acid forms. This can be achieved by virtue of the fact that in the compound according to formula (III) the nitrogen carrying the group R ¹ -CO- is also part of a cyclic amide or imide structure. The latter compounds may be referred to as acylamides or acylimides, wherein the name part "acyl" refers to the group R ¹ -CO-. The amide portion of such acylamides preferably consists of an optionally substituted capro or valerolactam group and the imide portion of such acylimides preferably consists of a succinimide, maleimide or phthalimide group, which groups optionally C ₁ - to C ₄ -alkyl-, hydroxyl , COOH and / or SO ₃ H substituents, the latter substituent groups may also be present in the form of their salts. Among the acylimides, N-nonanoyl and N-isononanoyl succinimide are preferred. Among the most preferred compounds is N, N, N ', N'-tetraacetylethylenediamine (TAED).

Bleach activators of the sulfonylphenyl ester type preferably correspond to the abovementioned compounds of the formula (III), in which case X is a phenoxy radical carrying a sulfonic acid group or its alkali metal salt, and n is, in particular, 1. Particularly preferred compounds of this type include sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and sodium lauroyloxybenzenesulfonate.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -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 mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist. Unter diesen sind kationische Nitrile, in denen R¹ für Methyl, Ethyl, Propyl, Isopropyl oder einen n-Butyl, n-Hexyl, n-Octyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Hexadecyl oder n-Octadecylrest steht, und R² und R³ aus Methyl, Ethyl, Propyl, Isopropyl und Hydroxyethyl ausgewählt werden, wobei einer oder beide dieser Reste vorteilhaft auch ein Cyanomethylenrest sein kann, bevorzugt. Besonders bevorzugt ist der Einsatz von Trimethylammoniumacetonitril-Salzen, beispielweise den Chloriden, Sulfaten, Hydrogensulfaten, Metho- oder Ethosulfaten. In einer bevorzugten Ausführungsform der Erfindung enthält ein erfindungsgemäßes Mittel 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-% Bleichaktivator der genannten Typen. Besonders bevorzugt ist, wenn Bleichaktivator vom Amid-Typ und Bleichaktivator vom Typ der mit quaternärem Stickstoff substituierten Acetonitrile gemeinsam vorliegen.Quaternary nitrogen-substituted acetonitrile bleach activators preferably correspond to the formula (IV)

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having 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 where n = 1, 2, 3, 4, 5 or 6 and X is an anion. Among these are cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n- Octadecyl radical, and R ² and R ^{3 are selected} from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both of these radicals may advantageously also be a Cyanomethylenrest, preferably. Particularly preferred is the use of trimethylammonium acetonitrile salts, for example the chlorides, sulfates, hydrogen sulfates, metho- or ethosulfates. In a preferred embodiment of the invention, an agent according to the invention contains from 0.5% by weight to 10% by weight, in particular from 1% by weight to 8% by weight, of bleach activator of the types mentioned. Particularly preferred is when amide type bleach activator and quaternary nitrogen substituted acetonitrile bleach activator are coexistent.

For use in particulate detergents, cleaners and disinfectants, the substances to be used in combination according to the invention are preferably solid at room temperature. The compounds of formula I or formula II are used in combination with the bleaching agents mentioned preferably for bleaching Farbanschmutzungen in the washing of textiles, especially in aqueous, surfactant-containing liquor. The phrase "bleaching of paint stains" is to be understood in its broadest sense and includes both bleaching of debris on the fabric, bleaching of debris found in the wash liquor and debris removed from the fabric, as well as oxidative destruction of itself in the wash liquor Textile dyes that detach under the washing conditions of textiles before they can be applied to different colored textiles. Also, when used in cleaning solutions for hard surfaces, especially for crockery, the term bleaching both the bleaching of on the hard surface befindendem dirt, especially tea, as well as the bleaching of befindlichem in the dishwashing liquor detached from the hard surface Dirt understood.,

In the method according to the invention and within the scope of a use according to the invention, the combination can be used wherever a particular increase in the oxidation effect, in particular of inorganic peroxygen compounds at low temperatures, is required, for example in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic substances or inorganic intermediates and in disinfection.

Essentially, the use of the present invention is to provide conditions under which the peroxygen compound can react with the compounds employed in combination, with the aim of producing more strongly oxidizing secondary products to obtain. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the

Peroxygen compound, the compound of formula (I) and / or formula (II) and the bleach activator in a separate form to an optionally washing or cleaning agent-containing solution. However, the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains the stated ingredients. The peroxygen compound may also be added separately, in bulk or as a preferably aqueous solution or suspension, to the washing, cleaning or disinfecting solution when an oxygen-free agent is used.

Depending on the purpose, the conditions can be varied widely. Thus, in addition to purely aqueous solutions and mixtures of water and suitable organic solvents as the reaction medium in question. The amounts of peroxygen compounds are generally chosen so that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm of active oxygen are present.

The detergents, cleaners and disinfectants according to the invention, which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, may contain, in addition to the combination to be used according to the invention, in principle all known ingredients customary in such compositions. The detergents and cleaners according to the invention may in particular be builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing active ingredients and shape-retaining active ingredients, and further adjuvants such as optical brighteners, foam regulators, additional peroxygen activators, dyes and fragrances.

A disinfectant according to the invention can be used to enhance the disinfecting action against special germs in addition to the previously mentioned Ingredients contain conventional antimicrobial agents. Such antimicrobial additives are contained in the disinfectants according to the invention preferably in amounts of up to 10 wt .-%, in particular from 0.1 wt .-% to 5 wt .-%.

In addition to the combination to be used according to the invention, customary substances mentioned at the outset, which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and / or customary bleach-activating transition metal complexes can be used.

The compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation of N-alkyl-amines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are present in the cleaning or washing agents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the disinfectant according to the invention as well as inventive cleaning agent preferably 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 5 wt .-% surfactants.

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 polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diene diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates of the international patent application WO 93/16110 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, though 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. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. 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 may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers can be prepared in particular by methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.

Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P. and optionally X, is preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Those with a molar ratio Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O y are used _{2x + 1} H ₂ O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (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 the international patent application WO 91/08171 is described. δ-Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 425 428 can be used in agents according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means. In a preferred embodiment of compositions according to the invention, a granular compound of alkali metal silicate and alkali metal carbonate is used, as described, for example, in the international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

Builders are preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free from the complexing only of the components of the water hardness Builder substances are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof, contain.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat,

wobei die Mengenangaben sich auf das gesamte Wasch- beziehungsweise Reinigungsmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben.In a preferred embodiment of the invention, an agent according to the invention has a water-soluble builder block. By the use of the term "builder block", it is intended to express that the agents contain no further builder substances than those which are water-soluble, ie all builder substances contained in the agent are present in the "block" thus characterized. summarized, at best, the amounts of substances are excluded, which may be commercially available as impurities or stabilizing additives in small amounts in the other ingredients of the agent. The term "water-soluble" is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use amount of the agent containing it in the customary conditions. Preferably, at least 15 wt .-% and up to 55 wt .-%, in particular 25 wt .-% to 50 wt .-% of water-soluble builder block in the inventive compositions. This is preferably composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
2. b) up to 10% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
4. d) up to 50% by weight of alkali metal phosphate, and
5. e) up to 10% by weight of polymeric polycarboxylate,

wherein the quantities are based on the total detergent or cleaning agent. This also applies to all following quantities, unless expressly stated otherwise.

In a preferred embodiment of the composition according to the invention, the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.

With regard to component a), in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate. In an alternative embodiment of inventive compositions are as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali carbonate and alkali bicarbonate are present, the Component a) alkali metal carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 1 to 1: 1.

With regard to component b), in a preferred embodiment of the composition according to the invention, 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5 are contained.

With regard to component c), in a preferred embodiment, agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate. Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and those described in German Auslegeschrift DE 11 07 207 described acylated derivatives of phosphorous acid, which can also be used in any mixtures.

With regard to component d), in a preferred embodiment of the composition according to the invention, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are contained. Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, very soluble in water powder that lose the water of crystallization on heating and at 200 ° C in the weak acid diphosphate (Disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is slightly soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances colorless crystals soluble in water with alkaline reaction. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: fused or annealed phosphates, Graham's salt, Kurrolsches and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

With regard to component e), in a preferred embodiment, agents according to the invention contain from 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Among these, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).

As enzymes which can be used in the compositions, apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, 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® and / or Carezyme®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes can, for example, in the European patent EP 0 564 476 or in the international patent applications WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are present in the detergents, cleaners and disinfectants according to the invention preferably in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particularly preferably enzymes which are 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 to be used.

In a preferred embodiment of the invention, the agent contains 5% by weight to 50% by weight, in particular 8-30% by weight of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight. % Builder and 0.2% to 2% by weight of enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases, and mixtures thereof.

Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms , in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compound ethers. Such water-miscible solvents are preferably present in the detergents, cleaners and disinfectants according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.

In order to establish a desired pH, which does not result from the mixture of the other components, the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.

Soil release polymers, often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, for example fiber, are, for example, nonionic or cationic cellulose derivatives. The particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example Adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ₁₁ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ₁₁ -) _a O- and also polymeric diol units - ( O- (CHR ¹¹ -) _a ) _b O-before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000 The acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a Number from 2 to 6, and those in which a has the value 2 and R ^{11 is selected} from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3 C-atoms. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH in which R ^{11 has} the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be endgruppenverschlossen, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 have and the Molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.

Polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers belong to the color transfer inhibitors which are suitable for use in laundry detergents according to the invention.

The inventive compositions for use in the textile laundry may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brightener can be used.

In particular, when used in automatic washing and cleaning processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

In agents according to the invention it is also possible to use active substances for avoiding the tarnishing of silver objects, so-called silver corrosion inhibitors. Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the Metals in one of the oxidation states II, III, IV, V or VI are present.

The terpyridine compound, which is capable of complexing with iron and manganese ions, and the correspondingly preformed iron or manganese complex may be in the form of powders or as granules, which may optionally also be coated and / or colored, and conventional support materials and / or or granulation aids may be present. In the case of their use as granules, if desired, they may also contain the amide-type, the sulfonylphenyl-ester type bleach activator and / or the quaternary nitrogen-substituted acetonitrile type.

The preparation of solid compositions according to the invention presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, with peroxygen compound and bleach activator combination optionally being added later. For the preparation of inventive compositions having an increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one of the European patent EP 486 592 known method comprising an extrusion step is preferred. Detergents, cleaners or disinfectants according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer. In a preferred embodiment of means for the particular machine cleaning of dishes they are tablet-shaped and can be based on those in the European patents EP 0 579 659 and EP 0 591 282 disclosed methods are produced.

Claims (15)

1. A detergent, cleansing composition or disinfectant composition comprising peroxygen-containing bleaching agent, bleach activator of the amide type, the sulfonyl phenyl ester type and/or of the type with quaternary nitrogen substituted acetonitriles, and a compound according to formula (I),

   

   in which Y^m- stands for an anion and the product (m.n) equals 2, besides conventional, ingredients that are compatible with the bleaching agent, the bleach activator and this compound.
2. The composition according to claim 1, comprising 0.01 wt.% to 2 wt.%, particularly 0.1 wt.% to 1 wt.% of the compound according to formula (I).
3. The composition according to claim 1 or 2, wherein said composition additionally comprises a manganese and/or iron salt and/or a manganese and/or iron complex without a ligand that corresponds to the compound according to formula (I).
4. Composition according to claim 3, wherein the molar ratio of manganese or iron or the sum of manganese and iron to the compound according to formula (I) is in the range from 0.001: 1 to 2:1 particularly 0.01: 1 to 1: 1.
5. A detergent, cleansing composition or disinfectant composition comprising peroxygen-containing bleaching agent, bleach activator of the amide type, the sulfonyl phenyl ester type and/or of the type of quaternary nitrogen substituted acetonitriles, and a bleach catalyst according to formula (II),

   

   in which M stands for manganese or iron, X for an inorganic ligand and Y^m- for an anion and the product (m.n) equals 2, besides conventional ingredients that are compatible with the bleach activator and the bleach catalyst.
6. Composition according to claim 5, comprising 0.01 wt.% to 1.5 wt.%, particularly 0.05 wt.% to 1 wt.% of the bleach catalyst according to formula (II).
7. Composition according to one of claims 1 to 6, wherein the anion Y^m- in the compound according to formula (I) and/or formula (II) is an organic anion and/or the inorganic ligand in the compound according to formula (II) is a halide, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, hydrogen sulfate, hydroxide or hydroperoxide.
8. Composition according to one of Claims 1 to 7, comprising up to 50 wt.%, particularly from 5 wt.% to 30 wt.% of a peroxygen bleaching agent.
9. Composition according to one of claims 1 to 8, wherein the peroxygen compound is selected from the group including hydrogen peroxide, alkali metal perborate that can be present as the monohydrate or the tetrahydrate, alkali metal percarbonate and mixtures thereof.
10. Composition according to one of Claims 1 to 9, particularly comprising 0.5 wt.% to 10 wt.%, particularly 1 wt.% to 8 wt.% bleach activator of the amide type, the sulfonyl phenyl ester type and/or of the type with quaternary nitrogen substituted acetonitriles.
11. Composition according to one of claims 1 to 10, wherein the bleach activator of the amide type is an acyldialkylamine, a diacylalkylamine and/or a tetraacylalkylenediamine, particularly tetraacetylethylenediamine, the bleach activator of the sulfonyl phenyl ester type is sodium nonanoyloxybenzene sulfonate, sodium isononanoyloxybenzene sulfonate and/or sodium lauroyloxybenzene sulfonate, and/or the bleach activator of the type of quaternary nitrogen substituted acetonitriles is a trimethyl ammonium acetonitrile salt.
12. Composition according to one of claims 1 to 11, wherein said composition possesses a water-soluble builder block.
13. Composition according to one of claims 1 to 12 comprising 5 wt.% to 50 wt.%, particularly 8 wt.% to 30 wt.% anionic and/or non-ionic surfactant, up to 60 wt.%, particularly 5 wt.% to 40 wt.% builder and 0.2 wt.% to 2 wt.% enzyme, selected from the proteases, lipases, cutinases, amylases, pullulanases, cellulases, oxidases and peroxidases as well as their mixtures.
14. Use of a combination of peroxygen-containing bleaching agents, bleach activators of the amide type, the sulfonyl phenyl ester type and/or of the type of quaternary nitrogen substituted acetonitriles, and a bleach catalyst of the general formula (II),

    

    in which M stands for manganese or iron, X for halogen and Y^m- for an anion and the product (m.n) equals 2, for bleaching colored stains and/or disinfecting washing during the washing of fabrics, particularly in aqueous, surfactant-containing liquors.
15. Use of a combination of peroxygen-containing bleaching agents, bleach activators of the amide type, the sulfonyl phenyl ester type and/or of the type of quaternary nitrogen substituted acetonitriles, and a bleach catalyst of the general formula (I),

    

    in which Y^m- stands for an anion and the product (m.n) equals 2, for bleaching colored stains and/or disinfecting washing during the washing of fabrics, particularly in aqueous, surfactant-containing liquor that comprises manganese ions and/or iron ions.