EP3406698A1 - Bleaching detergent composition comprising oxaziridine precursor - Google Patents

Abstract

The oxidation and bleaching action of peroxygen compounds at low temperatures should be improved. This was achieved essentially by the use of a combination of 0.001 wt .-% to less than 0.05 wt .-%, in particular 0.005 wt .-% to 0.04 wt .-% of 3-methyl-benzisothiazol-1,1-dioxide and 0.1% to 5% by weight, especially 0.4% to 0.6% by weight, of peroxycarboxylic acid-providing compound under perhydrolysis conditions.

Description

The present invention relates to the use of 3-methylbenzisothiazole-1,1-dioxide in small amounts for the activation of peroxygen compounds in connection with the bleaching of soils when washing textiles and cleaning hard surfaces, as well as detergents and cleaners containing small amounts of 3 Contain methylbenzisothiazole 1,1-dioxide.

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 alkali 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 several times acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides, in particular phthalic anhydride and alkylsuccinic anhydrides, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulphonate, 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 action of aqueous peroxide liquors can be 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 the search for energy-saving washing and bleaching processes in recent years application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance.

At low temperatures, the effect of the previously known activator compounds usually decreases noticeably.

From the European patent application EP 0 453 003 A2 Bleaching agents are known which contain 1 to 60% by weight of peroxygen compound and 0.05 to 10% by weight of an oxygen transfer agent of a general formula R ¹ R ² C = NSO ₂ R ³ , which also contains N-heterocycloaromatic sulfonimines such as 3 Methylbenzisothiazole-1,1-dioxide. Such sulfonimines can form oxaziridines by oxygen addition to the C = N double bond which can transfer the oxygen atom taken up by a primary oxidant to substrates and thus act as secondary oxidants. From SÖFW-Journal 140 (2014), 48 it is known that Oxaziridine in application concentrations of 0.05 to 0.25% in combination with 0.5 to 2% TAED significantly improve the performance of powdered detergents.

Surprisingly, it has now been found that even significantly lower amounts of sulfonimines are suitable for increasing the bleaching effect of detergents and cleaners containing peroxygen.

The invention relates to the use of a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight of 3-methylbenzisothiazole-1,1-dioxide and 0, 1 wt .-% to 5 wt .-%, in particular 0.4 wt .-% to 0.6 wt .-% under perhydrolysis conditions peroxycarboxylic acid-supplying compound to enhance the cleaning performance of peroxygen-containing detergents or cleaning agents in aqueous, especially surfactant-containing liquor , The percentages by weight relate to the entire detergent or cleaning agent; this also applies to all following percentages by weight, unless expressly stated otherwise.

Essentially, the use of the present invention is to provide conditions under which the peroxygen compound and said combination can react with one another, with the aim of obtaining more strongly oxidizing secondary products. Such conditions are particularly present when the reactants meet in an aqueous system. This can be done by separately adding the peroxygen compound and the components of the combination to a possibly washing or cleaning agent-containing liquor. However, it is particularly advantageously carried out using a washing or cleaning agent which contains said combination and a peroxidic oxidizing agent. The peroxygen compound may also be added separately, in bulk or as a preferably aqueous solution or suspension, to the aqueous system when a peroxygen-free detergent or cleaner 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.

Further objects of the invention are a method for washing laundry and a method for cleaning hard surfaces, comprising the steps of (a) providing a aqueous liquor containing H ₂ O ₂ or a water H ₂ O ₂ supplying, in particular inorganic peroxygen compound and a combination of 3-methylbenzisothiazole-1,1-dioxide and under perhydrolysis conditions peroxycarboxylic acid-providing compound prepared by using a detergent or cleaning agent containing a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight of 3-methylbenzisothiazole-1,1-dioxide and 0.1% by weight. % to 5 wt .-%, in particular 0.4 wt .-% to 0.6 wt .-% under perhydrolysis conditions peroxycarboxylic acid-supplying compound, and (b) contacting this liquor with textiles to be washed or to be cleaned hard surfaces. Preferably, the contact between the aqueous liquor and the object to be washed or cleaned at temperatures in the range of 20 ° C to 40 ° C, in particular from 20 ° C to 30 ° C, forth. Preferably, the object to be washed or cleaned remains in contact with the aqueous liquor for a period of from 20 minutes to 120 minutes, in particular from 30 minutes to 90 minutes. The methods according to the invention can be carried out manually or with the aid of conventional devices, for example washing machines or dishwashers. In the context of a use according to the invention and of a process according to the invention, the amounts of peroxygen compounds used are generally selected such that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen are present in the liquor.

A peroxygen compound together with said combination of 3-methylbenzisothiazole-1,1-dioxide and peroxycarboxylic acid-yielding perhydrolysis compound is preferably used for bleaching soils, especially tea, in the washing of textiles, especially in aqueous, surfactant-containing liquor. The phrase "bleaching stains" is to be understood in its broadest sense and includes both the bleaching of colored stains on the textile, the bleaching of stained debris located in the wash liquor and the oxidative staining of itself textile dyes in the wash liquor, which under the washing conditions of textiles come off before they can be put on differently colored textiles.

Another preferred embodiment of the invention is the use of a peroxygen compound together with said combination of 3-methylbenzisothiazole-1,1-dioxide and under perhydrolysis conditions peroxycarboxylic acid-providing compound in particular aqueous surfactant cleaning solutions for hard surfaces, especially for dishes, for bleaching of colored stains, for example tea. In this case, the term bleaching is understood as meaning both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the cleaning liquor, for example a dishwashing liquor.

The uses according to the invention for enhancing the cleaning performance of detergents and cleaning agents and for bleaching dyed soiling can be realized particularly simply by introducing said combination into a preferably surfactant-containing aqueous liquor which also contains the peroxygen compound and the textile or fabrics to be cleaned Contains hard-surface article, wherein the order of introduction of essential combination, peroxygen compound and textile or hard-surface article is arbitrary, or a preferably surfactant-containing aqueous liquor containing said combination and peroxygen compound on the textile to be cleaned or to be cleaned hard surface applies. Preferably, the combination essential to the invention is used as a constituent of a washing or cleaning agent, which particularly preferably also contains the peroxygen compound.

Further objects of the invention are therefore detergents and cleaners which comprise a combination of from 0.001% by weight to less than 0.05% by weight, in particular from 0.005% by weight to 0.04% by weight, of 3-methylbenzisothiazole-1, 1-dioxide and 0.1 wt .-% to 5 wt .-%, in particular 0.4 wt .-% to 0.6 wt .-% under perhydrolysis conditions peroxycarboxylic acid-supplying compound. In aqueous washing or cleaning liquors, amounts of from 1 g / l to 10 g / l, in particular from 2 g / l to 5 g / l, of such agents are preferably used.

The detergents and cleaners according to the invention, which may be present as particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may contain, in principle, all known ingredients customary in such agents besides the bleach-enhancing compound used according to the invention and preferably peroxygen compound. The detergents and cleaners according to the invention may contain, in particular, builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, dye transfer inhibitors, foam regulators, additional peroxygen activators and dyes and fragrances ,

Suitable organic or inorganic peroxygen compounds are organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, but especially inorganic peroxygen compounds such as hydrogen peroxide and inorganic salts releasing hydrogen peroxide under the conditions of purification, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide Inclusion compounds, such as H ₂ O ₂ -urea adducts. 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, can these are used in the form of powders or granules, which may also be enveloped in a manner known in principle. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of these containing agents, which may in principle contain all conventional detergent or cleaner ingredients. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. Here and below, sodium is the preferred alkali metal. If a washing or cleaning agent according to the invention contains peroxygen compounds, in particular sodium percarbonate, these are preferably present in amounts of from 1% by weight to 15% by weight, in particular from 4% by weight to 6% by weight, therein.

Compounds which give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable are the bleach activators cited at the beginning, which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyl oxybenzenesulfonate (NOBS or iso-NOBS or LOBS), 4- (2-decanoyloxyethoxycarbonyloxy ) -benzenesulfonate (DECOBS) or decanoyloxybenzoate (DOBA), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose ( PAG), Pentaacetylfruktose, tetraacetylxylose and Octaacetyllactose, acetylated, optionally N-alkylated glucamine and Gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. A washing or cleaning agent according to the invention preferably contains TAED.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls 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, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluss des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden.In addition to, or in place of, compounds which form peroxycarboxylic acids under perhydrolysis conditions, other bleach activating compounds, such as nitriles, from which perimic acids are formed may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 alkyl group (s) and optionally further substituents 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, R ⁴ and R ⁵ independently of one another have the meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , also include the Nitrogen atom and optionally further heteroatoms may be linked ring-wise and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C _9-15 -alkylbenzenesulfonates, the C _1-20 -alkyl sulfates, C _8-22 carboxylic _acid methyl _ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof can be used.

The additional presence of bleach-catalyzing transition metal complexes is possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in the transition metal complexes are both inorganic and organic compounds, in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl -1,5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis (1-methylimidazole-2-yl) yl) -methyl) -ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N' Tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (bis) 2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted salene , Porphins and porphyrins belong. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group may also be chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or η ¹ -O-bridge. Apart from the ligands mentioned, the transition metal complexes to be used in the activator system according to the invention may also contain further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate, citrate or oxalate. Examples of such additional transition metal complex compounds are Mn (IV) ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) di-hexafluorophosphate, [N, N'-bis [( 2-hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1, 2-diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N ' -Bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminoethane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonato-phenyl) -methylene] -1,2-diaminoethane] -manganese (III) chloride, manganese oxalate Nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

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. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety 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, alkane sulfonates 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 in the detergents or detergents according to the invention in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%, while the inventive compositions for the purification of hard Surfaces, especially of tableware, 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, sugar acids and carboxymethylinulines, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid ), Ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (polycarboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form Molecular weight (here and below: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. As water-soluble Organic builders may also be used terpolymers containing as monomers two unsaturated acids and / or salts thereof and as the third monomer vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate. 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, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers 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, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are 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 is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in agents according to the invention in amounts of from 1% by weight to 20% by weight, in particular from 5% by weight to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. 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. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. 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-Natriumdisitikate (Na ₂ Si ₂ O ₅ · y H ₂ O) is preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions. 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 can be prepared from sand and soda. Sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further embodiment of inventive agents. In a preferred embodiment of compositions according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Machine dishwashing detergents according to the invention are preferably of low alkalinity and contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali atom) of from 1.5: 1 to 2.5: 1. Alkali silicates may be used in amounts of up to 30% by weight. %, based on the total mean. The use of the highly alkaline metasilicates as alkali carriers is preferably completely dispensed with. The alkali carrier system preferably used in the inventive compositions is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is present in an amount of up to 60 wt .-%, preferably 10 wt .-% to 40 wt .-% , Depending on which pH is ultimately desired, the ratio of carbonate used and hydrogen carbonate used varies, but usually an excess of sodium bicarbonate is used so that the weight ratio between bicarbonate and carbonate is generally from 1: 1 to 15: 1.

In a further embodiment of dishwashing detergent compositions according to the invention, these contain from 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, from 5% by weight to 15% by weight of alkali metal carbonate and from 20% by weight to 40 wt .-% Alkalidisilikat included.

Suitable enzymes in the compositions according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters which Dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of grayness inhibitors and / or soil-release active ingredients in compositions according to the invention is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.

Examples of optical brighteners for textiles made of cellulose fibers (for example cotton) include derivatives of diaminostilbenedisulfonic acid or alkali metal salts thereof. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers, brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment of the invention, the agent is free of such agents.

The usual foam regulators which can be used in the compositions according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

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 present in compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% 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 alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contained in the inventive compositions.

The preparation of the solid compositions according to the invention presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.

Solutions 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.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach-activating system can be expected to be prepared. For the preparation of compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 · 10 ⁵ Pa to 1 500 · 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

The preparation of compositions 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 g / l to 1000 g / l can also be effected by using at least one of the builder components in a first process substep Mixing proportion of liquid mixture components to increase the bulk density of this premix and subsequently - if desired, after an intermediate drying - the other ingredients of the agent, including the performance enhancing agent or the performance enhancing agent combination combined with the thus obtained premix.

Examples: Bleaching experiments

Wash tests were carried out at 30 ° C. with the standardized soiling on cotton given in the table below using a wash liquor containing 3.8 g / l of a detergent V1 containing 5% by weight of sodium percarbonate. For comparison, otherwise identical washing liquors were used, the otherwise as V1 composite detergent V2 with an additional 0.5 wt .-% TAED or the otherwise like V2 composed detergent M1 with an additional 0.025 wt .-% 3-methylbenzisothiazole-1,1-dioxide (Compensation in each case over reduction of Füllsalzmenge) contained. The evaluation was carried out by color distance measurement according to the L * a * b * values and the Y values calculated therefrom as a measure of the brightness. The following table shows the Y values that resulted after washing. Soiling / medium V1 V2 M1 Beetroot 68.5 69.7 72.4 red wine 64.7 66.5 68.7 blackberry 71.0 nb 74.5 Blackcurrant juice 63.8 66.4 70.4 Blueberry juice 63.6 65.6 68.6 blood 69.8 nb 73.0 coffee 67.4 67.7 71.2 tea 52.4 53.4 55.9 cocoa drink 48.1 48.3 51.4 nb: not determined

The Y values when using the combination of active substances essential to the invention are greater than those resulting from the use of only the bleach-containing or the bleach-activating and bleach-activating detergent, which corresponds to a higher degree of whiteness and thus improved stain removal.

Claims (10)

Use of a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight of 3-methylbenzisothiazole-1,1-dioxide and 0.1% by weight up to 5% by weight, in particular from 0.4% by weight to 0.6% by weight, of peroxycarboxylic acid-yielding compound under perhydrolysis conditions in order to enhance the cleaning performance of peroxygen-containing detergents or cleaners in aqueous, in particular surfactant-containing liquor. Use of a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight of 3-methylbenzisothiazole-1,1-dioxide and 0.1% by weight up to 5% by weight, in particular from 0.4% by weight to 0.6% by weight, of the peroxycarboxylic acid-yielding compound under the conditions of perhydrolysis for bleaching dye soils when washing textiles, in particular in aqueous, surfactant-containing liquors, or in especially aqueous, Surfactant-containing cleaning solutions for hard surfaces, especially for dishes, for bleaching dyed stains, especially tea. Washing or cleaning agent, characterized in that it contains a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight of 3-methylbenzisothiazole-1,1- dioxide and 0.1 wt .-% to 5 wt .-%, in particular 0.4 wt .-% to 0.6 wt .-% under perhydrolysis conditions peroxycarboxylic acid-supplying compound. Composition according to claim 3, characterized in that it contains peroxygen compound. Composition according to claim 4, characterized in that it contains 1 wt .-% to 15 wt .-%, in particular from 4 wt .-% to 6 wt .-% peroxygen compound. Use according to claim 1 or 2 or agent according to claim 4 or 5, characterized in that it is an inorganic peroxygen compound. A method for washing laundry, comprising the steps of (a) providing an aqueous liquor containing H ₂ O ₂ or in water H ₂ O _2, in particular inorganic peroxygen compound and a combination of 3-Methylbenzisothiazol-1,1-dioxide and Perhydrolysis conditions peroxycarboxylic acid-providing compound prepared by use of a washing or cleaning agent containing a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight 3 Methylbenzisothiazole-1,1-dioxide and from 0.1% to 5% by weight, in particular from 0.4% to 0.6% by weight, of peroxycarboxylic acid-providing compound under perhydrolysis conditions, and (b) Contacting this liquor with textiles to be washed. A process for cleaning hard surfaces, comprising the process steps of (a) providing an aqueous liquor containing H ₂ O ₂ or a water H ₂ O ₂ supplying, in particular inorganic peroxygen compound and a combination of 3-methylbenzisothiazole-1,1-dioxide and lower Perhydrolysis conditions peroxycarboxylic acid-providing compound prepared by use of a washing or cleaning agent containing a combination of 0.001% by weight to less than 0.05% by weight, in particular 0.005% by weight to 0.04% by weight 3 Methylbenzisothiazole-1,1-dioxide and from 0.1% to 5% by weight, in particular from 0.4% to 0.6% by weight, of peroxycarboxylic acid-providing compound under perhydrolysis conditions, and (b) Contacting this liquor with hard surfaces to be cleaned. A method according to claim 7 or 8, characterized in that the contact between the aqueous liquor and the object to be washed or cleaned at temperatures ranging from 20 ° C to 40 ° C, in particular from 20 ° C to 30 ° C, produces , and / or that the object to be washed or cleaned remains in contact with the aqueous liquor for a period of from 20 minutes to 120 minutes, in particular from 30 minutes to 90 minutes. Use, means or process according to any one of the preceding claims, characterized in that the peroxygen compound is sodium percarbonate and / or the peroxycarboxylic acid-yielding compound TAED under perhydrolysis conditions.