EP2714877A1

EP2714877A1 - Activator systems for peroxygen compounds

Info

Publication number: EP2714877A1
Application number: EP12722337.8A
Authority: EP
Inventors: André HÄTZELT
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2011-05-24
Filing date: 2012-05-16
Publication date: 2014-04-09
Anticipated expiration: 2032-05-16
Also published as: PL2714877T3; WO2012159944A1; EP2714877B1; DE102011076417A1

Abstract

The oxidation effect and bleaching effect of peroxygen compounds at low temperatures was to be improved. This has been accomplished essentially through the use of a system comprising Lewis acid and a compound which yields peroxycarboxylic acid under perhydrolysis conditions.

Description

Activator systems for peroxygen compounds

The present invention relates to the use of systems of Lewis acid and Peroxocarbonsäureliefernder under perhydrolysis conditions for the activation of peroxygen compounds, in particular for bleaching of Farbanschmutzungen in the washing of textiles, and detergents, cleaners and disinfectants containing such systems.

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 0 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 the addition of so-called bleach activators, which are capable of being among those mentioned

Perhydrolysis conditions to provide peroxycarboxylic acids and for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, Urazoles, diketopiperazines, sulphurylamides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride and alkylsuccinic anhydrides, carboxylic esters, in particular sodium nonanoyloxy-benzenesulphonate, sodium isononanoyloxy-benzenesulphonate, O-acylated sugar derivatives, such as pentaacetylglucose, and N-acylated lactams, such as N-Benzoylcaprolactam, 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 effort to achieve energy-saving washing and bleaching processes, application temperatures significantly below 60 ° C., in particular below 45 ° C., down to the cold water temperature have become increasingly important in recent years. At low temperatures, the effect of the previously known activator compounds usually decreases noticeably. In addition, the detergent user endeavors to make the washing process as short as possible, so that there is little time available for the formation of the peroxycarboxylic acid. The same difficulty of only briefly making available the peroxycarboxylic acid as the actual bleach-active component occurs if the manufacturer of the detergent packs the bleach bleach and activator bleach system so that at least one of the components does not take place until well after the beginning of the bleaching cycle

Washing process is available, for example by suitable wrapping measures.

The present invention has the object of improving the oxidation and bleaching performance of inorganic peroxygen compounds by accelerating the formation of peroxycarboxylic acid from peroxycarboxylic acid-containing bleach activator and peroxygen bleach,

especially at low temperatures in the range of about 15 ° C to 45 ° C, to the destination.

The invention relates to the use of a system of Lewis acid and under Perhy- drolysebedingungen peroxocarbonsäureliefernder substance as an activator for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfecting solutions.

Another object of the invention is the use of Lewis acid to accelerate the Peroxocarbonsäurebildung particular inorganic peroxygen compound and Peroxocarbonsäureliefernder under perhydrolysis conditions, especially when washing textiles or when cleaning hard surfaces, and in particular in aqueous systems.

Another object is a process for the preparation of peroxycarboxylic acid, especially in aqueous solution, in particular inorganic peroxygen compound and peroxocarbonsäureliefernder under perhydrolysis conditions, which is characterized in that one uses Lewis acid.

In all aspects of the present invention, the mole ratio of peroxycarboxylic acid to the compound to Lewis acid is preferably 100: 1 to 1:50, more preferably 10: 1 to 1: 5, and most preferably 2: 1 to 1: 4.

The system of Lewis acid and perhydrolysis peroxocarboxylic acid-yielding compound is preferably used for bleaching paint stains during the washing of textiles, especially in aqueous, surfactant-containing liquor. The phrase "bleaching of color stains" is to be understood in its broadest sense and includes both the bleaching of dirt present on the textile, the bleaching of debris located in the wash liquor, and the deoxidation of the wash liquor in the wash liquor Textile dyes that detach under the washing conditions of textiles before they can be applied to different colored textiles. Another preferred embodiment of the invention is the use of the Lewis acid system and the peroxycarboxylic acid perhydrolysis compound in cleaning solutions for hard surfaces, especially for dishes, for bleaching stained soils, for example tea. Here too, the term bleaching is understood as meaning both the bleaching of dirt on the hard surface, in particular tea, and the bleaching of dirt removed from the hard surface in the dishwashing liquor.

Further objects of the invention are detergents, cleaners and disinfectants which contain the abovementioned system of Lewis acid and peroxycarboxylic acid-yielding compound under perhydrolysis conditions.

In the method according to the invention and in the context of a use according to the invention, the system of Lewis acid and under perhydrolysis Peroxocarbonsäure- leaching compound in the sense of an activator can be used wherever it depends on a particular increase in the oxidation effect of the peroxygen compounds at low temperatures, for example the bleaching of textiles or hair, in the oxidation of organic or inorganic intermediates and in the disinfection.

Lewis acids are electrophilic electron pair acceptors, so they can attach electron pairs. They have at least one unoccupied orbital in their valence electron shell. In the present invention, Lewis acids are preferably selected from bismuth (III) salts, indium (III) salts, and samarium (III) salts and mixtures thereof, among which

Bismuth (III) oxinitrate, indium (III) sulfate and samarium (III) nitrate and mixtures of these are particularly preferred.

As under perhydrolysis conditions peroxycarboxylic acid-releasing compound can

in particular, compounds which give, under perhydrolysis conditions, optionally substituted perbenzoic acid 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, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or Isononanoyl- or Lauroyloxybenzol- sulfonate (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol or their

Mixtures (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.

Essentially, the use of the present invention is to provide conditions under which the peroxygen compound and the bleach-enhancing system of Lewis acid and peroxycarboxylic acid-yielding compound can react with each other under perhydrolysis conditions, with the aim of obtaining more strongly oxidizing secondary products. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the bleach-enhancing system to an optionally detergent or cleaner-containing solution. However, the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent which contains the said bleaching-intensifying system and optionally a peroxidic oxidizing agent. The peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a peroxygen-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.

An inventive washing, cleaning or disinfecting agent preferably contains 0.01 wt .-% to 10 wt .-%, in particular 1 wt .-% to 3 wt .-% under perhydrolysis conditions peroxocarboxylic acid-liederder compound in addition to conventional, with the peroxygen compound and the inventively used system compatible ingredients. The system or its individual components used in accordance with the invention may or may, as well as the peroxygen compound, if desired, be adsorbed to carriers in a manner known in principle and / or embedded in enveloping substances. In particular, by wrapping can be achieved in addition to a generally improved storage stability, that the peroxycarboxylic acid formation takes place accelerated according to the invention, but uses the formation or acceleration only after release from the wrapping material, so that other washing or

Detergent ingredients, such as enzymes, can exert their effect without being affected by the formation of peroxycarboxylic acid. The detergents, cleaners and disinfectants 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 system used according to the invention. The detergents and cleaners according to the invention may in particular be builders, surface-active surfactants, organic and / or inorganic peroxygen compounds, 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 included.

A disinfectant according to the invention may contain conventional antimicrobial active ingredients in addition to the previously mentioned ingredients to enhance the disinfecting action against special germs. Such antimicrobial additives are preferably not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight, in the disinfectants according to the invention.

Suitable peroxygen compounds are, in particular, organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, 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 0 ₂ -Harnstoffaddukte, into consideration. 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. 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 detergents, cleaners or disinfectant ingredients. Particular preference is given to alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions containing 3% by weight to

10 wt .-% hydrogen peroxide contained used. If a washing or cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 25% by weight, in particular from 1% by weight to 20% by weight and more preferably from 7% by weight to 15% by weight. % present, while in disinfectants according to the invention preferably from 0.5 wt .-% to 40 wt .-%, in particular from 5 wt .-% to 20 wt .-%, of peroxygen compounds are included. 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 products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C 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 from 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

Amounts 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 means for cleaning dishes 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 -diphosphonic acid, polymers

Hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable May contain copolymerized substances without carboxylic acid functionality. The relative average molecular weight (here and below: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, 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 of 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 may 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 benzene or benzene derivatives derives, 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 and 200,000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000. Further preferred copolymers are those which are used as monomers acrolein and

Acrylic acid / acrylic acid salts or vinyl acetate. The organic ones

Builders can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 weight percent aqueous solutions are used. 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 are the crystalline ones

Detergent grade sodium aluminosilicates, in particular 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 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding inhibitor is usually 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 Si0 ₂ below 0.95, in particular from 1: 1, 1 to 1: 12 and may be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ 0: Si0 ₂ of 1: 2 to 1: 2.8. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na ₂ Si _x _O ₂ _X + iy H ₂ O, in which x, the so-called modulus, is a number from 1 to 9 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-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are 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 compositions according to the invention. In a preferred embodiment of compositions according to the invention, a granular compound of alkali silicate and alkali carbonate is used, as it is known, for example

Nabion® 15 is commercially available.

Machine dishwashing detergents according to the invention are preferably of low alkalinity and contain the customary alkali carriers such as, for example, alkali metal silicates, alkali metal carbonates and / or alkali hydrogencarbonates. The alkali carriers customarily used include carbonates, bicarbonates and alkali metal silicates having a molar ratio Si0 ₂ / M ₂ O (M = alkali atom) of from 1.5: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 30% by weight, based on the total agent. 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 bicarbonate used varies, but usually an excess of sodium bicarbonate is used, so that the weight ratio of bicarbonate to carbonate is generally from 1: 1 to 15: 1.

In a further embodiment of dishwashing compositions according to the invention, 20 wt.% To 40 wt.% Of water-soluble organic builders, in particular alkali citrate, 5 wt.% To 15 wt.% Alkali carbonate and 20 wt 40 wt .-% Alkalidisilikat included.

In addition to the compounds that 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 R ² -N ⁽⁺⁾ - (CR ⁴ R ⁵⁾ -CN X ^w R ³ in which R is -H, -CH _3, a C ₂ -24 alkyl or alkenyl group, a substituted 4-alkyl CI_ ₂ - 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 with a CI_ ₂₄ alkyl group, or a substituted alkyl or alkenylaryl group having at least one, preferably two, optionally substituted Ci_ 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 with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have the meaning given above for R, R ² or R ³ , where at least 2 of said radicals, in particular R ² and R ³ , may also be linked to one another with inclusion of the nitrogen atom and optionally further heteroatoms and then preferably form a morpholino ring, and X is a charge-balanced anion, preferably selected from benzenesulfonate, toluenesulfonate,

Cumene sulfonate, the C9.15-Alkylbenzolsulfonat.en, the CI_ ₂₀ alkyl sulfates, the C ₈ - methyl ester ₂₂ -carboxylic acid, sulfate, hydrogen sulfate, and their mixtures, can be used.

Oxygen-carrying sulfonimines and / or acylhydrazones can also be used. The presence of bleach-catalyzing transition metal complexes is also 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, which 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 , amine 2,2 ^{'-Bispyridyl-} triazole, 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) -methyl) -ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, Ν, Ν, Ν ^' , Ν ^' - tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1, 3-bis- (bis (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and given optionally substituted salene, porphins and porphyrins. To belong to the inorganic neutral ligands especially 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 attached to a transition metal be chelate-bound or asymmetric or VO-bridged to two transition metal atoms. 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, actetate, 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, it is not necessary for both metal atoms in the complex to 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

In the presence of anionic ligands does not lead to charge balance in the complex anionic counterions are present in the transition metal complex compounds to be used according to the invention, which neutralize the cationic transition metal complex. 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 or citrate.

Examples of transition metal complex compounds are , 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, [Ν, Ν'-bis [(2 -hydroxy-5-sulfonatophenyl) -methylene] -1, 2-diaminoethane] -manganese (III) chloride, nitro-pentammine cobalt (III) chloride, nitrite pentammine cobalt (III) chloride, hexammine cobalt (III) chloride, Chloropentammin-cobalt (III) chloride and the peroxo complex [(NH ₃₎ 5Co-0-0-Co (NH ₃₎ 5] Cl4.

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 particularly preferred is. The proportion is preferably 0.2 wt .-% to 1, 5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed on carriers in the usual way and / or in

Enveloping substances embedded or be incorporated as concentrated, preferably 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 containing 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.

As optical brightener for particular textiles made of cellulose fibers (for example, cotton), for example, derivatives of Diaminostilbendisulfonsäure or their

Be contained alkali metal salts. 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 are particularly well brighteners of the type of 1, 3-diaryl-2-pyrazolines, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds. 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 have 12 to 22 carbon atoms. Among them, preferred is sodium monoalkyl phosphate and / or dialkyl phosphate with d ₆ - to C- | _8- alkyl groups used. The proportion of foam regulators can preferably 0.2 wt .-% to 2 wt .-% amount.

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 naturally 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 principle, for example by spray-drying or granulation, wherein peroxygen compound and bleach catalyst are optionally added separately later.

Compositions according to the invention in the form of solutions containing aqueous or other conventional solvents are produced particularly advantageously 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-shaped preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable material

Components and admixing the more sensitive components, which in particular enzymes, bleach and the bleach-activating system can be expected, can be produced. For the preparation of inventive compositions 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 detergents according to the invention 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 presses or

Rotary presses, pressed with pressing pressures in the range of 200 10 ⁵ Pa to 1 500 10 ⁵ Pa. you thus obtains without difficulty fracture-resistant, yet sufficiently rapidly soluble under application conditions tablets with flexural strength of usually over 150 N. Preferably, such a tablet produced in a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm up 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 to 1000 g / l can also be effected by using the builder components with at least a proportion of liquid mixture components in a first process substep while increasing the bulk density of this premix and subsequently - if desired after intermediate drying - the other constituents of the agent, including the bleach-activating system, combined with the thus obtained premix.

Examples

example 1

0.5 g (2 mmol) TAED were suspended in 50 ml H ₂ 0 and almost completely dissolved within 90 minutes with stirring at 60 ° C. 500 ml of 35% H ₂ O ₂ solution (4 mmol) was added and the formation of peracetic acid with the aid of commercially available peracetic acid test strips whose accuracy was previously determined by measuring peracetic acid solutions of known concentration (100 mg / l, 150 mg / l, 200 mg / l, 250 mg / l, 300 mg / l, 400 mg / l, 500 mg / l, 1000 mg / l, 1500 mg / l, 2000 mg / l). The peracetic acid concentrations indicated in the table below were obtained after the times indicated in each case:

Time peracetic acid

[min] [mg / l]

0 0

0.5 <100

10,300

30 300-400

50 400-500

70 500-1000

120 1000-1500

150 1500-2000

300> 2000 Example 2

0.25 g of TAED (1 mmol) and 1.8 g (4 mmol) of samarium (II) nitrate hexahydrate (A) or 2.1 g (4 mmol) of indium (III) sulfate (B) were dissolved in 50 ml H ₂ 0 suspended and stirred for 30 minutes at 35 ° C to 40 ° C. In addition, a comparison solution C was used which contained only 0.25 g TAED in 50 ml H ₂ 0. After 0.5 h, 250 ml of 35% strength H ₂ O ₂ solution (2 mmol) were added in each case and the formation of peracetic acid was monitored with the aid of the peracetic acid test strips. The peracetic acid concentrations indicated in the table below were obtained after the times indicated in each case:

Example 3

0.5 g (2 mmol) of TAED and 1.8 g (4 mmol) of samarium (II) nitrate hexahydrate (A) or 2.1 g (4 mmol) of indium (III) sulfate (B) were dissolved in 50 ml H ₂ 0 suspended and stirred for 30 min at 20 ° C to 25 ° C. In addition, a pure TAED comparison solution (C) was used. In each case, 500 [iL 35% H ₂ 0 ₂ solution (4 mmol) was added and the formation of peracetic acid was monitored by means of the peracetic acid test strips. The peracetic acid concentrations indicated in the table below were obtained after the times indicated in each case:

Time [min] peracetic acid [mg / l] in

A B C

0 0 0 0

1 200-250 250-300 0

3 200-250 250-300 0

5 250-300 250-300 0 250-300 250-300 0

250-300 250-300 100-150

250-300 250-300 200-250

Claims

claims

1. Use of a system of Lewis acid and under perhydrolysis conditions

peroxycarboxylic acid-supplying substance as an activator for peroxygen compounds in oxidation, washing, cleaning or disinfecting solutions.

2. Use of Lewis acid to accelerate the formation of peroxycarboxylic acid from persu erstoffverbind ung and under perhydrolysis conditions peroxocarbonsäureliefernder substance.

3. Use of a system of Lewis acid and under Perhydrololysebedingungen peroxycarboxylic acid-yielding compound for bleaching of Farbanschmutzungen in the washing of textiles, especially in aqueous, surfactant-containing liquor, or in cleaning solutions for hard surfaces, especially for dishes, for bleaching dyed stains , especially tea.

4. A process for the preparation of peroxycarboxylic acid from peroxygen compound and Peroxocarbonsäureliefernder under perhydrolysis conditions, characterized in that Lewis acid is used.

5. washing, cleaning or disinfecting agent, characterized in that it contains Lewis acid and under Perhydolysebedingungen peroxycarboxylic acid-yielding compound.

6. Composition according to claim 5, characterized in that it contains peroxygen compound.

7. Use according to one of claims 1 to 3, or process according to claim 4, or agent according to claim 6, characterized in that it is an inorganic peroxygen compound.

8. Use, method or means according to any one of the preceding claims, characterized in that the molar ratio of peroxycarboxylic acid-leaching compound to Lewis acid is 100: 1 to 1: 50, in particular 10: 1 to 1: 5.

9. Use, method or means according to one of the preceding claims, characterized in that the Lewis acid among the bismuth (III) salts, the indium (III) salts and the samarium (III) salts and mixtures thereof, in particular from bismuth (III) oxinitrate, indium (III) sulfate and samarium (III) nitrate and mixtures thereof.

10. Use, method or means according to any one of the preceding claims, characterized in that under perhydrolysis conditions peroxycarboxylic acid-issuing compound from the compounds, the perhydrolysis under certain conditions optionally substituted perbenzoic acid and / or aliphatic peroxycarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 C atoms, alone or in mixtures, selects.