EP1445305B1 - Use of transition metal complexes as bleach catalysts - Google Patents

Description

The present invention relates to the use of certain transition metal complex compounds for enhancing the bleaching effect of peroxygen compounds in bleaching colored stains on textiles as well as on hard surfaces, as well as detergents and cleaners containing such complex compounds.

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 adding so-called bleach activators. For this purpose, numerous compounds have been proposed, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles. Diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate (NOBS), sodium isononanoyloxybenzenesulfonate (ISONOBS) and acylated sugar derivatives, such as pentaacetylglucose. By adding these substances, the bleaching effect of aqueous peroxide solutions 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 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 without a convincing success to date.

A starting point for this results from the use of transition metal salts and their complex compounds, as described, for example, in EP 0 392 592, EP 0 443 651, EP 1001009, WO2004 / 039932, US Pat. No. 6,139,769, EP 0 458 397, EP 0 544 490 or EP 0 549 271 are described. In EP 0 272 030 cobalt (II) complexes with ammonia ligands, which may also have any other mono-, di-, tri- and / or tetradentate ligands, as activators for H ₂ O ₂ for use in Textilwasch- or Bleaches described. WO 96/23859, WO 96/23860 and WO 96/23861 describe the use of corresponding Co (III) complexes in automatic dishwashing compositions. Although certain manganese complexes are known from EP 0 630 964 which, although they have no pronounced effect on bleach reinforcement of peroxygen compounds, do not discolor dyed textile fibers, they can cause the bleaching of soil or dye removed from the fiber in wash liquors. From DE 44 16 438 manganese, copper and cobalt complexes are known which can carry ligands from a variety of groups of substances and are to be used as bleaching and oxidation catalysts. WO 97/07191 proposes complexes of manganese, iron, cobalt, ruthenium and malenbdenum with salen-type ligands as activators for peroxygen compounds in hard surface cleaning solutions. EP 1 225 215 describes the use of transition metal complexes containing oxime ligands as a catalyst for peroxygen compounds.

The present invention has the object of improving the oxidation and bleaching action of peroxygen compounds, especially inorganic peroxygen compounds, at low temperatures below 80 ° C. especially in the temperature range of about 10 ° C to 45 ° C, the goal. The required metal complexes should be easily accessible and easy to prepare.

Surprisingly, it has now been found that certain simply constructed transition metal complexes with nitrogen-containing ligands contribute significantly to the cleaning performance against colored stains that are on textiles or on hard surfaces.

M

ein Metallatom aus der Gruppe Mn, Fe, Co, Ni, Mo, W,

L

ein Ligand aus der Gruppe der stickstoffhaltigen Heterocyclen,

X

Chlorid, Bromid, Nitrat, Perchlorat, Ammoniak, Tetrafluoroborat, Hexafluorophosphat oder ein Anion einer organischen Säure mit 1 bis 22 Kohlenstoffatomen, n eine Zahl von 2 bis 4 und m eine Zahl von 0 bis 4 bedeuten.

The invention relates to the use of transition metal complexes with nitrogen-containing ligands as bleaching catalysts for peroxygen compounds, characterized in that the transition metal complexes have the formula (1)

M (L) _n X _m (1)

have, where

M

a metal atom from the group Mn, Fe, Co, Ni, Mo, W,

L

a ligand from the group of nitrogenous heterocycles,

X

Chloride, bromide, nitrate, perchlorate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of an organic acid having 1 to 22 carbon atoms, n is a number from 2 to 4 and m is a number from 0 to 4.

These transition metal complexes are used in detergents, bleaches, and cleaners containing peroxygen compounds, particularly in laundry and hard surface cleaners, particularly for utensils, and in solutions for bleaching colored stains.

Complexes of the formula (1) with transition metal central atoms in the oxidation states +2, +3 or +4 and complexes with manganese or iron as central atoms are preferably used.

Examples of the ligand L are pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine, lutidines or similar nitrogen-containing heterocycles, which are unsubstituted or substituted by one or two C ₁ -C ₄ alkyl groups

For the ligand X in particular the halides such as chloride, bromide and iodide are used, but also nitrate, sulfate, perchlorate, ammonia and complex anions such as tetrafluoroborate and hexafluorophosphate or anions of organic C ₁ -C ₂₂ carboxylic acids such as citrates, acetates, propionates , Butyrates, hexanoates, octanoates, nonanoate and laurate. The anion ligands provide charge balance between the transition metal central atom and the ligand system.

Particularly preferred complexes are compounds of the structure Fe (L) ₂ X ₂ or Mn (L) ₂ X ₂ such as bis (pyridine) dichloro-iron (II), bis (pyridine) dichloro-manganese (II), such as bis (morpholine) dichloro-iron (II), bis (morpholine) dichloro-manganese (II), bis (methylimidazole) dichloro-iron (II), bis (methylimidazole) dichloro-manganese (II), bis (ethylimidazole) dichloro-iron (II) , Bis (ethylimidazole) dichloro-manganese (II), bis (pyrazole) dichloro-manganese (II), bis (pyrazole) dichloro-iron (II), bis (pyridine) dibromoiron (II), bis (pyridine) dibromo-manganese (II), such as bis (pyridine) diacetato-iron (II), bis (pyridine) diacetato-manganese (II), and complexes of the type Fe (L) ₄ X ₂ , Mn (L) ₄ X ₂ .

Corresponding complexes are described in the literature, e.g. in G.J. Long, D.L. Whitney, and J.E. Kennedy, Inorg. Chemistry, 1971, 10 (7), 1406-1410, H.T. Witteveen, B. Nieuwenhuijse, and J. Reedijk, J. Inorg. Nucl. Chem., 1974, 36, 1535-1541, H.T. Witteveen and J. Reedijk, Solid State Commun., 1973, 12, 557. However, their effectiveness as bleach catalysts has not previously been described.

The peroxygen compound used are primarily alkali metal perborate mono- or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal. In addition, however, it is also possible to use alkali metal or ammonium peroxosulfates, such as, for example, potassium peroxomonosulfate (technical name: Caroat® or Oxone®). The concentration of these peroxygen compounds on the total formulation of detergents, bleaches and cleaners is 5 - 90%, preferably 10 - 70%.
The amounts of peroxygen compounds are generally chosen so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the solutions of the detergents and cleaners. Also the amount of bleach-enhancing Complex connection depends on the purpose of use. Depending on the desired degree of activation, it is used in amounts such that 0.01 mmol to 25 mmol, preferably 0.1 mmol to 2 mmol complex per mole of peroxygen compound are used, but in special cases, these limits can also be exceeded or fallen below. In washing, bleaching and cleaning agents are preferably 0.0025 to 0.25 wt .-%, in particular 0.01 to 0.5 wt .-% of the above-defined bleach-enhancing complex compound.

In addition or as an alternative, the washing, bleaching and cleaning agents may also contain hydrogen peroxide or organic-based oxidizing agents in the concentration range of 1 to 20%. These include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, dodecanediperoxyacid or phthalimidoperoxycarboxylic acids such as PAP and related systems or the amido peracids mentioned in EP-A-170386.

The term bleaching here encompasses both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies analogously to the bleaching of soiling on hard surfaces. Other potential applications are in personal care, e.g. in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, the described metal complexes find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.

Furthermore, the invention relates to a process for the purification of textiles as well as hard surfaces, in particular crockery, using said complex compounds together with peroxygen compounds in aqueous, optionally further detergent or detergent ingredients containing solution, and detergents and cleaners for hard surfaces, in particular detergents for dishes, those preferred for use in machine processes containing such complex compounds.

The use according to the invention essentially consists in providing conditions for hard surfaces contaminated with colored soiling or, in the case of soiled textiles, conditions under which a peroxidic oxidizing agent and the complex compound of the formula (1) can react with one another, 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 complex of formula (1) to the aqueous solution of the detergent and cleaner. However, the process according to the invention is particularly advantageously carried out using a detergent or hard surface cleaning agent which contains the complex compound of the formula (1) and, if appropriate, a peroxygen-containing 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 non-oxygen detergent or cleaner is used.

The washing and cleaning agents, which may be in the form of granules, powdery or tablet-like solids, other shaped bodies, homogeneous solutions or suspensions, may contain, in principle, all known ingredients customary in such agents, as well as the said bleach-enhancing metal complex. The compositions may contain, in particular, builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, enzymes, and special additives with color- or fiber-sparing action. Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators, as well as dyes and fragrances are possible.

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof. Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents.

The washing, bleaching and cleaning agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants in question. Such surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight. , in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included. Dishwashing detergents typically use low-foam compounds.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof. Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₈ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. Also 2,3-Alkyl sulfates prepared, for example, according to US Pat. Nos. 3,234,158 and 5,075,041 are suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols with on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ -fatty alcohols with 1 up to 4 EO.

The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₁₈ fatty alcohol residues or mixtures of these. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate). As further anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position . or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

in der Rest R¹-CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab.The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I)

in the radical R ¹ -CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ² for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Preferably, the Polyhydroxyfatty acid amides of reducing sugars with 5 or 6 carbon atoms, in particular from the glucose.

in der R³ einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 21 Kohlenstoffatomen, R⁴ einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 6 bis 8 Kohlenstoffatomen und R⁵ einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen bedeutet, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy - substituierten Verbindungen können dann beispielsweise gemäß WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest stands. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to WO 95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and the fatty acid alkanolamides may also be suitable.

mit den Resten R¹, R², R³ = C₁-C₂₂-Alkyl und n = 1 bis 5.Of the large group of cationic surfactants, in particular hydroxyalkyl quats of the general structures (III) and (IV) are preferred.

with the radicals R ¹ , R ² , R ³ = C ₁ -C ₂₂ -alkyl and n = 1 to 5.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in WO 95/19953, WO 95/19954 and WO 95/19955. Other surfactant types may have dendrimeric structures.

A detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Natriumhexametaphosphat and the corresponding potassium salts or mixtures of sodium and potassium salts. The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram. Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders 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. 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 × + 1} . YH ₂ O is used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. Particularly both δ- and β-sodium (Na ₂ Si ₂ O ₅ · y H ₂ O) is preferably β-sodium silicates with a modulus from 1.9 to 3.2, according to Japanese Patent Application JP 04/238 809 or JP 04/260 610 are produced. Also prepared from amorphous silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used. In a further preferred embodiment of such agents, a crystalline sodium layer silicate with a modulus of 2 to 3 is used. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred 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 is commercially available, for example, under the name Nabion®. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, this is Weight ratio aluminosilicate to silicate, in each case based on anhydrous active substances, 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.

Such builder substances are preferably contained in agents according to the invention in amounts of up to 60% by weight, in particular from 5 to 40% by weight.

The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.

Polyphosphonic acids, especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used. Preference is also given to polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 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. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Also suitable 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. 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 generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% 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 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.

Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean. Other possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid. Preferred organic builder components include the salts of Citric acid, especially sodium citrate. As sodium citrate, anhydrous tri-sodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH value ultimately set in the cleaning agents according to the invention, the acids corresponding to the said co-builder salts may also be present.

In addition to the complex compounds used according to the invention, conventional bleach activators, that is to say compounds which release peroxocarboxylic acids under perhydrolysis conditions, can be used. Suitable are the usual bleach activators containing O- and / or N-acyl 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), acylated phenylsulfonates , in particular nonanoyl or Isononanoyloxybenzolsulfonat (NOBS or ISONOBS) or their amido derivatives, such as in EP 170 386, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. Furthermore, open-chain or cyclic nitrile quats are suitable for this purpose. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used.

The enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or those disclosed in International Patent Applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used may be adsorbed to carriers and / or embedded in encapsulants, as described for example in International Patent Applications WO 92/131347 or WO 94/23005, in order to protect them against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.

Machine dishwashing detergents according to the invention preferably comprise 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 metal) of from 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40% by weight. in particular 3 to 30 wt .-%, based on the total agent, be contained. The alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.

A further subject of the invention is a machine dishwashing composition containing from 15 to 65% by weight, in particular from 20 to 60% by weight of water-soluble builder component, from 5 to 25% by weight, in particular from 8 to 17% by weight. Oxygen-based bleaching agents, respectively; based on the total agent, and 0.1 to 5 wt .-% of one or more of the cyclic sugar ketones defined above. Such an agent is preferably low alkaline, that is, its weight percent solution has a pH of 8 to 11.5, especially 9 to 11.

In a further embodiment of inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.

If the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettsäureamide and mixtures thereof and other other known commercially available foam inhibitors are added. 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. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.

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 compounds ethers. Such water-miscible solvents are preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 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 hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.

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, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared. 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.

For the production of particulate 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 known from the European patent specification EP 0 486 592 is preferred. Another preferred preparation by means of a granulation process is described in the European patent EP 0 642 576. 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 achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.

For the preparation of compositions according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, for example Eccentric or rotary presses, pressed with pressing pressures in the range of 200 · 10 ⁵ Pa to 1500 · 10 ⁵ Pa. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N. Preferably, a tablet thus produced has a weight of 1 to 5 g to 40 g, in particular from 20 g to 30 g, with a diameter from 3 to 5 mm to 40 mm.

Examples example 1 Synthesis of bis (pyridine) dichloro-manganese (II) Mn (py) ₂ Cl ₂ (Cat1)

5.7 g (0.045 mol) of manganese (II) chloride were dissolved in 400 ml of ethanol and the solution was mixed with 49 g (0.62 mol) of pyridine (pyridine previously dried over KOH). The reaction mixture was heated at reflux for four hours. The resulting suspension was filtered at 60 ° C and the isolated solid washed successively with 100 ml of a 10% isopropanolic pyridine solution and 100 ml of petroleum spirit (50-70 ° C). After drying in vacuo, 12.5 g of the beige complex were obtained, which corresponds to a yield of 97.5%.

Analytical data:

Elemental analysis for C ₁₀ H ₁₀ N ₂ Cl ₂ Mn (284.86 g / mol): calculated: C 42.2%, H 3.5%, N 9.8%, Cl 24.9%, Mn 19.3% found: C 42.2%, H 3.1%, N 9.5%, Cl 25.0%, Mn 19.8%

Example 2 Synthesis of bis (pyridine) dichloro-iron (II) Fe (py) ₂ Cl ₂ (Cat2)

6.0 g (0.047 mol) of iron (II) chloride were dissolved in 400 ml of ethanol, then the solution is mixed with 49 g (0.62 mol) of pyridine (pyridine previously dried over KOH). The clear, intense yellow colored solution was allowed to stand for 12 hours at room temperature, after which the precipitated yellow solid filtered off and washed with 50 ml of petroleum benzine (50-70 ° C). After drying in vacuo, 9.9 g of the yellow-orange complex were obtained, which corresponds to a yield of 73.9%.

Analytical data:

Elemental analysis for C ₁₀ H ₁₀ N ₂ Cl ₂ Fe (284.94 g / mol): calculated: C 42.2%, H 3.5%, N 9.8%, Cl 24.9%, Fe 19.3% found: C 42.1%, H 3.3%, N 9.8%, Cl 25.5%, Fe 19.6%

Example 3 Synthesis of bis (methylimidazole) dichloro-manganese (II) Mn (Melm) ₂ Cl ₂ (Cat3)

44 g (0.54 mol) of N-methylimidazole were dissolved in 400 ml of methanol. Subsequently, 33 g (0.26 mol) of manganese (II) chloride was added, which almost completely dissolved. It was stirred for one hour at room temperature, then the precipitated light precipitate filtered off and washed twice with 25 ml of petroleum spirit (30-60 ° C). After drying in vacuo, 18.9 g of the white-gray complex were obtained. This corresponds to a yield of 25.1%.

Analytical data:

Elemental analysis for C ₈ H ₁₂ N ₄ Cl ₂ Mn (290.0 g / mol): calculated: C 33.13%, H 4.17%, N 19.32%, Cl 24.45%, Mn 18.93% found: C 33.25%, H 4.40%, N 19.05%, Cl 24.5%, Mn 18.7%

Example 4 Synthesis of bis (morpholine) dichloro-manganese (II) Mn (mopln) ₂ Cl ₂ (Cat 4)

27.7 g (0.32 mol) of morpholine were dissolved in 400 ml of methanol. Subsequently, 20.0 g of manganese (II) chloride were added, which almost completely dissolved. The mixture was stirred for 4 hours at room temperature, then the precipitated light precipitate filtered off and washed twice with 25 ml of petroleum spirit (30-60 ° C). After drying in vacuo, 17.2 g of the white-brown complex were obtained. This corresponds to a yield of 36.3%.

Analytical data:

Elemental analysis for C ₈ H ₁₆ N ₂ O ₂ Cl ₂ Mn (298.07 g / mol): calculated: Cl 23.8% found: Cl 23.5%

Example 5 Synthesis of bis (ethylimidazole) dichloro-manganese (II) Mn (eimide) ₂ Cl ₂ (Cat 5)

51.9 g (0.54 mol) of 2-ethylimidazole were dissolved in 400 ml of methanol. Subsequently, 33.0 g of manganese (II) chloride were added, which almost completely dissolved. Stirring was continued for 4 hours at room temperature, after which the resulting brown solution was concentrated by means of a rotary evaporator. Crystals precipitated, these were filtered off and washed twice with 25 ml of propanol. After drying in vacuo, 27.2 g of the white-brown complex were obtained. This corresponds to a yield of 32.8%.

Analytical data:

Analysis Chlorine for C ₁₀ H ₁₄ N ₄ Cl ₂ Mn (316.1 g / mol): calculated: Cl 22.1% found: Cl 22.7%

Example 6 bleaching power

The bleaching performance of the compounds of the invention Cat 1 to Cat 5 was tested in comparison to the bleach activator TAED. For this purpose, 10 mg / l of the catalyst were dissolved in a wash liquor prepared by dissolving 2 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld). After addition of 1 g / l of sodium percarbonate (Degussa), the washing experiments were carried out in a Linitest apparatus (Heraeus) at 20 to 40 ° C. The washing time was 30 min, water hardness 18 ° dH. As a bleaching test fabric tea served on cotton (BC-1) and curry on cotton (BC-4, both WFK, Krefeld). As a bleaching result, the remission difference, measured with an Elrepho apparatus, after washing compared to the unwashed fabric was evaluated. As a comparative experiment (V1) in each case 250 mg / l TAED were used instead of the inventive amount of 10 mg / l catalyst. connection Remission difference (ddR%) 20 ° C 40 ° C BC-1 BC-4 BC-1 BC-4 Cat 1 3.6 1.5 5.7 3.0 Cat 2 3.8 2.9 4.5 3.6 Cat 3 3.8 1.4 8.1 3.9 Cat 4 2.8 1.6 7.0 3.7 TAED (V1) 2.5 1.1 4.0 2.4

It can be seen that significantly better bleaching action can be achieved by the compounds according to the invention (Cat 1 to Cat 5) than by the conventional bleach activator TAED, which was used in a substantially higher concentration (V1). Substantially similar results were obtained when replacing sodium percarbonate with sodium perborate.

Example 7 pH dependence of the bleaching performance

The experiments were carried out analogously to Example 6, but with the addition of 0.5 g / l of hydrogen peroxide instead of the perborate at a constant pH in the beaker. connection Remission values (ddR%) pH 7 8th 9 10 11 12 Cat 1 0.1 1.2 4.8 8.8 9.2 4.5

The results show that the compounds according to the invention have a bleaching optimum in the range of pH 9 to 12.

Claims (8)

1. The use of specific transition metal complexes having nitrogen-containing ligands as catalyst for peroxygen compounds, wherein the transition metal complexes have the formula (1)
   
           M(L)_nX_m     (1)
   
   where

   M is a metal atom from the group Mn, Fe, Co, Ni, Mo, W,

   L is a ligand from the group pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine or lutidine, which are unsubstituted or which are substituted by one or two C₁-C₄-alkyl groups.

   X is chloride, bromide, nitrate, perchlorate, sulfate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of an organic acid having 1 to 22 carbon atoms,

   n is a number from 2 to 4 and m is a number from 0 to 4.
2. The, use of bis(pyridine)dichloroiron (II), bis(pyridine)dichloromanganese (II), such as bis(morpholine)dichloroiron (II), bis(morpholine)dichloromanganese (II), bis(methylimidazole)dichloroiron (II), bis(methylimidazole)dichloromanganese (II), bis(ethylimidazole)dichloroiron (II), bis(ethylimidazole)dichloromanganese (II), bis(pyrazole)dichloromanganese (II), bis(pyrazole)dichloroiron (II), bis(pyridine)dibromoiron (II), bis(pyridine)dibromomanganese (II), bis(pyridine)diacetatoiron (II) or bis(pyridine)diacetatomanganese (II), as catalyst for peroxygen compounds.
3. The use as claimed in claim 1, wherein the peroxygen compound used is organic peracids, hydrogen peroxide, perborate and percarbonate, and mixtures thereof.
4. The use as claimed in claim 1 in aqueous solutions for textile washing, in aqueous cleaning solutions for hard surfaces and for the bleaching of colored soilings.
5. The use as claimed in claim 1, wherein a compound which eliminates peroxocarboxylic acid under perhydrolysis conditions is used at the same time as the complex compound of the formula 1.
6. A washing, bleaching or cleaning composition comprising a transition metal complex of the formula 1 as in claim 1.
7. A washing, bleaching or cleaning composition comprising 0.0025 to 1 % by weight, in particular 0.01 % by weight to 0.1% by weight, of transition metal complex of the formula 1 as in claim 1.
8. A washing, bleaching or cleaning composition comprising a transition metal complex of the formula 1 as in claim 1, and also 1 to 10% by weight, in particular 2% by weight to 6% by weight, of a compound which eliminates peroxycarboxylic acid under perhydrolysis conditions.