EP1445305A1 - Use of transition metal complexes as bleach catalysts - Google Patents

Abstract

Use is claimed of nitrogen ligand-containing transition metal complexes as catalysts for peroxy compounds. Use is claimed of nitrogen ligand-containing transition metal complexes of formula (I) as catalysts for peroxy compounds. M(L)nXm (I) M : Mn, Fe, Co, Ni, Mo or W; L : a nitrogen-containing heterocyclic ligand; X = chloride, bromide, nitrate, perchlorate, sulfate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of a 1-22C organic acid; n : integer 2-4; and m : integer 0-4. Independent claims are also included for detergent, bleaching and cleansing agents containing (I).

Description

The present invention relates to the use of certain Transition metal complex compounds to enhance the bleaching effect of Peroxygen compounds when bleaching colored stains both on Textiles as well as on hard surfaces, as well as washing and cleaning agents, which contain such complex compounds.

Inorganic peroxygen compounds, especially 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 disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H ₂ O ₂ or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.

At lower temperatures, the oxidation effect of the inorganic Peroxygen compounds improved by adding so-called bleach activators become. Numerous connections have been proposed for this, especially from the Classes of N- or O-acyl compounds, for example multiple acylated Alkylenediamines, especially tetraacetylglycoluril, N-acylated hydantoins, Hydrazides, triazoles, hydrotriazines, urazoles. Diketopiperazines, sulfurylamides and Cyanurates, also carboxylic anhydrides, especially phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy benzenesulfonate (ISONOBS) and acylated sugar derivatives such as pentaacetyl glucose. By addition These substances can reduce the bleaching effect of aqueous peroxide solutions so far be increased that already at temperatures around 60 ° C essentially same effects as with the peroxide solution alone at 95 ° C.

In the effort to save energy in washing and bleaching, 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 these low temperatures, the effect of the activator compounds known to date generally diminishes noticeably. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date.

One starting point for this arises 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 0 458 397, EP 0 544 490 or EP 0 549 271. In EP 0 272 030, cobalt (II) complexes with ammonia ligands, which can also have any further one, two, three and / or tidentate ligands, are used as activators for H ₂ O ₂ in textile washing or - bleaches described. WO 96/23859, WO 96/23860 and WO 96/23861 describe the use of corresponding Co (III) complexes in agents for automatically cleaning dishes. From EP 0 630 964 certain manganese complexes are known which, although they have no pronounced effect with regard to a bleaching enhancement of peroxygen compounds and do not discolor dyed textile fibers, can, however, cause the bleaching of dirt or dye which is detached from the fiber and which is detached from the fiber. DE 44 16 438 discloses manganese, copper and cobalt complexes which can carry ligands from a large number 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 molybdenum with ligands of the salen type as activators for peroxygen compounds in cleaning solutions for hard surfaces. EP 1 225 215 describes the use of transition metal complexes which contain oxime ligands as a catalyst for peroxygen compounds.

The present invention has an improvement in the oxidation and bleaching effect of peroxygen compounds, especially inorganic ones Peroxygen compounds, at low temperatures below 80 ° C, especially in the temperature range of approx. 10 ° C to 45 ° C. The one required metal complexes should be easily accessible and easy to manufacture.

Surprisingly, it has now been found that certain simple structures Transition metal complexes with nitrogenous ligands significantly Cleaning performance against stained soils that contribute to 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 have, being

M

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

L

a ligand from the group of nitrogen-containing heterocycles,

X

Chloride, bromide, nitrate, perchlorate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of an organic acid with 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 washing, bleaching and cleaning agents, which contain peroxygen compounds used, especially in the Textile laundry and in cleaning agents for hard surfaces, especially for Dishes, and in solutions for bleaching colored stains.

Complexes of the formula (1) with transition metal central atoms in are preferred oxidation levels +2, +3 or +4 and complexes with manganese or Iron as central atoms.

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

The halides such as chloride, bromide and iodide are used in particular for the ligand X, 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, nonanoates and laurates. The anion ligands ensure 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) dibromo-iron (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. Yours However, effectiveness as bleaching catalysts has not been described so far.

Suitable peroxygen compounds are primarily alkali perborate mono- or tetrahydrate and / or alkali percarbonates, with sodium being the preferred alkali metal. In addition, however, alkali metal or ammonium peroxosulfates, such as potassium peroxomonosulfate (technically: Caroat® or Oxone®) can also be used. The concentration of these peroxygen compounds in the overall formulation of the washing, bleaching and cleaning agents is 5-90%, preferably 10-70%.
The amounts of peroxygen compounds used are generally selected so that between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen, are present in the detergent and cleaning agent solutions. The amount of bleach-boosting complex compound used also depends on the application. 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, of complex per mol of peroxygen compound are used, but these limits can also be exceeded or fallen below in special cases. Washing, bleaching and cleaning agents preferably contain 0.0025 to 0.25% by weight, in particular 0.01 to 0.5% by weight, of the bleach-enhancing complex compound defined above.

Additionally or alternatively, the washing, bleaching and cleaning agents can also Hydrogen peroxide or organic-based oxidizing agents in Concentration range from 1 - 20% included. This includes all known ones Peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, dodecanediperoxy acid or Phthalimidoperoxycarboxylic acids such as PAP and related systems or those in Amidoper acids mentioned in EP-A-170 386.

The concept of bleaching here includes both the bleaching of on the Textile surface dirt as well as the bleaching of in the wash liquor dirt that is detached from the textile surface. For bleaching the same applies analogously to soiling on hard surfaces. Further potential applications can be found in the personal care area e.g. at bleaching of hair and to improve the effectiveness of denture cleaners. Of the metal complexes described are also used in commercial applications Laundries, in the wood and paper bleaching, the bleaching of cotton and in Disinfectants.

Furthermore, the invention relates to a method for cleaning textiles as well of hard surfaces, especially dishes, using the aforementioned Complex compounds together with peroxygen compounds in aqueous, optionally further detergent or cleaning agent components containing solution, as well as detergents and cleaning agents for hard surfaces, in particular cleaning agents for dishes, such for use in machine processes are preferred, such complex compounds contain.

The use according to the invention consists essentially in having colored Soiling contaminates hard surfaces or soiled textiles to create conditions under which a peroxidic Oxidizing agent and the complex compound of formula (1) react with each other can, with the aim of obtaining more oxidizing secondary products. Such Conditions exist especially when the reactants are in aqueous Solution meet. This can be done by adding the Peroxygen compound and the complex of formula (1) to the aqueous Detergent and cleaning agent solution. Is particularly advantageous however, the method according to the invention using a detergent or cleaning agent for hard surfaces that the Complex compound of formula (1) and optionally a peroxygen-containing Contains oxidizing agents. The peroxygen compound can also separately in bulk or as a preferably aqueous solution or suspension for Solution can be added if a peroxygen-free washing or Detergent is used.

The detergents and cleaning agents, which are granules, powder or tablet Solids, as other shaped bodies, homogeneous solutions or suspensions can be present in addition to the bleach-enhancing metal complex mentioned in principle contain all known ingredients that are common in such agents. The agents can in particular builder substances, surface-active surfactants, Peroxygen compounds, additional peroxygen activators or organic Peracids, water-miscible organic solvents, sequestering agents, Enzymes, as well as special additives with color or fiber-protecting effect. Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, Foam regulators as well as colors and fragrances are possible.

A cleaning agent for hard surfaces according to the invention can also abrasive components, especially quartz flours, wood flours, Contain plastic flour, chalks and micro glass balls and their mixtures. Abrasives are preferably not more than 20% by weight in the cleaning agents, in particular from 5 to 15% by weight.

The washing, bleaching and cleaning agents can contain one or more surfactants contain, in particular anionic surfactants, nonionic surfactants and their Mixtures, but also cationic, zwitterionic and amphoteric surfactants in question come. Such surfactants are in detergents according to the invention in Quantities of preferably 1 to 50 wt .-%, in particular from 3 to 30% by weight, whereas in cleaning agents for hard surfaces normally lower proportions, i.e. amounts up to 20% by weight, in particular Contain up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are. In cleaning agents for use in automatic dishwashing processes low-foam connections are normally used.

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

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from 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) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical. 2,3-Alkyl sulfates, which are produced, for example, in accordance with US Pat. Nos. 3,234,158 and 5,075,041, are also suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₁₈ fatty alcohol residues or mixtures thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcosinate) are suitable as further anionic surfactants. Soaps, for example in amounts of 0.2 to 5% by weight, are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including the soaps, can be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as Mono-, di- or triethanolamine. The anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts. Anionic surfactants are in detergents according to the invention preferably in amounts of 0.5 to 10% by weight and in particular in amounts of Contain 5 to 25 wt .-%.

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

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I)

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

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

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide and the Fatty acid alkanolamides can be suitable.

mit den Resten R¹, R², R³ = C₁-C₂₂-Alkyl und n = 1 bis 5.From the large group of cationic surfactants, particular preference is given to hydroxyalkyl quats of the general structures (III) and (IV).

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

So-called gemini surfactants can be considered as further surfactants. this includes are generally understood to mean those compounds which are two hydrophilic Have groups per molecule. These groups are usually by one so-called "spacers" separated from each other. This spacer is usually one Carbon chain that should be long enough for the hydrophilic groups to unite are at a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low level critical micelle concentration and the ability to control the surface tension of the Greatly reduce water from. Gemini polyhydroxy fatty acid amides can also be used or poly-polyhydroxy fatty acid amides as described in WO 95/19953, WO 95/19954 and WO 95/19955 can be described. Further Types of surfactants can 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.

Particularly suitable water-soluble inorganic builder materials are alkali silicates and polymeric alkali phosphates, which can be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. In particular, crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from the zeolites A and X, are preferred. Your calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram. Suitable builder substances are furthermore crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x + 1} .YH ₂ O, in which x, the so-called modulus, is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both δ- and β-sodium disilicates (Na ₂ Si ₂ O ₅ .y H ₂ O) are preferred. Β-sodium silicates with a modulus between 1.9 and 3.2 can be according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the general formula mentioned above, in which x denotes a number from 1.9 to 2.1, can also be used, produced from amorphous silicates. In a further preferred embodiment of such agents, a crystalline layered sodium 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 agents according to the invention. In a preferred embodiment of agents 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 aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

Such builder substances are preferably in agents according to the invention in Amounts up to 60 wt .-%, in particular from 5 to 40 wt .-%, contain.

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. Also preferred are polymeric (poly) carboxylic acids, in particular the polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers made from them, which can be obtained by oxidation of polysaccharides or dextrins, and which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative 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 free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Commercial products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight, are also suitable. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid.

The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a relative molecular mass between 1000 and 200,000. Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.

The organic builder substances can, in particular for the production of liquid Agents, in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions are used. All of the acids mentioned are usually used in the form of their water-soluble salts, especially their alkali salts.

Such organic builder substances can, if desired, be used in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight be included. Amounts close to the upper limit mentioned are preferably in pasty or liquid, in particular water-containing agents used.

As water-soluble builder components in cleaning agents according to the invention for hard surfaces, all come in principle for mechanical Cleaning dishes typically used by builders in question, for example the above-mentioned alkali phosphates. Their quantities can range up to about 60% by weight, in particular 5 to 20% by weight, based on the total agent lie. Other possible water-soluble builder components are besides Polyphosphonates and phosphonate alkyl carboxylates for example organic Polymers of native or synthetic origin of the type listed above Polycarboxylates, which act as co-builders, especially in hard water regions, and naturally occurring hydroxycarboxylic acids such as mono-, Dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. To the preferred organic builder components include the salts of Citric acid, especially sodium citrate. As sodium citrate come anhydrous Triatrium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimately in the cleaning agents according to the invention adjusted pH value can also be used for the co-builder salts mentioned corresponding acids are present.

In addition to the complex compounds used according to the invention conventional bleach activators, that is compounds that are under Perhydrolysis conditions peroxocarboxylic acids are used. The usual bleach activators, the O- and / or N-acyl groups, are suitable contain. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), acylated triazine derivatives - especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyl sulfonates, in particular Nonanoyl or isononanoyloxybenzenesulfonate (NOBS or ISONOBS) or their Amido derivatives, e.g. described in EP 170 386, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated, glucamine and Gluconolactone. There are also open-chain or cyclic nitrile quats for this Suitable for use. Also from the German patent application DE 44 43 177 known combinations of conventional bleach activators can be used become.

Enzymes which may be present in 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 from the 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 can, as for example in the international Patent applications WO 92111347 or WO 94/23005 described Carriers can be adsorbed and / or embedded in coating substances to counter them protect early inactivation. They are in washing and Detergents preferably in amounts up to 10 wt .-%, especially of 0.05 to 5 wt .-%, contain, with particular preference against oxidative degradation stabilized enzymes.

Machine dishwashing detergents according to the invention preferably contain the usual alkali carriers, such as, for example, alkali silicates, alkali carbonates and / or alkali hydrogen carbonates. The alkali carriers usually used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO ₂ / M ₂ O (M = alkali atom) of 1: 1 to 2.5: 1. Alkali silicates can be used in amounts of up to 40% by weight, in particular 3 to 30 wt .-%, based on the total agent, may be included. The alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, which can be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.

Another object of the invention is a means for machine cleaning Tableware containing 15 to 65% by weight, in particular 20 to 60% by weight water-soluble builder component, 5 to 25 wt .-%, in particular 8 to 17% by weight. Oxygen-based bleaches, each; based on the whole Agent, and 0.1 to 5% by weight of one or more of the cyclic groups defined above Sugar ketones. Such an agent is preferably lower alkaline, that is, his % by weight solution has a pH of 8 to 11.5, in particular 9 to 11 on.

In a further embodiment, means for automatic Cleaning dishes is 20 to 60% by weight water-soluble organic builder, especially alkali citrate, 3 to 20% by weight alkali carbonate and 3 to 40% by weight Contain alkali disilicate.

In order to provide protection against silver corrosion, in accordance with the invention Detergents for dishes silver corrosion inhibitors are used. 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, and salts and / or complexes of metals contained in the complexes suitable according to the invention with other than ligands given in formula (I).

If the agents foam too much during use, they can still up to 6 wt .-%, preferably about 0.5 to 4 wt .-% of a foam regulating Compound, preferably from the group comprising silicones, paraffins, paraffin-alcohol combinations, hydrophobicized silicas, bis fatty acid amides as well their mixtures and other other known commercially available Foam inhibitors are added. The foam inhibitors are preferably in particular silicone and / or paraffin-containing foam inhibitors granular, water-soluble or dispersible carrier substance bound. Mixtures of paraffins and Bistearylethylenediamide preferred. Other optional ingredients in the Agents according to the invention are, for example, perfume oils.

To those in the agents according to the invention, especially when they are in liquid or pasty form, usable organic solvents belong Alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and Propylene glycol, as well as their mixtures and those from the above Classes of derivable ether. Such water-miscible solvents are preferably not in the cleaning agents according to the invention 20% by weight, in particular from 1 to 15% by weight, is present.

To set a desired one by mixing the rest Components of non-self-determined pH can Agents according to the invention systemic 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, especially sulfuric acid or alkali hydrogen sulfates, or bases, in particular Contain ammonium or alkali hydroxides. Such pH regulators are in the Agents according to the invention preferably do not exceed 10% by weight, in particular of 0.5 to 6 wt .-% included.

The agents according to the invention are preferably powdered, granular or tablet-shaped preparations in a known manner, for example by Mixing, granulating, roller compacting and / or by spray drying the thermally resilient components and admixing the more sensitive ones Components, in particular enzymes, bleaches and Bleaching catalyst can be expected to be produced. invention Agents in the form of aqueous or other conventional solvent-containing solutions are particularly beneficial by simply mixing the ingredients in Substance or solution can be placed in an automatic mixer, manufactured.

For the production of particulate agents with increased bulk density, especially in the range from 650 g / l to 950 g / l, is one from the European Patent EP 0 486 592 known, which has an extrusion step Process preferred. Another preferred production using a Granulation process is in European patent EP 0 642 576 described. The preparation of agents according to the invention in the form of dusty, 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 in that in a first process step, the builder components with at least one Proportion of liquid mixture components while increasing the bulk density of this Premixed mixed and then - if necessary after a Intermediate drying - the other components of the agent, including the Bleaching catalyst, combined with the premix thus obtained.

For the preparation of agents according to the invention in tablet form, the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 · 10 ⁵ Pa to 1500 · 10 ⁵ Pa pressed. In this way, break-proof tablets are obtained with ease, but nevertheless dissolve sufficiently quickly under conditions of use, with a bending strength of normally over 150 N. A tablet produced in this way preferably has a weight of 1 to 5 g to 40 g, in particular 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 49 g (0.62 mol) of pyridine were added (pyridine previously dried over KOH). The The reaction mixture was heated to reflux for four hours. The received Suspension was filtered at 60 ° C and the isolated solid with successively 100 ml of a 10% isopropanolic pyridine solution and 100 ml Petroleum spirit (50-70 ° C) washed. After drying in vacuo, 12.5 g of the beige complex 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 49 g (0.62 mol) of pyridine are added to the solution (pyridine previously over KOH dried). The clear, intensely yellow colored solution was at 12 hours Allow to stand at room temperature, then the precipitated yellow solid filtered off and washed with 50 ml of petroleum spirit (50-70 ° C). After drying in Vacuum gave 9.9 g of the yellow-orange complex, which yielded 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 were added, which is almost completely dissolved. The mixture was stirred at room temperature for one hour, then the precipitated light precipitate is filtered off and twice with 25 ml each Petroleum spirit (30-60 ° C) washed. After drying in vacuo, 18.9 g of the white-gray complex. 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 was dissolved in 400 ml of methanol. Subsequently 20.0 g of manganese (II) chloride were added, which is almost completely dissolved. The mixture was stirred for 4 hours at room temperature, then the precipitated bright precipitate filtered off and twice with 25 ml of petroleum spirit (30-60 ° C) washed. After drying in vacuo, 17.2 g of the white-brown Get complex. 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 (eimid) 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 dissolved almost completely. The mixture was stirred at room temperature for 4 hours, after which the The resulting brown solution is concentrated using a rotary evaporator. there crystals precipitated, these were filtered off and twice with 25 ml of propanol washed. After drying in vacuo, 27.2 g of the white-brown Get complex. This corresponds to a yield of 32.8%.

Analytical data:

Analysis of 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 Cat 1 to Cat 5 according to the invention 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 adding 1 g / l sodium percarbonate (from Degussa), the washing tests were carried out in a Linitest device (from Heräus) at 20 to 40 ° C. The washing time was 30 min, water hardness 18 ° dH. Tea on cotton (BC-1) and curry on cotton (BC-4, both WFK, Krefeld) served as the bleach test fabric. The difference in remission, measured with an Elrepho device, after washing, was compared to the unwashed fabric as the bleaching result. As a comparison test (V1), 250 mg / l TAED were used instead of the amount of 10 mg / l catalyst according to the invention. 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 the compounds according to the invention (Cat 1 to Cat 5) significantly better bleaching effect can be achieved than by the conventional bleach activator TAED, which in much higher concentration was used (V1). Substantially the same results were obtained when the sodium percarbonate was replaced by 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 Reflectance values (ddR%)
PH value 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 of the invention Optimal bleaching in the pH range 9 to 12.

Claims (8)

Use of transition metal complexes with nitrogen-containing ligands as a catalyst for peroxygen compounds, characterized in that the transition metal complexes have the formula (1) M (L) _n X _m have, being

M

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

L

a ligand from the group of nitrogen-containing heterocycles,

X

Chloride, bromide, nitrate, perchlorate, sulfate, ammonia, tetrafluoroborate, hexafluorophosphate or an anion of an organic acid with 1 to 22 carbon atoms,

n

is a number from 2 to 4 and m is a number from 0 to 4.

Use according to claim 1, characterized in that L in the formula (1) is pyridine, imidazole, picoline, imidazoline, pyrrole, pyrazole, triazole, hexamethyleneimine, piperidine or lutidine. Use according to claim 1, characterized in that organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof are used as the peroxygen compound. Use according to claim 1 in aqueous solutions for textile washing, in aqueous cleaning solutions for hard surfaces and for bleaching colored ones Soils. Use according to Claim 1, characterized in that a compound which cleaves off peroxocarboxylic acid under perhydrolysis conditions is used simultaneously with the complex compound of the formula 1. Detergents, bleaches and cleaning agents containing one Transition metal complex of formula 1 according to claim 1. Detergents, bleaches and cleaning agents containing 0.0025 to 1% by weight, in particular 0.01 wt .-% to 0.1 wt .-% transition metal complex Formula 1 according to claim 1. Detergents, bleaches and cleaning agents containing one Transition metal complex of formula 1 according to claim 1 and 1 to 10 wt .-% in particular 2% by weight to 6% by weight of one under perhydrolysis conditions Peroxycarboxylic acid releasing compound.