EP1148118B1 - Detergent comprising dendrimeric ligands and their metallo-complexes as bleach activators - Google Patents

Description

It is known that the bleaching power of peroxidic bleaches, such as Hydrogen peroxide, perborates, percarbonates, persilicates and perphosphates, in Detergents and cleaning agents and thus the efficiency of these bleaches Removal of tea, coffee, fruit or red wine stains only at higher ones Temperatures of well over 60 ° C fully developed. To improve at lower temperatures, especially below 60 ° C, greatly reduced Bleaching action can be compounds to activate the peroxide bleach be used. For this purpose, a number of Transition metal salts or corresponding complexes with mostly chelating Compounds proposed, but the effectiveness of a metal or special combination of transition metal and complex ligand not predictable.

In a large number of documents, for example in WO 96/06154 and EP 458 397, metal complexes with a high activation potential are claimed. DE 1 980 9713 describes transition metal complexes with polyamidoamine dendrimer ligand systems.
The aim is to find bleaching catalysts that show a high oxidation and bleaching capacity and at the same time damage the colors of dyed textiles or surfaces as well as the textile fibers as little as possible.

A dendritic polyamine and its cobalt complex are described in Chem. Ber. 1993 Pp. 2133-2135. DE-A-196 21 510 describes dendrimers with planarchiral or axial-chiral end groups.

It has now been found that transition metal complexes with dendrimers of Polyalkyleneimine type, the bleaching effect of the peroxygen compounds during bleaching of colored stains both on textiles and on hard surfaces improve without destroying colors and fibers. It was also found that the use of dendrimers that are not complex with transition metals are bound in washing and cleaning agents, the oxidation and Increase the bleaching power of the agents in aqueous solution.

R¹ eine Gruppe der Formel (R²R³)N-(CH₂)_n-,

R² und R³ jeweils eine Gruppe der Formel (R⁴R⁵)N-(CH₂)_n-, n die Zahlen 2 oder 3, oder R² und R³ zusammen die Gruppe der Formel A oder R² Wasserstoff und R³ eine Gruppe der Formel

R⁴ und R⁵ jeweils eine Gruppe der Formel (R⁶R⁷)-N-(CH₂)_n-, n die Zahlen 2 oder 3 oder R⁴ und R⁵ zusammen die Gruppe der Formel A oder R⁴ Wasserstoff und R⁵ eine Gruppe der Formel

R⁶ und R⁷ jeweils eine Gruppe der Formel (R⁸R⁹)N-(CH₂)_n-, n die Zahlen 2 oder 3 oder R⁶ und R⁷ zusammen die Gruppe der Formel A oder R⁸ Wasserstoff und R⁹ eine Gruppe der Formel

R⁸ und R⁹ zusammen die Gruppe der Formel A oder

R⁸ Wasserstoff und R⁹ eine Gruppe der Formel

A eine Gruppe der Formel

bedeutet, worin a eine ganze Zahl von 1 bis 4 und R¹⁰ Wasserstoff, C₁-C₃₀-Alkyl-, Cycloalkyl- oder Arylreste, C₁-C₄-Alkoxygruppen, substituierte oder unsubstituierte Amino- bzw. Ammoniumgruppen, Halogenatome, Sulfogruppen, Carboxylgruppen oder Gruppierungen der Formel -(CH₂)_r-COOH, -(CH₂)_r-SO₃H, -(CH₂)_r-PO₃H₂, -(CH₂)_r-OH bedeuten, wobei r eine ganze Zahl von 0 bis 4 bedeutet und die genannten Säuregruppen auch in Salzform vorliegen können, und

X eine Gruppe der Formeln
-(CH₂)_n-, -(CH₂)₃-NR¹¹-(CH₂)₃-, -(CH₂)₂-NR¹¹-(CH₂)₂-, C₂-C₂₀-Alkylen, - (CH₂)_l-[O-(CH₂)_k]_m-O-CH₂)_l)- bedeutet, n eine Zahl von 2 bis 20, l und k eine Zahl von 2 bis 6, m eine Zahl von 1 bis 40,
R¹¹ C₁-C₂₀-Alkyl, C₂-C₂₀-Dialkylamino-C₂-C₁₀-alkyl, C₁-C₁₀-Alkoxy- C₂-C₁₀-alkyl, C₂-C₂₀-Hydroxyalkyl, C₃-C₁₂-Cycloalkyl, C₄-C₂₀-Cycloalkyl-alkyl, C₂-C₂₀-Alkenyl, C₄-C₃₀-Dialkylamino-alkenyl, C₃-C₃₀-Alkoxyalkenyl, C₃-C₂₀-Hydroxyalkenyl, C₅-C₂₀-Cycloalkyl-alkenyl, Aryl oder C₇-C₂₀-Aralkyl, die unsubstituiert oder durch C₁-C₈-Alkyl, C₂-C₈-Dialkylamino, C₁-C₈-Alkoxy, Hydroxy, C₃-C₈-Cycloalkyl, C₄-C₁₂-Cycloalkyl-alkyl substituiert sein können, oder zwei dieser Substituenten gemeinsam eine gegebenenfalls durch Stickstoff oder Sauerstoff unterbrochene Alkylenkette wie Ethylenoxid, Propylenoxid, Butylenoxid und -CH₂-CH(CH₃)-O- bedeuten.

The invention relates to washing and cleaning agents containing a compound of formula I. (R ¹ R ¹ ) N - X - N (R ¹ R ¹ ) wherein

R ^{1 is} a group of the formula (R ² R ³ ) N- (CH ₂ ) _n -,

R ² and R ³ each represent a group of the formula (R ⁴ R ⁵ ) N- (CH ₂ ) _n -, n the numbers 2 or 3, or R ² and R ³ together the group of the formula A or R ^{2 are} hydrogen and R ³ a group of the formula

R ⁴ and R ⁵ each represent a group of the formula (R ⁶ R ⁷ ) -N- (CH ₂ ) _n -, n the numbers 2 or 3 or R ⁴ and R ⁵ together the group of the formula A or R ^{4 are} hydrogen and R ⁵ a group of the formula

R ⁶ and R ⁷ each represent a group of the formula (R ⁸ R ⁹ ) N- (CH ₂ ) _n -, n the numbers 2 or 3 or R ⁶ and R ⁷ together the group of the formula A or R ^{8 are} hydrogen and R ⁹ a group of the formula

R ⁸ and R ⁹ together form the group of the formula A or

R ^{8 is} hydrogen and R ^{9 is} a group of the formula

A is a group of the formula

means in which a is an integer from 1 to 4 and R ^{10 is} hydrogen, C ₁ -C ₃₀ alkyl, cycloalkyl or aryl radicals, C ₁ -C ₄ alkoxy groups, substituted or unsubstituted amino or ammonium groups, halogen atoms, sulfo groups , Carboxyl groups or groupings of the formula - (CH ₂ ) _r -COOH, - (CH ₂ ) _r -SO ₃ H, - (CH ₂ ) _r -PO ₃ H ₂ , - (CH ₂ ) _r -OH, where r is an integer from 0 to 4 and the acid groups mentioned can also be in salt form, and

X is a group of the formulas
- (CH ₂ ) _n -, - (CH ₂ ) ₃ -NR ¹¹ - (CH ₂ ) ₃ -, - (CH ₂ ) ₂ -NR ¹¹ - (CH ₂ ) ₂ -, C ₂ -C ₂₀ alkylene, - (CH ₂ ) _l - [O- (CH ₂ ) _k ] _m -O-CH ₂ ) _l ) - means, n is a number from 2 to 20, l and k is a number from 2 to 6, m is a number of 1 to 40,
R ^{11 is} C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ dialkylamino-C ₂ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy- C ₂ -C ₁₀ alkyl, C ₂ -C ₂₀ hydroxyalkyl, C ₃ -C ₁₂ cycloalkyl, C ₄ -C ₂₀ cycloalkyl alkyl, C ₂ -C ₂₀ alkenyl, C ₄ -C ₃₀ dialkylamino alkenyl, C ₃ -C ₃₀ alkoxyalkenyl, C ₃ -C ₂₀ - Hydroxyalkenyl, C ₅ -C ₂₀ cycloalkyl alkenyl, aryl or C ₇ -C ₂₀ aralkyl which are unsubstituted or by C ₁ -C ₈ alkyl, C ₂ -C ₈ dialkylamino, C ₁ -C ₈ alkoxy, Hydroxy, C ₃ -C ₈ cycloalkyl, C ₄ -C ₁₂ cycloalkyl-alkyl may be substituted, or two of these substituents together an alkylene chain which may be interrupted by nitrogen or oxygen, such as ethylene oxide, propylene oxide, butylene oxide and -CH ₂ -CH (CH ₃ ) -O- mean.

The invention further relates to detergents and cleaning agents containing Complexes of the compounds defined above with cobalt, manganese, iron, Ruthenium, vanadium, molybdenum or tungsten. Manganese complexes are preferred.

These compounds and the corresponding metal complexes are suitable as Bleaching and oxidation catalysts for peroxygen compounds, especially in detergents and cleaning agents containing such peroxygen compounds, for example heavy duty detergents or machine dishwashing detergents. This Catalysts improve the oxidation and bleaching effects of the inorganic Peroxygen compounds at temperatures below 80 ° C, especially in Temperature range from 15 to 45 ° C while reducing the color and Textile fiber damage. In addition, the connections defined above and their metal complexes are also used in paper bleaching.

The preparation of the poly-salen dendrimers of the formula I was carried out by a method described in the specialist literature (R. Moors, F. Vögtle, Chem. Ber. 1993, 126, 2133-2135). The initiator core here is ethylenediamine, which is reacted with acrylonitrile by a Michael addition. The terminal nitrile groups are reduced to the amine, which enables a further addition of acrylonitrile. Repeating this synthesis frequency doubles the number of functionalities. At each of these stages of synthesis, the amino groups can be reacted with salicylaldehyde, whereby compounds of formula I with group A are obtained. Reaction of the amino groups with a derivative of α, β-diamino-propionic acid and subsequent reaction with salicylaldehyde gives the compounds of the formula I which contain groups of the formula -COCHNA-CH ₂ NA.

The products are obtained as yellow solids or oils.
The complexation with metal cations can be done in three different ways. In the first method, the ligand is prepared as described by Moors and Vögtle. The reaction with the metal cation, for example to give the dendritic complex, is then carried out in a suitable solvent, for example chloroform, methylene chloride, ethanol, methanol, dimethylformamide, water, dimethyl sulfoxide or mixtures thereof.
In a second embodiment, salicylaldehyde, dendritic polyamine and metal salt, in a suitable solvent, for example chloroform, methylene chloride, ethanol, methanol, dimethylformamide, water, dimethyl sulfoxide or mixtures thereof, are combined in a one-pot reaction, thereby forming the catalysts according to the invention.
In the third embodiment, the metal-free poly-salen dendrimer can be used. In this case, the dendrimer absorbs the metal cations in the water during use and acts as a catalyst. It is also possible to use the metal-free poly-salen dendrimer, optionally enclosed in a matrix, and a suitable metal salt separately in a detergent formulation. By dissolving the detergent formulation, the reactants can come together and form the catalyst.

The compounds of the formula I which contain the groups A are preferred. The compounds or their metal complexes are particularly preferred 4-cascade: ethylenediamine [4] :( 1-azabutylidene): 2-methine phenol, 8-cascade: ethylenediamine [4] :( 1-azabutylidene) ² : 2-methine phenol, 16- Cascade: ethylenediamine [4] :( 1-azabutylidene) ³ : 2-methine phenol, 32-cascade: ethylenediamine [4] :( 1-azabutylidene) ⁴ : 2-methine phenol.

In the case of dendritic compounds, Newkome proposed dendrimer nomenclature applied [G.R. Newkome, C. Morefield, F. Vögtle in Dendritic Macromolecules, VCH, Weinheim 1996].

Such dendrimers can be used with stoichiometrically different amounts Transition metal can be loaded. In the maximum case, all nitrogen atoms of the dendrimer saturated with transition metal.

In addition to the peripheral N atoms, inner nitrogen atoms of the dendrimer can also complex and the resulting complex can have a catalytic effect. The total number of peripheral and internal nitrogen atoms are: generation 0 1 2 3 4 5 ... Number of N atoms 2 6 14 30 62 126

Depending on the metal, the transition metals in the complexes to be used according to the invention can have oxidation states in the range from + II to + V. Manganese, cobalt and molybdenum are among the preferred transition metals. Multinuclear systems with mixed oxidation numbers and / or several different transition metals are also possible.
In addition to the dendrimer ligand, the complex compounds to be used according to the invention can also carry other ligands, generally of a simpler structure, in particular neutral or mono- or polyvalent anion ligands. For example, water, nitrate, acetate, formate, citrate, perchlorate and the halides such as chloride, bromide and iodide and complex anions such as hexafluorophosphate are suitable. The anion ligands ensure charge balance between the transition metal center and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. These additional ligands can also act as bridges, so that oligomeric multinuclear complexes are formed with at least one dendrimer ligand.

The transition metal dendrimer complexes described, but also the Dendrimers as such are excellent as bleaching and Oxidation catalysts, especially in washing and cleaning agents Cleaning textiles as well as hard surfaces, especially dishes and in textile and paper bleaching. Of particular note here Textile detergents in the form of powder detergents or as liquid formulations and dish detergent. An advantage of the bleaching catalysts according to the invention is their stability against hydrolysis and oxidation as well as their catalytic Effect already at low temperatures. You improve in such Formulations not only the bleaching effect of hydrogen peroxide, but also of organic and inorganic peroxy compounds.

The present invention accordingly also relates to a method for Bleaching soiled substrates, taking the soiled substrate in aqueous bleaching liquor with peroxy compounds and an effective amount of one or more of the compounds of formula I or brings the corresponding metal complexes into contact as bleaching catalysts. Next Purely aqueous solutions also come in mixtures of water and suitable ones organic solvents as a reaction medium in question. The quantities used Peroxygen compounds are generally chosen so that in the Solutions between 10 ppm and 10% active oxygen, preferably between 50 ppm and 5000 ppm active oxygen are present. Also the amount used on compounds of the formula I according to the invention or their metal complexes depends on the application. Depending on the desired degree of activation, it will 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, however In special cases, these limits can also be exceeded or undershot.

The washing and cleaning agents according to the invention thus contain them Bleaching catalysts, in amounts by weight from 0.0001 to 0.5% by weight, in particular 0.00025 to 0.25% by weight, especially 0.0005 to 0.1% by weight on the weight of the formulations.

These detergents and cleaning agents, which are powdered, granular or tablet-like solids, homogeneous solutions or suspensions are present can, in addition to the bleaching catalysts used according to the invention in Principle of all known ingredients common in such agents, such as Peroxygen compounds, bleach activators, other conventional ones Bleaching catalysts, surfactants, builders, water-miscible organic solvents, Enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as Silver corrosion inhibitors, foam regulators, thickeners, Preservatives, pearlescent agents and emulsifiers, as well as colors and fragrances contain.

Suitable peroxygen compounds in particular come into question organic peracids or peracid salts of organic acids. Examples include peroxynaphthoic acid, peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, perbenzoic acid, diperdodecanedioic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, Diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonylbisperoxybenzoic acid. Hydrogen peroxide is also suitable Washing and cleaning conditions Compounds releasing hydrogen peroxide such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts, and inorganic persalts, such as the alkali perborates, percarbonates, - perphosphates, persilicates and persulfates. Are particularly preferred Sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred. Sodium percarbonate can be made Environmental reasons may be preferred. Alkyl hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are Cumene hydroperoxide and butyl hydroperoxide. Are also suitable as Peroxy compounds inorganic peroxyacid salts, e.g. B. Potassium monopersulfate. Mixtures of two or more of these compounds are also suitable.

The detergent and cleaning agent formulations according to the invention contain usually 1 to 30% by weight, in particular 2 to 25% by weight Peroxy compounds.

The addition of small amounts of known bleach stabilizers such as of phosphonates, borates, metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can be useful.

In addition to the bleaching catalysts according to the invention, it is also possible to use known bleach activators which, under perhydrolysis conditions, give aliphatic percarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetate, 2,5-diacetyl, 2,5-glycold, ethylene glycol 2 5-dihydrofuran, sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, sodium 4-benzoyloxy-benzenesulfonate, sodium trimethyl-hexanoyloxy-benzenesulfonate, lactones, acylals, carboxylic acid amides, acyl lactams, acylated ureas, acylated ureas, and oxamides, for example acylated ureas, and oxamides, acylated ureas, and oxamides, acylated ureas, and oxamides, such as acylated ureas, acylated ureas and oxamides -3-acetylhydantoin, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazides, sulfurylamides, and / or N-acylated lactams, for example N-benzoyl-caprolactam, but also quaternary nitrile compounds, for example quaternary trialkylammonium nitrile salts, in particular the cyanomethyltrimethylammonium salt, but also heterocyclically substituted quaternary nitrile compounds and the enol esters and acyl esters known from German patent applications DE 196 16 693 and DE 196 16 767 or their mixtures described in EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone.
Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1 to 10% by weight, in particular 2 to 8% by weight, based on the total agent.
In addition to the conventional bleach activators listed above or in their place, sulfonimines and / or other bleach-enhancing transition metal salts or transition metal complexes may also be present. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from DE 195 29 905 and DE 196 05 688.

The detergents and cleaning agents according to the invention can contain anionic surfactants in amounts of approximately 1 to 50% by weight, based on the total amount of all surfactants, as surface-active agents. Preferred anionic surfactants are C ₈ -C ₂₀ fatty acid alpha-methyl ester sulfonates, alkyl ether sulfates and sec. Alkanesulfonates.
The alkyl ether sulfates used in the agents according to the invention are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, in which R is an unsubstituted C ₁₀ -C ₂₄ -alkyl or C ₁₀ -C ₂₄ -hydroxyalkyl radical, preferably a C ₁₂ -C ₂₀ alkyl or C ₁₂ -C ₂₀ hydroxyalkyl radical, particularly preferably C ₁₂ -C ₁₈ alkyl or C ₁₂ -C ₁₈ hydroxyalkyl radical. "A" is an ethoxy or propoxy unit, m is a number greater than 0, preferably between 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for example a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine. Examples of these alkyl ether sulfates are C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, (C ₁₂ -C ₁₈ E (1.0) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate (C ₁₂ -C ₁₈ E (2.25) M), C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, (C ₁₂ -C ₁₈ E (3.0) M), C ₁₂ - C ₁₈ alkyl polyethoxylate (4.0) sulfate (C ₁₂ -C ₁₈ E (4.0) M), where E is an ethoxy unit.

In the secondary alkanesulfonates, the alkyl group can either be saturated or unsaturated, branched or linear and optionally with a hydroxyl group be substituted. The sulfo group is statistically distributed over the entire C chain, with the primary methyl groups at the beginning and end of the chain none Possess sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 20 Carbon atoms and particularly preferably 13 to 17 carbon atoms. The cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium as a cation is simplicity preferred for the sake of it.

In addition to these or instead of these preferred anionic surfactants, the Formulations according to the invention also other types of anionic surfactants contained within the limits specified above, such as Alkyl sulfates, sulfonates, carboxylates, phosphates and mixtures of the mentioned connections. Suitable cations are e.g. Sodium, potassium, calcium or magnesium, as well as ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, as well as mixtures of these cations. The anionic surfactants for the present invention are suitable, have surfactant properties and are water-soluble or in Water dispersible.

Here, alkyl sulfates are water-soluble salts or acids of the formula ROSO ₃ M, where R is preferably a C ₁₀ -C ₂₄ hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C ₁₀ -C ₂₀ alkyl components, particularly preferably a C ₁₂ -C ₁₈ alkyl radical or hydroxyalkyl radical. M is hydrogen or a cation, for example sodium, potassium, lithium or ammonium or substituted ammonium, for example methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and Mixtures of these.

Another suitable anionic surfactant is alkylbenzenesulfonate. The alkyl group can be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
The preferred alkylbenzenesulfonates contain linear alkyl chains with 9 to 25 carbon atoms, preferably from 10 to 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.

Other suitable anionic surfactants are carboxylates, for example fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can contain various substituents such as hydroxyl groups or alpha-sulfonate groups. Linear saturated or unsaturated hydrocarbon residues are preferred as the hydrophobic component in the soaps. The hydrophobic components usually contain 6 to 30 carbon atoms, preferably 10 to 18 carbon atoms.
Other anionic surfactants are salts of acylaminocarboxylic acids, which are formed by reacting fatty acid chlorides with sodium sarcosinate in an alkaline medium (acylsarcosinates), and fatty acid-protein condensation products, which are obtained by reacting fatty acid chlorides with oligopeptides. The salts of alkylsulfamidocarboxylic acids and the salts of alkyl and alkylaryl ether carboxylic acids also have surfactant properties.

Other anionic surfactants which are useful for use in detergents are C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB 1 082 179, alkyl glycerol sulfates, fatty acylglycerol sulfates, oleyl glycerol sulfates, alkylphenol ethersulfates, alkylphenol ethersulfates paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ - Diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl glycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COOM wherein R is a C ₈ -C ₂₂ alkyl, k is a number from 0 to 10 and M is a soluble salt-forming cation. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also described in US 3,929,678.

Typical examples of anionic surfactants are also alkyl ether sulfonates, glycerol ether, sulfofatty acids, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, alkyl oligoglucoside sulfates, Alkylaminozuckersulfate and alkyl (ether) phosphates , If the anionic surfactants contain polyglycol ether chains, they can have a conventional or narrow homolog distribution.
Nonionic surfactants, such as fatty acid alkyl ester alkoxylates, alkyl and / or alkenyl oligoglycosides, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, and fatty acid fatty acid orborbyl esters, polyglycol fatty acids or fatty acid glycobloyl esters, fatty acid polyglycol ethers, fatty acid polyglycol ethers, fatty acid polyglycol ethers, fatty acid polyglycol ethers, and alkoxylated triglycerides, fatty oil fatty acid sorbyl esters, polyglycol fatty acid sorbyl esters, fatty acid polyglycol ethers, fatty acid polyglycol ethers, fatty acid polyglycol ethers, and alkoxylated triglycerides, fatty acid fatty acid glyceryl esters and fatty acid fatty acid glycoblates. The total proportion of nonionic surfactants in the total amount of all surfactants in the cleaning agents according to the invention is generally 1 to 50% by weight.

Furthermore, co-surfactants from the group can be used in the agents according to the invention Alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, Imidazolinium betaines and sulfobetaines, amine oxides and fatty acid alkanolamides, especially the monoethanolamides from palm kernel and coconut oil fatty acids or Polyhydroxyamides are used in the amounts by weight of 1 to 50%.

The total proportion of surface-active compounds can be up to 50% by weight. amount, preferably 1 to 40 wt .-%, in particular 4 to 25 wt .-% of total detergent or cleaning agent.

Neutral or are suitable as organic and inorganic builders especially alkaline salts that precipitate calcium ions or can bind complex. Suitable and especially ecologically harmless Builder substances are crystalline, layered silicates of the general formula NaMSi (x) O (2x + 1), where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 and y is a number from 0 to 33, for example Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, natrosilite), Na-SKS-9 (NaHSi2O5 * H2O), Na-SKS-10 (NaHSi2O3 * 3H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) and Na-SKS-13 (NaHSi2O5), but especially Na-SKS-6 (δ-Na2Si2O5) as well. finely crystalline, synthetic water-containing zeolites, in particular of the NaA type, which have a calcium binding capacity in the range from 100 to Have 200 mg CaO / g.

Zeolites and layered silicates can be contained in an amount of up to 20% by weight.
Non-partially or partially neutralized (co) polymeric polycarboxylic acids are also suitable. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as, for example, acrolein, dimethylacrylic acid, ethylacrylic acid, vinyl acetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, (meth) -allylsulfonic acid, vinyl sulfonic acid, styrenesulfonic acid group, and acrylamidomethyl phosphonic acid, as well as acrylamidomethyl Monomers such as vinyl phosphoric acid, allyl phosphoric acid and acrylamidomethylpropane phosphoric acid and their salts, as well as hydroxyethyl (meth) acrylate sulfate, allyl alcohol sulfate and allyl alcohol phosphates.

Preferred (co) polymers have an average molecular weight of 1000 to 100,000 g / mol, preferably of 2000 to 75,000 g / mol and in particular of 2000 to 35,000 g / mol.
The degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.

Suitable polymers include, above all, homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.

Other suitable copolymers are derived from terpolymers that are Polymerization of 10 to 70 wt .-% monoethylenically unsaturated Dicarboxylic acids with 4 to 8 carbon atoms, their salts, 20 to 85% by weight monoethylenically unsaturated monocarboxylic acids with 3 to 10 carbon atoms or their salts, 1 to 50 wt .-% monounsaturated monomers, which according to Saponification release hydroxyl groups on the polymer chain, and 0 to 10 wt .-% further free-radically copolymerizable monomers can be obtained.

Graft polymers of monosaccharides are also suitable, Oligosaccharides, polysaccharides and modified polysaccharides as well animal or vegetable proteins.

Copolymers of sugar and other polyhydroxy compounds and a monomer mixture of 45 to 96% by weight of monoethylenically unsaturated C ₃ -C ₁₀ monocarboxylic acid or mixtures of C3 to C10 monocarboxylic acids and / or their salts with monovalent cations, 4 to 55% by weight are preferred % monomers containing monoethylenically unsaturated monosulfonic acid groups, monoethylenically unsaturated sulfuric acid esters, vinyl phosphoric acid esters and / or the salts of these acids with monovalent cations and 0 to 30% by weight of water-soluble unsaturated compounds which are modified with 2 to 50 moles of alkylene oxide per mole of monoethylenically unsaturated compounds ,

Other suitable polymers are polyaspartic acid or its derivatives in non-neutralized or only partially neutralized form.
Graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers on salts of polyaspartic acid, as are usually obtained in the previously described hydrolysis of the polysuccinimide, are also particularly suitable. The otherwise necessary addition of acid to produce the only partially neutralized form of polyaspartic acid can be dispensed with here. The amount of polyaspartate is usually chosen so that the degree of neutralization of all carboxyl groups incorporated in the polymer does not exceed 80%, preferably 60%.

Further builders which can be used are, for example, the percarboxylic acids preferably used in the form of their sodium salts, such as citric acid, in particular trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, mono-, dihydroxysuccinic acid, α-hydroxypropionic acid, gluconic acid, mellitic acid, benzopolycarboxylic acids and as disclosed in U.S. Patents 4,144,226 and 4,146,495.
Phosphate-containing builders, for example alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts, are also suitable.

Examples of this are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with oligomerization amounts in the range from 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.
The builder substances can be present from 5 to 80% by weight, a proportion of 10 to 60% by weight is preferred.

The desired viscosity of the agent can be added by adding water and / or organic solvents or by adding a combination of organic Solvents and thickeners can be adjusted.

, In principle, all mono- or polyvalent come as organic solvents Alcohols into consideration. Alcohols having 1 to 4 carbon atoms, such as Methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, Glycerin and mixtures of the alcohols mentioned. Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000. In particular, the use of polyethylene glycol with a relative Molecular mass between 200 and 600 and in amounts up to 45 wt .-% and from Polyethylene glycol with a molecular weight between 400 and 600 in Amounts of 5 to 25% by weight are preferred. An advantageous mix of Solvents consist of monomeric alcohol, such as ethanol and Polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1.

Other suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.

Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, Polyvinyl alcohol and polyvinyl pyrrolidone and electrolytes such as table salt and ammonium chloride are used.
Suitable thickeners are water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million. Examples of these are the polymers available under the name Carbopol® 940 and 941. The crosslinked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.

Enzymes come from the class of proteases such as BLAP, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purifect® OxP and / or Durazym®, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, Amylases such as Termamyl®, Ainylase®-LT, Maxamyl®, Duramyl® and / or Purafect® OxAm, as well as cutinases, pullulanases or their mixtures in question. Their share can be 0.2 to 1% by weight. The enzymes can be carried on carrier substances be adsorbed and / or be embedded in coating substances.

Silver corrosion inhibitors which can be mentioned in DE 196 49 375 Connections are used.

As foam regulators, preferably up to 6% by weight, in particular about 0.5 to 4% by weight, of foam-suppressing compounds, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized Silicic acid, the bis fatty acid amides and other other known commercially available defoamers can be added.
To set a desired pH value which does not result from the mixture of the other components, the agents 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 contain mineral acids, especially sulfuric acid or alkali hydrogen sulfates or bases, especially ammonium or alkali hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 10% by weight, in particular from 0.5 to 6% by weight.
Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid.

Examples of pearlescent agents are glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.

Sodium sulfate, sodium carbonate, for example, come as salts or adjusting agents or sodium silicate (water glass).

Typical examples for other additives are sodium borate, starch, Sucrose, polydextrose, RAED, stilbene compounds, methyl cellulose, Toluene sulfonate, cumene sulfonate, soaps and silicones.

The bleach catalysts of this invention can be in a variety of products be used. These include textile detergents, textile bleaches, Surface cleaners, toilet cleaners, dishwasher cleaners, and also Denture cleaners. The detergents can be in solid or liquid form available.

It is advantageous for reasons of stability and manageability To use bleach activators in the form of granules, in addition to the Bleach catalyst contain a binder. Different methods, such Producing granules are described in the patent literature, for example in Canada Pat. No. 1 102 966, GB 1 561 333, US 4 087 369, EP 240 057, EP 241 962, EP 101 634 and EP 62 523. The bleaching catalysts according to the invention Granules containing are generally the detergent composition along with the other dry ingredients like enzymes, added inorganic peroxide bleaching agents. The detergent composition, to which the catalyst granules are added can be done in various ways can be obtained, such as mixing the dry components, extruding or Spray drying.

In a further embodiment, the bleaching catalysts according to the invention are particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxide compound. These are compositions in Form of a non-aqueous, liquid medium in which a solid phase is dispersed can be. The non-aqueous, liquid medium can be a liquid, be a surface-active substance, preferably a nonionic surface-active substance Substance, a non-polar liquid medium such as liquid paraffin polar solvents, such as polyols, for example glycerol, sorbitol, Ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol or mixtures thereof.

The solid phase can consist of builder substances, alkalis, abrasive substances, Polymers and solid ionic surface-active compounds, bleaches, fluorescent substances and other common solid ingredients.

The following examples are intended to explain the invention in more detail without referring to it limit.

Example 1 [4-cascade: ethylenediamine [4] :( 1-azabutylidene): 2-methine phenol] manganese

5.16 g (43 mmol) of salicylaldehyde was dissolved in a suspension of 100 ml of toluene and 30 g of Na ₂ SO ₄ . 3.05 g (10.6 mmol) of the 4-cascade: ethylenediamine [4]: 3-propylamine previously suspended in toluene were added dropwise over a period of 1 h. The mixture was stirred for a further 24 h at room temperature and then filtered off. The solvent was removed in vacuo.

1.3 g of the compound thus obtained (1.84 mmol) were mixed with 900 mg (3.67 mmol) Manganese diacetate in 50 ml of ethanol heated under reflux for 6 h. The reaction solution was concentrated to about 15 ml, left in the refrigerator overnight, the Solvent completely removed and the residue was treated with about 10 ml of MeOH added. The complex crystallizes from the solution as a brown solid (Yield: 1.8 g).

Example 2: [8-cascade: ethylenediamine [4] :( 1-azabutylidene) ² : 2-methinephenol] manganese

2.2 g (18 mmol) of salicylaldehyde were dissolved in a suspension of 50 ml of toluene and 15 g of Na ₂ SO ₄ . This was added dropwise over a period of 1 hour 1.53 g (2.05 mmol) of the previously suspended in 50 ml of toluene Octaamins (CH ₂ N (CH ₂ CH ₂ N (CH ₂ CH ₂ NH _{2) 2) 2) 2} , the solution turning yellow. The mixture was stirred for a further 24 h at room temperature and then filtered off. The solvent was removed in vacuo and the highly viscous yellow residue was washed several times with hot methanol.

2.93 g of the compound thus obtained (1.86 mmol) in 150 ml of ethanol were first mixed with 30 ml of 0.5 M KOH and heated under reflux for 30 min. Manganese diacetate was then added (4.6 g, 18.77 mmol) under reflux for 45 min and cooled. After adding 0.95 g of LiCl in 7.5 ml of water, the mixture is stirred at room temperature for a further 45 min.
The complex crystallized out of the solution as a brown solid (yield: 3.8 g).

bleaching tests

By combining an aqueous solution of reference detergent WMP (laundry research Krefeld, 2 g / l in water with 15 ° dH), 1 g / l percarbonate, 0.5 g / l tetraacetylethylene diamine (TAED) and 10 mg / l of the respective catalyst or additionally a bleach composition was prepared with 0.5 g / l tetraacetylethylenediamine (TAED). With this composition, tissue pieces soiled with the standard soiling Curry BC-4 and BC-1 tea (laundry research Krefeld) were subjected to a treatment at a temperature of 40 ° C. under isothermal washing conditions in a Linitest device (Heraeus). After a thirty minute wash, the fabric pieces were rinsed with water, dried and ironed; then the bleaching effect was quantified by determining the differences ΔR _{(KAT-TAED) of} the remissions before and after the bleaching using an ELREPHO 2000 whiteness measuring device (from Datacolor). From these ΔR _(KAT-TAED) values and the ΔR _(TAED) values determined in control experiments without a bleaching catalyst, the ΔΔR values listed in Table 1 were calculated, which represent a direct yardstick for the improvement in the bleaching effect caused by the addition of catalyst : ΔΔR = ΔR (Kat-TAED) - ΔR (TAED) Mean values of the remission differences bleach tea Mn complex according to Example 2 5.0 Mn complex according to Example 2 + TAED 4.6 The bleaching capacity depends on the washing temperature Reflectance ΔR in [%] Temperature in [° C] WMP + SPC Catalyst according to Ex. 2 20 43.6 46.7 40 48.9 54.9 60 59.9 63.8 80 64.9 64.8

The tests were carried out in the Linitest device with a washing time of 30 minutes carried out. The amounts used were 2 g / l basic detergent WMP and 1 g / l sodium percarbonate (SPC) and 10 mg / l catalyst according to Example 2. As Test fabric was used WFK-BW tea (BC-1).

At temperatures below 80 ° C the bleaching performance of the catalyst-containing detergent is higher than without the catalyst. Dependence of the bleaching effect on the pH Reflectance ΔR in [%] PH value 7 42.2 8th 41.8 9 41.7 10 43.2 11 50.7 12 47.3

The tests were carried out in the Linitest device with a washing time of 30 minutes and a washing temperature of 23 ° C. The amounts used were 2 g / l Basic detergent WMP and 0.5 g / l sodium perborate monohydrate and 10 mg / l Catalyst according to Example 2. WFK-BW tea (BC-1) was used as the test fabric used.

The pH optimum is reached at 11. The tested connection is therefore suitable for use in commercially available detergents. Color damage to the bleaching catalyst according to the invention compared to other detergent formulations laundry detergent Reflectance ΔR in [%] Brilliant red GG Remazol Black B. WMP + SPC 30.8 9.5 Cat. According to Ex. 2 31 9.5 Mn-triazacyclononane 39.5 22.4

The tests were carried out in the Linitest device with a washing time of 30 minutes. The amounts used were 2 g / l basic detergent WMP and 1 g / l
Sodium percarbonate and 10 mg / l catalyst. Cotton with brilliant red GG and Remazol Black B was used as the test fabric.
Accordingly, the manganese-dendrimer complex according to the invention, like the catalyst-free detergent, causes only minor color damage. Fiber damage to the bleaching catalyst according to the invention compared to other detergent formulations laundry detergent Degree of depolymerization (DP) WMP / SPC / TAED 1904 + Mn-triazacyclononane 506 Mn complex according to Example 2 1490

The degree of depolymerization (DP) of is used as a measure of the fiber damage Cotton listed. In the absence of catalysts, DP values are reduced Found in 2000. These correspond to less, fiber damage. Lower values stand for greater fiber damage. Table 5 shows the DP values of catalyst-containing detergent formulations compared to catalyst-free Basic detergent. To determine the DP values, a five-fold wash in carried out a catalyst concentration of 2000 ppm.

Claims (8)

1. A laundry detergent or cleaner comprising a peroxy compound and a compound of the formula (R¹R¹)N - X - N(R¹R¹) or metal complexes thereof with transition metals, in which

   R¹ is a group of the formula (R²R³)N-(CH₂)_n-,

   R² and R³ are in each case a group of the formula (R⁴R⁵)N-(CH₂)_n-, n is the numbers 2 or 3, or R² and R³ together are the group of the formula A or R² is hydrogen and R³ is a group of the formula

   

   R⁴ and R⁵ are in each case a group of the formula (R⁶R⁷)-N-(CH₂)_n-, n is the numbers 2 or 3, or R⁴ and R⁵ together are the group of the formula A or R⁴ is hydrogen and R⁵ is a group of the formula

   

   R⁶ and R⁷ are in each case a group of the formula (R⁸R⁹)N-(CH₂)_n-, n is the numbers 2 or 3, or R⁶ and R⁷ together are the group of the formula A or R⁸ is hydrogen and R⁹ is a group of the formula

   

   R⁸ and R⁹ together are the group of the formula A or

   R⁸ is hydrogen and R⁹ is a group of the formula

   

   A is a group of the formula

   

   in which a is an integer from 1 to 4, and R¹⁰ is hydrogen, C₁-C₃₀-alkyl, cycloalkyl or aryl radicals, C₁-C₄-alkoxy groups, substituted or unsubstituted amino or ammonium groups, halogen atoms, sulfo groups, carboxyl groups or groups of the formula -(CH₂)_r-COOH, -(CH₂)_r-SO₃H, -(CH₂)_r-PO₃H₂, -(CH₂)_r-OH, where r is an integer from 0 to 4, and said acid groups may also be present in salt form, and

   X is a group of the formulae -(CH₂)_n-, -(CH₂)₃-NR¹¹-(CH₂)₃-, -(CH₂)₂-NR¹¹-(CH₂)₂-, C₂-C₂₀-alkylene, - (CH₂)_l-[O-(CH₂)_k]_m-O-CH₂)_l)-, n is a number from 2 to 20, l and k are a number from 2 to 6, m is a number from 1 to 40,

   R¹¹ is C₁-C₂₀-alkyl, C₂-C₂₀-dialkylamino-C₂-C₁₀-alkyl, C₁-C₁₀-alkoxy-C₂-C₁₀-alkyl, C₂-C₂₀-hydroxyalkyl, C₃-C₁₂-cycloalkyl, C₄-C₂₀-cycloalkyl-alkyl, C₂-C₂₀-alkenyl, C₄-C₃₀-dialkylamino-alkenyl, C₃-C₃₀-alkoxyalkenyl, C₃-C₂₀-hydroxyalkenyl, C₅-C₂₀-cycloalkyl-alkenyl, aryl or C₇-C_2o-aralkyl, each of which may be unsubstituted or substituted by C₁-C₈-alkyl, C₂-C₈-dialkylamino, C₁-C₈-alkoxy, hydroxyl, C₃-C₈-cycloalkyl, C₄-C₁₂-cycloalkyl-alkyl, or two of these substituents together are an alkylene chain optionally interrupted by nitrogen or oxygen, such as ethylene oxide, propylene oxide, butylene oxide or -CH₂-CH(CH₃)-O-.
2. The laundry detergent or cleaner as claimed in claim 1, which comprises complexes of the compounds of the formula I with Co, Mn, Fe, Ru, V, Mo or W.
3. The laundry detergent or cleaner as claimed in claim 1, which comprises complexes of the formula I with Mn.
4. The laundry detergent or cleaner as claimed in claim 1, which comprises compounds of the formula I which contain groups A.
5. The laundry detergent or cleaner as claimed in claim 1, which comprises compounds of the formula I or metal complexes thereof, where X is a group of the formula -(CH₂)_n- and n is a number from 2 to 20.
6. The laundry detergent or cleaner as claimed in claim 1, which comprises a compound of the formula I or metal complexes thereof in an amount of from 0.0001 to 0.5% by weight, based on the total amount of laundry detergent or cleaner.
7. The laundry detergent or cleaner as claimed in claim 1, in the form of a bleaching composition.
8. A bleaching composition for paper comprising a peroxy compound and a compound of the formula I as in claim 1.