EP0880579A2

EP0880579A2 - Transition-metal complexes used as activators for peroxy compounds

Info

Publication number: EP0880579A2
Application number: EP97904389A
Authority: EP
Inventors: Helmut Blum; Bernd Mayer; Ulrich Pegelow; Horst-Dieter Speckmann; Bernt Krebs; Mark Duda; Cetin Nazikkol; Jörg REIM
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1996-02-16
Filing date: 1997-02-07
Publication date: 1998-12-02
Also published as: WO1997030144A3; WO1997030144A2; US6153576A; DE19605688A1

Abstract

Described are complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and/or copper containing one or more ligands of general formula (I) ou (II) in which R is a direct bond or an optionally amin-group-substituted alkylene group with 1 to 4 C-atoms, A is a condensed or non-condensed ring system containing at least one nitrogen atom, B is hydrogen, an OH-group or the same as A, and X is a phenyl ring optionally substituted with hydroxy and/or C1-4 alkyl or an optionally hydroxy-substituted C1-4 alkylene group. The complexes are suitable for use as activators or peroxy compounds in oxidative washing, cleaning and disinfectant solutions, washing and cleaning agents preferably containing 0.0025 to 0.25 % by wt. of such activator complexes.

Description

Transition metal complexes as activators for peroxygen compounds

The present invention relates to the use of certain complexes of transition metals with nitrogen-containing polydental ligands as activators or catalysts for peroxygen compounds, in particular for bleaching color stains when washing textiles and cleaning hard surfaces, for example dishes, as well as washing, cleaning and disinfecting agents that contain such activators or catalysts.

Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of 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 strongly depends on the temperature in dilute solutions; 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 can be improved by the addition of so-called bleach activators, for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, moreover carboxylic acid anhydrides, especially phthalic anhydride, carbonic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium-isonononolonate, sodium-isonononolonate, sodium-isonononolonate, sodium-isononolonate, have become known in the literature. By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor 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 hitherto generally decreases 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 is the use of transition metal salts and complexes, as proposed, for example, in European patent applications EP 392 592, EP 443 651, EP 458 397, EP 544490 or EP 549271, as so-called bleaching catalysts. These, presumably because of the high reactivity of the oxidizing intermediates formed from them and the peroxygen compound, pose a risk of changing the color of colored textiles and, in extreme cases, of oxidative textile damage. Certain manganese complexes are known from European patent application EP 630964, which have no pronounced effect with regard to bleaching enhancement of peroxygen compounds and do not discolor dyed textile fibers, but can cause the bleaching of dirt or dye which is detached from the fiber and which is detached from the fiber. Manganese, copper and cobalt complexes are known from German patent application DE 44 16438, which can carry ligands from a large number of groups of substances and are to be used as bleaching and oxidation catalysts.

The aim of the present invention is to improve the oxidation and bleaching effect of organic peroxygen compounds at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 55 ° C.

It has now been found that transition metal complexes which have certain nitrogen-containing compounds with tripod structure as ligands have a clear bleaching-catalyzing effect. The invention relates to the use of complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper which have one or more of the ligands of the general formula I,

R '. ^N - R (D

I R

A I B

A

in which R is a direct bond or an optionally amino-substituted alkylene group having 1 to 4 carbon atoms, A is a condensed or uncondensed ring system which contains at least one nitrogen atom, and B is hydrogen, an OH group or A, as Activators for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfection solutions. In the alkylene groups R, one or more non-adjacent CH ₂ units which are not bound directly to the central N atom can optionally be replaced by NH units.

Compounds of the general formula I can be converted into ligands of the general formula II by formal linking modification of their B units,

in which A and R have the meaning given above and X is an optionally hydroxyl- and / or C _M -alkyl-substituted phenylene ring or an optionally hydroxyl-substituted C _M -alkylene group, and which may be able to use two overs to bind gang metal atoms complex. The invention therefore furthermore relates to the use of optionally bi- or polynuclear complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper which have one or more of the ligands of the general formula II, as Activators for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfection solutions.

In the part R-B of the compounds of the formula I, R is preferably a direct bond if B is hydrogen and preferably not a direct bond if B is a hydroxyl group. Not all of the R groups in a ligand molecule have to be identical. The preferred nitrogen-containing ring systems (A in formulas I and II) include the 2-pyridyl group, the 2-imidazolyl group, the l-methyl-2-imidazolyl group and the 2-benzimidazolyl group. Not all of the residues A in a ligand molecule have to be identical. R in the compounds of the formulas I or II is preferably a methylene group. X in the compounds according to formula II is preferably selected from the 1,3-phenylene group, the 2-hydroxy-1,3-phenylene group, the 2-hydroxy-5-methyl-1,3-phenylene group and the hydroxymethylene group.

The substances according to general formulas I or II which can be used as ligands for the bleaching catalysts to be used according to the invention can be obtained by processes which are known in principle, for example in the review by K. Wieghardt in Angew. Chem. IÜ1 (1989), pp. 1179-1198 and the original works cited there. Commercially available raw materials are usually converted into the desired ligands via condensation reactions, for example with the elimination of hydrogen halides. These can then, typically in common solvents, be reacted with salts of corresponding transition metals. The complexes to be used according to the invention as bleaching catalysts generally form already at room temperature and are normally obtained in crystalline form from common solvents.

The transition metals mentioned in the bleach catalysts to be used according to the invention are preferably in the oxidation states +2, +3 or +4. Complexes with transition metal central atoms in the oxidation states +3 or +4 are preferably used. Systems with mixed oxidation numbers are possible. In the case of multinuclear complexes, not all metal atoms in the complex need to be the same. To the preferred complexes include those with iron and / or manganese as central atoms.

In addition to the ligands according to general formulas I and II, the transition metal complexes 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, ammonia, nitrate, nitrite, hydroxide, carbonate, hydrogen carbonate, acetate, formate, citrate, perchlorate and the halides such as chloride, bromide and iodide and complex anions such as hexafluorophosphate. The anion ligands are intended to balance the charge between the transition metal central atom and the ligand system. If there are not enough anion ligands to accomplish this charge balance, the then cationically charged complexes can have common anions, such as sulfate, hydrogen sulfate, methosulfate, ethosulfate and the anions mentioned above under the anion ligands, as counterions. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. These additional ligands can also act as bridges, so that multinuclear complexes with at least one ligand according to general formulas I or II are formed.

The preferred bleaching catalysts according to the invention include those with the tris- (2-pyridylmethyl) amine ligand,

with the (bis - ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine ligand,

^{^ no}

with the N-bis (2-benzimodazolylmethyl) aminoethanol ligand,

H w

and with the N, N '- (bis- (l-methylimidazol-2-yl) methyl) ethylenediamine ligand,

The preferred ligands according to general formula II include 2,6-bis (bis- (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol,

N, N, N ', N' - tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane,

1,3-bis (bis- (2-benzimidazolylmethyl) amuomomethyl) benzene,

and 2,6-bis (bis- (2-pyridylmethyl) aminomethyl) -4-methylphenol,

A transition metal bleaching catalyst with the ligands according to formula I or formula II is preferably used for the bleaching of color stains when washing textiles, in particular in an aqueous, surfactant-containing liquor. The wording "bleaching of color stains" is to be understood in its broadest meaning and includes both the bleaching of dirt on the textile, the bleaching of dirt in the wash liquor, detached from the textile, as well as the oxidative destruction of textile colors in the wash liquor, which detach from textiles under the washing conditions before they can be drawn onto textiles of a different color.

Another preferred application form according to the invention is the use of the transition metal bleaching catalysts with the ligands according to formula I or formula II in cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains, in particular tea. Here too, the term bleaching is understood to mean both the bleaching of dirt located on the hard surface and the bleaching of dirt located in the dishwashing liquor and detached from the hard surface.

The invention further relates to washing, cleaning and disinfecting agents which contain an abovementioned transition metal bleaching catalyst with a ligand of the formula I or formula II and a process for activating peroxygen compounds using such a bleaching catalyst.

In the process according to the invention and in the context of a use according to the invention, the bleaching catalyst can be used in the sense of an activator wherever there is a particular increase in the oxidizing effect of the peroxygen compounds at low temperatures, for example in the bleaching of textiles or hair, in the oxidation of organic or inorganic intermediates and in disinfection.

The use according to the invention essentially consists in creating conditions under which the peroxygen compound and the bleaching catalyst can react with one another with the aim of obtaining secondary products which have a stronger oxidizing action. Such conditions exist in particular when the two reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the bleaching catalyst to an optionally detergent-containing solution. The method according to the invention is particularly advantageous however, using a washing, cleaning or disinfecting agent according to the invention which contains the bleaching catalyst and optionally a peroxidic oxidizing agent. The peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxygen-free agent is used.

The conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents are also suitable as the reaction medium. The amounts of peroxygen compounds used are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen. The amount of bleaching catalyst used also depends on the application. Depending on the desired degree of activation, 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.002 mol, of activator per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen short of.

A washing, cleaning or disinfecting agent according to the invention preferably contains 0.0025% by weight to 0.25% by weight, in particular 0.01% by weight to 0.1% by weight, of the bleaching catalyst with the ligands according to formula I or formula II in addition to conventional ingredients which are compatible with the bleaching catalyst. The bleaching catalyst can be adsorbed onto carriers and / or embedded in coating substances in a manner known in principle.

The detergents, cleaning agents and disinfectants according to the invention, which can be present in particular as pulverulent solids, in post-compacted particle form, as homogeneous solutions or suspensions, can, in addition to the bleaching catalyst used according to the invention, in principle contain all known ingredients customary in such agents. The washing and cleaning agents according to the invention can in particular builder substances, surface-active surfactants, organic and / or inorganic peroxygen compounds, water-miscible organic solvents, en- zymes, enzyme stabilizers, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators, additional peroxygen activators, colorants and fragrances.

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

A further subject of the invention is an agent for the machine cleaning of dishes, containing 15% by weight to 65% by weight, in particular 20% by weight to 55% by weight of water-soluble builder component, 5% by weight to 25% by weight. %, in particular 8% by weight to 17% by weight, of an oxygen-based bleaching agent, in each case based on the total agent, which contains a bleach-catalyzing transition metal complex with the ligand of the formula I or formula II, in particular in amounts of 0.005% by weight to 0 , 1 wt .-%, contains. Such an agent is in particular lower alkaline, ie its 1% by weight solution has a pH of 8 to 11.5, preferably 9 to 11.

In addition to the transition metal bleaching catalysts, in particular in combination with inorganic peroxygen compounds, conventional bleach activators, that is to say compounds which contain perbenzoic acid and / or aliphatic peroxocarboxylic acids with 1 to 10 C atoms, in particular 2 to 4 C atoms, which are optionally substituted under perhydrolysis conditions result, are used. Suitable are the conventional bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenol sulfonates, especially nonanoyl or isononanoyloxybene benzenesulfonate, 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, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetacetylxylose, and optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE 4443 177 can also be used. In a preferred embodiment of agents according to the invention, 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight, of such a compound which releases peroxocarboxylic acid under perhydrolysis conditions are present in addition to the bleach-enhancing transition metal complex. The weight ratio of compound releasing peroxocarboxylic acid under perhydrolysis conditions to transition metal complex compound is preferably in the range from 8000: 1 to 1: 1, in particular from 1000: 1 to 10: 1. The presence of additional transition metal bleaching catalysts which have no ligands according to formula I or II is also possible.

The agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof. Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10, alkyl ether groups. Corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical are also useful.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized. The surfactants of the sulfate type include the salts of Sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the non-ionic surfactants mentioned with a low degree of ethoxylation. The surfactants of the sulfonate type that can be used include linear alkyl benzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkanesulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are used in the reaction of corresponding monoolefins with sulfur trioxide arise, as well as alpha-sulfo fatty acid esters, which arise in the sulfonation of fatty acid methyl or ethyl esters.

Such surfactants are present in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight, while the disinfectants according to the invention and agents according to the invention for cleaning dishes preferably contain 0.1% by weight to 20% by weight, in particular 0.2% by weight to 10% by weight of surfactants.

Suitable peroxygen compounds are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate. If solid per compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. The peroxygen compounds can be added to the washing or cleaning liquor as such or in the form of agents containing them, which can in principle contain all the usual washing, cleaning or disinfectant components. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide is particularly preferably used in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide. If a washing or cleaning agent according to the invention contains peroxygen compounds, these are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight, whereas in the disinfectants according to the invention preferably from 0.5% by weight to 40% by weight, in particular from 5% by weight to 20% by weight, of peroxygen compounds are contained.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenediphosphonic acid), phosphonic acid (1) Hydroxy ethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain a small amount of polymerizable substances in copolymerized form without carboxylic acid functionality. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 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. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, vinyl ester, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. 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 a vinyl alcohol derivative 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. The third monomeric unit in this case is preferably vinyl alcohol and / or an esterified vinyl alcohol. In particular, vinyl alcohol derivatives vorzugt which an ester of short-chain carboxylic acids, for example of C _r C ₄ - represent carboxylic acids, with vinyl alcohol. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate. Polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleinate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1, are very particularly preferred and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an alkyl sulfonic acid which is in the 2-position with an alkyl radical, preferably with a C _r C ₄ alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methallylsulfonic acid or metal sulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate . This carbohydrate can be, for example, a mono-, di-, oligosaccharide or polysaccharide, with mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared in particular by processes which are described in German patent DE 42 21 381 and German patent application DE 43 00 772, and generally have a relative molecular weight between 1,000 and 200,000, preferably between 200 and 50 000 and in particular between 3,000 and 10,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The Organic builder substances, in particular for the production of liquid agents, can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, be present in amounts of up to 50% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing agents according to the invention.

Particularly suitable water-soluble inorganic builder materials are alkali metal phosphates, which can be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium. In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid compositions in particular from 1% by weight to 5% by weight. used. Among these, the crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali metal silicates which can be used as builders in the agents according to the invention 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 Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Those with a Na ₂ O: SiO ₂ molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427. As crystalline silicates, which may be present alone or in a mixture with amorphous silicates, preference is given to using crystalline sheet silicates of the general formula Na ₂ Si _x O _{2x +]} y H ₂ O, in which x, the so-called modulus, is a number of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicate (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO 91/08171 is. δ-sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0452 428 , can be used in agents according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as can be obtained by the processes of European patent EP 0 164 552 and / or EP 0293 753, are in a further preferred embodiment agents according to the invention used. If alkali aluminum silicate, in particular zeolite, is also present as an additional builder substance, the weight ratio aluminum silicate to silicate, in each case based 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.

Builder substances are contained in the washing or cleaning agents according to the invention preferably in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free of only the components of the Water hardness complexing builder substances are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy metal complexing substances, preferably from the group comprising amino polycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids, and the like water-soluble salts and mixtures thereof.

In a preferred embodiment, machine cleaning agents according to the invention for dishes contain customary 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, based on the total agent. However, the use of the highly alkaline metasilicates as alkali carriers is preferably omitted entirely. The alkali carrier system preferably used in such agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight, preferably 5% by weight to 40% by weight, is included. Depending on which pH value is ultimately desired, the ratio of the carbonate used and the hydrogen carbonate used varies. In a further embodiment of agents according to the invention for cleaning dishes, these contain 20% by weight to 60% by weight of water-soluble organic builders, in particular alkali metal citrate, 3% by weight to 20% by weight of alkali metal carbonate and 5% by weight to Contain 40 wt .-% alkali disilicate.

Enzymes which can be used in the agents are those from the class of proteases, lipases, cutinases, amylases, pullulanases, hemicellulase, cellulases, oxidases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia, are particularly suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxac , Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The optionally used enzymes can, as described for example in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. They are contained in the detergents, cleaning agents and disinfectants according to the invention in amounts of preferably not more than 5% by weight, in particular from 0.2% by weight to 3% by weight, particular preference being given to enzymes stabilized against oxidative degradation , as known, for example, from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.

The customary enzyme stabilizers which are optionally present, in particular in liquid agents according to the invention, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, as known, for example, from European patent applications EP 376 705 and EP 378 261 , Boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, boric acid esters, such as from international patent application WO 93/11215 or the European patent application EP 511 456 known. Boronic acid derivatives, such as known from European patent application EP 583 536, calcium salts, for example the Ca-formic acid combination known from European patent EP 28 865, magnesium salts, such as known from European patent application EP 378 262, and / or sulfur-containing Re¬ Production agents, such as known from European patent applications EP 080 748 or EP 080 223.

Suitable foam inhibitors include long-chain soaps, in particular beech soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 3436 194, European patent applications EP 262 588, EP 301 414, EP 309931 or European patent EP 150 386.

A detergent according to the invention can also contain graying inhibitors. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example partially hydrolysed starch. Na carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.

The organic solvents which can be used in the agents according to the invention, in particular if they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned. Such water-miscible solvents are preferably present in the washing, cleaning and disinfecting agents according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight.

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 mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not contained in the agents according to the invention in excess of 20% by weight, in particular from 1.2% by weight to 17% by weight.

Although transition metal complexes are known to counteract the corrosion of silver, the complexes which bleach catalyze according to the invention are generally used in amounts which are too small to be able to provide silver corrosion protection, so that silver corrosion inhibitors are additionally used in dishwashing detergents according to the invention can. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl-, aminoalkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper salts and / or complexes in which the metals mentioned are in one of the oxidation states II, III, IV, V or VI, depending on the metal.

The preparation of the solid compositions according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation, the peroxygen compound and bleaching catalyst optionally being added later. For the production of agents according to the invention with increased Bulk weight, in particular in the range from 650 g / 1 to 950 g / 1, a process known from European patent EP 486 592 and having an extrusion step is preferred. Detergents, cleaning agents or disinfectants according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. In a preferred embodiment of agents for the in particular machine cleaning of dishes, these are tablet-shaped and can be produced on the basis of the processes disclosed in European patent specifications EP 0 579 659 and EP 0 591 282.

Beisfele

Example 1: Preparation of a Mn bleaching catalyst to be used according to the invention 1.A: Synthesis of Tris-f2-pyridylmethvlVamin ftpa)

5.0 g (30.5 mmol) of 2-picolyl chloride hydrochloride were dissolved in 13 ml of water and 6 ml of 5.3 N NaOH were added while cooling with ice. The red suspension obtained was cooled to 0 ° C. and a solution of 1.64 g (15.25 mmol) of picolylamine in 26 ml of dichloromethane was added. The mixture was warmed to room temperature and reacted with a further 6 ml of 5.3 N NaOH over a period of several days. Care was taken to ensure that the pH did not exceed 9.5. The entire mixture was then washed twice with 7 ml of 15 percent NaOH and the organic phase was dried over sodium sulfate. After the desiccant was removed, the solvent was evaporated. The brown residue was extracted with ether and the solid obtained was recrystallized from ether. 2.4 g of tris (2-pyridylmethyl) amine were obtained.

2.45 g (10 mmol) Mn (OAc) ₂ x 4H ₂ O and 2.7 g (20 mmol) sodium acetate were dissolved in methanol and reacted with 2.9 g (10 mmol) tpa. The solution was stirred at room temperature for 2 h and then cooled to 0 ° C. for 24 h. The dark brown solid formed was separated and dried (2.2 g).

Example 2: Preparation of an Fe bleaching catalyst to be used according to the invention

2.A; Synthesis of NNN ^, .N ^, -Tetrakisf2-fl-methvlbenzimidazolynV2-hvdroxy-l-3-diaminopropane fthpn.

1.06 g (9.7 mmol) of 1,2-diaminobenzene was mixed well with 0.5 g (1.6 mmol) of 2-hydroxy-1,3-diaminopropanetetraacetic acid and heated to 170-180 ° C. The mixture was cooled and taken up with about 15 ml of 4N HCl. A gray one formed Precipitate, which was filtered off and washed with acetone. The solid was dissolved in water and neutralized with dilute ammonia. The white precipitate was separated off, recrystallized from acetone and dried. 0.5 g of the diaminopropane derivative was obtained.

2.B: Synthesis of [Fe ₂ ftbpo ¥ OAcY,], ^' CIO _i ) ₁ fB2 ^

2.58 g (5 mmol) of Fe (CIO ₄ ) ₃ × 9H ₂ O and 2.7 g (20 mmol) of sodium acetate were dissolved in about 50 ml of methanol and 1.53 g (2.5 mmol) of tbpo were added. The solution was stirred at room temperature for 2 h and then cooled to 0 ° C. for 24 h. The green-brown solid formed was separated off and dried (1.6 g).

Example 3

98 mg of sodium perborate monohydrate were dissolved in a solution containing 2.5 mg of morin in 99.5 ml of fully demineralized water. The pH was adjusted to 9.5 and kept at this value with the aid of a pH stat device during the entire subsequent measurement period. The temperature was also kept constant at 20 ° C. 0.5 ml of a solution containing the bleaching catalyst to be tested in a concentration of 50 ppm based on transition metal was added. The absorbance E of the solution at 400 nm was measured every minute over a period of 30 minutes. The table below shows the values for the percent decolorization D (t), calculated according to D (t) = [E (t) - E (0)] / E (0) * 100.

The manganese complex (B1) prepared according to Example 1 with the tris (2-pyridylmethyl) amine ligand and the iron complex (B2) prepared according to Example 2 with the N, N, N ', N'-tetrakis were tested - (2- (l-methylbenzimidazolyl)) - 2-hydroxy-l, 3-diaminopropane ligands in the sense of the invention. For comparison, the conventional bleach activator N, N, N ', N'-tetraacetylethylenediamine (TAED) was otherwise included same conditions, but in a concentration of 6% by weight, also tested (VI).

Table 1: Decolorization as a function of time

It can be seen that a significantly better bleaching effect can be achieved by the use according to the invention (B1 and B2) than by the conventional bleach activator TAED in a substantially higher concentration (VI).

Claims

claims

1. Use of complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper which have one or more of the ligands of the general formula I,

R ^ ~ R (D

A ι ^B A in which R is a direct bond or an optionally amino-substituted alkylene group having 1 to 4 carbon atoms, A represents a condensed or uncondensed ring system which contains at least one nitrogen atom, and B hydrogen, one OH group or A is, as activators for peroxygen compounds in oxidation, washing, cleaning or disinfection solutions.

2. Use of complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper which have one or more of the ligands of the general formula II,

A A

^VR Y dD

ANXNA ^** R ' ^S R' ^ R ' ^V R'

in which R is a direct bond or an optionally amino-substituted alkylene group having 1 to 4 C atoms, A is a condensed or uncondensed ring system which contains at least one nitrogen atom, and X is an optionally hydroxyl and / or C _M alkyl-substituted phenylene ring or an optionally hydroxy-substituted C _M alkylene group is used as activators for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfecting solutions.

3. Use of complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper with the ligands according to formula I or II for the bleaching of color stains when washing textiles.

4. Use of complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper with the ligands according to formula I or formula II in cleaning solutions for hard surfaces, in particular for dishes, for bleaching stained stains.

5. Use according to one of claims 1 to 4, characterized in that the transition metal in the bleaching catalyst complex is iron and / or manganese.

6. Use according to one of claims 1 to 5, characterized in that the transition metal is in the oxidation state +2, +3 or +4.

7. Use according to one of claims 1 to 6, characterized in that in the unit R-B of the compounds of formula I R is a direct bond when B is hydrogen and is not a direct bond when B is a hydroxyl group.

8. Use according to one of claims 1 to 7, characterized in that the nitrogen-containing ring system A in the compounds according to formulas I and II, the 2-pyridyl group, the 2-imidazolyl group, the l-methyl-2-imidazolyl group or the 2- Is benzimidazolyl group.

9. Use according to one of claims 1 to 8, characterized in that R in the compounds of formulas I or II is a methylene group.

10. Use according to one of claims 1 to 9, characterized in that X in the compounds of formula II under the 1,3-phenylene group, the 2-hydroxy-1,3-phenylene group, the 2-hydroxy-5-methyl- 1, 3-phenylene group and the hydroxymethylene group is selected.

11. Use according to one of claims 1 to 10, characterized in that in the alkylene groups R of the compounds of formula I or formula II one or more of the non-adjacent CH ₂ units not directly bound to the central N atom by NH- Units is (are) replaced.

12. Use according to one of claims 1 to 11, characterized in that the transition metal complexes, in addition to the ligands according to the general formulas I and II, also carry further ligands, in particular mono- or polyvalent anion ligands.

13. Use according to one of claims 1 to 12, characterized in that the peroxygen compound to be activated is selected from the group comprising organic peracids, hydrogen peroxide, perborate and percarbonate and mixtures thereof.

14. Detergent, cleaning agent or disinfectant, characterized in that it contains 0.0025% by weight to 0.25% by weight, in particular 0.01% by weight to 0.1% by weight, of a bleaching catalyst Form of complexes of the transition metals manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and / or copper, which have one or more of the ligands of the general formula I or II, in addition to conventional ingredients which are compatible with the bleaching catalyst.

15. Composition according to claim 14, characterized in that it is 5 to 50 wt .-%, in particular 8 to 30 wt .-% anionic and / or nonionic surfactant, up to 60 wt .-%, in particular 5 to 40 wt % Builder substance, up to 5% by weight, in particular 0.2 to 3% by weight, enzyme, up to 30% by weight, in particular 6 to 20% by weight, organic solvent from the group comprising alcohols with 1 to 4 carbon atoms, diols with 2 to 4 carbon atoms and their mixtures and the ethers derivable from these classes of compounds and up to 20% by weight, in particular 1.2-17% by weight pH regulator contains.

16. Means for machine cleaning of dishes, containing 15% by weight to 65% by weight, in particular 20% by weight to 55% by weight of water-soluble builder component and 5% by weight to 25% by weight, in particular 8% by weight to 17% by weight of an oxygen-based bleach, characterized in that it contains a bleach-catalysing transition metal complex with the ligand of the formula I or formula II, in particular in amounts of 0.005% by weight to 0.1% by weight. -%, contains.

17. Composition according to claim 16, characterized in that it contains 0.1 wt .-% to 20 wt .-%, in particular 0.2 wt .-% to 10 wt .-% surfactants.

18. Composition according to claim 16 or 17, characterized in that it contains 20% by weight to 60% by weight of water-soluble organic builder, in particular alkali citrate, 3% by weight to 20% by weight of alkali carbonate and 5% by weight contains up to 40 wt .-% alkali disilicate.

19. Composition according to one of claims 14 to 18, characterized in that it in addition to the components mentioned up to 50 wt .-%, in particular from 5 wt .-% to 30 wt .-% peroxygen compound selected from the group comprising organic peracids or peracidic salts of organic acids, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the cleaning conditions, such as perborate, percarbonate and / or persilicate, and mixtures thereof.

20. Composition according to one of claims 14 to 19, characterized in that it contains 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight, of compound releasing peroxocarboxylic acid under conditions of perhydrolysis.

21. Composition according to Anspmch 20, characterized in that the weight ratio of the compound which releases peroxocarboxylic acid under perhydrolysis conditions to the transition metal complex compound is in the range from 8000: 1 to 1: 1, in particular from 1000: 1 to 10: 1.