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

Transition-metal complexes used as activators for peroxy compounds

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Publication number
EP0880579A2
EP0880579A2 EP97904389A EP97904389A EP0880579A2 EP 0880579 A2 EP0880579 A2 EP 0880579A2 EP 97904389 A EP97904389 A EP 97904389A EP 97904389 A EP97904389 A EP 97904389A EP 0880579 A2 EP0880579 A2 EP 0880579A2
Authority
EP
European Patent Office
Prior art keywords
weight
group
ligands
formula
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP97904389A
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German (de)
French (fr)
Inventor
Helmut Blum
Bernd Mayer
Ulrich Pegelow
Horst-Dieter Speckmann
Bernt Krebs
Mark Duda
Cetin Nazikkol
Jörg REIM
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0880579A2 publication Critical patent/EP0880579A2/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3932Inorganic compounds or complexes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005Compounds without a metal-carbon linkage
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02Iron compounds
    • C07F15/025Iron compounds without a metal-carbon linkage
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82Metals of the platinum group
    • B01J2531/821Ruthenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/842Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/845Cobalt

Definitions

  • Transition metal complexes as activators for peroxygen compounds are 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.
  • 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.
  • bleach activators for which numerous
  • 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.
  • application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years.
  • 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.
  • 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 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
  • B is hydrogen, an OH group or A, as Activators for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfection solutions.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • ligands generally of a simpler structure, in particular neutral or mono- or polyvalent anion ligands.
  • 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.
  • 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.
  • common anions such as sulfate, hydrogen sulfate, methosulfate, ethosulfate and the anions mentioned above under the anion ligands, as counterions.
  • 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,
  • the preferred ligands according to general formula II include 2,6-bis (bis- (2-benzimidazolylmethyl) 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.
  • 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.
  • 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.
  • 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.
  • 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, tetraacet
  • 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.
  • 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 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.
  • 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.
  • solid per compounds 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
  • 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.
  • 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 copo
  • 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.
  • 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.
  • 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.
  • 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.
  • alkali metal phosphates which can be in the form of their alkaline neutral or acidic sodium or potassium salts.
  • alkali metal phosphates examples include 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.
  • 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.
  • 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 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • 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.
  • crystalline silicates which may be present alone or in a mixture with amorphous silicates
  • 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.
  • both ⁇ - and ⁇ -sodium disilicate are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in the international patent application WO 91/08171 is.
  • ⁇ -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.
  • 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 are in a further preferred embodiment agents according to the invention used.
  • 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.
  • 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.
  • 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.
  • 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 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®.
  • 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.
  • 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.
  • 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 or alkali borates
  • boric acid-carboxylic acid combinations as known, for example, from European patent application EP 451 921
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • Example 1 Preparation of a Mn bleaching catalyst to be used according to the invention 1.A: Synthesis of Tris-f2-pyridylmethvlVamin ftpa)
  • 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.
  • 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).

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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

Ühergangsmetallkomple-ce als Aktivatoren für Persauerstoffverbindungen Transition metal complexes as activators for peroxygen compounds
Die vorliegende Erfindung betrifft die Verwendung bestimmter Komplexe von Über¬ gangsmetallen mit stickstoffhaltigen polydentalen Liganden als Aktivatoren beziehungsweise Katalysatoren für Persauerstoffverbindungen, insbesondere zum Bleichen von Farbanschmutzungen beim Waschen von Textilien und Reinigen harter Oberflächen, beispielsweise von Geschirr, sowie Wasch-, Reinigungs- und Desinfektions¬ mittel, die derartige Aktivatoren beziehungsweise Katalysatoren enthalten.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.
Anorganische Persauerstoffverbindungen, insbesondere Wasserstoffperoxid und feste Per¬ sauerstoffverbindungen, die sich in Wasser unter Freisetzung von Wasserstoffperoxid lö¬ sen, wie Natriumperborat und Natriumcarbonat-Perhydrat, werden seit langem als Oxida¬ tionsmittel zu Desinfektions- und Bleichzwecken verwendet. Die Oxidationswirkung die¬ ser Substanzen hängt in verdünnten Lösungen stark von der Temperatur ab; so erzielt man beispielsweise mit H2O2 oder Perborat in alkalischen Bleichflotten erst bei Temperaturen oberhalb von etwa 80 °C eine ausreichend schnelle Bleiche verschmutzter Textilien. Bei niedrigeren Temperaturen kann die Oxidationswirkung der anorganischen Persauerstoff¬ verbindungen durch Zusatz sogenannter Bleichaktivatoren verbessert werden, für die zahlreiche Vorschläge, vor allem aus den Stoffklassen der N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendi- amin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Hydrotriazine, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbon¬ säureester, insbesondere Natrium-nonanoyloxy-benzolsulfonat, Natrium-isononanoyloxy- benzolsulfonat und acylierte Zuckerderivate, wie Pentaacetylglukose, in der Literatur bekannt geworden sind. Durch Zusatz dieser Substanzen kann die Bleichwirkung wäßri¬ ger Peroxidflotten so weit gesteigert werden, daß bereits bei Temperaturen um 60 °C im wesentlichen die gleichen Wirkungen wie mit der Peroxidflotte allein bei 95 °C eintreten. Im Bemühen um energiesparende Wasch- und Bleichverfahren gewinnen in den letzten Jahren Anwendungstemperaturen deutlich unterhalb 60 °C, insbesondere unterhalb 45 °C bis herunter zur Kaltwassertemperatur an Bedeutung.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.
Bei diesen niedrigen Temperaturen läßt die Wirkung der bisher bekannten Aktivatorver¬ bindungen in der Regel erkennbar nach. Es hat deshalb nicht an Bestrebungen gefehlt, für diesen Temperaturbereich wirksamere Aktivatoren zu entwickeln, ohne daß bis heute ein überzeugender Erfolg zu verzeichnen gewesen wäre. Ein Ansatzpunkt dazu ergibt sich durch den Einsatz von Übergangsmetallsalzen und -komplexen, wie zum Beispiel in den europäischen Patentanmeldungen EP 392 592, EP 443 651, EP 458 397, EP 544490 oder EP 549271 vorgeschlagen, als sogenannte Bleichkatalysatoren. Bei diesen besteht, ver¬ mutlich wegen der hohen Reaktivität der aus ihnen und der Persauerstoffverbindung ent¬ stehenden oxidierenden Intermediate, die Gefahr der Farbveränderung gefärbter Textilien und im Extremfall der oxidativen Textilschädigung. Aus der europäischen Patentanmel¬ dung EP 630964 sind bestimmte Mangankomplexe bekannt, welche keinen ausgeprägten Effekt hinsichtlich einer Bleichverstärkung von Persauerstoffverbindungen haben und ge¬ färbte Textilfasern nicht entfärben, aber die Bleiche von in Waschlaugen befindlichem, von der Faser abgelöstem Schmutz oder Farbstoff bewirken können. Aus der deutschen Patentanmeldung DE 44 16438 sind Mangan-, Kupfer- und Kobalt-Komplexe bekannt, welche Liganden aus einer Vielzahl von Stoffgruppen tragen können und als Bleich- und Oxidationskatalysatoren verwendet werden sollen.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.
Die vorliegende Erfindung hat die Verbesserung der Oxidations- und Bleichwirkung an¬ organischer Persauerstoffverbindungen bei niedrigen Temperaturen unterhalb von 80 °C, insbesondere im Temperaturbereich von ca. 15 °C bis 55 °C, zum Ziel.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.
Es wurde nun gefunden, daß Übergangsmetallkomplexe, die als Liganden bestimmte stickstoffhaltige Verbindungen mit Tripodstruktur aufweisen, eine deutliche bleichkataly¬ sierende Wirkung haben. Gegenstand der Erfindung ist die Verwendung von Komplexen der Ubergangsmetalle Mangan, Eisen, Cobalt, Ruthenium, Molybdän, Titan, Vanadium und/oder Kupfer, die einen oder mehrere der Liganden der allgemeinen Formel I besitzen,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 (DR '. N - R (D
I RI R
A I BA I B
AA
in denen R eine direkte Bindung oder eine gegebenenfalls aminogruppen-substituierte Alkylengruppe mit 1 bis 4 C-Atomen ist, A für ein kondensiertes oder nichtkondensiertes Ringsystem steht, welches mindestens ein Stickstoffatom enthält, und B Wasserstoff, eine OH-Gruppe oder A ist, als Aktivatoren für insbesondere anorganische Persauerstoffver¬ bindungen in Oxidations-, Wasch-, Reinigungs- oder Desinfektionslösungen. In den Al- kylengruppen R können eine oder mehrere nicht benachbarte CH2-Einheiten, die nicht direkt an das zentrale N-Atom gebunden sind, gegebenenfalls durch NH-Einheiten ersetzt sein.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.
Verbindungen der allgemeinen Formel I können durch formale verknüpfende Modi¬ fikation ihrer B-Einheiten zu Liganden der allgemeinen Formel II umgewandelt werden,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 denen A und R die oben gegebene Bedeutung haben und X ein gegebenenfalls hy¬ droxy- und/oder CM-alkylsubstiuierter Phenylenring oder eine gegebenenfalls hydroxy¬ substituierte CM- Alkylengruppe ist, und die in der Lage sein können, jeweils zwei Über¬ gangsmetallatome komplex zu binden. Ein weiterer Gegenstand der Erfindung ist daher die Verwendung von gegebenenfalls zwei- oder mehrkernigen Komplexen der Uber¬ gangsmetalle Mangan, Eisen, Cobalt, Ruthenium, Molybdän, Titan, Vanadium und/oder Kupfer, die einen oder mehrere der Liganden der allgemeinen Formel II aufweisen, als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen in Oxidations-, Wasch-, Reinigungs- oder Desinfektionslösungen.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 dem Teil R-B der Verbindungen gemäß Formel I ist R vorzugsweise eine direkte Bin¬ dung, wenn B Wasserstoff ist, und vorzugsweise keine direkte Bindung, wenn B eine Hy¬ droxylgruppe ist. Es müssen nicht sämtliche Gruppen R in einem Ligandenmolekül iden¬ tisch sein. Zu den bevorzugten stickstoffhaltigen Ringsystemen (A in den Formeln I und II) gehören die 2-Pyridylgruppe, die 2-Imidazolylgruppe, die l-Methyl-2-Imidazolylgrup- pe und die 2-Benzimidazolylgruppe. Es müssen nicht sämtliche Reste A in einem Ligan¬ denmolekül identisch sein. R in den Verbindungen der Formeln I oder II ist vorzugsweise eine Methylengruppe. X in den Verbindungen gemäß Formel II wird vorzugsweise unter der 1,3-Phenylengruppe, der 2-Hydroxy-l,3-Phenylengruppe, der 2-Hydroxy-5-Methyl- 1,3-Phenylengruppe und der Hydroxymethylengruppe ausgewählt.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.
Die als Liganden für die erfindungsgemäß zu verwendenden Bleichkatalysatoren brauch¬ baren Substanzen gemäß den allgemeinen Formeln I oder II können nach im Prinzip be¬ kannten Verfahren, wie zum Beispiel in dem Übersichtsartikel von K. Wieghardt in Angew. Chem. IÜ1 (1989), S. 1179 - 1198 und den dort zitierten Originalarbeiten beschrieben, hergestellt werden. Üblicherweise werden kommerziell verfügbare Rohstoffe über Kondensationsreaktionen, beispielsweise unter Abspaltung von Halogenwasser¬ stoffen, zu den gewünschten Liganden umgesetzt. Diese können anschließend, üblicherweise in gängigen Lösungsmitteln, mit Salzen entsprechender Ubergangsmetalle umgesetzt werden. Die erfindungsgemäß als Bleichkatalysatoren zu verwendenden Komplexe bilden sich in der Regel bereits bei Raumtemperatur und werden normalerweise aus gängigen Lösungsmitteln in kristalliner Form erhalten.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.
Die genannten Ubergangsmetalle in den erfindungsgemäß zu verwendenden Bleichkataly¬ satoren liegen vorzugsweise in den Oxidationsstufen +2, +3 oder +4 vor. Bevorzugt werden Komplexe mit Übergangsmetallzentralatomen in den Oxidationsstufen +3 oder +4 verwendet. Systeme mit gemischten Oxidationszahlen sind möglich. Im Falle mehrkerniger Komplexe müssen nicht alle Metallatome im Komplex gleich sein. Zu den bevorzugt verwendeten Komplexen gehören diejenigen mit Eisen und/oder Mangan als Zentralatomen.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.
Außer den Liganden gemäß den allgemeinen Formeln I und II können die erfindungsge¬ mäß zu verwendenden Übergangsmetallkomplexe noch weitere, in der Regel einfacher aufgebaute Liganden, insbesondere Neutral- oder ein- oder mehrwertige Anionliganden, tragen. In Frage kommen beispielsweise Wasser, Ammoniak, Nitrat, Nitrit, Hydroxid, Carbonat, Hydrogencarbonat, Actetat, Formiat, Citrat, Perchlorat und die Halogenide wie Chlorid, Bromid und lodid sowie komplexe Anionen wie Hexafluorophosphat. Die Anionliganden sollen für den Ladungsausgleich zwischen Übergangsmetall-Zentralatom und dem Ligandensystem sorgen. Falls Anionliganden nicht in ausreichender Anzahl vorhanden sind, um diesen Ladungsausgleich zu bewerkstelligen, können die dann kationisch geladenen Komplexe übliche Anionen, wie Sulfat, Hydrogensulfat, Methosulfat, Ethosulfat und die vorstehend unter den Anionliganden genannten Anionen, als Gegenionen aufweisen. Auch die Anwesenheit von Oxo-Liganden, Peroxo-Liganden und Imino-Liganden ist möglich. Diese zusätzlichen Liganden können auch verbrückend wirken, so daß mehrkernige Komplexe mit mindestens einem Liganden gemäß den allgemeinen Formeln I oder II entstehen.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.
Zu den bevorzugten Bleichkatalysatoren gemäß der Erfindung gehören solche mit dem Tris-(2-pyridylmethyl)amin-Liganden,The preferred bleaching catalysts according to the invention include those with the tris- (2-pyridylmethyl) amine ligand,
mit dem (Bis-((1 -methylimidazol-2-yl)-methyl))-(2-pyridylmethyl)-amin-Liganden, with the (bis - ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine ligand,
^ n o ^ no
mit dem N-Bis-(2-benzimodazolylmethyl)-aminoethanol-Liganden,with the N-bis (2-benzimodazolylmethyl) aminoethanol ligand,
H wH w
und mit dem N,N'-(Bis-(l-methylimidazol-2-yl)-methyl)-ethylendiamin-Liganden,and with the N, N '- (bis- (l-methylimidazol-2-yl) methyl) ethylenediamine ligand,
Zu den bevorzugten Liganden gemäß allgemeiner Formel II gehören 2,6-Bis-(bis-(2-benz- imidazolylmethyl)aminomethyl)-4-methylphenol,The preferred ligands according to general formula II include 2,6-bis (bis- (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol,
N,N,N ' ,N '-Tetrakis-(2-benzimidazolylmethy l)-2-hydroxy- 1 ,3 -diaminopropan,N, N, N ', N' - tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane,
l,3-Bis-(bis-(2-benzimidazolylmethyl)amüιomethyl)-benzol, 1,3-bis (bis- (2-benzimidazolylmethyl) amuomomethyl) benzene,
und 2,6-Bis-(bis-(2-pyridylmethyl)aminomethyl)-4-methylphenol,and 2,6-bis (bis- (2-pyridylmethyl) aminomethyl) -4-methylphenol,
Ein Übergangsmetall-Bleichkatalysator mit den Liganden gemäß Formel I oder Formel II wird vorzugsweise zum Bleichen von Farbanschmutzungen beim Waschen von Textilien, insbesondere in wäßriger, tensidhaltiger Flotte, verwendet. Die Formulierung "Bleichen von Farbanschmutzungen" ist dabei in ihrer weitesten Bedeutung zu verstehen und um¬ faßt sowohl das Bleichen von sich auf dem Textil befindendem Schmutz, das Bleichen von in der Waschflotte befindlichem, vom Textil abgelöstem Schmutz als auch das oxidative Zerstören von sich in der Waschflotte befindenden Textilfarben, die sich unter den Waschbedingungen von Textilien ablösen, bevor sie auf andersfarbige Textilien aufziehen können.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.
Eine weitere bevorzugte Anwendungsform gemäß der Erfindung ist die Verwendung der Übergangsmetall-Bleichkatalysatoren mit den Liganden gemäß Formel I oder Formel II in Reinigungslösungen für harte Oberflächen, insbesondere für Geschirr, zum Bleichen von gefärbten Anschmutzungen, insbesondere Tee. Auch dabei wird unter dem Begriff der Bleiche sowohl das Bleichen von sich auf der harten Oberfläche befindendem Schmutz als auch das Bleichen von in der Geschirrspülflotte befindlichem, von der harten Oberfläche abgelöstem Schmutz verstanden.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.
Weitere Gegenstände der Erfindung sind Wasch-, Reinigungs- und Desinfektionsmittel, die einen obengenannten Übergangsmetall-Bleichkatalysator mit einem Liganden gemäß Formel I oder Formel II enthalten und ein Verfahren zur Aktivierung von Persauerstoff¬ verbindungen unter Einsatz eines derartigen Bleichkatalysators.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.
Bei dem erfindungsgemäßen Verfahren und im Rahmen einer erfindungsgemäßen Ver¬ wendung kann der Bleichkatalysator im Sinne eines Aktivators überall dort eingesetzt werden, wo es auf eine besondere Steigerung der Oxidationswirkung der Persauerstoffver¬ bindungen bei niedrigen Temperaturen ankommt, beispielsweise bei der Bleiche von Textilien oder Haaren, bei der Oxidation organischer oder anorganischer Zwischen¬ produkte und bei der Desinfektion.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.
Die erfindungsgemäße Verwendung besteht im wesentlichen darin, Bedingungen zu schaffen, unter denen die Persauerstoffverbindung und der Bleichkatalysator miteinander reagieren können, mit dem Ziel, stärker oxidierend wirkende Folgeprodukte zu erhalten. Solche Bedingungen liegen insbesondere dann vor, wenn beide Reaktionspartner in wä߬ riger Lösung aufeinandertreffen. Dies kann durch separate Zugabe der Persauerstoffver¬ bindung und des Bleichkatalysators zu einer gegebenenfalls wasch- oder reinigungsmittel- haltigen Lösung geschehen. Besonders vorteilhaft wird das erfindungsgemäße Verfahren jedoch unter Verwendung eines erfindungsgemäßen Wasch-, Reinigungs- oder Desinfek¬ tionsmittels, das den Bleichkatalysator und gegebenenfalls ein peroxidisches Oxidations¬ mittel enthält, durchgeführt. Die Persauerstoffverbindung kann auch separat, in Substanz oder als vorzugsweise wäßrige Lösung oder Suspension, zur Lösung zugegeben werden, wenn ein persauerstofffreies Mittel verwendet wird.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.
Je nach Verwendungszweck können die Bedingungen weit variiert werden. So kommen neben rein wäßrigen Lösungen auch Mischungen aus Wasser und geeigneten organischen Lösungsmitteln als Reaktionsmedium in Frage. Die Einsatzmengen an Persauerstoffver¬ bindungen werden im allgemeinen so gewählt, daß in den Lösungen zwischen 10 ppm und 10 % Aktivsauerstoff, vorzugsweise zwischen 50 und 5000 ppm Aktivsauerstoff vorhanden sind. Auch die verwendete Menge an Bleichkatalysator hängt vom Anwendungszweck ab. Je nach gewünschtem Aktivierungsgrad werden 0,00001 Mol bis 0,025 Mol, vorzugsweise 0,0001 Mol bis 0,002 Mol Aktivator pro Mol Persauerstoffverbindung verwendet, doch können in besonderen Fällen diese Grenzen auch über- oder unterschritten werden.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.
Ein erfindungsgemäßes Wasch-, Reinigungs- oder Desinfektionsmittel enthält vorzugs¬ weise 0,0025 Gew.-% bis 0,25 Gew.-%, insbesondere 0,01 Gew.-% bis 0,1 Gew.-% des Bleichkatalysators mit den Liganden gemäß Formel I oder Formel II neben üblichen, mit dem Bleichkatalysator verträglichen Inhaltsstoffen. Der Bleichkatalysator kann in im Prinzip bekannter Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen ein¬ gebettet sein.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.
Die erfindungsgemäßen Wasch-, Reinigungs- und Desinfektionsmittel, die als insbeson¬ dere pulverförmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können außer dem erfindungsgemäß verwendeten Bleichkatalysator im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhalts¬ stoffe enthalten. Die erfindungsgemäßen Wasch- und Reinigungsmittel können ins¬ besondere Buildersubstanzen, oberflächenaktive Tenside, organische und/oder anorganische Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, En- zyme, Enzymstabilisatoren, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungs- inhibitoren, Schaumregulatoren, zusätzliche Persauerstoff-Aktivatoren, Färb- und Duft¬ stoffe enthalten.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.
Ein erfindungsgemäßes Desinfektionsmittel kann zur Verstärkung der Desin¬ fektionswirkung gegenüber speziellen Keimen zusätzlich zu den bisher genannten Inhaltsstoffen übliche antimikrobielle Wirkstoffe enthalten. Derartige antimikrobielle Zusatzstoffe sind in den erfindungsgemäßen Desinfektionsmitteln vorzugsweise nicht über 10 Gew.-%, besonders bevorzugt von 0,1 Gew.-% bis 5 Gew.-%, enthalten.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.
Ein weiterer Erfindungsgegenstand ist ein Mittel zum maschinellen Reinigen von Geschirr, enthaltend 15 Gew.-% bis 65 Gew.-%, insbesondere 20 Gew.-% bis 55 Gew.-% wasserlösliche Builderkomponente, 5 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis, jeweils bezogen auf das gesamte Mittel, welches einen bleichkatalysierenden Übergangsmetallkomplex mit dem Liganden gemäß Formel l oder Formel II, insbesondere in Mengen von 0,005 Gew.-% bis 0,1 Gew.-%, enthält. Ein derartiges Mittel ist insbesondere niederalkalisch, das heißt dessen 1 -ge¬ wichtsprozentige Lösung weist einen pH- Wert von 8 bis 11,5, vorzugsweise 9 bis 11 auf.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.
Zusätzlich zu den Übergangsmetall-Bleichkatalysatoren können, insbesondere in Kombination mit anorganischen Persauerstoffverbindungen, konventionelle Bleichakti¬ vatoren, das heißt Verbindungen, die unter Perhydrolysebedingungen gegebenenfalls substituierte Perbenzoesäure und/oder aliphatische Peroxocarbonsäuren mit 1 bis 10 C- Atomen, insbesondere 2 bis 4 C-Atomen ergeben, eingesetzt werden. Geeignet sind die eingangs zitierten üblichen Bleichaktivatoren, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendi- amin (TAED), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), acylierte Triazinderivate, insbesondere l,5-Diacetyl-2,4-dioxohexahydro-l,3,5-triazin (DADHT), acylierte Phenolsulfonate, insbesondere Nonanoyl- oder Isononanoyloxyben- zolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldi¬ acetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbit und Mannit, und acy¬ lierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton. Auch die aus der deutschen Patentanmeldung DE 4443 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. In einer bevorzugten Ausführungsform erfindungsgemäßer Mittel sind zusätzlich zu bleichverstärkendem Übergangsmetall-Komplex 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 6 Gew.-% an derartiger unter Perhydrolysebedingungen Per- oxocarbonsäure abspaltender Verbindung anwesend. Das Gewichtsverhältnis von unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung zu Übergangsme¬ tall-Komplexverbindung liegt vorzugsweise im Bereich von 8000:1 bis 1:1, insbesondere von 1000:1 bis 10:1. Auch die Anwesenheit zusätzlicher Übergangsmetallbleichkatalysa- toren, die keine Liganden gemäß Formel I oder II aufweisen, ist gleichfalls möglich.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.
Die erfindungsgemäßen Mittel können ein oder mehrere Tenside enthalten, wobei insbe¬ sondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kom¬ men. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxy- lierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder ver¬ zweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkylaminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkohol¬ derivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomem im Alkylrest brauchbar.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.
Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwefelsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfa- tierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxy- lierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkyl¬ benzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C- Atomen, sowie Olefinsulfonate mit 12 bis 18 C-Atomen, die bei der Umsetzung entsprechender Monoolefine mit Schwefeltrioxid entstehen, sowie alpha- Sulfofettsäureester, die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern ent¬ stehen.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.
Derartige Tenside sind in den erfindungsgemäßen Reinigungs- oder Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten, während die erfindungsgemäßen Desinfektionsmittel wie auch erfindungsgemäße Mittel zur Reinigung von Geschirr vorzugsweise 0,1 Gew.-% bis 20 Gew.-%, insbesondere 0,2 Gew.-% bis 10 Gew.-% Tenside, enthalten.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.
Als geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren be¬ ziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Per- benzoesäure oder Salze der Diperdodecandisäure, Wasserstoffperoxid und unter den Reinigungsbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, in Betracht. Sofern feste Perverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Die Persauerstoffverbindungen können als solche oder in Form diese enthaltender Mittel, die prinzipiell alle üblichen Wasch-, Reinigungs- oder Desinfektionsmittelbestandteile enthalten können, zu der Wasch- beziehungsweise Reinigungslauge zugegeben werden. Besonders bevorzugt wird Alkalipercarbonat, Alkaliperborat-Monohydrat oder Wasserstoffperoxid in Form wäßriger Lösungen, die 3 Gew.-% bis 10 Gew.-% Wasserstoffperoxid enthalten, eingesetzt. Falls ein erfindungsgemäßes Wasch- oder Reinigungsmittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden, während in den erfindungsgemäßen Desinfektionsmitteln vor- zugsweise von 0,5 Gew.-% bis 40 Gew.-%, insbesondere von 5 Gew.-% bis 20 Gew.-%, an Persauerstoffverbindungen enthalten sind.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.
Ein erfindungsgemäßes Mittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasser¬ löslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, ins¬ besondere Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessig- säure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylen- phosphonsäure), Emylendiamintetrakis(methylenphosphonsäure) und 1 -Hydroxy ethan- 1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden zugäng¬ lichen Polycarboxylate der internationalen Patentanmeldung WO 93/16110, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch ge¬ ringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymeri- siert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättiger Car¬ bonsäuren liegt im allgemeinen zwischen 5 000 und 200000, die der Copolymeren zwi¬ schen 2 000 und 200000, vorzugsweise 50000 bis 120000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50 000 bis 100 000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethem, wie Vinylmethylethem, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/ oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8- Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate be¬ vorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von CrC4- Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Polymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders bevorzugt Acrylsäure beziehungsweise Acrylat, und Ma¬ leinsäure beziehungsweise Maleinat sowie 5 Gew.-% bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Ganz besonders bevorzugt sind dabei Polymere, in denen das Gewichtsverhältnis von (Meth)acrylsäure bezie¬ hungsweise (Meth)acrylat zu Maleinsäure beziehungsweise Maleinat zwischen 1:1 und 4:1, vorzugsweise zwischen 2:1 und 3:1 und insbesondere 2:1 und 2,5:1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen. Das zweite saure Monomer beziehungsweise dessen Salz kann auch ein Derivat einer Al- lylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem CrC4- Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol- Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure beziehungsweise (Meth)acrylat, besonders bevorzugt Acrylsäure beziehungsweise Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallylsulfonsäure bzw. Methal- lylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew.-%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide be¬ vorzugt sind. Besonders bevorzugt ist Saccharose. Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in das Polymer eingebaut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Patentschrift DE 42 21 381 und der deutschen Patentanmeldung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000, vorzugs¬ weise zwischen 200 und 50 000 und insbesondere zwischen 3 000 und 10000 auf. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wäßriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.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.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 50 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.- % enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, erfindungsgemäßen Mitteln eingesetzt.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.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkaliphosphate, die in Form ihrer alkalischen neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können, in Betracht. Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, so¬ genanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie die ent¬ sprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumo¬ silikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, bevor¬ zugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teil¬ chenformigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm. Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amoφhen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe brauchbaren Alkalisi¬ likate weisen vorzugsweise ein molares Verhältms von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1:1,1 bis 1:12 auf und können amoφh oder kristallin vorliegen. Be¬ vorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amoφhen Natriumsili¬ kate, mit einem molaren Verhältnis Na2O:SiO2 von 1:2 bis 1:2,8. Solche mit einem molaren Verhältnis Na2O:SiO2 von 1:1,9 bis 1 :2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0 425 427 hergestellt werden. Als kristalline Silikate, die allein oder im Gemisch mit amoφhen Silikaten vorliegen können, werden vorzugs¬ weise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+] y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1 ,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 y H2O) bevorzugt, wobei ß-Natriumdi- silikat beispielsweise nach dem Verfahren erhalten werden kann, das in der interna¬ tionalen Patentanmeldung WO 91/08171 beschrieben ist. δ-Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den japanischen Patentanmeldungen JP 04/238 809 oder JP 04/260 610 hergestellt werden. Auch aus amoφhen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, herstellbar wie in den europäischen Patentanmeldungen EP 0 548 599, EP 0 502 325 und EP 0452 428 beschrieben, können in erfindungsgemaßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natrium- schichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0436 835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0293 753 erhältlich sind, werden in einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel eingesetzt. Falls als zusätzliche Buildersubstanz auch Alkali- alumosilikat, insbesondere Zeolith, vorhanden ist, beträgt das Gewichtsverhältnis Alumo- silikat zu Silikat, jeweils bezogen auf wasserfreie Aktivsubstanzen, vorzugsweise 1 :10 bis 10:1. In Mitteln, die sowohl amoφhe als auch kristalline Alkalisilikate enthalten, beträgt das Gewichtsverhältnis von amoφhem Alkalisilikat zu kristallinem Alkalisilikat vorzugsweise 1 :2 bis 2:1 und insbesondere 1:1 bis 2:1.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.
Buildersubstanzen sind in den erfindungsgemäßen Wasch- oder Reinigungsmitteln vor¬ zugsweise in Mengen bis zu 60 Gew.-%, insbesondere von 5 Gew.-% bis 40 Gew.-%, enthalten, während die erfindungsgemäßen Desinfektionsmittel vorzugsweise frei von den lediglich die Komponenten der Wasserhärte komplexierenden Buildersubstanzen sind und bevorzugt nicht über 20 Gew.-%, insbesondere von 0,1 Gew. -% bis 5 Gew.-%, an schwermetallkomplexierenden Stoffen, vorzugsweise aus der Gruppe umfassend Amino- polycarbonsäuren, Aminopolyphosphonsäuren und Hydroxypolyphosphonsäuren und de¬ ren wasserlösliche Salze sowie deren Gemische, enthalten.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 einer bevorzugten Ausführungsform enthalten erfindungsgemäße maschinelle Reini¬ gungsmittel für Geschirr übliche Alkaliträger wie zum Beispiel Alkalisilikate, Alkalicar- bonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgem zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2/M2O (M = Alkaliatom) von 1 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 40 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Auf den Einsatz der hoch alkalischen Metasilikate als Alkaliträger wird jedoch vorzugs¬ weise ganz verzichtet. Das in derartigen erfindungsgemäßen Mitteln bevorzugt ein¬ gesetzte Alkaliträgersystem ist ein Gemisch aus Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und -hydrogencarbonat, das in einer Menge von bis zu 50 Gew.-%, vorzugsweise 5 Gew.-% bis 40 Gew.-%, enthalten ist. Je nachdem, welcher pH- Wert letztendlich gewünscht wird, variiert das Verhältnis von eingesetztem Carbonat und eingesetztem Hydrogencarbonat. In einer weiteren Ausführungsform erfmdungsgemäßer Mittel zur Reinigung von Geschirr sind in diesen 20 Gew.-% bis 60 Gew.-% wasserlöslicher organischer Builder, insbesondere Alkalicitrat, 3 Gew.-% bis 20 Gew.-% Alkalicarbonat und 5 Gew.-% bis 40 Gew.-% Alkalidisilikat enthalten.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.
Als in den Mitteln verwendbare Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Cutinasen, Amylasen, Pullulanasen, Hemicellulase, Cellulasen, Oxidasen und Peroxidasen sowie deren Gemische in Frage. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes oder Pseudomonas cepacia gewonnene enzymatische Wirkstoffe, beispielsweise Proteasen wie BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase® und/oder Savinase®, Amylasen wie Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® und/oder Purafect® OxAm, Lipasen wie Lipolase®, Lipomax®, Lumafast® und/oder Lipozym®. Die gegebenenfalls verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/11347 oder WO 94/23005 beschrieben, an Trägerstoffen ad¬ sorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Wasch-, Reinigungs- und Desinfektionsmitteln in Mengen von vorzugsweise nicht über 5 Gew.-%, insbesondere von 0,2 Gew.-% bis 3 Gew.-%, enthalten, wobei besonders bevorzugt gegen oxidativen Abbau stabilisierte Enzyme, wie zum Beispiel aus den intemationalen Patentanmeldungen WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 oder WO 95/07350, bekannt, eingesetzt werden.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.
Zu den gegebenenfalls, insbesondere in flüssigen erfindungsgemäßen Mitteln vorhandenen üblichen Enzymstabilisatoren gehören Aminoalkohole, beispielsweise Mono-, Di-, Triethanol- und -propanolamin und deren Mischungen, niedere Carbon¬ säuren, wie beispielsweise aus den europäischen Patentanmeldungen EP 376 705 und EP 378 261 bekannt, Borsäure beziehungsweise Alkaliborate, Borsäure-Carbonsäure- Kombinationen, wie beispielsweise aus der europäischen Patentanmeldung EP 451 921 bekannt, Borsäureester, wie beispielsweise aus der internationalen Patentanmeldung WO 93/11215 oder der europäischen Patentanmeldung EP 511 456 bekannt. Boronsäurederivate, wie beispielsweise aus der europäischen Patentanmeldung EP 583 536 bekannt, Calciumsalze, beispielsweise die aus der europäischen Patentschrift EP 28 865 bekannte Ca-Ameisensäure-Kombination, Magnesiumsalze, wie beispielsweise aus der europäischen Patentanmeldung EP 378 262 bekannt, und/oder schwefelhaltige Re¬ duktionsmittel, wie beispielsweise aus den europäischen Patentanmeldungen EP 080 748 oder EP 080 223 bekannt.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.
Zu den geeigneten Schauminhibitoren gehören langkettige Seifen, insbesondere Behen- seife, Fettsäureamide, Paraffine, Wachse, Mikrokristallinwachse, Organopolysiloxane und deren Gemische, die darüberhinaus mikrofeine, gegebenenfalls silanierte oder anderweitig hydrophobierte Kieselsäure enthalten können. Zum Einsatz in partikelförmigen Mitteln sind derartige Schauminhibitoren vorzugsweise an granuläre, wasserlösliche Trägersub¬ stanzen gebunden, wie beispielsweise in der deutschen Offenlegungsschrift DE 3436 194, den europäischen Patentanmeldungen EP 262 588, EP 301 414, EP 309931 oder der europäischen Patentschrift EP 150 386 beschrieben.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.
Femer kann ein erfindungsgemäßes Waschmittel Vergrauungsinhibitoren enthalten. Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen der Fasern zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasser¬ löslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäu¬ reestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die obengenannten Stärkeprodukte verwenden, zum Beispiel teilhydroly- sierte Stärke. Na-Carboxymethylcellulose, Methylcellulose, Methylhydroxyethylcellulose und deren Gemische werden bevorzugt eingesetzt.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.
Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den erfindungsgemäßen Wasch-, Reinigungs- und Desinfektionsmitteln vorzugsweise nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.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.
Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH- Werts können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfel¬ säure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium¬ oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsge¬ mäßen Mitteln vorzugsweise nicht über 20 Gew.-%, insbesondere von 1,2 Gew.-% bis 17 Gew.-%, enthalten.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.
Obwohl Übergangsmetallkomplexe bekanntermaßen der Korrosion von Silber entgegen¬ wirken können, werden die erfindungsgemäß bleichkatalysierenden Komplexe in der Regel in Mengen eingesetzt, die zu gering sind, um einen Silberkorrosionsschutz bewirken zu können, so daß in erfindungsgemäßen Reinigungsmitteln für Geschirr Sil¬ berkorrosionsinhibitoren noch zusätzlich eingesetzt werden können. Bevorzugte Sil- berkorrosionsschutzmittel sind organische Sulfide wie Cystin und Cystein, zwei- oder dreiwertige Phenole, gegebenenfalls alkyl-, aminoalkyl- oder arylsubstituierte Triazole wie Benzotriazol, Isocyanursäure, Mangan, Eisen, Cobalt, Ruthenium, Molybdän, Titan, Vanadium und/oder Kupfersalze und/oder -komplexe, in denen die genannten Metalle je nach Metall in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.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.
Die Herstellung der erfindungsgemäßen festen Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Persauerstoffverbindung und Bleichkatalysator gegebenenfalls später zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/1 bis 950 g/1, ist ein aus der europäischen Patentschrift EP 486 592 bekanntes, einen Extrusionschritt aufweisendes Verfahren bevorzugt. Erfindungsgemäße Wasch-, Reinigungs- oder Desinfektionsmittel in Form wäßriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt. In einer bevorzugten Ausführung von Mitteln für die insbesondere maschinelle Reinigung von Geschirr sind diese tablettenförmig und können in Anlehnung an die in den europäischen Patentschriften EP 0 579 659 und EP 0 591 282 offenbarten Verfahren hergestellt werden. 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.
BeispfeleBeisfele
Beispiel 1 : Herstellung eines erfindungsgemaß zu verwendenden Mn-Bleichkatalvsators 1.A: Synthese von Tris-f2-pyridylmethvlVamin ftpa)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) 2-Picolylchlorid-hydrochlorid wurden in 13 ml Wasser gelöst und unter Eiskühlung mit 6 ml 5,3 n NaOH versetzt. Die dabei erhaltene rote Suspension wurde auf 0 °C abgekühlt und mit einer Lösung von 1,64 g (15,25 mmol) Picolylamin in 26 ml Dichlormethan versetzt. Die Mischung wurde auf Raumtemperatur erwärmt und im Zeitraum von mehreren Tagen mit weiteren 6 ml 5,3 n NaOH zur Reaktion gebracht. Dabei wurde darauf geachtet, daß der pH- Wert 9,5 nicht überstieg. Anschließend wurde die gesamte Mischung zweimal mit 7 ml 15-prozentiiger NaOH gewaschen und die organische Phase über Natriumsulfat getrocknet. Nach Entfernen des Trockenmittels wurde das Lösemittel abgedampft. Der braune Rückstand wurde mit Ether extrahiert und der erhaltene Feststoff aus Ether umkristallisiert. Es wurden 2,4 g Tris-(2-pyridylmethyl)- amin erhalten.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 4H2O und 2,7 g (20 mmol) Natriumacetat wurden in Methanol gelöst und mit 2,9 g (10 mmol) tpa umgesetzt. Die Lösung wurde 2 h bei Raumtemperatur gerührt und anschließend für 24 h auf 0°C gekühlt. Der gebildete dunkelbraune Feststoff wurde abgetrennt und getrocknet (2,2 g).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).
Beispiel 2: Herstellung eines erfindung.sgemäß zu verwendenden Fe-BleichkatalysatorsExample 2: Preparation of an Fe bleaching catalyst to be used according to the invention
2.A; Synthese von N.N.N,.N,-Tetrakisf2-fl-methvlbenzimidazolynV2-hvdroxy-l-3- diaminopropan fthpn.2.A; Synthesis of NNN , .N , -Tetrakisf2-fl-methvlbenzimidazolynV2-hvdroxy-l-3-diaminopropane fthpn.
1,06 g (9,7 mmol) 1,2-Diaminobenzol wurde mit 0,5 g (1,6 mmol) 2-Hydroxy-l,3- diaminopropantetraessigsäure gut verschmischt und auf 170-180 °C erhitzt. Die Mischung wurde abgekühlt und mit etwa 15 ml 4 n HCl aufgenommen. Es bildete sich ein grauer Niederschlag, der abfiltriert und mit Aceton gewaschen wurde. Der Feststoff wurde in Wasser gelöst und mit verdünntem Ammoniak neutralisiert. Der weiße Niederschlag wurde abgetrennt, aus Aceton umkristallisiert und getrocknet. Es wurden 0,5 g des Diaminopropanderivats erhalten.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: Synthese von [Fe2ftbpo¥OAcY,],'CIOi)1 fB2^2.B: Synthesis of [Fe 2 ftbpo ¥ OAcY,], ' CIO i ) 1 fB2 ^
2,58 g (5 mmol) Fe(CIO4)3 x 9H2O und 2,7 g (20 mmol) Natriumacetat wurden in etwa 50 ml Methanol gelöst und mit 1,53 g (2,5 mmol) tbpo versetzt. Die Lösung wurde 2 h bei Raumtemperatur gerührt und anschließend für 24 h auf 0 °C gekühlt. Der gebildete grün- braune Feststoff wurde abgetrennt und getrocknet (1,6g).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).
Beispiel 3Example 3
In einer Lösung, die 2,5 mg Morin in 99,5 ml vollentsalztem Wassser enthielt, wurden 98 mg Natriumperborat-Monohydrat gelöst. Der pH- Wert wurde auf 9,5 eingestellt und mit Hilfe eines pH-Stat-Gerätes während der gesamten nachfolgenden Meßdauer bei diesem Wert gehalten. Ebenso wurde die Temperatur konstant bei 20 °C gehalten. 0,5 ml einer Lösung, die den zu testenden Bleichkatalysator in einer Konzentration von 50 ppm bezogen auf Ubergangsmetall enthielt, wurden zugesetzt. Über einen Zeitraum von 30 Minuten wurde minütlich die Extinktion E der Lösung bei 400 nm gemessen. In der nachfolgenden Tabelle sind die Werte für die prozentuale Entfärbung D(t), berechnet nach D(t) = [E(t) - E(0)] / E(0) * 100, angegeben.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.
Getestet wurden der gemäß Beispiel 1 hergestellte Mangan-Komplex (Bl) mit dem Tris- (2-Pyridylmethyl)amin-Liganden und der gemäß Beispiel 2 hergestellte Eisen-Komplex (B2) mit dem N,N,N',N'-Tetrakis-(2-(l-methylbenzimidazolyl))-2-hydroxy-l,3- diaminopropan-Liganden im Sinne der Erfindung. Zum Vergleich wurde der herkömm¬ liche Bleichaktivator N,N,N',N'-Tetraacetyl-ethylendiamin (TAED) unter ansonsten gleichen Bedingungen, aber in einer Konzentration von 6 Gew.-%, ebenfalls gestestet (VI).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).
Tabelle 1 : Prozentuale Entfärbung in Abhängigkeit der ZeitTable 1: Decolorization as a function of time
Man erkennt, daß durch die erfindungsgemäße Verwendung (Bl wie auch B2) eine signifikant bessere Bleichwirkung erreicht werden kann als durch den konventionellen Bleichaktivator TAED in wesentlich höherer Konzentration (VI). 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

Patentansprüche claims
1. Verwendung von Komplexen der Ubergangsmetalle Mangan, Eisen, Cobalt, Rutheni¬ um, Molybdän, Titan, Vanadium und/oder Kupfer, die einen oder mehrere der Liganden der allgemeinen Formel I besitzen,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 (DR ^ ~ R (D
A ι B A in denen R eine direkte Bindung oder eine gegebenenfalls aminogmppen-substituierte Alkylengruppe mit 1 bis 4 C-Atomen ist, A für ein kondensiertes oder nichtkonden- siertes Ringsystem steht, welches mindestens ein Stickstoffatom enthält, und B Was¬ serstoff, eine OH-Gruppe oder A ist, als Aktivatoren für Persauerstoffverbindungen in Oxidations-, Wasch-, Reinigungs- oder Desinfektionslösungen.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. Verwendung von Komplexen der Ubergangsmetalle Mangan, Eisen, Cobalt, Rutheni¬ um, Molybdän, Titan, Vanadium und/oder Kupfer, die einen oder mehrere der Ligan¬ den der allgemeinen Formel II aufweisen,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 AA A
VR Y dD VR Y dD
A N X N A ** R' S R' ^ R' V R'ANXNA ** R ' S R' ^ R ' V R'
in denen R eine direkte Bindung oder eine gegebenenfalls aminogruppen-substituierte Alkylengruppe mit 1 bis 4 C-Atomen ist, A für ein kondensiertes oder nichtkonden¬ siertes Ringsystem steht, welches mindestens ein Stickstoffatom enthält, und X ein gegebenenfalls hydroxy- und/oder CM-alkylsubstiuierter Phenylenring oder eine ge¬ gebenenfalls hydroxysubstituierte CM- Alkylengruppe ist als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen in Oxidations-, Wasch-, Reini¬ gungs- oder Desinfektionslösungen.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. Verwendung von Komplexen der Ubergangsmetalle Mangan, Eisen, Cobalt, Rutheni¬ um, Molybdän, Titan, Vanadium und/oder Kupfer mit den Liganden gemäß Formel I oder II zum Bleichen von Farbanschmutzungen beim Waschen von Textilien. 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. Verwendung von Komplexen der Ubergangsmetalle Mangan, Eisen, Cobalt, Rutheni¬ um, Molybdän, Titan, Vanadium und/oder Kupfer mit den Liganden gemäß Formel I oder Formel II in Reinigungslösungen für harte Oberflächen, insbesondere für Ge¬ schirr, zum Bleichen von gefärbten Anschmutzungen.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. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Ubergangsmetall im Bleichkatalysator-Komplex Eisen und/oder Mangan ist.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. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Übergangsmetali in der Oxidationsstufe +2, +3 oder +4 vorliegt.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. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß in der Einheit R-B der Verbindungen gemäß Formel I R eine direkte Bindung ist, wenn B Wasserstoff ist, und keine direkte Bindung ist, wenn B eine Hydroxylgruppe ist.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. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das stickstoffhaltige Ringsystem A in den Verbindungen gemäß den Formeln I und II die 2-Pyridylgruppe, die 2-Imidazolylgruppe, die l-Methyl-2-Imidazolylgmppe oder die 2-Benzimidazolylgruppe ist.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. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß R in den Verbindungen der Formeln I oder II eine Methylengruppe ist.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. Verwendung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß X in den Verbindungen gemäß Formel II unter der 1,3-Phenylengruppe, der 2-Hydroxy- 1,3-Phenylengruppe, der 2-Hydroxy-5 -Methyl- 1, 3 -Phenylengruppe und der Hydroxy- methylengruppe ausgewählt wird.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. Verwendung nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß in den Alkylengruppen R der Verbindungen gemäß Formel I oder Formel II eine oder mehrere der nicht direkt an das zentrale N-Atom gebundenen, nicht benachbarten CH2-Einheiten durch NH-Einheiten ersetzt ist (sind). 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. Verwendung nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die Übergangsmetallkomplexe zusätzlich zu den Liganden gemäß den allgemeinen For¬ meln I und II noch weitere Liganden, insbesondere ein- oder mehrwertige Anionli¬ ganden, tragen.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. Verwendung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die zu aktivierende Persauerstoffverbindung aus der Gruppe umfassend organische Per¬ säuren, Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische aus¬ gewählt wird.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. Wasch-, Reinigungs- oder Desinfektionsmittel, dadurch gekennzeichnet, daß es 0,0025 Gew.-% bis 0,25 Gew.-%, insbesondere 0,01 Gew.-% bis 0,1 Gew.-% eines Bleichkatalysators in Form von Komplexen der Ubergangsmetalle Mangan, Eisen, Cobalt, Ruthenium, Molybdän, Titan, Vanadium und/oder Kupfer, die einen oder mehrere der Liganden der allgemeinen Formel I oder II besitzen, neben üblichen, mit dem Bleichkatalysator verträglichen Inhaltsstoffen enthält.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. Mittel nach Anspruch 14, dadurch gekennzeichnet, daß es 5 bis 50 Gew.-%, insbeson¬ dere 8 bis 30 Gew.-% anionisches und/oder nichtionisches Tensid, bis zu 60 Gew.-%, insbesondere 5 bis 40 Gew.-% Buildersubstanz, bis zu 5 Gew.-%, insbesondere 0,2 bis 3 Gew.-%, Enzym, bis zu 30 Gew.-%, insbesondere 6 bis 20 Gew.-%, organisches Lösungsmittel aus der Gruppe umfassend Alkohole mit 1 bis 4 C-Atomen, Diole mit 2 bis 4 C-Atomen sowie deren Gemische und die aus diesen Verbindungsklassen ab¬ leitbaren Ether und bis zu 20 Gew.-%, insbesondere 1,2 - 17 Gew.-% pH-Regulator enthält.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. Mittel zum maschinellen Reinigen von Geschirr, enthaltend 15 Gew.-% bis 65 Gew.- %, insbesondere 20 Gew.-% bis 55 Gew.-% wasserlösliche Builderkomponente und 5 Gew.-% bis 25 Gew.-%, insbesondere 8 Gew.-% bis 17 Gew.-% Bleichmittel auf Sauerstoffbasis, dadurch gekennzeichnet, daß es einen bleichkatalysierenden Über¬ gangsmetallkomplex mit dem Liganden gemäß Formel I oder Formel II, insbesondere in Mengen von 0,005 Gew.-% bis 0,1 Gew.-%, enthält. 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. Mittel nach Anspruch 16, dadurch gekennzeichnet, daß es 0,1 Gew.-% bis 20 Gew.- %, insbesondere 0,2 Gew.-% bis 10 Gew.-% Tenside enthält.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. Mittel nach Anspruch 16 oder 17, dadurch gekennzeichnet, daß es 20 Gew.-% bis 60 Gew.-% wasserlöslichen organischen Builder, insbesondere Alkalicitrat, 3 Gew.-% bis 20 Gew.-% Alkalicarbonat und 5 Gew.-% bis 40 Gew.-% Alkalidisilikat enthält.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. Mittel nach einem der Ansprüche 14 bis 18, dadurch gekennzeichnet, daß es zusätz¬ lich zu den genannten Bestandteilen bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-% Persauerstoffverbindung, ausgewählt aus der Gruppe umfassend organische Persäuren beziehungsweise persaure Salze organischer Säuren, Wasser¬ stoffperoxid und unter den Reinigungsbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, sowie deren Gemische, enthält.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. Mittel nach einem der Ansprüche 14 bis 19, dadurch gekennzeichnet, daß es 1 Gew.- % bis 10 Gew.-%, insbesondere 2 Gew.-% bis 6 Gew.-% an unter Perhydrolysebe¬ dingungen Peroxocarbonsäure abspaltender Verbindung enthält.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. Mittel nach Anspmch 20, dadurch gekennzeichnet, daß das Gewichtsverhältnis von unter Perhydrolysebedingungen Peroxocarbonsäure abspaltender Verbindung zu Übergangsmetall-Komplexverbindung im Bereich von 8000:1 bis 1:1, insbesondere von 1000:1 bis 10:1 liegt. 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.
EP97904389A 1996-02-16 1997-02-07 Transition-metal complexes used as activators for peroxy compounds Withdrawn EP0880579A2 (en)

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DE19605688A DE19605688A1 (en) 1996-02-16 1996-02-16 Transition metal complexes as activators for peroxygen compounds
PCT/EP1997/000550 WO1997030144A2 (en) 1996-02-16 1997-02-07 Transition-metal complexes used as activators for peroxy compounds

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