EP0968270A1 - Systemes contenant des complexes de metaux de transition comme activateurs pour les composes peroxyde - Google Patents

Systemes contenant des complexes de metaux de transition comme activateurs pour les composes peroxyde

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Publication number
EP0968270A1
EP0968270A1 EP97908290A EP97908290A EP0968270A1 EP 0968270 A1 EP0968270 A1 EP 0968270A1 EP 97908290 A EP97908290 A EP 97908290A EP 97908290 A EP97908290 A EP 97908290A EP 0968270 A1 EP0968270 A1 EP 0968270A1
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EP
European Patent Office
Prior art keywords
weight
transition metal
metal complex
compounds
compound
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.)
Withdrawn
Application number
EP97908290A
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German (de)
English (en)
Inventor
Horst-Dieter Speckmann
Helmut Blum
Karlheinz Hill
Bernd Mayer
Christian Nitsch
Ulrich Pegelow
Hans-Jürgen Riebe
Andreas Wilde
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0968270A1 publication Critical patent/EP0968270A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to the use of bleach activator / bleach catalyst systems composed of substances providing peroxocarboxylic acid under perhydrolysis conditions and certain complex compounds of transition metals for activating peroxygen compounds, in particular for bleaching color stains when washing textiles, as well as detergents, cleaners and disinfectants which contain such bleach activator / bleach catalyst systems.
  • 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 adding so-called bleach activators, which are able to deliver peroxocarboxylic acids under the perhydrolysis conditions mentioned and for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic acid anhydoyl esters, especially phthaloyl anoxides, especially phthaloyl ananoic acid, especially phthaloyl ananoids, especially phthaloyl ananoic acid, benzenesulfonate, sodium is
  • European patent application EP 272 030 describes cobalt (III) complexes with ammonia ligands, which may also have any further one, two, three and / or tidentate ligands, as activators for H 2 O 2 .
  • European patent application EP 630 964 certain manganese complexes are known which have no pronounced effect with regard to a bleaching enhancement of peroxygen compounds and which do not discolor dyed textile fibers, but which can cause bleaching of dirt or dye which is detached from the fiber and which is detached from the fiber.
  • German patent application DE 44 16 438 discloses manganese, copper and cobalt complexes which can carry ligands from a large number of groups of substances and are to be used as bleaching and oxidation catalysts.
  • the combination of conventional bleach activators which result in peroxocarboxylic acids under perhydrolysis conditions and transition metal bleach catalysts has also been proposed, for example in international patent application WO 95/27775.
  • the present invention also aims to improve the oxidation and bleaching effect of inorganic peroxygen compounds at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 ° C. to 45 ° C.
  • the invention relates to the use of a system of peroxocarboxylic acid-providing compound and transition metal complex compounds under perhydrolysis conditions, which electrochemically in 1 millimolar aqueous solution in the potential range from 0.8 V to 1.4 V, in each case based on the standard hydrogen electrode maximum current densities of at least 5 mA / cm are oxidizable, as an activator for in particular inorganic peroxygen compounds in oxidation, washing. Cleaning or disinfection solutions.
  • the electrochemical measurements for determining the current density maximum in the specified potential range can be carried out in a known manner using a standard electrochemical measuring cell with the aid of a three-electrode arrangement consisting of a measuring electrode, preferably made of gold, a counter electrode, preferably also made of gold, and a customary reference electrode , at 25 ° C in approximately 1 mmolar solution of the transition metal compound to be investigated in approximately 0.1 molar conductive salt solution.
  • the system consisting of the substance providing peroxocarboxylic acid under perhydrolysis conditions and the special transition metal complexes is preferably used for bleaching • color stains when washing textiles, in particular in an aqueous, surfactant-containing liquor.
  • the formulation "bleaching of color stains” is to be understood in its broadest meaning and includes both the bleaching of dirt on the textile and the bleaching of in the wash liquor existing dirt detached from the textile as well as the oxidative destruction of textile dyes in the wash liquor, which detach from textiles under the washing conditions before they can be drawn onto differently colored textiles.
  • Another preferred application form according to the invention is the use of the system consisting of peroxocarboxylic acid-providing substance under perhydrolysis conditions and the special transition metal complexes in cleaning solutions for hard surfaces, in particular for dishes, for bleaching colored stains.
  • bleaching is understood to mean both the bleaching of dirt located on the hard surface, in particular tea, and the bleaching of dirt located in the dishwashing liquor and detached from the hard surface.
  • Further objects of the invention are detergents, cleaning agents and disinfectants which contain the above-mentioned system and a method for activating peroxygen compounds using such a system.
  • the system consisting of the substance providing peroxocarboxylic acid under perhydrolysis conditions and the special transition metal complexes in the sense of an activator can be used wherever there is a particular increase in the oxidation effect of the peroxygen compounds at low temperatures arrives, for example in the bleaching of textiles or hair, in the oxidation of organic or inorganic intermediates and in disinfection.
  • Another object of the invention is a method for the selection of transition metal complex compounds suitable for use in bleach-boosting systems which contain peroxocarboxylic acid-providing compound under perhydrolysis conditions. This is characterized in that a 1 millimolar aqueous solution of the transition metal complex compound is prepared, this is examined electrochemically in the potential range from 0.8 V to 1.4 V and selected such transition metal complex compounds which can be oxidized with maximum current densities of at least 5 mA / cm " are.
  • transition metal complexes which are suitable according to the invention and which are electrochemical in 1 millimolar aqueous solution in the potential range from 0.8 V to 1.4 V with maximum current densities of at least 5 mA / cm, preferably at least 10 mA / cm 'and in particular in the range from 12 mA / cm to 25 mA / cm are oxidizable, must have a corresponding minimum solubility in water and are preferably among the cobalt, iron, copper, manganese and ruthenium complexes, in particular among the complex compounds of trivalent cobalt. selected.
  • Suitable ligands in the transition metal complexes which can be used according to the invention are customary substances of both inorganic and organic nature which do not negatively influence the oxidizability which is essential to the invention.
  • the organic ligands include, in particular, compounds having primary, secondary and / or tertiary amine and / or alcohol functions.
  • the inorganic neutral ligands include, in particular, ammonia and water.
  • the Co (III) complexes in particular, in which the central atom is normally present with the coordination number 6, the presence of at least 1 arnmoniac ligand is preferred.
  • a complex to be used in the system according to the invention contains further, preferably anionic and, in particular, monodentate ligands.
  • anionic and, in particular, monodentate ligands include in particular the halides, preferably chloride, and the (NO 2 ) " group.
  • a (NO 2 ) " group is understood to mean a nitro ligand which is bonded to the transition metal via the nitrogen atom or a nitrito ligand which is bonded to the transition metal via an oxygen atom (NO 2 ) ⁇ group can also chelate on a transition metal M.
  • the transition metal complexes to be used in the activator system according to the invention can also carry other ligands of generally simple structure, in particular mono- or polyvalent anion ligands.
  • examples include hydroxide, nitrate, acetate, formate, citrate, perchlorate and the halides such as fluoride, chloride, bromide and iodide as well as complex anions such as hexafluorophosphate.
  • the anion ligands are supposed to balance the charge between the transition metal central atom and the ligand system.
  • oxo ligands peroxo ligands and imino ligands
  • Such ligands can also act as bridges, so that multinuclear complexes are formed. These preferably contain at least 1 ammonia ligand and / or at least 1 (NO 2 ) " group per transition metal atom.
  • the two metal atoms in the complex do not have to be the same.
  • Gear metal complex compounds present anionic counterions that neutralize the cationic transition metal complex.
  • anionic counterions include, in particular, nitrate, hydroxide, hexafluorophosphate. Sulphate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate or citrate.
  • the preferred transition metal complex compounds in the systems to be used according to the invention include nitropentammine-cobalt (III) chloride, nitritopentammine-cobalt (III) chloride, nitrate-pentarnine-cobalt (III) chloride, tetrammine-carbonato-cobalt (III) chloride , Tetrammin-carbonato-cobalt (III) bicarbonate, Tetrammin-carbonate-cobalt (III) nitrate, Hexammincobalt (III) chloride and Chloropentammin-cobalt (III) chloride and the peroxo complex [(NH 3 ) 5 Co-OO-Co (NH 3 ) 5 ] Cl 4 .
  • the second component of the system to be used according to the invention consists of a substance which delivers a peroxocarboxylic acid.
  • These include the usual bleach activators cited at the beginning. These are preferably compounds which are capable of splitting off peroxocarboxylic acids having 1 to 18, in particular 2 to 12, carbon atoms during the perhydrolysis. Compounds which split off peroxocarboxylic acids are preferably obtained from the compounds of the formula (I),
  • R l for an aryl, alkyl.
  • R phenyl, C r to C M alkyl, 9-decenyl and mixtures thereof are preferred, it being possible for the alkyl radicals to be linear or branched-chain.
  • the compounds of formula (I) with linear alkyl radicals those having 1 to 9 carbon atoms are particularly preferred.
  • the compounds of the formula (I) to be used according to the invention in combination with transition metal complexes can be obtained by O- or N-acylation with reactive R -CO derivatives.
  • the corresponding unsubstituted compounds H n X can be prepared by known processes.
  • Preferred nitrogen-containing leaving groups X are those in which the nitrogen bears at least one further acyl group in addition to the acyl group R'-CO- to be split off.
  • Examples of such compounds according to formula (I) are the triacylation products of ammonia and the diacylation products of primary amino groups, such as those of ethylenediamine.
  • the at least one other acyl group mentioned is also not an acyl radical R 1 - CO-, it is preferred if it has such a graded perhydrolysis activity that under the conditions of use essentially only the corresponding group R -CO- Peroxocarboxylic acid forms.
  • This can be achieved in that in the compound of the formula (I) the nitrogen carrying the R'-CO group is also part of a cyclic amide or imide structure.
  • the latter compounds can be referred to as acylamides or acylimides, the name part "acyl” referring to the group R'-CO-.
  • the amide part of such acylamides preferably consists of an optionally substituted capro or valerolactam group and the imide part of such acylimides preferably consists of a succinimide, maleimide or phthalimide group, which groups optionally contain C 1 -C 4 -alkyl, hydroxyl- , COOH and / or SO 3 H substituents, where the latter substituent groups can also be present in the form of their salts.
  • acylimides N-nonanoyl and N-isononanoyl succinimide is particularly preferred.
  • Suitable compounds are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU).
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetylglycoluril
  • acylated triazine derivatives in particular l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine (DADHT), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, acylated phenol sulfonates, especially nonanoyl or isononanoyl oxybenzenesulfonic, and acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose.
  • PAG pentaacetyl glucose
  • PAG pentaacetyl fructose
  • Tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone.
  • Perhydrolysis conditions give optionally substituted perbenzoic acid and / or peroxocarboxylic acids with 1 to 5 carbon atoms, in particular 2 to 4 carbon atoms, with those which, under perhydrolysis conditions, give linear or branched chain peroxocarboxylic acids with 6 to 18 carbon atoms, in particular 7 to 12 carbon atoms Atoms result, are used in a preferred embodiment of the invention.
  • the corresponding peroxocarboxylic acid can also be used directly.
  • the weight ratio of peroxocarboxylic acid-releasing substance to transition metal is preferably in the range from 100,000: 1 to 1: 1. in particular from 50,000: 1 to 25: 1.
  • the use according to the invention essentially consists in creating conditions under which the peroxygen compound and the activating system according to the invention can react with one another with the aim of obtaining secondary products which have a more oxidizing effect.
  • Such conditions exist in particular when the reactants meet in aqueous solution.
  • This can be done by adding the peroxygen compound and the activating system or both components of the activating system separately in separate form to a detergent or cleaning agent solution, if appropriate.
  • the method according to the invention is particularly advantageously carried out using a washing, cleaning or disinfectant according to the invention which contains the activating system and, if appropriate, a peroxidic oxidizing agent.
  • the peroxygen compound can also be added separately, in bulk or as a preferably aqueous solution or suspension, to the washing, cleaning or disinfecting solution 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 between 10 ppm in the solutions and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen.
  • the amount of activating system used also depends on the application. Depending on the desired degree of activation, so much of the system to be used according to the invention is used that 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.002 mol, of transition metal per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen short of become.
  • a washing, cleaning or disinfecting agent according to the invention preferably contains such an amount of activating system to be used according to the invention that 0.0025% by weight to 0.25% by weight, in particular 0.01% by weight to 0 , 1% by weight of the transition metal complex compound is contained in addition to conventional ingredients which are compatible with the activating system.
  • the activating system or its components to be used according to the invention can or can be adsorbed onto carrier substances and / or embedded in enveloping 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 compacted particle form, as homogeneous solutions or suspensions, can, in addition to the system to be used according to the invention, in principle all known ingredients customary in such agents contain.
  • the detergents and cleaning agents according to the invention can in particular builder substances, surface-active surfactants, organic and / or in particular inorganic peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, Foam regulators, additional peroxygen activators, dyes and fragrances contain.
  • a disinfectant according to the invention can contain customary antimicrobial active substances in addition to the previously mentioned ingredients in order to enhance the disinfectant action against special germs.
  • Such antimicrobial The disinfectants according to the invention preferably contain additives in amounts of up to 10% by weight, in particular from 0.1% by weight to 5% by weight.
  • transition metal bleach catalysts which can be oxidized in the potential range mentioned with the high current densities required according to the invention
  • customary transition metal complexes known as bleach activators can be used.
  • 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, can also be used.
  • 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 useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the surfactants of the sulfonate type that can be used include linear alkylbenzenesulfonates 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 involved in the reaction of corresponding monoolefins Sulfur trioxide and alpha Sulfofatty acid esters which are formed 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. contain, while the disinfectants according to the invention as well as agents according to the invention for cleaning dishes are preferably 0.1% by weight to 20% by weight. in particular 0.2 wt .-% to 5 wt .-% 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 washing or 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 washing or cleaning conditions, such as perborate, percarbonate and / or persilicate .
  • solid peroxygen 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 which, in principle, can contain all the usual
  • 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, while in the disinfectants according to the invention preferably 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, and also polyaspartic acid, polyphosphonic acids, especially aminotris (methylenephosphonic acid).
  • polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids.
  • polycarboxylates of international patent application WO 93/161 10 which are accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 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 ethers, vinyl esters, 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 an esterified vinyl alcohol or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which are preferably acrolein and acrylic acid / acrylic acid as monomers. have salts or vinyl acetate.
  • the organic builder substances can be used, in particular for the production of liquid agents, 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 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing agents according to the invention.
  • Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate.
  • 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 detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X are preferred. Amounts close to the above upper limit 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.
  • 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 aluminosilicate 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.
  • Loading 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.
  • Crystalline phyllosilicates of the general formula are preferably crystalline silicates, which may be present alone or in a mixture with amorphous silicates y H 2 O used, in the x. the so-called module, a number from 1.9 to 4 and y a number from 0 to 20 and preferred values for x 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.
  • 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 0 436 835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of agents according to the invention.
  • alkali aluminum silicate in particular zeolite
  • the weight ratio of aluminum silicate to silicate, based in each case 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. on heavy metal complexing substances, preferably from the group comprising amino polycarboxylic acids. Aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.
  • 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 their mixtures in question. 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.
  • the optionally used enzymes can, as described for example in international patent applications WO 92/1 1347 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 washing, cleaning and disinfecting agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.2% by weight to 2% by weight.
  • the organic solvents which can be used in the agents according to the invention include alcohols having 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 in the washing, Detergents and disinfectants preferably 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.
  • 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 density 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. -Ift-
  • the oxidizability of various transition metal complex compounds was measured in a standard electrochemical measuring cell at a temperature of 25 ° C. while introducing a stream of nitrogen.
  • a three-electrode arrangement consisting of a measuring electrode made of gold, a counter electrode made of gold and a conventional reference electrode was used.
  • the test solution contained 1 mmol / 1 of the complex compound to be examined and 0.1 mol / 1 sodium borate as the conductive salt.
  • the potential of the measuring electrode was varied in a range from 0.6 V to 1.4 V, based on the standard hydrogen electrode, at a speed of 20 mV / s. Has been tested
  • Nitritopentamine cobalt (III) chloride (B1) in addition to the complex compound known from German patent application 196 05 688.8 [Mn 2 (tpa) 2 (OAc) 2 ] (OAc) 2 (VI). In the range from 0.8 V to 1.4 V, the maximum current densities specified in Table 1 below occurred.
  • Test tissue determined photometrically.
  • an agent W2 which contained 3% by weight of TAED and 97% by weight of WI
  • an agent according to the invention, Ml in the same dosage 3% by weight of TAED and 97% by weight of W3, an agent W4 which contained WI and 50 ppm (parts by weight, based on Mn) VI, and an agent W5 which contained 3% by weight of TAED and 97% by weight.
  • % W4 contained, tested under the same conditions.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

On utilise des complexes contenant des métaux de transition, qui peuvent être électrochimiquement oxydés dans une solution aqueuse 1 millimolaire à l'intérieur d'une plage de potentiels comprise entre 0,8 et 1,4 V, avec des densités de courant maximales d'au moins 5 mA/cm2, combinés à des composés libérant de l'acide peroxocarboxylique dans des conditions de perhydrolyse, comme activateurs pour les composés peroxyde dans des solutions oxydantes, lavantes, détergentes et désinfectantes. Ces solutions contiennent de préférence 0,0025 à 0,25 % en poids de ces complexes de métaux de transition.
EP97908290A 1996-04-01 1997-03-24 Systemes contenant des complexes de metaux de transition comme activateurs pour les composes peroxyde Withdrawn EP0968270A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1996113103 DE19613103A1 (de) 1996-04-01 1996-04-01 Übergangsmetallkomplex-haltige Systeme als Aktivatoren für Persauerstoffverbindungen
DE19613103 1996-04-01
PCT/EP1997/001481 WO1997036987A1 (fr) 1996-04-01 1997-03-24 Systemes contenant des complexes de metaux de transition comme activateurs pour les composes peroxyde

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EP0968270A1 true EP0968270A1 (fr) 2000-01-05

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JP (1) JP2000507627A (fr)
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WO (1) WO1997036987A1 (fr)

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JP2000507627A (ja) 2000-06-20
WO1997036987A1 (fr) 1997-10-09

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