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EP0891416A1 - Transition metal ammine complexes as activators for peroxide compounds - Google Patents

Transition metal ammine complexes as activators for peroxide compounds

Info

Publication number
EP0891416A1
EP0891416A1 EP97916381A EP97916381A EP0891416A1 EP 0891416 A1 EP0891416 A1 EP 0891416A1 EP 97916381 A EP97916381 A EP 97916381A EP 97916381 A EP97916381 A EP 97916381A EP 0891416 A1 EP0891416 A1 EP 0891416A1
Authority
EP
European Patent Office
Prior art keywords
weight
transition metal
cobalt
compound
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.)
Withdrawn
Application number
EP97916381A
Other languages
German (de)
French (fr)
Inventor
Helmut Blum
Bernd Mayer
Hans-Jürgen Riebe
Ulrich Pegelow
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
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0891416A1 publication Critical patent/EP0891416A1/en
Withdrawn legal-status Critical Current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 certain oligoammine complexes of transition metals as activators or catalysts for peroxygen compounds, in particular for bleaching color stains when washing textiles, and detergents, cleaning agents and disinfectants which contain such bleach activators or bleach 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, in particular tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins.
  • bleach activators for which numerous suggestions, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins.
  • Hydrazides triazoles, Hydrotriazine, urazols, diketopiperazine, sulfuryl amides and cyanurates, also carboxylic, in particular phthalic anhydride, carboxylic klareester, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxy- benzene sulfonate, and acylated sugar derivatives such as pentaacetylglucose, have been reported 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.
  • 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 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 45 ° C.
  • transition metal complexes which have at least one ammonia molecule as ligand have a clear bleach-catalyzing effect.
  • the invention relates to the use of complex compounds of the general formula I.
  • M is a transition metal selected from cobalt, iron, copper and ruthenium
  • L is a ligand selected from the group comprising water, hydroxide, chlorate, perchlorate, (NO 2 ) ⁇ carbonate, hydrogen carbonate, nitrate, acetate and rhodanide
  • x is a number from 0 to 5
  • A is a salt-forming anion
  • n which can also be 0, is a number such that the compound of the formula (I) has no charge, as activators for in particular inorganic peroxygen compounds in oxidation , Washing, cleaning or disinfection solutions.
  • 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.
  • the (NO 2 ) ⁇ - Group can also chelate on a transition metal M.
  • 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 state +3 are preferably used.
  • the complexes used with preference include those with cobalt as central atoms.
  • the transition metal complexes to be used according to the invention can also carry further, generally simple ligands of an inorganic nature (L in formula I), in particular mono- or polyvalent anion ligands, as long as at least one ammonia molecule is used as the ligand in the complex is included.
  • L in formula I generally simple ligands of an inorganic nature
  • anion ligands for example, nitrate, acetate, rhodanide, chlorate and perchlorate are suitable.
  • the anion ligands are supposed to balance the charge between the transition metal central atom and the ligand system.
  • ligands can also act as bridges, so that multinuclear complexes are formed.
  • These contain at least 1 ammonia ligand and preferably at least 1 (NO 2 ) " group per transition metal atom.
  • both metal atoms in the complex do not have to be the same.
  • anionic counterions are present in the compounds to be used according to the invention, which counteract the cationic complex neutralize.
  • anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride, fluoride, iodide and bromide or the anions of carboxylic acids such as formate, acetate, benzoate or citrate.
  • anionic counterions are present in such a number (n in formula I) in the compounds according to formula I that the sum of the product of their number with their charge and the product of the number of anion ligands (L in formula I) with their charge the amount is exactly as large, but has a negative sign as the charge of the transition metal central atom (M in formula I).
  • L is a bidentate ligand, such as the carbonato ligand.
  • the (NO 2 ) " ligand or the nitrato ligand, which occupies two binding sites of the transition metal central atom in a mononuclear complex is optionally the formula (I) can only give an analogous representation of the structure of the complex.
  • Such complex compounds are those more clearly represented by the general formula (II)
  • L is a ligand bound via one coordination point and L is the ligand bound via two coordination points and y is a number from 0 to 2, with the proviso that x + 2y at most 5 is shown.
  • the preferred bleaching catalysts according to the invention include nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, nitratopentammine cobalt (III) chloride, tetrammine carbonato cobalt (III) chloride, tetrammine carbonato cobalt (III) - hydrogen carbonate and tetrammin-carbonato-cobalt (III) nitrate.
  • Such a transition metal bleaching catalyst is preferably used for the bleaching of color stains when washing textiles, in particular in an aqueous, surfactant-containing liquor.
  • 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 differently colored textiles.
  • Further objects of the invention are detergents, cleaning agents and disinfectants which contain an abovementioned transition metal bleaching catalyst 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. However, the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains the bleaching catalyst 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 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 the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen.
  • the amount of bleach-catalyzing transition metal compound 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 transition metal compound 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 transition metal bleaching catalyst according to formula I. in addition to the usual ingredients which are compatible with the bleaching catalyst.
  • the bleaching catalyst can be adsorbed on carriers in a manner known in principle and / or embedded in coating substances.
  • 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, enzymes, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators ⁇ gates, additional peroxygen activators, dyes and fragrances.
  • 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 of not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight.
  • transition metal bleaching catalysts according to formula I which have at least one ammonia molecule as ligands, customary transition metal complexes known as bleach activators and / or, in particular in combination with inorganic peroxygen compounds, conventional bleach activators, that is to say compounds which are substituted perbenzoic acid under perhydrolysis conditions and / or aliphatic peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms.
  • conventional bleach activators that is to say compounds which are substituted perbenzoic acid under perhydrolysis conditions and / or aliphatic peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms.
  • 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.
  • Multi-acylated 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 are preferred sulfonates, especially nonanoyl or isononanoyloxybenzenesulfonate, 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) and pentaacetylructate, pentaacetylructate
  • 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 which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 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 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 contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the disinfectants according to the invention as well as 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 5% 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 which, in principle, can contain all the usual washing, cleaning or disinfecting agent 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.
  • 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 preferably 0 in the disinfectants according to the invention , 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 arninotris (methylenediaminophenylphosphonic acid) Hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which are also suitable ⁇ rings of polymerizable substances without carboxylic
  • 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, although less preferred, • compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl, Vinylester, ethylene, propylene and styrene, in which the proportion of the acid is at least 50 wt .-%.
  • 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 preferably have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
  • 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.
  • Under the crystalline sodium aluminosilicates in detergent quality, in particular 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 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.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 y H 2 O
  • ⁇ -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.
  • crystalline alkali silicates of the abovementioned made from amorphous alkali silicates General formula in which x is a number from 1.9 to 2.1, which can be prepared as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428, 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 aluminosilicate is used as an additional builder.
  • the weight ratio of aluminosilicate 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 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 their water-soluble salts and mixtures thereof.
  • Enzymes that can be used in the agents come from the class of proteases, lipases. Cutinases, amylases, pullulanases, hemicellulase, cellulases, oxidases and peroxidases as well as 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.
  • Any enzymes used 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 preferably contained in the washing, cleaning and disinfecting agents according to the invention not more than 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, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the compound classes 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 acids which are compatible with the system and the environment, 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.
  • acids which are compatible with the system and the environment 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.
  • 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, with 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 Solutions containing aqueous or other customary solvents are particularly advantageously prepared 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.

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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

Complexes of the transition metals cobalt, iron, copper or ruthenium with at least one ammonia group as ligands are used as activators for peroxide compounds in oxidation, washing, cleaning or disinfectant solutions. These agents preferably contain 0.0025 to 0.25 wt% of such activator complexes.

Description

UhergangsmetaIlamminkomp.exe als Aktivatoren für Persauerstoffverbindungen UhergangsmetaIlamminkomp.exe as activators for peroxygen compounds
Die vorliegende Erfindung betrifft die Verwendung bestimmter Oligoamminkomplexe von Übergangsmetallen als Aktivatoren beziehungsweise Katalysatoren für Persauerstoff¬ verbindungen, insbesondere zum Bleichen von Farbanschmutzungen beim Waschen von Textilien, sowie Wasch-, Reinigungs- und Desinfektionsmittel, die derartige Bleichaktiva¬ toren beziehungsweise Bleichkatalysatoren enthalten.The present invention relates to the use of certain oligoammine complexes of transition metals as activators or catalysts for peroxygen compounds, in particular for bleaching color stains when washing textiles, and detergents, cleaning agents and disinfectants which contain such bleach activators or bleach 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.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, in particular tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins. Hydrazides, triazoles, Hydrotriazine, urazols, diketopiperazine, sulfuryl amides and cyanurates, also carboxylic, in particular phthalic anhydride, carboxylic säureester, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxy- benzene sulfonate, and acylated sugar derivatives such as pentaacetylglucose, have been reported 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.
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. 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 544 490 oder EP 549 271 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. In der europäischen Patentanmeldung EP 272 030 werden Cobalt(III)-Komplexe mit Ammoniak-Liganden, die außerdem belie¬ bige weitere ein-, zwei-, drei- und/oder vierzähnige Liganden aufweisen können, als Aktivatoren für H2O2 beschrieben. Aus der europäischen Patentanmeldung EP 630 964 sind bestimmte Mangankomplexe bekannt, welche keinen ausgeprägten Effekt hinsichtlich einer Bleichverstärkung von Persauerstoffverbindungen haben und gefärbte Textilfasern nicht entfärben, aber die Bleiche von in Waschlaugen befindlichem, von der Faser abgelöstem Schmutz oder Farbstoff bewirken können. Aus der deutschen Patent¬ anmeldung DE 44 16 438 sind Mangan-, Kupfer- und Kobalt-Komplexe bekannt, welche Liganden aus einer Vielzahl von Stoffgruppen tragen können und als Bleich- und Oxidationskatalysatoren verwendet werden sollen.In the effort to save energy in washing and bleaching, application temperatures significantly below 60 ° C, in particular below 45 ° C, down to the cold water temperature have become increasingly important in recent years. At these low temperatures, the effect of the activator compounds known hitherto generally decreases noticeably. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date. One approach to this arises from 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 544 490 or EP 549 271, 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. 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 . From 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.
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 45 °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 45 ° C.
Es wurde nun gefunden, daß bestimmte Übergangsmetallkomplexe, die mindestens ein Ammoniakmolekül als Liganden aufweisen, eine deutliche bleichkatalysierende Wirkung haben. Gegenstand der Erfindung ist die Verwendung von Komplex-Verbindungen der allgemeinen Formel IIt has now been found that certain transition metal complexes which have at least one ammonia molecule as ligand have a clear bleach-catalyzing effect. The invention relates to the use of complex compounds of the general formula I.
[M(NH3)6-x(L)JAn (I)[M (NH 3 ) 6-x (L) YES n (I)
in denen M ein Ubergangsmetall ist, ausgewählt aus Cobalt, Eisen, Kupfer und Ruthenium, L ein Ligand ist, ausgewählt aus der Gruppe umfassend Wasser, Hydroxid, Chlorat, Perchlorat, (NO2)\ Carbonat, Hydrogencarbonat, Nitrat, Acetat und Rhodanid, x eine Zahl von 0 bis 5 ist, A ein salzbildendes Anion ist und n, das auch 0 sein kann, eine Zahl der Größe ist, daß die Verbindung gemäß Formel (I) keine Ladung aufweist, als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen in Oxidations-, Wasch-, Reinigungs- oder Desinfektionslösungen.in which M is a transition metal selected from cobalt, iron, copper and ruthenium, L is a ligand selected from the group comprising water, hydroxide, chlorate, perchlorate, (NO 2 ) \ carbonate, hydrogen carbonate, nitrate, acetate and rhodanide, x is a number from 0 to 5, A is a salt-forming anion and n, which can also be 0, is a number such that the compound of the formula (I) has no charge, as activators for in particular inorganic peroxygen compounds in oxidation , Washing, cleaning or disinfection solutions.
Unter einer (NO2)"-Gruppe soll im vorliegenden Fall ein Nitro-Ligand, der über das Stickstoffatom an das Übergangsmetali gebunden ist, oder ein Nitrito-Ligand, der über ein Sauerstoffatom an das Ubergangsmetall gebunden ist, verstanden werden. Die (NO2)~- Gruppe kann an ein Ubergangsmetall M auch chelatbildendIn the present case, 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. The (NO 2 ) ~ - Group can also chelate on a transition metal M.
/ \/ \
M NM N
\ / o\ / o
gebunden sein. Sie kann auch zwei Übergangsmetallatome asymmetrisch verbrückenbe bound. It can also bridge two transition metal atoms asymmetrically
^^
/ \ oder η '-O- verbrücken:/ \ or η '-O- bridge:
*>*>
//
Die genannten Übergangsmetalle in den erfindungsgemäß zu verwendenden Bleichkataly¬ satoren liegen vorzugsweise in den Oxidationsstufen +2, +3 oder +4 vor. Bevorzugt werden Komplexe mit Übergangsmetallzentralatomen in der Oxidationsstufe +3 verwendet. Zu den bevorzugt verwendeten Komplexen gehören diejenigen mit Cobalt 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 state +3 are preferably used. The complexes used with preference include those with cobalt as central atoms.
Außer den Ammoniak-Liganden können die erfindungsgemäß zu verwendenden Über¬ gangsmetallkomplexe noch weitere, in der Regel einfach aufgebaute Liganden anorganischer Natur (L in Formel I), insbesondere ein- oder mehrwertige Anionliganden, tragen, solange im Komplex wenigstens ein Ammoniak-Molekül als Ligand enthalten ist. In Frage kommen beispielsweise Nitrat, Actetat, Rhodanid, Chlorat und Perchlorat. Die Anionliganden sollen für den Ladungsausgleich zwischen Übergangsmetall-Zentralatom und dem Ligandensy stern sorgen. Auch die Anwesenheit von Oxo-Liganden, Peroxo- Liganden und Imino-Liganden, zusätzlich oder anstatt der genannten Liganden L, ist möglich. Diese Liganden können auch verbrückend wirken, so daß rnehrkernige Komplexe entstehen. Diese enthalten pro Übergangsmetallatom mindestens 1 Ammoniak- Liganden und vorzugsweise mindestens 1 (NO2)"-Gruppe. Im Falle verbrückter, zweikerniger Komplexe müssen nicht beide Metallatome im Komplex gleich sein. Der Einsatz zweikerniger Komplexe, in denen die beiden Übergangsmetallzentralatome unter¬ schiedliche Oxidationszahlen aufweisen, ist möglich.In addition to the ammonia ligands, the transition metal complexes to be used according to the invention can also carry further, generally simple ligands of an inorganic nature (L in formula I), in particular mono- or polyvalent anion ligands, as long as at least one ammonia molecule is used as the ligand in the complex is included. For example, nitrate, acetate, rhodanide, chlorate and perchlorate are suitable. The anion ligands are supposed to balance the charge between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands, in addition to or instead of the ligands L mentioned, is also possible. These ligands can also act as bridges, so that multinuclear complexes are formed. These contain at least 1 ammonia ligand and preferably at least 1 (NO 2 ) " group per transition metal atom. In the case of bridged, dinuclear complexes, both metal atoms in the complex do not have to be the same. The use of dinuclear complexes in which the two transition metal central atoms have different oxidation numbers have is possible.
Falls Anionliganden fehlen oder die Anwesenheit von Anionliganden nicht zum Ladungs¬ ausgleich im Komplex führt, sind in den erfindungsgemäß zu verwendenden Verbindungen anionische Gegenionen anwesend, die den kationischen Komplex neutralisieren. Zu diesen anionischen Gegenionen gehören insbesondere Nitrat, Hydroxid, Hexafluorophosphat, Sulfat, Chlorat, Perchlorat, die Halogenide wie Chlorid, Fluorid, lodid und Bromid oder die Anionen von Carbonsäuren wie Formiat, Acetat, Benzoat oder Citrat. Diese anionischen Gegenionen sind in einer solchen Anzahl (n in Formel I) in den Verbindungen gemäß Formel I enthalten, daß die Summe aus dem Produkt ihrer Anzahl mit ihrer Ladung und dem Produkt aus der Anzahl der Anionliganden (L in Formel I) mit deren Ladung dem Betrag nach genau so groß, aber mit negativem Vorzeichen behaftet ist wie die Ladung des Übergangsmetallzentralatoms (M in Formel I).If anion ligands are missing or the presence of anion ligands does not lead to charge balancing in the complex, anionic counterions are present in the compounds to be used according to the invention, which counteract the cationic complex neutralize. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride, fluoride, iodide and bromide or the anions of carboxylic acids such as formate, acetate, benzoate or citrate. These anionic counterions are present in such a number (n in formula I) in the compounds according to formula I that the sum of the product of their number with their charge and the product of the number of anion ligands (L in formula I) with their charge the amount is exactly as large, but has a negative sign as the charge of the transition metal central atom (M in formula I).
In den Fällen, in denen L ein zweizähniger Ligand, wie zum Beispiel der Carbonato- Ligand. wie oben ausgeführt gegebenenfalls der (NO2)"-Ligand oder der Nitrato-Ligand ist, welcher zwei Bindungsstellen des Übergangsmetallzentralatoms in einer einkernigen Komplexverbindung besetzt, kann Formel (I) die Struktur des Komplexes nur sinngemäß wiedergeben. Bei derartigen Komplexverbindungen handelt es sich um solche, die anschaulicher durch die allgemeine Formel (II)In cases where L is a bidentate ligand, such as the carbonato ligand. As stated above, the (NO 2 ) " ligand or the nitrato ligand, which occupies two binding sites of the transition metal central atom in a mononuclear complex, is optionally the formula (I) can only give an analogous representation of the structure of the complex. Such complex compounds are those more clearly represented by the general formula (II)
[M(NH3)6.x.2yLx(L2)y]An (II)[M (NH 3 ) 6 . x . 2y L x (L 2 ) y ] A n (II)
in denen M, A, n und x die oben angegebene Bedeutung haben, L ein über eine Koordina- tionsstelle gebundener und L der über zwei Koordinationsstellen gebundene Ligand und y eine Zahl von 0 bis 2 ist mit der Maßgabe, daß x + 2y höchstens 5 ist, dargestellt werden.in which M, A, n and x have the meaning given above, L is a ligand bound via one coordination point and L is the ligand bound via two coordination points and y is a number from 0 to 2, with the proviso that x + 2y at most 5 is shown.
Zu den bevorzugten Bleichkatalysatoren gemäß der Erfindung gehören Nitropentammin- cobalt(III)-chlorid, Nitritopentammin-cobalt(III)-chlorid, Nitratopentammin-cobalt(III)- chlorid, Tetrammin-carbonato-cobalt(III)-chlorid, Tetrammin-carbonato-cobalt(III)- hydrogencarbonat und Tetrammin-carbonato-cobalt(III)-nitrat.The preferred bleaching catalysts according to the invention include nitropentammine cobalt (III) chloride, nitritopentammine cobalt (III) chloride, nitratopentammine cobalt (III) chloride, tetrammine carbonato cobalt (III) chloride, tetrammine carbonato cobalt (III) - hydrogen carbonate and tetrammin-carbonato-cobalt (III) nitrate.
Ein derartiger Übergangsmetall-Bleichkatalysator 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 umfaßt 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.Such a transition metal bleaching catalyst 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 differently colored textiles.
Weitere Gegenstände der Erfindung sind Wasch-, Reinigungs- und Desinfektionsmittel, die einen obengenannten Übergangsmetall-Bleichkatalysator enthalten und ein Verfahren zur Aktivierung von Persauerstoffverbindungen unter Einsatz eines derartigen Bleichkatalysators.Further objects of the invention are detergents, cleaning agents and disinfectants which contain an abovementioned transition metal bleaching catalyst 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 Wasch- beziehungsweise Desinfektionslösung zugegeben werden, wenn ein persauerstofffreies Mittel verwendet wird. 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 bleichkatalysierender Übergangsmetallverbindung hängt vom Anwendungszweck ab. Je nach gewünschtem Ak¬ tivierungsgrad werden 0,00001 Mol bis 0,025 Mol, vorzugsweise 0,0001 Mol bis 0,002 Mol Übergangsmetallverbindung pro Mol Persauerstoffverbindung verwendet, doch können in besonderen Fällen diese Grenzen auch über- oder unterschritten werden.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. However, the process according to the invention is particularly advantageously carried out using a washing, cleaning or disinfecting agent according to the invention which contains the bleaching catalyst 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 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 the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen. The amount of bleach-catalyzing transition metal compound 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 transition metal compound 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 Übergangsmetall-Bleichkatalysators gemäß Formel I neben üblichen, mit dem Bleichkata¬ lysator verträglichen Inhaltsstoffen. Der Bleichkatalysator kann in im Prinzip bekannter Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet 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 transition metal bleaching catalyst according to formula I. in addition to the usual ingredients which are compatible with the bleaching catalyst. The bleaching catalyst can be adsorbed on carriers in a manner known in principle and / or embedded in coating substances.
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 erfindungsgemaßen Wasch- und Reinigungsmittel können ins¬ besondere Buildersubstanzen, oberflächenaktive Tenside, organische und/oder anorganische Persauerstoffverbindungen, wassermischbare organische Lösungsmittel, En¬ zyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schaumregula¬ toren, zusätzliche Persauerstoff-Aktivatoren, Färb- und Duftstoffe 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, enzymes, sequestering agents, electrolytes, pH regulators and further auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, foam regulators ¬ gates, additional peroxygen activators, dyes 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 erfindungsgemaßen 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 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 of not more than 10% by weight, particularly preferably from 0.1% by weight to 5% by weight.
Zusätzlich zu den Übergangsmetall-Bleichkatalysatoren gemäß Formel I, die mindestens ein Ammoniak-Molekül als Liganden besitzen, können übliche als Bleichaktivatoren bekannte Übergangsmetallkomplexe und/oder, insbesondere in Kombination mit anorganischen Persauerstoffverbindungen, konventionelle Bleichaktivatoren, 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 Tetraacetylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), acylierte Triazinderivate, insbesondere l,5-Diacetyl-2,4-dioxohexahydro-l,3,5-triazin (DADHT), acylierte Phenol sulfonate, insbesondere Nonanoyl- oder Isononanoyloxybenzolsulfonat, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5- Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbit und Mannit, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetra- acetylxylose 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 addition to the transition metal bleaching catalysts according to formula I, which have at least one ammonia molecule as ligands, customary transition metal complexes known as bleach activators and / or, in particular in combination with inorganic peroxygen compounds, conventional bleach activators, that is to say compounds which are substituted perbenzoic acid under perhydrolysis conditions and / or aliphatic peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms. 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. Multi-acylated 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 are preferred sulfonates, especially nonanoyl or isononanoyloxybenzenesulfonate, 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) and pentaacetylructate, pentaacetylructate, pentaacetyl, tetraacetyl, pentaacetyl, pentaacetyl, pentaacetyl, pentaacetyl, Octaacetyllactose and acetylated, optionally N-alkylated, glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE 4443 177 can also be used.
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-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten lang- kettigen Alkoholderivaten 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-alkyl amines, 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 also from alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
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 which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 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 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 erfindungsgemaßen Desinfektionsmittel wie auch erfindungsgemäße Mittel zur Reinigung von Geschirr vorzugsweise 0,1 Gew.-% bis 20 Gew.-%, insbesondere 0,2 Gew.-% bis 5 Gew.-% Tenside, enthalten.Such surfactants are contained in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, while the disinfectants according to the invention as well as 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 5% by weight of surfactants.
Als geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren beziehungsweise 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 erfindungsgemaßen 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 which, in principle, can contain all the usual washing, cleaning or disinfecting agent 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, while preferably 0 in the disinfectants according to the invention , 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 Arninotris(methylen- phosphonsäure), Ethylendiamintetrakis(methylenphosphonsäure) und 1 -Hydroxyethan- 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 200 000, die der Copolymeren zwi¬ schen 2 000 und 200 000, vorzugsweise 50 000 bis 120 000, 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 Vinylethern, wie Vinylmethylethern, 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 einem veresterten Vinylalkohol oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättig¬ ten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbeson¬ dere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Alkyl- oder Aryl- rest substituiert ist, sein. Derartige Polymere lassen sich insbesondere nach Verfahren her¬ stellen, die in der deutschen Patentschrift DE 42 21 381 und der deutschen Patentanmel¬ dung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 be¬ schrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäure- salze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen kön¬ nen, insbesondere zur Herstellung flüssiger Mittel, in Form wäßriger Lösungen, vorzugs¬ weise 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 arninotris (methylenediaminophenylphosphonic acid) Hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which are also suitable ¬ rings of polymerizable substances without carboxylic acid functionality can be copolymerized. 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, although less preferred, • compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl, Vinylester, ethylene, propylene and styrene, in which the proportion of the acid is at least 50 wt .-%. As a water-soluble organic Builders can also be used in terpolymers 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 preferably have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. 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.
Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 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 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.
Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Polyphos- phate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche, wasserdisper- gierbare 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 Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosi- likate 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.Particularly suitable water-soluble inorganic builder materials are polyphosphates, preferably sodium triphosphate. 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. Under the crystalline sodium aluminosilicates in detergent quality, in particular 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 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.
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 Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1 :1,1 bis 1 :12 auf und können amorph 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 0 452 428 beschrieben, können in erfindungsgemäßen 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 0 436 835 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 0 293 753 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.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. Also practically water-free crystalline alkali silicates of the abovementioned made from amorphous alkali silicates General formula in which x is a number from 1.9 to 2.1, which can be prepared as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428, 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 0 436 835. 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 0 293 753, are used in a further preferred embodiment of agents according to the invention. If alkali aluminosilicate is used as an additional builder. Zeolite in particular is present, the weight ratio of aluminosilicate 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 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 their water-soluble salts and mixtures thereof.
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. Die gegebenenfalls verwendeten Enzyme können, wie zum Beispiel in den internationalen Patentanmeldungen WO 92/1 1347 oder WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen ein¬ gebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfin¬ dungsgemäßen Wasch-, Reinigungs- und Desinfektionsmitteln vorzugsweise nicht über 5 Gew.-%, insbesondere von 0,2 Gew.-% bis 2 Gew.-%, enthalten.Enzymes that can be used in the agents come from the class of proteases, lipases. Cutinases, amylases, pullulanases, hemicellulase, cellulases, oxidases and peroxidases as well as 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. Any enzymes used 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 preferably contained in the washing, cleaning and disinfecting agents according to the invention not more than 5% by weight, in particular from 0.2% by weight to 2% by weight.
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 having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol. Diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, as well as their mixtures and the ethers which can be derived from the compound classes 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 acids which are compatible with the system and the environment, 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.
Die Herstellung erfindungsgemäßer fester 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 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, with the peroxygen compound and bleaching catalyst optionally being added later. For the preparation of 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 Solutions containing aqueous or other customary solvents are particularly advantageously prepared 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.
BeispieleExamples
In einem Launderometer wurden unter Verwendung eines bleichaktivatorfreien Wasch¬ mittels Bl, enthaltend 16 Gew.-% Natriumperborat-Monohydrat, ein mit Tee verunrei¬ nigtes Gewebe aus weißer Baumwolle bei 30 °C 20 Minuten gewaschen. Nach Spülen und Trocknen wurde die Remission (Meßwellenlänge 460 nm) des augenscheinlich sau¬ beren Testgewebes photometrisch bestimmt. Zusätzlich wurde in gleicher Dosierung ein Mittel B2, das 6 Gew.-% TAED und 94 Gew.-% Bl enthielt, unter den gleichen Bedingungen getestet. Den aus diesen Vergleichsversuchen erhaltenen Werten ist der unter Einsatz eines Mittels Ml, das Bl, 3 Gew.-% TAED und den Komplex Nitritopentammincobalt(III)chlorid in einer Konzentration von 50 ppm bezogen auf Cobalt enthielt, erhaltene Wert klar überlegen (Tabelle 1).In a launderometer, using a bleach activator-free detergent Bl containing 16% by weight sodium perborate monohydrate, a tea-contaminated white cotton fabric was washed at 30 ° C. for 20 minutes. After rinsing and drying, the reflectance (measuring wavelength 460 nm) of the apparently clean test tissue was determined photometrically. In addition, an agent B2 which contained 6% by weight of TAED and 94% by weight of B1 was tested in the same dosage under the same conditions. The values obtained from these comparative experiments are clearly superior to the values obtained using an agent Ml containing B1, 3% by weight of TAED and the complex nitritopentamine cobalt (III) chloride in a concentration of 50 ppm based on cobalt (Table 1) .
Tabelle 1 : Remissionswerte [%]Table 1: Remission values [%]
Man erkennt, daß durch die erfindungsgemäße Verwendung (Ml) eine signifikant bessere Bleichwirkung erreicht werden kann als durch den konventionellen Bleichaktivator TAED in wesentlich höherer Konzentration (B2). It can be seen that a significantly better bleaching effect can be achieved by the use according to the invention (Ml) than by the conventional bleach activator TAED in a substantially higher concentration (B2).

Claims

Patentansprüche claims
1. Verwendung von Komplex-Verbindungen der allgemeinen Formel I1. Use of complex compounds of the general formula I
[M(NH3)6.x(L)x]An (I) in denen M ein Ubergangsmetall ist, ausgewählt aus Cobalt, Eisen, Kupfer und Ruthenium, L ein Ligand ist, ausgewählt aus der Gruppe umfassend Wasser, Hydroxid, Chlorat, Perchlorat, (NO2)", Carbonat, Hydrogencarbonat, Nitrat, Acetat und Rhodanid, x eine Zahl von 0 bis 5 ist, A ein salzbildendes Anion ist und n eine Zahl der Größe ist, daß die Verbindung gemäß Formel (I) keine Ladung aufweist, als Aktivatoren für insbesondere anorganische Persauerstoffverbindungen in Oxidations-. Wasch-. Reinigungs- oder Desinfektionslösungen.[M (NH 3 ) 6 . x (L) x ] A n (I) in which M is a transition metal selected from cobalt, iron, copper and ruthenium, L is a ligand selected from the group comprising water, hydroxide, chlorate, perchlorate, (NO 2 ) " , Carbonate, hydrogen carbonate, nitrate, acetate and rhodanide, x is a number from 0 to 5, A is a salt-forming anion and n is a number such that the compound of the formula (I) has no charge, as activators for in particular inorganic peroxygen compounds in oxidation, washing, cleaning or disinfection solutions.
2. Verwendung von Komplex-Verbindungen der allgemeinen Formel I2. Use of complex compounds of the general formula I
[M(NH3)6-x(L)x]An (I) in denen M ein Ubergangsmetall ist, ausgewählt aus Cobalt, Eisen. Kupfer und Ru¬ thenium. L ein Ligand ist, ausgewählt aus der Gruppe umfassend Wasser, Hydroxid. Chlorat, Perchlorat, (NO2)\ Carbonat, Hydrogencarbonat, Nitrat, Acetat und Rhodanid, x eine Zahl von 0 bis 5 ist, A ein salzbildendes Anion ist und n eine Zahl der Größe ist, daß die Verbindung gemäß Formel (I) keine Ladung aufweist, zum Bleichen von Farbanschmutzungen beim Waschen von Textilien.[M (NH 3 ) 6-x (L) x ] A n (I) in which M is a transition metal selected from cobalt, iron. Copper and ru¬ thenium. L is a ligand selected from the group comprising water, hydroxide. Chlorate, perchlorate, (NO 2 ) \ carbonate, hydrogen carbonate, nitrate, acetate and rhodanide, x is a number from 0 to 5, A is a salt-forming anion and n is a number such that the compound of the formula (I) is none Has a charge for bleaching color stains when washing textiles.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Ubergangsmetall M in der Oxidationsstufe +2, +3 oder +4 vorliegt.3. Use according to claim 1 or 2, characterized in that the transition metal M is in the oxidation state +2, +3 or +4.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Ubergangsmetall M in der Komplex- Verbindung gemäß Formel I Cobalt ist.4. Use according to one of claims 1 to 3, characterized in that the transition metal M in the complex compound according to formula I is cobalt.
5. Verwendung nach Anspruch 4, dadurch gekennzeichnet, daß die Komplexverbindung Nitropentammin-cobalt(III)-chlorid oder Nitτitopentammin-cobalt(III)-chlorid ist.5. Use according to claim 4, characterized in that the complex compound is nitropentammine-cobalt (III) chloride or Nitτitopentammin-cobalt (III) chloride.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Komplex kationisch ist und anionische Gegenionen A, insbesondere ausgewählt aus Nitrat, Hydroxid, Hexafluorophosphat, Sulfat, Chlorat, Perchlorat, den Halogeniden wie Chlorid oder den Anionen von Carbonsäuren wie Formiat, Acetat, Benzoat oder Citrat, anwesend sind, die den kationischen Komplex neutralisieren.6. Use according to one of claims 1 to 5, characterized in that the complex is cationic and anionic counterions A, in particular selected from Nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, benzoate or citrate are present, which neutralize the cationic complex.
7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Übergangsmetallkomplex-Verbindungen gemäß Formel I zusammen mit Ver¬ bindungen, die unter Perhydrolysebedingungen gegebenenfalls substituierte Perbenzoesäure und/oder aliphatische Peroxocarbonsäuren mit 1 bis 10 C-Atomen ergeben, einsetzt.7. Use according to one of claims 1 to 6, characterized in that the transition metal complex compounds of the formula I are used together with compounds which, under perhydrolysis conditions, give substituted or unsubstituted perbenzoic acid and / or aliphatic peroxocarboxylic acids having 1 to 10 carbon atoms .
8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die zu aktivierende Persauerstoffverbindung aus der Gruppe umfassend organische Per¬ säuren, Wasserstoffperoxid, Perborat und Percarbonat sowie deren Gemische aus¬ gewählt wird.8. Use according to one of claims 1 to 7, 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.
9. Wasch-, Reinigungs- oder Desinfektionsmittel, dadurch gekennzeichnet, daß es 0,0025 Gew.-% bis 0,25 Gew.-%, insbesondere 0,01 Gew.-% bis 0,1 Gew.-% einer Komplex-Verbindung der allgemeinen Formel I9. washing, cleaning or disinfectant, characterized in that it is 0.0025 wt .-% to 0.25 wt .-%, in particular 0.01 wt .-% to 0.1 wt .-% of a complex Compound of the general formula I
[M(NH3)6.x(L)x]An (I) in der M ein Ubergangsmetall ist, ausgewählt aus Cobalt, Eisen, Kupfer und Ruthenium, L ein Ligand ist, ausgewählt aus der Gruppe umfassend Wasser. Hydroxid, Chlorat, Perchlorat, (NO2)\ Carbonat, Hydrogencarbonat, Nitrat, Acetat und Rhodanid, x eine Zahl von 0 bis 5 ist, A ein salzbildendes Anion ist und n eine Zahl der Größe ist, daß die Verbindung gemäß Formel (I) keine Ladung aufweist, neben üblichen, mit der Komplex- Verbindung verträglichen Inhaltsstoffen enthält.[M (NH 3 ) 6 . x (L) x ] A n (I) in which M is a transition metal selected from cobalt, iron, copper and ruthenium, L is a ligand selected from the group comprising water. Hydroxide, chlorate, perchlorate, (NO 2 ) \ carbonate, hydrogen carbonate, nitrate, acetate and rhodanide, x is a number from 0 to 5, A is a salt-forming anion and n is a number such that the compound of the formula (I ) has no charge, in addition to the usual ingredients compatible with the complex compound.
10. Mittel nach Anspruch 9, 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 2 Gew.-%, insbesondere 0,2 bis 0,7 Gew.-%, Enzym, bis zu 30 Gew.-%, insbesondere 6 bis 20 Gew.-%, orga¬ nisches 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 Verbindungs- klassen ableitbaren Ether und bis zu 20 Gew.-%, insbesondere 1,2 - 17 Gew.-% pH- Regulator enthält.10. Composition according to claim 9, 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% by weight builder substance, up to 2% by weight, in particular 0.2 to 0.7% 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 mixtures thereof and those of these compounds Class derivable ether and contains up to 20 wt .-%, in particular 1.2-17 wt .-% pH regulator.
1. Mittel nach einem der Ansprüche 9 bis 10, dadurch gekennzeichnet, daß es zusätzlich zu den genannten Bestandteilen bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-% Persauerstoffverbindung, ausgewählt aus der Gruppe umfassend Wasser¬ stoffperoxid, Perborat und Percarbonat sowie deren Gemische, enthält. 1. Composition according to one of claims 9 to 10, characterized in that it contains up to 50 wt .-%, in particular from 5 wt .-% to 30 wt .-% peroxygen compound selected from the group comprising water in addition to the ingredients mentioned ¬ contains peroxide, perborate and percarbonate and their mixtures.
EP97916381A 1996-04-01 1997-03-24 Transition metal ammine complexes as activators for peroxide compounds Withdrawn EP0891416A1 (en)

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