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WO1997007191A1 - Detergents a complexes activateurs pour composes peroxyde - Google Patents

Detergents a complexes activateurs pour composes peroxyde Download PDF

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Publication number
WO1997007191A1
WO1997007191A1 PCT/EP1996/003465 EP9603465W WO9707191A1 WO 1997007191 A1 WO1997007191 A1 WO 1997007191A1 EP 9603465 W EP9603465 W EP 9603465W WO 9707191 A1 WO9707191 A1 WO 9707191A1
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weight
formula
group
use according
carbon atoms
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PCT/EP1996/003465
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German (de)
English (en)
Inventor
Helmut Blum
Christian Nitsch
Peter Jeschke
Jürgen Härer
Ulrich Pegelow
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to DE59608926T priority Critical patent/DE59608926D1/de
Priority to EP96927691A priority patent/EP0846156B1/fr
Publication of WO1997007191A1 publication Critical patent/WO1997007191A1/fr

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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 transition metal complexes as catalytically active activators for in particular inorganic peroxygen compounds for bleaching colored stains on hard surfaces and cleaning agents for hard surfaces which contain such activators or catalysts.
  • Inorganic peroxygen compounds in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • the oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for which numerous suggestions, especially from the 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, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, moreover carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-acyl benzene sulfonate, benzyl sulfonate, benzyl sulfonate, have become known in the literature.
  • bleach activators
  • transition metal complexes the ligands of which correspond to the Bis-Schiff bases available from salicylaldehyde or salicylaldehyde derivatives and bisamines, have a clear bleach-catalyzing effect on colored stains which are found on hard surfaces.
  • the invention accordingly relates to the use of transition metal (III) complexes of the formula (I),
  • UM stands for manganese, iron, cobalt, ruthenium or molybdenum
  • R represents an alkylene, alkenylene, phenylene or cycloalkylene radical which, in addition to the substituent X, can optionally be alkyl and / or aryl-substituted, with a total of 1 to 12 carbon atoms, R within being the shortest distance between the UM complexing N atoms is 1 to 5 C atoms,
  • X represents -H, -OR 3 , -NO 2 , -F, -Cl, -Br or -J,
  • R 1 , R 2 and R independently of one another represent hydrogen or an alkyl radical having 1 to 4 carbon atoms
  • Y 1 and Y 2 independently of one another represent hydrogen or an electron-shifting substituent
  • Z 'and Z 2 independently of one another represent hydrogen, -CO 2 M, -SO 3 M or -NO 2 ,
  • M stands for hydrogen or an alkali metal such as lithium, sodium or potassium and A stands for a charge-balancing anion ligand, as activators for in particular inorganic peroxygen compounds in cleaning solutions for hard surfaces, in particular for dishes.
  • the preferred transition metal (UM in formula I) is manganese.
  • the preferred compounds of the formula (I) include those in which R is a methylene group, 1,2-ethylene group, 1,3-propylene group, in position 2 hydroxyl- or nitro-substituted 1,3-propylene group, 1,2-cycloalkylene group with 4 is up to 6 carbon atoms, in particular a 1,2-cyclohexylene group, or an o-phenylene group.
  • the electron-shifting substituents Y 1 and Y 2 in formula (I) include the hydroxyl group, alkoxy groups with 1 to 4 carbon atoms, arylox groups, the nitro group, halogens such as fluorine, chlorine, bromine and iodine, the amino group, which are also mono- or may be dialkylated or -arylated, linear or branched chain alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, linear or branched chain alkenyl groups having 2 to 5 carbon atoms, and aryl groups, which in turn have the aforementioned substituents can wear.
  • the alkenyl groups which may contain 1 or 2 CC double bonds, preferably have at least one double bond conjugated to the benzene ring.
  • the preferred alkenyl substituents include the allyl and vinyl groups.
  • the substituents Y 1 and Y 2 are preferably in the 5-position.
  • the compounds of formula (I) used with preference include those in which Y 1 and Y 2 are identical.
  • the alkyl radicals having 1 to 4 carbon atoms include in particular the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl and tert-butyl group.
  • the charge-balancing anion ligand A in the compounds of the formula (I) can be mono- or polyvalent, in which case it can neutralize a plurality of transition metal atoms with the organic ligands mentioned. It is preferably a halide, in particular chloride, a hydroxide, hexafluorophosphate, perchlorate or the anion of a carboxylic acid, such as formate, acetate, benzoate or citrate.
  • the compounds of the formula (I) used according to the invention can be prepared by processes known in principle by the reaction of salicylaldehyde or corresponding ketones (if R 1 and / or R 2 are not hydrogen), which, if appropriate, define the above Substitutes Y 1 , Y 2 , Z 1 and / or Z 2 , be prepared with diamines H 2 NR-NH 2 and the reaction of the salen ligand thus obtainable with transition metal salts, as described for example in European patent application EP 630 694 or by BB De, BB Lohraj, S. Sivaram and PK Dhal in Macromolecules 27 (1994), 1291-1296.
  • the invention relates to cleaning agents for hard surfaces, in particular cleaning agents for dishes, and among these preferably those for use in mechanical cleaning processes which contain a bleaching catalyst of the formula (I) described above, and a process for cleaning hard surfaces, especially of dishes, using such a bleaching catalyst.
  • the use according to the invention essentially consists in creating, in the presence of a hard surface contaminated with colored soils, conditions under which a peroxidic oxidizing agent and the bleaching catalyst according to formula (I) can react with one another with the aim of obtaining secondary products having a more oxidizing effect .
  • Such conditions exist in particular when both reactants meet in aqueous solution.
  • This can be done by separately adding the peroxygen compound and the bleaching catalyst to an optionally detergent-containing solution.
  • the process according to the invention is particularly advantageously carried out using a cleaning agent according to the invention for hard surfaces, which contains the bleaching catalyst and optionally an oxidizing agent containing peroxygen.
  • the peroxygen compound can also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, if a peroxide-free cleaning 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 ppm and 5,000 ppm active oxygen.
  • the amount of bleach catalyst used also depends on Application purpose. Depending on the desired degree of activation, 0.00001 mol to 0.025 mol, preferably 0.0001 mol to 0.02 mol, of activator per mol of peroxygen compound are used, but in special cases these limits can also be exceeded or fallen short of.
  • the invention further relates to a cleaning agent for hard surfaces, in particular for dishes, which contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.1% by weight, of a bleaching catalyst of the formula ( I) in addition to conventional ingredients compatible with the bleaching catalyst.
  • a bleaching catalyst of the formula ( I) in addition to conventional ingredients compatible with the bleaching catalyst.
  • the bleaching catalyst can be adsorbed onto carriers and / or embedded in coating substances in a manner known in principle.
  • the cleaning agents according to the invention can in principle contain all the known ingredients which are customary in such agents.
  • the agents according to the invention can contain builder substances, surface-active surfactants, peroxygen compounds, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as silver corrosion inhibitors, foam regulators, additional peroxygen activators, and colorants and fragrances.
  • a cleaning agent for hard surfaces according to the invention can moreover have abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and micro-glass balls and mixtures thereof, contain.
  • Abrasives are preferably not contained in the cleaning agents according to the invention in excess of 20% by weight, in particular from 5% by weight to 15% by weight.
  • Another subject matter of the invention is a low-alkaline agent for the mechanical cleaning of dishes, the 1% by weight solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing 15% by weight to 60% by weight. %, in particular 30% by weight to 50% by weight of water-soluble builder component, 5% by weight to 25% by weight, in particular 10% by weight to 15% by weight, oxygen-based bleaching agent, in each case based on the total Agent which contains a bleaching catalyst according to formula (I), in particular in amounts of 0.005% by weight to 0.1% by weight.
  • all builders customarily used in machine dishwashing detergents are suitable as water-soluble builder components, in particular in such low-alkaline cleaning agents, for example polymeric alkali metal phosphates which may be present in the form of their alkaline neutral or acidic sodium or potassium salts.
  • polymeric alkali metal phosphates which may be present in the form of their alkaline neutral or acidic sodium or potassium salts.
  • examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Their amounts can range up to about 35% by weight, based on the total agent; however, the agents according to the invention are preferably free of such phosphates.
  • water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, particularly in hard water regions.
  • examples include polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids.
  • Commercial products are, for example, Sokalan® CP 5 and PA 30 from BASF.
  • Polymers of native origin that can be used as co-builders include, for example, oxidized starch, as known, for example, from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • hydroxycarboxylic acids such as mono-, di-hydroxy succinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • the preferred builder components include the salts of citric acid, especially sodium citrate.
  • Sodium citrate can be anhydrous trisodium citrate and preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the co-builder salts mentioned can also be present.
  • Suitable oxygen-based bleaches are primarily alkali perborate mono- or tetrahydrate and / or alkali percarbonate, with sodium being the preferred alkali metal.
  • the oxygen-based bleach is therefore preferably an alkali percarbonate, especially sodium percarbonate.
  • known peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can also be useful.
  • bleach-activating agents ie compounds which contain perbenzoic acid and / or peroxocarboxylic acids with 1 to 10 carbon atoms which are optionally substituted under perhydrolysis conditions , especially 2 to 4 carbon atoms, are used.
  • Suitable are the conventional bleach activators cited at the outset which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenyls are preferred , in particular nonanoyloxy or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-di-acetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar deri- vate, in particular pentaacetylglucose (PAG), pentaacetylfructose,
  • the lower alkaline machine dishwashing agents according to the invention preferably contain the usual alkali carriers such as, for example, alkali silicates, alkali metal carbonates and / or alkali metal hydrogen carbonates.
  • alkali carriers commonly used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiÜ2 / M2O (M.
  • Alkali atom Alkali atom
  • Alkali silicates can be present in amounts of up to 30% by weight, based on the total agent.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably omitted entirely.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight , is included.
  • the ratio of carbonate and hydrogen carbonate used varies, but an excess of sodium hydrogen carbonate is usually used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • agents according to the invention 20% by weight to 40% by weight of water-soluble organic builders, in particular alkali citrate, 5% by weight to 15% by weight of alkali carbonate and 20% by weight to 40% by weight Contain alkali disilicate.
  • surfactants in particular weakly foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty soils, as wetting agents and, if appropriate, as granulating aids in the course of the preparation of the cleaning agents.
  • Their amount can be up to 10% by weight, in particular up to 5% by weight, and is preferably in the range from 0.5% by weight to 3% by weight.
  • Extremely low-foaming compounds are usually used, in particular, in cleaning agents for use in machine dishwashing processes. These preferably include C 2 -C 8 -alkyl polyethylene glycol polypropylene glycol ether each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • C ⁇ 2 - Cig-Alkylpolyethylenglycol-polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ether and the foaming, but ecologically attractive Cg-C ⁇ 4 - alkyl polyglucosides with a degree of polymerization of about 1 to 4 (e.g. APG® 225 and APG® from Henkel) and / or C ⁇ -C ⁇ -alkyl polyethylene glycols with 3 to 8 ethylene oxide units in the molecule.
  • C ⁇ 2 - Cig-Alkylpolyethylenglycol-polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule
  • end-capped alkyl polyalkylene glycol mixed ether and the foaming
  • Cg-C ⁇ 4 - alkyl polyglucosides with a degree of
  • surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably comes from a fatty alcohol with the C chain length C ⁇ -C ⁇ 4 . It is sometimes advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alkiol ethoxylates or glucamide with alkyl polyglycosides.
  • transition metal complexes in particular manganese complexes
  • the compounds of the formula (I) are generally used in amounts which are too small to provide protection against silver corrosion, so that silver corrosion inhibitors are still present in dishwashing detergents according to the invention can also be used, the effect of which can be enhanced by the compounds of the formula (I).
  • Preferred silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally substituted benzotriazole, manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes, in which the metals mentioned exist in one of the oxidation states ⁇ , HI, IV, V or VI.
  • the agents according to the invention can contain enzymes such as proteases, amylases, pullulanases, cutinases and lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase® and / or Savinase®, amylases such as Termamyl® , Amylase-LT®, Maxamyl® and / or Duramyl®, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Esperase® and / or Savinase®
  • amylases such as Termamyl® , Amylase-LT®, Maxamyl® and / or Duramyl®
  • lipases such as Lipolase®, Lipomax®, Lumafast®
  • the optionally used enzymes can, as described for example in the international patent applications WO 92/11347 or WO 94/23005, adsorbed on carriers and / or in Envelope substances are embedded to protect them against premature inactivation. They are preferably contained in the cleaning agents according to the invention not more than 2% by weight, in particular from 0.1% by weight to 0.7% by weight.
  • the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5% by weight to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bisfatty acid amides, and other other known commercially available defoamers.
  • a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bisfatty acid amides, and other other known commercially available defoamers.
  • Other optional ingredients in the agents according to the invention are, for example, perfume oils.
  • 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 derived from the compound classes mentioned.
  • Such water-miscible solvents are preferably not present in the cleaning agents according to the invention in excess of 20% by weight, in particular from 1% by weight to 15% by weight.
  • the agents according to the invention can contain system and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, especially sulfuric acid or alkali hydrogen sulfates, or bases, especially ammonium or alkali hydroxides.
  • Such pH regulators are preferably contained in the agents according to the invention not more than 10% by weight, in particular from 0.5% by weight to 6% by weight.
  • the preparation of the solid compositions according to the invention is not difficult and can be carried out in a manner known in principle, for example by spray drying or granulation. take place, the peroxygen compound and bleaching catalyst optionally being added separately later.
  • Cleaning agents according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the agents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which are known in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleaching catalyst can be expected to be produced.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 10 5 Pa to 1 500 10 5 Pa ve ⁇ resst.
  • conventional tablet presses for example eccentric presses or rotary presses
  • pressures in the range from 200 10 5 Pa to 1 500 10 5 Pa ve ⁇ resst.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • Agents according to the invention can be produced in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / 1 in that the builder components are at least partially liquid in a first process stage Mixing components are mixed while increasing the bulk density of this premix and then, if desired after an intermediate drying, the further constituents of the composition, including the bleaching catalyst, are combined with the premix obtained in this way.
  • Agents for cleaning dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / 1, preferably 2 to 5 g / 1.
  • a machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water following the cleaning cycle and a rinse cycle with a customary rinse aid. After drying, when using agents according to the invention, completely clean dishes which are an in terms of hygiene are obtained.
  • a cleaning agent (Ml) for the mechanical cleaning of dishes containing 45 parts by weight of sodium citrate, 5 parts by weight of sodium carbonate, 31 parts by weight of sodium hydrogen carbonate, 1 part by weight of protease and amylase granules, 2 Parts by weight of nonionic surfactant and 12 parts by weight of sodium percarbonate and 2 parts by weight of N, N, NW tetraacetylethylene diamine (TAED), an agent according to the invention (M2), which was otherwise composed like MI, but instead of the TAED 0.05 part by weight [NN 1 - Bis [(2-hydroxy-5-sulfonatophenyl) methylene] - 1, 2-diaminoethane] -manganese (III) chloride ent ent, and another agent according to the invention (M3), which instead 0.05 wt Parts. [N, N'-bis [(2-hydroxy-5-methylphenyl) methylene] -1, 2-diammocyclohexane]
  • the grades of the agents according to the invention (M2 and M3) given in Table 2 below are significantly better than the value for the comparative product M1.

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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)
  • Detergent Compositions (AREA)

Abstract

On utilise comme activateurs pour des composés peroxyde dans des solutions détergentes pour surfaces dures, en particulier pour la vaisselle, des complexes de métaux de transition (III) de formule (I), où UM est le manganèse, le fer, le cobalt, le ruthénium ou le molybdène; R est un reste alkyle, alcénylène, phénylène ou cycloalkylène, qui en plus des substituants X peut être substitué par un groupe alkyle et/ou aryle, avec en tout 1 à 12 atomes de carbone, l'écart le plus court au sein de R entre les atomes d'azote complexant avec UM étant de 1 à 5 atomes de carbone; X est -H, -OR3, -NO2, -F, -Cl, -Br ou -J; R?1, R2 et R3¿ sont indépendamment l'un de l'autre l'hydrogène ou un reste alkyle avec 1 à 4 atomes de carbone; Y1 et Y2 sont indépendamment l'un de l'autre l'hydrogène ou des substituants déplaceurs d'électrons; Z1 et Z2 sont indépendamment l'un de l'autre l'hydrogène, -CO¿2?M, -SO3M ou -NO2; M est l'hydrogène ou un métal alcalin comme le lithium, le sodium ou le potassium; et A est un ligand anionique compensateur de charge. Ces détergents pour la vaisselle contiennent de préférence entre 0,005 et 0,1 % en poids de complexes activateurs de ce type.
PCT/EP1996/003465 1995-08-15 1996-08-06 Detergents a complexes activateurs pour composes peroxyde WO1997007191A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59608926T DE59608926D1 (de) 1995-08-15 1996-08-06 Reinigungsmittel mit aktivatorkomplexen für persauerstoffverbindungen
EP96927691A EP0846156B1 (fr) 1995-08-15 1996-08-06 Detergents a complexes activateurs pour composes peroxyde

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19529904.3 1995-08-15
DE19529904A DE19529904A1 (de) 1995-08-15 1995-08-15 Reinigungsmittel mit Aktivatorkomplexen für Persauerstoffverbindungen

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DE (2) DE19529904A1 (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5969171A (en) * 1997-07-01 1999-10-19 Clariant Gmbh Metal complexes as bleach activators
WO2000011129A1 (fr) * 1998-08-19 2000-03-02 Ciba Specialty Chemicals Holding Inc. Complexes de manganese utilises comme catalyseurs pour des composes peroxygenes servant à nettoyer des surfaces dures, notamment de la vaisselle
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US7094745B2 (en) 2003-09-30 2006-08-22 Clariant Gmbh Use of transition metal complexes having lactam ligands as bleaching catalysts
US7205267B2 (en) 2004-01-24 2007-04-17 Clariant Produkte (Deutschland) Gmbh Use of transition metal complexes as bleach catalysts in laundry detergents and cleaning compositions
WO2012107187A1 (fr) 2011-02-10 2012-08-16 Clariant International Ltd Utilisation de complexes de métaux de transition en tant que catalyseurs de blanchiment dans des produits détergents et nettoyants
CN105350277A (zh) * 2015-12-16 2016-02-24 上海市纺织科学研究院 一种用于纤维素纤维水刺无纺布的低温漂白配方及其工艺

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
DE19620267A1 (de) * 1996-05-20 1997-11-27 Henkel Kgaa Katalytisch wirksame Aktivatorkomplexe mit N¶4¶-Liganden für Persauerstoffverbindungen
DE19710370A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Verwendung von in Käfigverbindungen eingeschlossenen Übergangsmetallkomplexen zur Verstärkung der Beichwirkung
DE19713851B4 (de) * 1997-04-04 2006-07-20 Henkel Kgaa Verwendung von Komplexen des Molybdäns, Vanadiums oder Wolframs zur Verstärkung der Bleichwirkung

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EP0408131A2 (fr) * 1989-07-10 1991-01-16 Unilever N.V. Activation de blanchiment
EP0458397A2 (fr) * 1990-05-21 1991-11-27 Unilever N.V. Activation du blanchiment
EP0549271A1 (fr) * 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
EP0630964A2 (fr) * 1993-06-19 1994-12-28 Ciba-Geigy Ag Inhibition de la réadsorption des colorants migrants dans le liquide lessiviel
EP0693550A2 (fr) * 1994-07-21 1996-01-24 Ciba-Geigy Ag Composition de blanchiment de tissu
WO1996023860A1 (fr) * 1995-02-02 1996-08-08 The Procter & Gamble Company Compositions pour lave-vaisselles automatiques comprenant des catalyseurs chelates au cobalt

Cited By (10)

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US5969171A (en) * 1997-07-01 1999-10-19 Clariant Gmbh Metal complexes as bleach activators
WO2000011129A1 (fr) * 1998-08-19 2000-03-02 Ciba Specialty Chemicals Holding Inc. Complexes de manganese utilises comme catalyseurs pour des composes peroxygenes servant à nettoyer des surfaces dures, notamment de la vaisselle
US6306808B1 (en) * 1998-08-19 2001-10-23 Ciba Specialty Chemicals Corporation Manganese complexes as catalysts for peroxygenated compounds to clean hard surfaces, especially dishes
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US7094745B2 (en) 2003-09-30 2006-08-22 Clariant Gmbh Use of transition metal complexes having lactam ligands as bleaching catalysts
US7205267B2 (en) 2004-01-24 2007-04-17 Clariant Produkte (Deutschland) Gmbh Use of transition metal complexes as bleach catalysts in laundry detergents and cleaning compositions
WO2012107187A1 (fr) 2011-02-10 2012-08-16 Clariant International Ltd Utilisation de complexes de métaux de transition en tant que catalyseurs de blanchiment dans des produits détergents et nettoyants
DE102011010818A1 (de) 2011-02-10 2012-08-16 Clariant International Ltd. Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
CN105350277A (zh) * 2015-12-16 2016-02-24 上海市纺织科学研究院 一种用于纤维素纤维水刺无纺布的低温漂白配方及其工艺

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EP0846156A1 (fr) 1998-06-10
ES2174093T3 (es) 2002-11-01
EP0846156B1 (fr) 2002-03-20
DE59608926D1 (de) 2002-04-25
DE19529904A1 (de) 1997-02-20

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