EP0869171A2 - Metal complexes as bleach activators - Google Patents
Metal complexes as bleach activators Download PDFInfo
- Publication number
- EP0869171A2 EP0869171A2 EP98105257A EP98105257A EP0869171A2 EP 0869171 A2 EP0869171 A2 EP 0869171A2 EP 98105257 A EP98105257 A EP 98105257A EP 98105257 A EP98105257 A EP 98105257A EP 0869171 A2 EP0869171 A2 EP 0869171A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- compounds
- iii
- integer
- oxidation state
- 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.)
- Granted
Links
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
- C11D3/16—Organic compounds
- C11D3/168—Organometallic compounds or orgometallic complexes
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- the ligands of formula 2 are prepared by reacting salicylaldehyde and 2,6-diaminopyridine or their correspondingly substituted derivatives analogously to the information in J. Inorg. Nucl. Chem. 1975, vol. 37, pp. 2005 - 2006.
- the Production of the metal complexes according to the invention by reacting Mn or Co-salts with these ligands are also carried out analogously to the information this reference.
- the mono- or polynuclear complexes of the general formula according to the invention 1 are particularly suitable as bleaching and oxidation catalysts, in particular in detergents and cleaning agents and in textile and paper bleaching. Especially Textile detergents in the form of powder detergents or as liquid formulations and dish detergents.
- An advantage of Bleach catalysts according to the invention are their stability against hydrolysis and oxidation and their catalytic effect even at low temperatures. In such formulations, they not only improve the bleaching effect of Hydrogen peroxide, but also from organic and inorganic peroxy compounds.
- the present invention accordingly also relates to a method for Bleaching soiled substrates, taking the soiled substrate in aqueous bleaching liquor with peroxy compounds and an effective amount of one or more of the metal complexes according to the invention as bleaching catalysts in Brings contact.
- the aqueous bleaching liquor preferably contains these metal complexes based on the weight of the bleaching liquor, in an amount of 0.001 to 100 ppm Metal, especially 0.01 to 50 ppm metal, especially 0.03 to 20 ppm metal (ppm means parts per million based on weight). Higher levels Metal complexes, up to about 500 ppm, can be used in industrial bleaching processes, for example in the textile or paper sector.
- the first mentioned low metal contents mainly refer to Household textile detergent.
- the invention also relates to the use of these bleaching catalysts in bleaching detergents and cleaning agents.
- These detergents and cleaners contain in addition to a peroxide compound or a peroxide releasing Compound and the bleaching catalyst usually also surface-active Compounds and other known ingredients.
- Suitable peroxides or peroxide-releasing compounds are Alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts, and inorganic persalts, such as the alkali perborates, percarbonates, -perphosphates, -persilicates and -persulfates.
- Alkali metal peroxides such as urea-hydrogen peroxide adducts
- inorganic persalts such as the alkali perborates, percarbonates, -perphosphates, -persilicates and -persulfates.
- Alkyl hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are Cumene hydroperoxide and t-butyl hydroperoxide.
- aliphatic or aromatic Mono- or dipercarboxylic acids and the corresponding salts are suitable as Peroxy compounds.
- Peroxy compounds include peroxy- ⁇ -naphthoic acid, Peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, Diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonylbisperoxybenzoic acid.
- peroxy compounds inorganic peroxyacid salts e.g. B. Potassium monopersulfate. Mixtures of two or more of these compounds are also suitable.
- the detergent and cleaning agent formulations according to the invention contain usually 1 to 30% by weight, in particular 2 to 25% by weight Peroxy compounds.
- the detergents and cleaning agents can additionally also so-called bleach activators in usual amounts (approx. 1 to 10 Wt .-%) included.
- bleach activators are compounds with quaternary Ammonium structures such as 2- (N, N, N-triethylammonio) ethyl-4-sulfophenyl carbonate, N-octyl-N, N-dimethyl-N-10-carbophenoxydecylammonium chloride, 3- (N, N, N-trimethylammonio) propyl sodium 4-sulfobenzoate and N, N, N-trimethylammonium toluyl-oxybenzenesulfonate.
- 2- (N, N, N-triethylammonio) ethyl-4-sulfophenyl carbonate N-octyl-N, N-dimethyl-N-10-carbophenoxydecylammonium chloride
- esters such as. B. acylphenolsulfonates and the acylalkylphenolsulfonates and acylamides are preferred as bleach activators.
- esters such as. B. acylphenolsulfonates and the acylalkylphenolsulfonates and acylamides are preferred as bleach activators.
- Amounts are usually the effective amount of the metal complexes of the formula 1 from 0.0001 to 0.5% by weight of metal, in particular 0.00025 to 0.25% by weight of metal, especially 0.0005 to 0.1 wt .-% metal, based on the weight of the Formulations contained in these detergent and cleaning agent formulations. These quantities can fluctuate slightly depending on local custom.
- the surface-active substance in the detergents and cleaning agents can be from Natural products, such as soap, or is synthetic Compound from the group of anionic, nonionic, amphoteric, (zwitterionic) or cationic surface-active substances, or Mixtures of these. Many suitable substances are commercially available, and are described in the literature, for example in "Surface active agents and detergents ", Vol. 1 and 2, by Schwartz, Perry and Berch.
- the total proportion of surface-active compounds can be up to 50% by weight, preferably 1 % By weight to 40% by weight, in particular 4% by weight to 25% by weight, of the total Detergent or cleaning agents.
- Synthetic anionic surfactants are common water-soluble alkali metal salts organic sulfates and sulfonates with alkyl radicals from about 8 to 22 carbon atoms, the term "alkyl” being the Includes alkyl substituents of higher aryl groups.
- Suitable anionic detergents are sodium and ammonium alkyl sulfonates, especially the sulfates obtained by sulfating higher (C 8 to C 18 ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C 9 to C 20 , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C 10 to C 15 ; Sodium alkyl glycerol ether sulfates, especially the esters of higher alcohols derived from tallow and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides; Sodium and ammonium salts of the sulfuric acid esters of higher (C 9 to C 18 ) oxalkylated, especially the fatty alcohols alkoxylated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide; Sodium and ammonium
- nonionic surface-active compounds which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C 5 to C 22 ), the reaction products generally 5 to 25 ethylene oxide (EO ) Units contained in the molecule; the reaction products of aliphatic (C 8 to C 18 ) primary or secondary, linear or branched alcohols with ethylene oxide, with generally 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine.
- Other nonionic surfactants are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.
- Amphoteric or zwitterionic surfactants can also be used can be used in the compositions according to the invention, but what is usually not desired because of its high cost. If amphoteric or zwitterionic compounds are used, so this usually happens in small amounts in compositions that are mainly anionic and contain non-ionic surfactants.
- Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / nonionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants.
- the soaps used are preferably the sodium salts, and less preferably the potassium salts of saturated and unsaturated C 10 to C 24 fatty acids, or mixtures thereof.
- the proportions of such soaps can be from 0.5% by weight to 25% by weight, smaller amounts from 0.5% by weight to 5% by weight are generally sufficient for foam control. Soap contents between about 2% and about 20%, especially between about 5% and about 10%, have a positive effect. This is particularly the case in hard water, where the soap serves as an additional builder.
- the detergents and cleaning agents generally also contain a builder.
- Builders come into consideration: calcium-binding substances, precipitants, calcium-specific Ion exchangers and their mixtures.
- Examples of calcium binding Fabrics include alkali metal polyphosphates such as sodium tripolyphosphate; Nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of Carboxymethyloxy succinic acid, ethylenediaminetetraacetic acid, Oxydisuccinic acid, mellitic acid, benzopolycarboxylic acids, citric acid; and Polyacetal carboxylates as disclosed in U.S. Pat. 4144226 and 4146495.
- Examples for precipitating agents are sodium orthophosphate, sodium carbonate and soaps long chain fatty acids.
- ion exchangers that are specific for calcium are different types of water-insoluble, crystalline or amorphous Aluminum silicates, of which the zeolites are the best known representatives.
- the builder substances can be present in amounts of 5% by weight to 80% by weight a proportion of 10% by weight to 60% by weight is preferred.
- the washing and Cleaning agents contain conventional additives in amounts that one usually found in such means.
- foaming agents such as such as alkanolamides, especially the monoethanolamides from palm kernel oil fatty acids and coconut fatty acids; anti-foam substances such as Alkyl phosphates and silicones; Graying inhibitors and similar aids, such as such as sodium carboxymethyl cellulose and alkyl or substituted Alkyl cellulose ether; Stabilizers such as ethylenediaminetetraacetic acid; Plasticizers for textiles; inorganic salts such as sodium sulfate; and, usually small Quantities, fluorescent substances, perfumes, enzymes such as proteases, cellulases Lipases and amylases, disinfectants and dyes.
- the bleaching catalysts This invention can be used in a variety of products. This include textile detergents, textile bleaches, surface cleaners, Toilet cleaner, dishwasher cleaner, and also denture cleaner.
- the Detergents can be in solid or liquid form.
- the granules containing the bleaching catalysts according to the invention are in the general of the detergent composition together with the others, dry ingredients such as enzymes, inorganic peroxide bleaches added.
- the detergent composition to which the catalyst granules added can be obtained in various ways, such as Mixing the dry components, extruding, spray drying.
- the bleaching catalysts according to the invention are particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxide compound, such as sodium perborate, around the detergent great cleaning ability for fabrics and textiles.
- a bleaching peroxide compound such as sodium perborate
- Such non-aqueous, liquid detergents, pasty and gelatinous detergents Including compositions are described, for example, in US 2864770, US 2940938, US 4772412, US 3368977, GB 1205711, GB 1370377, GB 1270040, GB 1292352, GB 2194536, DE 2233771, EP 28849.
- These are compositions in the form of a non-aqueous liquid medium in which a solid phase can be dispersed.
- the non-aqueous, liquid medium can be a liquid, surface-active substance, preferably a nonionic surface-active substance, a non-polar liquid medium such as liquid Paraffin, a polar solvent, such as polyols, for example glycerol, Sorbitol, ethylene glycol, possibly in combination with low molecular weight monovalent Alcohols such as ethanol or isopropanol or mixtures thereof.
- a nonionic surface-active substance preferably a nonionic surface-active substance
- a non-polar liquid medium such as liquid Paraffin
- a polar solvent such as polyols, for example glycerol, Sorbitol, ethylene glycol, possibly in combination with low molecular weight monovalent Alcohols such as ethanol or isopropanol or mixtures thereof.
- the solid phase can consist of builder substances, alkalis, abrasive substances, Polymers and solid ionic surface-active compounds, bleaches, fluorescent substances and other common solid ingredients.
- a bleaching composition was prepared by combining 200 ml of an aqueous solution of reference detergent WMP (laundry research institute Krefeld, 5 g / l in water at 15 ° dH), 150 mg of sodium perborate monohydrate, 50 mg of tetraethylene diamine (TAED) and 2 mg of the respective catalyst.
- WMP laundry research institute Krefeld
- TAED tetraethylene diamine
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Pyridine Compounds (AREA)
- Paper (AREA)
Abstract
Description
Es ist bekannt, daß sich das Bleichvermögen peroxidischer Bleichmittel in Wasch- und Reinigungsmitteln, wie Wasserstoffperoxid, Perboraten, Percarbonaten, Persilikaten und Perphosphaten und somit die Effizienz dieser Bleichmittel zur Entfernung von Tee-, Kaffee-, Obst- oder Rotweinflecken erst bei höheren Temperaturen von deutlich über 60 °C voll entfaltet. Zur Verbesserung der bei niedrigeren Temperaturen, vor allem unter 60 °C, stark herabgesetzten Bleichwirkung können Verbindungen zur Aktivierung der Peroxidbleichmittel eingesetzt werden. Für diesen Zweck wurden eine Reihe von Übergangsmetallsalzen bzw. entsprechende Komplexe mit meist chelatisierenden Verbindungen vorgeschlagen, doch ist die Wirksamkeit eines Metalls bzw. einer speziellen Kombination von Übergangsmetall und Komplexligand nicht voraussagbar.It is known that the bleaching power of peroxidic bleaching agents in washing and Cleaning agents, such as hydrogen peroxide, perborates, percarbonates, Persilicate and perphosphate and thus the efficiency of these bleaching agents Removal of tea, coffee, fruit or red wine stains only at higher ones Temperatures well above 60 ° C fully developed. To improve at lower temperatures, especially below 60 ° C, greatly reduced Bleaching action can be compounds for activating the peroxide bleach be used. For this purpose, a number of Transition metal salts or corresponding complexes with mostly chelating Compounds proposed, but the effectiveness of a metal or special combination of transition metal and complex ligand not predictable.
Solche Metall-Komplexe zur Aktivierung von Peroxyverbindungen sind beschrieben in US 4728455, US 5314635, US 5244594, US 5114611, US 5114606, EP 549272, EP 544519, EP 544490, EP 544440, EP 509787, EP 458398, WO 9615136.Such metal complexes for activating peroxy compounds are described in US 4728455, US 5314635, US 5244594, US 5114611, US 5114606, EP 549272, EP 544519, EP 544490, EP 544440, EP 509787, EP 458398, WO 9615136.
Aus J. Inorg. Nucl. Chem. 1975, Vol. 37, pp. 2005 - 2006 sind auch neutrale Metallkomplexe mit Bis-(2-hydroxybenzyliden)-2,6-pyridindiamin als Ligand bekannt.From J. Inorg. Nucl. Chem. 1975, vol. 37, pp. 2005 - 2006 are also neutral Metal complexes with bis- (2-hydroxybenzylidene) -2,6-pyridinediamine are known as ligands.
Gegenstand der vorliegenden Erfindung sind bisher nicht bekannte Verbindungen
der allgemeinen Formel 1
- M
- für Mangan in der Oxidationsstufe II, III, IV, V und/oder VI oder Kobalt in der Oxidationsstufe II und/oder III,
- X
- eine Koordinations- oder Brückengruppe,
- Y
- ein Gegenion in der entsprechenden stöchiometrischen Menge zum Ausgleich einer vorhandenen Ladung z, wobei
- z
- als Ladung des Metall-Komplexes positiv, null oder negativ sein kann,
- n und m
- unabhängig voneinander ganze Zahlen von 1 bis 4
- p
- eine ganze Zahl von 0 bis 15,
- q
- z/Ladung von Y
- L
- einen Liganden der Formel (2)
- R1, R2
- unabhängig voneinander Wasserstoff, einen C1- bis C10-Alkyl-, Cycloalkyl- oder Arylrest,
- R3, R4, R5, R6, R7, R8
- unabhängig voneinander Wasserstoff, C1- bis C30-Alkyl-, Cycloalkyl- oder Arylreste, C1- bis C4-Alkoxygruppen, substituierte oder unsubstituierte Amino- bzw. Ammoniumgruppen, Halogenatome, Sulfogruppen, Carboxylgruppen, oder Gruppierungen der Formel -(CH2)r-COOH, -(CH2)r-SO3H, -(CH2)r-PO3H2, -(CH2)l-OH bedeuten, wobei r eine ganze Zahl von 0 bis 4 und l eine ganze Zahl von 1 bis 4 bedeutet und die genannten Säuregruppen auch in Salzform vorliegen können, ausgenommen Verbindungen der Formel 1 worin M = Mn, x = H2O, z = Null und R1, R2, R3, R4, R5, R6, R7 und R8 Wasserstoff sind.
- X
- ist vorzugsweise eine der folgenden Gruppen:
F-, Cl-, Br-, SCN-, OH-, O2 2-, O2-, O2 -, HOO-, R9OO-, H2O, SH-, CN-, OCN-, S2-, N3 -, NH3, NR9 3, NR9 2 -, R9O-, R9COO-, R9SO3 - und R9SO4 -, wobei R9 jeweils für Wasserstoff, C1 - bis C8-Alkyl, Cycloalkyl oder C6-bis C18-Aryl steht. Das Gegenion Y ist vorzugsweise ein Ion der folgenden Formeln:
- bei positivem z: F-, Cl-, Br-, NO3-, ClO4 -, SCN-, PF6 -, R9SO4 -, R9COO-, R9SO3 -, BF4 -, BPh4 -, SO4 2- und SO4 2-;
- bei negativem z: Li+, Na+, K+, Mg2+, Ca2+, Al3+, NH4 +, R9NH3 +, R9 2NH2 +, R9 3NH+ und R9 4N+,
wobei R9 die zuvor genannte Bedeutung hat. - M
- ist vorzugsweise Mangan, R1, R2, R3, R4, R5 und R6 sind vorzugsweise eine der oben genannten Gruppen, ausgenommen Wasserstoff, und R7 und R8 sind vorzugsweise Wasserstoff.
- M
- for manganese in oxidation state II, III, IV, V and / or VI or cobalt in oxidation state II and / or III,
- X
- a coordination or bridge group,
- Y
- a counter ion in the corresponding stoichiometric amount to balance an existing charge z, where
- e.g.
- the charge of the metal complex can be positive, zero or negative,
- n and m
- independently of one another integers from 1 to 4
- p
- an integer from 0 to 15,
- q
- z / charge of Y
- L
- a ligand of the formula (2)
- R 1 , R 2
- independently of one another hydrogen, a C 1 to C 10 alkyl, cycloalkyl or aryl radical,
- R 3 , R 4 , R 5 , R 6 , R 7 , R 8
- independently of one another hydrogen, C 1 - to C 30 -alkyl, cycloalkyl or aryl radicals, C 1 - to C 4 -alkoxy groups, substituted or unsubstituted amino or ammonium groups, halogen atoms, sulfo groups, carboxyl groups, or groups of the formula - (CH 2 ) r -COOH, - (CH 2 ) r -SO 3 H, - (CH 2 ) r -PO 3 H 2 , - (CH 2 ) l -OH, where r is an integer from 0 to 4 and l is an integer from 1 to 4 and the acid groups mentioned can also be in salt form, except for compounds of the formula 1 in which M = Mn, x = H 2 O, z = zero and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen.
- X
- is preferably one of the following groups:
F - , Cl - , Br - , SCN - , OH - , O 2 2- , O 2- , O 2 - , HOO - , R 9 OO - , H 2 O, SH - , CN - , OCN - , S 2- , N 3 - , NH 3 , NR 9 3 , NR 9 2 - , R 9 O - , R 9 COO - , R 9 SO 3 - and R 9 SO 4 - , where R 9 each represents hydrogen, C 1 - to C 8 alkyl, cycloalkyl or C 6 to C 18 aryl. The counter ion Y is preferably an ion of the following formulas:
- with positive z: F - , Cl - , Br - , NO 3 -, ClO 4 - , SCN - , PF 6 - , R 9 SO 4 - , R 9 COO - , R 9 SO 3 - , BF 4 - , BPh 4 - , SO 4 2- and SO 4 2- ;
- with negative z: Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , NH 4 + , R 9 NH 3 + , R 9 2 NH 2 + , R 9 3 NH + and R 9 4 N + ,
where R 9 has the meaning given above. - M
- is preferably manganese, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are preferably one of the groups mentioned above, except hydrogen, and R 7 and R 8 are preferably hydrogen.
Die Liganden der Formel 2 werden hergestellt durch Umsetzung von Salicylaldehyd und 2,6-Diaminopyridin oder deren entsprechend substituierten Derivaten analog zu den Angaben in J. Inorg. Nucl. Chem. 1975, Vol. 37, pp. 2005 - 2006. Die Herstellung der erfindungsgemäßen Metallkomplexe durch Umsetzung von Mn- oder Co-Salzen mit diesen Liganden erfolgt ebenfalls analog zu den Angaben dieser Literaturstelle.The ligands of formula 2 are prepared by reacting salicylaldehyde and 2,6-diaminopyridine or their correspondingly substituted derivatives analogously to the information in J. Inorg. Nucl. Chem. 1975, vol. 37, pp. 2005 - 2006. The Production of the metal complexes according to the invention by reacting Mn or Co-salts with these ligands are also carried out analogously to the information this reference.
Die erfindungsgemäßen ein- oder mehrkernigen Komplexe der allgemeinen Formel 1 eignen sich hervorragend als Bleich- und Oxidationskatalysatoren, insbesondere in Wasch- und Reinigungsmitteln und bei der Textil- und Papierbleiche. Besonders hervorzuheben sind hier Textilwaschmittel in Form von Pulverwaschmitteln oder als flüssige Formulierungen und Geschirreinigungsmittel. Ein Vorteil der erfindungsgemäßen Bleichkatalysatoren ist hierbei ihre Stabilität gegen Hydrolyse und Oxidation sowie ihre katalytische Wirkung bereits bei niedrigen Temperaturen. Sie verbessern in solchen Formulierungen nicht nur die Bleichwirkung von Wasserstoffperoxid, sondern auch von organischen und anorganischen Peroxy-Verbindungen. The mono- or polynuclear complexes of the general formula according to the invention 1 are particularly suitable as bleaching and oxidation catalysts, in particular in detergents and cleaning agents and in textile and paper bleaching. Especially Textile detergents in the form of powder detergents or as liquid formulations and dish detergents. An advantage of Bleach catalysts according to the invention are their stability against hydrolysis and oxidation and their catalytic effect even at low temperatures. In such formulations, they not only improve the bleaching effect of Hydrogen peroxide, but also from organic and inorganic peroxy compounds.
Gegenstand der vorliegenden Erfindung ist demgemäß auch ein Verfahren zum Bleichen von verschmutzten Substraten, wobei man das verschmutzte Substrat in wäßriger Bleichflotte mit Peroxyverbindungen und einer wirksamen Menge eines oder mehrerer der erfindungsgemäßen Metall-Komplexe als Bleichkatalysatoren in Kontakt bringt.The present invention accordingly also relates to a method for Bleaching soiled substrates, taking the soiled substrate in aqueous bleaching liquor with peroxy compounds and an effective amount of one or more of the metal complexes according to the invention as bleaching catalysts in Brings contact.
Dabei enthält die wäßrige Bleichflotte vorzugsweise diese Metall-Komplexe bezogen auf das Gewicht der Bleichflotte, in einer Menge von 0,001 bis 100 ppm Metall, insbesondere 0,01 bis 50 ppm Metall, vor allem 0,03 bis 20 ppm Metall (ppm bedeutet parts per million, bezogen auf das Gewicht). Höhere Gehalte an Metallkomplexen, etwa bis zu 500 ppm, können bei industriellen Bleichprozessen, beispielsweise auf dem Textil- oder Papiersektor, zweckmäßig sein. Die zuerst genannten niedrigen Metall-Gehalte beziehen sich vornehmlich auf Haushaltstextilwaschmittel.The aqueous bleaching liquor preferably contains these metal complexes based on the weight of the bleaching liquor, in an amount of 0.001 to 100 ppm Metal, especially 0.01 to 50 ppm metal, especially 0.03 to 20 ppm metal (ppm means parts per million based on weight). Higher levels Metal complexes, up to about 500 ppm, can be used in industrial bleaching processes, for example in the textile or paper sector. The first mentioned low metal contents mainly refer to Household textile detergent.
Gegenstand der Erfindung ist auch die Verwendung dieser Bleichkatalysatoren in bleichenden Wasch- und Reinigungsmitteln. Diese Wasch- und Reinigungsmittel enthalten neben einer Peroxidverbindung oder einer peroxidfreisetzenden Verbindung und dem Bleichkatalysator üblicherweise auch oberflächenaktive Verbindungen und weitere bekannte Inhaltsstoffe.The invention also relates to the use of these bleaching catalysts in bleaching detergents and cleaning agents. These detergents and cleaners contain in addition to a peroxide compound or a peroxide releasing Compound and the bleaching catalyst usually also surface-active Compounds and other known ingredients.
Geeignete Peroxide bzw. peroxidfreisetzende Verbindungen sind Alkalimetallperoxide, organische Peroxide wie Harnstoff-Wasserstoffperoxid-Addukte, und anorganische Persalze, wie die Alkaliperborate, -percarbonate, -perphosphate, -persilikate und -persulfate. Besonders bevorzugt sind Natriumperborat-Tetrahydrat und insbesondere Natriumperborat-Monohydrat. Natriumperborat-Monohydrat ist wegen seiner guten Lagerbeständigkeit und seiner guten Löslichkeit in Wasser bevorzugt. Natriumpercarbonat kann aus Umweltschutzgründen bevorzugt sein. Alkylhydroperoxide sind eine weitere geeignete Gruppe von Peroxidverbindungen. Beispiele für diese Stoffe sind Cumolhydroperoxid und t-Butylhydroperoxid. Auch aliphatische oder aromatische Mono- oder Dipercarbonsäuren sowie die entsprechenden Salze eignen sich als Peroxyverbindungen. Beispiele hierfür sind Peroxy-α-naphthoesäure, Peroxylaurinsäure, Peroxystearinsäure, N,N-Phthaloylaminoperoxycapronsäure, 1,12-Diperoxydodecandisäure, 1,9-Diperoxyazelainsäure, Diperoxysebacinsäure, Diperoxyisophthalsäure, 2-Decyldiperoxybutan-1,4-disäure und 4,4'-Sulfonylbisperoxybenzoesäure. Weiterhin eignen sich als Peroxyverbindungen anorganische Peroxysäure-Salze, z. B. Kaliummonopersulfat. Mischungen aus zwei oder mehreren dieser Verbindungen sind ebenfalls geeignet.Suitable peroxides or peroxide-releasing compounds are Alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts, and inorganic persalts, such as the alkali perborates, percarbonates, -perphosphates, -persilicates and -persulfates. Are particularly preferred Sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred. Sodium percarbonate can be made Environmental reasons may be preferred. Alkyl hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are Cumene hydroperoxide and t-butyl hydroperoxide. Also aliphatic or aromatic Mono- or dipercarboxylic acids and the corresponding salts are suitable as Peroxy compounds. Examples include peroxy-α-naphthoic acid, Peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, Diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonylbisperoxybenzoic acid. Also suitable as peroxy compounds inorganic peroxyacid salts, e.g. B. Potassium monopersulfate. Mixtures of two or more of these compounds are also suitable.
Die erfindungsgemäßen Wasch- und Reinigungsmittel-Formulierungen enthalten üblicherweise 1 bis 30 Gew.-%, insbesondere 2 bis 25 Gew. -% an Peroxyverbindungen.The detergent and cleaning agent formulations according to the invention contain usually 1 to 30% by weight, in particular 2 to 25% by weight Peroxy compounds.
Neben den Peroxyverbindungen können die Wasch- und Reinigungsmittel zusätzlich auch sogenannte Bleichaktivatoren in üblichen Mengen (ca. 1 bis 10 Gew.-%) enthalten.In addition to the peroxy compounds, the detergents and cleaning agents can additionally also so-called bleach activators in usual amounts (approx. 1 to 10 Wt .-%) included.
Beispiele für solche Bleichaktivatoren sind Verbindungen mit quaternären Ammonium-Strukturen wie beispielsweise 2-(N,N,N-Triethylammonio)ethyl-4-sulfophenylcarbonat, N-Octyl-N,N-dimethyl-N-10-carbophenoxydecylammoniumchlorid, 3-(N,N,N-Trimethylammonio)-propyl-Natrium-4-sulfobenzoat und N,N,N-Trimethylammonium-toluyl-oxybenzolsulfonat.Examples of such bleach activators are compounds with quaternary Ammonium structures such as 2- (N, N, N-triethylammonio) ethyl-4-sulfophenyl carbonate, N-octyl-N, N-dimethyl-N-10-carbophenoxydecylammonium chloride, 3- (N, N, N-trimethylammonio) propyl sodium 4-sulfobenzoate and N, N, N-trimethylammonium toluyl-oxybenzenesulfonate.
Neben den oben genannten quaternären Ammoniumsalzen sind Ester wie z. B.
Acylphenolsulfonate und der Acylalkylphenolsulfonate sowie Acylamide als
Bleichaktivator bevorzugt. Von besonderem Interesse sind hierbei die in der Praxis
gerne eingesetzten Verbindungen Natrium-4-benzoyloxybenzol-sulfonat, N,N,N,N
Als wirksame Menge der Metall-Komplexe der Formel 1 sind üblicherweise Mengen von 0,0001 bis 0,5 Gew.-% Metall, insbesondere 0,00025 bis 0,25 Gew.-% Metall, vor allem 0,0005 bis 0,1 Gew.-% Metall, bezogen auf das Gewicht der Formulierungen, in diesen Wasch- und Reinigungsmittelformulierungen enthalten. Diese Mengen können je nach landesüblichen Gepflogenheiten leicht schwanken.Amounts are usually the effective amount of the metal complexes of the formula 1 from 0.0001 to 0.5% by weight of metal, in particular 0.00025 to 0.25% by weight of metal, especially 0.0005 to 0.1 wt .-% metal, based on the weight of the Formulations contained in these detergent and cleaning agent formulations. These quantities can fluctuate slightly depending on local custom.
Die oberflächenaktive Substanz in den Wasch- und Reinigungsmitteln kann von Naturprodukten abgeleitet sein, wie etwa Seife, oder ist eine synthetische Verbindung aus der Gruppe der anionischen, nichtionischen, amphoteren, (zwitterionischen) oder kationischen oberflächenaktiven Substanzen, oder Mischungen aus diesen. Viele geeignete Substanzen sind kommerziell erhältlich, und sind in der Literatur beschrieben, beispielsweise in "Surface active agents and detergents", Vol. 1 und 2, von Schwartz, Perry und Berch. Der Gesamtanteil der oberflächenaktiven Verbindungen kann bis zu 50 Gew.-% betragen, vorzugsweise 1 Gew.-% bis 40 Gew.-%, insbesondere 4 Gew.-% bis 25 Gew.-% des gesamten Wasch- oder Reinigungsmittels betragen.The surface-active substance in the detergents and cleaning agents can be from Natural products, such as soap, or is synthetic Compound from the group of anionic, nonionic, amphoteric, (zwitterionic) or cationic surface-active substances, or Mixtures of these. Many suitable substances are commercially available, and are described in the literature, for example in "Surface active agents and detergents ", Vol. 1 and 2, by Schwartz, Perry and Berch. The total proportion of surface-active compounds can be up to 50% by weight, preferably 1 % By weight to 40% by weight, in particular 4% by weight to 25% by weight, of the total Detergent or cleaning agents.
Synthetische anionische oberflächaktive Substanzen sind üblicherweise wasserlösliche Alkalimetallsalze organische Sulfate und Sulfonate mit Alkylresten von etwa 8 bis 22 Kohlenstoffatomen, wobei der Ausdruck "Alkyl" die Alkylsubstituenten höherer Arylreste einschließt.Synthetic anionic surfactants are common water-soluble alkali metal salts organic sulfates and sulfonates with alkyl radicals from about 8 to 22 carbon atoms, the term "alkyl" being the Includes alkyl substituents of higher aryl groups.
Beispiele geeigneter anionischer Detergentien sind Natrium- und Ammoniumalkylsulfonate, speziell die durch Sulfatierung höherer (C8 bis C18) Alkohole erhaltenen Sulfate; Natrium- und Ammoniumalkylbenzolsulfonate mit einem Alkylrest von C9 bis C20, insbesondere lineare sekundäre Natriumalkylbenzolsufonate mit einem Alkylrest von C10 bis C15; Natriumalkylglycerinethersulfate, besonders die Ester der höheren, von Talg- und Kokosnußöl abgeleiteten Alkohole; die Natriumsulfate und -sulfonate der Kokosfettsäuremonoglyceride; Natrium- und Ammoniumsalze der Schwefelsäureester höherer (C9 bis C18) oxalkylierter, insbesondere der mit Ethylenoxid oxalkylierten Fettalkohole; die Reaktionsprodukte der Veresterung von Fettsäuren mit Isethionsäure und nachfolgender Neutralisierung mit Natriumhydroxid; Natrium- und Ammoniumsalze der Fettsäureamide des Methyltaurins; Alkan-Monosulfonate wie diejenigen aus der Reaktion von α-Olefinen (C8-C20) mit Natriumbisulfit und diejenigen aus der Reaktion von Paraffinen mit SO2 und Cl2 mit anschließender basischer Hydrolyse, wobei ein Gemisch verschiedener Sulfonate entsteht; Natrium- und Ammoniumdialkylsulfosuccinate mit Alkylresten von C7 bis C12; und Olefinsulfonate, die bei der Reaktion von Olefinen insbesondere C10- bis C20-α-Olefinen, mit SO3 und nachfolgender Hydrolyse der Reaktionsprodukte entstehen. Die bevorzugten anionischen Detergentien sind Natriumalkylbenzolsulfonate mit Alkylresten von C15 bis C18, und Natriumalkylether-sulfate mit Alkylresten von C8 bis C18.Examples of suitable anionic detergents are sodium and ammonium alkyl sulfonates, especially the sulfates obtained by sulfating higher (C 8 to C 18 ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C 9 to C 20 , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C 10 to C 15 ; Sodium alkyl glycerol ether sulfates, especially the esters of higher alcohols derived from tallow and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides; Sodium and ammonium salts of the sulfuric acid esters of higher (C 9 to C 18 ) oxalkylated, especially the fatty alcohols alkoxylated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide; Sodium and ammonium salts of the fatty acid amides of methyl taurine; Alkane monosulfonates such as those from the reaction of α-olefins (C 8 -C 20 ) with sodium bisulfite and those from the reaction of paraffins with SO 2 and Cl 2 with subsequent basic hydrolysis, resulting in a mixture of different sulfonates; Sodium and ammonium dialkyl sulfosuccinates with alkyl radicals from C 7 to C 12 ; and olefin sulfonates which are formed in the reaction of olefins, in particular C 10 -C 20 -α-olefins, with SO 3 and subsequent hydrolysis of the reaction products. The preferred anionic detergents are sodium alkylbenzenesulfonates with alkyl radicals from C 15 to C 18 , and sodium alkyl ether sulfates with alkyl radicals from C 8 to C 18 .
Beispiele für geeignete nichtionische oberflächenaktive Verbindungen, die bevorzugt zusammen mit anionischen oberflächenaktiven Verbindungen benutzt werden, sind insbesondere die Reaktionsprodukte von Alkylenoxiden (gewöhnlich Ethylenoxid) mit Alkylphenolen (Alkylreste von C5 bis C22), wobei die Reaktionsprodukte im allgemeinen 5 bis 25 Ethylenoxid (EO)-Einheiten im Molekül enthalten; die Reaktionsprodukte aliphatischer (C8 bis C18) primärer oder sekundärer, linearer oder verzweigter Alkohole mit Ethylenoxid, mit im allgemeinen 6 bis 30 EO, und die Additionsprodukte von Ethylenoxid an Reaktionsprodukte aus Propylenoxid und Ethylendiamin. Andere nichtionische oberflächenaktive Verbindungen sind Alkylpolyglycoside, langkettige tertiäre Aminoxide, langkettige tertiäre Phosphinoxide und Dialkylsulfoxide.Examples of suitable nonionic surface-active compounds, which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C 5 to C 22 ), the reaction products generally 5 to 25 ethylene oxide (EO ) Units contained in the molecule; the reaction products of aliphatic (C 8 to C 18 ) primary or secondary, linear or branched alcohols with ethylene oxide, with generally 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine. Other nonionic surfactants are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.
Amphotere oder zwitterionische oberflächenaktive Verbindungen können ebenfalls in den erfindungsgemäßen Zusammensetzungen verwendet werden, was aber wegen deren hoher Kosten meistens nicht erwünscht ist. Wenn amphotere bzw. zwitterionische Verbindungen verwendet werden, so geschieht das in der Regel in kleinen Mengen in Zusammensetzungen, die hauptsächlich anionische und nichtionische Tenside enthalten.Amphoteric or zwitterionic surfactants can also be used can be used in the compositions according to the invention, but what is usually not desired because of its high cost. If amphoteric or zwitterionic compounds are used, so this usually happens in small amounts in compositions that are mainly anionic and contain non-ionic surfactants.
Auch Seifen können in den erfindungsgemäßen Zusammensetzungen verwendet werden, vorzugsweise mit einem Anteil von weniger als 25 Gew.-%. Sie sind besonders geeignet in geringen Mengen in binären (Seife/nichtionisches Tensid) oder in ternären Mischungen zusammen mit nichtionischen oder gemischten synthetischen anionischen und nichtionischen Tensiden. Die verwendeten Seifen sind bevorzugt die Natriumsalze, und weniger bevorzugt die Kaliumsalze gesättigter und ungesättigter C10- bis C24-Fettsäuren, oder deren Mischungen. Die Anteile solcher Seifen können von 0,5 Gew.-% bis 25 Gew.-% betragen, geringere Mengen von 0,5 Gew.-% bis 5 Gew.-% sind im allgemeinen ausreichend zur Schaumkontrolle. Seifenanteile zwischen etwa 2 % und etwa 20 %, besonders zwischen etwa 5 % und etwa 10 %, haben einen positiven Effekt. Dieses ist besonders der Fall in hartem Wasser, wo die Seife als zusätzliche Buildersubstanz dient.Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / nonionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants. The soaps used are preferably the sodium salts, and less preferably the potassium salts of saturated and unsaturated C 10 to C 24 fatty acids, or mixtures thereof. The proportions of such soaps can be from 0.5% by weight to 25% by weight, smaller amounts from 0.5% by weight to 5% by weight are generally sufficient for foam control. Soap contents between about 2% and about 20%, especially between about 5% and about 10%, have a positive effect. This is particularly the case in hard water, where the soap serves as an additional builder.
Die Wasch- und Reinigungsmittel enthalten im allgemeinen auch einen Builder. Als Builder kommen in Betracht: Calcium-bindende Stoffe, Fällungsmittel, Calcium-spezifische Ionenaustauscher und deren Mischungen. Beispiele für Calcium-bindende Stoffe umfassen Alkalimetallpolyphosphate, wie Natriumtripolyphosphat; Nitrilotriessigsäure und ihre wasserlöslichen Salze; die Alkalimetallsalze der Carboxymethyloxybernsteinsäure, Ethylendiamintetraessigsäure, Oxydibersteinsäure, Mellithsäure, Benzopolycarbonsäuren, Zitronensäure; und Polyacetalcarboxylate, wie in U. S. Pat. 4144226 und 4146495 offenbart. Beispiele für Fällungsmittel sind Natriumorthophosphat, Natriumcarbonat und Seifen aus langkettigen Fettsäuren.The detergents and cleaning agents generally also contain a builder. As Builders come into consideration: calcium-binding substances, precipitants, calcium-specific Ion exchangers and their mixtures. Examples of calcium binding Fabrics include alkali metal polyphosphates such as sodium tripolyphosphate; Nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of Carboxymethyloxy succinic acid, ethylenediaminetetraacetic acid, Oxydisuccinic acid, mellitic acid, benzopolycarboxylic acids, citric acid; and Polyacetal carboxylates as disclosed in U.S. Pat. 4144226 and 4146495. Examples for precipitating agents are sodium orthophosphate, sodium carbonate and soaps long chain fatty acids.
Beispiele für Ionenaustauscher, die für Calcium spezifisch sind, sind die verschiedenen Arten von wasserunlöslichen, kristallinen oder amorphen Aluminiumsilicate, von denen die Zeolithe die bekanntesten Vertreter sind.Examples of ion exchangers that are specific for calcium are different types of water-insoluble, crystalline or amorphous Aluminum silicates, of which the zeolites are the best known representatives.
Die Buildersubstanzen können in Mengen von 5 Gew.-% bis 80 Gew.-% vorhanden sein, bevorzugt ist ein Anteil von 10 Gew.-% bis 60 Gew.-%.The builder substances can be present in amounts of 5% by weight to 80% by weight a proportion of 10% by weight to 60% by weight is preferred.
Neben den bereits erwähnten Inhaltsstoffen können die Wasch- und Reinigungsmittel konventionelle Zusatzstoffe in Mengen enthalten, die man üblicherweise in solchen Mitteln vorfindet. Beispiele hierfür sind Schaumbildner, wie etwa Alkanolamide, besonders die Monoethanolamide aus Palmkernöl-Fettsäuren und Kokosnuß-Fettsäuren; schaumverhindernde Substanzen, wie etwa Alkylphosphate und -silicone; Vergrauungsinhibitoren und ähnliche Hilfsmittel, wie etwa Natriumcarboxymethylcellulose und Alkyl- oder substituierte Alkylcelluloseether; Stabilisatoren, wie Ethylendiamintetraessigsäure; Weichmacher für Textilien; anorganische Salze, wie Natriumsulfat; und, in üblicherweise kleinen Mengen, fluoreszierende Stoffe, Parfüme, Enzyme wie Proteasen, Cellulasen Lipasen und Amylasen, Desinfektionsmittel und Farbstoffe. Die Bleichkatalysatoren dieser Erfindung können in einer Vielzahl von Produkten eingesetzt werden. Diese umfassen Textilwaschmittel, Textilbleichmittel, Oberflächenreiniger, Toilettenreiniger, Geschirrspülmaschinenreiniger, und auch Gebißreiniger. Die Waschmittel können in fester Form oder flüssiger Form vorliegen.In addition to the ingredients already mentioned, the washing and Cleaning agents contain conventional additives in amounts that one usually found in such means. Examples of these are foaming agents, such as such as alkanolamides, especially the monoethanolamides from palm kernel oil fatty acids and coconut fatty acids; anti-foam substances such as Alkyl phosphates and silicones; Graying inhibitors and similar aids, such as such as sodium carboxymethyl cellulose and alkyl or substituted Alkyl cellulose ether; Stabilizers such as ethylenediaminetetraacetic acid; Plasticizers for textiles; inorganic salts such as sodium sulfate; and, usually small Quantities, fluorescent substances, perfumes, enzymes such as proteases, cellulases Lipases and amylases, disinfectants and dyes. The bleaching catalysts This invention can be used in a variety of products. This include textile detergents, textile bleaches, surface cleaners, Toilet cleaner, dishwasher cleaner, and also denture cleaner. The Detergents can be in solid or liquid form.
Es ist aus Gründen der Stabilität und Handhabbarkeit vorteilhaft, die Bleichaktivatoren in Form von Granulaten zu verwenden, die neben dem Bleichkatalysator ein Bindemittel enthalten. Verschiedene Methoden, solche Granulate herzustellen, sind in der Patentliteratur beschrieben, so beispielsweise in Kanada Pat. Nr. 1102966, GB 1561333, US 4087369, EP 240057, EP 241962, EP 101634 und EP 62523.It is advantageous for reasons of stability and manageability To use bleach activators in the form of granules, in addition to the Bleach catalyst contain a binder. Different methods, such Producing granules are described in the patent literature, for example in Canada Pat. No. 1102966, GB 1561333, US 4087369, EP 240057, EP 241962, EP 101634 and EP 62523.
Die die erfindungsgemäßen Bleichkatalysatoren enthaltenden Granulate werden im allgemeinen der Waschmittelzusammensetzung zusammen mit den anderen, trockenen Bestandteilen wie etwa Enzymen, anorganischen Peroxidbleichmitteln zugesetzt. Die Waschmittelzusammensetzung, zu der die Katalysatorgranulate zugegeben werden, kann auf verschiedenen Wegen erhalten werden, wie etwa Mischen der trockenen Komponenten, Extrudieren, Sprühtrocknung.The granules containing the bleaching catalysts according to the invention are in the general of the detergent composition together with the others, dry ingredients such as enzymes, inorganic peroxide bleaches added. The detergent composition to which the catalyst granules added can be obtained in various ways, such as Mixing the dry components, extruding, spray drying.
In einer weiteren Ausführungsform sind die erfindungsgemäßen Bleichkatalysatoren besonders geeignet für nicht-wäßrige flüssige Waschmittel, zusammen mit einer bleichenden Peroxidverbindung, etwa Natriumperborat, um dem Waschmittel ein großes Reinigungsvermögen für Gewebe und Textilien zu verleihen. Derartige nicht-wäßrige, flüssige Waschmittel, die pastöse und gelatinöse Detergentien zusammensetzungen mit einschließen, sind beispielsweise in US 2864770, US 2940938, US 4772412, US 3368977, GB 1205711, GB 1370377, GB 1270040, GB 1292352, GB 2194536, DE 2233771, EP 28849 beschrieben. Es handelt sich dabei um Zusammensetzungen in Form eines nichtwäßrigen, flüssigen Mediums, in dem eine feste Phase dispergiert sein kann. Das nicht wäßrige, flüssige Medium kann eine flüssige, oberflächenaktive Substanz sein, vorzugsweise eine nichtionische oberflächenaktive Substanz, ein nicht polares flüssiges Medium wie etwa flüssiges Paraffin, ein polares Lösungsmittel, wie etwa Polyole, zum Beispiel Glycerin, Sorbitol, Ethylenglycol, eventuell in Verbindung mit niedermolekularen einwertigen Alkoholen wie Ethanol oder Isopropanol oder Mischungen daraus.In a further embodiment, the bleaching catalysts according to the invention are particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxide compound, such as sodium perborate, around the detergent great cleaning ability for fabrics and textiles. Such non-aqueous, liquid detergents, pasty and gelatinous detergents Including compositions are described, for example, in US 2864770, US 2940938, US 4772412, US 3368977, GB 1205711, GB 1370377, GB 1270040, GB 1292352, GB 2194536, DE 2233771, EP 28849. These are compositions in the form of a non-aqueous liquid medium in which a solid phase can be dispersed. The non-aqueous, liquid medium can be a liquid, surface-active substance, preferably a nonionic surface-active substance, a non-polar liquid medium such as liquid Paraffin, a polar solvent, such as polyols, for example glycerol, Sorbitol, ethylene glycol, possibly in combination with low molecular weight monovalent Alcohols such as ethanol or isopropanol or mixtures thereof.
Die feste Phase kann aus Buildersubstanzen, Alkalien, abrasiven Stoffen, Polymeren und festen ionischen oberflächenaktiven Verbindungen, Bleichmitteln, fluoreszierenden Stoffen und anderen üblichen festen Inhaltsstoffen bestehen.The solid phase can consist of builder substances, alkalis, abrasive substances, Polymers and solid ionic surface-active compounds, bleaches, fluorescent substances and other common solid ingredients.
Die folgenden Beispiele sollen einen Überblick über die Ausführungsformen der Erfindung geben.
- Beispiel 1:
- Bis(3,5-di-tert.butyl-2-hydroxybenzyliden)-2,6-pyridindiamin-Mangan-Komplex
- Example 1:
- Bis (3,5-di-tert-butyl-2-hydroxybenzylidene) -2,6-pyridinediamine-manganese complex
Eine Lösung von 23,7 g 3,5-Ditert.butyl-2-hydroxybenzaldehyd in 100 ml Ethanol wurde mit 5,57 g 2,6-Diaminopyridin versetzt und die erhaltene Lösung zwei Stunden unter Rückfluß zum Sieden erhitzt. Der ausgefallene Feststoff wurde abgetrennt, mit Isopropanol gewaschen und getrocknet, dabei wurden 19,6 g Bis(3,5-ditert.butyl-2-hydroxybenzyliden)-2,6-pyridindiamin erhalten. 3,25 g der so erhaltenen Verbindung wurden in einem Gemisch aus 300 ml Ethanol und 105 ml Dimethylformamid gelöst und portionsweise 1,47 g Mangan-(II)-acetat (Tetrahydrat) zugegeben. Nach zweistündigem Rühren in der Siedehitze wurde das Solvens am Rotationsverdampfer (Wasserstrahlvakuum) entfernt und der Rückstand mit Ethanol gewaschen. Es wurden 3,60 g Bis(3,5-ditert.butyl-2-hydroxybenzyliden)-2,6-pyridindiamin-Mangan-Komplex in Form eines gelb-braunen amorphen Feststoffs erhalten.A solution of 23.7 g of 3,5-ditert.butyl-2-hydroxybenzaldehyde in 100 ml of ethanol 5.57 g of 2,6-diaminopyridine were added and the solution obtained two Heated to reflux for hours. The precipitated solid became separated, washed with isopropanol and dried, 19.6 g Get bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine. 3.25 g of the like Compound obtained were in a mixture of 300 ml of ethanol and 105 ml Dimethylformamide dissolved and in portions 1.47 g of manganese (II) acetate (tetrahydrate) admitted. After stirring for two hours at the boil, the solvent was removed on Rotary evaporator (water jet vacuum) removed and the residue with ethanol washed. 3.60 g of bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine-manganese complex were obtained in the form of a yellow-brown amorphous solid receive.
In analoger Weise werden die folgenden Metallkomplexe hergestellt. Soweit diese Metallkomplexe Kobalt enthalten, wurden diese Verbindungen ausgehend von Kobalt-(II)-acetat in Form des Tetrahydrats hergestellt:
- Beispiel 2:
- Bis(3,5-ditert.butyl-2-hydroxybenzyliden)-2,6-pyridindiamin-Kobalt-Komplex
- Beispiel 3:
- Bis(2-hydroxybenzyliden)-2,6-pyridindiamin-Mangan-Komplex
- Beispiel 4:
- Bis(2-hydroxybenzyliden)-2,6-pyridindiamin-Kobalt-Komplex
- Beispiel 5:
- Bis(2-hydroxy-3-methoxybenzyliden)-2,6-pyridindiamin-Mangan-Komplex
- Beispiel 6:
- Bis(2-hydroxy-3-methoxybenzyliden)-2,6-pyridindiamin-Kobalt-Komplex
- Beispiel 7:
- Bis(2-hydroxy-4-methoxybenzyliden)-2,6-pyridindiamin-Mangan-Komplex
- Beispiel 8:
- Bis(2-hydroxy-4-methoxybenzyliden)-2,6-pyridindiamin-Kobalt-Komplex
- Beispiel 9:
- Bis(2-hydroxy-4-diethylaminobenzyliden)-2,6-pyridindiamin-Mangan-Komplex
- Beispiel 10:
- Bis(2-hydroxy-4-diethylaminobenzyliden)-2,6-pyridindiamin-Kobalt-Komplex
- Beispiel 11:
- Bis(2-hydroxy-5-nitrobenzyliden)-2,6-pyridindiamin-Mangan-Komplex
- Beispiel 12:
- Bis(2-hydroxy-5-nitrobenzyliden)-2,6-pyridindiamin-Kobalt-Komplex
- Example 2:
- Bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine-cobalt complex
- Example 3:
- Bis (2-hydroxybenzylidene) -2,6-pyridinediamine-manganese complex
- Example 4:
- Bis (2-hydroxybenzylidene) -2,6-pyridinediamine cobalt complex
- Example 5:
- Bis (2-hydroxy-3-methoxybenzylidene) -2,6-pyridinediamine-manganese complex
- Example 6:
- Bis (2-hydroxy-3-methoxybenzylidene) -2,6-pyridinediamine cobalt complex
- Example 7:
- Bis (2-hydroxy-4-methoxybenzylidene) -2,6-pyridinediamine-manganese complex
- Example 8:
- Bis (2-hydroxy-4-methoxybenzylidene) -2,6-pyridinediamine cobalt complex
- Example 9:
- Bis (2-hydroxy-4-diethylaminobenzylidene) -2,6-pyridinediamine-manganese complex
- Example 10:
- Bis (2-hydroxy-4-diethylaminobenzylidene) -2,6-pyridinediamine-cobalt complex
- Example 11:
- Bis (2-hydroxy-5-nitrobenzylidene) -2,6-pyridinediamine-manganese complex
- Example 12:
- Bis (2-hydroxy-5-nitrobenzylidene) -2,6-pyridinediamine-cobalt complex
Durch Zusammengeben von 200 ml einer wäßrigen Lösung Referenzwaschmittel
WMP (Wäschereiforschungsinstitut Krefeld, 5 g/l in Wasser mit 15° dH), 150 mg
Natriumperborat-Monohydrat, 50 mg Tetraethylendiamin (TAED) und 2 mg des
jeweiligen Katalysators wurde eine Bleichmittelzusammensetzung hergestellt. Mit
dieser Zusammensetzung wurde mit schwarzem Tee verschmutzte Gewebestücke
(BC-1-Tee auf Baumwolle, Wäschereiforschungsinstitut Krefeld) in einem Linitest-Gerät
(Heraeus) einer Behandlung bei einer Temperatur von 40 °C unter
isothermen Waschbedingungen unterworfen. Nach einer dreißigminütigen
Waschzeit wurden die Gewebestücke mit Wasser gespült, getrocknet und gebügelt;
anschließend wurde die Bleichwirkung durch eine Bestimmung der Differenzen Δ
R(KAT-TAED) der Remissionen vor und nach dem Bleichen mittels eines Weißgrad-Meßgerätes
ELREPHO 2000 (Firma Datacolor) quantifiziert. Aus diesen Δ R(KAT-TAED)-Werten
und den in Kontrollversuchen ohne Bleichkatalysator ermittelten Δ
R(TAED)-Werten wurden die in Tabelle 1 aufgelisteten ΔΔ R-Werte berechnet, die
einen direkten Maßstab für die durch den Zusatz an Katalysator hervorgerufene
Verbesserung der Bleichwirkung darstellen:
Weitere vorteilhafte Eigenschaften der beschriebenen Komplexe sind geringe Farbschädigung und geringe Faserschädigung.Further advantageous properties of the complexes described are low Color damage and minor fiber damage.
Claims (11)
- M
- Mangan in der Oxidationsstufe II, III, IV, V und/oder VI oder Kobalt in der Oxidationsstufe II und/oder III,
- X
- eine Koordinations- oder Brückengruppe,
- Y
- ein Gegenion in der entsprechenden stöchiometrischen Menge zum Ausgleich einer vorhandenen Ladung z, wobei
- z
- als Ladung des Metall-Komplexes positiv, null oder negativ sein kann,
- n und m
- unabhängig voneinander ganze Zahlen von 1 bis 4,
- p
- eine ganze Zahl von 0 bis 15,
- q
- z/Ladung von Y
- L
- einen Liganden der Formel (2)
- R1, R2
- unabhängig voneinander Wasserstoff, einen C1- bis C10-Alkyl-, Cycloalkyl- oder Arylrest,
- R3, R4, R5, R6, R7, R8
- unabhängig voneinander Wasserstoff, C1- bis C30-Alkyl-, Cycloalkyl- oder Arylreste, C1- bis C4-Alkoxygruppen, substituierte oder unsubstituierte Amino- bzw. Ammoniumgruppen, Halogenatome, Sulfogruppen, Carboxylgruppen, oder Gruppierungen der Formel -(CH2)r-COOH, -(CH2)r-SO3H, -(CH2)r-PO3H2, -(CH2)1-OH bedeuten, wobei r eine ganze Zahl von 0 bis 4 und l eine ganze Zahl von 1 bis 4 bedeutet und die genannten Säuregruppen auch in Salzform vorliegen können, ausgenommen Verbindungen der Formel 1 worin M = Mn, x = H2O, z = Null und R1, R2, R3, R4, R5, R6, R7 und R8 Wasserstoff sind.
- M
- Manganese in oxidation state II, III, IV, V and / or VI or cobalt in oxidation state II and / or III,
- X
- a coordination or bridge group,
- Y
- a counter ion in the corresponding stoichiometric amount to balance an existing charge z, where
- e.g.
- the charge of the metal complex can be positive, zero or negative,
- n and m
- independently of one another integers from 1 to 4,
- p
- an integer from 0 to 15,
- q
- z / charge of Y
- L
- a ligand of the formula (2)
- R 1 , R 2
- independently of one another hydrogen, a C 1 to C 10 alkyl, cycloalkyl or aryl radical,
- R 3 , R 4 , R 5 , R 6 , R 7 , R 8
- independently of one another hydrogen, C 1 - to C 30 -alkyl, cycloalkyl or aryl radicals, C 1 - to C 4 -alkoxy groups, substituted or unsubstituted amino or ammonium groups, halogen atoms, sulfo groups, carboxyl groups, or groups of the formula - (CH 2 ) r -COOH, - (CH 2 ) r -SO 3 H, - (CH 2 ) r -PO 3 H 2 , - (CH 2 ) 1 -OH, where r is an integer from 0 to 4 and l is an integer from 1 to 4 and the acid groups mentioned can also be in salt form, with the exception of compounds of the formula 1 in which M = Mn, x = H 2 O, z = zero and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19714122A DE19714122A1 (en) | 1997-04-05 | 1997-04-05 | Bleach-active metal complexes |
DE19714122 | 1997-04-05 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0869171A2 true EP0869171A2 (en) | 1998-10-07 |
EP0869171A3 EP0869171A3 (en) | 1999-04-07 |
EP0869171B1 EP0869171B1 (en) | 2004-11-03 |
Family
ID=7825561
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98105257A Expired - Lifetime EP0869171B1 (en) | 1997-04-05 | 1998-03-24 | Metal complexes as bleach activators |
Country Status (6)
Country | Link |
---|---|
US (2) | US6139769A (en) |
EP (1) | EP0869171B1 (en) |
JP (1) | JP4049881B2 (en) |
BR (1) | BR9801148A (en) |
DE (2) | DE19714122A1 (en) |
ES (1) | ES2231913T3 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999064554A1 (en) * | 1998-06-05 | 1999-12-16 | Lg Chemical Ltd. | Bleaching activator |
GB2366575A (en) * | 2000-09-11 | 2002-03-13 | Unilever Plc | Bleaching composition |
WO2012000846A1 (en) | 2010-06-28 | 2012-01-05 | Basf Se | Metal free bleaching composition |
WO2013060708A1 (en) | 2011-10-25 | 2013-05-02 | Basf Se | Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes |
WO2013060706A1 (en) | 2011-10-25 | 2013-05-02 | Basf Se | Use of acrylate copolymers as soil antiredeposition agents and soil release agents in laundry processes |
WO2014154508A1 (en) | 2013-03-27 | 2014-10-02 | Basf Se | Block copolymers as soil release agents in laundry processes |
WO2017186480A1 (en) | 2016-04-26 | 2017-11-02 | Basf Se | Metal free bleaching composition |
US10214606B2 (en) | 2013-11-27 | 2019-02-26 | Basf Se | Random copolymers as soil release agents in laundry processes |
EP3524347A1 (en) | 2008-04-09 | 2019-08-14 | Basf Se | Use of metal hydrazide complex compounds as oxidation catalysts |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PH11999002188B1 (en) * | 1998-09-01 | 2007-08-06 | Unilever Nv | Method of treating a textile |
ES2244424T3 (en) * | 1999-04-01 | 2005-12-16 | Unilever N.V. | COMPOSITION AND PROCEDURE FOR WHITENING A SUBSTRATE. |
WO2000060043A1 (en) * | 1999-04-01 | 2000-10-12 | Unilever Plc | Composition and method for bleaching a substrate |
GB0004990D0 (en) | 2000-03-01 | 2000-04-19 | Unilever Plc | Composition and method for bleaching a substrate |
BR0013745A (en) | 1999-09-01 | 2002-05-14 | Unilever Nv | Bleaching composition for a textile |
BR0013593A (en) | 1999-09-01 | 2002-05-07 | Unilever Nv | Method for bleaching fabric stains |
BR0013592A (en) | 1999-09-01 | 2002-05-07 | Unilever Nv | Commercial packaging for bleaching fabric stains in an aqueous washing liquor, and using it |
AU2001256155A1 (en) | 2000-02-29 | 2001-09-12 | Unilever Plc | Composition and method for bleaching a substrate |
DE10304131A1 (en) * | 2003-02-03 | 2004-08-05 | Clariant Gmbh | Transition metal complexes with nitrogen-containing ligands are used as catalysts for peroxy compounds, especially in detergent, bleaching and cleansing agents |
US7572390B2 (en) * | 2005-06-22 | 2009-08-11 | Truox, Inc. | Composition and method for reducing chemical oxygen demand in water |
US7794607B2 (en) * | 2005-06-22 | 2010-09-14 | Truox, Inc. | Composition and method for enhanced sanitation and oxidation of aqueous systems |
US7476333B2 (en) * | 2005-06-22 | 2009-01-13 | Truox, Inc. | Composition and method for reducing chemical oxygen demand in water |
US7695631B2 (en) * | 2005-06-22 | 2010-04-13 | Truox, Inc. | Composition and method for reducing chemical oxygen demand in water |
JP2007126776A (en) * | 2005-11-02 | 2007-05-24 | Nisshin Kagaku Kenkyusho:Kk | Method for treatment of waste paper pulp and deinking assistant |
JP5352099B2 (en) * | 2007-03-09 | 2013-11-27 | 住友化学株式会社 | Redox catalyst using modified metal complex |
EP2970542B1 (en) | 2013-03-15 | 2019-07-24 | Lubrizol Advanced Materials, Inc. | Itaconic acid copolymers |
TWI637053B (en) | 2014-03-14 | 2018-10-01 | 美商盧伯利索先進材料有限公司 | Polymers, process for preparing polymer solution thereof, and process of chelating metal ions from solution |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5114611A (en) * | 1989-04-13 | 1992-05-19 | Lever Brothers Company, Divison Of Conopco, Inc. | Bleach activation |
GB2307250A (en) * | 1995-11-18 | 1997-05-21 | Ciba Geigy Ag | Fabric bleaching composition |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928328A (en) * | 1972-12-08 | 1975-12-23 | Du Pont | Schiff base and metal bisazomethine metal chelate |
GB1439048A (en) * | 1973-09-11 | 1976-06-09 | Ciba Geigy Ag | Metal complexes of bis-azomethines and processes for their manufacture |
CH596276A5 (en) * | 1974-07-31 | 1978-03-15 | Ciba Geigy Ag | |
US4728455A (en) * | 1986-03-07 | 1988-03-01 | Lever Brothers Company | Detergent bleach compositions, bleaching agents and bleach activators |
US4861904A (en) * | 1986-04-17 | 1989-08-29 | Agency Of Industrial Science And Technology | Schiff base metal complex compounds, and organometallic ultrathin film composed thereof and oxygen separation films composed thereof |
GB9003741D0 (en) * | 1990-02-19 | 1990-04-18 | Unilever Plc | Bleach activation |
US5266283A (en) * | 1990-05-11 | 1993-11-30 | Bend Research, Inc. | Sterically hindered, regenerable Schiff base complexes, solutions thereof and process using the same |
ES2100924T3 (en) * | 1990-05-21 | 1997-07-01 | Unilever Nv | WHITENING ACTIVATION. |
GB9108136D0 (en) * | 1991-04-17 | 1991-06-05 | Unilever Plc | Concentrated detergent powder compositions |
GB9124581D0 (en) * | 1991-11-20 | 1992-01-08 | Unilever Plc | Bleach catalyst composition,manufacture and use thereof in detergent and/or bleach compositions |
EP0544490A1 (en) * | 1991-11-26 | 1993-06-02 | Unilever Plc | Detergent bleach compositions |
US5194416A (en) * | 1991-11-26 | 1993-03-16 | Lever Brothers Company, Division Of Conopco, Inc. | Manganese catalyst for activating hydrogen peroxide bleaching |
CA2085642A1 (en) * | 1991-12-20 | 1993-06-21 | Ronald Hage | Bleach activation |
GB9127060D0 (en) * | 1991-12-20 | 1992-02-19 | Unilever Plc | Bleach activation |
ATE169330T1 (en) * | 1993-06-19 | 1998-08-15 | Ciba Geigy Ag | INHIBITION OF REABSORPTION OF MIGRING DYES IN THE WASH SOLUTION |
EP0804444A1 (en) * | 1994-11-14 | 1997-11-05 | Dublin Institute of Technology | Novel mn(ii) carboxylate complexes, processes for their preparation and their use as disproportionation catalysts |
GB9425296D0 (en) * | 1994-12-15 | 1995-02-15 | Ciba Geigy Ag | Inhibition of dye migration |
DE19719397A1 (en) * | 1997-05-07 | 1998-11-12 | Clariant Gmbh | Bleach-active metal complexes |
-
1997
- 1997-04-05 DE DE19714122A patent/DE19714122A1/en not_active Withdrawn
-
1998
- 1998-03-24 DE DE59812192T patent/DE59812192D1/en not_active Expired - Fee Related
- 1998-03-24 ES ES98105257T patent/ES2231913T3/en not_active Expired - Lifetime
- 1998-03-24 EP EP98105257A patent/EP0869171B1/en not_active Expired - Lifetime
- 1998-04-02 US US09/054,204 patent/US6139769A/en not_active Expired - Fee Related
- 1998-04-03 JP JP09204098A patent/JP4049881B2/en not_active Expired - Fee Related
- 1998-04-03 BR BR9801148-0A patent/BR9801148A/en not_active Application Discontinuation
-
2000
- 2000-07-10 US US09/613,211 patent/US6602441B1/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5114611A (en) * | 1989-04-13 | 1992-05-19 | Lever Brothers Company, Divison Of Conopco, Inc. | Bleach activation |
GB2307250A (en) * | 1995-11-18 | 1997-05-21 | Ciba Geigy Ag | Fabric bleaching composition |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 53, no. 01, 1959 Columbus, Ohio, US; abstract no. 1334, SAVICH I ET AL: "Synthesis of a series of Schiff bases formed from aromatic hydroxy aldehydes and heterocyclic amines" Seite 00; Spalte 1334; XP002087320 & IDEM, * |
TAYIM H A, A'MA A: "Schiff base complexes" AUS. J. INORG. NUCL. CHEM., Bd. 37, 1975, XP002087817 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999064554A1 (en) * | 1998-06-05 | 1999-12-16 | Lg Chemical Ltd. | Bleaching activator |
US6528470B1 (en) | 1998-06-05 | 2003-03-04 | Lg Chemical Ltd. | Bleaching activator |
GB2366575A (en) * | 2000-09-11 | 2002-03-13 | Unilever Plc | Bleaching composition |
EP3524347A1 (en) | 2008-04-09 | 2019-08-14 | Basf Se | Use of metal hydrazide complex compounds as oxidation catalysts |
WO2012000846A1 (en) | 2010-06-28 | 2012-01-05 | Basf Se | Metal free bleaching composition |
WO2013060708A1 (en) | 2011-10-25 | 2013-05-02 | Basf Se | Use of comb or block copolymers as soil antiredeposition agents and soil release agents in laundry processes |
WO2013060706A1 (en) | 2011-10-25 | 2013-05-02 | Basf Se | Use of acrylate copolymers as soil antiredeposition agents and soil release agents in laundry processes |
WO2014154508A1 (en) | 2013-03-27 | 2014-10-02 | Basf Se | Block copolymers as soil release agents in laundry processes |
US9790452B2 (en) | 2013-03-27 | 2017-10-17 | Basf Se | Block copolymers as soil release agents in laundry processes |
US10214606B2 (en) | 2013-11-27 | 2019-02-26 | Basf Se | Random copolymers as soil release agents in laundry processes |
WO2017186480A1 (en) | 2016-04-26 | 2017-11-02 | Basf Se | Metal free bleaching composition |
Also Published As
Publication number | Publication date |
---|---|
EP0869171A3 (en) | 1999-04-07 |
US6602441B1 (en) | 2003-08-05 |
BR9801148A (en) | 2000-02-08 |
DE19714122A1 (en) | 1998-10-08 |
JP4049881B2 (en) | 2008-02-20 |
EP0869171B1 (en) | 2004-11-03 |
JPH115993A (en) | 1999-01-12 |
DE59812192D1 (en) | 2004-12-09 |
ES2231913T3 (en) | 2005-05-16 |
US6139769A (en) | 2000-10-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0869171B1 (en) | Metal complexes as bleach activators | |
EP0877078B1 (en) | Bleach activating metal complex | |
DE69816981T2 (en) | BLEACH COMPOSITIONS CONTAINING METAL BLEACH CATALYSTS, AND BLEACH ACTIVATORS AND / OR ORGANIC PERCARBOXYLIC ACID | |
DE69827738T2 (en) | bleach activation | |
DE69825166T2 (en) | Washing and bleaching compositions | |
EP1148118B1 (en) | Detergent comprising dendrimeric ligands and their metallo-complexes as bleach activators | |
DE60033560T2 (en) | METHOD FOR TREATING TEXTILES | |
EP0825251A2 (en) | Use of sulphonylimine derivatives as bleach catalysts | |
EP0909810B1 (en) | Use of aminonitrile-N-oxides as bleach activators | |
CH655945A5 (en) | SILICATE-FREE, BLEACHING DETERGENT COMPOSITION. | |
EP0889050A2 (en) | Metal complexes as bleach activators | |
EP1083173B1 (en) | Metal complexes with bleaching activity | |
DE10037162A1 (en) | Bleaching and oxidizing agents and their use | |
DE2756583A1 (en) | BLEACHING AGENT SUITABLE FOR TEXTILE TREATMENT, CONTAINING PERCONNECTIONS AND OPTICAL BRIGHTENERS | |
DE3304848A1 (en) | ORGANIC CYANAMIDE COMPOUNDS AS ACTIVATORS FOR INORGANIC PER CONNECTIONS | |
AT394575B (en) | Bleach and detergent | |
EP0930358B1 (en) | Use of formamidinium salts as bleach activators | |
DE19738274A1 (en) | Cyanopyridine-N-oxides and salts | |
DE2843116A1 (en) | PEROXY BLEACHING AND COMPOSITIONS USED FOR IT | |
CH659081A5 (en) | PEROXY ACID CONTAINING WHITE OR BLEACHING DETERGENT. | |
DE102005005016A1 (en) | Polymers hydrophobic aminonitrile quats for bleach activation | |
DE19629162A1 (en) | Salts of cyanamides as bleach activators | |
DE102004041760A1 (en) | Diethylmethyl ammonium nitriles and detergents and cleaners containing these ammonium nitriles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL PT SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 19991007 |
|
AKX | Designation fees paid |
Free format text: AT BE CH DE DK ES FR GB IT LI LU NL PT SE |
|
17Q | First examination report despatched |
Effective date: 20020830 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): BE CH DE ES FR GB IT LI PT |
|
RBV | Designated contracting states (corrected) |
Designated state(s): BE CH DE ES FR GB IT LI |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IT LI |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59812192 Country of ref document: DE Date of ref document: 20041209 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20050210 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2231913 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
ET | Fr: translation filed | ||
26N | No opposition filed |
Effective date: 20050804 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH Free format text: CLARIANT GMBH#BRUENINGSTRASSE 50#65929 FRANKFURT AM MAIN (DE) -TRANSFER TO- CLARIANT PRODUKTE (DEUTSCHLAND) GMBH#BRUENINGSTRASSE 50#65929 FRANKFURT AM MAIN (DE) |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20070215 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20070221 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20070312 Year of fee payment: 10 |
|
BERE | Be: lapsed |
Owner name: *CLARIANT PRODUKTE DEUTSCHLAND G.M.B.H. Effective date: 20080331 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080331 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080331 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20080325 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20090302 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080325 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20090224 Year of fee payment: 12 Ref country code: DE Payment date: 20090327 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20090216 Year of fee payment: 12 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20100324 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20101130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100331 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101001 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100324 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100324 |