EP0869171B1 - Bleichaktive Metall-Komplexe - Google Patents

Bleichaktive Metall-Komplexe Download PDF

Info

Publication number
EP0869171B1
EP0869171B1 EP98105257A EP98105257A EP0869171B1 EP 0869171 B1 EP0869171 B1 EP 0869171B1 EP 98105257 A EP98105257 A EP 98105257A EP 98105257 A EP98105257 A EP 98105257A EP 0869171 B1 EP0869171 B1 EP 0869171B1
Authority
EP
European Patent Office
Prior art keywords
formula
compound
iii
alkyl
manganese
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.)
Expired - Lifetime
Application number
EP98105257A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0869171A3 (de
EP0869171A2 (de
Inventor
Bernd Dr. Nestler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP0869171A2 publication Critical patent/EP0869171A2/de
Publication of EP0869171A3 publication Critical patent/EP0869171A3/de
Application granted granted Critical
Publication of EP0869171B1 publication Critical patent/EP0869171B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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 given here Reference.
  • the mono- or polynuclear complexes of the general formula 1 according to the invention are excellent as bleaching and oxidation catalysts, especially 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).
  • ppm means parts per million based on weight.
  • the first mentioned low metal contents mainly refer to Household laundry detergents.
  • the invention also relates to the use of these bleach 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'-sulphonylbisperoxybenzoic 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-carbophenoxydecylammoniumchlorid, 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-carbophenoxydecylammoniumchlorid
  • 3- N, N, N-trimethylammonio
  • esters such as. B. Acylphenolsulfonate and the Acylalkylphenolsulfonate as well as Acylamide Bleach activator preferred.
  • esters such as. B. Acylphenolsulfonate and the Acylalkylphenolsulfonate as well as Acylamide Bleach activator preferred.
  • TAED sodium 4-benzoyloxybenzene sulfonate, N, N, N, N-tetraacetylethylenediamine (TAED), sodium 1-methyl-2-benzoyloxy-benzene-4-sulfonate, Sodium 4-methyl-3-benzoyloxybenzoate, sodium nonanoyloxybenzenesulfonate, Sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate, benzoylcaprolactam, 2-phenyl-4H-3,1-benzoxazin-4-one, but glucose pentaacetate and tetraacety
  • 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 the 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 ammoni
  • 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, generally with 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine.
  • Other nonionic surface active compounds 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 nonionic 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 ethers; Stabilizers such as ethylenediaminetetraacetic acid; softener 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.
  • non-aqueous, liquid detergents, pasty and gelatinous detergents include compositions are, 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 to 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 surfactant, 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 surfactant e.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.
  • Example 8 Bis (2-hydroxy-4-methoxybenzylidene) -2,6-pyridinediamine-cobalt complex
  • a bleaching agent 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)
EP98105257A 1997-04-05 1998-03-24 Bleichaktive Metall-Komplexe Expired - Lifetime EP0869171B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19714122A DE19714122A1 (de) 1997-04-05 1997-04-05 Bleichaktive Metall-Komplexe
DE19714122 1997-04-05

Publications (3)

Publication Number Publication Date
EP0869171A2 EP0869171A2 (de) 1998-10-07
EP0869171A3 EP0869171A3 (de) 1999-04-07
EP0869171B1 true EP0869171B1 (de) 2004-11-03

Family

ID=7825561

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98105257A Expired - Lifetime EP0869171B1 (de) 1997-04-05 1998-03-24 Bleichaktive Metall-Komplexe

Country Status (6)

Country Link
US (2) US6139769A (enExample)
EP (1) EP0869171B1 (enExample)
JP (1) JP4049881B2 (enExample)
BR (1) BR9801148A (enExample)
DE (2) DE19714122A1 (enExample)
ES (1) ES2231913T3 (enExample)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000005710A (ko) 1998-06-05 2000-01-25 성재갑 표백활성화제
PH11999002188B1 (en) * 1998-09-01 2007-08-06 Unilever Nv Method of treating a textile
WO2000060044A1 (en) * 1999-04-01 2000-10-12 Unilever Plc Composition and method for bleaching 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 (pt) 1999-09-01 2002-05-14 Unilever Nv Composição alvejante para um têxtil
BR0013592A (pt) 1999-09-01 2002-05-07 Unilever Nv Embalagem comercial para alvejar manchas de tecido em um licor de lavagem aquoso, e, uso da mesma
BR0013593A (pt) 1999-09-01 2002-05-07 Unilever Nv Método para alvejar manchas de tecido
AU2001256155A1 (en) 2000-02-29 2001-09-12 Unilever Plc Composition and method for bleaching a substrate
GB2366575A (en) * 2000-09-11 2002-03-13 Unilever Plc Bleaching composition
DE10304131A1 (de) * 2003-02-03 2004-08-05 Clariant Gmbh Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren
US7794607B2 (en) * 2005-06-22 2010-09-14 Truox, Inc. Composition and method for enhanced sanitation and oxidation of aqueous systems
US7572390B2 (en) * 2005-06-22 2009-08-11 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
US7476333B2 (en) * 2005-06-22 2009-01-13 Truox, Inc. Composition and method for reducing chemical oxygen demand in water
JP2007126776A (ja) * 2005-11-02 2007-05-24 Nisshin Kagaku Kenkyusho:Kk 古紙パルプの処理方法および脱墨助剤
JP5352099B2 (ja) * 2007-03-09 2013-11-27 住友化学株式会社 変性金属錯体を用いたレッドックス触媒
TR201905689T4 (tr) 2008-04-09 2019-05-21 Basf Se Hidrazit bileşiklerinin oksidasyon katalizörleri olarak kullanımı.
MX2012015285A (es) 2010-06-28 2013-02-07 Basf Se Composicion blanqueadora libre de metal.
RU2014120925A (ru) 2011-10-25 2015-12-10 Басф Се Применение гребенчатых или блок-сополимеров в качестве средств против повторного осаждения загрязнения и грязеотталкивающих средств в процессах стирки
CN104145012A (zh) 2011-10-25 2014-11-12 巴斯夫欧洲公司 丙烯酸酯共聚物作为抗污垢再沉积剂和去污剂在洗衣过程中的用途
CN110105480A (zh) 2013-03-15 2019-08-09 路博润先进材料公司 衣康酸聚合物
US9790452B2 (en) 2013-03-27 2017-10-17 Basf Se Block copolymers as soil release agents in laundry processes
KR20160105790A (ko) 2013-11-27 2016-09-07 바스프 에스이 세탁 방법에서 오염물 방출제로서의 랜덤 공중합체
KR102350475B1 (ko) 2014-03-14 2022-01-11 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 이타콘산 폴리머 및 코폴리머
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition

Family Cites Families (20)

* Cited by examiner, † Cited by third party
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 (enExample) * 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
GB8908416D0 (en) * 1989-04-13 1989-06-01 Unilever Plc Bleach activation
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
DE69125310T2 (de) * 1990-05-21 1997-07-03 Unilever Nv Bleichmittelaktivierung
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
GB9127060D0 (en) * 1991-12-20 1992-02-19 Unilever Plc Bleach activation
CA2085642A1 (en) * 1991-12-20 1993-06-21 Ronald Hage Bleach activation
DE69412188T2 (de) * 1993-06-19 1999-03-11 Ciba Specialty Chemicals Holding Inc., Basel Inhibierung der Wiederabsorption von migrierenden Farbstoffen in der Waschlösung
WO1996015136A1 (en) * 1994-11-14 1996-05-23 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
GB9523654D0 (en) * 1995-11-18 1996-01-17 Ciba Geigy Ag Fabric bleaching composition
DE19719397A1 (de) * 1997-05-07 1998-11-12 Clariant Gmbh Bleichaktive Metall-Komplexe

Also Published As

Publication number Publication date
US6602441B1 (en) 2003-08-05
JP4049881B2 (ja) 2008-02-20
ES2231913T3 (es) 2005-05-16
EP0869171A3 (de) 1999-04-07
US6139769A (en) 2000-10-31
BR9801148A (pt) 2000-02-08
DE19714122A1 (de) 1998-10-08
DE59812192D1 (de) 2004-12-09
EP0869171A2 (de) 1998-10-07
JPH115993A (ja) 1999-01-12

Similar Documents

Publication Publication Date Title
EP0869171B1 (de) Bleichaktive Metall-Komplexe
DE69125309T2 (de) Bleichmittelaktivierung
DE69222620T2 (de) Bleichaktivierung unter Verwendung einer Mangan- verbindung und einem organischen Ligand
DE69216786T2 (de) Mangan enthaltender Bleichkatalysator und seine Verwendung
DE69019617T2 (de) Bleichaktivierung.
EP0877078B1 (de) Bleichaktive Metall-Komplexe
DE69014384T2 (de) Bleichaktivierung.
DE69816981T2 (de) Bleichmittelzusammensetzungen enthaltend metalbleichmittelkatalysatoren,sowie bleichmittelaktivatoren und/oder organischepercarbonsäure
DE69511410T2 (de) Bleichaktivierung
DE69019781T2 (de) Bleichmittelzusammensetzung.
EP1148118B1 (de) Wasch- und Reinigungsmittel enthaltend bleichaktive Dendrimer-Liganden und deren Metallkomplexe
DE69705514T2 (de) Sulfanamine als bleichmittelkatalysatoren
DE60033560T2 (de) Verfahren zum behandeln von textilien
EP0909810B1 (de) Verwendung von Aminonitril-N-oxiden als Bleichaktivatoren
DE102011080099A1 (de) Wasch- oder Reinigungsmittel mit elektrochemisch aktivierbarer Mediatorverbindung
EP0889050A2 (de) Metall-Komplexe als Bleichaktivatoren
EP1083173B1 (de) Bleichaktive Metallkomplexe
DE10037162A1 (de) Bleich- und Oxidationsmittel und ihre Verwendung
DE2756583A1 (de) Zur textilbehandlung geeignetes, perverbindungen und optische aufheller enthaltendes bleichmittel
EP0930358B1 (de) Verwendung von Formamidinium-Salzen als Bleichaktivatoren
DE2843116A1 (de) Peroxybleichen und hierfuer verwendbare zusammensetzungen
DE19738274A1 (de) Verwendung von Cyanpyridin-N-oxiden als Bleichaktivatoren
CH659081A5 (de) Peroxysaeure enthaltendes bleich- oder bleichendes waschmittel.
DE19629162A1 (de) Salze von Cyanamiden als Bleichaktivatoren
DE102004041760A1 (de) Diethylmethyl-Ammoniumnitrile und Wasch- und Reinigungsmittel, enthaltend diese Ammoniumnitrile

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