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WO1994021777A1 - Composition de catalyseur de blanchiment - Google Patents

Composition de catalyseur de blanchiment Download PDF

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Publication number
WO1994021777A1
WO1994021777A1 PCT/EP1994/000640 EP9400640W WO9421777A1 WO 1994021777 A1 WO1994021777 A1 WO 1994021777A1 EP 9400640 W EP9400640 W EP 9400640W WO 9421777 A1 WO9421777 A1 WO 9421777A1
Authority
WO
WIPO (PCT)
Prior art keywords
manganese
granules
catalyst
fatty acids
charge
Prior art date
Application number
PCT/EP1994/000640
Other languages
English (en)
Inventor
Johannes Hendrikus M. Akkermans
Craig Cicciari
William Derek Emery
Clemens Osman Monir
Hermien Willemijn Plomp
Original Assignee
Unilever N.V.
Unilever Plc
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 Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to AU62082/94A priority Critical patent/AU6208294A/en
Publication of WO1994021777A1 publication Critical patent/WO1994021777A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • 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
    • 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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • This invention relates to bleach catalyst compositions.
  • it relates to bleach catalyst compositions comprising a manganese complex as the active bleach catalyst in a form which is suitable for use in or with a detergent and/or bleach composition.
  • the invention also relates to a process for manufacturing bleach catalyst compositions.
  • manganese complexes have been proposed as catalysts for enhancing the activity of peroxygen bleaches such as hydrogen peroxide, hydrogen peroxide liberating or generating compounds and inorganic and organic peroxyacids. They include manganese-gluoconate complexes as described in EP-A-237 111 and manganese polyol complexes as described in EP-A-443 651.
  • the effective amount of such manganese complexes needed in detergent and/or bleach compositions is of the order of hundredths of a percent.
  • the problems associated with using small quantities of materials include the difficulty of accurately dosing the material and achieving a homogeneous distribution thereof in the compositions. In order to ensure the performance of, for example, a detergent composition is consistent, it is essential that individual components of the compositions are homogeneous distributed throughout the composition.
  • wash catalyst Whilst spraying a solution of the manganese complex, hereinafter referred to as the "bleach catalyst" onto the base detergent formulation may result in a very good distribution it may also involve direct contact between the bleach catalyst and the other ingredients included in the base formulation, for example nonionic detergent active and peroxygen bleaching agent. This may result in a reduction in the levels of active ingredient as a result of redox reactions.
  • Another option would be to mix pure crystals of the catalyst with a particulate detergent composition. However, this may also result in interactions between individual components with consequential loss in levels of active components.
  • composite granules comprising a mixture of fatty acids or salts thereof, a manganese complex catalyst as herein defined and a dispersing agent when prepared according to the method of the invention, show also good bleach activity, particularly on cocoa stains and good storage stability.
  • Mn manganese which can independently be in the III or IV oxidation state
  • X is independently a coordinating or bridging species selected from the group consisting of H 2 0, 0 2" , 0 2 2 ⁇ , -OH, H0 2 " , SH ⁇ , S 2 ⁇ , >SO, Cl “ , SCN ⁇ , N 3 " , RS0 3 ⁇ , RCOO " , NH 2 ⁇ and NR 3 , with R being H, alkyl, aryl, both optionally substituted, and R-'-COO, where R 1 is an alkyl, or aryl radical, both optionally substituted; L is a ligand which is an organic molecule containing a number of nitrogen which coordinates via all or some of its nitrogen atoms to the manganese centres; Z denotes the charge of the complex and is an integer which can be positive or negative;
  • Mn is manganese in the +4 oxidation state
  • R is a C 1 -C 20 radical selected from the group alkyl, cycloalkyl, aryl, benzyl and radical combinations thereof; at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese; .
  • L is a ligand selected from a C 3 -C 6Q radical having at least 3 nitrogen atoms coordinating with the manganese; and Y is an oxidatively-stable counterion dependent; and
  • each X independently represents a coordinating species selected from Cl ⁇ , Br ⁇ , I “ , F ⁇ , NCS “ , N 3 ⁇ , I 3 ⁇ , NH 3 , RCOO “ , RS0 3 ⁇ , RS0 4 " in which R is alkyl or aryl, both optionally substituted, OH " , 0 2 2 ⁇ , HOO " , H 2 0, SH, CN “ , OCN “ , S 4 2 ⁇ or mixtures thereof;
  • p is an integer from 1-3;
  • z denotes the charge of the complex and is an integer which can be positive, zero or negative;
  • Y is a counter-ion the type of which is dependent upon the charge z of the complex;
  • q z / [charge Y] ;
  • L is a ligand being a macrocylic organic molecule of the following formula:
  • RECTIFIED SHEET (RULE 91) ISA/EP wherein t is 2 ; s is 3 and R 1 , R 2 and R 3 can each independently be H, C- ⁇ Cg alkyl, or aryl, both optionally substituted;
  • a carrier material selected from zeolite, alkali metal sulphate, citric acid, succinic acid and starch;
  • a binding agent selected from water-soluble non- oxidisable polymers, alkalimetal silicates, saturated fatty acids, fatty acid soaps and mixtures thereof.
  • the invention also provides a method for preparing a bleach catalyst composition in the form of non-friable granules, said composition comprising at least two fatty acids or salts thereof, a manganese complex catalyst as herein defined and a dispersing agent, and said method comprising the steps of
  • the invention further provides a detergent composition comprising non-friable composite granules comprising a manganese complex catalyst as hereinbefore defined, a carrier material and a binding agent.
  • the granules of the present invention when incorporated into detergent compositions, show improved bleaching performance on cocoa stains. Without being bound by theory, this is believed to be due to the fact that the bleach catalyst in the granules according to the invention is released at a slower rate, ie bleaching does not occur immediately when the detergent composition is contacted with water and therefore the other components in the detergent composition such as the surface active materials have time to start to perform their function before bleaching occurs.
  • a further advantage of the granules according to the invention is that storage stability, particularly in detergent compositions containing high levels of nonionic detergent active material such as 15 to 25% by weight is improved.
  • the granule according to the invention is substantially free from easily oxidisable organic material, especially primary and secondary alcohols: these easily oxidisable materials are present at levels of less than 1% by weight of the granule.
  • the granule preferably comprises 0.5 to
  • preferred complexes are those in which X is either CH 3 C00 " or O 2" or mixtures thereof, most preferably wherein the manganese is in the IV oxidation state and X is O 2" .
  • Preferred ligands are those which contain at least three nitrogen atom and which coordinate via three nitrogen atoms to one of the manganese centres, and are of a macrocyclic nature. Particularly preferred ligands are those of formula:
  • the type of counter-ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, chloride; sulphate; nitrate; ethylsulphate; surfactant-anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate; trifluormethylsulphonate; perchlorate (C10 4 ⁇ ) , BPh 4 " and PF 6 ⁇ ; , though some counter-ions are more preferred than others for reasons of product property and safety.
  • the preferred dinuclear manganese complexes usable in the granules of the present invention are:
  • manganese complex is a mononuclear complex of formula (B)
  • preferred complexes are those in which L is selected from 1, 4 ,7-trimethyl-l,4,7-triazacyclononane and 2-methyl-l,4,7-trimethyl-l,4, 7-triazacyclononane and R is a C alkyl.
  • L is selected from 1, 4 ,7-trimethyl-l,4,7-triazacyclononane and 2-methyl-l,4,7-trimethyl-l,4, 7-triazacyclononane and R is a C alkyl.
  • Such mononuclear complexes are further described in Applicants copending US Patent Application No 07/798 396.
  • Mononuclear complexes of formula (C) are further described in Applicants copending European Patent Application No. 93211580.2
  • the granules are coated with non-oxidisable water-soluble material.
  • Suitable materials include organic homopolymers or heteropolymers, organic nonionic compounds, long-chain C 10 -C 22 fatty acids and fatty acids soaps and the so-called glassy sodium phosphates of the following molecular structure.
  • n is from about 10 to 30.
  • suitable organic homo- or heteropolymers are modified starch, polyvinylpyrrolidone, polyvinyalcohol, and sodium carboxymethylcellulose.
  • Suitable nonionic compounds are for example polyethylene glycols having a molecular weight of from 1000 to 5000; C 15 -C 24 fatty alcohols or C 8 -C 12 alkyl-phenols having from about 10 to 60 ethylene oxide units; and the long-chain fatty acid alkylolamides, such as coconut fatty acid monoethanolamide.
  • the granules according to the invention will also comprise a pigment. Titanium dioxide is particularly preferred.
  • the bleach catalyst within the granules is of an average particle size as small as possible preferably below 200 ⁇ m for proper distribution and to ensure fast delivery of the catalyst to the wash, though too small particles may cause handling problems during the granulation process.
  • a preferred and optimum bleach catalyst particle size is within a range of between about 50 and about 150 ⁇ m.
  • Bleach catalyst particles larger than 150 ⁇ m may give distribution problems and are more difficult to granulate, whereas particles smaller than 50 ⁇ m may cause handling problems and excessive granule colouration.
  • Granule growth control is necessary to try to ensure the composite granules are of the same approximate size and bulk density as the main detergent or cleaning powder into which they are incorporated so as to avoid segregation by percolation or segregation by floating.
  • Percolation bringing the bleach catalyst composite granules to the bottom of a detergent powder batch, pack etc. , may occur during and after mixing by vibration, handling and aeration, and will specifically happen with too small and too dense granules.
  • the bulk density and size of the composite granules can be controlled via the composition, the process conditions or both.
  • the composite granules of the invention can be prepared by any of the conventional and known granulation techniques, such as using a pan-granulator, fluidised bed, Schugi mixer, L ⁇ dige ploughshare mixer, rotating drum and other low energy mixers; by compaction, including extrusion and tabletting optionally followed by pulverising and grinding; and by a high shear-energy process using a high-speed mixer/granulator equipment having both a stirring action of high energy and a cutting action.
  • Examples of such high- speed mixer/granulator equipment are the Fukae (Trade Mark) FS-G mixer manufactured by Fukae Powtech Kogyo Co. Japan.
  • Other mixers usable in the process of the invention include the Diosna (Trade Mark) V series ex.
  • Fatty acids suitable for use in the granules prepared according to the method of the invention are C 10 -C 18 fatty acids and salts thereof. It is particularly preferred to use a mixture of lauric and stearic acid. The fatty acid mixture is preferably present at a level of 45 to 75% by weight of the composite granule.
  • Particularly preferred dispersing aids for use in these granules are aluminosilicates such as zeolites present at a level of from 25 to 55% by weight.
  • the manganese complex catalyst is preferably present at a level of from 0 to 20%, most preferably 1 to 15% by weight.
  • the detergent composition according to the invention may further contain ingredients commonly present in such compositions. They include surface active materials including soaps, synthetic anionic, nonionic, cationic and zwitterionic detergent surfactants preferably present in an amount from 0.5 to 50% by weight.
  • composition contains both anionic and nonionic surfactant, it is preferred that the nonionic surfactant is present in excess amount.
  • Other ingredients include detergency builders such as aluminosilicates in particular zeolites, e.g. zeolite A, B, C, X and Y types as well as zeolite MAP as described in EP 384 070; and precipitating builders such as sodium orthophosphate and sodium carbonate. Such builders are preferably present in an amount from 5 to 80% by weight.
  • Other typical ingredients include enzymes, fluorescent agents, multifunctional polymers, stabilising agents such as ethylene diamine tetraacetate (EDTA) and the polyphosphonic acid derivatives (e.g Dequest R ) .
  • EDTA ethylene diamine tetraacetate
  • Dequest R polyphosphonic acid derivatives
  • Such detergent compositions can be used to bleach stained substrates by contacting the substrate in aqueous medium with the detergent composition.
  • Step I SYNTHESIS OF [Mn III 2 ( ⁇ -0) 1 ( ⁇ -OAc) 2 (Me 3 -TACN) 2 ] (C10 4 ) 2 . (H 2 0)
  • Step 2 SYNTHESIS OF [Mn IV 2 ( ⁇ -0) 3 (Me 3 -TACN) 2 ] (PF 6 ) 2 H 2 0
  • the red crystals were isolated by adding a few ml of acetonitrile to the filter. The crystals easily dissolved, while Mn0 2 , insoluble in acetonitrile, remained on the filter. Evaporation of the acetonitrile solution resulted in the product as red flocks.
  • This material was the Mn catalyst used in preparing the following granules.
  • composition of the base detergent powder used was as follows:
  • Zeolite MAP prepared by a method similar to that described in Examples 1 to 3 of EP-A-384 070.
  • Bleach tests Bleaching was assessed in an AEG turnette washing machine in the presence of a soiled load at a washing temperature of 30°C.
  • Detergent compositions containing of the granules according to the examples were dosed at a level of 87g per machine cycle.
  • the amount of composite granules added to the detergent base formulation was adjusted to ensure that 0.04% by weight of the manganese complex catalyst was present in the wash liquor.
  • the reflectance (R 46 o * ) °f two types of stained test cloth was measured before and after treatment.
  • the change in reflectance ( ⁇ R 460 *) gives a measure of the effectivenes of the treatment. Reflectance ( 6 0 *) was measured on a Zeiss Elrephometre.
  • the ( ⁇ R 460* ) results presented below are an average for 7 machine cycles with 1 test cloth per cycle.
  • the test cloths used in the experiments were a cotton cloth stained with chocolate (cloth A) and a cotton cloth stained with cocoa milk (cloth B) .
  • a fatty acids/soap mixture was made by blending 56.2 g of lauric acid, 34.2 g of stearic acid and 9.6 g of 50% caustic solution at 70°C.
  • a granule was produced by dry mixing 29.24 g of ground succinic acid with 0.76 g Mn catalyst crystals and subsequently adding the fatty acids/soap mixture in a high shear mixer. The pH of this granulate in aqueous solution was 3.4, mean particle diameter of 782 ⁇ m.
  • Mn catalyst/Zeolite/Fatty Acids-Soap Granules The same fatty acids-soap mixture as described above was used as the binder material for 29.16 g Zeolite and 0.84 g Mn catalyst. A granule was produced by agglomeration in a high shear mixer. pH of the material was 8.4, particle size 806 ⁇ .
  • a fatty acids blend was made by mixing 70 parts of lauric acid with 30 parts of stearic acid at 70°C.
  • a granulate was produced by first dry mixing 43.0 g sodium citrate with 1.0 g Mn catalyst and subsequently adding 6.0 g of said fatty acids blend under high shear conditions.
  • the pH of the granulate in aqueous solution was 7.0, mean particle diameter was 836 ⁇ m.
  • a fatty acids/soap mixture was made by blending 56.2 g of lauric acid 34.2 g of stearic acid and 9.6 g of 50% caustic solution at 70°C in a Lodige Recycler. Thereafter, zeolite A4 and the manganese catalyst was added. The product was cooled in a fluid bed. The nominal dry composition of the granule was 31.7% fatty acid soap 66.2% zeolite 2.1% Mn-catalyst.
  • Mn catalyst/Zeolite/Fatty Acids Granules A fatty acids/soap mixture was made by blending lauric acid, stearic acid and caustic solution. Into the resulting mixture was dispersed Mn-catalyst. This mixture was then placed in a batch Fukae mixer togeher wuth zeolite MAP an granulated. A futher portion of the fatty acid soap was added together with zeolite A4. The nominal composition of the granule was 27% fatty acid soap 33.5% zeolite MAP 18.5% zeolite A4 1.55 Mn catalyst.
  • Example 2 Preparation of bleach catalyst granules by spray cooling 2a.
  • 35.22 kg lauric acid and 20.21 kg stearic acid were blended and made molten at 70°C.
  • the resulting mixture was partly saponified by adding 6.57 kg 50% sodium caustic solution and mixing it in a high speed mixer.
  • 25.00 kg Zeolite A4, 10.00 kg titanium dioxide and 3.00 kg Mn-catalyst were added stepwise under constant high speed mixing. After total homogenization the mixture was spray cooled in a spray tower with ambient air.
  • the mean particle size of the product was in the range 700 to 1000 microns, with less than 0.2% below 180 microns.
  • the mean particle size of the product was 758 microns, with less than 0.2% below 180 microns.
  • a fatty acid soap mixture was made by mixing 62 parts of sodium salt of lauric acid with 38 parts of the sodium salt of stearic acid at 80°C. To the thus- formed melt were added zeolite A4 and the Mn catalyst. Thereafter, the resulting mixture was spray cooled in liquid nitrogen.

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

Abstract

Composition de catalyseur de blanchiment se présentant sous forme de granules composites non friables. Chaque granule est sensiblement dépourvu de matières organiques s'oxydant facilement et comprend une matière de support, un agent de liaison et un catalyseur de blanchiment renfermant une source de Mn et un ligand, ce ligand étant un composé organique macrocyclique de la formule: [NR?3-(CR1(R2¿q)t]s. Dans cette formule t représente un entier tel que 2 ou 3; s représente un entier tel que 3 ou 4; q représente zéro ou un; R1 et R2 sont chacun indépendamment sélectionnés parmi hydrogène, alkyle, aryle, tous deux étant facultativement substitués; et R3 est indépendamment sélectionné parmi hydrogène, alkyle, aryle, tous deux étant facultativement substitués. On a remarqué que ces granules de blanchiment ont une performance de blanchiment améliorée sur des types de taches spécifiques, plus particulièrement sur des taches de cacao.
PCT/EP1994/000640 1993-03-18 1994-03-04 Composition de catalyseur de blanchiment WO1994021777A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU62082/94A AU6208294A (en) 1993-03-18 1994-03-04 Bleach catalyst composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9305598.6 1993-03-18
GB939305598A GB9305598D0 (en) 1993-03-18 1993-03-18 Bleach catalyst composition

Publications (1)

Publication Number Publication Date
WO1994021777A1 true WO1994021777A1 (fr) 1994-09-29

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PCT/EP1994/000640 WO1994021777A1 (fr) 1993-03-18 1994-03-04 Composition de catalyseur de blanchiment

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AU (1) AU6208294A (fr)
GB (1) GB9305598D0 (fr)
WO (1) WO1994021777A1 (fr)

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995006710A1 (fr) * 1993-09-03 1995-03-09 Unilever Plc Composition de catalyseur de blanchiment
WO1995006711A1 (fr) * 1993-09-03 1995-03-09 Unilever Plc Composition de catalyseur de blanchiment
WO1996037593A1 (fr) * 1995-05-22 1996-11-28 Henkel Kommanditgesellschaft Auf Aktien Granules acides renfermant des substances a activite redox
WO1997009409A1 (fr) 1995-09-05 1997-03-13 Basf Aktiengesellschaft Utilisation d'acides polyaspartiques modifies dans des agents de lavage
WO1997016521A1 (fr) * 1995-10-30 1997-05-09 The Procter & Gamble Company Particules de catalyseur de blanchiment
EP0891410A4 (fr) * 1996-02-08 1999-12-01 Procter & Gamble Particules pour detergents contenant des catalyseurs de blanchiment metalliferes
US6093343A (en) * 1996-02-08 2000-07-25 The Procter & Gamble Company Detergent particles comprising metal-containing bleach catalysts
WO2003066793A1 (fr) * 2002-02-06 2003-08-14 Unilever Plc Granule et composition le contenant
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
US6992184B2 (en) 2000-08-23 2006-01-31 Carnegie Mellon University Macrocyclic tetraamido ligands as bleaching catalysts and synthesis thereof
US7060818B2 (en) 2003-02-21 2006-06-13 Carnegie Mellon University Synthesis of macrocyclic tetraamido compounds and new metal insertion process
US7074749B2 (en) 2000-06-16 2006-07-11 Basf Aktiengesellschaft Oxoalcohol-based detergent
GB2428694A (en) * 2005-07-28 2007-02-07 Unilever Plc Acidic granules comprising transition metal catalyst
DE102007006908A1 (de) * 2007-02-13 2008-08-14 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche")
DE102008034231A1 (de) 2008-07-23 2010-01-28 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche-Variante 3: All-in-one")
WO2010070088A1 (fr) 2008-12-18 2010-06-24 Basf Se Mélange de tensioactifs contenant des composants ramifiés à chaîne courte et des composants ramifiés à chaîne longue
WO2011003904A1 (fr) 2009-07-10 2011-01-13 Basf Se Mélange de tensioactifs contenant des constituants à chaîne courte et à chaîne longue
WO2011117350A1 (fr) 2010-03-25 2011-09-29 Basf Se Procédé électrochimique de nettoyage de textiles
WO2012095482A1 (fr) 2011-01-13 2012-07-19 Basf Se Utilisation de thioéthers éventuellement oxydés de poly(oxydes d'alkylène) dans des agents de lavage et de nettoyage
WO2012095481A1 (fr) 2011-01-13 2012-07-19 Basf Se Utilisation de thioéthers éventuellement oxydés d'alcoxylates d'alcools dans des détergents et produits de nettoyage
US8809252B2 (en) 2007-09-26 2014-08-19 Reckitt Benckiser N.V. Composition
WO2014177217A1 (fr) * 2013-05-02 2014-11-06 Ecolab Usa Inc. Composition détergente concentrée pour une meilleure élimination de l'amidon dans des applications de lavage de vaisselle
WO2014202954A1 (fr) 2013-06-20 2014-12-24 Chemsenti Limited Catalyseur de blanchiment et d'oxydation
WO2015000971A1 (fr) 2013-07-03 2015-01-08 Basf Se Composition polymère geliforme obtenue par la polymérisation d'un monomère contenant des groupes acides en présence d'un composé polyéther
US8951955B2 (en) 2011-01-13 2015-02-10 Basf Se Use of optionally oxidized thioethers of alcohol alkoxylates in washing and cleaning compositions
US8987183B2 (en) 2011-01-13 2015-03-24 Basf Se Use of optionally oxidized thioethers of polyalkylene oxides in washing and cleaning compositions
US9435073B2 (en) 2010-03-25 2016-09-06 Basf Se Electrochemical textile-washing process
US9624119B2 (en) 2014-06-13 2017-04-18 Ecolab Usa Inc. Enhanced catalyst stability in activated peroxygen and/or alkaline detergent formulations
WO2017158002A1 (fr) 2016-03-16 2017-09-21 Basf Se Films polymères à action détergente et nettoyante, procédé pour les produire et leur utilisation
WO2018109200A1 (fr) 2016-12-16 2018-06-21 Basf Se Feuilles multicouches, leur procédé de fabrication et leur utilisation
WO2018109201A1 (fr) 2016-12-16 2018-06-21 Basf Se Films multicouche à action détergente et nettoyante, procédé de production desdits films et utilisation correspondante
US10196592B2 (en) 2014-06-13 2019-02-05 Ecolab Usa Inc. Enhanced catalyst stability for alkaline detergent formulations
WO2019048474A1 (fr) 2017-09-06 2019-03-14 Basf Se Films polymères actifs de lavage et de nettoyage, leur procédé de production et leur utilisation
WO2020011627A1 (fr) 2018-07-11 2020-01-16 Basf Se Procédé de production de polymères stables contenant du vinylimidazole
WO2020035567A1 (fr) 2018-08-16 2020-02-20 Basf Se Films polymères hydrosolubles d'homopolymères ou de copolymères d'oxyde d'éthylène, procédé de calandrage pour leur production et leur utilisation
WO2021191175A1 (fr) 2020-03-24 2021-09-30 Basf Se Formulation d'un détergent sous la forme d'un corps tridimensionnel
US11225631B2 (en) 2018-03-19 2022-01-18 Ecolab Usa Inc. Acidic liquid detergent compositions containing bleach catalyst and free of anionic surfactant
EP3967742A1 (fr) 2020-09-15 2022-03-16 WeylChem Performance Products GmbH Compositions comprenant un catalyseur de blanchiment, procédé de fabrication associé et agent de blanchiment et de nettoyage comprenant ces compositions
EP4008765A1 (fr) 2020-12-07 2022-06-08 WeylChem Performance Products GmbH Compositions comprenant des composés triazacycliques protonés et agent de blanchiment et agent de nettoyage les contenant
EP4296344A1 (fr) 2022-06-24 2023-12-27 WeylChem Performance Products GmbH Compositions comprenant des composés triazacycliques protonés et de l'acétate de manganèse (ii), leur fabrication et agent de blanchiment et de nettoyage les comprenant
EP4410938A1 (fr) 2023-02-02 2024-08-07 AMSilk GmbH Composition pour lave-vaisselle automatique comprenant un polypeptide structurel

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