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WO1994023005A1 - Composition d'enzyme pour produits de lavage et de nettoyage - Google Patents

Composition d'enzyme pour produits de lavage et de nettoyage Download PDF

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Publication number
WO1994023005A1
WO1994023005A1 PCT/EP1994/000934 EP9400934W WO9423005A1 WO 1994023005 A1 WO1994023005 A1 WO 1994023005A1 EP 9400934 W EP9400934 W EP 9400934W WO 9423005 A1 WO9423005 A1 WO 9423005A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
enzyme
alkali
enzyme granules
carboxymethyl cellulose
Prior art date
Application number
PCT/EP1994/000934
Other languages
German (de)
English (en)
Inventor
Kathleen Paatz
Wilfried Rähse
Werner Pichler
Udo Sturm
Horst Upadek
Original Assignee
Cognis Gesellschaft Für Biotechnologie Mbh
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 Cognis Gesellschaft Für Biotechnologie Mbh filed Critical Cognis Gesellschaft Für Biotechnologie Mbh
Priority to DE59403879T priority Critical patent/DE59403879D1/de
Priority to EP94912528A priority patent/EP0692016B1/fr
Publication of WO1994023005A1 publication Critical patent/WO1994023005A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the invention relates to an enzyme granulate, a process for its production and the use of the granulate in solid washing and cleaning agents.
  • Enzymes are used extensively in washing, auxiliary washing and cleaning agents.
  • the enzymes are usually not used as concentrates, but in mixtures with a dilution and carrier material. If such enzyme preparations are admixed with conventional detergents, a considerable reduction in the enzyme activity can occur during storage, in particular if bleach-active compounds are present.
  • Embedding agents known from German published patent application DT 1803099 which consist of a mixture of solid acids or acidic salts and carbonates or bicarbonates and disintegrate when water is added Although the solvent power, they are very sensitive to moisture and therefore require additional protective measures.
  • Another disadvantage of the aforementioned preparation is the fact that the enzymes can only be processed in the form of dry powders.
  • the fermentation broths usually produced in enzyme production cannot be used in this form, but must be dewatered beforehand.
  • Processes in which only readily soluble carrier materials such as sugar, starch and cellulose ether are used as binders for the production of enzyme preparations are also bound to this requirement.
  • enzyme granules which contain starch which swells in water, zeolite and water-soluble granulating agents.
  • a production process for such formulations is proposed, which essentially consists in concentrating a fermenter solution freed from insoluble constituents, adding the additives mentioned and granulating the resulting mixture.
  • the process with the additive mixture proposed there is advantageously carried out with fermentation solutions which have been concentrated to a relatively high dry matter content, for example 55% by weight.
  • the granules produced in this way have such a high rate of dissolution or disintegration under washing conditions that the granules partially disintegrate relatively quickly during storage and the enzymes are deactivated.
  • enzyme granules for use in granular detergents and cleaning agents which contain 2% by weight to 20% by weight of enzyme, 10% by weight to 50% by weight of swellable starch, 5% by weight % to 50% by weight of water-soluble organic polymer as granulating aid, 10% by weight to 35% by weight of cereal flour and 3% by weight to 12% by weight of water.
  • Such additives enable enzyme processing without major loss of activity and the storage stability of the enzymes in the granules is also satisfactory.
  • sodium carboxymethyl cellulose reduces the disintegration and dis
  • the rate of pergulation of the granules in cold wash liquors is reduced, while this effect can be changed in the direction of a higher dissolution rate by adding higher molecular weight polyethylene glycol.
  • the enzyme granules described there do not always have such a high rate of disintegration that when they are used in detergents, sufficient enzyme is already present in the washing liquor in the initial phase of machine washing in order to remove enzymatically removable soiling.
  • the object was therefore to improve the storage properties of both the enzymes and the granules containing them by means of a production process which allows the use of low-concentration fermentation broths to improve the powder properties, in particular the solubility of the known products and to further reduce the loss of activity in enzyme processing.
  • This object is essentially achieved by the invention described below by means of a special granulation aid system which contains solubilizing or dust-binding components and granule-strengthening components in optimized ratios.
  • the invention relates to enzyme granules suitable for incorporation in particular particulate washing or cleaning agents, containing enzyme and inorganic and / or organic carrier material and carboxymethylcellulose-containing granulation aid, which is characterized in that it is a granulation aid system composed of alkali-carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl or alkenyl polyethoxylate contains with the proviso that, based in each case on the finished granulate, at least 0.5% by weight polyethylene glycol with an average molecular weight below 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups is present if more than 2% by weight of alkali metal carboxymethyl cellulose is present.
  • a granulation aid system composed of alkali-carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl or alkenyl polyethoxylate contains with the provis
  • the degree of substitution of carboxymethyl cellulose is to be understood as the number of etherified oxygen atoms bearing a carboxy ethyl group per saccharide monomer of cellulose.
  • the presence of sodium carboxymethyl cellulose with a degree of substitution of 0.85 to 0.95 allows quantities of 1 wt Degree of substitution correspond to 0.65 to 0.75.
  • a higher throughput through the extruder can be achieved by using the above-mentioned substituted carboxymethyl cellulose in the production of the granules in the extrusion step.
  • the enzyme granulate contains 1% by weight to 30% by weight, calculated as dry substance, protease, lipase, amylase and / or cellulase, 70% by weight to 94% by weight inorganic and / or organic African carrier material and 5 wt.% to 50 wt.% granulation aid containing carboxymethyl cellulose and the remainder to 100 wt.% water.
  • An enzyme granulate according to the invention preferably contains a mixture containing, in each case based on finished granulate, 0.1 wt.% To 10 wt.%, In particular 0.5 wt.% To 5 wt.% Carboxymethyl cellulose as the granulation aid system and 0.1% by weight to 10% by weight, in particular 0.5% by weight to 4% by weight, of polyethylene glycol with an average molecular weight of 200 to 600 and / or a polyethoxylate according to formula (I),
  • R is a straight-chain or branched alkyl or alkenyl radical with up to 3 CC double bonds with 10 to 22, in particular 16 to 18, C atoms and the average degree of ethoxylation n is a number from 20 to 80, in particular 30 to 45 means.
  • the invention relates to a method for producing such an enzyme granulate with a grain size of 0.1 mm to 2 mrc by ex- trudge an enzyme premix obtained by mixing a concentrated fermentation broth freed from insoluble constituents by microfiltration with the carrier material and the granulation aid, spheronization of the extrudate in a rounding machine, drying and optionally applying a coating containing dye or pigment , characterized in that the fermentation broth is mixed with an additive which contains a granulation auxiliary system consisting of alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate with the proviso that, in each case based on the finished granulate , at least 0.5 wt .-% polyethylene glycol with an average molecular weight below 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are used if more than 2 wt .-% alkali carboxy
  • the primary enzymes which can be used are the proteases, lipases, amylases and / or cellulases obtained from microorganisms, such as bacteria or fungi, proteases produced by Bacillus species and their mixtures with lipases being preferred. They are obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 1940488, DE 2044 161, DE 2201 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and 4264 738 and European patent application EP 006638.
  • the process according to the invention can be used particularly advantageously for the formulation of the very active proteases of the so-called second and higher generations, which include, for example, Savinase ( R ) and enzymes known from international patent application WO 91/2792, their storage-stable incorporation in washing and Cleaning agents often cause problems.
  • the invention it is possible to convert the broths of extracellular enzymes obtained in the fermentation processes immediately after separation of the insoluble accompanying substances by microfiltration and subsequent concentration by ultrafiltration and optionally subsequent evaporation in vacuo into storage-stable, largely odorless granules. The formation of undesirable enzyme dusts and the loss of activity which occurs during additional drying processes are avoided.
  • Enzymes are preferably contained in the granules according to the invention in amounts of 4% by weight to 20% by weight. If the enzyme granulate according to the invention is a protease-containing formulation, the protease activity is preferably 150,000 protease units (PE, determined according to the method described in Tenside 2 (1970), 125) to 350,000 PE, in particular 160,000 PU to 300,000 PU, per gram of enzyme granulate .
  • PE protease units
  • all organic or inorganic pulverulent substances which do not destroy or deactivate the enzymes to be granulated or only tolerably little and which are stable under granulation conditions can be used as carrier materials.
  • Such substances include, for example, starch, cereal flour, cellulose powder, alkali alumosilicate, in particular zeolite, layered silicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example alkali metal chloride, alkali metal sulfate, alkali metal carbonate or alkali metal acetate, sodium or potassium being the preferred alkali metals.
  • a carrier material mixture consisting of starch which is swellable in water, cereal flour and, if appropriate, cellulose powder and alkali carbonate is used.
  • the starch which is swellable in water is preferably maize starch, rice starch, potato starch or mixtures thereof, the use of maize starch being particularly preferred.
  • Swellable starch is contained in the enzyme granules according to the invention preferably in amounts of 20% by weight to 50% by weight, in particular from 25% by weight to 45% by weight.
  • the sum of the amounts of the swellable starch and the flour is preferably not more than 80% by weight, in particular 32% by weight to 65% by weight.
  • the cereal flour which is suitable according to the invention is in particular a product which can be produced from wheat, rye, barley or oats or a mixture of these flours, wholemeal flours being preferred.
  • a wholemeal flour is understood in the context of the invention to mean a flour which has not been fully milled and which has been produced from whole, unpeeled grains or at least predominantly consists of such a product, the rest consisting of fully milled flour or starch.
  • Commercial wheat flour qualities, such as Type 450 or Type 550, are preferably used.
  • the use of flour products too Cereals which lead to the aforementioned swellable starches are possible if care is taken to ensure that the flours have been produced from the whole grains.
  • the flour component of the additive mixture is known to achieve a substantial odor reduction in the enzyme preparation, which far exceeds the reduction in odor by incorporating the same amounts of corresponding starch types.
  • Such cereal flour is contained in the enzyme granules according to the invention preferably in amounts from 10% by weight to 35% by weight, in particular from 15% by weight to 25% by weight.
  • the enzyme granules according to the invention preferably contain 1% by weight to 50% by weight, preferably 5% by weight to 25% by weight of the granulating auxiliary system, the alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or contains alkyl polyethoxylate.
  • this granulation aid system based in each case on the finished enzyme granulate, 0.5% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight, of alkali carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and up to 5% by weight, in particular 0.5% by weight to 3% by weight, of polyethylene glycol and / or alkyl polyethoxylate, it being important that at least 0.5% by weight, in particular 0.8% by weight to 2% by weight of polyethylene glycol with an average molecular weight below 1000 and / or alkyl polyethoxylate with at least 20 ethoxy groups is present if more than 2% by weight of alkali metal carboxymethyl cellulose is present.
  • Highly substituted carboxymethyl cellulose, with degrees of substitution up to 3, is preferably not contained in the granulation aid system according to the invention.
  • Carboxymethyl celluloses with degrees of substitution below 0.5 are preferably also not contained in the granulation aid system according to the invention.
  • cellulose or starch ethers such as carboxymethyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, malodextextrose, sucrose, invert sugar, glucose syrup or other water-soluble syrups may also be used as additional components of the granulation aid system or readily dispersible oligomers or polymers of natural or synthetic origin are used.
  • Useful synthetic water-soluble polymers are polyacrylates, polymethacrylates, copo- polymers of acrylic acid with maleic acid or compounds containing vinyl groups, furthermore polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone.
  • the aforementioned compounds are those with free carboxyl groups, they are normally in the form of their alkali metal salts, in particular their sodium salts.
  • Such additional granulation aids can be contained in the enzyme granules according to the invention in amounts of up to 10% by weight, in particular from 0.5% by weight to 8% by weight.
  • Higher molecular polyethylene glycols that is to say those with an average molecular weight of more than 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but surprisingly, the higher molecular weight polyethylene glycols surprisingly bring about an undesired increase in the required granule dissolution time, so that these substances completely absent in the enzyme granules according to the invention.
  • fermentation broths are preferably used which are freed of insoluble accompanying substances by microfiltration.
  • the microfiltration is preferably carried out as cross-flow microfiltration using porous tubes with micro pores larger than 0.1 ⁇ , flow rates of the concentrate solution of more than 2 m / s and a pressure difference to the permeate side of less than 5 bar, as for example in the European patent application EP 200032 described.
  • the microfiltration permeate is then concentrated, preferably by ultrafiltration, optionally with subsequent vacuum evaporation.
  • the concentration can, as described in the international patent application WO 92/11347, be carried out in such a way that only relatively low dry matter contents of preferably 5% by weight to 50% by weight, in particular 10, are used % To 40% by weight.
  • the protease content at this stage of the concentrate is preferably 500000 PE / g to 1 500000 PE / g, in particular 600000 PE / g to 1 000 000 PE / g.
  • the concentrate is metered into a suitably previously prepared dry, powdery to granular mixture of the additives described above.
  • the water content of the mixture should be chosen so that it is in the processing with stirring and impact tools Transfer granular particles that are not sticky at room temperature and plastically deform and extrude them when using higher pressures.
  • the free-flowing premix is, in principle, subsequently processed in a kneader and a connected extruder to form a plastic mass, the result of the mechanical processing being the temperature of between 40 ° C. and 60 ° C., in particular 45 ° C. to 55 ° C. can heat.
  • the material leaving the extruder is passed through a perforated disk with a subsequent knock-off knife and is thereby comminuted to cylindrical particles of a defined size.
  • the diameter of the bores in the perforated disk is expediently 0.7 mm to 1.6 mm, preferably 0.8 mm to 1.2 mm.
  • the particles present in this form can then be dried and used for later use.
  • the still moist spheres are continuously or batchwise, preferably using a fluidized bed drying unit, preferably at 35 ° C. to 50 ° C. and in particular at a maximum product temperature of 45 ° C., to a residual moisture content of 4% by weight. up to 10 wt .-%, preferably 5 wt .-% to 8 wt .-% dried.
  • a fluidized bed drying unit preferably at 35 ° C. to 50 ° C. and in particular at a maximum product temperature of 45 ° C.
  • additional substances can be introduced to coat and coat the particles.
  • Suitable coating materials are, in particular, the film formers among the aforementioned water-soluble organic polymers.
  • dyes or pigments can also be applied to the particles at this stage in order to cover or change any intrinsic color that usually results from the enzyme concentrate.
  • Titanium dioxide in particular, has proven itself as an inert and physiologically harmless pigment. is introduced as an aqueous dispersion. The water supplied via the pigment dispersion or via the polymer solution is removed again during the drying which is carried out at the same time or is subsequently required again.
  • the enzyme granules are preferably used for the production of solid, in particular particulate detergents or cleaning agents which can be obtained by simply mixing the enzyme granules with other powder components customary in such agents.
  • the enzyme granules preferably have average grain sizes in the range from 0.1 mm to 2 mm, in particular from 0.4 mm to 1.6 ⁇ m.
  • any dust-like particles with a grain size below 0.1 mm, in particular below 0.4 mm, as well as possible coarse particles with a grain size above 2 mm, especially above 1.6 mm, can be removed and possibly in the Manufacturing process.
  • the granules according to the invention preferably contain less than 5% by weight, in particular at most 1% by weight, of particles with grain sizes outside the range from 0.2 mm to 1.6 mm.
  • the carrier material preferably contains 10% by weight to 70% by weight of cereal flour, 10% by weight to 70% by weight of starch which is swellable in water, 3% by weight to 10% by weight of sucrose and up to 10% by weight of cellulose powder, in each case based on finished enzyme granules.
  • the enzyme preparation obtained consists of largely rounded, dust-free particles which generally have a bulk density of about 500 to 900 grams per liter, in particular 650 to 880 grams per liter. Due to the flexible dry matter content of the broths prior to mixing with the additives, their enzyme activity can, when using protease-containing ferrous broths, reach values in the range of preferably 150,000 to 350,000 protease units per gram (PE / g), in particular 160000 PE / g to 300000 PE / g.
  • the granules according to the invention are notable for very high storage stability, in particular at temperatures above room temperature and high atmospheric humidity, and for rapid dissolution behavior in the wash liquor. The granules according to the invention preferably release 100% of their enzyme activity in water at 25 ° C. within 3 minutes, in particular within 90 seconds to 2 minutes.
  • a fermentation broth containing biomass was obtained by fermentation of Bacillus lichenifor is (ATCC 53926) modified according to the process described in international patent application WO 91/2792 by transforming a gene sequence from Bacillus lentus DSM 5483 analogous to the process given in German patent DE 2925427 containing about 65,000 protease units per gram (PE / g). This was concentrated to a protease content of 700,000 PE / g (B1) by decanting, cross-flow microfiltration, ultrafiltration (cut-off limit at molecular weight 10,000) and then evaporating in vacuo in accordance with the procedure described in international patent application WO 92/11347.
  • the fermenter broth thus concentrated was mixed in a mixer equipped with a rotating impact tool with the additives listed in Table 1 and homogenized in a kneader provided with external cooling.
  • the plastic mass was extruded using an extruder equipped with a perforated disc (hole diameter 0.9 mm) and a rotating knife.
  • extrudates XI to X4 and X5 and X6 characterized in Table 1 by their composition, in which a perforated disc with a hole diameter of 1.2 mm had been used, were obtained in accordance with the invention and for comparison extrudates VI to V3, each with Lengths from 0.7 mm to 1 mm, which were deformed and deburred in a spheronizing device (Marumerizer ( R )) during a processing time of about 1 minute while simultaneously dusting with powdered calcium carbonate (3% by weight).
  • the material leaving the spheronizer was dried in a fluidized bed dryer at temperatures from 40 ° C. to 45 ° C. within 15 minutes to a water content of 6% by weight.
  • the dissolution time was determined in a measuring apparatus consisting of a temperature-controlled, double-walled beaker, an inclined-blade stirrer, a temperature sensor and a conductivity measuring cell with 4 electrodes, which are connected to the conductivity measuring device (type LF 537, WTW) with an xt- Clerk is connected.
  • 500 ml of water were heated to 20 ° C. in the beaker while stirring.
  • 5.0 g of the enzyme granules were stirred in and the conductivity-time curve was recorded with the recorder.
  • the time in which 90% of the final value (after 15 minutes) is reached corresponds to the dissolution time in Table 2.
  • the enzyme granules according to the invention from Example 1 completely dissolved in times of less than 2 minutes, while the granules tested for comparison required significantly longer times. It is remarkable that the increase in the proportion of higher molecular weight polyethylene glycol (granules VG3 in comparison to VG2) led to a slowdown in the dissolution.

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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)
  • Detergent Compositions (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

Afin d'améliorer la solubilité, d'augmenter la durabilité et de réduire les pertes d'activité enzymatique pendant la production de granulés d'enzyme contenant un enzyme et un porteur inorganique et/ou organique, propres à être incorporés dans des produits de lavage ou de nettoyage, on utilise un système auxiliaire de granulation constitué de carboxyméthylcellulose alcaline avec des degrés de substitution allant de 0,5 à 1 et de polyéthylène-glycol et/ou de polyéthoxylate d'alkyle ou d'alcényle. Lorsque plus de 2 % en poids de carboxyméthylcellulose alcaline sont contenus dans les granulés, ceux-ci contiennent au moins 0,5 % en poids de glycol de polyéthylène ayant une masse molaire moyenne inférieure à 1000 et/ou de polyéthoxylate d'alcényle ou d'alkyle avec au moins 20 groupes éthoxy. Ces nouveaux granulés d'enzyme ont une vitesse de décomposition si élevée que lorsqu'ils sont utilisés dans des produits de lavage, le bain de lavage contient suffisamment d'enzyme pour éliminer des salissures éliminables par action enzymatique déjà dans la phase initiale du lavage en machine.
PCT/EP1994/000934 1993-03-31 1994-03-23 Composition d'enzyme pour produits de lavage et de nettoyage WO1994023005A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59403879T DE59403879D1 (de) 1993-03-31 1994-03-23 Enzymzubereitung für wasch- und reinigungsmittel
EP94912528A EP0692016B1 (fr) 1993-03-31 1994-03-23 Composition d'enzyme pour produits de lavage et de nettoyage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4310506A DE4310506A1 (de) 1993-03-31 1993-03-31 Enzymzubereitung für Wasch- und Reinigungsmittel
DEP4310506.8 1993-03-31

Publications (1)

Publication Number Publication Date
WO1994023005A1 true WO1994023005A1 (fr) 1994-10-13

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000934 WO1994023005A1 (fr) 1993-03-31 1994-03-23 Composition d'enzyme pour produits de lavage et de nettoyage

Country Status (5)

Country Link
EP (1) EP0692016B1 (fr)
AT (1) ATE157394T1 (fr)
DE (2) DE4310506A1 (fr)
DK (1) DK0692016T3 (fr)
WO (1) WO1994023005A1 (fr)

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DE102008013606A1 (de) 2008-03-11 2009-09-17 Clariant International Ltd. Verfahren zur Herstellung fester Erdalkalimetallsalze sekundärer Paraffinsulfonsäuren
US7888104B2 (en) 2000-11-28 2011-02-15 Henkel Ag & Co. Kgaa Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase
WO2012000846A1 (fr) 2010-06-28 2012-01-05 Basf Se Composition de blanchiment dépourvue de métal
WO2012080088A1 (fr) 2010-12-13 2012-06-21 Basf Se Catalyseurs de blanchiment
DE102011010818A1 (de) 2011-02-10 2012-08-16 Clariant International Ltd. Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
US8263541B2 (en) 2005-08-19 2012-09-11 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
US8361946B2 (en) 2004-04-08 2013-01-29 Akzo Nobel N.V. Detergent composition
DE102014009836A1 (de) 2014-07-03 2016-01-07 Weylchem Wiesbaden Gmbh Natriumsalze sekundärer Alkansulfonate enthaltende Compounds, ihre Herstellung und Verwendung sowie Wasch-, Desinfektion- und Reinigungsmittel enthaltend diese
EP2302025B1 (fr) 2009-09-08 2016-04-13 The Procter & Gamble Company Composition de détergent pour linge comprenant des particules de cellulose de carboxyméthyle fortement solubles dans l'eau
WO2017076771A1 (fr) 2015-11-03 2017-05-11 Basf Se Catalyseurs de blanchiment
EP3176157A1 (fr) 2015-12-01 2017-06-07 Basf Se Catalyseurs de blanchiment
WO2017186480A1 (fr) 2016-04-26 2017-11-02 Basf Se Composition de blanchiment sans métal
EP3372663A1 (fr) 2017-03-10 2018-09-12 Basf Se Catalyseurs de blanchiment
EP3524347A1 (fr) 2008-04-09 2019-08-14 Basf Se Utilisation de composés complexes hydrazides métalliques en tant que catalyseurs d'oxydation
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DE19615776A1 (de) 1996-04-20 1997-10-23 Henkel Kgaa Löslichkeitsverbessertes Enzymgranulat
DE19651446A1 (de) * 1996-12-11 1998-06-18 Henkel Kgaa Umhüllte Enzymzubereitung mit verbesserter Löslichkeit

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US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US7300782B2 (en) 2001-12-21 2007-11-27 B.R.A.I.N. Biotechnology Research And Information Network Ag Glycosyl hydrolases
US7015185B2 (en) 2002-03-15 2006-03-21 Clariant Gmbh Ammonium nitriles and the use thereof as hydrophobic bleaching activators
US6875734B2 (en) 2003-02-03 2005-04-05 Clariant Gmbh Use of transition metal complexes as bleach catalysts
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US8361946B2 (en) 2004-04-08 2013-01-29 Akzo Nobel N.V. Detergent composition
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EP1754781A1 (fr) 2005-08-19 2007-02-21 The Procter and Gamble Company Composition détergente solide comprenant un tensioactif anionique et une technologie augmentée de calcium
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US8426635B2 (en) 2008-03-11 2013-04-23 Clariant Finance (Bvi) Limited Process for preparing solid alkaline earth metal salts of secondary paraffinsulphonic acids
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ATE157394T1 (de) 1997-09-15
DK0692016T3 (da) 1998-04-20
DE4310506A1 (de) 1994-10-06
EP0692016A1 (fr) 1996-01-17
EP0692016B1 (fr) 1997-08-27

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