EP0692016B1 - Enzyme composition for washing and cleaning agents - Google Patents

Enzyme composition for washing and cleaning agents Download PDF

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Publication number
EP0692016B1
EP0692016B1 EP94912528A EP94912528A EP0692016B1 EP 0692016 B1 EP0692016 B1 EP 0692016B1 EP 94912528 A EP94912528 A EP 94912528A EP 94912528 A EP94912528 A EP 94912528A EP 0692016 B1 EP0692016 B1 EP 0692016B1
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EP
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Prior art keywords
weight
enzyme
granules
enzyme granules
granulation aid
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EP94912528A
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German (de)
French (fr)
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EP0692016A1 (en
Inventor
Kathleen Paatz
Wilfried Rähse
Werner Pichler
Udo Sturm
Horst Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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 preparation 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 mixed in with conventional detergents, a considerable reduction in the enzyme activity can occur during storage, especially if bleach-active compounds are present.
  • the storage stability of the enzymes can be significantly increased if the enzymes are encased or embedded in the carrier material and then converted into the desired particle shape by extrusion, pressing and marumerization, as described, for example, in German patent DE 16 17 232, German Offenlegungsschrift DT 20 32 768, and the German interpretations DE 21 37 042 and DE 21 37 043.
  • Such enzyme preparations have poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it, or they can be discharged unused into the wastewater.
  • Embedding agents known from German laid-open specification DT 18 03 099 which consist of a mixture of solid acids or acid 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 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 wt .-% water-soluble organic polymer as a granulating aid, 10 wt .-% to 35 wt .-% cereal and 3 wt .-% to 12 wt .-% 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 has the rate of disintegration and dispersion of the granules in cold wash liquors, while the addition of higher molecular weight polyethylene glycol can change this effect in the direction of a higher dissolution rate.
  • the enzyme granules described there do not always have such a high disintegration rate that when they are used in detergents, sufficient enzyme is already present in the washing liquor in the initial phase of machine washing to remove enzymatically removable soiling.
  • the invention relates to an enzyme granulate suitable for incorporation in particular particulate detergents or cleaning agents, containing enzyme and inorganic and / or organic carrier material and carboxymethyl cellulose-containing granulation aid, which is characterized in that it is a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl or alkenyl polyethoxylate contains the proviso that, based in each case on the finished granulate, at least 0.5% by weight of polyethylene glycol with an average molecular weight of less than 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are present is when more than 2 wt .-% alkali carboxymethyl cellulose is contained.
  • the degree of substitution of carboxymethyl cellulose is to be understood as the number of etherified oxygen atoms bearing a carboxymethyl group per saccharide monomer of cellulose.
  • the degree of substitution at preferably The carboxymethyl celluloses used are in the range from 0.8 to 0.95, since when they are used, particularly solid granules are obtained or smaller amounts are required to achieve a certain granule strength than when using cellulose with a lower degree of substitution.
  • the presence of sodium carboxymethyl cellulose with a degree of substitution of 0.85 to 0.95, even in quantities of 1% by weight, based on the granulate, in the granulating aid system enables the strength of the granules to be achieved which is the same as when double the amount of sodium carboxymethyl cellulose with a degree of substitution of 0 , 65 to 0.75 correspond.
  • 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 granules contain 1% by weight to 30% by weight, calculated as dry substance, protease, lipase, amylase and / or cellulase, 70% by weight to 94% by weight of inorganic and / or organic carrier material and 5% by weight to 50% by weight of granulation aid containing carboxymethyl cellulose and the remainder to 100% by weight of 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 and 0.1 as the granulation aid system %
  • the invention relates to a method for producing such an enzyme granulate with a grain size of 0.1 mm to 2 mm by extrusion an enzyme premix obtained by mixing a concentrated fermentation broth freed from insoluble constituents by microfiltration with the carrier material and the granulating aid, additives, spheronization of the extrudate in a rounding machine, drying and optionally application of a dye or pigment-containing coating, characterized in that the Fermentation broth mixed with an additive which contains a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate with the proviso that, based in each case on the finished granulate, at least 0.5% by weight polyethylene glycol an average molecular weight below 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are used if more than 2% by weight of alkali carboxymethyl cellulose is contained in the granulation aid system
  • the primary enzymes that 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 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738 and European patent application EP 006 638.
  • 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 detergents and cleaning agents often Problems.
  • the invention it is possible to convert the broths of extracellular enzymes obtained in the fermentation processes directly after removal of the insoluble accompanying substances by microfiltration and subsequent concentration by ultrafiltration and, if appropriate, subsequent evaporation in vacuo, into storage-stable, largely odorless granules. The formation of undesirable enzyme dusts and the loss of activity that 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 surfactants 7 (1970), 125) to 350,000 PE, in particular 160,000 PE to 300,000 PE , per gram of enzyme granules.
  • 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 of starch swellable in water, cereal flour and optionally cellulose powder and alkali carbonate is preferably used.
  • the starch which is swellable in water is preferably corn starch, rice starch, potato starch or mixtures thereof, the use of corn 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 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 that has not been fully ground, which has been produced from whole, unpeeled grains or at least predominantly consists of such a product, the rest consisting of fully ground 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 reduction in odor of 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 granulation aid system, the alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate contains.
  • alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and up to 5 wt .-%, in particular 0.5 wt .-% to 3 wt .-% polyethylene glycol and / or alkyl polyethoxylate, it being important that at least 0.5 wt .-%, especially 0.8 wt .-% to 2 wt .-% 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 wt .-% alkali carboxymethyl cellulose is contained.
  • 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.
  • additional cellulose or starch ethers such as carboxymethyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, maltodextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible oligomers can also be used as additional constituents of the granulation aid system natural or synthetic origin.
  • Usable synthetic water-soluble polymers are polyacrylates, polymethacrylates, copolymers acrylic acid with maleic acid or compounds containing vinyl groups, also 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 weight polyethylene glycols i.e. those with an average molecular weight above 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but it is precisely the higher molecular weight polyethylene glycols which surprisingly bring about an undesirable increase in the granule dissolution time required, so that these substances are preferably 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 micropores larger than 0.1 ⁇ m, 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 200 032.
  • the microfiltration permeate is then concentrated, preferably by ultrafiltration, if appropriate with subsequent vacuum evaporation.
  • the concentration can, as described in 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% by weight up to 40% by weight.
  • the protease content at this stage of the concentrate is preferably 500,000 PU / g to 1,500,000 PU / g, in particular 600,000 PU / g to 1,000,000 PU / 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 disc with a subsequent knock-off knife and is thereby crushed into 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 beads are continuously or in batches, 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 to 10% % By weight, preferably 5% by weight to 8% by weight, 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 inherent color, which usually results from the enzyme concentrate.
  • Titanium dioxide in particular has proven to be an inert and physiologically harmless pigment, which preferably is introduced in aqueous dispersion.
  • the water supplied via the pigment dispersion or via the polymer solution is removed again when drying 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 washing 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 mm.
  • any dusty particles with a grain size below 0.1 mm, in particular below 0.4 mm and any coarse particles with a grain size above 2 mm, in particular above 1.6 mm, can be removed and possibly returned to the manufacturing process will.
  • 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.
  • 10% by weight to 50% by weight of the concentrated fermentation broth is mixed with 70% by weight to 90% by weight of the carrier material and 0.5% by weight to 10% by weight. of the granulation aid system mixed.
  • 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 .-% cellulose powder, each 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 before they are mixed with the additives, their enzyme activity can, particularly when using protease-containing fermentation broths, in the range of preferably 150,000 to 350,000 protease units per gram (PE / g) 160,000 PE / g to 300,000 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 licheniformis (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 29 25 427, which obtained contained about 65,000 protease units per gram (PE / g). This was done by decanting. Cross-flow microfiltration, ultrafiltration (separation limit at molecular weight 10,000) and subsequent evaporation in vacuo according to the procedure described in international patent application WO 92/11347 concentrated to a protease content of 700,000 PE / g ( B1 ).
  • 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 X1 to X3 and X4 and X5 characterized in Table 1 by their composition, in which a perforated disk with a hole diameter of 1.2 mm was used, were obtained according to the invention and for comparison extrudates V1 to V3 , each with lengths of 0, 7 mm to 1 mm, which were deformed and deburred in a spheronization device (Marumerizer®) for 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 temperable, double-walled beaker, an inclined-blade stirrer, a temperature sensor and a conductivity measuring cell with 4 electrodes, which is connected to an x-t recorder via the conductivity measuring device (type LF 537, WTW).
  • 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.

Abstract

In order to improve the solubility, to increase the storage stability and to reduce enzyme activity losses during production of enzyme granulates suitable to be incorporated into washing or cleaning agents and containing an enzyme and an organic and/or inorganic carrier, a granulation-auxiliary system is used which consists of alkali-carboxymethylcellulose with substitution degrees from 0.5 to 1 and of polyethylene glycol and/or alkyl- or alkenylpolyethoxylate. When more than 2 % by weight alkali-carboxymethylcellulose are contained in the granulates, they contain at least 0.5 % by weight polyethylene glycol with less than 1000 mean molar mass and/or alkyl- or alkenylpolyethoxylate with at least 20 ethoxy groups. The new enzyme granulates have such a high speed of decomposition that when they are used in washing agents the wash bath contains enough enzyme to remove enzymatically removable soil already in the initial phase of machine washing.

Description

Die Erfindung betrifft ein Enzymgranulat, ein Verfahren zu seiner Herstellung und die Verwendung des Granulats in festen Wasch- und Reinigungsmitteln.The invention relates to an enzyme granulate, a process for its preparation and the use of the granulate in solid washing and cleaning agents.

Enzyme, insbesondere Proteasen, finden ausgedehnte Verwendung in Wasch-, Waschhilfs- und Reinigungsmitteln. Üblicherweise kommen die Enzyme dabei nicht als Konzentrate, sondern in Mischungen mit einem Verdünnungs- und Trägermaterial zum Einsatz. Mischt man solche Enzymzubereitungen üblichen Waschmitteln bei, so kann beim Lagern ein erheblicher Abbau der Enzymaktivität eintreten, insbesondere wenn bleichaktive Verbindungen zugegen sind. Das Aufbringen der Enzyme auf Trägersalze unter gleichzeitiger Granulation gemäß der deutschen Offenlegungsschrift DT 16 17 190 beziehungsweise durch Aufkleben mit nichtionischen Tensiden gemäß der deutschen Offenlegungsschrift DT 16 17 118 oder wäßrigen Lösungen von Celluloseethern gemäß der deutschen Offenlegungschrift DT 17 67 568 führt nicht zu einer nennenswerten Verbesserung der Lagerstabilität, da sich die empfindlichen Enzyme in solchen Aufmischungen in der Regel auf der Oberfläche der Trägersubstanz befinden. Zwar kann die Lagerstabilität der Enzyme wesentlich erhöht werden, wenn man die Enzyme mit dem Trägermaterial umhüllt beziehungsweise in dieses einbettet und anschließend durch Extrudieren, Pressen und Marumerisieren in die gewünschte Partikelform überführt, wie zum Beispiel in der deutschen Patentschrift DE 16 17 232, der deutschen Offenlegungsschrift DT 20 32 768, und den deutschen Auslegeschriften DE 21 37 042 und DE 21 37 043 beschrieben. Derartige Enzymzubereitungen besitzen jedoch nur mangelhafte Löslichkeitseigenschaften. Die ungelösten Partikel können sich im Waschgut verfangen und dieses verunreinigen bzw. sie werden ungenutzt in das Abwasser überführt. Aus der deutschen Offenlegungsschrift DT 18 03 099 bekannte Einbettungsmittel, die aus einem Gemisch fester Säuren beziehungsweise saurer Salze und Carbonaten beziehungsweise Bicarbonaten bestehen und bei Wasserzusatz zerfallen, verbessern zwar das Lösungsvermögen, sind aber ihrerseits sehr empfindlich gegen Feuchtigkeit und erfordern daher zusätzliche Schutzmaßnahmen.Enzymes, especially proteases, 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 mixed in with conventional detergents, a considerable reduction in the enzyme activity can occur during storage, especially if bleach-active compounds are present. The application of the enzymes to carrier salts with simultaneous granulation in accordance with German Offenlegungsschrift DT 16 17 190 or by sticking with nonionic surfactants in accordance with German Offenlegungsschrift DT 16 17 118 or aqueous solutions of cellulose ethers in accordance with German Offenlegungsschrift DT 17 67 568 does not lead to any significant improvement storage stability, since the sensitive enzymes in such mixtures are usually on the surface of the carrier substance. The storage stability of the enzymes can be significantly increased if the enzymes are encased or embedded in the carrier material and then converted into the desired particle shape by extrusion, pressing and marumerization, as described, for example, in German patent DE 16 17 232, German Offenlegungsschrift DT 20 32 768, and the German interpretations DE 21 37 042 and DE 21 37 043. However, such enzyme preparations have poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it, or they can be discharged unused into the wastewater. Embedding agents known from German laid-open specification DT 18 03 099, which consist of a mixture of solid acids or acid 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.

Ein weiterer Nachteil der vorgenannten Zubereitung ist darin zu sehen, daß die Enzyme nur in Form trockener Pulver verarbeitet werden können. Die üblicherweise bei der Enzymherstellung anfallenden Fermentationsbrühen lassen sich in dieser Form nicht einsetzen, sondern müssen zuvor entwässert werden. An diese Voraussetzung sind auch solche Verfahren gebunden, bei denen ausschließlich leicht lösliche Trägermaterialien, wie Zucker, Stärke und Celluloseether als Bindemittel zur Herstellung von Enzymzubereitungen eingesetzt werden.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.

Aus der europäischen Patentschrift EP 168 526 sind Enzymgranulate bekannt, die in Wasser quellfähige Stärke, Zeolith und wasserlösliches Granulierhilfsmittel enthalten. In diesem Dokument wird ein Herstellungsverfahren für derartige Formulierungen vorgeschlagen, das im wesentlichen darin besteht, eine von unlöslichen Bestandteilen befreite Fermenterlösung aufzukonzentrieren, mit den genannten Zuschlagstoffen zu versetzten und das entstandene Gemisch zu granulieren. Das Verfahren mit dem dort vorgeschlagenen Zuschlagstoffgemisch wird vorteilhaft mit Fermentationslösungen durchgeführt, die auf einen relativ hohen Trockensubstanzgehalt, beispielsweise 55 Gew.-%, aufkonzentriert worden sind. Außerdem weisen die derart hergestellten Granulate eine so hohe Lösungs- beziehungsweise Zerfallsgeschwindigkeit unter Waschbedingungen auf, daß die Granulate teilweise schon bei der Lagerung relativ rasch zerfallen und die Enzyme desaktiviert werden.From the European patent EP 168 526 enzyme granules are known which contain starch which swells in water, zeolite and water-soluble granulation aid. In this document, a manufacturing process for such formulations is proposed which essentially consists of 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. In addition, the granules so produced have such a high dissolution or disintegration rate under washing conditions that the granules disintegrate relatively quickly even during storage and the enzymes are deactivated.

Aus der internationalen Patentanmeldung WO 92/11347 sind Enzymgranulate zum Einsatz in körnigen Wasch- und Reinigungsmitteln bekannt, die 2 Gew.-% bis 20 Gew.-% Enzym, 10 Gew.-% bis 50 Gew.-% quellfähige Stärke, 5 Gew.-% bis 50 Gew.-% wasserlösliches organisches Polymer als Granulierhilfsmittel, 10 Gew.-% bis 35 Gew.-% Getreidemehl und 3 Gew.-% bis 12 Gew.-% Wasser enthalten. Durch derartige Zuschlagstoffe wird die Enzymverarbeitung ohne größere Aktivitätsverluste möglich und auch die Lagerbeständigkeit der Enzyme in den Granulaten ist zufriedenstellend. Aus diesem Dokument ist auch bekannt, daß Natriumcarboxymethylcellulose die Zerfalls- und Dispergiergeschwindigkeit der Granulate in kalten Waschlaugen herabsetzt, während durch einen Zusatz von höhermolekularem Polyethylenglykol diese Wirkung in Richtung auf eine höhere Auflösungsgeschwindigkeit verändert werden kann. Jedoch weisen die dort beschriebenen Enzymgranulate nicht immer eine so hohe Zerfallsgeschwindigkeit auf, daß bei deren Einsatz in Waschmitteln schon in der Anfangsphase der maschinellen Wäsche genügend Enzym in der Waschflotte vorhanden ist, um enzymatisch entfernbare Anschmutzungen zu beseitigen.From international patent application WO 92/11347, enzyme granules for use in granular detergents and cleaning agents are known 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 wt .-% water-soluble organic polymer as a granulating aid, 10 wt .-% to 35 wt .-% cereal and 3 wt .-% to 12 wt .-% water. Such additives enable enzyme processing without major loss of activity and the storage stability of the enzymes in the granules is also satisfactory. From this document it is also known that sodium carboxymethyl cellulose has the rate of disintegration and dispersion of the granules in cold wash liquors, while the addition of higher molecular weight polyethylene glycol can change this effect in the direction of a higher dissolution rate. However, the enzyme granules described there do not always have such a high disintegration rate that when they are used in detergents, sufficient enzyme is already present in the washing liquor in the initial phase of machine washing to remove enzymatically removable soiling.

Es bestand daher die Aufgabe, durch ein Herstellungsverfahren, das den Einsatz niedrigkonzentrierter Fermentationsbrühen erlaubt, die Pulvereigenschaften, insbesondere die Löslichkeit der bekannten Produkte zu verbessern, die Lagerbeständigkeit sowohl der Enzyme als auch der diese enthaltenden Granulate noch weiter zu erhöhen und die Aktivitätsverluste bei der Enzymverarbeitung weiter zu vermindern. Diese Aufgabe wird durch die nachfolgend geschilderte Erfindung im wesentlichen durch ein spezielles Granulierhilfsmittelsystem gelöst, welches löslichkeitsvermittelnde beziehungsweise staubbindende Komponente und kornverfestigende Komponente in optimierten Verhältnissen enthält.It was therefore an object to improve the powder properties, in particular the solubility of the known products, to further increase the shelf life of both the enzymes and the granules containing them, and to reduce the activity during enzyme processing by means of a production process which allows the use of low-concentration fermentation broths further decrease. This object is essentially achieved by the invention described below by means of a special granulation aid system which contains solubilizing or dust-binding component and grain-strengthening component in optimized ratios.

Die Erfindung betrifft ein für die Einarbeitung in insbesondere teilchenförmige Wasch- oder Reinigungsmittel geeignetes Enzymgranulat, enthaltend Enzym und anorganisches und/oder organisches Trägermaterial sowie carboxymethylcellulosehaltiges Granulierhilfsmittel, welches dadurch gekennzeichnet ist, daß es ein Granulierhilfsmittelsystem aus Alkali-Carboxymethylcellulose mit Substitutionsgraden von 0,5 bis 1 und Polyethylenglykol und/ oder Alkyl- beziehungsweise Alkenylpolyethoxylat enthält mit der Maßgabe, daß, jeweils bezogen auf fertiges Granulat, mindestens 0,5 Gew.-% Polyethylenglykol mit einer mittleren Molmasse unter 1000 und/oder Alkyl- beziehungsweise Alkenylpolyethoxylat mit mindestens 20 Ethoxygruppen vorhanden ist, wenn mehr als 2 Gew.-% Alkali-Carboxymethylcellulose enthalten ist.The invention relates to an enzyme granulate suitable for incorporation in particular particulate detergents or cleaning agents, containing enzyme and inorganic and / or organic carrier material and carboxymethyl cellulose-containing granulation aid, which is characterized in that it is a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl or alkenyl polyethoxylate contains the proviso that, based in each case on the finished granulate, at least 0.5% by weight of polyethylene glycol with an average molecular weight of less than 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are present is when more than 2 wt .-% alkali carboxymethyl cellulose is contained.

Unter dem Substitutionsgrad der Carboxymethylcellulose ist die Zahl der veretherten, eine Carboxymethylgruppe tragenden Sauerstoffatome pro Saccharid-Monomer der Cellulose zu verstehen. Der Substitutionsgrad bei vorzugsweise eingesetzten Carboxymethylcellulosen liegt im Bereich von 0,8 bis 0,95, da bei deren Einsatz besonders feste Granulatkörner erhalten werden beziehungsweise geringere Mengen erforderlich sind, um eine bestimmte Granulatfestigkeit zu errichen, als bei Einsatz von Cellulose mit niedrigerem Substitutionsgrad. So können beispielsweise durch die Anwesenheit von Natriumcarboxymethylcellulose mit Substitutionsgrad 0,85 bis 0,95 schon bei Mengen von 1 Gew.-%, bezogen auf Granulat, im Granulierhilfsmittelsystem, Garnulatfestigkeiten erreicht werden, welche derjenigen bei Einsatz der doppelten Menge an Natriumcarboxymethylcellulose mit Substitutionsgrad 0,65 bis 0,75 entsprechen. Außerdem kann durch den Einsatz der genannten höhersubstituierten Carboxymethylcellulose bei der Herstellung der Granulate im Extrusionsschritt ein höherer Durchsatz durch den Extruder erreicht werden.The degree of substitution of carboxymethyl cellulose is to be understood as the number of etherified oxygen atoms bearing a carboxymethyl group per saccharide monomer of cellulose. The degree of substitution at preferably The carboxymethyl celluloses used are in the range from 0.8 to 0.95, since when they are used, particularly solid granules are obtained or smaller amounts are required to achieve a certain granule strength than when using cellulose with a lower degree of substitution. For example, the presence of sodium carboxymethyl cellulose with a degree of substitution of 0.85 to 0.95, even in quantities of 1% by weight, based on the granulate, in the granulating aid system enables the strength of the granules to be achieved which is the same as when double the amount of sodium carboxymethyl cellulose with a degree of substitution of 0 , 65 to 0.75 correspond. In addition, 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.

Das Enzymgranulat enthält in einer bevorzugten Ausführungsform 1 Gew.-% bis 30 Gew.-%, berechnet als Trockensubstanz, Protease, Lipase, Amylase und/oder Cellulase, 70 Gew.-% bis 94 Gew.-% anorganisches und/oder organisches Trägermaterial und 5 Gew.-% bis 50 Gew.-% carboxymethylcellulosehaltiges Granulierhilfsmittel sowie als Rest auf 100 Gew.-% Wasser.In a preferred embodiment, the enzyme granules contain 1% by weight to 30% by weight, calculated as dry substance, protease, lipase, amylase and / or cellulase, 70% by weight to 94% by weight of inorganic and / or organic carrier material and 5% by weight to 50% by weight of granulation aid containing carboxymethyl cellulose and the remainder to 100% by weight of water.

Als Granulierhilfsmittelsystem enthält ein erfindungsgemäßes Enzymgranulat vorzugsweise ein Gemisch enthaltend, jeweils bezogen auf fertiges Granulat, 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,5 Gew.-% bis 5 Gew.-% Carboxymethylcellulose sowie 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,5 Gew.-% bis 4 Gew.-% Polyethylenglykol mit einer mittleren Molmasse von 200 bis 600 und/oder eines Polyethoxylats gemäß Formel (I),

        R-(OCH2CH2)n-OH     (I)

in der R einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit bis zu 3 C-C-Doppelbindungen mit 10 bis 22, insbesondere 16 bis 18 C-Atomen und der mittlere Ethoxylierungsgrad n eine Zahl von 20 bis 80, insbesondere 30 bis 45 bedeutet.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 and 0.1 as the granulation aid system % 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- (OCH 2 CH 2 ) n -OH (I)

in which R is a straight-chain or branched alkyl or alkenyl radical having up to 3 CC double bonds with 10 to 22, in particular 16 to 18, carbon atoms and the average degree of ethoxylation n is a number from 20 to 80, in particular 30 to 45.

Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung eines derartigen Enzymgranulates mit einer Korngröße von 0,1 mm bis 2 mm durch Extrudieren eines durch Vermischen einer durch Mikrofiltration von unlöslichen Bestandteilen befreiten, aufkonzentrierten Fermentationsbrühe mit dem Trägermaterial und dem Granulierhilfsmittel als Zuschlagstoffen entstandenen Enzym-Vorgemischs, Sphäronisierung des Extrudats in einem Rondiergerät, Trocknung und gegebenenfalls Aufbringen eines Farbstoff oder Pigment enthaltenden Überzugs, dadurch gekennzeichnet, daß man die Fermentationsbrühe mit einem Zuschlagstoff vermischt, der ein Granulierhilfsmittelsystem aus Alkali-Carboxymethylcellulose mit Substitutionsgraden von 0,5 bis 1 und Polyethylenglykol und/oder Alkylpolyethoxylat enthält mit der Maßgabe, daß, jeweils bezogen auf fertiges Granulat, mindestens 0,5 Gew.-% Polyethylenglykol mit einer mittleren Molmasse unter 1000 und/ oder Alkyl- beziehungsweise Alkenylpolyethoxylat mit mindestens 20 Ethoxygruppen eingesetzt werden, wenn mehr als 2 Gew.-% Alkali-Carboxymethylcellulose im Granulierhilfsmittelsystem enthalten ist.Furthermore, the invention relates to a method for producing such an enzyme granulate with a grain size of 0.1 mm to 2 mm by extrusion an enzyme premix obtained by mixing a concentrated fermentation broth freed from insoluble constituents by microfiltration with the carrier material and the granulating aid, additives, spheronization of the extrudate in a rounding machine, drying and optionally application of a dye or pigment-containing coating, characterized in that the Fermentation broth mixed with an additive which contains a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate with the proviso that, based in each case on the finished granulate, at least 0.5% by weight polyethylene glycol an average molecular weight below 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups are used if more than 2% by weight of alkali carboxymethyl cellulose is contained in the granulation aid system.

Als Enzyme kommen in erster Linie die aus Mikroorganismen, wie Bakterien oder Pilzen, gewonnenen Proteasen, Lipasen, Amylasen und/oder Cellulasen in Frage, wobei von Bacillus-Arten erzeugte Proteasen sowie ihre Gemische mit Lipasen bevorzugt sind. Sie werden in bekannter Weise durch Fermentationsprozesse aus geeigneten Mikroorganismen gewonnen, die zum Beispiel in den deutschen Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 22 01 803 und DE 21 21 397, den US-amerikanischen Patentschriften US 3 632 957 und US 4 264 738 sowie der europäischen Patentanmeldung EP 006 638 beschrieben sind. Besonders vorteilhaft kann das erfindungsgemäße Verfahren zur Formulierung der sehr aktiven Proteasen der sogenannten zweiten und höheren Generationen verwendet werden, zu denen beispielsweise Savinase(R) und aus der internationalen Patentanmeldung WO 91/2792 bekannte Enzyme gehören, deren lagerstabile Einarbeitung in Wasch- und Reinigungsmittel oft Probleme bereitet. Erfindungsgemäß ist es möglich, die bei den Fermentationsprozessen anfallenden Brühen extrazellulärer Enzyme nach Abtrennen der unlöslichen Begleitstoffe durch Mikrofiltration sowie nachfolgende Aufkonzentration durch Ultrafiltration und gegebenenfalls anschließendes Eindampfen im Vakuum unmittelbar in lagerbeständige, weitgehend geruchlose Granulate zu überführen. Die Entstehung unerwünschter Enzymstäube und die bei zusätzlichen Trocknungsprozessen auftretenden Aktivitätsverluste werden vermieden.The primary enzymes that 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 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738 and European patent application EP 006 638. 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 detergents and cleaning agents often Problems. According to the invention, it is possible to convert the broths of extracellular enzymes obtained in the fermentation processes directly after removal of the insoluble accompanying substances by microfiltration and subsequent concentration by ultrafiltration and, if appropriate, subsequent evaporation in vacuo, into storage-stable, largely odorless granules. The formation of undesirable enzyme dusts and the loss of activity that occurs during additional drying processes are avoided.

Enzyme sind in den erfindungsgemäßen Granulaten vorzugsweise in Mengen von 4 Gew.-% bis 20 Gew.-% enthalten. Falls es sich bei dem erfindungsgemäßen Enzymgranulat um eine proteasehaltige Formulierung handelt, beträgt die Proteaseaktivität vorzugsweise 150 000 Proteaseeinheiten (PE, bestimmt nach der in Tenside 7 (1970), 125 beschriebenen Methode) bis 350 000 PE, insbesondere 160 000 PE bis 300 000 PE, pro Gramm Enzymgranulat.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 surfactants 7 (1970), 125) to 350,000 PE, in particular 160,000 PE to 300,000 PE , per gram of enzyme granules.

Als Trägermaterialien sind im Prinzip alle organischen oder anorganischen pulverförmigen Substanzen brauchbar, welche die zu granulierenden Enzyme nicht oder nur tolerierbar wenig zerstören oder desaktivieren und unter Granulationsbedingungen stabil sind. Zu derartigen Substanzen gehören beispielsweise Stärke, Getreidemehl, Cellulosepulver, Alkalialumosilikat, insbesondere Zeolith, Schichtsilikat, zum Beispiel Bentonit oder Smectit, und wasserlösliche anorganische oder organische Salze, zum Beispiel Alkalichlorid, Alkalisulfat, Alkalicarbonat oder Alkaliacetat, wobei Natrium oder Kalium die bevorzugten Alkalimetalle sind. Bevorzugt wird ein Trägermaterialgemisch aus in Wasser quellfähiger Stärke, Getreidemehl und gegebenenfalls Cellulosepulver sowie Alkalicarbonat eingesetzt.In principle, 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 of starch swellable in water, cereal flour and optionally cellulose powder and alkali carbonate is preferably used.

Bei der in Wasser quellfähigen Stärke handelt es sich vorzugsweise um Maisstärke, Reisstärke, Kartoffelstärke oder Gemische aus diesen, wobei der Einsatz von Maisstärke besonders bevorzugt ist. Quellfähige Stärke ist in den erfindungsgemäßen Enzymgranulaten vorzugsweise in Mengen von 20 Gew.-% bis 50 Gew.-%, insbesondere von 25 Gew.-% bis 45 Gew.-% enthalten. Dabei beträgt die Summe der Mengen der quellfähigen Stärke und des Mehls vorzugsweise nicht über 80 Gew.-%, insbesondere 32 Gew.-% bis 65 Gew.-%.The starch which is swellable in water is preferably corn starch, rice starch, potato starch or mixtures thereof, the use of corn 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.

Bei dem erfindungsgemäß geeigneten Getreidemehl handelt es sich insbesondere um ein aus Weizen, Roggen, Gerste oder Hafer herstellbares Produkt oder um ein Gemisch dieser Mehle, wobei Vollkornmehle bevorzugt sind. Unter einem Vollkornmehl wird im Rahmen der Erfindung ein nicht voll ausgemahlenes Mehl verstanden, das aus ganzen, ungeschälten Körnern hergestellt worden ist oder zumindest überwiegend aus einem derartigen Produkt besteht, wobei der Rest aus voll ausgemahlenem Mehl beziehungsweise Stärke besteht. Vorzugsweise werden handelsübliche Weizenmehl-Qualitäten, wie Type 450 oder Type 550, eingesetzt. Auch die Verwendung von Mehlprodukten der zu vorgenannten quellfähigen Stärken führenden Getreidearten ist möglich, wenn darauf geachtet wird, daß die Mehle aus den ganzen Körnern hergestellt worden sind. Durch die Mehlkomponente des Zuschlagstoffgemisches wird bekanntermaßen eine wesentliche Geruchsreduzierung der Enzymzubereitung erreicht, welche die Geruchsverminderung durch die Einarbeitung gleicher Mengen entsprechender Stärkearten bei weitem übertrifft. Derartiges Getreidemehl ist in den erfindungsgemäßen Enzymgranulaten vorzugsweise in Mengen von 10 Gew.-% bis 35 Gew.-%, insbesondere von 15 Gew.-% bis 25 Gew.-% enthalten.The cereal flour 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 that has not been fully ground, which has been produced from whole, unpeeled grains or at least predominantly consists of such a product, the rest consisting of fully ground 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 reduction in odor of 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.

Die erfindungsgemäßen Enzymgranulate enthalten vorzugsweise 1 Gew.-% bis 50 Gew.-%, vorzugsweise 5 Gew.-% bis 25 Gew.-% des Granulierhilfsmittelsystems, das Alkali-Carboxymethylcellulose mit Substitutionsgraden von 0,5 bis 1 und Polyethylenglykol und/oder Alkylpolyethoxylat enthält. In diesem Granulierhilfsmittelsystem sind vorzugsweise, jeweils bezogen auf fertiges Enzymgranulat, 0,5 Gew.-% bis 10 Gew.-%, insbesondere 0,5 Gew.-% bis 5 Gew.-% Alkali-Carboxymethylcellulose mit Substitutionsgraden von 0,5 bis 1 und bis zu 5 Gew.-%, insbesondere 0,5 Gew.-% bis 3 Gew.-% Polyethylenglykol und/oder Alkylpolyethoxylat enthalten, wobei wichtig ist, daß mindestens 0,5 Gew.-%, insbesondere 0,8 Gew.-% bis 2 Gew.-% Polyethylenglykol mit einer mittleren Molmasse unter 1000 und/oder Alkylpolyethoxylat mit mindestens 20 Ethoxygruppen vorhanden ist, wenn mehr als 2 Gew.-% Alkali-Carboxymethylcellulose enthalten ist. Höher substituierte Carboxymethylcellulose, mit Substitutionsgraden bis zu 3, ist in dem erfindungsgemäßen Granulierhilfsmittelsystem vorzugsweise nicht enthalten. Carboxymethylcellulosen mit Substitutionsgraden unter 0,5 sind in dem erfindungsgemäßen Granulierhilfsmittelsystem vorzugsweise ebenfalls nicht enthalten.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 granulation aid system, the alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate contains. In this granulation aid system, based in each case on finished enzyme granules, 0.5% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight, of alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and up to 5 wt .-%, in particular 0.5 wt .-% to 3 wt .-% polyethylene glycol and / or alkyl polyethoxylate, it being important that at least 0.5 wt .-%, especially 0.8 wt .-% to 2 wt .-% 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 wt .-% alkali carboxymethyl cellulose is contained. 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.

Gegebenenfalls können als zusätzliche Bestandteile des Granulierhilfsmittelsystems auch weitere Cellulose- oder Stärkeether, wie Carboxymethylstärke, Methylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose sowie entsprechende Cellulosemischether, Gelatine, Casein, Traganth, Maltodextrose, Saccharose, Invertzucker, Glukosesirup oder andere in Wasser lösliche beziehungsweise gut dispergierbare Oligomere oder Polymere natürlichen oder synthetischen Ursprungs verwendet werden. Brauchbare synthetische wasserlösliche Polymere sind Polyacrylate, Polymethacrylate, Copolymere der Acrylsäure mit Maleinsäure oder vinylgruppenhaltige Verbindungen, ferner Polyvinylalkohol, teilverseiftes Polyvinylacetat und Polyvinylpyrrolidon. Soweit es sich bei den vorgenannten Verbindungen um solche mit freien Carboxylgruppen handelt, liegen sie normalerweise in Form ihrer Alkalisalze, insbesondere ihrer Natriumsalze vor. Derartige zusätzliche Granulierhilfsmittel können in den erfindungsgemäßen Enzymgranulaten in Mengen bis zu 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 8 Gew.-% enthalten sein. Höhermolekulare Polyethylenglykole, das heißt solche mit einem mittleren Molekulargewicht über 1000, sind zwar als synthetische wasserlösliche Polymere mit staubbindender Wirkung brauchbar, doch bewirken gerade die höhermolekularen Polyethylenglykole überraschenderweise eine unerwünschte Erhöhung der benötigten Granulatauflösezeit, so daß diese Substanzen in den erfindungsgemäßen Enzymgranulaten vorzugsweise völlig fehlen.Optionally, additional cellulose or starch ethers, such as carboxymethyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, maltodextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible oligomers can also be used as additional constituents of the granulation aid system natural or synthetic origin. Usable synthetic water-soluble polymers are polyacrylates, polymethacrylates, copolymers acrylic acid with maleic acid or compounds containing vinyl groups, also polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone. Insofar as 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 weight polyethylene glycols, i.e. those with an average molecular weight above 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but it is precisely the higher molecular weight polyethylene glycols which surprisingly bring about an undesirable increase in the granule dissolution time required, so that these substances are preferably completely absent in the enzyme granules according to the invention.

Zur Herstellung der erfindungsgemäßen Enzymgranulate geht man vorzugsweise von Fermentationsbrühen aus, die durch Mikrofiltration von unlöslichen Begleitstoffen befreit werden. Die Mikrofiltration wird dabei vorzugsweise als Querstrom-Mikrofiltration unter Verwendung poröser Rohre mit Mikroporen größer 0,1 µm, Fließgeschwindigkeiten der Konzentratlösung von mehr als 2 m/s und einem Druckunterschied zur Permeatseite von unter 5 bar durchgeführt, wie beispielsweise in der europäischen Patentanmeldung EP 200 032 beschrieben. Anschließend wird das Mikrofiltrationspermeat vorzugsweise durch Ultrafiltration, gegebenenfalls mit anschließender Vakuumeindampfung, aufkonzentriert. Die Aufkonzentration kann dabei, wie in der internationalen Patentanmeldung WO 92/11347 beschrieben, so geführt werden, daß man nur zu relativ niedrigen Gehalten an Trockensubstanz von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 10 Gew.-% bis 40 Gew.-% gelangt. Falls proteasehaltige Fermentationsbrühen eingesetzt werden, beträgt der Proteasegehalt auf dieser Stufe des Konzentrats vorzugsweise 500 000 PE/g bis 1 500 000 PE/g, insbesondere 600 000 PE/g bis 1 000 000 PE/g. Das Konzentrat wird einem zweckmäßigerweise zuvor hergestellten trockenen, pulverförmigen bis körnigen Gemisch der oben beschriebenen Zuschlagstoffe zudosiert. Der Wassergehalt der Mischung sollte so gewählt werden, daß sie sich bei der Bearbeitung mit Rühr- und Schlagwerkzeugen in körnige, bei Raumtemperatur nicht klebende Partikel überführen und bei Anwendung höherer Drücke plastisch verformen und extrudieren läßt.For the production of 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 micropores larger than 0.1 μm, 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 200 032. The microfiltration permeate is then concentrated, preferably by ultrafiltration, if appropriate with subsequent vacuum evaporation. The concentration can, as described in 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% by weight up to 40% by weight. If protease-containing fermentation broths are used, the protease content at this stage of the concentrate is preferably 500,000 PU / g to 1,500,000 PU / g, in particular 600,000 PU / g to 1,000,000 PU / 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.

Das rieselfähige Vorgemisch wird im Prinzip bekannter Weise anschließend in einem Kneter sowie einem angeschlossenen Extruder zu einer plastischen Masse verarbeitet, wobei als Folge der mechanischen Bearbeitung sich die Masse auf Temperaturen zwischen 40°C und 60°C, insbesondere 45°C bis 55°C erwärmen kann. Das den Extruder verlassende Gut wird durch eine Lochscheibe mit nachfolgendem Abschlagmesser geführt und dadurch zu zylinderförmigen Partikeln definierter Größe zerkleinert. Zweckmäßigerweise beträgt der Durchmesser der Bohrungen in der Lochscheibe 0,7 mm bis 1,6 mm, vorzugsweise 0,8 mm bis 1,2 mm. Die in dieser Form vorliegenden Partikel können anschließend getrocknet und der späteren Verwendung zugeführt werden. Es hat sich jedoch als vorteilhaft erwiesen, die den Extruder und Zerhacker verlassenden zylindrischen Partikel anschließend zu sphäronisieren, das heißt sie in geeigneten Vorrichtungen abzurunden und zu entgraten. Ein solches Sphäronisierungsverfahren ist beispielsweise in den deutschen Auslegeschriften DE 21 37 042 und DE 21 37 043 beschrieben. Man verwendet hierzu eine Vorrichtung, die aus einem zylindrischen Behälter mit stationären, festen Seitenwänden und einer bodenseitig drehbar gelagerten Reibplatte bestehen. Vorrichtungen dieser Art sind unter der Warenbezeichnung Marumerizer(R) in der Technik verbreitet.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 disc with a subsequent knock-off knife and is thereby crushed into 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. However, it has proven advantageous to subsequently spheronize the cylindrical particles leaving the extruder and chopper, ie to round them off and deburr them in suitable devices. Such a spheronization method is described, for example, in the German design documents DE 21 37 042 and DE 21 37 043. For this purpose, a device is used which consists of a cylindrical container with stationary, fixed side walls and a friction plate rotatably mounted on the bottom. Devices of this type are commonly known in the art under the Marumerizer (R) name .

Nach der Sphäronisierung werden die noch feuchten Kügelchen kontinuierlich oder chargenweise, vorzugsweise unter Verwendung einer Wirbelschichttrockenanlage, bei vorzugsweise 35 °C bis 50 °C und insbesondere bei einer maximalen Produkttemperatur von 45 °C, bis zu einem Restfeuchtegehalt von 4 Gew.-% bis 10 Gew.-%, vorzugsweise 5 Gew.-% bis 8 Gew.-% getrocknet. Nach oder vorzugsweise während der Trocknung können zusätzlich Stoffe zum Umhüllen und Beschichten der Partikel eingebracht werden. Geeignete Hüllstoffe sind insbesondere die Filmbildner unter den vorgenannten wasserlöslichen organischen Polymeren. Weiterhin lassen sich in diesem Stadium auch Farbstoffe oder Pigmente auf die Partikel aufbringen, um so eine eventuelle Eigenfarbe, die meist vom Enzymkonzentrat herrührt, zu überdecken beziehungsweise zu verändern. Als inertes und physiologisch unbedenkliches Pigment hat sich insbesondere Titandioxid bewährt, das vorzugsweise in wäßriger Dispersion eingebracht wird. Das über die Pigmentdispersion beziehungsweise über die Polymer-Lösung zugeführte Wasser wird bei der gleichzeitig vorgenommenen oder anschließend erneut erforderlichen Trocknung wieder entfernt.After spheronization, the still moist beads are continuously or in batches, 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 to 10% % By weight, preferably 5% by weight to 8% by weight, dried. After or preferably during drying, 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. Furthermore, dyes or pigments can also be applied to the particles at this stage in order to cover or change any inherent color, which usually results from the enzyme concentrate. Titanium dioxide in particular has proven to be an inert and physiologically harmless pigment, which preferably is introduced in aqueous dispersion. The water supplied via the pigment dispersion or via the polymer solution is removed again when drying is carried out at the same time or is subsequently required again.

Das Enzymgranulat wird vorzugsweise zur Herstellung fester, insbesondere teilchenförmiger Wasch- oder Reinigungsmittel verwendet, die durch einfaches Vermischen der Enzymgranulate mit in derartigen Mitteln üblichen weiteren Pulverkomponenten erhalten werden können. Für die Einarbeitung in teilchenförmige Wasch- und Reinigungsmittel weist das Enzymgranulat vorzugsweise mittlere Korngrößen im Bereich von 0,1 mm bis 2 mm, insbesondere von 0,4 mm bis 1,6 mm auf.The enzyme granules are preferably used for the production of solid, in particular particulate washing or cleaning agents, which can be obtained by simply mixing the enzyme granules with other powder components customary in such agents. For incorporation into particulate detergents and cleaning 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 mm.

Durch Sieben oder Windsichten können bei der Herstellung eventuell auftretende staubförmige Anteile mit einer Korngröße unter 0,1 mm, insbesondere unter 0,4 mm sowie eventuelle Grobanteile mit einer Korngröße über 2 mm, insbesondere über 1,6 mm entfernt und gegebenenfalls in den Herstellungsprozess zurückgeführt werden. Die erfindungsgemäßen Granulate enthalten vorzugsweise weniger als 5 Gew.-%, insbesondere höchstens 1 Gew.-% an Partikeln mit Korngrößen außerhalb des Bereichs von 0,2 mm bis 1,6 mm.By sieving or air sifting, any dusty particles with a grain size below 0.1 mm, in particular below 0.4 mm and any coarse particles with a grain size above 2 mm, in particular above 1.6 mm, can be removed and possibly returned to the manufacturing process will. 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.

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens werden 10 Gew.-% bis 50 Gew.-% der aufkonzentrierten Fermentationsbrühe mit 70 Gew.-% bis 90 Gew.-% des Trägermaterials und 0,5 Gew.-% bis 10 Gew.-% des Granulierhilfsmittelsystems vermischt. Das Trägermaterial enthält vorzugsweise 10 Gew.-% bis 70 Gew.-% Getreidemehl, 10 Gew.-% bis 70 Gew.-% in Wasser quellfähige Stärke, 3 Gew.-% bis 10 Gew.-% Saccharose und bis zu 10 Gew.-% Zellulosepulver, jeweils bezogen auf fertiges Enzymgranulat.In a preferred embodiment of the process according to the invention, 10% by weight to 50% by weight of the concentrated fermentation broth is mixed with 70% by weight to 90% by weight of the carrier material and 0.5% by weight to 10% by weight. of the granulation aid system mixed. 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 .-% cellulose powder, each based on finished enzyme granules.

Die erhaltene Enzymzubereitung besteht aus weitgehend abgerundeten, staubfreien Partikeln, die in der Regel ein Schüttgewicht von etwa 500 bis 900 Gramm pro Liter, insbesondere 650 bis 880 Gramm pro Liter aufweisen. Ihre Enzymaktivität kann, bedingt durch den flexiblen Trockensubstanzgehalt der Brühen vor dem Vermischen mit den Zuschlagstoffen, bei Einsatz von Protease-haltigen Fermenterbrühen auf Werte im Bereich von vorzugsweise 150 000 bis 350 000 Proteaseeinheiten pro Gramm (PE/g), insbesondere 160 000 PE/g bis 300 000 PE/g, eingestellt werden. Die erfindungsgemäßen Granulate zeichnen sich durch eine sehr hohe Lagerstabilität, insbesondere bei Temperaturen über Raumtemperatur und hoher Luftfeuchtigkeit, sowie ein rasches Lösungsverhalten in der Waschflotte aus. Vorzugsweise setzen die erfindungsgemäßen Granulate 100 % ihrer Enzymaktivität innerhalb von 3 Minuten, insbesondere innerhalb von 90 Sekunden bis 2 Minuten, in Wasser bei 25 °C frei.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 before they are mixed with the additives, their enzyme activity can, particularly when using protease-containing fermentation broths, in the range of preferably 150,000 to 350,000 protease units per gram (PE / g) 160,000 PE / g to 300,000 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.

BeispieleExamples Beispiel 1example 1

Durch Fermentation von nach dem in der internationalen Patentanmeldung WO 91/2792 beschriebenen Verfahren durch Transformation einer Gensequenz aus Bacillus lentus DSM 5483 modifiziertem Bacillus licheniformis (ATCC 53926) analog dem in der deutschen Patentschrift DE 29 25 427 angegebenen Verfahren wurde eine biomassehaltige Fermenterbrühe erhalten, die ca. 65 000 Proteaseeinheiten pro Gramm (PE/g) enthielt. Diese wurde durch Dekantieren. Querstrom-Mikrofiltration, Ultrafiltation (Trenngrenze bei Molekulargewicht 10 000) und anschließendes Eindampfen im Vakuum gemäß dem in der internationalen Patentanmeldung WO 92/11347 beschriebenen Vorgehen zu einem Proteasegehalt von 700 000 PE/g aufkonzentriert (B1). Die so aufkonzentrierte Fermenterbrühe wurde in einem mit rotierendem Schlagwerkzeug ausgerüsteten Mischer mit den in Tabelle 1 aufgeführten Zuschlägen vermischt und in einem mit einer Außenkühlung versehenen Kneter homogenisiert. Die Extrusion der plastischen Masse erfolgte mittels eines mit einer Lochscheibe (Lochdurchmesser 0,9 mm) und einem rotierenden Messer ausgerüsteten Extruder. Man erhielt die in Tabelle 1 durch ihre Zusammensetzung charakterisierten Extrudate X1 bis X3 sowie X4 und X5, bei denen eine Lochscheibe mit Lochdurchmesser 1,2 mm eingesetzt worden war, gemäß der Erfindung und zum Vergleich Extrudate V1 bis V3, jeweils mit Längen von 0,7 mm bis 1 mm, die in einer Sphäronisierungsvorrichtung (Marumerizer®) während einer Bearbeitungszeit von etwa 1 Minute unter gleichzeitigem Bestäuben mit pulverförmigem Calciumcarbonat (3 Gew.-%) zu abgerundeten Partikeln verformt und entgratet wurden. Das den Sphäronisator verlassende Gut wurde in einem Wirbelschichttrockner bei Temperaturen von 40 °C bis 45 °C innerhalb von 15 Minuten auf einen Wassergehalt von 6 Gew.-% getrocknet. Durch anschließendes Sieben wurden Partikel mit Teilchengrößen unter 0,4 mm und über 1,6 mm weitgehend entfernt, die dem Prozeß auf der Stufe des Vermischens mit den Zuschlagstoffen wieder zugeführt wurden. Die Enzymgranulate wurden durch Aufsprühen einer wäßrigen Titandioxidpigment-Suspension während der Wirbelschichttrocknung gecoatet. Man erhielt so die erfindungsgemäßen Enzymgranulate P1 bis P5 beziehungsweise zum Vergleich die Granulate VG1 bis VG3 mit den in Tabelle 2 angegebenen Lösezeiten. Tabelle 1 : Zusammensetzung der Enzymextrudate [Gew.-%] X1 X2 X3 X4 X5 V1 V2 V3 B1 32 32 32 32 32 32 32 32 Zellulosepulvera) 4,5 4,5 4,5 4,5 4,5 4,5 4,5 4,5 Saccharose 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 Weizenmehl T 450 19 19 19 17 19 19 16 15 Maisstärke 38 39 36 38 38 35 33 33 CMC-Ib) 2 - 3 4 - 6 10 10 CMC-IIc) - 1 - - 2 - - - PEG-Id) 1 - 2 1 1 - - - Tenside) - 1 - - - - - - PEG-IIf) - - - - - - 1 2 a): Technocel® 30 (Hersteller Cellulose Füllstoff Fabrik) b): Carbocel® 300 (Substitutionsgrad 0,65-0,75; Hersteller Lamberti CMC) c): Carbocel® 500 (Substitutionsgrad 0,85-0,95; Hersteller Lamberti CMC) d): Polyethylenglykol, mittleres Molekulargewicht 400 e): 40-fach ethoxylierter Talgfettalkohol (Hersteller Henkel) f): Polyethylenglykol, mittleres Molekulargewicht 2000 A fermentation broth containing biomass was obtained by fermentation of Bacillus licheniformis (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 29 25 427, which obtained contained about 65,000 protease units per gram (PE / g). This was done by decanting. Cross-flow microfiltration, ultrafiltration (separation limit at molecular weight 10,000) and subsequent evaporation in vacuo according to the procedure described in international patent application WO 92/11347 concentrated to a protease content of 700,000 PE / g ( B1 ). 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. The extrudates X1 to X3 and X4 and X5 characterized in Table 1 by their composition, in which a perforated disk with a hole diameter of 1.2 mm was used, were obtained according to the invention and for comparison extrudates V1 to V3 , each with lengths of 0, 7 mm to 1 mm, which were deformed and deburred in a spheronization device (Marumerizer®) for 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. Subsequent sieving largely removed particles with particle sizes below 0.4 mm and above 1.6 mm, which were returned to the process at the stage of mixing with the additives. The enzyme granules were coated by spraying an aqueous titanium dioxide pigment suspension during the fluidized-bed drying. This gave the enzyme granules P1 to P5 according to the invention or, for comparison, the granules VG1 to VG3 with the dissolution times given in Table 2. Table 1 : Composition of the enzyme extrudates [% by weight] X1 X2 X3 X4 X5 V1 V2 V3 B1 32 32 32 32 32 32 32 32 Cellulose powder a) 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Sucrose 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Wheat flour T 450 19th 19th 19th 17th 19th 19th 16 15 Cornstarch 38 39 36 38 38 35 33 33 CMC-I b) 2nd - 3rd 4th - 6 10th 10th CMC-II c) - 1 - - 2nd - - - PEG-I d) 1 - 2nd 1 1 - - - Surfactant e) - 1 - - - - - - PEG-II f) - - - - - - 1 2nd a): Technocel® 30 (manufacturer cellulose filler factory) b): Carbocel® 300 (degree of substitution 0.65-0.75; manufacturer Lamberti CMC) c): Carbocel® 500 (degree of substitution 0.85-0.95; manufacturer Lamberti CMC) d): polyethylene glycol, average molecular weight 400 e): 40-fold ethoxylated tallow fatty alcohol (manufacturer Henkel) f): polyethylene glycol, average molecular weight 2000

Beispiel 2Example 2

Die Bestimmung der Auflösezeit erfolgte in einer Meßapparatur, bestehend aus einem temperierbaren, doppelwandigen Becherglas, einem Schrägblattrührer, einem Temperaturfühler und einer Leifähigkeitsmeßzelle mit 4 Elektroden, die über das Leitfähigkeitsmeßgerät (Typ LF 537, Fa. WTW) mit einem x-t-Schreiber verbunden ist. In dem Becherglas wurden 500 ml Wasser unter Rühren auf 20 °C temperiert. Bei konstanter Temperatur wurde 5,0 g des Enyzmgranulates eingerührt und mit dem Schreiber die Leitfähigkeits-Zeit-Kurve aufgenommen. Die Zeit, in der 90 % des Endwertes (nach 15 Minuten) erreicht sind, entspricht der Auflösezeit in Tabelle 2.The dissolution time was determined in a measuring apparatus consisting of a temperable, double-walled beaker, an inclined-blade stirrer, a temperature sensor and a conductivity measuring cell with 4 electrodes, which is connected to an x-t recorder via the conductivity measuring device (type LF 537, WTW). 500 ml of water were heated to 20 ° C. in the beaker while stirring. At constant temperature, 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.

Die erfindungsgemäßen Enzymgranulate aus Beispiel 1 lösten sich in Zeiten unter 2 Minuten völlig auf, während die zum Vergleich getesteten Granulate wesentlich längere Zeiten benötigten. Bemerkenswert ist, daß die Erhöhung des Anteils an höhermolekularem Polyethylenglykol (Granulat VG3 im Vergleich zu VG2) zu einer Verlangsamung der Auflösung führte. Tabelle 2: Auflösezeit der Enzymgranulate Enzymgranulat Auflösezeit [Min,Sek] P1 1,22 P2 1,56 P3 1,48 P4 1,58 P5 1,45 VG1 4,48 VG2 4,16 VG3 5,30 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 compared to VG2 ) led to a slowdown in the dissolution. Table 2: Dissolution time of the enzyme granules Enzyme granules Dissolution time [min, sec] P1 1.22 P2 1.56 P3 1.48 P4 1.58 P5 1.45 VG1 4.48 VG2 4.16 VG3 5.30

Claims (14)

  1. Enzyme granules suitable for incorporation in detergents or cleaning formulations and containing enzyme, an inorganic and/or organic support material and a granulation aid containing carboxymethyl cellulose, characterized in that it contains a granulation aid system of alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and/or alkyl or alkenyl polyethoxylate, with the proviso that - based on the final granules - quantities of at least 0.5% by weight of polyethylene glycol with an average molecular weight below 1,000 and/or alkyl or alkenyl polyethoxylate containing at least 20 ethoxy groups are present where the granulation aid system contains more than 2% by weight of alkali metal carboxymethyl cellulose.
  2. Enzyme granules as claimed in claim 1, characterized in that they contain 1% by weight to 30% by weight, expressed as dry matter, of protease, lipase, amylase and/or cellulase, 70% by weight to 94% by weight of an inorganic and/or organic support material, 5% by weight to 50% by weight of a granulation aid containing carboxymethyl cellulose and - as the balance to 100% by weight - water.
  3. Enzyme granules as claimed in claim 1 or 2, characterized in that the granulation aid system is a mixture containing - based on the final granules - 0.1% by weight to 10% by weight and, more particularly, 0.5% by weight to 5% by weight of carboxymethyl cellulose and 0.1% by weight to 10% by weight and, more particularly, 0.5% by weight to 4% by weight of polyethylene glycol with an average molecular weight of 200 to 600 and/or of a polyethoxylate corresponding to formula (I):

            R-(OCH2CH2)n-OH     (I)

    in which R is a linear or branched alkyl or alkenyl radical with up to 3 C-C double bonds containing 10 to 22 carbon atoms and the average degree of ethoxylation n is a number of 20 to 80.
  4. Enzyme granules as claimed in any of claims 1 to 3, characterized in that the support material contains 20% by weight to 50% by weight and, more particularly, 25% by weight to 45% by weight, based on the enzyme granules, of water-swellable starch, more particularly corn starch.
  5. Enzyme granules as claimed in any of claims 1 to 4, characterized in that the support material contains - based on the enzyme granules - 10% by weight to 35% by weight and, more particularly, 15% by weight to 25% by weight of cereal flour, more particularly wheat flour, rye flour, barley flour, oat flour or mixtures thereof, up to 10% by weight and, more particularly, 2% by weight to 6% by weight of cellulose, layer silicate, alkali metal carbonate, alkali metal chloride, alkali metal sulfate and/or alkali metal acetate and/or the granulation aid additionally contains up to 10% by weight and, more particularly, 0.5% by weight to 8% by weight of water-soluble or water-dispersible oligomers or polymers of natural or synthetic origin.
  6. Enzyme granules as claimed in any of claims 1 to 5, characterized in that they contain protease with an activity of 150,000 to 350,000 PU and, more particularly, 160,000 PU to 300,000 PU per gram of enzyme granules.
  7. Enzyme granules as claimed in any of claims 1 to 6, characterized in that they have an average particle size of 0.1 mm to 2 mm and, more particularly, 0.4 mm to 1.6 mm and contain less than 5% by weight and, more particularly, at most 1% by weight of particles outside the 0.2 mm to 1.6 mm range in size.
  8. Enzyme granules as claimed in any of claims 1 to 7, characterized in that, in water at 25°C, they release 100% of their enzyme activity in 3 minutes and, more particularly, in 90 seconds to 2 minutes.
  9. A process for the production of enzyme granules from 0.1 to 2 mm in size suitable for incorporation in detergents or cleaning formulations by extrusion of an enzyme compound formed by mixing a concentrated fermentation broth freed from insoluble constituents by microfiltration with the support material and the granulation aid as additives, spheronizing the extrudate in a spheronizer, drying and optionally applying a dye- or pigment-containing coating, characterized in that the fermentation broth is mixed with an additive containing a granulation aid system of alkali metal carboxymethyl cellulose with degrees of substitution of 0.5 to 1 and polyethylene glycol and/or alkyl polyethoxylate, with the proviso that - based on the final granules - quantities of at least 0.5% by weight of polyethylene glycol with an average molecular weight below 1,000 and/or alkyl or alkenyl polyethoxylate containing at least 20 ethoxy groups are used where more than 2% by weight of alkali metal carboxymethyl cellulose is present in the granulation aid system.
  10. A process as claimed in claim 9, characterized in that 10% by weight to 50% by weight of the concentrated fermentation broth are mixed with 70% by weight to 90% by weight of the support material and 0.5% by weight to 10% by weight of the granulation aid system.
  11. A process as claimed in claim 9 or 10, characterized in that the support material contains - based on the final enzyme granules - 10% by weight to 70% by weight of cereal flour, 10% by weight to 70% by weight of water-swellable starch, 3% by weight to 10% by weight of sucrose and up to 10% by weight of cellulose powder.
  12. A process as claimed in any of claims 9 to 11, characterized in that the extrusion process is carried out using a multiple-bore die with bore diameters of 0.7 mm to 1.6 mm.
  13. A process as claimed in any of claims 9 to 12, characterized in that, after the extrudate has been spheronized, the granules are dried at temperatures of 35°C to 50°C to a water content of 4% by weight to 10% by weight.
  14. The use of the enzyme granules claimed in any of claims 1 to 8 for the production of solid, more especially particulate detergents.
EP94912528A 1993-03-31 1994-03-23 Enzyme composition for washing and cleaning agents Expired - Lifetime EP0692016B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4310506 1993-03-31
DE4310506A DE4310506A1 (en) 1993-03-31 1993-03-31 Enzyme preparation for detergents and cleaning agents
PCT/EP1994/000934 WO1994023005A1 (en) 1993-03-31 1994-03-23 Enzyme composition for washing and cleaning agents

Publications (2)

Publication Number Publication Date
EP0692016A1 EP0692016A1 (en) 1996-01-17
EP0692016B1 true EP0692016B1 (en) 1997-08-27

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EP (1) EP0692016B1 (en)
AT (1) ATE157394T1 (en)
DE (2) DE4310506A1 (en)
DK (1) DK0692016T3 (en)
WO (1) WO1994023005A1 (en)

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DE19600018A1 (en) 1996-01-03 1997-07-10 Henkel Kgaa Detergent with certain oxidized oligosaccharides
DE19620411A1 (en) 1996-04-01 1997-10-02 Henkel Kgaa Transition metal amine complexes as activators for peroxygen compounds
US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
DE19615776A1 (en) 1996-04-20 1997-10-23 Henkel Kgaa Solubility-enhanced enzyme granules
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DE19619219A1 (en) † 1996-05-13 1997-12-04 Hoechst Ag Enzyme pre-granules for animal feed granules
DE19649375A1 (en) 1996-11-29 1998-06-04 Henkel Kgaa Acetonitrile derivatives as bleach activators in detergents
DE19651446A1 (en) 1996-12-11 1998-06-18 Henkel Kgaa Enveloped enzyme preparation with improved solubility
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DE10211389A1 (en) 2002-03-15 2003-09-25 Clariant Gmbh Ammonium nitrile compounds, used as activator for peroxide bleach in laundry, dishwasher and other detergents and disinfectants and in bleaching textile, paper and wood are new
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
ES2326739T3 (en) 2003-12-13 2009-10-19 HENKEL AG & CO. KGAA MULTICOMPONENT VISCOSIZING SYSTEM.
US8361946B2 (en) 2004-04-08 2013-01-29 Akzo Nobel N.V. Detergent composition
EP1754781B1 (en) 2005-08-19 2013-04-03 The Procter and Gamble Company A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology
DE102005039580A1 (en) 2005-08-19 2007-02-22 Henkel Kgaa Color protecting detergent
DE102007016391A1 (en) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Detergent or cleaning agent for preventing transfer of textile color of colored textiles from uncolored or different colored textiles in laundry, particularly in tenside containing aqueous solution, has color transfer inhibitor
DE102007028310A1 (en) 2007-06-20 2008-12-24 Clariant International Ltd. Surfactant mixtures with synergistic properties
DE102008013606A1 (en) 2008-03-11 2009-09-17 Clariant International Ltd. Process for the preparation of solid alkaline earth metal salts of secondary paraffin sulphonic acids
PL2271426T3 (en) 2008-04-09 2019-08-30 Basf Se Use of hydrazide compounds as oxidation catalysts
EP2302025B1 (en) 2009-09-08 2016-04-13 The Procter & Gamble Company A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle
WO2012000846A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
EP2805942B1 (en) 2010-12-13 2016-03-16 Basf Se Bleach catalysts
DE102011010818A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd. Use of transition metal complexes as bleaching catalysts in detergents and cleaners
DE102014009836B4 (en) 2014-07-03 2017-04-06 Weylchem Wiesbaden Gmbh Sodium salts of secondary alkanesulfonates containing compounds, their preparation and use and washing, disinfecting and cleaning agents containing these
DE102015217816A1 (en) 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Use of highly concentrated enzyme granules to increase the storage stability of enzymes
WO2017076771A1 (en) 2015-11-03 2017-05-11 Basf Se Bleach catalysts
EP3176157A1 (en) 2015-12-01 2017-06-07 Basf Se Bleach catalysts
WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition
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DE4041752A1 (en) * 1990-12-24 1992-06-25 Henkel Kgaa ENZYME PREPARATION FOR WASHING AND CLEANING AGENTS

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DK0692016T3 (en) 1998-04-20
DE59403879D1 (en) 1997-10-02
ATE157394T1 (en) 1997-09-15
WO1994023005A1 (en) 1994-10-13
EP0692016A1 (en) 1996-01-17
DE4310506A1 (en) 1994-10-06

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