WO1994023005A1 - Enzyme composition for washing and cleaning agents - Google Patents

Enzyme composition for washing and cleaning agents Download PDF

Info

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)
French (fr)
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 EP94912528A priority Critical patent/EP0692016B1/en
Priority to DE59403879T priority patent/DE59403879D1/en
Publication of WO1994023005A1 publication Critical patent/WO1994023005A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—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.

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

"EnzvmzubereitunQ für Wasch- und Reinigungsmittel" "Preparation for detergents and cleaning agents"
Die Erfindung betrifft ein Enzymgranulat, ein Verfahren zu seiner Herstel¬ lung und die Verwendung des Granulats in festen Wasch- und Reinigungs¬ mitteln.The invention relates to an enzyme granulate, a process for its production 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 Enzymak¬ tivität eintreten, insbesondere wenn bleichaktive Verbindungen zugegen sind. Das Aufbringen der Enzyme auf Trägersalze unter gleichzeitiger Gra¬ nulation gemäß der deutschen Offenlegungsschrift DT 1617 190 beziehungs¬ weise durch Aufkleben mit nichtionischen Tensiden gemäß der deutschen Of¬ fenlegungsschrift DT 16 17 118 oder wäßrigen Lösungen von Celluloseethern gemäß der deutschen Offenlegungschrift DT 1767568 führt nicht zu einer nennenswerten Verbesserung der Lagerstabilität, da sich die empfindlichen Enzyme in solchen Aufmischungen in der Regel auf der Oberfläche der Trä¬ gersubstanz befinden. Zwar kann die Lagerstabilität der Enzyme wesentlich erhöht werden, wenn man die Enzyme mit dem Trägermaterial umhüllt be¬ ziehungsweise in dieses einbettet und anschließend durch Extrudieren, Pres¬ sen und Marumerisieren in die gewünschte Partikelform überführt, wie zum Beispiel in der deutschen Patentschrift DE 16 17232, der deutschen Offen¬ legungsschrift DT 2032 768, und den deutschen Auslegeschriften DE 21 37042 und DE 21 37043 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 Offen¬ legungsschrift DT 1803099 bekannte Einbettungsmittel, die aus einem Ge¬ misch fester Säuren beziehungsweise saurer Salze und Carbonaten beziehungs¬ weise 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 admixed with conventional detergents, a considerable reduction in the enzyme activity can occur during storage, in particular if bleach-active compounds are present. The application of the enzymes to carrier salts with simultaneous granulation according to German Offenlegungsschrift DT 1617 190 or by sticking with nonionic surfactants according to German Offenlegungsschrift DT 16 17 118 or aqueous solutions of cellulose ethers according to German Offenlegungsschrift DT 1767568 does not lead to this a noteworthy improvement in storage stability, since the sensitive enzymes in such mixtures are generally on the surface of the carrier substance. It is true that 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 for example in German patent DE 16 17232 , the German Offenlegungsschrift DT 2032 768, and the German interpretations DE 21 37042 and DE 21 37043. 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 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.
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 168526 sind Enzymgranulate bekannt, die in Wasser quellfähige Stärke, Zeolith und wasserlösliches Granulier¬ hilfsmittel enthalten. In diesem Dokument wird ein Herstellungsverfahren für derartige Formulierungen vorgeschlagen, das im wesentlichen darin be¬ steht, eine von unlöslichen Bestandteilen befreite Fermenterlösung aufzu¬ konzentrieren, mit den genannten Zuschlagstoffen zu versetzten und das entstandene Gemisch zu granulieren. Das Verfahren mit dem dort vorgeschla¬ genen Zuschlagstoffgemisch wird vorteilhaft mit Fermentationslösungen durchgeführt, die auf einen relativ hohen Trockensubstanzgehalt, beispiels¬ weise 55 Gew.-%, aufkonzentriert worden sind. Außerdem weisen die derart hergestellten Granulate eine so hohe Lösungs- beziehungsweise Zerfalls¬ geschwindigkeit unter Waschbedingungen auf, daß die Granulate teilweise schon bei der Lagerung relativ rasch zerfallen und die Enzyme desaktiviert werden.From the European patent EP 168526, enzyme granules are known which contain starch which swells in water, zeolite and water-soluble granulating agents. In this document, 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. In addition, 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.
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 Granulierhilfsmit¬ tel, 10 Gew.-% bis 35 Gew.-% Getreidemehl und 3 Gew.-% bis 12 Gew.-% Was¬ ser 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 Dis- pergiergeschwindigkeit 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 An¬ schmutzungen 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% 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. From this document it is also known that 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. However, 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.
Es bestand daher die Aufgabe, durch ein Herstellungsverfahren, das den Einsatz niedrigkonzentrierter Fermentationsbrühen erlaubt, die Pulverei¬ genschaften, insbesondere die Löslichkeit der bekannten Produkte zu ver¬ bessern, die Lagerbeständigkeit sowohl der Enzyme als auch der diese ent¬ haltenden 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 be¬ ziehungsweise staubbindende Komponente und körnverfestigende Komponente in optimierten Verhältnissen enthält.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.
Die Erfindung betrifft ein für die Einarbeitung in insbesondere teilchen- förmige Wasch- oder Reinigungsmittel geeignetes Enzymgranulat, enthaltend Enzym und anorganisches und/oder organisches Trägermaterial sowie carboxy- methylcellulosehaltiges Granulierhilfsmittel, welches dadurch gekennzeich¬ net ist, daß es ein GranulierhilfsmittelSystem aus Alkali-Carboxymethyl- cellulose 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.-% Poly¬ ethylenglykol mit einer mittleren Molmasse unter 1000 und/oder Alkyl- be¬ ziehungsweise Alkenylpolyethoxylat mit mindestens 20 Ethoxygruppen vor¬ handen ist, wenn mehr als 2 Gew.-% Alkali-Carboxymethylcellulose enthalten ist.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.
Unter dem Substitutionsgrad der Carboxymethylcellulose ist die Zahl der veretherten, eine Carboxy ethylgruppe tragenden Sauerstoffato e pro Saccha- rid-Monomer der Cellulose zu verstehen. Der Substitutionsgrad bei Vorzugs- weise 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 Gra¬ nulatfestigkeit zu errichen, als bei Einsatz von Cellulose mit niedrigerem Substitutionsgrad. So können beispielsweise durch die Anwesenheit von Na- triumcarboxymethylcellulose 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 Granu¬ late im Extrusionsschritt ein höherer Durchsatz durch den Extruder er¬ reicht werden.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 degree of substitution with preferential Carboxymethyl celluloses used in the range from 0.8 to 0.95, since particularly strong granules are obtained when they are used or smaller amounts are required to achieve a certain granule strength than when using cellulose with a lower degree of substitution. Thus, for example, 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. 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 orga¬ nisches Trägermaterial und 5 Gew.-% bis 50 Gew.-% carboxymethylcellulose- haltiges Granulierhilfsmittel sowie als Rest auf 100 Gew.-% Wasser.In a preferred embodiment, 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.
Als Granulierhilfsmittelsystem enthält ein erfindungsgemäßes Enzymgranulat vorzugsweise ein Gemisch enthaltend, jeweils bezogen auf fertiges Granu¬ lat, 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,5 Gew.-% bis 5 Gew.-% Car¬ boxymethylcellulose 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),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-(0CH2CH )n-0H (I)R- (0CH 2 CH) n -0H (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-Ato- men und der mittlere Ethoxylierungsgrad n eine Zahl von 20 bis 80, insbe¬ sondere 30 bis 45 bedeutet.in which 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.
Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung eines der¬ artigen Enzymgranulates mit einer Korngröße von 0,1 mm bis 2 mrc durch Ex- trudieren eines durch Vermischen einer durch Mikrofiltration von unlös¬ lichen Bestandteilen befreiten, aufkonzentrierten Fermentationsbrühe mit dem Trägermaterial und dem Granulierhilfsmittel als Zuschlagstoffen ent¬ standenen Enzym-Vorgemischs, Sphäronisierung des Extrudats in einem Ron- diergerät, Trocknung und gegebenenfalls Aufbringen eines Farbstoff oder Pigment enthaltenden Überzugs, dadurch gekennzeichnet, daß man die Fermen¬ tationsbrühe mit einem Zuschlagstoff vermischt, der ein Granulierhilfs¬ mittelsystem 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 Ethoxy- gruppen eingesetzt werden, wenn mehr als 2 Gew.-% Alkali-Carboxymethyl¬ cellulose 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 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 carboxymethyl cellulose in the granulation aid system m is included.
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 Fermenta¬ tionsprozesse aus geeigneten Mikroorganismen gewonnen, die zum Beispiel in den deutschen Offenlegungsschriften DE 1940488, DE 2044 161, DE 2201 803 und DE 21 21 397, den US-amerikanischen Patentschriften US 3 632957 und US 4264 738 sowie der europäischen Patentanmeldung EP 006638 beschrieben sind. Besonders vorteilhaft kann das erfindungsge¬ mäße 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 Reinigungs¬ mittel oft Probleme bereitet. Erfindungsgemäß ist es möglich, die bei den Fermentationsprozessen anfallenden Brühen extrazellulärer Enzyme nach Ab¬ trennen der unlöslichen Begleitstoffe durch Mikrofiltration sowie nachfol¬ gende Aufkonzentration durch Ultrafiltration und gegebenenfalls an¬ schließendes Eindampfen im Vakuum unmittelbar in lagerbeständige, weitge¬ hend geruchlose Granulate zu überführen. Die Entstehung unerwünschter En¬ zymstäube und die bei zusätzlichen Trocknungsprozessen auftretenden Akti¬ vitätsverluste werden vermieden. 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 150000 Proteaseeinheiten (PE, bestimmt nach der in Tenside 2 (1970), 125 beschriebenen Methode) bis 350000 PE, insbesondere 160000 PE bis 300000 PE, pro Gramm Enzymgranulat.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. According to 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 .
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 bei¬ spielsweise Stärke, Getreidemehl, Cellulosepulver, Alkalialumosilikat, insbesondere Zeolith, Schichtsilikat, zum Beispiel Bentonit oder Smectit, und wasserlösliche anorganische oder organische Salze, zum Beispiel Al- kalichlorid, Alkalisulfat, Alkalicarbonat oder Alkaliacetat, wobei Natrium oder Kalium die bevorzugten Alkalimetalle sind. Bevorzugt wird ein Träger¬ materialgemisch aus in Wasser quellfähiger Stärke, Getreidemehl und gege¬ benenfalls 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 consisting of starch which is swellable in water, cereal flour and, if appropriate, cellulose powder and alkali carbonate is used.
Bei der in Wasser quellfähigen Stärke handelt es sich vorzugsweise um Mais¬ stärke, 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 vorzugs¬ weise nicht über 80 Gew.-%, insbesondere 32 Gew.-% bis 65 Gew.-%.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.
Bei dem erfindungsgemäß geeigneten Getreidemehl handelt es sich insbeson¬ dere um ein aus Weizen, Roggen, Gerste oder Hafer herstellbares Produkt oder um ein Gemisch dieser Mehle, wobei Vollkornmehle bevorzugt sind. Un¬ ter einem Vollkornmehl wird im Rahmen der Erfindung ein nicht voll ausge¬ mahlenes 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 be¬ kanntermaßen eine wesentliche Geruchsreduzierung der Enzymzubereitung er¬ reicht, welche die Geruchsverminderung durch die Einarbeitung gleicher Mengen entsprechender Stärkearten bei weitem übertrifft. Derartiges Ge¬ treidemehl 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 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.
Die erfindungsgemäßen Enzymgranulate enthalten vorzugsweise 1 Gew.-% bis 50 Gew.-%, vorzugsweise 5 Gew.-% bis 25 Gew.-% des Granulierhilfsmittel¬ systems, 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.-% Polyethylen¬ glykol und/oder Alkylpolyethoxylat enthalten, wobei wichtig ist, daß min¬ destens 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 Carboxymethyl¬ cellulose, mit Substitutionsgraden bis zu 3, ist in dem erfindungsgemäßen Granulierhilfsmittelsystem vorzugsweise nicht enthalten. Carboxymethyl- cellulosen 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 granulating auxiliary system, the alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or contains alkyl polyethoxylate. In 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.
Gegebenenfalls können als zusätzliche Bestandteile des Granulierhilfsmit¬ telsystems auch weitere Cellulose- oder Stärkeether, wie Carboxymethyl- stärke, Methylcellulose, Hydroxyethylcellulose, Hydroxypropylcellulose sowie entsprechende Cellulosemischether, Gelatine, Casein, Traganth, Mal- todextrose, Saccharose, Invertzucker, Glukosesirup oder andere in Wasser lösliche beziehungsweise gut dispergierbare Oligomere oder Polymere natür¬ lichen oder synthetischen Ursprungs verwendet werden. Brauchbare synthe¬ tische wasserlösliche Polymere sind Polyacrylate, Polymethacrylate, Copo- lymere der Acrylsäure mit Maleinsäure oder vinylgruppenhaltige Verbin¬ dungen, ferner Polyvinylalkohol, teilverseiftes Polyvinylacetat und Poly- vinylpyrrolidon. Soweit es sich bei den vorgenannten Verbindungen um sol¬ che mit freien Carboxylgruppen handelt, liegen sie normalerweise in Form ihrer Alkalisalze, insbesondere ihrer Natriumsalze vor. Derartige zusätz¬ liche Granulierhilfsmittel können in den erfindungsgemäßen Enzymgranulaten in Mengen bis zu 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 8 Gew.-% ent¬ halten sein. Höhermolekulare Polyethylenglykole, das heißt solche mit einem mittleren Molekulargewicht über 1000, sind zwar als synthetische wasser¬ lösliche Polymere mit staubbindender Wirkung brauchbar, doch bewirken ge¬ rade die höhermolekularen Polyethylenglykole überraschenderweise eine un¬ erwünschte Erhöhung der benötigten Granulatauflösezeit, so daß diese Sub¬ stanzen in den erfindungsgemäßen Enzymgranulaten vorzugsweise völlig fehlen.If necessary, other 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. 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 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.
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 Mikro- poren größer 0,1 μ , 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 200032 beschrieben. Anschließend wird das Mikrofiltrationspermeat vor¬ zugsweise durch Ultrafiltration, gegebenenfalls mit anschließender Vakuum- eindampfung, aufkonzentriert. Die Aufkonzentration kann dabei, wie in der internationalen Patentanmeldung WO 92/11347 beschrieben, so geführt wer¬ den, daß man nur zu relativ niedrigen Gehalten an Trockensubstanz von vor¬ zugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 10 Gew.-% bis 40 Gew.-% gelangt. Falls proteasehaltige Fermentationsbrühen eingesetzt werden, be¬ trägt der Proteasegehalt auf dieser Stufe des Konzentrats vorzugsweise 500000 PE/g bis 1 500000 PE/g, insbesondere 600000 PE/g bis 1 000000 PE/g. Das Konzentrat wird einem zweckmäßigerweise zuvor hergestellten trockenen, pulverförmigen bis körnigen Gemisch der oben beschriebenen Zu¬ schlagstoffe 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 micro pores larger than 0.1 μ, 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. If protease-containing fermentation broths are used, 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.
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 Lochschei¬ be mit nachfolgendem Abschlagmesser geführt und dadurch zu zylinderförmi- gen Partikeln definierter Größe zerkleinert. Zweckmäßigerweise beträgt der Durchmesser der Bohrungen in der Lochscheibe 0,7 mm bis 1,6 mm, vorzugs¬ weise 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 Aus¬ legeschriften DE 2137042 und DE 2137043 beschrieben. Man verwendet hierzu eine Vorrichtung, die aus einem zylindrischen Behälter mit statio¬ nären, festen Seitenwänden und einer bodenseitig drehbar gelagerten Reib¬ platte 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 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. However, it has proven to be 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 process is described, for example, in the German design documents DE 2137042 and DE 2137043. For this purpose, a device is used which consists of a cylindrical container with stationary, fixed side walls and a friction plate which is 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 Wirbelschicht¬ trockenanlage, 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 Hüll¬ stoffe sind insbesondere die Filmbildner unter den vorgenannten wasser¬ löslichen 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 über¬ decken beziehungsweise zu verändern. Als inertes und physiologisch unbe¬ denkliches Pigment hat sich insbesondere Titandioxid bewährt, das Vorzugs- weise in wäßriger Dispersion eingebracht wird. Das über die Pigmentdisper¬ sion beziehungsweise über die Polymer-Lösung zugeführte Wasser wird bei der gleichzeitig vorgenommenen oder anschließend erneut erforderlichen Trocknung wieder entfernt.After spheronization, 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. 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 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.
Das Enzymgranulat wird vorzugsweise zur Herstellung fester, insbesondere teilchenförmiger Wasch- oder Reinigungsmittel verwendet, die durch ein¬ faches Vermischen der Enzymgranulate mit in derartigen Mitteln üblichen weiteren Pulverkomponenten erhalten werden können. Für die Einarbeitung in teilchenförmige Wasch- und Reinigungsmittel weist das Enzymgranulat vor¬ zugsweise mittlere Korngrößen im Bereich von 0,1 mm bis 2 mm, insbesondere von 0,4 mm bis 1,6 πrni auf.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. 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 μm.
Durch Sieben oder Windsichten können bei der Herstellung eventuell auftre¬ tende 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 Herstellungs- prozess zurückgeführt werden. Die erfindungsgemäßen Granulate enthalten vorzugsweise weniger als 5 Gew.-%, insbesondere höchstens 1 Gew.-% an Par¬ tikeln mit Korngrößen außerhalb des Bereichs von 0,2 mm bis 1,6 mm.By sieving or air sifting, 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.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wer¬ den 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 vor¬ zugsweise 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 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 of cellulose powder, in each case based on finished enzyme granules.
Die erhaltene Enzymzubereitung besteht aus weitgehend abgerundeten, staub¬ freien 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 Trockensubstanzge¬ halt der Brühen vor dem Vermischen mit den Zuschlagstoffen, bei Einsatz von Protease-haltigen Fer enterbrühen auf Werte im Bereich von vorzugs¬ weise 150000 bis 350000 Proteaseeinheiten pro Gramm (PE/g), insbesondere 160000 PE/g bis 300000 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 Enzymaktivitat innerhalb von 3 Mi¬ nuten, 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 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.
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 modif ziertem Bacillus lichenifor is (ATCC 53926) analog dem in der deutschen Patentschrift DE 2925427 ange¬ gebenen Verfahren wurde eine biomassehaltige Fermenterbrühe erhalten, die ca. 65000 Proteaseeinheiten pro Gramm (PE/g) enthielt. Diese wurde durch Dekantieren, Querstrom-Mikrofiltration, Ultrafiltation (Trenngrenze bei Molekulargewicht 10000) und anschließendes Eindampfen im Vakuum gemäß dem in der internationalen Patentanmeldung WO 92/11347 beschriebenen Vorgehen zu einem Proteasegehalt von 700000 PE/g aufkonzentriert (Bl). Die so auf- konzentrierte Fermenterbrühe wurde in einem mit rotierendem Schlagwerkzeug ausgerüsteten Mischer mit den in Tabelle 1 aufgeführten Zuschlägen ver¬ mischt und in einem mit einer Außenkühlung versehenen Kneter homogenisiert. Die Extrusion der plastischen Masse erfolgte mittels eines mit einer Loch¬ scheibe (Lochdurchmesser 0,9 mm) und einem rotierenden Messer ausgerüste¬ ten Extruder. Man erhielt die in Tabelle 1 durch ihre Zusammensetzung charakterisierten Extrudate XI bis X4 sowie X5 und X6, bei denen eine Loch¬ scheibe mit Lochdurchmesser 1,2 mm eingesetzt worden war, gemäß der Erfin¬ dung und zum Vergleich Extrudate VI bis V3, jeweils mit Längen von 0,7 mm bis 1 mm, die in einer Sphäronisierungsvorrichtung (Marumerizer(R)) 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 inner¬ halb 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 weitgehend entfernt, die dem Prozeß auf der Stufe des Ver- mischens mit den Zuschlagstoffen wieder zugeführt wurden. Die Enzymgranu¬ late wurden durch Aufsprühen einer wäßrigen Titandioxidpigment-Suspension während der Wirbelschichttrocknung gecoatet. Man erhielt so die erfindungs¬ gemäßen Enzymgranulate Pl bis P6 beziehungsweise zum Vergleich die Granu¬ late VG1 bis VG3 mit den in Tabelle 2 angegebenen Lösezeiten. Tabelle 1: Zusammensetzung der Extrudate [Gew.-%]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. The 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. Subsequent sieving largely removed particles with particle sizes below 0.4 mm and above 1.6, which were returned to the process at the stage of mixing with the additives. The enzyme granules were coated by spraying on an aqueous titanium dioxide pigment suspension during the fluidized-bed drying. This gave the enzyme granules P1 to P6 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 extrudates [% by weight]
XI X2 X3 X4 X5 X6 VI V2 V3XI X2 X3 X4 X5 X6 VI V2 V3
Bl 34 32 32 32 32 32 32 32 32Bl 34 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 4,5Cellulose powder a ) 4.5 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 3,5Sucrose 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Weizenmehl T 450 19 19 19 19 17 19 19 16 15Wheat flour T 450 19 19 19 19 17 19 19 16 15
Maisstärke 37 38 39 36 38 38 35 33 33Corn starch 37 38 39 36 38 38 35 33 33
CMC-lb) 2 2 - 3 4 - 6 10 10 ICMC-lb) 2 2 - 3 4 - 6 10 10 I.
CMC-IIC) - - 1 - - 2 - - - <→CMC-II C ) - - 1 - - 2 - - - <→
PEG-Id) - 1 - 2 1 1 - - -PEG-I d ) - 1 - 2 1 1 - - -
Tenside) - - 1 - - - - - -Surfactant e ) - - 1 - - - - - -
PEG-Ilf) - - - - - - 1 2PEG-Ilf) - - - - - - 1 2
""
a): Technocel(R) 30 (Hersteller Cellulose Füllstoff Fabrik) b): Carbocel(R) 300 (Substitutionsgrad 0,65-0,75; Hersteller Lamberti CMC) c): Carbocel(R) 500 (Substitutionsgrad 0,85-0,95; Hersteller Lamberti CMC) d): Polyethylenglykol, mittleres Molekulargewicht 400 e): 40-fach ethoxylierter Taigfettalkohol (Hersteller Henkel) f): Polyethylenglykol, mittleres Molekulargewicht 2000 a ): Technocel ( R ) 30 (manufacturer cellulose filler factory) b ): Carbocel ( R ) 300 (degree of substitution 0.65-0.75; manufacturer Lamberti CMC) c ): Carbocel ( R ) 500 (degree of substitution 0.85- 0.95; manufacturer Lamberti CMC) d): polyethylene glycol, average molecular weight 400 e ): 40-fold ethoxylated taig fat alcohol (manufacturer Henkel) f): polyethylene glycol, average molecular weight 2000
1414
Beispiel 2Example 2
Die Bestimmung der Auflösezeit erfolgte in einer Meßapparatur, bestehend aus einem temperierbaren, doppelwandigen Becherglas, einem Schrägblatt- rührer, einem Temperaturfühler und einer Leitfähigkeitsmeßzelle mit 4 Elek¬ troden, 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 Enzymgranulates 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 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. 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 getesten Granulate wesentlich längere Zeiten benötigten. Bemerkenswert ist, daß die Erhöhung des Anteils an höhermolekularem Polyethylenglykol (Granulat VG3 im Ver¬ gleich zu VG2) zu einer Verlangsamung der Auflösung führte.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.
Tabelle 2: Auflösezeit der EnzymgranulateTable 2: Dissolution time of the enzyme granules
Enzymgra¬ Auflösezeit nulat [Min.Sek]Enzymgra¬ dissolution time nulat [Min.Sec]
Pl 1,40Pl 1.40
P2 1,22P2 1.22
P3 1,56P3 1.56
P4 1,48P4 1.48
P5 1,58P5 1.58
P6 1,45P6 1.45
VG1 4,48VG1 4.48
VG2 4,16VG2 4.16
VG3 5,30 VG3 5.30

Claims

Patentansprüche Claims
1. Für die Einarbeitung in Wasch- oder Reinigungsmittel geeignetes Enzym¬ granulat, enthaltend Enzym und anorganisches und/oder organisches Trä¬ germaterial sowie carboxymethylcellulosehaltiges Granulierhilfsmittel, dadurch gekennzeichnet, daß es ein Granulierhilfsmittelsystem aus Al¬ kali-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.-% Al¬ kali-Carboxymethylcellulose enthalten ist.1. Enzyme granules suitable for incorporation in detergents or cleaning agents, containing enzyme and inorganic and / or organic carrier material and carboxymethyl cellulose-containing granulation aid, characterized in that it is a granulation aid system made from alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and contains polyethylene glycol and / or alkyl or alkenyl polyethoxylate with 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 below 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.
2. Enzymgranulat nach Anspruch 1, dadurch gekennzeichnet, daß es 1 Gew.-% bis 30 Gew.-%, berechnet als Trockensubstanz, Protease, Lipase, Amylä¬ se und/oder Cellulase, 70 Gew.-% bis 94 Gew.-% anorganisches und/oder organisches Trägermaterial und 5 Gew.-% bis 50 Gew.-% carboxymethyl¬ cellulosehaltiges Granulierhilfsmittel sowie als Rest auf 100 Gew.-% Wasser enthält.2. Enzyme granules according to claim 1, characterized in that it is 1% by weight to 30% by weight, calculated as dry substance, protease, lipase, amylase and / or cellulase, 70% by weight to 94% by weight. % contains inorganic and / or organic carrier material and 5% by weight to 50% by weight of carboxymethyl cellulose-containing granulating aid and the remainder to 100% by weight of water.
3. Enzymgranulat nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß es als Granulierhilfsmittelsystem ein Gemisch, enthaltend, jeweils bezo¬ gen 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),3. Enzyme granules according to claim 1 or 2, characterized in that it contains, as granulation aid system, a mixture containing, in each case with respect to finished granules, 0.1% by weight to 10% by weight, in particular 0.5% by weight. % to 5% by weight of carboxymethyl cellulose 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 one Polyethoxylate according to formula (I),
R-(0CH2CH2)n-0H (I)R- (0CH 2 CH 2 ) n-0H (I)
in der R einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit bis zu 3 C-C-Doppelbindungen mit 10 bis 22 C-Atomen und der mitt¬ lere Ethoxylierungsgrad n eine Zahl von 20 bis 80 bedeutet, enthält. in which R is a straight-chain or branched alkyl or alkenyl radical having up to 3 CC double bonds with 10 to 22 C atoms and the average degree of ethoxylation n is a number from 20 to 80.
4. Enzymgranulat nach einem der Ansprüche 1 bis 3, dadurch gekennzeich¬ net, daß das Trägermaterial, bezogen auf Enzymgranulat, 20 Gew.-% bis4. Enzyme granules according to one of claims 1 to 3, characterized gekennzeich¬ net that the carrier material, based on enzyme granules, 20 wt .-% to
• 50 Gew.-%, insbesondere 25 Gew.-% bis 45 Gew.-% in Wasser quellfähige Stärke, insbesondere Maisstärke, enthält.Contains 50% by weight, in particular 25% by weight to 45% by weight, of starch which is swellable in water, in particular corn starch.
5. Enzymgranulat nach einem der Ansprüche 1 bis 4, dadurch gekennzeich¬ net, daß das Trägermaterial, bezogen auf Enzymgranulat, 10 Gew.-% bis 35 Gew.-%, insbesondere 15 Gew.-% bis 25 Gew.-% Getreidemehl, insbe¬ sondere Weizenmehl, Roggenmehl, Gerstenmehl, Hafermehl und deren Ge¬ mische, bis zu 10 Gew.-%, insbesondere 2 Gew.-% bis 6 Gew.-% Cellulo¬ se, Schichtsilikat, Alkalicarbonat, Alkalichlorid, Alkalisulfat und/ oder Alkaliacetat enthält und/oder das Granulierhilfsmittel zusätzlich bis zu 10 Gew.-%, insbesondere 0,5 Gew.-% bis 8 Gew.-% wasserlösliche beziehungsweise -dispergierbare Oligomere oder Polymere natürlichen oder synthetischen Ursprungs enthält.5. Enzyme granules according to any one of claims 1 to 4, characterized gekennzeich¬ net that the carrier material, based on enzyme granules, 10 wt .-% to 35 wt .-%, in particular 15 wt .-% to 25 wt .-% cereal flour, in particular wheat flour, rye flour, barley flour, oat flour and their mixtures, up to 10% by weight, in particular 2% by weight to 6% by weight, cellulose, layered silicate, alkali carbonate, alkali chloride, alkali sulfate and / or Contains alkali acetate and / or the granulation aid additionally contains up to 10% by weight, in particular 0.5% by weight to 8% by weight, of water-soluble or dispersible oligomers or polymers of natural or synthetic origin.
6. Enzymgranulat nach einem der Ansprüche 1 bis 5, dadurch gekennzeich¬ net, daß es Protease mit einer Aktivität von 150000 PE bis 350000 PE, insbesondere 160000 PE bis 300000 PE, pro Gramm Enzymgranulat ent¬ hält.6. Enzyme granules according to one of claims 1 to 5, characterized gekennzeich¬ net that it contains protease with an activity of 150,000 PE to 350,000 PE, in particular 160,000 PE to 300,000 PE, per gram of enzyme granules ent.
7. Enzymgranulat nach einem der Ansprüche 1 bis 6, dadurch gekennzeich¬ net, daß es eine mittlere Korngröße von 0,1 bis 2 mm, insbesondere von 0,4 mm bis 1,6 aufweist und weniger als 5 Gew.-%, insbesondere höchstens 1 Gew.-% an Partikeln mit Korngrößen außerhalb des Bereichs von 0,2 mm bis 1,6 mm enthält.7. Enzyme granules according to one of claims 1 to 6, characterized gekennzeich¬ net that it has an average grain size of 0.1 to 2 mm, in particular from 0.4 mm to 1.6 and less than 5 wt .-%, in particular contains at most 1% by weight of particles with grain sizes outside the range from 0.2 mm to 1.6 mm.
8. Enzymgranulat nach einem der Ansprüche 1 bis 7, dadurch gekennzeich¬ net, daß es in Wasser bei 25 °C 100 % seiner Enzymaktivitä innerhalb von 3 Minuten, insbesondere innerhalb von 90 Sekunden bis 2 Minuten, freisetzt.8. Enzyme granules according to one of claims 1 to 7, characterized gekennzeich¬ net that it releases 100% of its enzyme activity in water at 25 ° C within 3 minutes, in particular within 90 seconds to 2 minutes.
9. Verfahren zur Herstellung eines für die Einarbeitung in Wasch- oder Reinigungsmittel geeigneten Enzymgranulates mit einer Korngröße von 0,1 mm bis 2 mm durch Extrudieren eines durch Vermischen einer durch Mikrofiltration von unlöslichen Bestandteilen befreiten, aufkonzen- trierten Fermentationsbrühe mit dem Trägermaterial und dem Granulier¬ hilfsmittel als Zuschlagstoffen entstandenen Enzym-Vorgemischs, Sphä- ronisierung des Extrudats in einem Rondiergerät, Trocknung und gege¬ benenfalls Aufbringen eines Farbstoff oder Pigment enthaltenden Über¬ zugs, dadurch gekennzeichnet, daß man die Fermentationsbrühe mit einem Zuschlagstoff vermischt, der ein Granulierhilfsmittelsystem aus Alka¬ li-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.-% Po¬ lyethylenglykol mit einer mittleren Molmasse unter 1000 und/oder Al¬ kyl- beziehungsweise Alkenylpolyethoxylat mit mindestens 20 Ethoxy- gruppen eingesetzt werden, wenn mehr als 2 Gew.-% Alkali-Carboxymethyl¬ cellulose im Granulierhilfsmittelsystem enthalten ist.9. A process for the preparation of an enzyme granulate suitable for incorporation in washing or cleaning agents and having a particle size of 0.1 mm to 2 mm by extruding a concentrated concentrate which has been freed from insoluble constituents by microfiltration. fermentation broth with the carrier material and the granulating auxiliary as premixes of the enzyme premix obtained, spheronization of the extrudate in a rounding machine, drying and, if appropriate, application of a dye or pigment-containing coating, characterized in that the fermentation broth with a Mixed admixture containing 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 with an average molecular weight below 1000 and / or alkyl or alkenyl polyethoxylate with at least 20 ethoxy groups if more than 2% by weight of alkali metal carboxymethyl cellulose is contained in the granulation aid system.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß man 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.10. The method according to claim 9, characterized in that 10 wt .-% to 50 wt .-% of the concentrated fermentation broth with 70 wt .-% to 90 wt .-% of the carrier material and 0.5 wt .-% to 10 % By weight of the granulation aid system is mixed.
11. Verfahren nach Anspruch 9 oder 10, dadurch gekennzeichnet, daß das Trägermaterial, jeweils bezogen auf fertiges Enzymgranulat, 10 Gew.-% bis 70 Gew.-% Getreidemehl, 10 Gew.-% bis 70 Gew.-% in Wasser quell¬ fähige Stärke, 3 Gew.-% bis 10 Gew.-% Saccharose und bis zu 10 Gew.-% Zellulosepulver enthält.11. The method according to claim 9 or 10, characterized in that the carrier material, based in each case on finished enzyme granules, 10% by weight to 70% by weight of cereal flour, 10% by weight to 70% by weight in water swell capable starch, 3 wt .-% to 10 wt .-% sucrose and up to 10 wt .-% cellulose powder.
12. Verfahren nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, daß man die Extrusion mit Hilfe einer Lochplatte, deren Löcher einen Durchmesser von 0,7 mm bis 1,6 mm aufweisen, durchführt.12. The method according to any one of claims 9 to 11, characterized in that one carries out the extrusion with the aid of a perforated plate, the holes of which have a diameter of 0.7 mm to 1.6 mm.
13. Verfahren nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, daß man nach der Sphäronisierung des Extrudats das Granulat bei Tempe¬ raturen von 35 °C bis 50 °C auf einen Wassergehalt von 4 Gew.-% bis 10 Gew.-% trocknet. 13. The method according to any one of claims 9 to 12, characterized in that after the spheronization of the extrudate, the granules at temperatures from 35 ° C to 50 ° C to a water content of 4 wt .-% to 10 wt .-% dries.
14. Verwendung eines Enzymgranulats gemäß einem der Ansprüche 1 bis 8 zur Herstellung fester, insbesondere teilchenförmiger Wasch- oder Reini¬ gungsmittel. 14. Use of an enzyme granulate according to one of claims 1 to 8 for the production of solid, in particular particulate washing or cleaning agents.
PCT/EP1994/000934 1993-03-31 1994-03-23 Enzyme composition for washing and cleaning agents WO1994023005A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP94912528A EP0692016B1 (en) 1993-03-31 1994-03-23 Enzyme composition for washing and cleaning agents
DE59403879T DE59403879D1 (en) 1993-03-31 1994-03-23 ENZYME PREPARATION FOR DETERGENT AND CLEANING AGENT

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4310506.8 1993-03-31
DE4310506A DE4310506A1 (en) 1993-03-31 1993-03-31 Enzyme preparation for detergents and cleaning agents

Publications (1)

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

Family

ID=6484354

Family Applications (1)

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

Country Status (5)

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

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016151A1 (en) * 1994-11-18 1996-05-30 Genencor International, Inc. Coated enzyme granules
US5571446A (en) * 1995-07-27 1996-11-05 Diversey Corporation Anionic stabilized enzyme based clean-in-place system
US6075001A (en) * 1996-04-26 2000-06-13 Henkel Kommanditgesellschaft Aug Aktien Enol esters as bleach activators for detergents and cleaners
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6221824B1 (en) 1999-02-25 2001-04-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of compounded acetonitrile derivatives
US6225274B1 (en) 1996-11-29 2001-05-01 Henkel Kommandigesellschaft Auf Aktien Acetonitrile derivatives as bleaching activators in detergents
US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
US6380147B1 (en) 1998-06-03 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Detergents containing amylase and protease
US6409770B1 (en) 1995-12-08 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Bleaching and washing agents with enzyme bleaching system
US6417152B1 (en) 1997-07-30 2002-07-09 Henkel Kommanditgesellshaft Auf Aktien Detergent containing glucanase
US6417151B1 (en) 1997-04-04 2002-07-09 Henkel Kommanditgesellschaft Auf Aktien Activators for peroxide compounds in detergents and cleaning agents
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6541233B1 (en) 1997-07-30 2003-04-01 Henkel Kommanditgesellschaft Auf Aktien β-glucanase from a bacillus
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
US6703357B1 (en) 1997-07-30 2004-03-09 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent for hard surfaces, containing glucanase
US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US6875734B2 (en) 2003-02-03 2005-04-05 Clariant Gmbh Use of transition metal complexes as bleach catalysts
US7015185B2 (en) 2002-03-15 2006-03-21 Clariant Gmbh Ammonium nitriles and the use thereof as hydrophobic bleaching activators
EP1754781A1 (en) 2005-08-19 2007-02-21 The Procter and Gamble Company A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology
US7300782B2 (en) 2001-12-21 2007-11-27 B.R.A.I.N. Biotechnology Research And Information Network Ag Glycosyl hydrolases
EP0917430B2 (en) † 1996-05-13 2008-03-12 Biovet JSC Enzyme pre-granules for granular fodder
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
EP2088186A1 (en) 2003-12-13 2009-08-12 Henkel AG & Co. KGaA Multi-component thin-to-thick system
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
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
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 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
WO2012080088A1 (en) 2010-12-13 2012-06-21 Basf Se Bleach catalysts
WO2012107187A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd Use of transition metal complexes as bleach catalysts in washing and cleaning compositions
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 (en) 2014-07-03 2016-01-07 Weylchem Wiesbaden Gmbh Sodium salts of secondary alkanesulfonates containing compounds, their preparation and use and washing, disinfecting and cleaning agents containing these
EP2302025B1 (en) 2009-09-08 2016-04-13 The Procter & Gamble Company A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle
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
EP3372663A1 (en) 2017-03-10 2018-09-12 Basf Se Bleach catalysts
EP3524347A1 (en) 2008-04-09 2019-08-14 Basf Se Use of metal hydrazide complex compounds as oxidation catalysts
EP3353274B1 (en) 2015-09-17 2020-11-04 Henkel AG & Co. KGaA Use of high-concentration enzyme granules for increasing the storage stability of enzymes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4420730A1 (en) * 1994-06-15 1995-12-21 Henkel Kgaa Process for the deodorization and stabilization of biotechnologically obtained valuable substances and their aqueous preparations
DE19615776A1 (en) 1996-04-20 1997-10-23 Henkel Kgaa Solubility-enhanced enzyme granules
DE19651446A1 (en) * 1996-12-11 1998-06-18 Henkel Kgaa Enveloped enzyme preparation with improved solubility

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4816188B1 (en) * 1970-08-27 1973-05-19
JPS60168385A (en) * 1984-02-09 1985-08-31 Showa Denko Kk Granulation of enzyme
EP0168526A1 (en) * 1983-12-07 1986-01-22 Henkel Kommanditgesellschaft auf Aktien Enzyme preparation for use in powder detergents
WO1992011347A2 (en) * 1990-12-24 1992-07-09 Henkel Kommanditgesellschaft Auf Aktien Enzyme preparation for washing and cleansing agents

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4816188B1 (en) * 1970-08-27 1973-05-19
EP0168526A1 (en) * 1983-12-07 1986-01-22 Henkel Kommanditgesellschaft auf Aktien Enzyme preparation for use in powder detergents
JPS60168385A (en) * 1984-02-09 1985-08-31 Showa Denko Kk Granulation of enzyme
WO1992011347A2 (en) * 1990-12-24 1992-07-09 Henkel Kommanditgesellschaft Auf Aktien Enzyme preparation for washing and cleansing agents

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 73-30179 *
PATENT ABSTRACTS OF JAPAN vol. 10, no. 13 (C - 323) 18 January 1986 (1986-01-18) *

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016151A1 (en) * 1994-11-18 1996-05-30 Genencor International, Inc. Coated enzyme granules
US5571446A (en) * 1995-07-27 1996-11-05 Diversey Corporation Anionic stabilized enzyme based clean-in-place system
US5783542A (en) * 1995-07-27 1998-07-21 Diversey Lever, Inc. Anionic stabilized enzyme based clean-in-place system
US6409770B1 (en) 1995-12-08 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Bleaching and washing agents with enzyme bleaching system
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
US6235695B1 (en) * 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6075001A (en) * 1996-04-26 2000-06-13 Henkel Kommanditgesellschaft Aug Aktien Enol esters as bleach activators for detergents and cleaners
EP0917430B2 (en) † 1996-05-13 2008-03-12 Biovet JSC Enzyme pre-granules for granular fodder
US6225274B1 (en) 1996-11-29 2001-05-01 Henkel Kommandigesellschaft Auf Aktien Acetonitrile derivatives as bleaching activators in detergents
US6417151B1 (en) 1997-04-04 2002-07-09 Henkel Kommanditgesellschaft Auf Aktien Activators for peroxide compounds in detergents and cleaning agents
US6703357B1 (en) 1997-07-30 2004-03-09 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent for hard surfaces, containing glucanase
US6417152B1 (en) 1997-07-30 2002-07-09 Henkel Kommanditgesellshaft Auf Aktien Detergent containing glucanase
US6541233B1 (en) 1997-07-30 2003-04-01 Henkel Kommanditgesellschaft Auf Aktien β-glucanase from a bacillus
US6462006B1 (en) * 1998-04-30 2002-10-08 Henkel Kommanditgesellschaft Auf Aktien Solid machine dishwashing detergent with phosphate and crystalline lamellar silicates
US6380147B1 (en) 1998-06-03 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Detergents containing amylase and protease
US6841614B1 (en) 1998-10-29 2005-01-11 Henkel Kommanditgesellschaft Auf Aktien Polymer granules produced by fluidized bed granulation
US6221824B1 (en) 1999-02-25 2001-04-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of compounded acetonitrile derivatives
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
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
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
US7737103B2 (en) 2003-12-13 2010-06-15 Henkel Ag & Co. Kgaa Multicomponent thin-to-thick system
EP2088186A1 (en) 2003-12-13 2009-08-12 Henkel AG & Co. KGaA Multi-component thin-to-thick system
US8361946B2 (en) 2004-04-08 2013-01-29 Akzo Nobel N.V. Detergent composition
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
EP1754781A1 (en) 2005-08-19 2007-02-21 The Procter and Gamble Company A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology
US8785362B2 (en) 2005-08-19 2014-07-22 Henkel Ag & Co. Kgaa Triazine derivative dye transfer inhibitors, washing products containing the same and uses therefor
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
US8426635B2 (en) 2008-03-11 2013-04-23 Clariant Finance (Bvi) Limited Process for preparing solid alkaline earth metal salts of secondary paraffinsulphonic acids
EP3524347A1 (en) 2008-04-09 2019-08-14 Basf Se Use of metal hydrazide complex 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
WO2012080088A1 (en) 2010-12-13 2012-06-21 Basf Se Bleach catalysts
EP2805942A1 (en) 2010-12-13 2014-11-26 Basf Se Bleach catalysts
WO2012107187A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd Use of transition metal complexes as bleach catalysts in washing and cleaning compositions
DE102011010818A1 (en) 2011-02-10 2012-08-16 Clariant International Ltd. Use of transition metal complexes as bleaching catalysts in detergents and cleaners
DE102014009836A1 (en) 2014-07-03 2016-01-07 Weylchem Wiesbaden Gmbh Sodium salts of secondary alkanesulfonates containing compounds, their preparation and use and washing, disinfecting and cleaning agents containing these
EP3353274B1 (en) 2015-09-17 2020-11-04 Henkel AG & Co. KGaA Use of high-concentration enzyme granules for increasing 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
EP3372663A1 (en) 2017-03-10 2018-09-12 Basf Se Bleach catalysts

Also Published As

Publication number Publication date
EP0692016B1 (en) 1997-08-27
DE59403879D1 (en) 1997-10-02
ATE157394T1 (en) 1997-09-15
DE4310506A1 (en) 1994-10-06
DK0692016T3 (en) 1998-04-20
EP0692016A1 (en) 1996-01-17

Similar Documents

Publication Publication Date Title
EP0692016B1 (en) Enzyme composition for washing and cleaning agents
EP0564476B1 (en) Enzyme preparation for washing and cleansing agents
EP0898613B1 (en) Improved-solubility enzyme granulate
EP0707628B1 (en) Coated enzyme composition for washing and cleaning products
EP0716685B1 (en) Multiple enzyme granulate
EP0944704B1 (en) Coated enzyme preparation with an improved solubility
EP0767830A1 (en) Production of multiple enzyme granulates
EP0168526B1 (en) Enzyme preparation for use in powder detergents
WO1999029820A1 (en) Enzyme granulate containing cellulase
DE19757215A1 (en) Enzyme granules for use in detergents
WO1997019160A1 (en) Enzyme preparation containing a co-builder
DE19543196A1 (en) Dirt-repellent polymer-containing enzyme preparation
EP0985018A1 (en) Method for preventing colours from running in textiles during washing
DE19543198A1 (en) Stable granulate containing enzyme, carrier, foam inhibitor, and optionally granulation aid
WO2006066730A1 (en) Method for the production of enzyme granules with improved resistance to abrasion

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1994912528

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1994912528

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1994912528

Country of ref document: EP